DE1946933C3 - In the heat self-curing, initially water-soluble resin products made from compounds containing free amino groups with epichlorohydrin, as well as processes for their production and their use - Google Patents

Description

CH ₂ CH-CH ₂ -OV "

CH,

begins.

5. Use of the initially water-soluble resin products, which harden themselves under heat according to claim 1 as a wet strength finishing agent for papers, textiles and others made of vegetable matter Fibers made fibers and webs with pH-dependent absorbency.

The wet strength finishing of papers, textiles and others made from vegetable fibers Fibers and webs are known. Here products are used as wet strength resins that z. B. in the Work "Polyamide-Polyamine-Epichlorohydrin Resins" (Moyer and Stagg, TAPPI Monograph Series No. 29, pp. 33 to 37), the German Auslegeschrift 1213 226 based on special polyamines and epichlorohydrin or dichlorohydrin and French patent 1420 321 based on a Epichlorohydrin-polyamide resin are described.

These products have the disadvantage that the suction height of the papers and textiles treated with them and other fibrous materials is practically impossible to adjust. While z. B. with paper for sanitary purposes (Paper towels, etc.) a high absorbency is desired, is used for other purposes - for example Door wrapping paper - low absorbency required.

* ^ 0-CH ₂ -CH-

The aim of the invention is now to provide a process for the manufacture of self-hardening products in the heat, initially To provide water-soluble resins available when used as a wet strength finishing agent Papers, textiles and other vegetable fibers can be produced with pH-dependent absorbency. This task is accomplished by the present Invention solved.

The invention relates to self-curing, initially water-soluble resin products from compounds bearing free amino groups with epichlorohydrin, which are characterized in that they have been prepared by a) polyamines of the general formula

II N-

-CII ₂₁₁ -N-

II

where χ has the value 1 to K) and 11 is at least 2, but not greater than 6, with intensive mixing and cooling at 20 to 30 "C polyepoxide compounds of the general formula

CH-CH ₂ -AH ₂ C-CH

CH,

whereby

A =

OH

f VO-CH ₂ -CH-CH, -

CH,

is where n 'is the average value from 0 to 12

owns, or where

Q QH QJ.J

A = / -OCHj-C-CH ₂ O-

where R ₁ = —CHj or —C ₂ H ₅ ISt, or where A = (- O - R ₂ - O -), where

or

R ₂ = -C ₂ M ₄ -

- CH.—

-C ₂ H ₄ -OC ₂ H ₄ -

is, added, the quantitative ratio being adjusted so that there is one mole of polyamine per epoxide equivalent, and the mixture is reacted by heating to 50 to 90 ⁰ C and b) the reaction product obtained, dissolved in water and / or a water-miscible solvent, with such amounts Epitj chlorohydrin can react in the heat at 50 to 70 "C that _{0.9 to 2 mol of epichlorohydrin are used per NH and NH 2} groups, and the reaction as long as the reaction product in the reaction medium

is still soluble, is terminated by cooling and adjusting the pH to 2 to 4 with acid.

In a preferred embodiment of the invention, χ has the value 1 to 6 in the general formula of the polyamines.

In a further preferred embodiment of the invention, ri has the value 0 to 0.5 in the general formula of the polyepoxide compounds.

A special embodiment is characterized in that the polyamines used are diethylenetriamine and triethylenetetramine, individually or as a mixture, is used.

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

Finally, the invention also relates to the use of the Resin products that harden under heat as a wet strength finishing agent for papers, Textiles and others made from vegetable fibers Fibers and webs with pH-dependent absorbency.

The invention also relates to the water-soluble resins as such, according to those mentioned above Process have been established.

To the polyamines of the general formula

H — N—

-N-

,-H

include, for example, ethylenediamine, diethylenetriamine, Triethyientetramine, Tetraäthylenpentamin, i, 4-Diaminobutane and 1,3-Diamino-butane. The preferred Polyamines are diethylenetriamine and triethylenetetramine.

The polyepoxide compounds include compounds of the formula

CH,

CH- CH, -

Q-CH ₂ -CH- CH ₂ -

where »Γ the average value 0 to 12, in particular 0 to 0.5, also has 1,1,1-Trimethylolüthantriglycidylülher, 1,1,1-trimethylolpropane triglycidyl 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 reaction in stage a) is generally carried out as follows: The polyamine is initially introduced and add the epoxy compound in portions with vigorous stirring and cooling to 20 to 30 ° C. The temperature is then increased to 50 to 90 ° C and held at the desired temperature for a few hours, until one can be sure that all epoxy groups have reacted with the polyamine; This is Among other things, it can be recognized by the fact that you have to add heat to the approach towards the end of the reaction, while you usually have to cool it at the beginning so that the desired temperature is not exceeded will. After the reaction has ended, the reaction product is cooled and dissolved in water and / or a water-soluble organic solvent, preferably ethyl alcohol. The solids content of the The solution can vary within wide limits, e.g. B. between 10 and 70%. After adding the epichlorohydrin, the amount of which is calculated to be one equivalent of primary and secondary amino groups 0.9 to 2 moles of epichlorohydrin are omitted and the mixture is heated to 50 to 70.degree. C., in general the higher the temperature, the lower the concentration worked in the solution

After the desired viscosity is reached, the reaction is broken by cooling and adjusting the pH value from 2 to 4 with acid. The acids used are usually hydrochloric acid and sulfuric acid or oxalic acid. If the reaction products have already started to gel, they will let through Bring the addition of solvent back into solution without any loss of quality being noticed.

The products produced according to the invention are generally used as wet strength finishing agents as follows. The fibers, ground in the Hollander or already cut to the staple length, are mixed in an aqueous slurry at a consistency of 3 percent by weight with such an amount of wet-strength resin that 1 to 3 parts by weight of 100% wet-strength resin are used for 100 parts by weight of paper, textiles or other vegetable fibers. The pH is then adjusted to the desired value, which is usually done with ammonia or alum. After production, the nonwovens and webs are usually dried in the sheet former for a few minutes at an oven temperature of 120 ^° C. and then conditioned for a few days. The weight of the fibers is 70 to 300 g / m ² .

The suction heights of the papers treated with the wet strength resins produced according to the invention are different depending on the pH in the manufacture of the papers. They are much larger at pH 5

ßer than at pH 7 and 9. This effect does not occur with untreated paper or with papers that - for comparison - had been made wet-proof with some commercially available products.

Test arrangement 1

400 g of bleached sulphite pulp with a content 360 g of absolutely dry (atro) Sulu cellulose are soaked in 14.4 liters of water for 30 minutes and then ground to a grinding fineness of 30 ° Schopper-Riegler (SR) in the test dutchman. In the distribution device ZAV is now made up to 101 per liter of ground cellulose and 0.952 g diluted to 10% for each batch Resin from example 1 added, which corresponds to 2.4% dry strength wet-strength resin addition, based on dry sulfite pulp. The first batch has a pH of 7.7 ± 0.2. In the 2nd batch, the pH is adjusted by adding brought by alum to 5 ± 0.2.

The third batch is adjusted to pH 9 ± 0.3 by adding ammonia.

Each of the approaches 1 to 3 is further processed individually as follows: A sheet is produced from each batch in the sheet former and then at an oven temperature of 120 ° C. for 10 minutes dried. The paper is then conditioned for 3 days at 20 ° C. and 65% relative humidity. The tests for breaking load and bursting pressure are then carried out in dry and wet conditions such as also the measurement of the suction height; the wet strength samples had previously been distilled for 2 hours Water has been stored.

Test setup 2

The procedure is as in test regulation 1, but the individual approaches are used as wet-strength resin 0.952 g of resin from Example 2 diluted to 10% was added. Batches 1 to 3 have the pH values again of 7.7, 5 and 9 respectively.

Test arrangement 3

The procedure is as in test arrangement 1, but the individual approaches are used as wet-strength resin 0.972 g of resin from Example 3 were added. The batches 1 to 3 again have the pH values of 7.7, 5 or 9.

Test arrangement 4

Relative Relative Suction lift Wet Wet strength, strength, based based on on well/ Breaking load Burst pressure 10 min. V ° Test arrangement 1 Paper from approach 1, 0 made at pH 7.7 27.1 30.1

40

The procedure is as in test arrangement 1, however 0.952 g of resin from Example 4 diluted to 10% are applied to the individual batches as wet-strength resin added. Batches 1 to 3 again have pH values of 7.7, 5 and 9, respectively.

Blind test

The procedure is as in test arrangement 1, but no wet-strength resin is added to the individual batches. Batches 1 to 3 again have pH values of 7.7, 5 and 9, respectively.

The papers obtained have the following properties: Test setup 1
Paper from batch 2, produced at pH 5 Paper from batch 3, produced at pH 9

Test setup 2

Approach 1

Approach 2

Approach 3

Test arrangement 3

Approach 1

Approach 2

Approach 3

Test arrangement 4

Approach 1

Approach 2

Approach 3

Blind test

Approach 1

Approach 2

Approach 3

Relative

NaB-Festigkeil, covered

on breaking load

29.1 24.0

24.0 26.2 20.6

21.6 25.1 24.4

20.0 19.3 15.5

1.2 7.5 1.2

Relative

Wet strength, based

on burst pressure

31.6 29.0

38.9 29.2

37.5

30.7 33.6 32.6

26.5 29.4 26.5

3.1 6.2

3.2

Suction lift

mm 10 min.

10 0

13 19 14

35 The weight per square meter of the papers listed here is between 70 and 90 g / m ² . In order to get a real comparison, all test results - except for the suction height - are converted to 100 g / m ² .

As a comparison, the suction heights of papers are given, those with commercially available wet-strength resins were treated in the same way as described in test arrangements 1 to 4 (2.4% atro Wet-strength resin addition on atro sulfite pulp). From the It can be seen from the table that when the wet strength resins listed below are used, the suction lift changes practically does not change depending on the pH value in the manufacture of the papers. The same pit for untreated paper, as shown in the test results of the blind test.

Suction height (in mm / 10 min.) pH: pH: Deployed 7.7 ± 0.2 9 ± 0.3 Wet strength resin .. pH: 5 ± 0.2 12th 12th Known wet solid resin 1 15th 10 10 Known wet solid resin 2 11th 15th 19th Known wet solid resin 3 14th 12th 15th Known wet 16 16 solid resin 4 12th Bundling test ... 14th

9 10

The products produced according to the invention have an average weight of 47.5. 38 g of this product are used in

So share the papers treated with them wet flask with cooling and stirring with 40 g of ethyl;

strength and, on the other hand, also result in paper mixed with alcohol and 35.8 g of epichlorohydrin. The tem-

significantly different suction height depending on the pH temperature is brought to 50 "C and at this temperature

Value in manufacturing. Maintained 5 temperature (about 3 hours) until a viscosity

As a known wet-strength resin 1, a water-soluble Z-I according to Ga rd nc r -H o Id t has been achieved. so

Lich condensate based on polyamidoamine and cooled to 20 to 30 "C, diluted at the same time ■

Epichlorohydrin is used, which according to the method, with 215 g of distilled water and adjusts the pH j

that described in German Auslegeschrift 1 177 824 by adding 38 g of 30% hydrochloric acid to 3.0

ben is, was made. io a. The solids content in this solution is.:;

A water-soluble 16.8 percent by weight was used as a known wet strength resin 2. The water dilutability is _f ;

Lich condensation product on the basis of an infinite. $

Polyamidoamine, which is made from ethylenediamine, diethylene- B e i s ρ i e I 3 "**

triamine and adipic acid, and Epi- L

chlorohydrin is used, with a similar 15 to 85 g of tri-ethylene tetramine being added with cooling

Procedure was worked as in the German and stirring in the flask at 20 to 30 "C 85 g of a _l

Auslegeschrift 1 177 824 is described. Epoxy resin based on trimethylolpropane and Epi- 't

A water-soluble chlorohydrin with an epoxy equivalent weight of 146 was used as the known wet-strength resin 3

Liches formaldehyde modified with diethylenetriamine and viscosity 12OcP at 25 ° C was added. so

hyd-urea resin is used. 20 the batch is ^{heated to 5O 0} C, 3 hours at the

AIs known wet strength resin 4 was maintained a water- soluble ser temperature, then compared with 170 g of water _ri

Liches formaldehyde-urea resin, like this door thins and cooled to 20 to 30 "C.,.

Production of wet-strength papers is used, 34 g of this tj are added at this temperature

used. Solution in the flask with stirring with 75 g of distilled ^

. 25 water, 35 g ethyl alcohol and 21.5 g epichlorohydrin, ^

Example 1 corresponds to one molecule of epichlorohydrin per ⁴

146g of triethylenetetramine are converted into a nitrogen atom. Then the temperature is poured into a flask equipped with a 50 ° C. condenser and stirrer. held introduced and at this temperature (4 hours), _t Now, with intensive stirring, 182g of a until a viscosity of ZI according to Gardner; ' Epoxy resin based on 2,2-bis (4-hydroxyphenyl) - 30 Holdt is achieved is now made to 20 to 30 ° C _t overall propane and epichlorohydrin with the cooled Epoxidäquiva-, diluted with 218 g of distilled water and) lentgewicht Ί82 and the viscosity was adjusted to a pH of 4 at 25 ° C. with 10 g of 30% strength hydrochloric acid. This is added in portions, the solids content in this solution being 9.8 Ge approach being kept at 20 to 30 ° C. by cooling. Then the weight percentage. The water dilutability is finite within half an hour to 90 ° C 35.

and hold at this temperature for 2 hours.

The mixture is then cooled within half an hour. 103 g of diethylenetriamine are added with cooling

6O ⁰ C and (then takes 700 g of ethyl alcohol and 325 g and stirring at 20 to 30 ⁰ C in portions 87 g of ethyl

add distilled water. After the tempera- 40 lenglycol diglycidyl ether, then brings the temperature

door has fallen to 20 to 30 ° C, at this temperature to 50 ° C and holds the approach for 2 hours at this

temperature to the approach 37Og epichlorohydrin added temperature. After cooling to 20 to 30 ⁰ C ν

given. The temperature is now increased to 60 ° C. 38 g of this reaction product in 20 g of water

brings. At this temperature, l '/ ₂ hours solved on and g under cooling and stirring with 111 epi- <·

initially by cooling, later by adding weak chlorohydrin. It is heated to 70 ° C. and kept <

warm, held until a viscosity of Z after at this temperature, until a viscosity of Z-I

G ardner — Holdt is reached Thereupon cools after Gardner — Holdt is reached. Well cools

one immediately to 20 to 30 ° C, add 887g of distilled to auf20 to 30 ⁰ C, added simultaneously 113 g of distilled

Add water and adjust the pH with 170 g of water and adjust by adding 25 g

30% hydrochloric acid to 4.0. 50 30% hydrochloric acid adjusts the pH to 4.0. The i

The solids content in this solution is the solids content in this solution is 42.7 Geti

25.1 percent by weight. The water dilutability is weight percent. The water dilutability is infinite- «

infinite, d. h \, the resin solution is without turbidity with Hch. 1-.

Water can be diluted indefinitely. Should the procedure according to Examples 1

. 55 to 4 after the last addition of Epichlorhydnnnn and the

Example 2 _s j _cn subsequent reaction a gelation of the

206 g of diethylenetriamine will have occurred in an approach with a cooler, if this can be passed through

flask equipped with a stirrer. Fast cooling and simultaneous acidic

Sive stirring will remove a total of 185 g in proportions and the addition of solvent again without

an epoxy resin based on 2 ^ -Bis (4-hydroxyphenyl) - 60 that the loss of quality of the reaction product

propane and epichlorohydrin with the epoxide equiva entry

lentgewicht, wherein the mixture is maintained at 20 to 30 ⁰ C was added 185 by cooling Example 5. Fig. Then it will be

the temperature is set to within half an hour in pulpers or refiners

90 ⁰ C increased, 2 hours at this temperature 65 paper stock with a freeness of 30 ° Schopper-

held and then cooled to 20 to 30 ° C. Riegler made long-fiber and knot-free Dem

This conversion product has the following properties of its own - are provided in one of the paper machines

properties: viscosity 800OcP at 25 ° C, H-active-equi-switched mixing unit the wet-strength resin and even-

Some other additives were 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 fiber. The paper web with the desired square meter weight is produced on the wire section of the paper machine. Before final drying, the paper web passes various embossing rollers so that it has a non-slip surface. ^{The usual drying temperature of 120 °} C. on the paper machine is absolutely necessary for the condensation to take place. The paper only reaches its final strength after a storage time of 4 to 6 weeks.

The wet-strength resin addition of 2% absolutely dry, which is customary in the industry, ensures sufficient Wet strength and rib resistance, d. In other words, 1 t of absolutely dry paper weighs 200 kg LOVOiges wet-strength resin given.

The products according to Example 1 or 2 were used as wet-strength resins. The paper treated in this way can can be made into paper towels.

Claims (4)

Patent claims: 1. In the heat self-hardening, initially water-soluble resin products made of free amino groups bearing compounds with epichlorohydrin, characterized in that they have been prepared by a) polyamines of the general formula ti H — N— -CH ₂₁ -N -, - H where χ has the value 1 to IO and is at least 2, but not greater than al 6, with intensive mixing and cooling at 20 to 30 ° C polyepoxide compounds of the general formula CH ₂ CH-CH ₂ -AH ₂ C-CH CH ₂ A = OH CH ₂ -CH-CH ₂ - CH ₃ where η 'has the average value from 0 to 12, or where q CH ₂ -O-CH ₂ -CH CH ₂ A = / -OCH ₂ -C- 35 where R ₁ = —CH, or —C ₂ H ₅ , or where A = (- O - R ₂ - O -), in which NH ₂ groups are used from 0.9 to 2 mol of epichlorohydrin, and the The reaction is terminated as long as the reaction product is still soluble in the reaction medium by cooling and adjusting the pH to 2 to 4 with acid. 2. Process for the production of a self-curing, initially water-soluble Resin product by reacting compounds containing free amino groups with epichlorohydrin, characterized in that a) to polyamines of the general formula R ₂ = - C ₂ H ₄ - -C ₃ H ₆ - -C ₂ H ₄ -OC ₂ H ₄ - 40 H-N- L- _n -N-, -H is, added, the quantitative ratio is adjusted so that there is one mole of polyamine per epoxide equivalent, and the mixture is reacted by heating to 50 to 90 ⁰ C and b) the reaction product obtained, dissolved in water and / or a water-miscible solvent, can react with such amounts of epichlorohydrin in the heat at 50 to 70 ⁰ C that per NU and where χ has the value 1 to 10 and η is at least 2, but not greater than 6, with intensive mixing and cooling at 20 to 30 "C polyepoxide compounds of the general formula CH ₂ CH-CH ₂ -A- H ₂ C-CH - ■ - CH ₂ O O whereby CH ₃ OH -o-V C- / VO-CH ₂ -CH-CH ₂ - CH ₃ where ri has the average value 0 to 12, or where C) CH ₂ -OCH ₂ -CH A = / -OCH ₂ -C-CH ₂ O- ¹ CH, 65 where R ₁ = —CH ₃ or —C ₂ H ₅ , or where A = (- O - R ₂ - O -) where R ₂ = -C ₂ H ₄ - -C ₃ H ₆ -
or _ _{C2 H4} _ ο - C ₂ H ₄ - is, adds, the quantitative ratio so matched is that one Mo! Polyamine present, and reacting the mixture by heating to 50 to 90 ° C and b) the obtained reaction product, dissolved in water and / or can be a water-miscible solvent, react with such amounts of epichlorohydrin under heat at 50 to 70 ⁰ C, that 0.9 to 2 moles of epichlorohydrin are used per NH and NH ₂ groups and, as long as the reaction product is still soluble in the reaction medium, the reaction is terminated by cooling and adjusting the pH to 2 to 4 with acid. 3. The method according to claim 2, characterized in that the polyamines are diethylenedriamine and triethylenetetramine, individually or as a mixture, is used. 4. The method according to claim 2 or 3, characterized in that the polyepoxide compound the connection