DE2364443C3 - Cellulosic tangled nonwovens with improved wet strength and process for their manufacture - Google Patents

Description

H,

V LJ

where m is an integer from 4 to 15 and ρ

or 1 means

in a molar ratio of 0.5: 1 to 0.95: 1, characterized in that this condensation product is additionally combined with epichlorohydrin, Epibromohydrin and / or epijodhydrin in a molar ratio of 1.25 to 2.5 mol epihalohydrin reacted per mole of amine group in the condensation product, in the water-soluble state was applied to the fleece and then cured.

2. Fleece according to claim 1, characterized in that that the substrate is paper.

3. Fleece according to claim 1 to 2, characterized in that the molar ratio of epihalohydrin to amine 1.5 to 2.25 mol epihalohydrin per mole of amine group.

4. Fleece according to one of claims 1 to 3, characterized in that it is a! S amine component Contains 1,6-hexamethylenediamine.

5. A method for producing the fleece according to claims 1 -4. characterized in that the Formation of an aqueous fiber slurry / ugeset / t will.

6. Process / ur production of the fleece according to claims I -4. characterized in that the preparation is applied to the cellulose substrate is applied.

subsequently condensed with formaldehyde showed that the papers treated with these resinous products had unsatisfactory wet strength and in particular the condensation reaction with formaldehyde is too slow.

From UE-PS 9 55 835 is a method for Impregnation of paper known, in which the paper pulp is added basic products that are free from reactive halogen or epoxy groups are and by condensation of polyamines with crosslinking Compounds such as epichlorohydrin and dichloroethane can be obtained. The here used Basic products should not contain cellulose under the conditions customary in the manufacture of paper still react to form a water-insoluble resin. Although these products increase the wet strength of paper, however, they have other disadvantages. For example, a resin preparation that can be obtained by reacting Dichloroethane with a polyalkylenepolyamine, such as ethylenediamine, is unsatisfactory because it too long time to cure in some cases up to needed a year.

It has now surprisingly been found that tangled cellulose nonwovens imparted improved wet strength with the aid of cationic resin formulations can be applied to the substrates in their water-insoluble state and then to be cured. These cationic resin preparations are the reaction product from a reaction product

(a) a dihaloalkane of the formula
R.

From DE-PS 8 97 015 a method is for Manufacture of a water-soluble resinous condensation product known, which is obtained by having a dihaloalkane with no more than Carbon atoms and a polyethylene polyamine with a molecular weight of at least 146 initeir.ander converts the condensation product then with urea heated and the resulting Reiiktionsprodukl

X CH ₂ KH ₂ Z _n Γ H ₂ X

wherein X is chlorine. Bromine or iodine atom, R a hydrogen atom, a hydroxy or an alkyl group with 1 to 4 carbon atoms, and π is 0 or 1, and

(b) a polyalkylene polyamine of the formula

M ₁ NK JI ₂ , "NH) _p C", H _2m NH ₂

where / «is an integer from 4 to 15 and ρ0 or 1 is.

in a molar ratio of 0.5: I to O. ^Q 5: I. and

(c) an epiphytic eye hydrin. namely epichlorohydrin. Epibromhyririn and / or F.pijodhydrin in a molar ratio of 1.25 to 2.5 mol of epthalohydrin per mole of amine group.

The invention therefore also relates to a method for Manufacture of tangled cellulose fibers. in which one in sufficient quantity / ur increase the Wet strength the above-described I lar // rescheduling in their unhardened condition an aqueous one Fiber slurry insulation adds or on the fleece applies and then hardens.

Preferably, the Harzzubereituftgen are under Made using water as a solvent. Appropriately contains the aqueous, by reaction of the Reaction products »solution obtained from dihaloalkane and polyalkylenepolyamine with epihalohydrin about 40% heart solids, which is determined by

that one determines the total weight of the reactants used and then by the total weight the solution including the added water divides. Be by controlling the reaction Aqueous solutions are obtained having a viscosity which generally has a resin solids content of 40% the Gardner-Holdt scale at 25 ° C from A to Z, preferably D to H.

The aqueous solutions can be adjusted to any resin solids concentration if they be applied to cellulosic substrates. solutions having a resin solids content of about 5 to 40%, preferably 20 to 35% and less pH value than 6 at 25 ° C are longer time. i.e. over 3 months, stable. A pH of 4.5 to 5.5 will be preferred. In general, the pH is at least 3, so that the solutions in devices from stainless steel can be used.

In general, aqueous solutions of the new resin preparations, each of which has the molar ratio of epihalohydrin to Am in over 2.5 :! is not thermosetting and solutions below 1.25: 1 generally gel. Molar ratios are preferably used from about 1.5 1 to about 2.25: 1.

The reaction products obtained by reacting the dihaloalkane with the polyalkylenepolyamine contains essentially linear or branched ones Groups with few or no cyclic groups. Preferably more than 85% linear or branched groups. These reaction products generally result from this produced that the solvent used is water, water-miscible Alcohols or their geniuses are used. Aqueous solutions are clear, blaugelb unü have one pH value from about 8 to 11 at 25 ° C. Someone thought Concentration can be used as long as it is suitable for further reaction with epihalohydrin. A suitable concentration is in the range of about 25 to 55% by weight based on the total weight of the Solution. It can also increase the concentration by adding or removing solvent with the formation of the desired viscosity can be set. For example, a viscosity of about A to H is on the Gardner-Holdt scale at 25 ° C suitable for reaction with epihalohydrin.

To dihaloalkanes. where π is 0. include, for example: 1,2-dichloroethane. 1,2-dibromoethane. 1,2-diiodoethane. and where η is 1: 1,3-diiodopropane.

1 _r 3-dichloro-2-methylpropane, 1,3-dibromo-2-butylpropane, l _r 3-dichloro-2-isobutylpropane, l _r 3-dichloro-2-hydroxymethylpropane and 1,3-dibromo-2-hydroxypropane. It is preferred that π is 0 and 1,2-dichloroethane is particularly preferred, α, ω-DihalogenaIkanes having 4 to 6 carbon atoms between the halogen substituents form structures of the piperidine type and are unsuitable as main components. However, there may be reaction products that instead of part of the linear ouer

ίο branched units cyclic units up to about 15 or 20% can be used.

Polyalkylene polyamines where ρ is 0 include: 1,4-tetramethylene diamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine, 1,10-decamethylene diamine, 1,12 dodecamethylene diamine, 1,15-pentadecymethylene diamine, and where ρ is 1 : Bis-tetramethylene triamine, bis-hexamethylene triamine, bis-heptamethylene triamine, bis-nonamethylene triamine, bis-pentadecylmethyl-triamine. It is preferred that ρ be 0 and that m be 4 to 10; 1,6-hexamethylenediamine is particularly preferred.

Di- or triamines. that contain fewer than 4 carbon atoms between the amine groups tend to To form products that essentially contain cyclic units and for the implementation of the Invention are unsuitable. However, a minor proportion, i.e. 15 to 20%, of the adduct of this invention can be used are replaced by adducts which essentially contain a total of cyclic units.

Other useful reaction products are those in which

1) the polyalkylene polyamine has more than 15 carbon atoms contains, such as 1.19-NonadecyIdiamine,

2) wherein the polyalkylenepolyamine has one, two or more simple substituents, the. Lower alkyl. z. B. methyl, ethyl. Butyl, nitro, sulfate, sulfonyloxy. Carboxy. Carbo-lower alkoxy, e.g. B. carbomethoxy, carboethoxy, amido, hydroxy. Lower alkoxy. ζ. B. Melhoxy-. Ethoxy and lower alkanoyloxy. ι. B. AcetoxjgrupptM. Or

3) in which the polyalkyl polyamines are more than 15 Have carbon atoms and have one, two or more simple substituents.

Epichlorohydrin. Are epibromohydrin and epiiodohydrin the epihalohydrins which can be used in the practice of this invention.

The following tables show examples of inventions appropriate compositions.

35

Table I.

Dih.ilngenalkan

A 1.2-dichloro-2-hydroxypropane

B I. V dichloro-2-iithylpropiine

C l, 2nd rdichloroalhan

D i ^ Dichlof-l-buiylpiopan

E 1,2-dibromopropane

F 1,2-dibfofnethati

G l ^ dichlor ^ bulylpronan

Polyalkylene polyamine Molar ratio *) + 1,6-hexamethylene dianiine 0.7 + 1.10-decamethylenediamine 0.8 p + 1,6-hexamelhylenedianiine OM + liS-Oclamethylenediamine 0.6 + 1,14-telradecamethylene diamine 0 ₍ 95 + Bis-hexamelhylenediamine 0.5 + Bis-iridecamethylenediarriin 0.75

*) dihalogen: polyalkylene.

Table II

Case-reaction game product of the
Table I.

Epihalohydrin

Molar ratio *)

A.
B.
C.
D.
E.
F.
G

Epichlorohydrin

Epiiodohydrin

Epichlorohydrin

Epibromohydrin

Epichlorohydrin

Epibromohydrin

Epichlorohydrin

1.25: 1

1.5: 1

1.75: 1

1.25: 1

2.25: 1

1.87: 1

2.0: 1

*) Moles of epihalohydrin per mole of amine group of the polyalkylenepolyamine.

The dihaloalkanes can with polyalkylene »mines by the process of US Pat. No. 2,834,675 implemented.

For example, dihaloalkanes are preferably reacted with Polyallcylenpolyaminen in the proportions indicated above in a temperature range of about 25 ° C to reflux or above, at about 60 to 90 ^c C. in a solvent such as preferably water, water-miscible alcohols or mixtures thereof. As the reaction proceeds, the viscosity increases and it is convenient to keep it at G to S on the Gardner-Holdt scale by adding solvents. The viscosity is measured at -5 ° C. In order to maintain a reasonable reaction rate, any strong base or other acid acceptor can be added to neutralize the HCl formed. Such bases include the alkali metal hydroxides or alkali metal alkoxides. The reaction is continued until there are essentially no more free dihaloalkyls in the reaction mixture.

The reaction product of dihaloalkane and polyalkylenepolyamine can with the epihalohydrin be implemented by the process of US-PS 25 95 935. For example, one gives epihalohydrin in Presence of a solvent such as water, water-miscible Alcohols or t, er mixtures for one Temperature range from about 25 to 45 "C. Preferably about 25 to 35 C 10 minutes to 120 minutes, preferably 30 to 90 minutes, / u. The solids concentration of the reactants in the reaction mixture is about 20 to 60% by weight during the reaction. preferably about 30 to 40%. related to the total weight of the reaction mixture. When the addition is complete, the temperature is increased to about 60 to 80 C. The reaction is carried out at this temperature by adding further heat until the resin reaction product has a viscosity at 40% resin solids content. measured at 25 "C the Gardner-Holdt scale on the order of A to about /. preferably about D to about H Man has lowers the pH value, for example with H2SO4 or HCI.

Aqueous solutions of the new resin preparations are particularly valuable for increasing the wet strength of paper. In general, they contain 5 to 40% by weight of uncured resin solids, preferably 20 to 35% and 60 to 95%, preferably 65 to 80% by weight of water, based on the total weight of the aqueous solution. Any convenient concentration of the uncured resin solids to increase the wet strength of paper can be used. The preformed and partially or fully printed paper can be impregnated by dipping or spraying with an aqueous solution of the resin, after which the paper is ^{heated for about 0.5 to 30 minutes at temperatures of 90 to 100 °} C. or more in order to dry it and curing the resin to the water-insoluble state. Since the paper obtained has increased wet strength, the process according to the invention is particularly suitable for the impregnation of paper towels, absorbent fabrics, as well as for wrapping paper and sack paper.

However, the resin preparations according to the invention of the aqueous fiber slurry are preferred added, wherein an aqueous solution of the resin in the uncured and hydrophilic state to one aqueous pulp in the Dutchman, the pulp chest, a lordan machine, centrifugal pump, etc. before the Formation of the fibrous web is added. The sheet material is then poured out and in the usual way dried, causing the resin to harden in its polymerized and water-insoluble state and the Paper wet strength is imparted.

To provide sufficient wet strength, the resins must be added in amounts of about 0.1-5% or more based on the dry weight of the paper, the amount depending on the desired level of wet strength in the final product and the amount of resin retained by the paper fibers . The resins can be used under acidic, neutral or alkaline conditions, i.e. h be cured at a pH of from about 3.0 to 13, including subjecting the paper to a heat treatment for about 0.5 to 30 minutes at a temperature of about 90 to 100 ⁰ C. Optimal results are obtained under alkaline conditions. It can therefore be made alkaline (pH 8-13) for those where short curing times are desired, such as for hygiene papers, aie resin preparations before use. Such a pretreatment leads to shorter curing times and increased wet strength.

B c i s ρ i e! 1

58 g (0.5 mol) of 1,6-hexamethylenediamine are placed in a 4-necked flask. which is equipped with a thermometer, mechanical stirrer, cooler and an additional funnel. For this purpose, 10.2 g of water are added and the mixture heated to 70 ⁰ C. 42 g (0.43 mol) of 1,2-dichloroethane are slowly added so that the reaction temperature remains below 75 ° C., which takes about 3 hours. During these 3 hours, 8 g of water are added in order to keep the viscosity of the reaction mixture below Gardner S. After the addition of 1,2-dicorethane is complete, 8 g of 50% aqueous sodium hydroxide are added. The reaction is held at 70 ° C. until the viscosity Gardner V is reached. At this point in time, 8 g of water are added. The temperature is increased to 80 ^° C. and this temperature is maintained until the viscosity reaches Gardner T. 315 g of water are then added and the mixture is cooled to 25.degree. 184.8 g (2 mol) of epichlorohydrin are added to this mixture over the course of one hour, as a result of which the reaction temperature rises to 45.degree. After a

b5 another hour at 45 ° C., the reaction temperature is increased to 65 ° C and maintains this temperature until the viscosity of the solution Gardner D achieved. At this viscosity one gives 9 g '

percent sulfuric acid and 227 g of water. The final pH is set to ~ 5 and the final solids content is added to 25% mil local sulfuric acid and water.

1200 g of a solution which has 25% solids and a pH of 4.5 at 25 ^° C. are obtained.

Example 2

Following the procedure of Example 1, the products of Tables Hl and IV are prepared by

Table III

instead of 1,2-dichloroethane, 0.43 mol of 1,2-dibromalane. 0.43 mol of U-diiodoethane, 0.43 mol of I J-dichloro-2-methylpropane, 0.43 mol of l, 3-diiodo-2-bulylpropane or 0.43 mol of l, 3-dich! Or-2-isobuly! Propane and instead of Epichlorohydrin 2 moles of epiiodohydrin or 2 moles of EpibPOinhydrin or instead of 0.5 mol of I ^ -hexamethylene diamine, 0.5 mol of 1,5-pentamethylene diamine, 0.5 mol of 1,7-heplamethylene diamine, 0.5 mol of 1,12-dodccamethylenediamine, 0.5 mol of bis-Hptamelhylenetriamine or 0.5 mol bis-tetradecamelhylenetriamine is used.

Dihaloalkane

Polyalkylene polyamines

Molar ratio *)

A 1,2-dibromoalkane +

B 1,2-DijodaIkan +

G 1,3-dichloro-2-methylpropane +

D 1,3-Diiodo-2-butylpropane +

E I, 3-dichloro-2-isobutylpropane +

F i, 2-dichloroalkane +

G 1,2-dichloroalkane +

H 1,2-dichloroalkane +

I 1,2-dichloroalkane +

J 1,2-dichloroalkane + *) dihaloalkane: polyalkylene polyamine.

Table IV

Reaction product*) 1 A. 2 B. 3 C. 4th D. S. F. 6th F. 7th G 8th H 9 I. 10 J

Epihalohydrin

Molar ratio **)

+ Epibromohydrin 2: 1

+ Epiiodohydrin 2: 1

+ Epichlorohydrin 2: 1

+ Epichlorohydrin 2: 1

+ Epichlorohydrin 2: 1

+ Epichlorohydrin 2: 1

+ Epibromohydrin 2: 1

+ Epibromohydrin 2: 1

+ Epichlorohydrin 2: 1

+ Epichlorohydrin 2: 1 *) From Table III.

**) moles of epihalohydrin per mole of amine group of the adduct.

Example 3

Following the procedure of Example 1, the products of Tables III and IV are made, but with different They are described in Tables V and VI.

Table V

product

Molar ratio

A.
A.
A.
B.
B.
B.

0.7: 1 0.8: 1 0.9: I 0.6: 1 0.5: 1 0.94: I.

1,6-hexamethylenediamine 0.86: 1

1,6-hexamethylenediamine 0.86:

1,6-hexamethylenediamine 0.86:

1,6-hexamethylenediamine 0.86:

1,6-hexamethylenediamine 0.86:

1,3-pentamethylenediamine 0.86:

1,7-heptamethylene diamine 0.86:

11,12-dodecamethylenediamine 0.86:

Bisheptamethylene triamine 0.86:

BisteiTamethylene triamine 0.86:

product

Molar ratio

0.85: 1 0.6: 1 0.65: 1 0.55: 1 0.78: 1 0.9: 1 0.89: 1 0.86: 1 0.74: i

Table VI
Resin reaction products

product
from
Table V

Epihalohydrin

Molar ratio *)

Epibromohydrin

Epibromohydrin

Epibromohydrin

Epiiodohydrin

Epiiodohydrin

Epiiodohydrin

Epichlorohydrin

Epichlorohydrin

Epichlorohydrin

Epichlorohydrin

Epichlorohydrin

Epibromohydrin

Epibromohydrin

Epichlorohydrin

Epichlorohydrin

2.25: 1 1.25: 1 1.6: 1 2.45: 1 1.45: 1 1.9: 1 1.85: 1 2: 1 2.0: 1 2.25: 1 1.9: 1 1.8: 1 1.45: 1 1.6: 1 1.75: 1

*) MoI epihalohydrin per mole of amine group.

Example 4

A suitable amount of the resin according to Example I is added to an aqueous pulp of unbleached softwood kraft fibers with a consistency of 03% and a pH of 8.0, changed to a Canadian Standard Freeness of 455 ml adjusts the pulp to pH 8 with 1% sodium hydroxide, stirs briefly and lets the resin spread. The fibers are formed into a wet web at a consistency of 34% on a Noble and Wood laboratory hand papermaking machine. The wet web is pressed onto a felt and ^{dried at 95 °} C. for 2 minutes. The heavy g 2.5 sample obtained sheet (20 χ 20 cm) is cut into 2.5 cm χ 20 \ s wide strips. The strips are cured in the oven ^{at 105 ° C. for 10 minutes.} The hardened ones

Strips are immersed in water for 10 minutes and tested for wet strength wedge.

The experiment provides those given in Table VI Results.

Table ViI

Resin content

Wet sand (kg / cni) *)

0.25
0.50
0.75

1.094 5.67 9.31 10.58

*) Measured using an Instrom strength tester.

Claims (1)

Patent claims: 1. Cellulose nonwovens with improved wet strength, containing a condensation product of (a) a dihaloalkane of the formula X-CH ₁ -ICH ₁ L-CH, X wherein X is a chlorine, bromine or iodine atom, R is a hydrogen atom, a hydroxy or alkyl is group with 1 to 4 carbon atoms and η = O or 1, and
(b) a polyalkylene polyamine of the formula