DE865587C - Process for the production of impregnations and coatings in the textile, paper and paint industry - Google Patents

Description

A process for the preparation of impregnations and Uber trains in the textile, paper and paint industries E s has become known from a large number of patent specifications that can condense formaldehyde with- urea and urea derivatives, and beterocvclischen amino compounds and these Köndensationsprodukte are suitable for various uses.

It is also known that some other. #. # Ldehydes agree with Heterocyclic amino compounds also condense into usable products let (see e.g. patent specification 671 724).

It has now been found that: condensation products of the abovementioned Amino compounds and the aldehydes mentioned for impregnation and coatings in in the textile, paper and paint industry.

The impregnations and coatings produced according to the invention can by varying the condensation products used for this purpose, in particular through Choice of starting materials, reaction conditions or other additives, adapt to the respective purposes.

According to the present invention, oxymethyl aldehydes serve as the aldehyde component, such as D. Trimethylol acetaldehyde, dimethylol propionaldehyde, methyl isobutyraldehyde. Usable amine components are urea, thiourea, dicyandiamide, Guanidine, aminotriazines and their substitution products, aminodiazines, aminochinazolines, Guanazole et al.

The condensation can be carried out in various molar ratios of the components, preferably in the presence of water. The pli value in the reaction is suitably about 8 thus obtained water-soluble addition compounds - the form of more or less pronounced # crystals. The shelf life of the products can be increased by adding small amounts of organic bases during or after the reaction. By further heating or changing the pn range to below 7 , the condensation to products of limited water solubility can be continued. This condensation stage can be maintained by cooling down # or by changing the pli value above 8 . If the above-mentioned more or less water-soluble products are etherified in the presence of a monohydric alcohol in the acidic pi range, then water-insoluble resins which are soluble in many organic solvents are obtained. Polyester resins, in particular alkydals, can be condensed into these even before all of the water of condensation is distilled off.

depending on the properties of the condensation products obtained This according to the invention z. B. use for the following purposes. The solutions of Easily water-soluble condensation products are suitable for a crease-proof finish of fabrics and to increase the wet strength z. B. of viscose rayon fabrics, when small amounts of organic acids are added to the impregnation solutions. The limited water-soluble products are suitable for. B. to make waterproof Papers as well as the water-insoluble and therefore to be used in emulsion form Products, whereby pre-ripening of the preparations is not necessary. Through this their use differs significantly from the known methods according to which Melamine-formaldehyde condensation products for the purpose mentioned here only then be useful if their aqueous solutions with the addition of considerable amounts strong acid can be converted into a more highly condensed state. The 'need the addition of large amounts of acids is known to be undesirable to the papermaker. In contrast, the new method means a significant simplification; it owns the following advantages: easy solubility of the products used, which can be carried out without heating; Elimination of odor nuisance; immediately after diluting the products possible application of the solutions; Avoidance of a further thermal process for the finished paper.

The water-insoluble products, which are therefore to be used in emulsion form, can also be used as stoving lacquers which, when stoved at around 12,000, usually produce white films of good elasticity and high gloss. The co-condensation products of the partially etherified products with polyester resins can also be used as coating resins. Example i 63 parts by weight of melamine are mixed with 160 parts of a concentrated 83.5% solution of trimethylolacetaldehyde (prepared from acetaldehyde and formaldehyde with soda as a catalyst) with the addition of 50 parts of water. Sufficient sodium hydroxide solution is added to the mixture until it has a clearly alkaline reaction. The mixture is gradually heated to 80 "with stirring; if necessary, the alkalinity is maintained during the addition process with the aid of small amounts of concentrated soda solution. The resulting solution is immediately cooled. About 305 parts of a viscous solution are obtained which, on further cooling or after standing for several hours it assumes an ointment consistency or solidifies to a pulp of fine crystals. The product contains about 64.5% of the adduct of 2 moles of trimethylolacetaldehyde with 1 mole of melamine. The product is clearly soluble in a little warm water; the concentrated solution can be further diluted with cold water as required.

An even better storable, in its other properties in the essentially the same product is obtained by following the approach given above before heating to 80-14 parts of triethanolamine are added. Another It is then no longer necessary to add soda during heating.

3 g of the product thus obtained (ethanolamine-free or ethanolamine-containing) (corresponding to about 18.5 g 10% product) are dissolved in 3o to 50 ccm warm water at about 4o: '. This solution is made up to 1 liter with water. Viscose rayon fabric is soaked in this solution for a few minutes, pressed and dried. After heating the fabric for 10 minutes to 10 minutes, it shows a considerable increase in the crease angle in comparison with the untreated fabric; if it is heated to 130 minutes for 10 minutes, there is a further increase.

If 4 ccm per liter of 35.71% glycolic acid is added to the impregnation solution before the fabric is soaked, the result is, after the same further treatment as indicated above, a fabric which, in addition to an increase in crease resistance, also shows an increase in wet strength.

An approximately 52% solution of mono- (fl-trioxymethyl-α-oxyethyl) -melamine which can be prepared in a similar manner from 1 mol of melamine and 1 mol of trimethylolacetaldehyde results. on the same rayon fabric there was also an increase in the angle of the crease when the fabric was subsequently heated to iiol.

The compound of 1 mol of melamine and 6 M-01 trimethylolacetaldehyde is obtained partly in crystallized form as a star-shaped needle. The N content of the dried crystallized product is 9.23% ; the theoretical N content of hexa- (fl-trioxymethanol-o, -oxyethyl) -inelamine is 9.03 1 / o. When using 30 9/1 of the product obtained in the form of a 68% concentrated solution (corresponding to 2o "4 g of anhydrous product), a similar effect is achieved without the addition of an acidic catalyst after heating the tissue to 10 minutes or 10 minutes .

With 31 g / fine 77% concentrated solution of a low molecular weight condensation product prepared in an analogous manner from 1 mol of urea and 1 mol of trimethylolacetaldehyde, a considerable increase in the wrinkle angle is achieved. By treating the fabric in the same impregnating solution mixed with 4 "glycolic acid per liter, an increase in wet strength is achieved at the same time.

Good shelf life of the products described in this example can also be achieved by subsequent addition of small amounts of organic bases to the freshly prepared concentrated solutions, e.g. B. -of pyridine, piperidine, ethanolamines, etc. Example: 2-9.6 parts of acetogua, na.min # are mixed with 3o4.6 parts of a 981% solution of trimethylolacetaldehyde and 75 parts of water. The mixture is made slightly alkaline with sodium hydroxide solution and heated to 70 'with stirring, a clear solution being formed. The solution is heated for a further 1 hour at 801 '. During this time, the alkalinity is maintained by adding soda solution. After cooling, 449 parts of a viscous clear solution with a content of 73.6% of the condensation product of 1 mol of acetoguanamine and 4% of 1 mol of trimethylol acetaldehyde are obtained. The viscous solution of the compound can be clearly diluted with any amount of water. After standing for a long time, the solution turns into a slurry of crystal agglomerates. In this condition, the product can be diluted with any 7th amount of cold water after it has been dissolved with about the same amount of lukewarm water. The product probably consists of a mixture of the monomolecular compound and an intraniolecularly etherified compound.

84 g / l of this product (corresponding to 1359 iool / oige product) are dissolved with water at normal temperature. After adding 8.5 g of formic acid, rayon fabric is briefly soaked in this solution (expediently at 3o to 4o0), pressed off, dried at 7o to 8o, and then post-condensed for 10 minutes at 130- '. A fabric is obtained which, compared with the untreated fabric, shows a considerable increase in the crease angle, the dry tear strength and, in particular, the wet strength. Example 3 315 parts of melamine are dissolved in a mixture of 44o parts of water and 65 parts of i 1 86.31 / oigern trimethylolacetaldehyde dissolved by brief heating under stirring at 75 "'. The solution is with some Natrönlauge to a pi-value of 8 to Adjusted to 9 and held at 8o 'for 30 to 40 minutes until a sample becomes clearly cloudy when diluted with water. During this time, a pH value of about 8.5 is maintained by adding concentrated sodium carbonate solution. Then it is immediately cooled to room temperature. About 1930 parts of a viscous, clear solution are obtained with a content of about .68% of the condensation product of 1 mole - \, lelanliii and 3 '- \ lol''trimetholacetaldehyde.

5 parts of the product produced in this way are dissolved in 65 parts of ethyl alcohol denatured with toluene. The solution is diluted with water until a distinct opalescence appears, which takes about 3 parts. The colloidal solution obtained in this way is added to a paper pulp consisting of 100 parts of bleached sulfite pulp with a degree of freeness of about 501 SR. After thorough mixing, 21/2 parts of aluminum sulfate are added. The paper stock is worked out in the usual way on the Fourdrinier machine to give paper with a weight per square meter of 6og.

Without the paper produced in this way having to be thermally aftertreated in a further operation, it is characterized by a high degree of wet strength. If it is also treated with a small amount of resin glue (1 1/9, calculated on rosin is sufficient), a good sizing effect is achieved in addition to the wet strength. Example 4 63 parts of melamine are mixed with 140 parts of water and 40 parts of a concentrated 83.5% solution of trimethylol acetaldehyde. The neutral mixture is heated as quickly as possible to 70 'without the addition of alkali, in which case solution occurs. Thereupon enough soda and finally concentrated soda solution is added that the solution reacts clearly alkaline. A temperature of So 'is then maintained for about 30 minutes, followed by immediate cooling. About 600 parts are obtained of a solution which is viscous at ordinary temperature and which, on standing for a long time, assumes a somewhat higher viscosity and weak opalescence; the solution contains about 65 % of the condensation product formed.

If paper is treated with this product in accordance with the method of Example 3, paper of increased wet strength is obtained.

Example 5 84 parts of dicyandiamide and: 233 parts of 86.3% trimethylolacetaldehyde are dissolved at 70 to 8 ° with the addition of 70 parts of water. The condensation is then continued for 1/2 hour at about 951 #, the weak alkalinity of the solution being maintained by adding small amounts of soda solution. About 70 parts of water are then distilled off over the course of about 50 minutes at 951 with stirring in a stream of air. Without further distillation, the resulting viscous product is stirred at 951 ' until a sample removed becomes cloudy when diluted with more than 3 parts of water. About 317 parts of a highly viscous condensation product of 1 mole of dicyandiamide and 11/2 moles of trimethylolacetaldehyde are obtained.

With this product, in a manner similar to that given in Example 3 , paper of increased wet strength can be produced if 4 to 5 parts of the product in the form of its aqueous solution are added to a paper pulp containing 100 parts of cellulose. The use of this condensation product has the advantage that it can only be incorporated into the paper pulp in an aqueous solution without the use of alcohol. Example 6 315 parts of melamine are stirred with 2310 parts of 86.5% strength trimethylolacetaldehyde and 800 parts of water. After the mixture has been made weakly alkaline, 340o parts of butanol are added. After filling the DesÜllationsvorlage with toluene is heated and azeotropically distilled until about 700 parts of water are distilled off. The butanol-töluene mixture runs back into the reaction vessel. 10 parts of phthalic anhydride, dissolved in a little butanol, are then added. The azeotropic distillation is continued until a total of about 400 parts of aqueous solution have distilled off. The total distillation time is 4 hours, the internal temperature of the lacquer solutions increasing to about 118-1. About 5350 parts of raw paint are obtained. Then impurities such. B. precipitated from the trimethylolacetaldehyde derived small amounts of salt, filtered off. The pure lacquer obtained is adjusted to a content of 50% lacquer resin. 540 parts of 50% strength lacquer resin solution are obtained.

The lacquer resin solution produced in this way, when used as a self-binding agent, results in a white film with good elasticity and good hardness, even when baked in without the addition of an alkyd resin. If, in addition to a pigment, an alkyd resin is added to the paint in a ratio of 3: 7 before spraying, this mixture results in films which, when baked at i2o ', result in a greatly increased elasticity and very good hardness. Even at a baking temperature of 180 °, this elasticity is only slightly reduced, while the hardness increases.

If the condensation described here is carried out with about 1 part of ionic hydrochloric acid instead of phthalic acid catalyst, the condensation temperature finally increasing to 1: 2o ', and a little more water of condensation is distilled off, the paint resin produced in this way is obtained after mixing with alkyd resin, films of good elasticity and high gloss. If the etherification is carried out in place of n-butanol with benzyl alcohol up to a final temperature of i 7o 'during the condensation, a varnish resin is produced which, even without mixing in an alkyd resin, at i2o'- baked films with very high gloss and very good Gives elasticity. If condensation is only up to a temperature of 411 ', the result is a varnish resin which, especially when mixed with a modified alkyd resin made from phthalic anhydride, glycerine and linseed oil, produces films that have a very good gloss and gloss when stoving at both i2o' and i8o ' very high elasticity, baked in at 180 ", also have very good hardness. Example 7 V, 5 parts of melamine are dissolved in a solution of 192.5 parts of 86.5% triniethylol acetaldehyde in 80 parts of water by heating to 80 °. Then 444 parts of butanol are added. The mixture is subjected to azeotropic distillation until 65 parts of water have been distilled off. After adding 1 part of phthalic anhydride, the mixture is distilled with stirring until 1: 2o parts of water have distilled off. Then 148 parts of a 37: 2% solution of a polyester containing 3 M01 pentaerythritol and 4 moles of adipic acid containing cyclohexanone and butanol er SZ = 134) added. The co-condensation is carried out with further azeotropic distillation until an internal temperature of 1170 ° is reached and a total of 148 parts of water have been distilled off. About 53o parts of a 50% solution of the mixed condensation product are obtained. This coating resin results in i - o, branded, white films with an average silky sheen, which are characterized by good toughness and very high E lastizität.

Claims (1)

PATENT CLAIM: Process for the production of impregnations and coatings in the textile, paper and paint industry, characterized in that amine-aldehyde condensation products are used, which contain compounds of the urea group containing amino groups or heterocyclic amino compounds as the amine component and oxymethylaldehydes as the aldehyde component.