Aqueous polyurethane emulsion for finishing leather raw materials

 

(57) Abstract:

The inventive aqueous polyurethane emulsion obtained on the basis of the product of the interaction of isocyanate prepolymer having srednekamennogo molecular weight of 1500 to 3200 and polyetherdiol formula

and glycolic monomer of the formula

< / BR>
where n and m = 1 - 2, p = 0 - 1. When using the emulsion increases as spillway skin. 4 C.p. f-crystals, 1 tab., 1 Il.

The present invention relates to the finishing of raw hides, leather and similar fibrous substrates, and more specifically to aqueous polyurethane emulsion for finishing leather materials.

In the field of tanning hides ago offers a variety of processing techniques using water-enhancing substances, in particular aqueous polyurethane emulsions containing polyurethane and water, aimed at eliminating or at least reducing serious pollution problems that arise due to the use of organic solvents.

In these technologies, the thickness of the enhancing film is in the range from 0.2 to 0.4 mm, due to which the final product has a plastic-like appearance, softness to the touch and texture.

Cromie "gaps" in its ennobling layer, and "breaks" often grow in cracks on the surface of the product.

The final product obtained when using such technology refinement spillway skin aqueous polyurethane emulsions, shows almost always insignificant strength flexometer.

Common deficiencies can add another one that stems from the poor performance of systems suitable for implementation of quality improvement processes. In fact, currently used systems do not allow to maintain the speed of advancement of the fabric of cushioning securities at a level higher than about 3 to 4 meters per minute, and low hourly throughput of the complete system is determined by the speed of promotion. Attempts to increase the speed of advancement of the fabric of cushioning paper, on the one hand, resulted in obtaining products with even more unsatisfactory aesthetic characteristics, and on the other hand, entailed the use of larger systems, especially in relation to the drying chambers.

The aim of the present invention is to provide such aqueous polyurethane emulsion for finishing leather raw material, leather and similar voloknistoyj improved performance, and to achieve a high time processing performance.

This objective is achieved in that the aqueous polyurethane emulsion for finishing leather raw material containing polyurethane and water, according to the invention, the polyurethane contains the product of the interaction of isocyanate prepolymer having srednekamennogo molecular weight of 1500 to 3200 on the basis of Monomeric diisocyanate selected from the group comprising: hexamethylenediisocyanate, isophoronediisocyanate, methylendysiclogecsyldiizosyonat and polyester diol of the formula:

< / BR>
< / BR>
where and glycolic monomer of the formula:

< / BR>
where n and m 1 2, p 0 1, in the amount of 3 to 15% by weight of the polyester, and the concentration of polyurethane in the emulsion is 25 to 50% wt.

Preferably, polyetherdiol is polypropylenglycol formula:

,

where , preferably 27 to 40.

It is advisable to polyetherdiol was a polyethylene glycol of the formula:

< / BR>
where , preferably 40 to 65.

It is possible to polyetherdiol was poliatilenglikol formula:

,

where , preferably 22 to 45.

Useful additional content in the emulsion is 5 to 15% of glycol ether based on the weight agemy drawing, which schematically shows an example for the implementation of the method using the aqueous polyurethane emulsion according to the invention.

On the drawing canvas 1 gasket paper, rotate with the reel 2, the pre-treated in the pre-treatment 3 solution traditional protective anti-adhesive means and then dried in a drying chamber such as an oven with gas heating 4. When exiting the drying chamber 4 blade from gasket paper covered with a layer thickness of 0.05 to 0.1 mm aqueous polyurethane emulsion according to example 3 below. The coating is preferably carried out in station 5 using the cutter device 6, whereby it is possible to control and regulate small thickness provided for this layer. When exiting the station 5 blade from gasket paper is dried in the drying chamber 7, which can be oven with gas heating, the internal temperature of which is regulated in the range from 70 to 90oC. At the exit from the drying chamber 7 around the first polyurethane layer, which is dry, apply a second coat of the same aqueous polyurethane emulsion. This imposition is carried out in the chamber 8 with modulating the output from chamber 8 around the layer of aqueous polyurethane emulsion (forming essentially glue) is applied and pressed spillway skin 9, be ennobling. Test carried out by using a pair of pressure rollers 10, 11, subjecting them to a controlled pressure with the introduction of the protective paper sheet 12. When the operation is completed by coating on spillway the skin under pressure, canvas lining paper is passed through the final drying chamber 13, in which the final stage of drying when the drying chamber is heated to a temperature of from 70 to 90oC, which can be adjusted in this interval. When exiting the drying chamber 13 ennobled spillway skin extract by removal of the underlying canvas lining paper, which, in turn, is attached to a specially placed the reel 14.

To achieve different stiffness, from 5 to 30% (of the weight of polyethers) polyetherdiol choose those which have the formula:

< / BR>
< / BR>
< / BR>
Aqueous polyurethane emulsion according to the invention is obtained from isocyanate-prepolymer by slowly adding the specified prepolymer in an aqueous solution containing a tertiary amine, does not interact with isocyanate groups, which are selected from amines having the formula:

< / BR>
,

where n denotes 1 to 2, m, m' oboznachaet what about the glycol, containing isocyanate-prepolymer. The molar ratio of carboxyl glycol contained in the prepolymer, to amine can be the following:

.

The water may optionally contain small amounts (from 0.3 to 1.5% by weight water) non-ionic dispersant, so that the emulsion was more stable.

The type of dispersant used is not critical and does not affect the practical characteristics of the final emulsion during the implementation stage of blending, provided that the amount does not exceed much the recommended percentage.

The prepolymer adds to the solution with vigorous stirring. The water temperature should be between 10 to 20oC, and the temperature of the prepolymer should be between 40 to 70oC.

The viscosity of the resulting solution will depend on the type of amine and carboxyl content of the glycol prepolymer, and can be adjusted by changing these two values are within the limits as stated in the claims.

After receiving the emulsion of the prepolymer lengthening must be caused by saturation of the emulsion equimolar quantities (relative to NCO groups is carried out from 0 to 6;

< / BR>
< / BR>
or other comparable amines.

Isocyanate-prepolymer reacts with the diamine to obtain the final polyurethane.

The concentration of polyurethane in the final emulsion can vary from 25 to 50 mass%.

A few minutes after the addition of the diamine polymerization is completed and the resulting polyurethane has a high molecular weight and is suitable for the stated use.

When using aqueous polyurethane emulsion in accordance with the present invention it was found that around a thin layer deposited on the interlayer paper, formed by the skin, which allows the pair, which is formed within the layer itself, "leak" while applying heat. This unexpected sign, as shown, prevents the formation of salt dents and cracking of the layer, and in the case when with the aim of increasing the time-bandwidth considerably raise the heat level during the stage of drying of the layer, while maintaining the invariant size of the drying chamber.

This characteristic was further improved when the emulsification of the polyurethane of the present invention in the azeotropic mixture is used water, allowing a more gradual evaporation of water even at higher temperatures of drying.

Such solvents may be selected from propilenglikolmonostearata and dipropylenetriamine and etilenglikolevykh esters, are presented in the table.

The temperature at which a thin (0.05 to 0.1 mm) layer of aqueous polyurethane emulsion in accordance with the present invention can be dried, allow the speed to 8 to 10 ml/min for the fabric cushioning paper, with no disadvantages inherent in the known refined product.

Other distinctive features and advantages of the invention can be seen from the following description of some examples of the preparation of aqueous polyurethane emulsion in accordance with the present invention.

Example 1

Complex polyester /A/=polybutylenglycolether with srednekamennogo molecular weight equal to 2032

Complex polyester /B/=polypropylenglycol with srednekamennogo molecular weight equal 1960

In a reactor with a volume of 2000 liters, previously neutralized with anhydrous nitrogen at a temperature of 70 80oC 75 kg dimethylpropionic acid /558,8 mol/ dispersion is /A/ at a temperature of 70oC was added together with 300 kg of liquid complex polyester /B/, corresponding to 98.4 mole of complex polyester /A/ and 408,2 mole of complex polyester /B/.

The temperature of the mixture was raised to 75oC with vigorous stirring while maintaining a neutral environment using a stream of anhydrous nitrogen at 0.3 nm3/h and heat control so as to maintain the temperature at 753oC.

Then added 558,2 kg 4,4'-diisocyanatohexane /2130 mol/ and the temperature was lowered to approximately 65oC, shortly thereafter, there was added 0.3 kg dibutyltindilaurate and the temperature was raised to full completion of the exothermic reaction, the cooling was carried out only at temperatures exceeding 110oC.

The temperature in the range from 100 to 110oC was maintained for 3 h with simultaneous addition, within 30-minute intervals, 0.3 kg dibutyltindilaurate until complete consumption of 1.5 kg of the catalyst.

After cooling slowly (within about 4 hours) to a temperature of 55 60oC isocyanate group was titrated. It was found NCO value equal 5,34% (versus theoretical equal to 5.47% per annum), and molecular gaspolimerservice, was equal 216,6 kg

In a reactor with a volume of 5000 l, equipped with a double helix to vigorous mixing, got 2223 kg of deionized water, 17 kg of a dispersant (ethoxylated Nonylphenol with 10 moles of ethylene oxide) and 67,7 kg of triethylamine.

To this aqueous solution was added a solution of isocentrically at a temperature of 55 60oC.

The addition was carried out with simultaneous vigorous stirring an aqueous solution, and the temperature was trying not to raise above 30oC.

After all the solution of the prepolymer was added, was carried out by adding 216,6 kg 24% aqueous solution of hydrazine hydrate is added.

Temperature educated in this way the emulsion was raised to 8 to 10oC.

Stirring is maintained for about 30 minutes and then the resulting emulsion was ready to use.

Example 2

Using the same equipment as in example 1 and under the same conditions, a prepolymer was prepared by mixing 1039 kg poliatilenglikola with srednekamennogo molecular weight equal to 1900, 144 kg N-methylpyrrolidone and 78,2 kg dimethylolpropionic acid. The temperature was raised to 70oC, have been exothermic reaction, following the procedure described in example 1.

Isocyanate group was titrated and the value of 2,77% was obtained for a group of NCO (versus a theoretical value equal to 2.86 per cent) along with molecular weight equal to from 2500 to 2700. Stoichiometric hydrazinehydrate calculate when to 110.7 kg

An aqueous solution prepared as in example 1, by dissolving in 2033 kg of water to 20 kg of a dispersant (ethoxylated Nonylphenol with 10 moles of ethylene oxide) and 60 kg of dimethylethanolamine.

The solution of the prepolymer was added in an aqueous solution as described in example 1, after which was added to 110.7 kg 24% aqueous solution of hydrazine hydrate is added. Thus was obtained a polyurethane emulsion which had a solid content material about 38% and a pH in the range of 9.

The emulsion contained a polyurethane with already broken chain and ready for use in the method of improving the quality of raw hides.

Example 3

Using the same equipment and conditions as in example 1, a prepolymer was prepared by mixing to 678.4 kg polypropylenglycol with srednekamennogo molecular weight equal to 1958, with 120,6 kg N-methylpyrrolidone, 22,2 kg block copolymer of polyethylene glycol and polypropylenglycol (with srednekamennogo molecular matura mixture was raised to 70oC and was performed by the addition of the first portion to 114.7 kg 4,4'-diisocyanatohexane and 0.13 kg dibutyltindilaurate. Performed isometric reaction and the temperature began to fall after it has reached the value of about 85oC. and Then added the second portion 229,4 kg dicyclohexylmethane and 0.13 kg dibutyltindilaurate.

When implementing aksiomaticheskoi reaction temperature reached 110oC.

With 30-minute intervals was added portion of 0.13 kg dibutyltindilaurate to the total number of 0.65 kg of catalyst. The mixture is then cooled for about 5 hours to a temperature of 60oC, and the prepolymer was possible to emulsify (NCO 3,31% molecular weight 2200-2350).

Got an aqueous solution in accordance with the methodology described in example 1, with the use of 1842 kg demineralizovannoj water, 15.8 kg dispersant and 62,0 kg dimethylethanolamine.

The prepolymer was emulsiable specified in aqueous solution then was added 98,0 kg 24% aqueous hydrazine hydrate is added.

The resulting emulsion had a solids content of 35% and a pH of from 9 to 10.

Of inspections conducted rigorously, at the exit of the drying chamber is relatively bestowal salt dents or cracks, or such gaps in coverage. Spilkova leather of high quality was flawless finish, and the thickness of the polyurethane film was from 0.08 to 0.1 mm

The evaluation by experts in the leather industry spilkova leather made in accordance with the method of using the aqueous polyurethane emulsion according to the present invention, comparable to the skin with a natural face, although they cannot be distinguished from each other.

It should be noted that the above results were achieved when the rate of advance of the sheet is 1 equal to 6 meters per minute.

Also deserves attention that the entire length of the system provided for the implementation of the method of using the aqueous polyurethane emulsion according to the present invention, is 50 m with a total length of drying chambers, equal to 28 m

When using the systems described above, and identical stages of the process, the aqueous polyurethane emulsion of example 2 is used to improve the quality of spillway skin and produce the same results, both from the point of view of quality refined product, and from a technical point of view.

Aqueous polyurethane emulsion of example 2 oropou emulsion of the same polyurethane.

Using the system described above, the method of using the aqueous polyurethane emulsion according to the present invention, can be carried out at higher operating temperatures of several drying chambers to values in the interval from 90 to 120oC, thereby advancing speed of the blade cushioning paper can be increased to 8 meters per minute.

As a result of improved time performance ennobled spillway skin (in the latter case) is not observed neither one disadvantage inherent in the known technical solutions.

Comparable excellent results are obtained when the molecular weight of the prepolymer modified with 1500 to 3200.

By reacting polyether having the formula:

< / BR>
complex polyetherdiol having the formula:

< / BR>
carboxylating diol having the formula:

< / BR>
diisocyanate, such as 4,4'-diisocyanatohexane,

< / BR>
and using the methodology and the percentage defined in example 1 can be obtained isocyanate-prepolymer, which when emulsification in accordance with the procedure described in example 1, and polymerization to the most possible high molecular weight leads Cree using the above system and add about 10% glycol ether by weight of the water causes an increase in temperature of the drying chambers to 130-135oC and raises the performance to the promotion of the canvas with a speed of 10 meters per minute without the formation of surface cracking or salt dents.

Spilkova leather, processed in accordance with the method of using the aqueous polyurethane emulsion according to the present invention, constantly manifests characteristics that are comparable with the characteristics of the skin with a natural person, as well as the ability to make different drawings of the various facial layers, such as the skin of the bull and goat natural person, corrugated and bizarre images. From the point of view of mechanical characteristics spilkova leather made in accordance with this method, shows unusual strength against tensile and bending strength in dry and wet conditions, high resistance to wear and tear, so it can favorably be used in the manufacture of leather goods, traditional shoes, sports shoes and so on. Thin (0.05 to 0.1 mm) enhancing film allows mestena spillway skin essentially the same way as mestena skin with a natural face. Thus, spilkova leather made in accordance with the present izobretatel.

You should not ignore the fact that environmental protection is also guaranteed by the use of polyurethane emulsions are water-based.

1. Aqueous polyurethane emulsion for finishing leather raw material containing polyurethane and water, characterized in that it contains polyurethane product of the interaction of isocyanate prepolymer having srednekamennogo mol. m 1500 3200 on the basis of Monomeric diisocyanate selected from the group comprising hexamethylenediisocyanate, isophoronediisocyanate, methylendysiclogecsyldiizosyonat, and polyetherdiol formula

< / BR>
< / BR>
< / BR>
where

and glycolic monomer of the formula

< / BR>
where n and m 1 2;

p 0 1,

in the amount of 3 to 15% by weight polyetherdiol, and the concentration of polyurethane in the emulsion is 25 to 50 wt.

2. The emulsion under item 1, characterized in that polyetherdiol is polypropylenglycol formula

< / BR>
where preferably 27 to 40.

3. The emulsion under item 1, characterized in that polyetherdiol is a polyethylene glycol of the formula

< / BR>
where is preferably 40 to 65.

4. The emulsion under item 1, characterized in that polyetherdiol is poliatilenglikol formula


 

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