DE1946933A1 - Thermosetting resin suitable for use as wet strength - impregnant - Google Patents

Abstract

Initially water-soluble resins are produced by adding to a polyaminde of formula: (wherein x is 1 to 10, pref. 1 to 6, n is at least 2 but not more than 6); a polyepoxide compound of formula: wherein A is as shown below, n is zero to 12, especially zero to 0.5; the quantitative proportion of the reactants being such that one mol. polyamine is present for each epoxide equivalent,. The reaction mass is heated and the product is heated, in form of an aquous solution and/or in a water miscible solvent, with epichlorohydrin, in amounts such that 0.9 to 2, molecules epichlorohydrin are used for each NH- and NH2 group. The rection is stopped while the product is still soluble in the reaction medium. A may have formula: wherein n' is zero to 12, esp. zero to 0.5, on average; or A may Be wherein R1 is CH3 or C2H5; or A may be (O R2 O) wherein R2 is -C2H4, C3H6 or C2H4 O C2H4. Reaction products, when used as impregnants for e.g. paper, textiles and other fibrous products, allow the absorptivity of the substrate to be controlled closely.

Description

Process for making a thermosetting resin for wet-strength finishing The wet-strength finishing of papers, textiles and others Fibers and webs made from vegetable fibers are known. Here products are used as wet-strength resins, which, for example, in the work "Polyamide-n Polyamine-Epichlorohydrin Resins "(Moyer and Stagg, Tapp i Monograph Series No. 29, pp. 33-37), the German Auslegeschrift 1 213 226 based on special polyamines and epichlorohydrin or dichlorohydrin and French patent 1,420 32l are described on the basis of an epichlorohydrin-polyamide Harses.

These products have the disadvantage that the suction height of them treated papers, textiles and other fibrous materials are practically impossible to adjust is. While s.B.

for paper for sanitary purposes (paper towels, etc.) a high Absorbency is desired, is used for other purposes - for example for wrapping paper - a low absorbency required.

The aim of the invention is now to provide a method for producing new, self-hardening in the heat, next water soluble resins to make available, when used as a wet strength finishing agent, papers, Textiles and other vegetable fibers produced with pH-dependent absorbency can be. This object is achieved: by the present invention.

The invention relates to a process for producing a self-curing, initially water-soluble resin product by reacting compounds bearing free amino groups with epichlorohydrin, characterized in that a) polyamines of the general formula are obtained where x has the value 1 to 10, preferably 1 to 6, and n is at least 2, but not greater than 6 ', with intensive mixing polyepoxide compounds of the general formula whereby where n 'has the average value zero to 12, in particular zero to 0.5 or where N H2 - 0 - CH2 CH - OHa A = (0GH2 -o - OH2O -) is where, R1 R1 = -CH3 or - C2H5, or where A = (-0 - R2 - O-), in which R2 = -C C2H4-, - C3H6- or O 2H4 -0-0 02H4 - is added, the quantitative ratio is matched so that there is one mole of polyamine per epoxide equivalent, and the mixture is reacted by heating and b) the reaction product obtained, dissolved in water and / or a water-miscible solvent, reacts with heat such amounts of epichlorohydrin that per NH - and NH2 group 0.9 to 2 molecules of epichlorohydrin are used, and the reaction is terminated as long as the reaction product is still soluble in the reaction medium.

A special embodiment is characterized in that one preferred polyamines are diethylenetriamine and triethylenetetramine, individually or im Mixture, begins.

Another preferred embodiment is characterized in that that the preferred polyepoxide compound is 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether begins.

Finally, the invention also relates to the use of the after self-curing resin products obtainable above as a wet strength finishing agent for paper, textiles and others made from vegetable fibers Manufactured fibers and webs with pH-dependent absorbency.

The invention also relates to the water-soluble resins as such, which are obtainable by the processes mentioned above.

The invention also relates to papers with a wet strength finish, Textiles and other fibrous materials and webs made from vegetable fibers, the resins obtainable in the cured form according to the processes described above Condition included.

To the polyamines of the general formula include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine, 1,4-diaminobutane and 1,3-diamino-butane. The preferred polyamines are diethylenetriamine and triethylenetetramine.

The polyepoxide compounds include compounds of the formula where n 'has the average value zero to 12, in particular zero to 0.5, furthermore 1,1,1-trimethylol-ethane triglycidyl ether, 1,1,1-trimethylolpropane triglyoidyl ether, 1,3-propylene glycol diglycidyl ether and diethylene glycol diglycidyl ether. The preferred compound is 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether.

The conversion in stage e) is generally carried out as follows: the polyamine is presented and given with intensive stirring and cooling the epoxy compound added in portions to 20-30 ° C. Then you raise the temperature - preferably to 50-90 ° C - and. holds a few hours at the desired temperature., until one is aware that all epoxy groups have reacted with the polyamine; This can be seen, among other things, from the fact that heat is added to the approach towards the end of the reaction must feed, while you usually have to cool it at the beginning so that the desired Temperature is not exceeded.

After the reaction has ended, the mixture is cooled and the reaction product is dissolved in water and / or a water-soluble organic solvent, preferably Ethyl alcohol. The solids content of the solution can vary within wide limits, e.g. between 10 and 70. After adding the epichlorohydrin, the amount is calculated is that for one equivalent of primary and secondary amino groups 0.9 to 2 mol Epichlorohydrin is omitted, it is heated to about 50-7000, whereby in general a higher temperature can be chosen, in the lower consentrations in the Solution is being worked on. After the desired viscosity is reached, one breaks the reaction by cooling and adjusting the pH value with acid to approx. 2 - 4. The acids used are usually hydrochloric acid, sulfuric acid or oxalic acid. If the reaction products have already started to gel, they will let through rapid cooling and simultaneous addition of acid and solvent again in Bring a solution without any loss of quality being noticed.

The products of the invention are generally as follows Wet strength finishing agent used. The flour in the Dutch or already on Staple-length cut fibers are in aqueous suspension at one consistency of approx. 3% by weight with such an amount of wet-strength resin that to 100 parts by weight Paper, Textiles or other vegetable fibers approx. 1 - 3 parts by weight of 100% wet fiber resin omitted.

The pH is then adjusted to the desired value, which is usually the case happens with ammonia or alum. The fleeces and sheets are made after manufacture in the sheet former usually a few minutes at an oven temperature of approx. 120 ° C dried and then air-conditioned for a few days.-The weight of the fibrous material is at 70-300 g / m2.

The suction lift of those treated with the wet strength resins according to the invention Papers are different depending on the pH in the manufacture of the papers. They are much larger at pH5 than at pH7 and 9. This effect does not occur on with untreated paper or with papers that - for comparison - with some commercial products had been made wet-proof.

Test arrangement 1 400 g of bleached sulphite pulp with a content on 360 g of absolutely dry (absolutely dry) sulfite pulp in 14.4 L of water for 30 minutes soaked and then to a grinding fineness of approx. 300 Schopper-Riegler (SR) im Experimental Dutch ground. In the ZAV distribution device, 1 l of ground cellulose is now added to each made up to 10 1 and each batch 0.952 g resin diluted to 10% from example 1 added, which corresponds to 2.4% dry weight wet-strength resin addition, based on dry weight sulphite pulp. The 1st

Approach has a pH of 7.7 # 0.2. In the second approach, the The pH value was brought to 5 t 0.2 by adding alum.

The 3rd batch is adjusted to pH 9 # 0.3 by adding ammonia, Each of Approaches 8 through 9 becomes broadly as follows on its own processed: A sheet is produced from each batch in the sheet former and then at 1200C for 10 minutes Oven temperature dried.

Then the paper is 3 at 200C and 65% relative humidity Days air-conditioned. The tests for breaking load and bursting pressure are then carried out in dry and wet as well as the measurement of the suction lift; the samples for the wet strength had previously been stored in distilled water for 2 hours.

Test setup 2 The procedure is as in test setup 1, however are applied to the individual batches as wet-strength resin 0.952 g resin diluted to 100% from example 2 added.

The batches 1 to 3 again have the pH values of approx.

7.7; 5 or 9.

Test setup 3 The procedure is as in test setup 1, however 0.972 g of resin from Example 3 are added to the individual batches as wet-strength resin. The batches 1 to 3 again have the pH values of approx. 7.7; 5 or 9.

Test setup 4 The procedure is as in test setup 1, however are applied to the individual batches as wet-strength resin 0.952 g resin diluted to 10% from Example 4 was added.

The batches 1 to 3 again have the pH values of approx.

7.7; 5 or 9.

Blind test The procedure is as in test arrangement 1, however no wet-strength resin was added to the individual batches.

The batches 1 to 3 again have the pH values of approx.

7.7; 5 or 9.

The papers obtained have the following properties: Relative wet Relative wet suction height strength, strength, mm / 10min.

based on based on breaking load bursting pressure test arrangement 1 paper from batch 1, produced at pH 7.7 27.1% 30.1% 0 Paper from batch 2, produced at pH 5 29.1% 31.6% 10 paper from batch 3, produced at pH 9 24.0% 29.0% 0 Test setup 2 approach 1 24.0% 38.9% 0 approach 2 26.2% 29.2% 14 approach 3 20.6% t7.5% 0 test setup 3 approach 1 21.6% 30.7% 0 approach 2 25.1% 33.6% approach 3 24.4% 32.6% 0 Test arrangement 4 Approach 1 20.0% 26.5% 13 Approach 2 19.3% 29.4% 19 Approach 3 15.5% 26.5% 14 blank test batch 1 1.2% 3.1% 14 batch 2 7.50 -6.2% 16 batch 3 1.2% 3.2% 16 The weight per square meter of the papers listed here is between approx. 70 - 90 g / m2. To get a real comparison, all test results except the suction height are converted to 100 g / m².

As a comparison, the suction heights of papers with commercially available wet strength resins in the same way as in the test arrangements 1 - 4 is described, were treated (2.4 ffi atro wet-strength resin addition to atro Sulphite pulp). The table shows that when using the im the following wet strength resins, the suction height depending on the pH value the production of the papers practically does not change.

The same applies to untreated paper, as from the test results of the blind test.

Suction height (in mm / 10 min.) Wet strength resin used pH: 5 # 0.2 pH: 7.7 # 0.2 pH: 9 # 0.3 known wet strength resin 1 15 12 12 known wet strength resin 2 11 10 10 known Wet strength resin 3 14 15 19 known wet strength resin 4 12 12 15 blind test 14 16 16 die Products according to the invention thus impart wet strength to the papers treated with them and on the other hand also result in papers with clearly different suction heights depending on the the pH value during production.

A water-soluble condensate appeared as the known wet-strength resin 1 Based on polyamidoamine and epichlorohydrin used which according to the procedure described in German Auslegeschrift 1 177 824, was produced.

A water-soluble condensation product became a known wet strength resin 2 based on a polyamidoamine, which is made up of ethylenediamine, diethylenetriamine and Adipienic acid was made, and epichlorohydrin used, according to a similar one Process was worked as described in German Auslegeschrift 1 177 824 is.

-A1's well-known wet strength resin 3 became a water-soluble one with diethylenetriamine modified formaldehyde urea resin used.

A water-soluble formaldehyde-urea resin, as is used for the production of wet strength papers.

Example 1: 146 g of triethylene; tetramine are poured into one with a cooler and The flask is filled with a stirrer. Now 182 g of one are stirred vigorously Epoxy resin based on 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin with the epoxy equivalent weight 182 and the viscosity 10,000 cP at 50C in portions added, the batch being kept at 20 to 3000 by cooling. Then it will be the temperature increased to 900C within half an hour and two hours held at this temperature.

Now cool to 600C within half an hour and then add Add 700 g of ethyl alcohol and 325 g of distilled water. After the temperature has fallen to 2o to 3000: t, become the approach at this temperature 370 g epichlorohydrin added. The temperature is now brought to 60 ° C. At this Temperature is about 1 1/2 hours, initially by cooling, later by weak Heating, held until a Gardner-Holdt viscosity of Z is reached. Thereupon cool immediately to about 20 to 30 ° C, add 887 g of distilled water and adjusts the pH to 4.0 with about 170 g of 30% hydrochloric acid.

The solids content in this solution is 25.1 percent by weight. The water dilutability is infinite, i.e. the resin solution is without cloudiness Water can be diluted indefinitely.

Example 2: 206 g of diethylenetriamine are in a cooler and The flask is filled with a stirrer. With vigorous stirring are in proportions a total of 185 g of an epoxy resin based on 2,2-bis (4-hydroxyphenyl) propane and Epichlorohydrin with the epoxy equivalent weight 185 added, whereby by cooling the approach is kept at 20 to 3000. Then the temperature is within a increased to 90 ° C for half an hour, kept at this temperature for two hours and then cooled to 20 to 30 ° C.

This reaction product has the following properties: Viscosity 8000 cP at 2500, H-active equivalent weight 47.5. 38 g of this product are in the flask 40 g of ethyl alcohol and 35.8 g of epichlorohydrin were added while cooling and poking. The temperature is brought to 5000 and held at this temperature (approx Hours) until a viscosity of Z-1 according to Gardner-Holdt is reached. Now you cool to 20 to 30 ° C, diluted at the same time with 215 g of distilled water and represents adjust the pH to 3.0 by adding about 38 g of 30% hydrochloric acid. The solids content in this solution is 16.8 percent by weight. The water thinnability is infinite.

Example 3 To 85 g of triethylenetetramine are added with cooling and stirring in the flask at 20 to 300C 85 g of an epoxy resin based on trimethylolpropane and Epichlorohydrin with an epoxy equivalent weight of 146 and a viscosity of 120 cP 250C added. The batch is now heated to 50 ° C. for three hours at this temperature held, then diluted with 170 g of water and cooled to 20-300C.

At this temperature, 34 g of this solution are added to the flask Stir with 75 g of distilled water, 35 g of ethyl alcohol and 21.5 g of epichlorifydrin, this corresponds to one molecule of epichlorohydrin per nitrogen atom. Then the temperature brought to 5000 and held at that temperature (4 hours) until viscosity from Z-1 to Gardner-Holdt is reached. Now it is cooled to 20 to 300C, with 218 g distilled water and adjusted to pH 4 with approx. 10 g 30% hydrochloric acid. The solids content in this solution is 9.8 percent by weight. The water thinnability is infinite.

Example 4 To 103 g of diethylenetriamine are added with cooling and stirring at 20 to 300C in portions 87 g of ethylene glycol diglycidyl ether, then brings the Temperature to 500C and holds the batch for 2 hours at this temperature. After this Cooling to 20 to 3000, 38 g of this reaction product are dissolved in 20 g of water and 111 g of epichlorohydrin are added with cooling and stirring. It is heated to 700C and holds at this temperature until a viscosity of Z-1 according to Gardner-Holdt is reached is. Now you cool to 20 to 3000, add 113 g at the same time distilled Add water and adjust the pH by adding approx. 25 g of 30% hydrochloric acid to 4.0. The solids content in this solution is 42? Weight percent. The water dilutability is infinite.

Should in the procedure according to Examples 1 to 4 according to the last addition of epichlorohydrin and the subsequent reaction a gelation the approach may have occurred, this can be done by cooling down quickly and through eliminate the simultaneous addition of acid and solvent again without the Loss of quality of the implementation product occurs.

Example 5: In pulpers or refiners, the paper Long-fiber and knot-free fabric with a grinding degree of approx. 300 Schopper-Riegler manufactured. The stock is in a mixing unit upstream of the paper machine the wet strength resin and any other additives added.

Good mixing without extremely high turbulence must be ensured. As a result of its cation-active character, the resin is absorbed directly onto the paser. On the wire section of the paper machine, the paper fleece is made with the desired square meter weight manufactured. Before the final drying, the paper web passes various embossing rollers, so that it gets a non-slip surface. The usual one on the paper machine Drying temperature around 120 ° C is essential for condensation to take place. the The paper only reaches its final strength after a storage time of 4-6 weeks. Of the In the industry usual wet strength additive of 2% absolutely dry guaranteed Sufficient wet strength and ribbing strength, i.e. it is 1 t absolute dry paper given 200 kg of 10% strength wet strength resin.

The products according to Example 1 or 2 were used as wet-strength resins. The paper treated in this way can become too Paper towels made up will.

Claims (6)

Claims 1) Process for producing a self-curing, initially water-soluble resin product by reacting compounds bearing free amino groups with epichlorohydrin, characterized in that a) polyamines of the general formula are obtained where x has the value 1 to 10, preferably 1 to 6, and n is at least 2, but not greater than 6, with intensive mixing of polyepoxide compounds of the general formula whereby where n 'has the average value zero to 12, in particular zero to 0.5, or where O CH2 - 0 - CH2 CS CH2 A = (- OCH2. - p - CH2O -) where R1 = - CH3 or - C2H5, or where A = (- O - R2 - O -), in which R2 = - C2H4-, - C3H6- or C2H4- O - C2H4- is added, the quantitative ratio being so adjusted is that there is one mole of polyamine per epoxy equivalent, and the mixture reacts by heating -and b) the reaction product obtained, dissolved in water and / or a water-miscible solution, reacts with heat such amounts of epichlorohydrin that per NH - and NH2 groups 0.9 to 2 molecules of epichlorohydrin are used, and the reaction is terminated as long as the reaction product is still soluble in the reaction medium. 2) Method according to claim P, characterized in that as Polyamines preferably diethylenetriamine and triethylenetetramine, individually or in a mixture, begins. 3) Process according to claim 1 or 2, characterized in that the compound is preferred as the polyepoxide compound use. 4) Use of the available according to claims 1 to 3, Resin products that self-harden in the heat as a wet strength finishing agent for papers, Textiles and other fibrous materials and webs made from vegetable fibers with pH-dependent absorbency. 5) New water-soluble Ilarze, obtainable according to the claims 1 to 3 mentioned procedures. 6) Wet-strength treated papers, textiles and others made from vegetable Fibers made fibrous materials and webs which are according to the claims in the claims 1 to 3 mentioned processes contain resins available in the cured state.