FI58363C - FOERFARANDE FOER UPPHAEVANDE ELLER FOERHINDRANDE AV DEN VITHETSFOERHOEJANDE EFFEKT VILKEN AOSTADKOMMITS MED OPTISKA BLEKMEDEL - Google Patents

Description

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Switzerland-Switzerland (CH) 1V808 / 73 (71) Sandoz AG, Basel, Switzerland-Switzerland (CH) (72) Giuseppe Raspanti, Fiorano ai Serio (Bergamo), Italy-Italy (lT) (7V) Oy Kolster Ab (5V) ) Method for reversing or preventing the bleaching effect obtained with optical brighteners - Förfarande för upphävande eller för-hindrande av den vithetsförhöjande effekt, vilken ästadkonmits med optiska blekmedel

The invention relates to a method by means of which the bleaching effect produced by anionic optical brighteners in materials, in particular fibrous materials, can be reversed or prevented by treating these materials in such a way! water-soluble acid addition salts or quaternary ammonium salts of the compounds having a group of the formula - ^ vf-3 I N -N- (X)

B

wherein the phenyl ring substituents are joined together in the m or p position.

The bleaching effects provided by optical brighteners on fibrous materials are not always desirable, resulting in the need for agents that remove the effect of optical brighteners. Elimination of the effect of optical brighteners is of practical importance in the paper industry. Once bleached paper has been produced on a paper machine and then the production of unbleached paper is started, the entire machine and the entire circulation system must be thoroughly cleaned beforehand to remove residual optical brighteners.

This cleaning is very expensive and reduces production capacity. Therefore, it is much more sensible to dispense with the purification of optical brightener residues and to add to the unbleached pulp, before or after sheet formation, compounds that negate the bleaching performance of the optical brighteners. Thus, the bleach residues transferred from the entire system of the paper machine to the paper are rendered ineffective. Such compounds can also be added to bleached waste paper when it is desired to make unbleached new paper from it.

Polymeric salts having a group X as a repeating unit and used to remove the bleaching effect obtained by means of optical brighteners from fibrous materials are described in German Application Publication No. 1,912.6 ^ 7 ·

They are prepared according to this application by acylating 1 mole of triethylenetetraamine with 1 mole of phthalic acid, namely terephthalic acid or isophthalic acid or their functional derivatives, such as anhydrides, acid halides or esters, and then cyclizing and converted to the acid addition or quaternary forms of ammonium.

The salts of the invention attenuate or inhibit the bleaching effect of optical brighteners which contain anionic groups, for example sulfonic acid groups, and will hereinafter be referred to as dimming agents.

The optical brighteners used are mainly compounds belonging to the stilbene series. Anionic optical brighteners are used primarily for fibrous materials of natural or synthetic origin that contain hydroxyl groups.

The fibrous materials used are, for example, textile fibers which are natural or regenerated cellulose or polyvinyl alcohol. But a particularly large amount of paper is used.

The salts are used by impregnating the optically bleached fibrous materials with a damping agent, preferably in the form of its aqueous solution.

If the fibrous materials are paper, the damper may be added to the pulp before or after forming the sheet. But it is also possible to coat the paper with a coating composition. In this case, the damping agents are simply added to the coating composition, e.g. starch, and they end up in the paper during the coating step, the so-called using fulard technology.

It is known to the invention to use salts of the compounds obtained by acylation of more than 1.5 moles of polyethylene polyamine of the formula H (HN-CH2-CH2) p-NH2 in which p = 2-5, with 1 mole of terephthalic acid or isophthalic acid or their functional derivatives and cyclization to compounds containing imidazoline groups and optionally by alkylation and / or further acylation with 0.3 to 1.0 moles of an aliphatic dicarboxylic acid having an alkylene group having 1 to 6 carbon atoms, or with a functional derivative thereof, or with a carbonic acid function.

The salts used according to the invention are the acid addition salts or quaternary salts of the compounds of the formula: R, -p —— N-Z-V '' S v ^ “L | (I) j 'Vn i wherein X is as defined above, n = 1-it, Y is -CO-NH when n = 1, and - || -ch2-ch-ff-4-

li V '/ n-2 when n = 2-U

N R 31 and the substituents on the phenyl ring are, as in group X, attached to each other in the m or p position, R 1, R 2> R 3 * and R 5 are hydrogen or an alkyl group having 1 to 2 carbon atoms, and optionally is substituted with phenyl or naphthyl.

k 58363 i may in addition be a hyphen. and when R 1 is a bond line,

Rr represents a group -C- or -C-alkylene-C- in which the alkylene group contains 1 to 6 carbon atoms and in this case the group of formula I is a repeating unit of an oligomeric or polymeric compound.

The salts of the compounds of the formula I have a stronger effect and a higher maximum reversal of the bleaching effects than the damping agents known to date.

Salts of the compounds of formula I are prepared in a known manner.

When preparing a group of monomeric salts of formula I wherein. R 1 - R 2 represent hydrogen, an acylation of an excess of more than 1.5 moles of polyethylene polyamine of the formula H (HN-CH 2 -CH 2) p -NH 2 where P = 2-5, for example moles of diethylenetriamine or triethylenetetraamine towards terephthalic acid or isophthalic acid or their functional derivatives such as their acid halides or esters. Stoichiometrically, 3 moles of polyethylene polyamine react with 2 moles of phthalic acid. The resulting acylation products are then cyclized to compounds of formula I containing imidazoline groups. The acylation and cyclization are described in U.S. Pat. No. 2,337,355, in particular on page 1, column 2, from line 52 to page 2, column 1, line 22. This is likely to give mainly monomeric compounds of the formula Hc.K-cVcVri_c V = 7 -'VX- (C1I2-CH2-SI0 - H (II) wherein X, n and Y are as defined above.

The compounds used according to the invention can be obtained, for example, by converting the compounds of the formula II into acid addition salts in a known manner, e.g. as described in DE-A-1 912 6b7. However, the preferred compounds for use in the invention are prepared by acylation of the compounds of formula II 58363 before being converted into water-soluble acid addition salts with bifunctional acylating agents. The acylation can be carried out using a bifunctional carbonic acid derivative such as a carbonic acid halide, e.g. phosgene or a carbonic acid ester such as ethyl carbonate, or a combined carbonic acid halide such as ethyl chlorocarbonate and an acidic derivative such as anhydrides or esters. The process of acylation using these acylating agents is previously known and described, for example, in U.S. Pat.

One of the best acylation topics is adipic acid, especially its bifunctional derivative, e.g. diester, especially adipic acid dimethyl ester. Another very good acylating agent is phosgene, or especially urea.

In the acylation, as mentioned above, previously known, 1 mol of the compound of the formula II and 0.6 to 2.0, in particular 0.8 to 1.0, in particular about 1 mol of an acylating agent such as adipic acid dimethyl ester or urea, are condensed. in a solvent, e.g. propylene glycol, at a higher temperature, preferably between 150-180 ° C.

In the preparation of the compounds to be used according to the invention, the starting materials of the formula II are preferred. n = 1 and in the manufacture of which diethylenetriamine is used because they are simple and inexpensive. In addition, when condensed using a bifunctional, molecular coupling agent, a very large amount of pure compounds is formed with diethylenetriamine, which can be characterized by clear structural formulas.

Particularly preferred compounds have the following repeating unit of the formula n (111) * wHN- (CH) -NC Jt \ _% o In V— 'CN-CU_-CHo “NH-CO-R-CO 2

O

and wherein R is an alkylene group containing 1 to 6 carbon atoms, predominantly butylene, or a repeating unit of formula IV

6! 58363

-ϊ-S-Q

J --- N-CH2 “CH2-NH-COvw o

Substituents on the phenyl ring are attached in the units of formula III and IV primarily to the p-position.

After the intermolecular coupling of the compounds of the formula II, acid addition takes place, in which case the acids mentioned in DE-A-1 912 6U7 can be used. In the preparation of compounds of formula I in which at least one of the radicals R 1 -R 2, optionally substituted, represents alkyl, the H atoms of the amino group in formula II are replaced in a manner known per se and replaced by alkyl groups.

After alkylation, conversion to the acid addition salt can then take place. For quaternization, an excess of alkylating agent is taken compared to the amount required for alkylation.

The alkylating and / or quaternizing agents used are compounds which give alkyl groups having 1 to 2 carbon atoms, optionally substituted by phenyl or naphthyl, such as, for example, dimethyl sulphate, diethyl sulphate, benzyl chloride, benzene or toluenesulphonic acid ethyl or ethyl ester or ethyl ester or ethyl; y ^ -kloorietyylibentseeniä.

When an alkylating agent and a quaternary agent which introduces a phenyl- or naphthyl-substituted alkyl group having 1 to 2 carbon atoms are used, up to two such groups can be introduced into the amino nitrogen atom.

The salts used according to the invention mainly contain cationic groups formed by acid addition or by quaternizing nitrogen atoms with an alkyl group containing 1-2 carbon atoms.

The anions of these salts are mainly anions of a strong inorganic acid, e.g. Cl, Br, SO 2 or anions of a strong organic inorganic acid, such as, for example, CH 2 SO 4, C 6 H 2 SO 4, benzene or toluenesulphonic acid anions. The preferred anions are those of a strong inorganic acid, especially Cl.

Preferably, a saline acid addition salt, especially the hydrochloride salt, is used.

The water-soluble acid addition salts and quaternary ammonium salts according to the invention are generally used in an amount of up to 50 times τ 58363, based on the amount of optical brightener.

The following examples are percentages by weight and parts by weight.

Preparation Example 1 19U parts (1 mol) of terephthalic acid dimethyl ester are poured with stirring onto 877 parts of diethylenetriamine (8.5 mol). The mixture is heated at about 187 ° C for 1 1/2 hours. During this time, 6k parts of distillate with a boiling point of 60 to 10 ° C are collected. The distillate consists primarily of methanol.

The temperature rises to 200 ° C within 30 minutes. At this time, the reaction water and excess diethylenetriamine begin to distill at 160 ° C. As the distillation rate decreases, the temperature of the reaction mixture is raised to 225 ° C in a 3 1/2 hour wedge.

The apparatus is then connected to a vacuum, 12-13 Torr, and distillation is continued for another hour. In total, 758 parts of the second distillate are obtained.

It is evaporated under a nitrogen atmosphere and a portion of ethylene glycol is added dropwise to the residue at 220-190 ° C. The solution is cooled to 130 ° C and 27 parts (0.15 moles) of urea are added. The resulting ammonia is bound with dilute hydrochloric acid. When gas evolution has ceased, heat to 150 ° C and stir the reaction mass for a further 3 hours at this temperature.

It is then cooled to 90-95 ° C and 167 parts of 33 # hydrochloric acid are added dropwise so that the temperature always remains between 90-100 ° C without cooling. When the addition is complete, stir for another quarter of an hour. The pH of the product is then about 5> 5 and it contains a solution of the hydrochloride of the compound having a group of formula IV as a repeating unit.

Preparation Example 2 19, 2 parts of terephthalic acid dimethyl ester are poured with stirring at 25 ° C into a vessel containing 1031 parts of diethylenetriamine (molar ratio 1:10):

Stir under a nitric acid atmosphere for 3 hours at 180 ° C. During this time, 52 parts of distillate with a boiling point between 80 and 162 ° C are collected.

The distillate consists mainly of methanol.

Stirring is continued for a further 1787 ° C for 7 1/2 hours, at which time the reaction water is distilled off together with diethylenetriamine. The excess diethylenetriamine is then distilled off in vacuo. The residue is 255 »5 parts of a product. This product is dissolved in 115 parts of propylene glycol, 26.3 parts of urea (molar ratio of terephthalic acid: urea = 1: 0.5) are added, and the reaction mixture is stirred at 155 ° C to 170 ° C for 2 hours. The reaction product is then cooled to 80 ° C. and neutralized by cooling to 211 parts of 26.6 # hydrochloric acid, cooled to give a 50 #, slightly viscous brown solution of the hydrochloride salt of the compound having a group of formula IV as a repeating unit.

8! 58363

Preparation Example 3

Proceed according to Preparation Example 1 with the difference that 255.5. To a portion of the residue dissolved in 115 parts of propylene glycol, 7 parts of adipic acid dimethyl ester are added and the reaction mixture is stirred at 155 DEG-175 DEG C. for 2 hours. A slightly viscous solution of the hydrochloride di salt of the compound 50) is obtained in which the group of formula III is present with the butylene group which is R as a repeating unit.

Examples of use 1. A 2.5 "cellulose suspension consisting of 50 of 52 bleached beech celluloses and 50 # of bleached sulphite cellulose is bleached with an optical brightener of the formula

C, H CN

"-0 / 1%" OH

"Y (V) NH-O-s ° 3Na 2 in an amount of 0.1% based on cellulose. The absorption time of the optical brightener is 10 minutes. The suspension is glued using 2% resin glue and 3% Aluminum sulphate. ^ O ^, calculated on cellulose.

Parts of this suspension are separated and 1% solutions containing the hydrochloride salt of the compound of formula III, wherein R is a butylene group, or the hydrochloride salt of the compound of formula IV are added. The amount added contains 1% of a diluent, the amount of the active ingredient of the damping agent being calculated relative to the cellulose.

5 minutes after the addition of the damping solutions, the suspensions are formed into a plate using a Rapid-Köthen device. This plate is pressed and dried at a temperature of 90-100 ° C. For comparison, a glued cellulose sheet and a glued and bleached cellulose ale vy are prepared. In neither of these cases is an attenuator added.

9 58363

Fluorescence measurements indicate the attenuation of the bleaching effect of the optical brightener. The hydrochloride salt of the compound of formula IV then has the strongest damping effect.

2. The dry paper is glued on the surface in a surface gluing machine with a Size-Press solution containing 80 g of starch per liter and 0.6 g of optical brightener of formula V, using a pick-up roller (100%).

The bleached paper web thus obtained is dried, then treated with 1 μl of a solution containing the hydrochloride salt of the compound of formula IV in a size-Press surface sizing machine using a pick-up roller (100%) and dried.

The bleaching effect of the optical brightener has virtually disappeared.

Comparative experiments A 2.5 ~ / l cellulose suspension containing 50% bleached beech cellulose and 50% bleached sulphite cellulose is bleached with 0.1 # of an optical brightener of the formula> - ~

f / \ N .C-H, CN

= =. CH -U NH - ^ "Vlj / 2 ^

\ _ / 1 H XC_H, 0H

V V-rw, j

The fixation time of the optical brightener is 10 minutes. The suspension is treated with 2 # of resin adhesive and 3 # of aluminum sulfate / Al 2 SO 4 -18HgQ 7 · 18. cellulose per 200 ml of suspension (amounts of resin adhesive and aluminum sulphate are calculated on the dry weight of air-dry cellulose). These 18 separate doses of cellulose, to which the latter suspension has been added, are divided into three groups of 6 doses, stirring constantly. Solutions containing a specific damping agent are added to each group. The three different damping agents are: - the hydrochloride salt of the compound of formula III - the hydrochloride salt of the compound of formula IV, and - DE 1 912 6b "(a known compound with the repeating unit formula 10 5 8 3 6 3

I N + \ - / N J

nch_ chx 3 3 '·

Three different dampers are pipetted into three groups, each containing 6 doses, in 6 different amounts, while stirring the doses.

Addition: 0.05 0.1 0.2 1 2 U% of damping agent, the amount of solid in the damping agent being calculated from solid air-dry cellulose.

5 minutes after the addition of the damping solutions, the suspension is formed into sheets with a Rapid-Köthen device. These sheets are pressed and dried at 90-100 ° C, after which the fluorescence values of the sheets are determined. A glued cellulose sheet and a glued and bleached cellulose sheet are prepared for blank samples. No damping agent is added to either. The fluorescence photometer is calibrated using a blank.

Zero equalization of the galvanometer is performed using a glued unbleached cellulose sheet. The bleached cellulose sheet is then measured and the galvanometer is calibrated to 100.

All test sheets are measured from both the front and the back. The calculated average is the final measured value. The averages are plotted as a function of the amounts of attenuator added to the semi-logarithmic paper. In this case, it appears that the hydrochloride salt of the compound of the formula III and in particular the hydrochloride salt of the compound of the formula IV has a lower fluorescence value than the known compounds.

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Claims (15)

A process by which it is possible to abolish or prevent the whiteness effect obtained by anionic optical bleaching on materials, particularly fiber materials, by treating these materials with water-soluble acid addition salts or quaternary ammonium salts of compounds containing a group of the formula -CHp-HC- (X) CN- (X) where the substituents of the phenyl ring are bonded to each other in the m or p position, the equator thereof, using salts obtained by acylation of more than 1.5 moles of polyethylene polyamine of the formula H (HN-CH 3 with 0.3 ~ 1 »0 mol of an aliphatic dicarboxylic acid having an alkylene group of 1-6 carbon atoms, or a functional derivative thereof or a functional derivative of carbonic acid. 2. A process according to claim 1, characterized in that diethylenetriamine is used as polyethylene polyamine. 3. A process according to claim 1 or 2, characterized in that in the continued acylation, adipic acid or a reactive derivative of adipic acid is used. Process according to claim 1 or 2, characterized in that phosgene is used in the continued acylation. 5. A method according to claim 1 or 2, characterized in that urea is used in the continued acylation. 6. A process according to claim 1, characterized in that salts of compounds of the formula 58363 are used in the form of compounds represented by the formula 58363 16 yrs \ R2 n YX-4-ch2-ch2-n-4-r5 (I) meaning, n = 1-U, * Ϊ § when n = 1, -CO-NH-, and when n = 2-U - CH - ijv% V- and phenyl ring substituents are in group X linked to each other in the m or p position, R 2, R 9, R 2, R 2 and R 2,. represents hydrogen or an alkyl group having 1-2 carbon atoms optionally substituted by phenyl or naphthyl, R 2 may additionally be a bond and, since R is a bond, the R group is -C- or -C-alkylene-C-I And the alkylene group contains 1-6 carbon atoms and in this case the group of formula I is a repeating unit of an oligomer or polymeric compound. Process according to claims 1-6, characterized in that salts of a compound of the following formula are used: 1} [N - / YX- (CH 2 -CH 2 -NH) n-R 5 where R 1 is the group -C - or -C-alkyl en-C-II-II-O-OO having 1-6 carbon atoms in the alkylene group, X, n and Y have the same meaning as in claim 1. 8. A process according to claim 7, characterized in that R 1 is a residue of the formula -C- (CHp). A process according to claims 6-8, characterized in that salts of compounds of formula I in claim 2 are used, wherein X has the same