FI61221B - SAETT ATT REDUCERA DEN MEKANISKA HAOLLFASTHETEN OCH / ELLER FOERBAETTRA MJUKHETEN HOS CELLULOSA ELLER PAPPER - Google Patents

Description

ίΤ ^ ΕΓΓΙ .... NOTICE OF PUBLICATION £ -100-1 NBV W '"» UTLAeeNINOiSKRIiT 6' * * 'C Patent granted 10 06 1982 ^ ratent meddelat (51) K ».ik.Vci.3 D 21 H 3/12 // C 07 C 93/0 * ENGLISH —FINLAND (21) Ptt-nttIh.k.mu.-PK.nttndMinIn, 32 ^ 1/72 (22) H «k * mUpUvl - AnaBknlngadtf 17 · 11« 72 (23 ) Alkupllvft — Glklfhatadif 17.11.72 (41) Tullut luikikuksi - Blhrtt off «mll | 20.05.73 ^ tantti. J« r «ki« t * rihallitu · Nttaviluip ^ o o μ moonLfull.1 ^ „*, -. Β

Patent- och ragiataratyralaan '' AmMcm utl ^ d och uti. »Krift * n puMiond 26.02.82 (32) (33) (31) Requested privilege — B« gtrd prtoritet 19.11.71

Sweden-Sweden (SE) 1 ^ 792/71 Statement-Styrkt (71) MoDoKemi AB, Fack, S — U-UU 01 Stenungsund 1, Sweden-Sweden (SE) (72) Jan Gunnar Emanuelsson, Stenungsund, Svante Ludvig Vähiin,

Stenungsund, Sweden-Sweden (SE) (7! +) Oy Kolster Ab (5 ^) The method reduces the mechanical strength and / or improves the softness of cellulose or paper - Sätt att reducera den Mekaniska hällfastheten och / eller förbättra mjukheten hos Cellulosa eller papper

The present invention relates to a way to reduce the mechanical strength of cellulose or paper and / or to improve their softness while maintaining good hydrophilic properties.

The process according to the invention is characterized in that a compound of the general formula fi1-0- (C2H | (O) -CH2-CHfom-CH2) is added to the pulp • before or during its conversion into cellulose or paper.

Rxx-o- (c2Hlto) n -ch2k: h (oh) -ch2. II. . . . . ...

wherein R and R independently represent a hydrocarbon group having 12 to 22 carbon atoms and independently represent a methyl, ethyl or hydroxyethyl group, n 1 and n 2 are independently a number having an average value of 0 to 10, and X is anion.

2 61221

The invention also relates to a novel quaternary ammonium compound.

It is previously known that the treatment of wet cellulosic pulp with a surfactant before or during the shaping of the cellulosic pulp in a drying or paper machine reduces the adhesion of the cellulosic fibers to each other. In this case, cellulose or paper with improved softness and low mechanical strength are obtained, which are desirable properties if, for example, the cellulose is disintegrated into a flocculant product. Surfactants useful for this purpose include quaternary mono- and di-alkylammonium compounds having at least 12 carbon atoms in at least one alkyl chain. Such compounds are described in U.S. Patent 3,395,708. The special effect of cationic surfactants has been attributed to the hydrophilic cationic moiety adhering to negatively charged cellulosic fibers, while the hydrophobic moieties expose and render the fiber surfaces hydrophobic. This reduces the adhesion of the fibers to each other and facilitates disintegration into a flaky product. However, as such, a strongly hydrophilic cellulosic pulp treated with a cationic surfactant of the type shown shows a more hydrophobic nature than the corresponding untreated pulp. In cases where the cellulose or paper produced is used to make highly absorbent, e.g. sanitary, products, such a hydrophobic property is not desirable because it significantly reduces the absorbency. As a result, in these cases it has been forced to improve the wetting properties by adding wetting agents, which, due to the low affinity of these wetting agents for cellulose, preferably takes place in the formed sheet by a separate technical treatment.

It has now unexpectedly been found that it is possible to obtain cellulose and paper which have improved softness and low mechanical strength and at the same time retain their good hydrophilic properties, as stated in the characterizing part of the main claim. The new quaternary ammonium compound according to the invention gives considerably better wettability to cellulose and paper compared to the cationic surfactants used hitherto. In general, it can be said that the wettability increases, while the fiber dissolving properties decrease to some extent as the number of ethylene glycol units increases. Similarly, the fiber-dissolving properties in the positive direction and the wetting ability in the negative direction are affected as the number of carbon atoms in the substituents R 1 and R 2 increases. By varying the number of carbon atoms in the substituents R 1 "and R 2" and the number of ethylene glycol units, it is therefore possible to obtain a combination of wettability and fiber-binding properties suitable for each specific application. Very good properties 3 61221 in both of these ratios have been found R "1 and R ** independently of one another denote a hydrocarbon group having 1 to 20 carbon atoms, and R" 1 and R 2 independently of one another denote a methyl or ethyl group and and are a number from 2 to 6.

The substance according to the invention is suitably added to the wet cellulosic pulp after the removal of lignin or the completion of bleaching, either before or during the formation into the sheet material in a cellulose or paper machine. The region is preferably used in the form of an aqueous solution with a concentration of 1-15% of active substance. Viscosity-lowering additives, e.g. ethanol or ethyl glycol, or nonionic surfactants, such as addition products of ethylene oxide or propylene oxide and aliphatic alcohols or alkylphenols, which are added to improve the rewetting ability of cellulose or paper, can also be added to this solution. The amount of substance added varies due to the desired effect, but is usually 0.02-2%, preferably 0.1-1.0%, based on the weight of dry cellulose. The cellulose or paper treated with the compounds of the invention can be used in a variety of fields. Cellulose can be disintegrated, for example, into so-called "fluff pulp" and used in this form in various hygienic products, and can also be used in the production of paper with a soft feel, such as hygienic paper, tissue paper and paper used in various textile replacement materials such as textile substitutes. hand towels, tablecloths, clothes, etc.

The substance according to the invention can be prepared by adding 1-10 moles of ethylene oxide in a manner known per se to 1 mole of alcohol having 12-22 carbon atoms. The alcohol polyethylene glycol ether thus obtained is then reacted with epichlorohydrin to give the corresponding chloroglyceryl ether, which is reacted with a secondary amine of formula

RIIIRIVNH

wherein R 1 and R 2 independently represent a methyl, ethyl or hydroxyethyl group, as a quaternary compound in the form of its chloride salt. If considered suitable, the chloride ion can be exchanged for other anions in a manner known per se, e.g. by adding a sodium salt having a higher solubility constant than with sodium chloride or using an anion exchanger in ion exchange In addition to chloride ion, hydroxyl, bromide, methyl sulfate, acetate, sulfate, carbonate, citrate and tartrate ions may be mentioned as anions, and monovalent ions are preferred.

> * 61221

The coupling of ethylene oxide to the alcohol is carried out in the presence of an alkaline catalyst, preferably sodium hydroxide, in a manner known per se. The reaction between the ethylene oxide adduct and epichlorohydrin is carried out at an elevated temperature of 100 to 150 ° C in the presence of a catalyst. As catalysts, SnCl 2, BF 3 and HCl 2 in particular have proven to be excellent and provide a rapid and easily controlled reaction, but other acid catalysts such as toluenesulfonic acid and sulfuric acid are also useful. To achieve a complete reaction of the alcohol compound, epichlorohydrin is usually added in excess. Quaternization of the secondary amine with chloro-glyceryl ether is performed in the presence of an alkaline catalyst, usually formed by sodium hydroxide, at a temperature of about 100-150 ° C. The reaction is usually carried out in the presence of an organic solvent having a boiling point of at least 60 ° C. Suitable organic solvents are, for example, methanol, ethanol and ethyl diglycol.

The region of the invention can also be prepared using various variations of the method described above. Thus, the chloroglyceryl ether can be reacted with ammonia or a primary amine having a methyl, ethyl or hydroxyethyl substituent, followed by quaternization using, for example, methyl or ethyl chloride or dimethyl or diethyl sulfate.

However, this process is more complex than previously described and involves several reaction steps simultaneously while providing a higher amount of by-products and a lower overall yield.

The alcohols having from 8 to 22 carbon atoms used according to the invention can be both synthetic and derived from natural products. "Occurring in nature" so-called. fatty alcohols are usually prepared by reducing fatty acid esters or fatty acids derived from vegetable oils such as coconut oil, palm oil, soybean oil, linseed oil, corn oil or castor oil, and animal oils or fats such as fish oil, whale oil, whale oil. Examples of suitable specific fatty alcohols include octyl alcohol, desyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, icosyl alcohol, oleyl alcohol and icocenyl alcohol. Synthetic alcohols are preferably prepared by the Ziegler method or the oxidation method. Most alcohols prepared by oxidation methods have a more or less branched chain, making a large number of isomers possible. The physical properties of these alcohols are remarkably similar to those of straight-chain primary alcohols.

5 ¢ 1221

Suitable secondary amines in the process of the invention include dimethylamine, diethylamine, diethanolamine, methylethylamine and methylhydroxyethylamine, all of which are marketed. Useful primary amines include methyl, ethyl and hydroxyethylamine.

The following embodiments illustrate the invention.

Examples 1-5

A reaction vessel equipped with heating and stirring equipment and a reflux condenser was charged with 2 moles of an alcohol mixture derived from tallow fat (16-20 carbon atoms in the alkyl chain). To this alcohol mixture was attached 12 moles of ethylene oxide using an alkaline catalyst. The resulting ethylene oxide adduct was then reacted with 2.2 moles of epichlorohydrin at about 125 ° C for 150 minutes. 6 g of SnCl 3 was used as catalyst in this reaction. The residual epichlorohydrin was removed by vacuum treatment to give the reaction product as a pale yellow thick-colored n-Stee. An autoclave equipped with a stirrer and a heating apparatus was then charged with 1.8 moles of the above reaction product, 250 g of ethanol in which 0.9 moles of dimethylamine, 50 g of sodium hydroxide and 30 g of water were dissolved. The mixture was autoclaved for 3 hours at 125 ° C, after which the remaining dimethylamine was removed by blowing with nitrogen gas. The reaction product consisted of a slightly yellow substance and was found to contain 89% of the quaternary amine and 7% of the tertiary amine based on the theoretical amount of amine. The quaternary compound is denoted by the letter A below.

Using the same procedure as in the preparation of Compound A, the following Compounds B-E were prepared.

B. Reaction product obtained from 2 moles of tallow fatty alcohol, U moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

C. Reaction product obtained from 2 moles of lauryl alcohol, 8 moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of dimethylamine.

D. Reaction product obtained from 2 moles of icosyl alcohol, 20 moles of ethylene oxide, 2 moles of epichlorohydrin and 2 moles of dimethylamine.

E. Reaction product obtained from 2 moles of octadecyl alcohol, 8 moles of ethylene oxide, 2 moles of epichlorohydrin and 1 mole of methylhydroxyethylamine.

Example 6

To a bleached pine sulphate pulp having a pulp concentration of 2 %% was added 0.5% of one of the products A-G, where A-E denotes the 61221 compounds shown in Examples 1-5. Product F is a reference product consisting of dioctadecyldimethylammonium chloride, a commercial additive in the production of flocculant, while G is a reaction product within the scope of the invention obtained from 2 moles of octyl alcohol, 2 moles of epichlorohydrin and 1 mole of dimethylamine. Test sheets were formed from the pulps in the usual manner, after which the mechanical strength (burst value by the method SCAIi-P 2 ^ +: 60) and the water absorption capacity by the Klemm method (SCAN-P 13: 61+) were tested. The results are shown in Table 1.

table 1

Addition p »hif« t «tin value Water absorption

Without additions 18.0 105 A 7.8 98 B 6.7 65 C 9.9 95 D 8.1+ 89 E 9.1 82 F 7.0 1 + 5 G 8.0 73

The results show that the additives A-E according to the invention give the cellulose considerably better water-absorbing properties than their structurally similar compounds F and G, while the mechanical strength is regularly approximately as good or deteriorated only to a negligible extent. Comparing, for example, compound B, the compound of the invention which gives the cellulose the worst water absorption properties, to the compound F used previously, it is surprisingly found that the compound B gives the cellulose both a more favorable burst value and a significantly better water absorption capacity. This clearly shows that the compounds of the invention are superior to previously used compounds of similar structure.

Example 7

A sheet of bleached pine sulphate cellulose weighing 800 g / m 3 was made in a paper machine. To the headbox before the paper machine was added 0.15 resp. 0.5% by weight # of products A, B and F based on dry cellulose. The dried pulps were defibrated as dry cellulose flakes in a spike roll type dry defibrator. Table 2 shows the relative energy consumption in relation to the mass to which no additions had been made, as well as the wetting time of a small amount of 7 61221 floating on the water for the corresponding masses. The following results were obtained:

Table 2

Product Additive Defibrillation- # Wetting time sec.

amount %

No increase - 100 2.0 A 0.15 57 3.3 A 0.5 35 3.3 B 0.15 57 2.2 B 0.5 32 6.6 F 0.15 62 7.5 F 0, 5 32 25.0

The results show that the use of compounds A, B or F does not cause significant differences in the defibration work required. In contrast, the absorption capacity of cellulose is strongly negatively affected by the addition of compound F. The use of compounds A and B according to the invention, compared to compound F, results in a significant reduction in the wetting time.

Claims (8)

A method of reducing the mechanical strength and / or improving the softness of cellulose or paper while maintaining good hydrophilic properties, characterized in that a compound of general formula IX / is added to the cellulose pulp before or during its formation into cellulose or paper. R -ο- (σ2ΗΗ ο) η -ch2-ch (oh) -ch2 where R ^ and R * "1" independently represent a hydrocarbon group having 12-22 carbon atoms, R ^ and R R independently of each other represents a methyl, ethyl or hydroxyethyl group, n1 and n2 independently of each other is a tai having an average value of 1-10, and X represents an anion. 2. A process according to claim 1, characterized in that R 1 and R 2 independently represent a hydrocarbon group having IU-carbon atoms, R * IV and R independently represent a methyl or ethyl group, n average value of 2-6, and X is a monovalent anion. 3. A process according to claim 2, characterized in that R111 and IVR denote a methyl group. A process according to claims 1-3, characterized in that R 2 and R 11 are derived from a fatty alcohol. 5. A process according to claims 1-3, characterized in that R and R 11 are derived from a synthetic alcohol. 6. A process according to claims 1-5, characterized in that the compound is 0.02-2, preferably 0.1-1% by weight, based on the dry weight of the cellulose. 7. Agent for carrying out the process according to claim 1, characterized in that the agent is a quaternary ammonium compound of the general formula RI-O- (C2H1 + O) n -CH2-CH (OH) -CH2 RIT-0 - (COH 1 O) -CH 2 -CH (OH) -CH 2 2. n 2 2 2 where R 2 and R 2 independently represent a hydrocarbon group having 12-22 carbon