KR0182196B1 - Disperse liquid of polyurethanes and processes for producing thereof - Google Patents

Abstract

1. Technical field to which the invention described in the claims belongs

The present invention relates to a polyurethane water dispersion and a method for producing the same.

2. Technical Challenges to be Solved by the Invention

The present invention relates to a coating agent or an impregnation agent which is used as a coating agent or an impregnation agent in the processing of an adherend, such as touch feeling, bulkiness, wet feeling, waxy feeling, glossiness, washability, abrasion resistance, And a process for producing the polyurethane water dispersion.

3. The point of the solution of the invention

The water-dispersible polyurethane of the present invention can be produced by reacting a diol or triol in a crystalline or amorphous polyester polyol, a diol or triol in a polyether polyol, a block copolymer type polyol to which ethylene oxide and propylene oxide are added, 40 to 85% by weight of a mixture of a polyol composed of polyhydric alcohols having 4 or more gums and a low molecular weight polyol and 4 to 50% by weight of an aromatic or aliphatic polyisocyanate with respect to the polyurethane solid content, Reacting compound in an amount of 1.5 to 20% by weight based on the solids content of polyurethane to obtain an ionic prepolymer having a terminal isocyanate, blocking agent is added to the ionic prepolymer to block the terminal, The neutralization agent is added to adjust the liquidity, which is dissolved in distilled water By providing a polyurethane dispersion, characterized in that obtained by using a vacuum pump extracts the solvent viscosity adjusting agent is added under a reduced pressure can solve the above problems.

4. Important Uses of the Invention

The polyurethane water dispersion of the present invention has utility as an adhesive, a coating agent or an impregnation agent.

Description

[Title of the Invention]

Multifunctional polyurethane water dispersion and method for producing the same

DETAILED DESCRIPTION OF THE INVENTION [

[Object of the invention]

[TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]

The present invention relates to an aqueous dispersion of a polyurethane, and more particularly to a polyurethane dispersion which is excellent in touch sensation, bulky feeling, wet feeling, waxy feeling, glossiness, washability, abrasion resistance, durability And a multifunctional polyurethane dispersion having excellent antistatic properties, and a process for producing the polyurethane.

Generally, polyurethane is used in many fields requiring flexibility, rebound resilience, abrasion resistance, and strong adhesiveness, and is used in many fields requiring adhesiveness. In particular, polyurethane is excellent in gloss and durability, .

Conventionally, the polyurethane for use as an adhesive, a coating agent, and the like has been produced and used in an oily state. However, in order to use the polyurethane in an oily state to have an appropriate viscosity, a polyurethane such as ethyl acetate, methyl ethyl ketone, dimethyl formamide, When organic solvent is used as a solvent, it causes environmental pollution such as air and water quality, deteriorates health and productivity of workers, and has the risk of fire by using an organic solvent having a very low flash point .

Due to such problems, studies have been made on the development of aqueous polyurethanes, and the conventional polyurethane dispersions thus developed have a problem in that the emulsifier is added to a prepolymer having an isocyanate terminal group and then emulsified under strong stirring at a high speed And a diamine as a chain extender. However, the polyurethane dispersion prepared in this way was not only unstable in storage, but also caused migration, adhesion and durability of the emulsion on the surface.

Therefore, a self-emulsifying method for synthesizing a polyurethane dispersion liquid in which an ion group is added to the main chain without using an emulsifier has been developed in order to improve such various physical properties. As a method of using a cationic ionomer as a method of imparting ionic groups, 4,016,123, 4,190,567, 4,277,383, and 5,320,331. Examples of methods using anionic ionomers include U.S. Patent Nos. 4,016,122, 4,914,148, and 4,914,148, And Japanese Patent Application Laid-Open No. 5-39340. Examples of methods using nonionic systems include U.S. Patent No. 4,794,147.

However, as described above, the polyurethane dispersion prepared by the method of imparting ionic groups has insufficient touch feeling, antistatic property and wet feeling as well as adhesiveness, hydrolysis resistance, solvent resistance, abrasion resistance, glossiness and durability All properties were unsatisfactory for imparting versatility.

[Technical Problem]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive studies to improve the above-described polyurethane water dispersion. As a result, the present inventors have completed the present invention and have found that the present invention provides a polyurethane dispersion liquid having excellent adhesiveness to an adherend and having flexibility, rebound resilience, Functional polyurethane dispersion having excellent antistatic properties, washing resistance, solvent resistance, gloss, abrasion resistance and weather resistance, and a process for producing the same.

[Structure and operation of the invention]

The polyurethane water dispersion of the present invention can be prepared by reacting a diol or triol in a crystalline or amorphous polyester polyol, a diol or triol in a polyether polyol, a block copolymer type polyol to which ethylene oxide and propylene oxide are added, Polyhydric alcohols having 4 or more gums and polyols having a low molecular weight are used alone or in a mixture thereof in an amount of 40 to 85% by weight based on the polyurethane solid content and 4 to 50% by weight of the aromatic or aliphatic polyisocyanate based on the polyurethane solid content % And the ionic property-imparting compound in the presence of 1.5 to 20% by weight based on the polyurethane solid content to obtain an ionic prepolymer having a terminal isocyanate, blocking agent is added to the ionic prepolymer to block the terminal, A viscosity adjusting agent and a neutralizing agent are added to adjust the liquidity, and this is distilled By using a vacuum pump and then dissolved in a solvent is added to adjust the viscosity of the extraction agent under a reduced pressure to obtain a polyurethane dispersion.

The present invention will be described in more detail. A crystalline or amorphous polyester polyol containing 20 to 75 wt% (preferably 35 to 65 wt%) of a diol or triol having a molecular weight of 400 to 6000 with respect to the polyurethane solid content, , Diol or triol having a molecular weight of 400 to 4,000 in the polyether polyol in an amount of 15 to 60% by weight (preferably 20 to 45% by weight) and 4 or more hydroxyl groups (-OH) 0 to 30% by weight, based on the polyurethane solid content, of a polyhydric alcohol of 500 to 5000, a block copolymer type polyol which is composed of ethylene oxide and propylene oxide and has a molecular weight of 500 to 6000 in an amount of 0 to 45% Molecular polyol having a molecular weight of 500 or less having a terminal isocyanate prepolymer and a reactive group in the range of 0 to 25% by weight based on the polyurethane solid content, (Preferably 2.1 to 15% by weight) based on the polyurethane solid content and diisocyanate alone or a mixture thereof in the aromatic or aliphatic polyisocyanate in an amount of 4 to 50% by weight (based on the polyurethane solid content) Preferably 8 to 45% by weight) to obtain an ionic prepolymer having a terminal isocyanate, and then a viscosity adjuster corresponding to 5 to 20% by weight based on the active ingredient, a ketoxime or a monoalcohol having a molecular weight of 300 or less A neutralizing agent for adjusting the liquidity after the reaction with the blocking agent, and a chain extender at least one dibasic acid are added to obtain an aqueous dispersion of polyurethane.

Any diol or triol of a polyester polyol which can be used in the present invention and has a molecular weight of 400 to 6000 within the above-mentioned molecular weight range can be used, and the polyether polyol can be represented by the following formula (Diethylene glycol), poly (oxyethylene) glycol, poly (oxypropylene) glycol, and the like can be used as the diol, and examples thereof include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6- hexanediol, neopentyl glycol, In addition,

[Chemical Formula 1]

(Provided that R is hydrogen or an alkyl group, m is an integer of 2 to 4, and n is an integer of 1 to 60)

As the triol, trimols such as trimethylol propane, glycerol, trimethylol propane, and adducts of glycerol and alkylene oxide having 2 to 3 carbon atoms can be used.

Examples of the ionic-imparting compound include dimethylolpropionic acid (DMPA), dimethylol sulfonic acid, and N-methyldimethylolamine, N-methyldiethylolamine and the like represented by the following formula (2).

(2)

(Wherein R is an alkyl group and R 'is an alkylene group)

Examples of the aromatic or aliphatic polyisocyanate include 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,3-cyclophenylene diisocyanate, 1,4- (HMDI), 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate (IPDI), bis (4-naphthalene diisocyanate) (Isocyanatocyclohexyl) methane, bis (4-isocyanatophenyl) methane, meta-xylylene diisocyanate, N, N ', N "-tris (6-isocyanatohexamethylene) Can be used.

The solvent used as the viscosity adjuster is a solvent which can be easily separated from the dispersion under reduced pressure with N-methylpyrrolidone, acetone, methyl ethyl ketone, ethyl acetate, cyclohexanone, methyl propyl ketone or the like.

Examples of the compound that can be used as a blocking agent include 3-pentanone oxime, 3-methyl-2-butanone oxime, 2-butanone oxime, cyclohexanone oxime, phenol, ethanol, ethyl mercaptan, acetone oxime, , And sodium bisulfite.

When the ionic substance is acidic, the compound used as the neutralizing agent is NR ₃ (R is an alkyl group), N-ethylmorpholine, N-methylmorpholine or the like is used. When the ionic substance is basic, Sulfate, epichlorohydrin and the like are used.

Examples of the chain extender include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, toluylenediamine, 4,4'-biphenylene diamine, isophoronediamine, and the like.

Polyhydric alcohols having four or more hydroxyl groups (-OH) are added in order to form a network structure to give bulky property and strong adhesion, and may be used within a range of 30 wt% or less, if necessary. Examples of the compound include pentaerythritol, D-sorbitol and the like. In order to give a specific feeling of tackiness and durability, copolymers of copolymer type polyester diol and copolymers of caprolactone poly (meth) acrylate having a molecular weight of 500 to 6000 (preferably 1,000 to 4,000) Ester, 0 to 45% by weight of a block copolymer type polyol to which ethylene oxide and propylene oxide are added.

In addition, low molecular weight polyol may be used in a range of 25% or less as a means for imparting specific physical properties.

The polyurethane water dispersion of the present invention composed of the above compound is obtained by mixing a polyester polyol having a molecular weight of 400 to 6000 with a polyurethane resin solids in a reactor equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, a stirrer and a vacuum pump A polyether polyol having 20 to 75% by weight and a molecular weight of 400 to 4000 in an amount of 15 to 60% by weight based on the solid content of the polyurethane resin, a polyhydric alcohol having 4 or more hydroxyl groups (-OH) and a molecular weight of 500 to 5000, 0 to 45% by weight of a copolymer type polyol having 0 to 30% by weight and a molecular weight of 500 to 6,000 based on the solid content of the resin, based on the solids of the polyurethane resin, and 0 to 25% by weight of the low molecular weight polyol with respect to the solid content of the polyurethane resin By weight of an ionic compound having a molecular weight of 500 or less in an amount corresponding to 1.5 to 20% by weight based on the solids of the polyurethane resin, While the reaction temperature is raised to 90 ° C with the injection of a small gas, the mixture is stirred and melted. The mixture is cooled to a temperature of 45 ° C or lower and the reaction temperature is maintained at 45 ° C. Diisocyanate is added dropwise, and the mixture is gradually heated to react at 60 to 120 DEG C to obtain a prepolymer having an isocyanate terminal.

A blocking agent having a molecular weight of 300 or less is added to the prepolymer obtained by the above reaction, and the reaction temperature is gradually raised to 70 ° C to 80 ° C for 90 minutes to block the prepolymer isocyanate.

The blocked prepolymer is cooled to 60 to 70 캜 and a solution prepared by dissolving the neutralizing agent in a viscosity adjusting agent is added dropwise to the neutralized prepolymer while being carefully kept at a temperature of 60 to 70 캜 over 1.5 to 2 hours, A chain extender is added in an appropriate amount to elongate the chain, and then an appropriate amount of distilled water is added thereto and sufficiently mixed. Thereafter, the previously added viscosity adjuster is removed by using a vacuum pump.

When the blocked polyurethane water dispersion prepared by the above method is applied to an adherend, when the blocking temperature reaches a predetermined temperature, the blocking agent dissociates and strongly bonds with the adherend.

In the above production method, it is described that the use of a polyester polyol, a polyether polyol, a polyhydric alcohol, an ionicity-imparting compound, a diisocyanate, a viscosity modifier, a blocking agent and a chain extender is used as a single compound, In the compound indicated, two or more compounds may be mixed and used.

Hereinafter, the production of the polyurethane water dispersion of the present invention will be described by way of examples.

Example 1

A reactor equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, a stirring device and a vacuum pump was prepared, and 152.6 g of 1,4-butanediol adipate having a molecular weight of 1000 as polyester polyol 1000, polyethylene glycol having a molecular weight of 1500, 136.5 g of neopentyl glycol, and 52.3 g of dimethyolpropionic acid as an ionic property-imparting compound, and while nitrogen gas was being injected and stirred, the temperature in the reaction vessel was adjusted to 90 The mixture was cooled to 45 ° C and 292.7 g of toluylene diisocyanate (-80) as a polyisocyanate compound was added dropwise over about 20 minutes, and then the temperature was gradually raised to adjust the temperature of the reaction tank to 62 ° C For 6.5 hours to prepare a prepolymer having a terminal isocyanate group.

152.0 g of 2-butanone oxime as a blocking agent was added to the prepared prepolymer having a terminal isocyanate group while maintaining the above reaction temperature, the temperature of the reaction vessel was gradually raised to 76 ° C and the temperature of the reaction vessel was 76 ± 2 ° C And reacted for 80 minutes to prepare a prepolymer in which the -NCO group is blocked.

After cooling the reaction vessel containing the blocked prepolymer to 67 ° C, 42.7 g of N-ethylmorpholine as a neutralizing agent was dissolved in 160.9 g of methyl propyl ketone as a viscosity controlling agent so that the temperature of the reaction tank was 67 ± 1.5 ° C And the reaction product was neutralized by dropwise addition over 90 minutes. 2.1 g of ethylenediamine and 2.5 g of triethylenetetramine were charged and reacted to elongate the molecular chain, and 1688.0 g of distilled water was added thereto and mixed.

Methylpropyl ketone added as a viscosity modifier under reduced pressure is removed from the mixed solution by using a vacuum pump under reduced pressure to obtain a polyurethane water dispersion having an effective content of 35%.

Examples 2 to 4

The kinds and contents of the compounds to be used are shown in Table 1 below. The reaction time, reaction temperature, blocking temperature and reaction time of the prepolymer in the reaction conditions are as shown in Table 2 below. 1, a polyurethane water dispersion was obtained.

Example 2 Example 3 Example 4 Polyester polyol compound 1,6-hexanediol adipate 1,4-butanediol adipate 1,4-butanediol adipate 1,6-hexanediol adipate Molecular Weight 1500 2000 1000 1500 Addition amount (g) 218.7 88.7 51.3 35.1 Polyether polyol compound Polyethylene glycol Polypropylene glycol Polyethylene glycol Polypropylene glycol Polyethylene glycol Polypropylene glycol Molecular Weight 1500 1000 2000 2000 1500 2000 Addition amount (g) 72.4 48.1 102.5 62.8 161.8 241.6 Copolymer type polyol compound Carolactone polyester diol 1,4-butanediol (EO / PO = 75/25 molar ratio) Ethylene glycol (EP / PO = 80/20 mole ratio) Molecular Weight 1500 2000 2000 Addition amount (g) 21.2 191,3 34.2 Ionic property-imparting compound compound Dimethylolpropionic acid Dimethylolpropionic acid Dimethylolpropionic acid Addition amount (g) 44.6 39.1 48.3 Low molecular weight polyol compound Glycerol Addition amount (g) 3.8 Isocyanate compound Tolylene diisocyanate-80 Isophorone diisocyanate Hexamethylene diisocyanate Isophorone diisocyanate Addition amount (g) 175.8 176.2 26.7 285.4 Blocking agent compound ? -caprolactam 2-butanone oxime 2-butanone oxime Addition amount (g) 92.3 73.8 91.6 corrector compound Triethylamine N-ethylmorpholine N-methylmorpholine Addition amount (g) 32.0 31.9 34.6 Chain extender compound 4,4'-biphenylene diamine Isophoronediamine Hexamethylenediamine Addition amount (g) 8.5 5.8 4.9 Viscosity modifier compound Ethyl acetate Methyl propyl ketone Cyclohexanone Addition amount (g) 132.1 108.7 132.4 Amount of distilled water added (g) 1516.4 1483.4 1488.9

Example 2 Example 3 Example 4 Prepolymer production Reaction temperature 62 ° C 115 ℃ 108 ° C Reaction time 6.5 hours 3.5 hours 4 hours Brocking condition Reaction temperature 76 ° C 76 ° C 73 ℃ Reaction time 1.3 hours 1.6 hours 1.5 hours

The aqueous dispersions prepared according to Examples 1 to 4 were applied to physical properties and polyester fabrics and performance tests were conducted.

Example 1 Example 2 Example 3 Example 4 General properties Exterior milk white milk white Translucent Translucent Active ingredient (%) 35.0 32.0 35.0 40.0 Viscosity (cps / 25 캜) 270 18 230 310 Ionic (ION) Anion Anion Anion Anion pH (1% solution) 7.2 7.3 6.8 6.7 100% modulus (kg / cm2) 34 37 25 29 Tensile strength (kg / cm2) 418 386 241 313 Slope (%) 580 628 685 710 Performance evaluation Tatchin ○ ○ ◎ ◎ Antistatic property ◎ △ ○ ◎ Abrasion resistance ◎ ◎ ◎ ◎ Friction fastness ○ ◎ ○ ○ Light fastness △ ○ ◎ ◎ Wash fastness ◎ ◎ ◎ ◎ Solvent fastness ◎ ◎ ◎ ◎

In the performance evaluation of Table 3,?: Indicates very good,? Indicates excellent, and? Indicates normal.

Among the methods of physical properties test shown in Table 3, antistatic property was KSK 0555, abrasion resistance was KSK 0540, friction resistance was KSK 0650, day light fastness was KSK 0700, washing fastness was KSK 0645, solvent fastness was KSK 0658, The touch of the fingertips and the appearance are by visual discrimination.

100% modulus, tensile strength and elongation were preliminarily dried at 80 ° C. for 5 minutes at room temperature, and the curing type was cured at 130 ° C. for 2 minutes and the high temperature curing type at 170 ° C. Curing was carried out for 2 minutes and then measured at a rate of 300 mm / min at 25 ° C. The DST-200DL manufactured by the machine was used instead of the tensile strength tester.

As can be seen from the results of the test on the compounds obtained from Examples 1 to 4 above, it was found that the abrasion resistance, washing fastness, solvent fastness and the like were extremely excellent, and the tackiness or rubbing fastness It is excellent or very good, and antistatic property and light fastness can be found from the normal level to a very good level.

Claims (8)

A diol or triol in a crystalline or amorphous polyester polyol, a diol or triol in a polyether polyol, a block copolymer type polyol to which ethylene oxide and propylene oxide are added, if necessary, a polyhydric alcohol having 4 or more OH groups, A mixture of polyols composed of low molecular weight polyols in an amount of 40 to 85% by weight based on the polyurethane solid content and 4 to 50% by weight of polyisocyanate alone or a mixture thereof selected from aromatic or aliphatic polyisocyanate based on the polyurethane solid content, Reacting the ionic property-imparting compound in the presence of 1.5 to 20% by weight based on the polyurethane solid content to obtain an ionic prepolymer having a terminal isocyanate, adding a blocking agent to the ionic prepolymer to block the terminal, And a neutralizing agent were added to adjust the liquidity, The number by using a vacuum pump and then dissolved in distilled water, characterized in that polyurethane is obtained by extracting the solvent, the viscosity adjusting agent is added under reduced pressure to give a dispersion. The composition of claim 1, wherein the mixture of 40-85 wt% Crystalline or amorphous polyester polyol A single or mixed polyol selected from a diol or a triol having a molecular weight of 400 to 6000 is contained in an amount of 20 to 75% by weight based on the polyurethane solid content, Polyether polyol A polyol having a molecular weight of from 400 to 4,000 selected from the group consisting of a diol and a triol, A copolymer type polyol to which ethylene oxide and propylene oxide are added, a copolymer type polyol having a molecular weight of 500 to 6000 in an amount of 0 to 45% 0 to 30% of a polyhydric alcohol having 4 or more hydroxyl groups (-OH) and a molecular weight of 500 to 5000, Low molecular weight polyol 0 to 25% ≪ / RTI > or a mixture thereof. 3. A process according to claim 1 or 2, wherein a mixture of 40 to 85 wt% Crystalline or amorphous polyester polyol having a molecular weight of 400 to 6000 is selected from the group consisting of 35 to 65% by weight based on the polyurethane solid content, The polyether polyol is a polyol having a molecular weight of 400 to 4000, or a mixed polyol selected from the group consisting of triols, A copolymer type polyol to which ethylene oxide and propylene oxide are added, a copolymer type polyol having a molecular weight of 1,000 to 4,000, 30% by weight or less of a polyhydric alcohol having 4 or more hydroxyl groups (-OH) and a molecular weight of 500 to 5000, 25% by weight or less of low molecular weight polyol, Wherein the ionic property-imparting compound is 2.1 to 15% by weight. 3. A process according to claim 1 or 2, wherein a mixture of 40 to 85 wt% Crystalline or amorphous polyester polyol having a molecular weight of 400 to 6000 is selected from the group consisting of 35 to 65% by weight based on the polyurethane solid content, The polyether polyol is a polyol having a molecular weight of 400 to 4000, or a mixed polyol selected from the group consisting of triols, Wherein the ionic property-imparting compound is 2.1 to 15% by weight. The polyurethane water dispersion according to claim 1 or 2, wherein the diisocyanate alone or a mixture thereof is 8 to 45% by weight based on the polyurethane solid content. The polyurethane water dispersion according to claim 3, wherein the diisocyanate alone or a mixture thereof is 8 to 45% by weight based on the polyurethane solid content. The polyurethane water dispersion according to claim 4, wherein the diisocyanate alone or a mixture thereof is 8 to 45% by weight based on the polyurethane solid content. In a reactor equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, a stirring device, and a vacuum pump, a diol or triol in a crystalline or amorphous polyester polyol with respect to the polyurethane resin to be produced, , A copolymer type polyol to which ethylene oxide and propylene oxide are added, a polyhydric alcohol having 4 or more OH groups and a low molecular weight polyol, if necessary, in an amount of 40 to 85% by weight based on the polyurethane solid content, a molecular weight of 500 Of an ionic compound in an amount corresponding to 1.5 to 20% based on the solids content of the polyurethane and then stirring the solution while raising the reaction temperature to 90 DEG C in a nitrogen gas atmosphere to complete the first reaction, Cool down to a temperature of 45 ° C or less and keep the temperature of the reaction not exceeding 45 ° C, Based polyisocyanate alone or mixed diisocyanate is added dropwise to the polyurethane solid content to be prepared and the mixture is gradually heated to react at 60 to 120 ° C to obtain a prepolymer having an isocyanate terminal, A blocking agent having a molecular weight of 300 or less was added to the obtained prepolymer, and the reaction temperature was slowly raised to 70 ° C to 80 ° C for 90 minutes to block the prepolymer isocyanate. The blocked prepolymer was cooled to 60 to 70 ° C And a solution prepared by dissolving a neutralizing agent in a viscosity adjusting agent is added dropwise to neutralize the solution so that the temperature of the reaction tank becomes 60 to 70 ° C over a period of 1 to 2 hours and an appropriate amount of a chain extender is added to the neutralized prepolymer, Then, an appropriate amount of distilled water was added thereto and sufficiently mixed. Thereafter, Utilized in the production of polyurethane-based method, it characterized in that the dispersion to remove the viscosity adjusting agent is added.