KR100728809B1 - A water-dispersed polyurethane and a manufacturing method thereof - Google Patents

Abstract

Provided are a water dispersible polyurethane dispersion which is improved in adhesive strength and can be prepared more simply, and a method for preparing the water dispersible polyurethane dispersion. The water dispersible polyurethane dispersion is prepared from a polyurethane prepolymer prepared from a polyisocyanate and a polyol comprising the caprolactone polyol containing a carboxyl group. Preferably the caprolactone polyol containing a carboxyl group is represented by the formula(I), wherein n and m are an integer of 1-10; R is a linear or branched C2-C10 alkyl containing a carboxyl group. Preferably the content of the caprolactone polyol containing a carboxyl group is 20-80 wt% of the total polyol; and the caprolactone polyol containing a carboxyl group has a molecular weight of 500.

Description

Water-dispersed polyurethane and its manufacturing method {A WATER-DISPERSED POLYURETHANE AND A MANUFACTURING METHOD THEREOF}

The present invention relates to a water dispersion polyurethane, and more particularly, to a water dispersion polyurethane using a polycaprolactone polyol having an acetic acid functional group and a method for producing the same.

Polyurethanes are manufactured in a wide variety of products such as rigid foams, flexible foams, films, soft and rigid elastomers and fibers, and the like. The polyurethane industry has been developed in Korea as the center of household goods, such as clothing, shoes, bags, toys, sofas, beds, etc. related to daily life until the 1980s, and is now used in heavy chemical industry such as automobile, electronics, civil engineering, shipbuilding, etc. As used, the market continues to grow. Recently, due to environmental problems, polyurethane coatings have been in the spotlight due to enhanced emission regulations such as organic solvents and VOCs (volatile organic compounds).

Looking at the prior art associated with the present invention, US Pat. No. 5,504,145 proposes a method for preparing a water-dispersed polyurethane resin by introducing dimethylolpropionic acid to a hydrophilic group. US Pat. No. 5,672,653 also describes a process for producing anionic water dispersible polyurethanes using polybutanediol terminated with hydroxyl groups. In this patent, a method for synthesizing anionic water-dispersed polyurethane is proposed. First, a prepolymer is prepared from a polybutadiene terminated with a hydroxyl group, a diol having an aromatic isocyanate and a carboxyl group, and then neutralized with triethylamine and then dispersed in water. It introduces. In addition, U.S. Patent No. 5,086,110 describes a composition for improving water resistance and physical properties by using 1,12-dodecane diisocyanate, polyoxytetraethylene glycol, dimethylolpropionic acid and triethylamine and 1,4-cyclohexadiamine. Producing a water-dispersible polyurethane. On the other hand, in the United States Patent No. 5,717,024, in the preparation of water-dispersed polyurethane, carbon dioxide is generated when water is contacted with isocyanate groups when water is dispersed.

However, in the case of water-dispersed polyurethane, there have been environmental problems, but the problem of poor adhesion has been raised. In the case of Korean Patent No. 10-0557838, in order to solve the problem of poor adhesion of water-dispersed polyurethane, (a) an organic polyisocyanate having an average molecular weight of 100-300 and (b) a crystalline polyester of a number average molecular weight of 2000-3000 A water-dispersed polyurethane consisting of a polyol, (c) a polyol having a number average molecular weight of 100 to 1200 or more of a bifunctional group, (d) a polyamine having a number average molecular weight of 200 to 600 having a sulfonate salt, and (e) a polyamine having a molecular weight of 20 to 200 Suggesting.

However, such a water-dispersed polyurethane has a problem that it is complicated to manufacture, and there is a demand for a method for improving the adhesion of the water-dispersed polyurethane while having a simple manufacturing method.

It is an object of the present invention to provide a novel water dispersion polyurethane with improved adhesive properties.

Another object of the present invention is to provide a water-dispersed polyurethane prepared by introducing a new water dispersant.

It is another object of the present invention to provide a method for producing a water-dispersed polyurethane prepared by introducing a new water-dispersion group.

It is still another object of the present invention to provide a water-dispersed polyurethane in which adhesion is improved by introducing a new water-dispersed group into the water-dispersed polyurethane.

In order to achieve the above object, the water-dispersed polyurethane of the present invention

It consists of an aqueous dispersion polyurethane dispersion prepared from a polyurethane prepolymer made from a polyol comprising a polyisocyanate and a caprolactone polyol comprising a carboxyl group.

In the present invention, the carolactone polyol containing the carboxyl group is represented by the following formula (I)

(I)

(I)

Wherein n and m are 1-10 integers, preferably 1-5, and R is a polycaprolactone diol comprising a carboxyl group represented by a C2-C10 linear or branched alkyl comprising a -COOH group.

In a preferred embodiment of the present invention, the polycaprolactone diol comprising the carboxyl group is a polycaprolactone diol polyol comprising a carboxyl group having a molecular weight of 300-3,000, preferably 500 to 2,000, more preferably 500.

In the present invention, the caprolactone polyol containing the carboxyl group is commercially available and can be used, preferably n = 2, m = 1, R is

Placcel 205BA from Daicel Chemical Industries.

In the present invention, the content of the caprolactone polyol including the carboxyl group included in the polyol may be appropriately adjusted according to the use of the polyurethane. In a preferred embodiment of the invention, the content of the caprolactone polyol including the carboxyl group is used in an amount of 20-80% by weight, preferably 30-70% by weight of the total polyol so as to provide adequate water dispersibility to the polyurethane to be produced. It is desirable to. In another embodiment according to the present invention it is also possible to use a caprolactone polyol containing a carboxyl group alone.

In the practice of the present invention, as the polyol which can be used together with the caprolactone polyol containing the carboxyl group, ordinary polyols used for polyurethane production can be used. In a preferred embodiment of the present invention, the polyol that can be used together with the caprolactone polyol containing the carboxyl group. For example, it may be polyether polyol, polyester polyol, polyamide polyol, polyesteramide polyol, polythioether polyol, polycarbonate polyol, polyacetal polyol, polyolefin polyol, polysiloxane polyol and the like. Polyether polyols which can be used are alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide or tetrahydro, in the presence of a polyfunctional initiator which contains approximately 2 to 8 active hydrogen atoms per molecule. Products obtained by polymerizing furan. Suitable initiator compounds contain a number of active hydrogen atoms and include water, butanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluenediamine, diethyl Toluene diamine, phenylene diamine, toluene diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol , Pentaerythritol, sorbitol and sucrose. Mixtures of initiators and / or cyclic oxides can be used. Particularly useful polyether polyols are polyoxypropylene diols and triols and poly (oxyethylene-oxypropylene) obtained by the simultaneous or successive addition of ethylene and propylene oxide to di- or trifunctional initiators as fully described in the prior art. Diols and triols. Other particularly useful and preferred polyether polyols include polytetramethylene glycols obtained by the polymerization of tetrahydrofuran. Polyester polyols that can be used include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane, pentaerythritol or poly Hydroxyl-terminated reaction products of polyhydric alcohols, such as ether polyols, or mixtures of such polyhydric alcohols, and polycarboxylic acids, in particular dicarboxylic acids or ester-forming derivatives thereof, such as succinic acid, glutaric acid and Diphthalic acid, or dimethyl ester sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof.

In the present invention, the polyisocyanate includes any known in the art for the production of polyurethane, and may be selected from aromatic, aliphatic, cycloaliphatic and aromatic polyisocyanates. In a preferred embodiment of the invention, the organic isocyanate is toluene diisocyanate, isophorone diisocyanate, cyclohexane-1.4-diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 3,3-dimethyl, 4, 4-di (aminocyclohexyl) methanehexamethylene diisocyanate, 1,4phenylenediiso cyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, 1,5 naphthalenedi isocyanate, trimethylhexamethylene di Isocyanate, noborane diisocyanate, etc. can be used.

The content of the polyisocyanate to the final aqueous polyurethane resin solids is preferably used at 10-80% by weight, preferably 30-70% by weight so that the adhesion is maintained.

The polyurethane prepolymer according to the invention is formed by the reaction of a polyisocyanate with a polyol comprising a caprolactone polyol comprising a carboxyl group. As a method of forming the prepolymer, a conventional water-dispersed polyurethane production method may be used. In a preferred embodiment of the present invention, the polyurethane prepolymer of the present invention is a polyol and a polyisocyanate comprising a caprolactone polyol containing a carboxyl group and a polyisocyanate mixed with an organic solvent, such as a tin catalyst, for example dibutyltin di Can be progressed by the uriator. The organic solvent used in the preparation of the polyurethane prepolymer may be a conventional organic solvent known in the art, for example, benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, Methyl acetate, acetonitrile, chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyrrolidone, and the like, which may be used alone or in combination. Can be. In the present invention, the polyurethane prepolymer is preferably present in an NCO equivalent amount of about 1-6% relative to the OH equivalent and preferably in an excess of 2-4% so that the NOC group is located at the terminal.

The water-dispersed polyurethanes according to the invention are obtained by dispersing polyurethane prepolymers in water according to conventional methods. In a preferred embodiment of the invention, the polyurethane prepolymer is prepared by reacting with triethylamine to dissolve it, chain extending with a chain extender such as ethylene diamine and dispersing it.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

Example

Example 1 Preparation of Polyurethane Prepolymer

After preparing a chiller, thermometer, stirrer and mantle in a clean 1L four-necked flask, 406 g of polytetramethyl ether glycol (PTMEG) (MW: 2000), 105 g of Placcel 205BA (MW: 500), dibutyltin diurauri 0.5 g of latex (DBTDL), 130 g of n-methylpyrrolidone (NMP), and 153 g of 4,4'-dicyclohexylmethane diisocyanate were added and reacted for 4 hours to prepare a polyurethane prepolymer.

Example 2

Prepare a cooler, thermometer, stirrer, and mantle in a clean 1 L four-necked flask, and then 406 g of polytetramethyl ether glycol (PTMEG) (MW: 2000), 85 g of Placcel 205BA (MW: 500), dibutyltin diurauri 0.5 g of latex (DBTDL), 130 g of n-methylpyrrolidone (NMP), and 142 g of 4,4'-dicyclohexylmethane diisocyanate were added and reacted for 4 hours to prepare a polyurethane prepolymer.

Example 3

Prepare a cooler, thermometer, stirrer, and mantle in a clean 1 L four-necked flask, and then 406 g of polytetramethyl ether glycol (PTMEG) (MW: 2000), 70 g of Placcel 205BA (MW: 500), dibutyltindira 0.5 g of urirate (DBTDL), 130 g of n-methylpyrrolidone (NMP), and 166 g of 4,4'-dicyclohexylmethane diisocyanate were added and reacted for 4 hours to prepare a polyurethane prepolymer.

Example 4

Prepare a chiller, thermometer, stirrer, and mantle in a clean 1 L four-necked flask, and then 406 g of polytetramethyletherglycol (PTMEG) (MW: 2000), 118 g of Placcel 205BA (MW: 500), dibutyltin diuriure 0.5 g of latex (DBTDL), 130 g of n-methylpyrrolidone (NMP), and 136 g of 4,4′-dicyclohexylmethane diisocyanate were added and reacted for 4 hours to prepare a polyurethane prepolymer.

Example 5 Preparation of Dispersed Polyurethane

420 g of ion-exchanged water, 12.3 g of triethylamine, and 50 g of isopropyl alcohol were mixed in a 2 L beaker and vigorously stirred, and 350 g of the polyurethane prepolymer prepared in Example 1 was slowly added to be allowed to receive. At this time, vigorously stirred and solubilized for about 30 minutes, 80 g of ion-exchanged water and 1.7 g of ethylenediamine were mixed and slowly added. After the addition, the mixture was stirred for 20 minutes and then heated to 70 ° C. and stirred at low speed for 1 hour. . After completion, a water-soluble polyurethane resin having a solid content of 32% pH 8.7 was obtained.

Example 6

410 g of ion-exchanged water, 10 g of triethylamine, and 53 g of isopropyl alcohol were mixed in a 2 L beaker and vigorously stirred, and 350 g of the polyurethane prepolymer prepared in Example 2 was slowly added to be allowed to receive. At this time, vigorously stirred for about 30 minutes, 80 g of ion-exchanged water and 1.7 g of ethylenediamine were mixed and then slowly added. After the addition, the mixture was stirred vigorously for 20 minutes and then heated to 70 ° C. and stirred for 1 hour at low speed. After completion, a water-soluble polyurethane resin having a solid content of 32% pH 8.5 was obtained.

Example 7

400 g of ion-exchanged water, 9.3 g of triethylamine, and 63 g of isopropyl alcohol were mixed in a 2 L beaker and vigorously stirred, and 350 g of the polyurethane prepolymer prepared in Example 3 was slowly added to be allowed to receive. At this time, vigorously stirred for about 30 minutes, 80 g of ion-exchanged water and 1.7 g of ethylenediamine were mixed and then slowly added. After the addition, the mixture was stirred vigorously for about 20 minutes and then heated to 70 ° C. and stirred for 1 hour at low speed. After completion, a water-soluble polyurethane resin having a solid content of 32% pH 8.5 was obtained.

Example 8

430 g of ion-exchanged water, 13.8 g of triethylamine, and 50 g of isopropyl alcohol were mixed in a 2 L beaker and vigorously stirred, and 350 g of the polyurethane prepolymer prepared in Example 4 was slowly added to be allowed to receive. At this time, vigorously stirred for about 30 minutes, 80 g of ion-exchanged water and 1.7 g of ethylenediamine were mixed and then slowly added. After the addition, the mixture was stirred vigorously for about 20 minutes and then heated to 70 ° C. and stirred for 1 hour at low speed. After completion, a water-soluble polyurethane resin having a solid content of 32% pH 8.9 was obtained.

Comparative Example 1

CWP-926 (CN 32%) from Chemine (Korea), a water-soluble polyurethane manufactured using dimethyl propionic acid (DMPA) and DMBA instead of Placce 205 BA, and CWP-209 (NV :) from Chemine (Korea) 32%) was tested for adhesion.

Example 9 Adhesion Comparison Test

The prepared water-dispersed polyurethane resin was mixed with RED ink (KFtech), a wetting agent (Tego), an antifoaming agent (Tego), and a thickener (MungingChemie) in the ratio of Table 1 to prepare a sample.

Suzy Example 5 Example 6 Example 7 Example 8 content 82.9 82.9 82.9 82.9 RED ink 15 15 15 15 Humectant 0.5 0.5 0.5 0.5 Antifoam 0.1 0.1 0.1 0.1 Thickener 1.5 1.5 1.5 1.5 Remarks Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4

The prepared samples were measured for adhesion to PET film and OPP film by Bar Cota # 9 (consideration after drying for 30 seconds at 80 ℃ after coating once). The results are shown in Table 2.

 division Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 CWP-926 CWP-209 PET film adhesion ◎ ◎ ◎ ◎ △ △ OPP film adhesion ◎ ◎ ◎ ○ X X

Cellophane tape taping test after cross cut

◎: Excellent, ○: Normal, △: Defective, X: Whole peeling

It will be appreciated by those skilled in the art that the present invention has been described in detail as above, but that the above examples are not intended to limit the invention but merely to illustrate. In addition, various modifications may be made without departing from the spirit and scope of the invention, and such modifications will be included in the claims set forth below.

According to the present invention, a water-dispersed polyurethane dispersion having high adhesion is provided. Such a water dispersion polyurethane dispersion has the advantage that it is easy to manufacture because it does not use a water dispersant conventionally used.

Claims (6)

A water-dispersed polyurethane dispersion prepared from a polyurethane prepolymer made from a polyol comprising a polyisocyanate and a caprolactone polyol comprising a carboxyl group. According to claim 1, wherein the caprolactone polyol containing the carboxyl group is Formula (I)

(I) Wherein n and m are 1-10 integers and R is a polycaprolactone diol comprising a carboxyl group represented by a C2-C10 linear or branched alkyl comprising a -COOH group. The compound of claim 2, wherein R is Phosphorus Dispersed Polyurethane Dispersion. The water dispersion polyurethane dispersion according to claim 1 or 2, wherein the caprolactone polyol comprising the carboxyl group is 20-80% by weight of the total polyol. The water-dispersed polyurethane dispersion according to claim 1 or 2, wherein the NCO equivalent in the prepolymer is present in an excess of about 1-6% relative to the OH equivalent. The water dispersion polyurethane dispersion of Claim 1 or 2 whose Mw molecular weight of the caprolactone polyol containing the said carboxyl group is 500.