Water-dispersible polyurethane, water-dispersible polyurethane composition comprising same, adhesive composition comprising same water-dispersible polyurethane composition, and article having same adhesive composition applied thereto

Abstract

The present invention relates to a water-dispersible polyurethane, a water-dispersible polyurethane composition comprising same, an adhesive composition comprising the same water-dispersible polyurethane composition, and an article having the same adhesive composition applied thereto and, more specifically, to a water-dispersible polyurethane, a water-dispersible polyurethane composition comprising same, an adhesive composition comprising the same water-dispersible polyurethane composition, and an article (for example, an electrical steel sheet laminate) having the same adhesive composition applied thereto, wherein the water-dispersible polyurethane comprises, as polymerization units, a polyol component including an anhydrosugar alcohol-alkylene oxide adduct, a polyisocyanate component, a (meth)acrylic group-containing phosphoric acid-based compound, and a hydrophilic ion group-containing diol compound, and with a combination thereof at a specific weight ratio, the water-dispersible polyurethane, when used in an adhesive composition, can provide remarkably improved adhesive strength (particularly, metal-metal adhesive strength) compared to the prior art, while also exhibiting excellent water-dispersion stability and storage stability.

Description

Water-dispersible polyurethane, a water-dispersible polyurethane composition comprising the same, an adhesive composition comprising the water-dispersible polyurethane composition, and an article to which the adhesive composition is applied

[0001] The present invention relates to a water-dispersible polyurethane, a water-dispersible polyurethane composition comprising the same, an adhesive composition comprising the water-dispersible polyurethane composition, and an article to which the adhesive composition is applied, and more specifically, to a water-dispersible polyurethane comprising, as polymerized units, a polyol component comprising an anhydrous sugar alcohol-alkylene oxide adduct, a polyisocyanate component, a (meth)acrylic group-containing phosphoric acid compound, and a hydrophilic ionic group-containing diol compound, and by combining these at a specific weight ratio, when used in an adhesive composition, it is possible to provide significantly improved adhesive strength (particularly, metal-to-metal adhesive strength) compared to the prior art, and at the same time, excellent water-dispersible stability and storage stability, a water-dispersible polyurethane composition comprising the same, an adhesive composition comprising the water-dispersible polyurethane composition, and an article to which the adhesive composition is applied (e.g., an electrical steel laminate).

[0002] Polyols and isocyanates, which are essential components of polyurethane, are usually manufactured from petroleum-based raw materials. However, due to various reasons such as accelerated depletion of petroleum resources, demand for greenhouse gas reduction due to climate change, rising raw material prices, and increasing need for renewable raw materials, there is a demand in the urethane field for ways to partially or completely replace polyols and isocyanates manufactured from petroleum-based raw materials with environmentally friendly components.

[0003] Polyols can be produced from renewable biomass, such as vegetable oils, cellulose, and lignin. Biopolyols derived from vegetable oils are already being produced on a commercial scale. The physical properties of the produced biopolyols vary depending on the type of biomass used in their production. Castor oil and palm oil are typically used in the production of flexible and rigid polyurethanes and synthetic polyols, while soybean oil is used in the production of flexible polyurethane polyols. However, biopolyols currently being produced from biomass have the disadvantage of high viscosity.

[0004] Isocyanates derived from plant-based natural oils are inherently aliphatic compounds, which means they are less reactive than petroleum-based aromatic diisocyanates. Consequently, research into the production of diisocyanates using biomass is limited.

[0005] Hydrogenated sugars (also called “sugar alcohols”) are compounds obtained by adding hydrogen to the reducing end groups of sugars, generally HOCH2(CHOH). n It has the chemical formula CH2OH (where n is an integer from 2 to 5) and is classified into tetrintol, pentitol, hexitol, and heptitol (having 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0006] Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the interior of hydrogenated sugar. When one water molecule is removed, it has the form of a tetraol with four hydroxyl groups in the molecule. When two water molecules are removed, it has the form of a diol with two hydroxyl groups in the molecule. It can be manufactured using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Anhydrosugar alcohol has been the subject of much interest for a long time and research on its manufacturing method has been conducted because it is an environmentally friendly substance derived from renewable natural resources. Among these anhydrosugar alcohols, isosorbide manufactured from sorbitol currently has the widest range of industrial applications.

[0007] Anhydrous sugar alcohols have a wide range of applications, including treating heart and vascular diseases, as adhesives for patches, as pharmaceuticals such as mouthwashes, as solvents in cosmetics, and as emulsifiers in the food industry. Furthermore, they can raise the glass transition temperature of polymers such as polyester, PET, polycarbonate, polyurethane, and epoxy resins, improving their strength. Furthermore, as an eco-friendly material derived from natural products, they are also very useful in the plastics industry, including bioplastics. Furthermore, they are known to be useful as eco-friendly solvents for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers. Due to their diverse applications, anhydrous sugar alcohols are attracting significant attention, and their industrial use is gradually increasing.

[0008] Meanwhile, electrical steel is a steel material that has its crystal arrangement adjusted in a direction in which iron is easily magnetized and silicon is added. Because it has superior electromagnetic properties compared to other steel materials, it is used in electrical devices such as motors, generator cores, electric motors, and small transformers to increase efficiency.

[0009] These electrical steel sheets are typically used in the form of laminates, combining multiple electrical steel sheets. Conventionally, methods such as welding, clamping, and interlocking were used to laminate electrical steel sheets. However, recently, a method has been proposed that bonds the electrical steel sheets by forming a fusion layer between them.

[0010] For example, Korean Patent Publication Nos. 10-2021-0079939 and 10-2021-0079843 disclose an electrical steel sheet adhesive coating composition comprising polyethylene acrylate as a resin component, and an electrical steel sheet laminate manufactured by forming a fusion layer between electrical steel sheets using the composition. However, in this case, the adhesive strength of the electrical steel sheets is insufficient, and improvements thereto are limited.

[0011] In addition, Korean Patent Publication No. 10-2010-0020007 and U.S. Patent Publication No. 2023-0033514 disclose coating compositions for bonding electrical steel sheets containing polyurethane, but even in these cases, the bonding strength of electrical steel sheets is insufficient, and there are limits to its improvement.

[0012] Therefore, there is a demand for the development of an adhesive coating composition capable of laminating multiple electrical steel plates with excellent adhesive strength without using conventional fastening methods such as welding, clamping, and interlocking.

[0013] The purpose of the present invention is to provide a water-dispersible polyurethane which can provide significantly improved adhesive strength (particularly, metal-to-metal adhesive strength) compared to the prior art when used in an adhesive composition, and at the same time has excellent water dispersion stability and storage stability, a water-dispersible polyurethane composition comprising the same, an adhesive composition comprising the water-dispersible polyurethane composition, and an article (e.g., an electrical steel laminate) to which the adhesive composition is applied.

[0014] One aspect of the present invention is a water-dispersible polyurethane comprising: a polyol component comprising an anhydrous alcohol-alkylene oxide adduct; a polyisocyanate component; a phosphoric acid compound containing a (meth)acrylic group; And a hydrophilic ionic group-containing diol compound; as polymerization units, and based on a total of 100 parts by weight of the polymerization units, the content of the anhydrous sugar alcohol-alkylene oxide adduct-derived polymerization units is more than 0.5 parts by weight to less than 35 parts by weight, the content of the polyol component-derived polymerization units is more than 45 parts by weight to less than 70 parts by weight, the content of the polyisocyanate component-derived polymerization units is more than 15 parts by weight to less than 35 parts by weight, the content of the (meth)acrylic group-containing phosphoric acid compound-derived polymerization units is more than 0.5 parts by weight to less than 15 parts by weight, and the content of the hydrophilic ionic group-containing diol compound-derived polymerization units is more than 3 parts by weight to less than 20 parts by weight, a water-dispersible polyurethane is provided.

[0015] Another aspect of the present invention provides a method for producing a water-dispersible polyurethane, comprising the step of polymerizing a mixture comprising: a polyol component comprising an anhydrous sugar alcohol-alkylene oxide adduct; a polyisocyanate component; a (meth)acrylic group-containing phosphoric acid compound; and a hydrophilic ionic group-containing diol compound; wherein, based on 100 parts by weight of the total solid content of the mixture, the content of the anhydrous sugar alcohol-alkylene oxide adduct in the mixture is greater than 0.5 parts by weight and less than 35 parts by weight, the content of the polyol component is greater than 45 parts by weight and less than 70 parts by weight, the content of the polyisocyanate component is greater than 15 parts by weight and less than 35 parts by weight, the content of the (meth)acrylic group-containing phosphoric acid compound is greater than 0.5 parts by weight and less than 15 parts by weight, and the content of the hydrophilic ionic group-containing diol compound is greater than 3 parts by weight and less than 20 parts by weight.

[0016] Another aspect of the present invention provides a water-dispersible polyurethane composition comprising the water-dispersible polyurethane of the present invention and water.

[0017] Another aspect of the present invention provides an adhesive composition comprising the water-dispersed polyurethane composition of the present invention.

[0018] Another aspect of the present invention provides an article to which the adhesive composition of the present invention is applied.

[0019] As a specific example of an article to which the adhesive composition of the present invention is applied, the present invention provides an article comprising: a metal article; and an adhesive coating layer formed on a surface of the metal article, wherein the adhesive coating layer comprises the adhesive composition of the present invention.

[0020] As another specific example of an article to which the adhesive composition of the present invention is applied, the present invention provides an electrical steel plate laminate comprising: a plurality of electrical steel plates; and a fusion layer positioned between the plurality of electrical steel plates; wherein the fusion layer comprises the adhesive composition of the present invention.

[0021] Another aspect of the present invention provides a method for manufacturing an electrical steel plate laminate, comprising the steps of: applying an adhesive composition of the present invention to one or both sides of an electrical steel plate, and then curing the adhesive composition to form an adhesive coating layer; and laminating a plurality of electrical steel plates on which the adhesive coating layers are formed, and thermally fusing them to form a fusion layer.

[0022] The water-dispersible polyurethane according to the present invention has excellent water dispersion stability and storage stability, and can provide significantly improved adhesive strength (particularly, metal-to-metal adhesive strength) compared to conventional technologies when used in an adhesive composition, so it can be particularly suitably used for manufacturing a laminate by bonding a plurality of electrical steel sheets, and furthermore, it is excellent in environmental friendliness because it utilizes anhydrous sugar alcohol derived from natural resources.

[0023] Hereinafter, the present invention will be described in more detail.

[0024] [Water-dispersible polyurethane]

[0025] The water-dispersible polyurethane of the present invention comprises, as polymerization units, a polyol component including an anhydrous sugar alcohol-alkylene oxide adduct; a polyisocyanate component; a (meth)acrylic group-containing phosphoric acid compound; and a hydrophilic ionic group-containing diol compound; wherein, based on 100 parts by weight of the total of the polymerization units, the content of the polymerization units derived from the anhydrous sugar alcohol-alkylene oxide adduct is more than 0.5 parts by weight to less than 35 parts by weight, the content of the polymerization units derived from the polyol component is more than 45 parts by weight to less than 70 parts by weight, the content of the polymerization units derived from the polyisocyanate component is more than 15 parts by weight to less than 35 parts by weight, the content of the polymerization units derived from the (meth)acrylic group-containing phosphoric acid compound is more than 0.5 parts by weight to less than 15 parts by weight, and the content of the polymerization units derived from the hydrophilic ionic group-containing diol compound is more than 3 parts by weight to less than 20 parts by weight.

[0026] If the content of the anhydrous sugar alcohol-alkylene oxide adduct-derived polymerization unit in the water-dispersible polyurethane of the present invention is 0.5 parts by weight or less based on 100 parts by weight of the total of the polymerization units, the adhesive strength is reduced when used in an adhesive composition, and conversely, if the content is 35 parts by weight or more, the polyurethane is not dispersed in water and precipitation occurs.

[0027] In one specific example, the content of the anhydrous sugar alcohol-alkylene oxide adduct-derived polymerization unit in the water-dispersible polyurethane may be more than 0.5 parts by weight, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the total sum of the polymerization units, and may also be less than 35 parts by weight, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less, but is not limited thereto.

[0028] If the content of the polymerization unit derived from the polyol component in the water-dispersible polyurethane of the present invention is 45 parts by weight or less based on 100 parts by weight of the total sum of the polymerization units, the soft segment content of the polyurethane decreases, resulting in a decrease in elongation, and as a result, the peel strength of the adhesive layer may decrease when used in an adhesive composition. Conversely, if the content is 70 parts by weight or more, the hard segment content of the polyurethane decreases, resulting in an excessive elongation, and as a result, the peel strength of the adhesive layer may also decrease when used in an adhesive composition.

[0029] In one specific example, the content of the polymerization unit derived from the polyol component in the water-dispersible polyurethane may be more than 45 parts by weight, 46 parts by weight or more, 47 parts by weight or more, 48 parts by weight or more, 49 parts by weight or more, 50 parts by weight or more, 51 parts by weight or more, 52 parts by weight or more, 53 parts by weight or more, 54 parts by weight or more, or 55 parts by weight or more, based on 100 parts by weight of the total sum of the polymerization units, and may also be less than 70 parts by weight, 69 parts by weight or less, 68 parts by weight or less, 67 parts by weight or less, 66 parts by weight or less, or 65 parts by weight or less, but is not limited thereto.

[0030] If the content of the polymerization unit derived from the polyisocyanate component in the water-dispersible polyurethane of the present invention is 15 parts by weight or less based on 100 parts by weight of the total sum of the polymerization units, the hard segment content of the polyurethane decreases, resulting in excessive elongation, and as a result, the peel strength of the adhesive layer may decrease when used in an adhesive composition. Conversely, if the content is 35 parts by weight or more, the soft segment content of the polyurethane decreases, resulting in decreased elongation, and as a result, the peel strength of the adhesive layer may also decrease when used in an adhesive composition.

[0031] In one specific example, the content of the polymerization unit derived from the polyisocyanate component in the water-dispersible polyurethane may be more than 15 parts by weight, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, or 20 parts by weight or more, based on 100 parts by weight of the total sum of the polymerization units, and may also be less than 35 parts by weight, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less, but is not limited thereto.

[0032] If the content of the polymerization unit derived from the (meth)acrylic group-containing phosphoric acid compound in the water-dispersible polyurethane of the present invention is 0.5 parts by weight or less based on 100 parts by weight of the total of the polymerization units, the interaction between the adhesive layer and the substrate may be reduced when used in an adhesive composition, resulting in a decrease in adhesive strength. Conversely, if the content is 15 parts by weight or more, the heat resistance and adhesiveness of the adhesive layer may be reduced when used in an adhesive composition due to the increased phosphoric acid groups.

[0033] In one specific example, the content of the polymerization unit derived from the (meth)acrylic group-containing phosphoric acid compound in the water-dispersible polyurethane may be more than 0.5 parts by weight, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, or 1 part by weight or more, based on 100 parts by weight of the total sum of the polymerization units, and may also be less than 15 parts by weight, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, or 10 parts by weight or less, but is not limited thereto.

[0034] If the content of the polymerization unit derived from the hydrophilic ionic group-containing diol compound in the water-dispersible polyurethane of the present invention is 3 parts by weight or less based on 100 parts by weight of the total of the polymerization units, the water-dispersible stability of the polyurethane may be reduced, causing phase separation, and the adhesiveness may be reduced when used in an adhesive composition. Conversely, even if the content is 20 parts by weight or more, the water-dispersible stability of the polyurethane may be reduced, causing phase separation, and the adhesiveness may be reduced when used in an adhesive composition.

[0035] In one specific example, the content of the polymerization unit derived from the hydrophilic ionic group-containing diol compound in the water-dispersible polyurethane may be more than 3 parts by weight, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, or 5 parts by weight or more, based on 100 parts by weight of the total sum of the polymerization units, and may also be less than 20 parts by weight, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, or 15 parts by weight or less, but is not limited thereto.

[0036] Hereinafter, each component included as a polymerization unit in the water-dispersible polyurethane of the present invention will be described.

[0037] Anhydrous alcohol-alkylene oxide adducts

[0038] Anhydrous sugar alcohols can be produced by dehydration of hydrogenated sugars derived from natural sources. Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end groups of sugars, generally HOCH2(CHOH). n It has the chemical formula CH2OH (where n is an integer from 2 to 5) and is classified into tetrintol, pentitol, hexitol, and heptitol (having 4, 5, 6, and 7 carbon atoms, respectively) depending on the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0039] The above anhydrous alcohol may be monoanhydrous alcohol, dianhydrous alcohol or a mixture thereof, and although not particularly limited, dianhydrous alcohol may be used.

[0040] Monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the interior of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monoanhydrosugar alcohol is not particularly limited, but preferably, it may be monoanhydrosugar hexitol, and more specifically, it may be 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0041] Anhydrosugar alcohols are anhydrosugar alcohols formed by the removal of two water molecules from the interior of hydrogenated sugars. They have a diol structure with two hydroxyl groups within the molecule and can be manufactured using hexitols derived from starch. Anhydrosugar alcohols have long been the subject of considerable interest and research into their manufacturing methods, as they are environmentally friendly substances derived from renewable natural resources. Among these dianhydrosugar alcohols, isosorbide, manufactured from sorbitol, currently has the widest range of industrial applications.

[0042] The type of the above-mentioned dianhydrosugar alcohol is not particularly limited, but preferably it may be a dianhydrosugar hexitol, and more specifically, it may be 1,4:3,6-dianhydrohexitol. The above-mentioned 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0043] The above-mentioned alkylene oxide adduct of anhydrous alcohol (also referred to as “anhydrous alcohol-alkylene glycol”) is an adduct obtained by reacting hydroxyl groups at both terminals or one terminal (preferably both terminals) of anhydrous alcohol with an alkylene oxide, and refers to a compound in which the hydrogen of the hydroxyl groups at both terminals or one terminal (preferably both terminals) of anhydrous alcohol is replaced with a hydroxyalkyl group, which is a ring-opened form of an alkylene oxide.

[0044] In one specific embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically, may be ethylene oxide, propylene oxide, or a combination thereof.

[0045] In one specific example, the alkylene oxide adduct of the anhydrous sugar alcohol may be a compound represented by the following chemical formula 1 or a mixture of two or more thereof.

[0046] [Chemical Formula 1]

[0047]

[0048] In the above chemical formula 1,

[0049] R 1 and R 2 Each independently represents a linear or branched alkylene group having 2 to 8 carbon atoms,

[0050] m and n each independently represent an integer from 0 to 15,

[0051] m+n represents an integer from 1 to 30.

[0052] More preferably, in the above chemical formula 1,

[0053] R 1 and R 2 Each independently represents an ethylene group, a propylene group or an isopropylene group, preferably R 1 and R 2 are identical to each other,

[0054] m and n each independently represent an integer from 0 to 14,

[0055] However, m+n is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0056] In one specific example, the alkylene oxide adduct of the anhydrous sugar alcohol may be a propylene oxide adduct of the anhydrous sugar alcohol represented by the following chemical formula 1-1, an ethylene oxide adduct of the anhydrous sugar alcohol represented by the following chemical formula 1-2, or a mixture thereof.

[0057] [Chemical Formula 1-1]

[0058]

[0059] In the above chemical formula 1-1,

[0060] a and b each independently represent an integer from 0 to 15,

[0061] a+b represents an integer from 1 to 30.

[0062] More preferably, in the above chemical formula 1-1,

[0063] a and b each independently represent an integer from 0 to 14,

[0064] However, a+b is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0065] [Chemical Formula 1-2]

[0066]

[0067] In the above chemical formula 1-2,

[0068] c and d each independently represent an integer from 0 to 15,

[0069] c+d represents an integer from 1 to 30.

[0070] More preferably, in the above chemical formula 1-2,

[0071] c and d each independently represent an integer from 0 to 14,

[0072] However, c+d is an integer greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3, and also an integer less than or equal to 25, less than or equal to 20, less than or equal to 15, or less than or equal to 12, for example, an integer from 1 to 25, preferably an integer from 2 to 20, and more preferably an integer from 3 to 15.

[0073] In one specific example, the alkylene oxide adduct of the anhydrous sugar alcohol may be produced by a production method comprising the steps of (1) treating the anhydrous sugar alcohol with an acid component; and (2) performing an addition reaction between the anhydrous sugar alcohol treated with the acid component obtained in step (1) and the alkylene oxide.

[0074] More specifically, the alkylene oxide adduct of the anhydrous sugar alcohol may be produced by a production method comprising the steps of (1) treating the anhydrous sugar alcohol with an acid component; (2) performing an addition reaction between the anhydrous sugar alcohol treated with the acid component obtained in step (1) and the alkylene oxide; and (3) performing an addition reaction between the product obtained in step (2) and the alkylene oxide in the presence of a base catalyst.

[0075] The acid component is not particularly limited, and may be selected from the group consisting of phosphoric acid, sulfuric acid, acetic acid, formic acid, heteropolyacid, or a mixture thereof. In one specific example, the heteropolyacid may be phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, or silicomolybdic acid. In addition, a commercially available acid component such as Amberlyst 15 (manufactured by Dow Chemical) may be used.

[0076] In one specific example, the acid treatment may be performed at an elevated temperature (e.g., 80°C to 200°C, or 90°C to 180°C) under a nitrogen atmosphere using 0.1 to 10 moles, preferably 0.1 to 8 moles, and more preferably 0.1 to 5 moles of the acid component per mole of the anhydrous sugar alcohol, and then vacuum depressurization may be performed to remove moisture within the reactor, but is not limited thereto.

[0077] The acid component used in the above acid treatment is intended to facilitate ring opening of the alkylene oxide in the addition reaction of the alkylene oxide described below.

[0078] Typically, the addition reaction of an alkylene oxide to an alcohol proceeds in the presence of a base catalyst. However, in the case of anhydrosugar alcohols, due to their structural characteristics, the rate at which the alkylene oxide is added competes with the rate at which the anhydrosugar alcohol's ring structure is opened and decomposed by the base catalyst. Accordingly, not only the anhydrosugar alcohol but also the decomposition product of the anhydrosugar alcohol reacts with the alkylene oxide, and the reaction product between the decomposition product of the anhydrosugar alcohol decomposed by the base catalyst and the alkylene oxide can act as a factor that reduces product quality and storage stability. However, if the anhydrosugar alcohol is first treated with an acid component and then the alkylene oxide is added, not only does the acid component facilitate the ring opening of the alkylene oxide, but also the decomposition product of the anhydrosugar alcohol by the base catalyst is not generated, so the addition reaction of the anhydrosugar alcohol and the alkylene oxide can easily produce an anhydrosugar alcohol-alkylene oxide adduct. Therefore, when acid-treated anhydrous sugar alcohol and alkylene oxide are subjected to an addition reaction, the conventional problems can be solved.

[0079] In one specific example, the addition reaction of the anhydrous sugar alcohol treated with the acid component and the alkylene oxide may be carried out at an elevated temperature (e.g., 100°C to 180°C, or 120°C to 160°C) while slowly adding the alkylene oxide to the anhydrous sugar alcohol treated with the acid component for, for example, 1 to 8 hours or 2 to 4 hours, but is not limited thereto. The reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mol or more or 2 mol or more of the alkylene oxide per 1 mol of the anhydrous sugar alcohol, and also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, and may be, for example, 1 mol to 30 mol, preferably 2 to 20 mol, but is not limited thereto.

[0080] In one specific example, the addition reaction of the product obtained by the addition reaction of the alkylene oxide with an additional alkylene oxide may be performed, for example, in a high-pressure reactor capable of pressurization (for example, a pressure of 3 MPa or more), in the presence of a base catalyst (for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or a hydroxide of an alkaline earth metal such as calcium hydroxide), at an elevated temperature (for example, 100°C to 180°C, or 120°C to 160°C), for, for example, 1 hour to 8 hours or 2 hours to 4 hours, but is not limited thereto. The reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mol or more, 2 mol or more, or 3 mol or more of the alkylene oxide per 1 mol of the anhydrous sugar alcohol, and also 30 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, and may be, for example, 1 mol to 30 mol, preferably 2 mol to 20 mol, and more preferably 3 mol to 15 mol, but is not limited thereto. Before adding the base catalyst, the acid component used in the treatment can be removed by filtration.

[0081] The product obtained by the addition reaction of an acid-treated anhydrosugar alcohol and an alkylene oxide (i.e., a compound in which an alkylene oxide is added to an anhydrosugar alcohol) has a very stable structure. Therefore, even in the presence of a base catalyst, the ring structure of the anhydrosugar alcohol does not easily open or decompose at high temperatures. Therefore, it is very advantageous for the additional addition reaction of alkylene oxide. If the acid catalyst continues to be used during the additional addition reaction of alkylene oxide, although the acid catalyst helps promote the ring opening of the alkylene oxide, the reaction rate decreases as the number of moles of alkylene oxide added increases. In other words, the rate of alkylene oxide addition competes with the rate of ring opening of the alkylene oxide itself. At this time, the rate of alkylene oxide addition slows down, and the self-condensation reaction and by-product formation of the ring-opened alkylene oxides can occur, resulting in a deterioration in quality. Therefore, the additional addition reaction of alkylene oxide is carried out in the presence of a base catalyst.

[0082] Afterwards, a step of removing metal ions flowing out from the base catalyst used above can be additionally performed, and for this purpose, a metal ion adsorbent such as Ambosol MP20 (magnesium silicate component) can be used.

[0083] polyol components

[0084] The above polyol component essentially includes the anhydrous sugar alcohol-alkylene oxide adduct described above.

[0085] The above polyol component further includes a polyol compound other than an anhydrous alcohol-alkylene oxide adduct (hereinafter also referred to as “additional polyol compound”).

[0086] In one specific embodiment, the additional polyol compound may be a polyether polyol, and more specifically, the polyether polyol may be a polyalkylene glycol.

[0087] In one specific example, the polyalkylene glycol may include, but is not limited to, one selected from polytetrahydrofuran (polytetramethylene ether glycol), polypropylene glycol, polyethylene glycol, polyoxytrimethylene ether glycol, or combinations thereof.

[0088] In one specific example, the number average molecular weight (Mn) of the polyether polyol is not particularly limited, but may be specifically 200 to 3,000 g / mol, more specifically 500 to 2,500 g / mol, even more specifically 700 to 2,300 g / mol, and still more specifically 1,000 to 2,000 g / mol.

[0089] polyisocyanate component

[0090] The polyisocyanate component may include at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, or combinations thereof.

[0091] In one embodiment, the polyisocyanate component is an aromatic polyisocyanate, such as, for example, methylenediphenyl diisocyanate (MDI) (e.g., 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI), phenylene diisocyanate (e.g., 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4'-dibenzyldiisocyanate; Aliphatic such as hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI) (e.g., 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanates, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (e.g., cyclohexane-1,4-diisocyanate), or ethylene diisocyanate polyisocyanate; or a combination thereof, but is not limited thereto.

[0092] In another specific example, the polyisocyanate component is methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene Diisocyanate, toluene diisocyanate mixed with 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio=80 / 20), diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate or a combination thereof, but is not limited thereto.

[0093] More specifically, the polyisocyanate component may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

[0094] Phosphoric acid compound containing (meth)acrylic group

[0095] The above (meth)acrylic group-containing phosphoric acid compound may include a phosphoric acid compound having one or more (e.g., 1 to 4) (meth)acrylic groups in the molecule, which serves to improve the adhesive strength of the water-dispersible polyurethane of the present invention.

[0096] In one specific example, the (meth)acrylic group-containing phosphoric acid compound may be, but is not limited to, 2-methacryloxyethyl phosphate having the following structure, bis(2-methacryloyloxyethyl) phosphate having the following structure, or a combination thereof.

[0097] [2-methacryloxyethyl phosphate]

[0098]

[0099] [Bis(2-methacryloxyethyl) phosphate]

[0100]

[0101] Diol compounds containing hydrophilic ionic groups

[0102] The above hydrophilic ionic group-containing diol compound plays a role in imparting water dispersibility to polyurethane.

[0103] In one specific example, the hydrophilic ionic group-containing diol compound may include a diol compound containing one or more carboxyl groups, and more specifically, may include, but is not limited to, dimethylol propionic acid (DMPA), dimethylolbutanoic acid (DMBA), or a combination thereof.

[0104] The presence of the hydrophilic ionic group-containing diol compound as a polymerization unit increases the hydrophilicity of the polyurethane prepolymer, thereby reducing the amount of diluting solvent (e.g., acetone), thereby ensuring storage stability even when the solids content of the polyurethane aqueous dispersion increases. In addition, the particle size of the polyurethane can increase and the mechanical strength can be enhanced.

[0105] Using a diol compound containing a hydrophilic ionic group forms a hydrophilic polyurethane prepolymer with a hydrophilic ionic group introduced. In this case, a neutralizing agent can be added to the prepolymer to neutralize the hydrophilic prepolymer. Examples of neutralizing agents include, but are not limited to, triethylamine (TEA), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

[0106] In one specific example, when the water-dispersible polyurethane of the present invention is dispersed in water to produce an aqueous dispersion, the water-dispersible polyurethane may have a core-shell structure, which may be formed, for example, by a hydrophobic portion (core) which is a (meth)acrylic group portion of a (meth)acrylic group-containing phosphate compound and a hydrophilic portion (shell) which is a hydrophilic ionic group portion of a hydrophilic ionic group-containing diol compound. This core-shell structure can uniformly disperse the portion derived from the (meth)acrylic group-containing phosphate compound, thereby uniformly improving the adhesive strength and water-dispersibility of the polyurethane.

[0107] Another aspect of the present invention provides a method for producing a water-dispersible polyurethane, comprising the step of polymerizing a mixture comprising: a polyol component comprising an anhydrous sugar alcohol-alkylene oxide adduct; a polyisocyanate component; a (meth)acrylic group-containing phosphoric acid compound; and a hydrophilic ionic group-containing diol compound; wherein, based on 100 parts by weight of the total solid content of the mixture, the content of the anhydrous sugar alcohol-alkylene oxide adduct in the mixture is greater than 0.5 parts by weight and less than 35 parts by weight, the content of the polyol component is greater than 45 parts by weight and less than 70 parts by weight, the content of the polyisocyanate component is greater than 15 parts by weight and less than 35 parts by weight, the content of the (meth)acrylic group-containing phosphoric acid compound is greater than 0.5 parts by weight and less than 15 parts by weight, and the content of the hydrophilic ionic group-containing diol compound is greater than 3 parts by weight and less than 20 parts by weight.

[0108] The specific types and amounts of each component used in the method for producing the water-dispersible polyurethane of the present invention are as described above.

[0109] In one specific example, the method for producing the water-dispersible polyurethane may further include a step of neutralizing the prepolymer, which is a polymerization result, by adding a neutralizing agent. At this time, the neutralizing agent that can be used is as described above.

[0110] [Water-dispersed polyurethane composition]

[0111] Another aspect of the present invention provides a water-dispersible polyurethane composition comprising the water-dispersible polyurethane of the present invention and water. The water-dispersible polyurethane composition of the present invention refers to an aqueous dispersion in which the water-dispersible polyurethane of the present invention is dispersed in water.

[0112] When preparing a water-dispersible polyurethane of the present invention by dispersing it in water, the water-dispersible polyurethane can have a core-shell structure as described above, and due to this morphological advantage, the (meth)acrylic-containing phosphoric acid compound-derived moiety can be uniformly dispersed in water, thereby uniformly improving the adhesive strength and water-dispersibility of the polyurethane.

[0113] The solid content of the water-dispersed polyurethane composition according to the present invention may be 15 wt% to 40 wt%, preferably 20 wt% to 35 wt%, and more preferably 25 wt% to 35 wt%, based on the total weight of the water-dispersed polyurethane composition, but is not particularly limited thereto. If the solid content is less than the above level, based on the total weight of the water-dispersed polyurethane composition, the viscosity may be too low, causing uneven coating on the substrate and thus reducing adhesive strength. If the solid content is greater than the above level, the viscosity may be too high, causing uneven coating on the substrate and thus reducing adhesive strength.

[0114] [Adhesive composition]

[0115] Another aspect of the present invention provides an adhesive composition comprising the water-dispersed polyurethane composition of the present invention described above.

[0116] When the adhesive composition of the present invention is used for bonding electrical steel sheets, the water-dispersible polyurethane of the present invention plays a role in improving the adhesion between the fusion layer to which the adhesive composition is applied and the metal (specifically, the electrical steel sheet).

[0117] The water in the adhesive composition of the present invention evaporates during the fusion process and does not remain in the fusion layer.

[0118] In one specific embodiment, the adhesive composition may further include, in addition to the water-dispersible polyurethane of the present invention and water, one or more additive components commonly used in polyurethane-based adhesive compositions.

[0119] [Coated metal article, electrical steel plate laminate, and method for manufacturing the same]

[0120] Another aspect of the present invention provides an article to which the adhesive composition of the present invention is applied.

[0121] In one specific example, the article may be a mechanical part, an electrical part, or an electronic part, and more specifically, may be, but is not limited to, an electrical steel sheet.

[0122] As a specific example of an article to which the adhesive composition of the present invention is applied, the present invention provides an article comprising: a metal article; and an adhesive coating layer formed on a surface of the metal article, wherein the adhesive coating layer comprises the adhesive composition of the present invention.

[0123] As another specific example of an article to which the adhesive composition of the present invention is applied, the present invention provides an electrical steel plate laminate comprising: a plurality of electrical steel plates; and a fusion layer positioned between the plurality of electrical steel plates; wherein the fusion layer comprises the adhesive composition of the present invention.

[0124] Another aspect of the present invention provides a method for manufacturing an electrical steel plate laminate, comprising the steps of: applying an adhesive composition of the present invention to one or both sides of an electrical steel plate, and then curing the adhesive composition to form an adhesive coating layer; and laminating a plurality of electrical steel plates on which the adhesive coating layers are formed, and thermally fusing them to form a fusion layer.

[0125] There is no particular limitation on the method for forming a coating layer of the adhesive composition of the present invention on the above article, and it can be performed using a conventional coating method and equipment.

[0126] During the above-described bonding layer formation process, the polyurethane component included in the adhesive composition of the present invention remains within the bonding layer. The solvent (e.g., water) evaporates during the drying process and does not remain within the bonding layer.

[0127] In one specific example, the thickness of the fusion layer may be 0.1 to 5 μm, more specifically 2 to 3 μm. If the thickness of the fusion layer is too thin, the adhesive strength may be drastically reduced, and if it is too thick, defects due to sticky properties may become a problem after coating and winding.

[0128] A method for manufacturing an electrical steel plate laminate according to one specific example of the present invention is as follows, but is not limited thereto.

[0129] First, the adhesive composition of the present invention is prepared. Next, the adhesive composition of the present invention is coated on the surface of an electrical steel sheet, and then cured to form an adhesive coating layer. This step can be performed at a temperature range of 100 to 250°C to cure the adhesive composition of the present invention. Next, a plurality of electrical steel sheets having adhesive coating layers formed thereon are laminated and heat-sealed to form a fusion layer. Through the heat-sealing step, the polymer components within the adhesive coating layer heat-sealed to form a fusion layer.

[0130] The thermal bonding step can be performed under conditions of a temperature of 100 to 250°C, a pressure of 0.05 to 10.0 Mpa, and a pressurization time of 0.1 to 20 minutes. By controlling the temperature, pressure, and time conditions in the thermal bonding step, dense thermal bonding can be achieved between the electrical steel sheets without a gap or organic phase.

[0131] Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the scope of the present invention is not limited to these examples.

[0132] [Example]

[0133] <Preparation of anhydrous alcohol-alkylene oxide adducts>

[0134] Manufacturing Example A1: Preparation of 5 mol isosorbide-ethylene oxide adduct

[0135] Into a pressurizable reactor, 146 g of isosorbide was placed, and 0.15 g of phosphoric acid (85%) was added as an acid component. The inside of the reactor was purged with nitrogen, heated to 100°C, and moisture inside the reactor was removed through vacuum depressurization. Next, 88 g of ethylene oxide was slowly added to the reactor for the first time, and the reaction was carried out at a temperature of 100°C to 140°C for 2 to 3 hours. The reaction temperature was controlled so as not to exceed 140°C. Afterwards, the internal temperature of the reactor was cooled to 50°C, 0.3 g of potassium hydroxide was added to the reactor, the inside of the reactor was purged with nitrogen, heated to 100°C, and moisture inside the reactor was removed through vacuum depressurization. Next, 132 g of ethylene oxide was slowly added for the second time, and the reaction was carried out at 100°C to 140°C for 2 to 3 hours. When the reaction was completed, the internal temperature of the reactor was cooled to 50°C, 4.0 g of Ambosol MP20 was added as an adsorbent, and the mixture was heated again and stirred at a temperature of 100°C to 120°C for 1 to 5 hours to remove metal ions. At this time, the interior of the reactor was purged with nitrogen and / or vacuum pressure was applied. When no more metal ions were detected, the internal temperature of the reactor was cooled to 60°C to 90°C, and the residual byproducts were removed, thereby obtaining 362 g of a transparent liquid isosorbide-ethylene oxide 5-mole adduct.

[0136] Manufacturing Example A2: Preparation of 10 mol isosorbide-ethylene oxide adduct

[0137] Except that the secondary input of ethylene oxide was changed from 132 g to 352 g, the same method as in Manufacturing Example A1 was performed to obtain 551 g of a 10-mol isosorbide-ethylene oxide adduct in a transparent liquid state.

[0138] Manufacturing Example A3: Preparation of 5 mol isosorbide-propylene oxide adduct

[0139] Instead of using ethylene oxide as an additional reaction raw material, propylene oxide was used, and specifically, instead of first adding 88 g of ethylene oxide, 116 g of propylene oxide was first added, and instead of second adding 132 g of ethylene oxide, 174 g of propylene oxide was second added, the same method as in Manufacturing Example A1 was performed, thereby obtaining 423 g of a transparent liquid isosorbide-propylene oxide 5 mol adduct.

[0140] Manufacturing Example A4: Preparation of 10 mol isosorbide-propylene oxide adduct

[0141] Instead of using ethylene oxide as an additional reaction raw material, propylene oxide was used, and specifically, instead of first adding 88 g of ethylene oxide, 116 g of propylene oxide was first added, and instead of second adding 132 g of ethylene oxide, 465 g of propylene oxide was second added, the same method as in Manufacturing Example A1 was performed, thereby obtaining 698 g of a 10-mol isosorbide-propylene oxide adduct in a transparent liquid state.

[0142] <Manufacture of water-dispersible polyurethane and water-dispersible polyurethane compositions>

[0143] Example A1

[0144] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0145] Specifically, 100 g of polytetrahydrofuran (number average molecular weight: 2,000 g / mol, Sigma-Aldrich) as a polyol, 18 g of the 5-mol isosorbide-ethylene oxide adduct obtained in Preparation Example A1, 10 g of bis(2-methacryloxyethyl) phosphate as a (meth)acrylic group-containing phosphoric acid compound, and 19 g of dimethylolbutanoic acid (DMBA) as a hydrophilic ionic group-containing diol compound were added to a three-necked glass reactor equipped with a stirrer, and mixed at 100°C for 30 minutes. After cooling to 40°C, 0.1 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst was added, and 50 g of isophorone diisocyanate was slowly added while the reaction proceeded. After the addition of isophorone diisocyanate was completed, the reaction was further performed at 80°C for 3 hours under a nitrogen atmosphere. After obtaining the product of the above reaction, it was cooled to 40℃ and 197g of methyl ethyl ketone (MEK) was added to reduce the viscosity. Thereafter, triethylamine (TEA) was added in an amount equal to the mole number of dimethylolbutanoic acid (DMBA) and neutralized by high-speed stirring at 600 rpm for 30 minutes at a temperature of 40℃. Distilled water was added dropwise to the neutralized reaction product so that the solid content became 30 wt% and high-speed stirring was performed at 600 rpm for 1 hour. Thereafter, it was cooled to 30℃ and methyl ethyl ketone was distilled under vacuum conditions, thereby obtaining 650g of a water-dispersed polyurethane composition.

[0146] Example A2

[0147] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 10 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0148] Specifically, a water-dispersible polyurethane was prepared by performing the same method as Example A1, except that 21 g of a 10-mol isosorbide-ethylene oxide adduct obtained in Preparation Example A2 was used instead of the 5-mol isosorbide-ethylene oxide adduct obtained in Preparation Example A1, and this was dispersed in water to obtain 643 g of a water-dispersible polyurethane composition.

[0149] Example A3

[0150] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-propylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0151] Specifically, a water-dispersible polyurethane was prepared by performing the same method as Example A1, except that 20 g of the 5-mol isosorbide-propylene oxide adduct obtained in Preparation Example A3 was used instead of the 5-mol isosorbide-ethylene oxide adduct obtained in Preparation Example A1, and this was dispersed in water to obtain 652 g of a water-dispersible polyurethane composition.

[0152] Example A4

[0153] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-propylene oxide 10 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0154] Specifically, a water-dispersible polyurethane was prepared by performing the same method as Example A1, except that 20 g of a 10-mol isosorbide-propylene oxide adduct obtained in Preparation Example A4 was used instead of the 5-mol isosorbide-ethylene oxide adduct obtained in Preparation Example A1, and this was dispersed in water to obtain 658 g of a water-dispersible polyurethane composition.

[0155] Example A5

[0156] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (59 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (1 part by weight) as a polyol, isophorone diisocyanate (25 parts by weight) as a polyisocyanate, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0157] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 1.8 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 9 g, the amount of dimethylolbutanoic acid was changed from 19 g to 16 g, and the amount of isophorone diisocyanate was changed from 50 g to 42 g, and this was dispersed in water to obtain 556 g of a water-dispersible polyurethane composition.

[0158] Example A6

[0159] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (55 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (5 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0160] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 9 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 9 g, the amount of dimethylolbutanoic acid was changed from 19 g to 18 g, and the amount of isophorone diisocyanate was changed from 50 g to 46 g, and this was dispersed in water to obtain 600 g of a water-dispersible polyurethane composition.

[0161] Example A7

[0162] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (45 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (15 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0163] Specifically, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 33 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 11 g, the amount of dimethylolbutanoic acid was changed from 19 g to 22 g, and the amount of isophorone diisocyanate was changed from 50 g to 56 g, a water-dispersible polyurethane was manufactured by performing the same method as in Example A1, and this was dispersed in water to obtain 731 g of a water-dispersible polyurethane composition.

[0164] Example A8

[0165] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (40 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (20 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0166] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 49 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 13 g, the amount of dimethylolbutanoic acid was changed from 19 g to 25 g, and the amount of isophorone diisocyanate was changed from 50 g to 62 g, and the same method as in Example A1 was performed to manufacture a water-dispersible polyurethane, which was dispersed in water to obtain 819 g of a water-dispersible polyurethane composition.

[0167] Example A9

[0168] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (30 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (30 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0169] Specifically, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 100 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 17 g, the amount of dimethylolbutanoic acid was changed from 19 g to 33 g, and the amount of isophorone diisocyanate was changed from 50 g to 83 g, a water-dispersible polyurethane was manufactured by performing the same method as in Example A1, and this was dispersed in water to obtain 1,090 g of a water-dispersible polyurethane composition.

[0170] Example A10

[0171] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (55 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (20 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0172] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that the amount of bis(2-methacryloxyethyl) phosphate used was changed from 10 g to 9 g and the amount of isophorone diisocyanate used was changed from 50 g to 37 g, and this was dispersed in water to obtain 601 g of a water-dispersible polyurethane composition.

[0173] Example A11

[0174] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (45 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (30 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0175] Specifically, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 22 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 11 g, the amount of dimethylolbutanoic acid was changed from 19 g to 22 g, and the amount of isophorone diisocyanate was changed from 50 g to 67 g, a water-dispersible polyurethane was manufactured by performing the same method as in Example A1, and this was dispersed in water to obtain 730 g of a water-dispersible polyurethane composition.

[0176] Example A12

[0177] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (54 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (1 part by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0178] Specifically, a water-dispersible polyurethane was manufactured by performing the same method as in Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 19 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 2 g, and the amount of isophorone diisocyanate was changed from 50 g to 46 g, and this was dispersed in water to obtain 615 g of a water-dispersible polyurethane composition.

[0179] Example A13

[0180] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (52 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (3 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0181] Specifically, a water-dispersible polyurethane was manufactured by performing the same method as in Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 19 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 6 g, and the amount of isophorone diisocyanate was changed from 50 g to 48 g, and this was dispersed in water to obtain 612 g of a water-dispersible polyurethane composition.

[0182] Example A14

[0183] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (45 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (10 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0184] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 22 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 22 g, the amount of dimethylolbutanoic acid was changed from 19 g to 22 g, and the amount of isophorone diisocyanate was changed from 50 g to 56 g, and the same method as in Example A1 was performed to manufacture a water-dispersible polyurethane, which was dispersed in water to obtain 728 g of a water-dispersible polyurethane composition.

[0185] Example A15

[0186] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (55 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (5 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0187] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that the amount of bis(2-methacryloxyethyl) phosphate used was changed from 10 g to 9 g, the amount of dimethylolbutanoic acid used was changed from 19 g to 9 g, and the amount of isophorone diisocyanate used was changed from 50 g to 46 g, and this was dispersed in water to obtain 600 g of a water-dispersible polyurethane composition.

[0188] Example A16

[0189] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (45 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (15 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0190] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 22 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 12 g, the amount of dimethylolbutanoic acid was changed from 19 g to 33 g, and the amount of isophorone diisocyanate was changed from 50 g to 55 g, and this was dispersed in water to obtain 731 g of a water-dispersible polyurethane composition.

[0191] Example A17

[0192] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polypropylene glycol (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0193] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that 100 g of polypropylene glycol was used instead of polytetrahydrofuran, and this was dispersed in water to obtain 643 g of a water-dispersible polyurethane composition.

[0194] Example A18

[0195] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polyethylene glycol (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0196] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that 100 g of polyethylene glycol was used instead of polytetrahydrofuran, and this was dispersed in water to obtain 640 g of a water-dispersible polyurethane composition.

[0197] Example A19

[0198] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, hexamethylene diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0199] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that 51 g of hexamethylene diisocyanate was used instead of isophorone diisocyanate, and this was dispersed in water to obtain 658 g of a water-dispersible polyurethane composition.

[0200] Example A20

[0201] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, toluene diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0202] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that 49 g of toluene diisocyanate was used instead of isophorone diisocyanate, and this was dispersed in water to obtain 655 g of a water-dispersible polyurethane composition.

[0203] Example A21

[0204] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as a polyol, methylenediphenyl diisocyanate (25 parts by weight) as a polyisocyanate, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0205] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that 50 g of methylenediphenyl diisocyanate was used instead of isophorone diisocyanate, and this was dispersed in water to obtain 650 g of a water-dispersible polyurethane composition.

[0206] Example A22

[0207] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, 2-methacryloxyethyl phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0208] Specifically, a water-dispersible polyurethane was prepared by performing the same method as Example A1, except that 10 g of 2-methacryloxyethyl phosphate was used instead of bis(2-methacryloxyethyl) phosphate as the (meth)acrylic group-containing phosphoric acid compound, and the water-dispersible polyurethane was dispersed in water to obtain 630 g of a water-dispersible polyurethane composition.

[0209] Example A23

[0210] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (50 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolpropionic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0211] Specifically, a water-dispersible polyurethane was prepared by performing the same method as Example A1, except that 20 g of dimethylolpropionic acid was used instead of dimethylolbutanoic acid as the hydrophilic ion-containing diol compound, and the water-dispersible polyurethane composition was dispersed in water to obtain 655 g of the water-dispersible polyurethane composition.

[0212] Comparative Example A1

[0213] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (60 parts by weight) as a polyol, isophorone diisocyanate (25 parts by weight) as a polyisocyanate, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0214] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was not used as a polyol, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 8 g, the amount of dimethylolbutanoic acid was changed from 19 g to 17 g, and the amount of isophorone diisocyanate was changed from 50 g to 42 g, and this was dispersed in water to obtain 550 g of a water-dispersible polyurethane composition.

[0215] Comparative Example A2

[0216] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (59.5 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (0.5 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0217] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 1 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 8 g, the amount of dimethylolbutanoic acid was changed from 19 g to 17 g, and the amount of isophorone diisocyanate was changed from 50 g to 42 g, and this was dispersed in water to obtain 550 g of a water-dispersible polyurethane composition.

[0218] Comparative Example A3

[0219] Based on 100 parts by weight of the total solid content of the components, polytetrahydrofuran (25 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (35 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound were used to prepare polyurethane, and this was dispersed in water to prepare a polyurethane composition.

[0220] Specifically, a polyurethane was manufactured by the same method as in Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 140 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 20 g, the amount of dimethylolbutanoic acid was changed from 19 g to 40 g, and the amount of isophorone diisocyanate was changed from 50 g to 100 g, and the polyurethane was dispersed in water to obtain 1,320 g of a polyurethane composition.

[0221] Comparative Example A4

[0222] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (60 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (15 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0223] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 17 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 8 g, the amount of dimethylolbutanoic acid was changed from 19 g to 17 g, and the amount of isophorone diisocyanate was changed from 50 g to 25 g, and this was dispersed in water to obtain 550 g of a water-dispersible polyurethane composition.

[0224] Comparative Example A5

[0225] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (40 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (35 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0226] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 25 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 13 g, the amount of dimethylolbutanoic acid was changed from 19 g to 25 g, and the amount of isophorone diisocyanate was changed from 50 g to 88 g, and this was dispersed in water to obtain 825 g of a water-dispersible polyurethane composition.

[0227] Comparative Example A6

[0228] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (55 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0229] Specifically, a water-dispersible polyurethane was prepared by performing the same method as in Example A1, except that bis(2-methacryloxyethyl) phosphate was not used, the amount of dimethylolbutanoic acid was changed from 19 g to 18 g, and the amount of isophorone diisocyanate was changed from 50 g to 46 g, and this was dispersed in water to obtain 600 g of a water-dispersible polyurethane composition.

[0230] Comparative Example A7

[0231] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (54.5 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (0.5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0232] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 19 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 1 g, the amount of dimethylolbutanoic acid was changed from 19 g to 18 g, and the amount of isophorone diisocyanate was changed from 50 g to 46 g, and the same method as in Example A1 was performed to manufacture a water-dispersible polyurethane, which was dispersed in water to obtain 550 g of a water-dispersible polyurethane composition.

[0233] Comparative Example A8

[0234] Based on 100 parts by weight of the total solid content of the components, a water-dispersible polyurethane was prepared using polytetrahydrofuran (40 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (15 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (10 parts by weight) as a hydrophilic ionic group-containing diol compound, and this was dispersed in water to prepare a water-dispersible polyurethane composition.

[0235] Specifically, a water-dispersible polyurethane was manufactured by the same method as Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Preparation Example A1 was changed from 18 g to 25 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 37 g, the amount of dimethylolbutanoic acid was changed from 19 g to 25 g, and the amount of isophorone diisocyanate was changed from 50 g to 63 g, and this was dispersed in water to obtain 825 g of a water-dispersible polyurethane composition.

[0236] Comparative Example A9

[0237] Based on 100 parts by weight of the total solid content of the components, polytetrahydrofuran (60 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) were used as polyols, isophorone diisocyanate (25 parts by weight) was used as polyisocyanate, and bis(2-methacryloxyethyl) phosphate (5 parts by weight) was used as a (meth)acrylic group-containing phosphoric acid compound to prepare polyurethane, which was then dispersed in water to prepare a polyurethane composition.

[0238] Specifically, a polyurethane was manufactured by performing the same method as in Example A1, except that the amount of the isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 17 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 8 g, dimethylolbutanoic acid was not used, and the amount of isophorone diisocyanate was changed from 50 g to 42 g, and this was dispersed in water to obtain 550 g of a polyurethane composition.

[0239] Comparative Example A10

[0240] Based on 100 parts by weight of the total solid content of the components, polytetrahydrofuran (57 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) as polyols, isophorone diisocyanate (25 parts by weight) as polyisocyanates, bis(2-methacryloxyethyl) phosphate (5 parts by weight) as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (3 parts by weight) as a hydrophilic ionic group-containing diol compound were used to prepare polyurethane, and this was dispersed in water to prepare a polyurethane composition.

[0241] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 17 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 9 g, the amount of dimethylolbutanoic acid was changed from 19 g to 5 g, and the amount of isophorone diisocyanate was changed from 50 g to 44 g, and the same method as in Example A1 was performed to manufacture a polyurethane, which was dispersed in water to obtain 630 g of a polyurethane composition.

[0242] Comparative Example A11

[0243] Based on 100 parts by weight of the total solid content of the components, polytetrahydrofuran (40 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) were used as polyols, isophorone diisocyanate (25 parts by weight) was used as polyisocyanate, bis(2-methacryloxyethyl) phosphate (5 parts by weight) was used as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (20 parts by weight) was used as a hydrophilic ionic group-containing diol compound, and the polyurethane was prepared by dispersing it in water to prepare a polyurethane composition.

[0244] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 25 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 13 g, the amount of dimethylolbutanoic acid was changed from 19 g to 50 g, and the amount of isophorone diisocyanate was changed from 50 g to 63 g, and the same method as in Example A1 was performed to manufacture a polyurethane, which was dispersed in water to obtain 825 g of a polyurethane composition.

[0245] Comparative Example A12

[0246] Based on 100 parts by weight of the total solid content of the components, polytetrahydrofuran (35 parts by weight) and isosorbide-ethylene oxide 5 mol adduct (10 parts by weight) were used as polyols, isophorone diisocyanate (25 parts by weight) was used as polyisocyanate, bis(2-methacryloxyethyl) phosphate (5 parts by weight) was used as a (meth)acrylic group-containing phosphoric acid compound, and dimethylolbutanoic acid (25 parts by weight) was used as a hydrophilic ionic group-containing diol compound, and the polyurethane was prepared by dispersing it in water to prepare a polyurethane composition.

[0247] Specifically, the amount of isosorbide-ethylene oxide 5 mol adduct obtained in Manufacturing Example A1 was changed from 18 g to 29 g, the amount of bis(2-methacryloxyethyl) phosphate was changed from 10 g to 15 g, the amount of dimethylolbutanoic acid was changed from 19 g to 72 g, and the amount of isophorone diisocyanate was changed from 50 g to 72 g, and the same method as in Example A1 was performed to manufacture a polyurethane, which was dispersed in water to obtain 946 g of a polyurethane composition.

[0248] The types and amounts of each component used in Examples A1 to A23 and Comparative Examples A1 to A12 are shown in Table 1 below.

[0249] <Physical property evaluation>

[0250] The adhesiveness and stability of the results of Examples A1 to A23 and Comparative Examples A1 to A12 were measured and evaluated by the following methods, and the results are shown in Table 1 below.

[0251] 1. Adhesion evaluation

[0252] (1) Shear strength (unit: MPa)

[0253] Each of the aqueous dispersions of polyurethane manufactured in Examples A1 to A23 and Comparative Examples A1 to A12 was applied to the surfaces of two rolled steel plates (manufactured by POSCO) cut to a size of 2.5 cm wide x 12 cm long, in an area of ​​2.5 cm wide x 2.0 cm long, and then the applied areas were overlapped and heat-sealed to manufacture metal bonded specimens. Thereafter, the shear strength (unit: MPa) of each manufactured metal bonded specimen was measured using a UTM (Instron 5967 product, manufactured by Instron).

[0254] Specifically, the shear strength was measured five times for each metal bonded specimen, and the average value was calculated. A higher shear strength indicates better adhesion.

[0255] (2) T-Peel Strength (unit: N / 25mm)

[0256] A stainless steel piece measuring 150 mm in length × 25 mm in width × 0.25 mm in thickness was bent at a right angle so that the lengths of each side after bending were 70 mm and 80 mm. Each of the aqueous dispersions of polyurethane manufactured in Examples A1 to A23 and Comparative Examples A1 to A12 was applied as an adhesive to the side measuring 80 mm in length × 25 mm in width. Thereafter, it was dried at 70°C to 250°C, another stainless steel piece was covered and fixed thereon, and then heat-sealed by applying a force of 0.1 MPa to 5 MPa for 1 hour to 6 hours at 50°C to 200°C. The T-peel strength of the bonded specimen cooled to 23°C after heat-sealing was measured using a UTM (Instron 5967 product, Instron Co., Ltd.). At this time, the measurement of T-peel strength was performed by applying a load in the 180-degree direction at a tensile speed of 50 mm / min.

[0257] Specifically, the T-peel strength was measured a total of five times for each specimen, and their average value was calculated. A higher T-peel strength indicates better adhesiveness.

[0258] 2. Stability Assessment

[0259] (1) Water dispersion stability

[0260] Each of the aqueous dispersions of polyurethanes manufactured in Examples A1 to A23 and Comparative Examples A1 to A12 was maintained in a hot air dryer at 40°C for 120 hours, and then visually checked to see if sedimentation or clumping occurred. As a result, if no sedimentation or clumping occurred, the aqueous dispersion stability was evaluated as excellent, and if sedimentation or clumping occurred, the aqueous dispersion stability was evaluated as poor.

[0261] O: Excellent water dispersion stability

[0262] X: Poor water dispersion stability

[0263] (2) Storage stability

[0264] Each of the aqueous dispersions of polyurethanes manufactured in Examples A1 to A23 and Comparative Examples A1 to A12 was placed in a 25 ml glass vial in an amount of 10 ml each so as to have sufficient air pockets, sealed, and stored at room temperature (25±5°C) for at least 30 days and at 40°C for at least 24 hours, while visually observing to measure the period of time during which the samples remained in a liquid state without curing. The longer the period during which the samples remained in a liquid state, the better the storage stability.

[0265] <Explanation of abbreviations shown in Table 1>

[0266] PTMEG: Polytetrahydrofuran

[0267] PPG: Polypropylene Glycol

[0268] PEG: polyethylene glycol

[0269] IPDI: Isophorone diisocyanate

[0270] HDI: Hexamethylene diisocyanate

[0271] TDI: Toluene diisocyanate

[0272] MDI: Methylenediphenyl diisocyanate

[0273] P-2M: Bis(2-methacryloxyethyl) phosphate (manufactured by Kyoeisha)

[0274] P-1M: 2-methacryloxyethyl phosphate (manufactured by Kyoeisha)

[0275] DMBA: Dimethylolbutanoic acid

[0276] DMPA: Dimethylolpropionic acid

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283] As shown in Table 1 above, in the case of a specimen to which the water-dispersible polyurethane according to the present invention and the water-dispersible polyurethane composition containing the same were applied, the shear strength was 9 MPa or more, the peel strength was 2.5 N / 25 mm or more, and the adhesion to metal (steel plate) was excellent, and excellent water dispersion stability was exhibited without sedimentation or clumping, and the liquid phase retention period at room temperature was 30 days or more, and the liquid phase retention period at 40°C was 24 hours or more, and the storage stability was also excellent.

[0284] On the other hand, the specimens of Comparative Examples A1 to A12 had poorer adhesiveness compared to the specimens of the examples according to the present invention. In addition, the specimens of Comparative Examples A3 and A9 to A12 had poor aqueous dispersion stability due to the observation of sediment during the aqueous dispersion stability evaluation, and their storage stability at room temperature and 40°C was also poor.

Claims

1. As a water-dispersible polyurethane, A polyol component comprising an anhydrous alcohol-alkylene oxide adduct; polyisocyanate component; Phosphoric acid compounds containing (meth)acrylic groups; and A hydrophilic ionic group-containing diol compound; comprising a polymerization unit; Based on a total of 100 parts by weight of the polymerization units, The content of the above anhydrous alcohol-alkylene oxide adduct-derived polymerization unit is more than 0.5 parts by weight and less than 35 parts by weight, The content of the polymerization unit derived from the above polyol component is more than 45 parts by weight and less than 70 parts by weight, The content of the polymerization unit derived from the polyisocyanate component is more than 15 parts by weight and less than 35 parts by weight, The content of the polymerization unit derived from the above (meth)acrylic group-containing phosphoric acid compound is more than 0.5 parts by weight and less than 15 parts by weight, The content of the polymerization unit derived from the hydrophilic ionic group-containing diol compound is more than 3 parts by weight and less than 20 parts by weight, Water dispersible polyurethane.

2. A water-dispersible polyurethane according to claim 1, wherein the polyol component further comprises a polyol compound other than an anhydrous sugar alcohol-alkylene oxide adduct.

3. A water-dispersible polyurethane in which the polyol compound other than the anhydrous sugar alcohol-alkylene oxide adduct in the second paragraph includes a polyether polyol.

4. A water-dispersible polyurethane according to claim 1, wherein the polyisocyanate component comprises at least one selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, or combinations thereof.

5. A water-dispersible polyurethane according to claim 1, wherein the (meth)acrylic group-containing phosphoric acid compound comprises a phosphoric acid compound having 1 to 4 (meth)acrylic groups in the molecule.

6. A water-dispersible polyurethane according to claim 1, wherein the hydrophilic ionic group-containing diol compound comprises a diol compound containing at least one carboxyl group.

7. A water-dispersible polyurethane having a core-shell structure in the first paragraph.

8. A step of polymerizing a mixture comprising a polyol component including an anhydrous alcohol-alkylene oxide adduct; a polyisocyanate component; a phosphoric acid compound containing a (meth)acrylic group; and a diol compound containing a hydrophilic ionic group; Here, based on 100 parts by weight of the total solid content of the mixture, the content of the anhydrous sugar alcohol-alkylene oxide adduct in the mixture is more than 0.5 parts by weight to less than 35 parts by weight, the content of the polyol component is more than 45 parts by weight to less than 70 parts by weight, the content of the polyisocyanate component is more than 15 parts by weight to less than 35 parts by weight, the content of the (meth)acrylic group-containing phosphoric acid compound is more than 0.5 parts by weight to less than 15 parts by weight, and the content of the hydrophilic ionic group-containing diol compound is more than 3 parts by weight to less than 20 parts by weight. Method for producing water-dispersible polyurethane.

9. A water-dispersible polyurethane according to any one of claims 1 to 7; and a water-dispersible polyurethane composition comprising water.

10. An adhesive composition comprising the water-dispersed polyurethane composition of clause 9.

11. Articles to which the adhesive composition of Article 10 is applied.

12. An article comprising a metal article in claim 11; and an adhesive coating layer formed on the surface of the metal article, wherein the adhesive coating layer comprises the adhesive composition of claim 10.

13. Multiple electrical steel plates; and including a fusion layer positioned between the plurality of electrical steel plates; The above-mentioned fusion layer comprises the adhesive composition of claim 10, Electrical steel laminate.

14. A step of applying the adhesive composition of Article 10 to one or both sides of an electrical steel plate and then curing it to form an adhesive coating layer; and A step of laminating a plurality of electrical steel plates having the adhesive coating layer formed thereon and thermally fusing them to form a fusion layer; comprising; Method for manufacturing an electrical steel laminate.

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