DE2524801A1 - OPTICAL LIGHTENING AGENTS AND METHOD FOR MANUFACTURING THEM - Google Patents

Description

Optical brightening agents and processes for their preparation

The invention relates to optical forming sym-triazine derivatives Whitening agents and a process for their preparation. These brighteners are used to increase the degree of whiteness, in particular of products made of cellulose fibers or of polyamide fibers and of papers mixed in a mass certainly.

In general, optical brightening agents are known and used, the active substance of which form compounds of the formula I or II

(ID

in which X is the radical of an aliphatic, aromatic or heterocyclic amine, Ar is an m- or p-phenylene radical and M is a monovalent cation. Although these brighteners are characterized by good whitening properties they owing to the high price, used in their manufacture Raw materials, relatively expensive. The high price of optical brightening agents can be due to excellent Lightening properties, in particular, are compensated for by a high degree of whiteness achieved.

The invention is based on the object of creating such optical brightening agents which, with regard to the degree of whiteness and their purity surpass previously known products.

Surprisingly, it has been found that the effectiveness of optical brightening agents that act as active substance compounds of the formulas I and / or II, in which Ar is a m- or p-phenylene radical, X the residue of an aliphatic or aromatic or heterocyclic amine and M is a monovalent cation, meaning by introducing compounds of formula III

(in) 509850/1024

can be increased, where Ar, X and M are those given above Have meaning. It has been found that the greatest effect is exhibited by such optical brightening agents, their active Substance, in addition to the two above-mentioned compounds of the formulas I and II, additionally the compound of the formula III contains, in which Ar, X and M have the meaning given above.

The subject of the invention therefore form optical brightening agents, which contain compounds of the formulas I and / or II as active substance, in which Ar is an m- or p-phenylene ^ adical, X is a radical of an aliphatic, aromatic or heterocyclic amine or a -NEp group and M is a monovalent cation which is characterized by a content of compounds of the general formula III in which Ar, X and M have the meaning given above. The compounds of formula III are preferably in one Amount of 20 to 65 parts by weight and the compounds of the form I and / or II in an amount of 35 to 80 parts by weight contained per 10C parts by weight of active substance.

Optical brightening agents that act as active oubstans one Constituent of the formula III in addition to the constituent of the formula I or in addition to the constituent of the formula II in which Ar, X and M have the meanings given above, are obtained by ordinary mixing of the ingredients. Optical brightening agents that are part of the

509850/102 *

Formula III in addition to the two components of the formula I.
and II are obtained by an appropriate method. The process of making optical
Lightening agents containing as active substance three components of formulas I, II and III, in which Ar, X and M
have the meaning mentioned above, consists according to the invention in the condensation reaction of the mixture of 2-methoxy-4,6-dichloro-sym-triazine and 4,6-dichloro-2-m- (or p -) -

sulfophenylamino-.sym-triazine with 4-, 4'-diaminostilbene disulfonic acid-2,2 ' or its disodium salt and subsequent condensation of the intermediate product obtained, which is a mixture of the compounds of the general formulas IV, V and VI

SO ₃ M

MOaSArHIH / ^v C-NH- <f> -HC = CH- <VhN-C * ^ C-NHApSO ₃ M

^ / 5O3M

I. CL

(IV)

l H

NN

Ct -.

(V)

509850/1024

SO ₃ M

VOCH

(VI)

in which Ar and M have the meaning given above, with aliphatic ^ aromatic or heterocyclic! Amine or with ammonia. For the reaction, one uses 4,4'-diaminostilbenedisulfonic acid-2,2 'for 1 mole 0.5 to 1.5 mol, preferably 0.85 to 1.15 mol of 2-methoxy-4,6-dichloro-sym-triazine and 0.5 to 1.5 mol, preferably 0.35 to 1.15 mol of 4,6-dichloro-2-m- (or p -) - sulfophenylamino-sym-triazine, the total amount of these two triazines from 1.9 to 2.3 mol amounts to. On 1 mole of the total amount of the intermediate, which forms a mixture of compounds of the formulas IV, V and VI, in which Ar and M have the meaning mentioned above, at least 2.3 mol of aromatic amine or at least 3 mol of aliphatic or heterocyclic amine are used or at least 6 moles of ammonia. The reaction mixture it is treated with sodium chloride or with mineral acid, e.g. hydrochloric acid, or with organic acid, e.g. acetic acid. Man the paste obtained is filtered and dried in any drying device or it is transferred by means of one of the known methods in liquid form, e.g. in a solution or suspension.

509850/1024

-6-

The optical brightening agents forming the subject of the invention produce excellent whitening effects on products made from fibers of natural and regenerated cellulose, on products made from polyamide fibers and on paper products. These agents lighten cellulose fibers significantly more than other optical brighteners such as sym-triazine derivatives and in particular those such as compounds of the formulas I or II, which have hitherto been considered to be the most effective, as well as the hitherto unknown compounds of the formula III. For example, cotton fabric was lightened by means of the compound of the formula I, in which Ar is an m-phenylene radical, X is a diethanolamine radical and M is a sodium cation; a maximum whiteness of I3I according to the Anni Berger formula (the color 1959 8, 187) was obtained. When using the compound according to formula II, in which X represents a diethanolamine radical and H is a sodium cation, a maximum whiteness of 135 is obtained. The compound according to formula III, in which Ar, X and M have the meaning mentioned above, gives a lightening to a whiteness of 136. The same fabric was tested under the same i. : ainqan ^ en treated with egg of the optical brightening agent according to the invention. As the active substance, 67 parts by weight of the compound of the formulas I and II, and 33 parts by weight of the compound of the formula III in which Ar, X and M have the meanings mentioned above, were used. A whiteness of 140 was achieved. The shade of the fabric lightened in this way is more blue, more brilliant and purer than when the above-mentioned compounds of the formulas I, II or ^IIIm 509850/1024 are used

The essence of the invention is explained in more detail on the basis of the examples given below.

example 1

An optical brightening agent that acts as an active substance 6? Parts by weight of the compound according to formulas I and II, in which Ar is an m-phenylene radical, X is an -N (CHpCHpOH ^ - Group and M is a sodium cation, and 33 parts by weight of the compound according to formula III, in which Ar, X and M have the meanings mentioned above, is used to increase the whiteness of fabrics made from mercerized cotton. The lightening of the fabric will come on carried out in the following way. In a bath containing 20 kg of sodium chloride, Contains 1 kg of sodium carbonate and 0.3 kg of the above-mentioned optical brightening agent in 4-nr water 100 kg of tissue introduced. Everything is heated up to a temperature of 40 ° C. After 30 minutes, the Tissues taken out of the bath, rinsed and dried. After this processing, the fabric becomes ": brilliant." and pure white with a shade of blue. The whiteness of the lightened tissue, determined according to the Anni Berger formula, is

The optical brightening agent given in this example is obtained in the following manner. In a 1 π methanol and reactor containing 560 kg of sodium bicarbonate 250 kg of cyanuric chloride introduced. The whole thing will be 2 1/2 Stirred for hours at a temperature of 12 ° C. The result of the process is 4,6-dichloro-2-methoxy-sym-

509850/1024

triazine. At the same time, 6 m of water, 2CK) 0 kg of ice, 5 kg of a surface-active agent which is a condensation product of 1 mole of fatty alcohol with 18 moles of ethylene oxide, and 250 kg of cyanuric chloride and 228 kg of metanilic acid are placed in a special reactor a. The whole is then stirred for 1 1/2 to 2 1/2 hours until the aromatic amine in the reaction mixture disappears, at a temperature of 0 to 5 ° C and simultaneous addition of a 10 percent aqueous sodium carbonate solution to neutralize the hydrogen chloride which separates out during the reaction. 4,6-dichloro-2m-sulfophenylaminosym-triazine is formed. The two sym-triazine derivatives obtained are poured into a single one without separating them from the reaction mixture. Reactor. To the resulting mixture are added to the 4,4'-diaminostilbene disulfonic acid-2,2 "515 kg disodium salt. The mixture is stirred JO minutes at a temperature of 0 to 5 ° C, then heated for 1 hour at 20 ⁰ C and stirred at this temperature until the end of the reaction. An intermediate product is formed which is a mixture of compounds of the formulas IV, V and VI in which Ar is an m-phenylene radical and M is a sodium cation. 540 kg of diethanolamine are added to this mixture and the whole is 2 stirred for hours at a temperature of 90 ° C. the solution obtained after this time is filtered. to the filtrate sodium chloride is added in an amount of 20% relative to the volume of the liquid. It is then cooled to a temperature of 25 ⁰ C, Stirred for 3 hours, filtered

509850/1024 _ ₉ _

and drying the obtained paste in a spray dryer. 1350 kg of a light yellow product which ^{does not melt up to a temperature of 30O 0} G are obtained. Its composition is given in the first part of the present example.

Example 2

An optical brightening agent that contains, as active substance, 67 parts by weight of compounds of the formulas I and II in which Ar is an m-phenylene radical, X is a -NHGtUCHpOH group and M is a sodium cation, and 33 parts by weight of the compound of the formula III, in> Whose Ar, X and V. have the meanings given above, are used to increase the whiteness of cotton fabric during the finishing. The lightening of the fabric is carried out as follows. The chemically bleached, made from mercerized cotton fiber? fabric produced with a finish of the following composition * insert 5 kg of cycloethylene urea formaldehyde resin, known under the trade name Silezjan EM, 1.5 kg of polyacrylic resin, known under the trade name Perapret HV, 1 kg of urea, 1 kg of magnesium chloride hexahydrate and 0.3 kg of the above mentioned optical brightener and 92 l water, saturated. The padded fabric is then passed between wringing rollers with a loss of approx. 100% liquid in relation to the mass of the dry fibers and exposed to ^{air at 145 °} C. for 5 minutes. After this processing, the fabric becomes brilliant and pure

509850/1024 -10-

White of a blue shade with a white grsd in front. 133.

The optical brightening agent given in this example is prepared in the following manner. 4-10 kg Monoathanolamin be in a mixture of compounds of formulas IV, V and VI obtained are listed in Example 1, _t introduced. The whole is stirred at a temperature of 85 ° C for 2 hours. After this time, the solution obtained is filtered, sodium chloride is added in an amount of 16% in relation to the volume of the liquid. It is then cooled to a temperature of 25 ° C., stirred for 3 hours, filtered and dried in a spray dryer. 125O kg of a light yellow product are obtained which does not melt up to a temperature of 300.degree. The composition of the optical brightening agent is given in the first part of this example.

Example 3

Chemically bleached fabric made from mercerized cotton is finished with the following composition: 3 kg polyvinyl acetate modified by dibutyl phthalate (trade name Winacet D-525), 0.25 kg of ethylene oxide adduct and stearic acid with the trade name Rokacet S-7, 0.3 kg optical brightening agent as in Example 2 and 96 1 padded water. The padded fabric is then passed between wringing rollers with a loss of approx. 100% liquid, based on the mass of the dry fibers, and then with one

509850/1 024

At a temperature of 100 ° C. After this processing the fabric reaches a whiteness of 143 and is characterized by a brilliant blue-red shade.

Example 4

An optical brightening agent which contains, as active substance, 67 parts by weight of compounds of the formulas I and II in which Ar is an m-phenylene radical, X is a -KHp group and M is a sodium cation, and 33 parts by weight of the formula III in which Ar , X and M have the meaning given above, is used for lightening fabrics made of viscose fibers. The fabric finishing is carried out in the following way. In one, up to a temperature of 5C ⁰ G heated solution kg in 4 m water 20 Sodium chloride, 5 kg sodium carbonate and 0.8 kg of the above-mentioned optical brightening agent contains, is carried out for a period of 45 minutes, 100 kg of a fabric made of viscose rayon. The fabric is then rinsed and dried at room temperature. After this treatment, the fabric reaches a degree of whiteness of 131. When lightening fabric made of viscose fibers, it was unfortunately not possible to achieve such a degree of whiteness with previously known optical brightening agents.

The optical brightening agent given in this example is prepared in the following manner. In an intermediate product, that is a mixture of compounds of the formulas

509850/1024

IV, V and VI, and has been obtained in the manner mentioned in Example 1, 1 nr 25% ammonia water is introduced. The whole is stirred for 4 hours at a temperature of 7O ⁰ C. The unreacted ammonia is then distilled off with steam. Sodium chloride is added to the liquid remaining after the ammonia distillation in an amount of 18% in relation to the volume of the mixture. Then it is cooled to a temperature of 25 ° G, stirred for 3 hours and filtered. The obtained paste is dried at a temperature of 80 to 9O ⁰ C. About 1200 kg of a light yellow product which ^{does not melt up to a temperature of 300 °} C. are obtained. Its composition is in the first part

given in this example

Example 5

An optical brightening agent which contains as active substance 77 parts by weight of compounds of the formulas I and II in which Ar is a p-phenylene radical, X is a morpholine radical and M is a sodium cation, and which also contains 23 parts by weight of a compound of the formula III in which Ar , X and M have the meaning given above, is used to increase the whiteness of products made from polyamide fibers. The lightening of the product is on

In a warmed up to 90 ⁰ C solution, which in 5 nr water

carried out in the following way.
In a heated up to 90 ^{0 C.}
2 1 100 percent acetic acid and 0.5 kg of the above

509850/1024

-13- «

Contains optical brightening agent, 100 kg of knitted fabric made of Pdycaproamide fibers are fed for a period of 30 minutes a. The knitted fabric is then rinsed and dried. The knitted fabric lightened in this way is pure, neutral Nuance and a whiteness of 14-0.

The optical brightening agent given in this example is prepared in the following manner. In a reactor 5 m of water, 2000 kg of ice, 3 kg are introduced one after the other Surfactant - condensation product of 1 mole of oleocetyl alcohol with 21 moles of ethylene oxide and 375 kg of cyanuric chloride a. A solution of 567 kg of the sodium salt is then metered into the mixture obtained in the course of 30 minutes Sulphanilic acid in 1.5 κ water and stir everything until Shrinkage of the aromatic amine in the reaction mixture while maintaining a temperature of 0 to 5 ° C and at the same time Dosage of a 10 percent aqueous sodium carbonate solution for the purpose of neutralizing the hydrogen chloride evolving during the reaction.

The reaction produces 4,6-dichloro-2-p-sulfophenylamino-sym-triazine sodium salt. Then 2-methoxy-4,6-dichloro-sym-triazine is introduced into the reactor, which from 125 kg Cyanuric chloride, 60 kg of sodium bicarbonate and 0.5 M methanol on the V / eise mentioned in Example 1 v; urde. To the obtained mixture is dosed in the course of 1 hour a solution of 515 kg disodium salt of 4,4'-diaminostilbene disulfone

■ 7.

acid-2.2 ¹ in 4 in water. The whole thing will last for 1 hour

509850/1024 <

a temperature of 0 to 10 ° C stirred. The contents of the reactor are then heated and stirred for 1 1/2 hours at a temperature of 20 to 25 ° C. and then at a temperature of 30 to 40 G until the aromatic amine in the reaction mixture has disappeared. During this time, a 10 percent aqueous sodium carbonate solution is metered in to neutralize the hydrogen chloride which is evolved during the reaction. As a result of the reaction is formed an intermediate product which is a mixture of "compounds of the formulas IV ₁ V and VI, wherein Ar is a p-phenylene radical and M is a sodium cation. To the obtained mixture was set 450 kg r'orpr.olin zi and stir the For 3 hours at a temperature of 93 to 98 ° C. After this time, sodium chloride is added to the mixture obtained in an amount of 15% in relation to the volume of the liquid, then the whole is cooled to a temperature of 25 ° C. The mixture is stirred for 1 hour at this temperature, filtered and dried is obtained at a temperature of 85 ° C. It is approximately 1300 kg of a light yellow product, which up to a temperature of 300 ⁰ G does not melt. Its composition is shown in this example in the first part.

Example 6

One after another 5 m of water is brought into a reactor, 2000 kg of ice, 3 kg of a surface-active agent - condensation product of 1 mole of oleoacetyl alcohol with 21 moles of ethylene

509850/1024 ₁

oxide and 250 kg of cyanuric chloride - a. To c: the suspension obtained, a solution of 246 kg of sodium salt of sulfanilic acid in 1 m of water is then dosed in the course of 30 minutes and the whole is stirred at a temperature of 0 to 5 C until the aromatic amine in the reaction mixture has disappeared. While stirring, a 10 percent strength aqueous solution of acidic sodium carbonate is metered in for the purpose of neutralizing the hydrogen chloride which is evolved during the reaction. 4,6-dichloro-2-p-sulfophenylamino-sym-triazine sodium salt is formed. Then 2-methoxy-4-, 6-dichloro-sym-triazine, obtained from 250 kg of cyanuric chloride, 350 kg of sodium bicarbonate and Λ m methanol, is introduced into the reactor in the manner mentioned in Example 1. 5 ^ 5 kg of the disodium salt of 4,4'-diamino3tilbe.ndisulfonic acid-2,2 ^{1 are added} to the mixture obtained and the mixture is stirred for 30 minutes at a temperature of 3 ° C. The mixture is heated for 1 hour to a temperature of 25 ° C. and stirred until the reaction has ended. An intermediate product is formed which is a mixture of compounds of the formulas IV, V and VI in which Ar is a p-phenylene radical and M is a sodium cation. 300 kg of aniline are then introduced into the reactor, the whole is warmed up to a temperature of 93 to 95 ° C. and stirred at this temperature for 6 hours. After this time, the mixture is made alkaline using sodium carbonate to a pH of 8.5. Sodium chloride is added in an amount of 10% in relation to the volume of the liquid, cooled to a temperature of 25 ^° C., stirred for 2 hours,

509850/1024

filtered and dried. About 1100 kg of a yellow product which ^{does not melt up to a temperature of 300 °} C. are obtained. The resulting optical brightening agent contains as active substance about 65 parts by weight of compounds of the formulas I and II, in which Ar is a p-phenylene radical, X is an aniline radical and M is a sodium cation, and about 35 parts by weight of the compound according to formula III, in which Ar , X and M have the meaning given above. The fabric made of viscose fibers, lightened by means of a product as in Example 4, has a maximum whiteness of 133.

Example?

An optical brightening agent, the active substance 35 parts by weight of the compound according to formula I, in which Ar is a p-phenylene radical, X is the -NCC ^ CH ^ OH ^ group and M is a triethanolammonium cation, and 65 parts by weight of the compound according to formula III contains, in which Ar is an m-phenylene radical, X is an -IT (CH ₅ ) CH ₇ CH ₂ OH group, and M has the meaning given above, is used to create

t increase the whiteness of sized papers. The procedure for lightening paper is carried out in the following manner. In a Dutchman one leads 7 ra? Water, 500 kg of chemically bleached cellulose and 4 kg of the above-mentioned optical brightening agent and conducts the cellulose fiberizing process in the usual manner. Then 50 kg of kaolin, 8 kg of resin glue and aluminum sulfate are added to the Dutchman to achieve a pH value of 4.5. After mixing the

509850/1024 _ _1? _

The whole thing is placed on the sprue of the paper machine. The papermaking process is on usual Way done. The paper obtained is characterized by a high degree of whiteness, which when determined on the The emission photometer Elrepho is 95%.

Example 8

An optical brightening agent which, as active substance, contains 65 parts by weight of the compound according to formula II, in which X is a -N (CH _{2 CHj 2} OH ₂ -GrUpPe and M is a / N (CH ₂ CH ₂ OK) ₅ 7 ⁺ -cation, and also contains 35 parts by weight of the compound according to formula III in which Ar is an m-phenylene radical, X is a -! J (CH ₃ ,) - CH ₂ CH ₂ OH group and M has the meaning given above, is used for increasing The process for lightening the paper is carried out in the following manner: 7 nr water, 500 kg of chemically bleached cellulose and 4 kg of the above-mentioned optical brightening agent are introduced into a dutchman and the cellulose fiberization process is carried out Then 50 kg of kaolin, 8 kg of resin glue and aluminum sulfate are added to the Hollander to achieve a pH of 4.5 The process is carried out in the usual way. The paper obtained is distinguished by a high degree of whiteness, which is 96% when determined on the Elrepho reemission photometer .

509850/1024

Claims (3)

Patentanwälte 2ELLEMTiN D 8 / Munich 22 ZweibrückciMr: ße 6 4 «June 1975 WZ / Hu PL 2256 patent claims 1. Optical brightening agents that act as active substance compounds of the general formula I and / or II contain, SO ₃ M (>f>  ^x C-NHAr50 ₃ M I Il ^ = T> = / I! I ^ _r / 0U3M % _c I I X X (D SO ₃ M ι v / »I JI Il "\ f - ·; ·, (ID where Ar is a u- or p-phenylene radical, X is the best one aliphatic, aromatic or heterocyclic amine I0S850 / 1024 or an -NHp group and K is a monovalent cation, characterized by ^ !: they additionally a compound of the general formula III MQ ₃ SAnHN- (T N N ι X (III) in which Ar, X and M have the meaning given above. 2. Optical brightening agent according to claim 1, characterized in that that they have compounds of the formula III, in which Ar, X and M have the meaning given above, in one Amount from 20 to 65 parts by weight per 100 parts by weight contain active substance. 3. Process for the preparation of optical brightening agents, the active substance of which are three compounds of the general Formulas I, II and III MCbSArHN-C ^ VNH- <f> -HC = CH- <f> -HN-C ^ VNHAnSOaM ^ _c / 5O ₃ M ^ _c / ι ι X X (D 509850 / 102A SO ₃ M H ₃ CO-C ^ ^X C-NH- <f> -HC = CH - /> - HN-C ^ N N * N \ ^S0 3 ^M ii N (II) SO ₃ M MO ₃ SArHN-C * (in) contain, in which Ar is an m- or p-phenylene radical, X is the radical of an aliphatic, aromatic or heterocyclic amine or a -NiL ^ group ^and M is a monovalent cation, characterized in that a mixture of 2-methoxy-4- , 6-dichloro-sym-triazine and 4,6-dichloro-2-msulfophenylamino-sym-triazine or 4-, 6-dichloro-2-p-sulfophenylamino-sym-triazine with 4,4 ^f -Piaminost; ilbendisulfoiisäure-2 , 2 'or its disodium salt is condensed and the intermediate product obtained thereby, which forms a mixture of compounds of the formulas IV, V and VI, SO ₃ M MO ₃ SArHhK * VNH- <f> -HC = CH- <f> -HN-C * ^ C-NHArSO ₃ M NN I _{n M} NN ^ p / 5O3M % ^ / ι CL (IV) fj H, CO-C * \ - NH- <f> -HC = üK> HN-C ^VN C-0CH ₃ N N (V) MO ₃ SArHN-C * CL (VI) in which Ar and M have the meaning given above, with an aliphatic, aromatic or heterocyclic Amine or condensed with ammonia. 4-, method according to claim 3, characterized in that to 1 mole of 4,4'-diaminostilbenedisulfonic acid-2,2 'for reaction 0.5 to 1.5 moles, preferably 0.85 to 1.15 moles, 2-methoxy-4,6-dichloro-sym-triazine and 0.5 to 1.5 mol, preferably 0.85 to 1.15 mol of 4,6-dichloro-2-m-sulfophenylamino-sym-triazine or 4,6-dichloro-2-p-sulfophenylamino-sym-triazine are used, the total amount of both triazines being 1.9 to 2.3 mol and on 1 mole of the total amount of the intermediate, which a Mixture of compounds of the formulas IV, V and VI forms, 503850 / ΊΟΙΙΜ " ⁵ " ικ in which Ar and M have the meaning given above, at least 2.3 mol of aromatic amine or at least 3 mol of aliphatic amine or heterocyclic amine or at least 6 moles of ammonia are used. ; '5J Sym-triazine derivatives of the general formula III SO ₃ M (in) wherein Ar is an m- or ρ-phenylene radical, X is the remainder of one aliphatic, aromatic or heterocyclic amine or an -NHp group and M is a monovalent cation. 509850/1024