Improved optical bleaching compositions

FIELD: chemistry.

SUBSTANCE: invention relates to a compound of formula (1) where R1 denotes hydrogen or SO 3 , R2 denotes hydrogen or SO 3 , R3 denotes hydrogen or CH 2 CO 2 , R4 denotes CH 2 CO 2 , C H ( C O 2 ) C H 2 C O 2 or C H ( C O 2 ) C H 2 C H 2 C O 2 , and where M denotes a stoichiometric cation equivalent required to balance the anionic charge in formula (1) and is a combination of Mg2+ with at least 1 additional cation. The additional cations are selected from a group consisting of H+, a cation of an alkali metal, a cation of an alkali-earth metal other than Mg2+, ammonium, mono-C1-C4 alkyl-di-C2-C3-hydroxyalkylammonium, di-C1-C4-alkyl-mono-C2-C3-hydroxyalkylammonium, ammonium, which is mono-, di- or trisubstituted with a C2-C3 hydroxyalkyl radical, and mixtures thereof. The invention also relates to versions of the method of producing said compound and use of said compound in binding compositions for bleaching paper.

EFFECT: compound is a more efficient paper bleaching agent.

8 cl, 4 tbl, 10 ex

 

The technical field to which the invention relates.

The present invention relates to mixed salts, optical brighteners containing Mg2+to provide excellent optical whitening effects when applied to the surface of the paper.

The level of technology

High degree of whiteness is an important parameter for the end-consumer paper products. The most important raw material for paper industry are cellulose, pulp and lignin, which naturally absorb blue light, so they have a yellowish color and give the paper an unsatisfactory visual characteristics. In the paper industry optical brighteners are used to compensate for the absorption of blue light by absorption of UV radiation with a maximum wavelength of 350-360 nm and converting it into visible blue light with a wavelength of 440 nm.

In the manufacture of paper optical brighteners can be added to or into the wet part of the paper machine, or on a paper surface, or in both places. As a rule, it is impossible to provide a high degree of whiteness required for paper high quality, plus bleach only wet part of the paper machine.

The usual way of adding an optical Brightener to the surface of the paper consists of applying vodno the solution of optical Brightener on the sizing press, together with a sizing agent, usually natural starch or starch, modified enzymes or chemically modified starch. The pre-formed sheet of paper is passed through the nip between the two rollers, and the entrance to the nip filled with a solution for gluing. The paper absorbs a quantity of a solution, the residue is removed in the nip.

Along with starch and optical bleach solution for gluing may contain other chemicals designed to provide specific properties. They include defoamers, paraffin wax, dyes, pigments, and inorganic salts.

With the aim of obtaining high degrees of whiteness, efforts were made to develop new optical brighteners. See, for example, Japanese Kokai 62-106965, PCT application WO 98/42685, U.S. Patent 5,873,913 and European patent 1.763,519.

In the United Kingdom patent 1239818 described hexachlorophane optical brighteners, obtained from triethynylbenzene. In examples 1-6 described their sodium salts. Magnesium is mentioned only in the list of possible counterions for hexachlorophane optical brighteners, starch as a component of the composition for sizing the surface is also mentioned only in the list of possible binding agents.

The need for more effective means to achieve you is okeh degrees of whiteness of the paper is still in place.

Disclosure of inventions

The authors of the present invention surprisingly found that the optical brighteners of the formula (1) when applied to the surface of the paper, not necessarily in combination with salts of magnesium, in the composition for sizing, starch-containing, enhance the bleaching action.

The object of the invention is a compound of formula (1),

where

R1denotes hydrogen or SO3-,

R2denotes hydrogen or SO3-,

R3denotes hydrogen, C1-4alkyl, C2-3hydroxyalkyl, CH2CO2-CH2CH2CONH2or CH2CH2SN,

R4stands With1-4alkyl, C2-3hydroxyalkyl, CH2CO2-CH(CO2-)CH2CO2-or CH(CO2-)CH2CH2CO2-, benzyl or

R3and R4together with the neighboring nitrogen atom denotes morpholino ring, and where

M denotes the stoichiometric cation equivalent, required to balance the anionic charge in the formula (1) and is a combination of Mg+with at least 1, preferably 1, 2, 3, 4, 5, or 6, more preferably 1, 2 or 3, more preferably 1 or 2, additional cations, and the additional is a cation selected from the group consisting of H+cation of an alkali metal, cation of the alkali earth metal other than Mg2+, ammonium, mono-C1-C4-alkyl-di-C2-C3hydroxyethylamine, di-C1-C4-alkyl-topo-C2-C3hydroxyethylamine, ammonium, mono-, di or triamese2-C3hydroxyalkyl radical, and mixtures thereof.

The molar ratio of Mg2+additional cation M is preferably from 0.01 to 99.99 and is 99.99 to 0.01, more preferably from 20 to 80 and from to 99.99 to 0.01, more preferably from 50 to 50 and from to 99.99 to 0.01. The cation of the alkali metal preferably is a Li+, Na+or K+. The cation of the alkaline earth metal other than Mg2+represents preferably CA2+.

Additional cation M is preferably selected from the group consisting of H+Li+, Na+, K+Ca2+N-methyl-N,N-diethanolamine, N,N-dimethyl-N-ethanolamine, triethanolamine, triisopropanolamine and mixtures thereof.

Preferred compounds of formula (1) are compounds in which R3denotes hydrogen, methyl, ethyl, n-propyl, isopropyl, β-hydroxyethyl, β-hydroxypropyl, CH2CO2-CH2CH2CONH2or CH2CH2CN and R4denotes methyl, ethyl, n-propyl, from the kerf, 2-butyl, β-hydroxyethyl, β-hydroxypropyl, CH2CO2-CH(CO2-)CH2CO2-CH(CO2-)CH2CH2CO2-or benzyl.

The compounds of formula (2) and (3) with M, as defined above, also in all its preferred embodiments are specific examples of compounds of formula (1); compounds of the formula (2) and (3), with M, which is a mixture of Mg2+with Na+and/or K+are additional specific examples, but the invention is not restricted to these specific examples.

The next object of the invention is a method of obtaining the compounds of formula (1) according to item 1, wherein a reaction, followed by reaction B, followed by the reaction of C,

where in the reaction of A compound of formula (10) is subjected to interaction with the compound of the formula (11), obtaining the compound of formula (12);

in reaction B, the compound of formula (12) is subjected to interaction with the compound of the formula (13), obtaining the compound of formula (14);

in reaction C, the compound of formula (14) is subjected to interaction with the compound of the formula (15), obtaining the compound of formula(1), where

R1, R2, R3and R4defined above, also in all its preferred embodiments, implementation,

M1 are the same or different in formulas (13) and (14), and M1 denotes the stoichiometric cation equivalent, required to balance the anionic charge in the above formulas represents at least 1 cation selected from the group consisting of H+, cation of an alkali metal, cation of the alkali earth metal other than Mg2+, ammonium, mono-C1-C4-alkyl-di-C2-C3hydroxyethylamine, di-C1-C4-alkyl-mono-C2-C3hydroxyethylamine, ammonium, mono-, di or triamese2-C3hydroxyalkyl radical, and mixtures thereof.

M2 independently from each other in formulas (10) and (12) are the same or different and M2 denotes a cationic stoichiometric equivalent required to balance the anionic charge in the above formulas when or R1or R2or R1and R2denote SO3and is defined as M1,

provided that at least one of the reactions A, B or C is carried out in the presence of cation CAT, and cation CAT represents Mg2+.

Cation CAT may be entered in reaction A, B and/or C with M1 in the formula (13)containing Mg2+ and/or M2 in the formula (10)containing Mg2+or the addition salts of magnesium MS1 as an additional component in the reaction of A, B and/or C. Salt magnesium MS 1 preferably selected from the group consisting of magnesium acetate, magnesium bromide, magnesium chloride, magnesium formate, magnesium iodide, magnesium nitrate, magnesium sulfate, magnesium thiosulfate, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, and mixtures thereof; more preferably, if the salt magnesium MS1 represents magnesium hydroxide, magnesium chloride, magnesium sulfate or magnesium thiosulfate. Even more preferably, if the salt magnesium MS1 represents magnesium hydroxide, magnesium chloride or magnesium thiosulfate.

One, two or all three reactions A, B and C can be carried out in the presence of magnesium salts MS1.

Preferably, if M1 and M2 are independently from each other selected from the group consisting of H+Li+Na+, K+Ca2+Mg2+N-methyl-N,N-diethanolamine, N, N-dimethyl-N-ethanolamine, triethanolamine, triisopropanolamine and mixtures thereof; more preferably, if M1 and M2 are independently from each other selected from the group consisting of H+, Na+K+and Mg2+even more preferably, if M1 and M2 are independently from each other selected from the group consisting of Na+, K+and Mg2+.

Each reaction A, B and C preferably p is avodat in water or in a mixture of water and non-aqueous organic solvent. The compound of the formula (11) is preferably suspended in water or a compound of the formula (11) is dissolved in a solvent.

The preferred solvent is acetone.

The compound of the formula (11) is preferably used in the form of a suspension in water.

Each connection formulas (10), (13) and (15) can be used without dilution or dilution if dilution of the compounds of formulas (10), (13) or (15) is preferably used in the form of an aqueous solution or suspension.

The compound of formula (10) is preferably subjected to interaction in 0-10 mol% excess relative to the compound of formula (11). One molar equivalent of a compound of the formula (13) is subjected to interaction with two molar equivalents of the compounds of formula (12) preferably 0-10 mol% excess relative to the compound of formula (12). Two equivalents of the compounds of formula (15) is subjected to interaction with one molar equivalent of a compound of the formula (14), the Compound of formula (15) is preferably subjected to interaction in 0-30 mol% excess relative to the compound of formula (14).

Any reactions A, B and C is preferably carried out at a pressure from atmospheric to 10 bar, more preferably at atmospheric pressure.

In the reaction, A reaction temperature is preferably from -10 to 20°C.

In reaction B, the reaction temperature is preferably the t 20 to 60°C.

In reaction C, the reaction temperature is preferably from 60 to 102°C.

Reaction A is preferably carried out under conditions of acidic or neutral pH, preferably at pH from 2 to 7.

Reaction B is preferably carried out under conditions of from weakly acidic to weakly alkaline, more preferably at pH 4 to 8.

Reaction C is preferably carried out under conditions of from weakly acidic to alkaline, more preferably at pH from 5 to 11.

In each of the reactions A, B and C pH usually adjusted by adding a suitable base, and the choice of the basis is usually dictated by the desired composition of the products. Preferred bases are selected from the group consisting of aliphatic tertiary amines and hydroxides, carbonates and bicarbonates of alkali and/or alkaline earth metals and mixtures thereof. Preferred alkali and alkaline earth metals are selected from the group consisting of lithium, sodium, potassium, calcium, magnesium. Preferred aliphatic tertiary amines are N-methyl-N,N-diethanolamine, N-dimethyl-N-ethanolamine, triethanolamine, triisopropanolamine. When using a combination of two or more different bases, the base can be added in any order or simultaneously. More preferably for regulating the pH to use the basic salt of magnesium. The basic salt of magnesium is preferably selected from the group consisting of magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, and mixtures thereof; more preferably, the basic magnesium salt is magnesium hydroxide.

Preferably, when the basic salt of magnesium used for pH control in one of the reactions A and/or B, then in subsequent reactions B and C or in a subsequent reaction C, respectively, the basis for regulation is also a basic salt of magnesium, more preferably, when it is the same basic salt of magnesium, which was first used in reactions A and/or B. When it is necessary to adjust the pH of the reaction the acid, the preferred acid is chosen from the group consisting of hydrochloric acid, sulfuric acid, formic acid and acetic acid.

Solutions containing one or more compounds of General formula (1), may not necessarily be desalted by filtration through a membrane.

How to filter through the membrane preferably is a ultrafiltration. Preferably use a thin-film membrane. The membrane is preferably made of polysulfone, polyvinylidene fluoride, or cellulose acetate.

The next object of the invention is a method of obtaining the compounds of formula (1), characterized by mixing the compounds of formula (20) with component b), which is a salt MAGN what I MS2, in the aquatic environment;

where

R1, R2, R3and R4determined, as described above, also with all their preferred embodiments of the invention;

and where

T balances anionic charge and indicates the desired stoichiometric equivalent of a cation selected from the group consisting of H+cation of an alkali metal, ammonium, mono-C1-C4-alkyl-di-C2-C3hydroxyethylamine, di-C1-C4-alkyl-topo-C2-C3hydroxyethylamine, ammonium, mono-, di or triamese2-C3hydroxyalkyl radical, and mixtures thereof.

The mixing is preferably carried out in aqueous solution.

Preferably, T. balances anionic charge and represents a cation selected from the group consisting of H+, Na+, K+, ammonium, N-methyl-N,N-diethanolamine, N,N-dimethyl-N-ethanolamine, triethanolamine, triisopropanolamine and mixtures thereof.

The compounds of formula (21) and (22) represent specific examples of the compounds of formula (20), but the invention is not limited to these specific examples.

Salt magnesium MS2 selected from the group consisting of magnesium acetate, magnesium bromide, magnesium chloride, magnesium formate, magnesium iodide, neath the ATA magnesium, magnesium sulfate and thiosulfate and magnesium.

The temperature of mixing is preferably from 0 to 100°C.

The mixing is preferably carried out at atmospheric pressure.

Preferably the magnesium salt is a magnesium chloride, magnesium sulfate, or magnesium thiosulfate. The most preferred magnesium salt is a chloride or magnesium thiosulfate.

The mixing time is preferably from 5 seconds to 24 hours.

Preferably, if other than water can be additional organic solvents, more preferably, if organic solvents are selected from the group consisting of C1-C4alcohols and acetone.

For mixing the compound of formula (20) is preferably used in a concentration of from 0.01 g/l to 20 g/L.

Preferably, if in the aquatic environment on one part of the component of formula (20) is 0.1 to 50, more preferably 0.1 to 45, more preferably 0.1 to 40, mostly 0.1 to 15, mainly 0.15 to 10 parts of component (b).

The next object of the invention is the use of compounds of formula (20) to obtain the compounds of formula (1).

The next object of the invention is the use of compounds of formula (1) in compositions for sizing for bleaching of paper, preferably in the sizing press. Composition for sizing preferably represents the t of an aqueous composition.

For processing of paper in the size press can be used compositions for sizing containing 0.2 to 30, preferably 1 to 15 grams of the compounds of formula (1) per litre.

Composition for sizing also contains one or more binders, preferably 1, 2, 3, 4 or 5 of the binder, more preferably 1, 2 or 3, more preferably 1 or 2 of the binder.

Composition for sizing preferably contains the binder in a concentration of preferably 2-15 wt%, counting on the total weight of the composition for sizing. Usually the pH is in the range of 5-9, preferably 6-8.

The binder is preferably selected from the group consisting of starch, gelatin, alkali metal alginates, casein, mezdrovogo glue, protein, cellulose derivatives, such as hydroxyethyl cellulose or carboxymethyl cellulose, polyvinyl alcohol, polyvinylidenechloride, polyvinylpyrrolidone, polyethylene oxide, polyacrylates, saponified copolymer of vinyl acetate and maleic anhydride, and mixtures thereof. More preferably, when the binder is a starch, polyvinyl alcohol, carbometalation or mixtures thereof.

Even more preferred binder or adhesive is starch. More preferably, if the starch is selected from the group consisting of natural to the making a movie, starch, modified enzymes and chemically modified starch. Modified starches preferably represent oxidized starch, gidroksietilirovanny starch or acetylated starch. Natural starch preferably is an anionic starch, cationic starch or amphoteric starch. Although the source of the starch may be of any preferred sources of starch are corn, wheat, potato, rice, tapioca or sago. Polyvinyl alcohol and/or carboxymethylcellulose preferably used as the second binder. In addition to the compounds of formula (1), a binder and water, the composition for sizing may contain by-products formed during obtaining compounds of formula (1) as well as other conventional additives to paper. Examples of such additives are antifreeze, biocides, defoamers, paraffin wax, dyes, inorganic salts, soljubilizatory, crosslinking agents, pigments, special resins and the like and mixtures thereof.

The next object of the invention is a method of optical bleaching of paper, which includes stages

a) applying the composition for sizing containing a compound of formula (1), on paper,

b) drying the treated paper.

To the composition for sizing preferably of primav Aut defoamers, paraffin wax, dyes and/or pigments, and inorganic salts.

The implementation of the invention

Examples

The content of the cation determined by capillary electrophoresis.

The following examples more detail about the invention, considered in the moment, without limiting the claimed scope of the invention. If not specified, it is understood that the terms "%" and "parts" refers to mass%" and "parts".

Example 1

Compositions for sizing receive the addition of optical Brightener of the formula (21) in such a quantity to achieve a final concentration of optical Brightener in the interval from 2.5 to 12.5 g/l, to a mixed aqueous solution of magnesium chloride (final concentration is 8 g/l) and anionic oxidized potato starch (Perfectarnyl A4692 from AVEBE, VA) (final concentration is 50 g/l) at 60°C.

The solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates. The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Eirepho".

The example is repeated, and in the absence of chlorine is IDA magnesium, i.e. in the presence of only sodium salts of optical Brightener, and replacing magnesium chloride an equivalent amount of calcium chloride.

The results are summarized in table 1 and convincingly demonstrate the advantages of using magnesium chloride as compared with the use of calcium chloride and using only sodium salts of optical Brightener to achieve high degrees of whiteness.

Non-obvious nature of the present invention is additionally illustrated by data indicating that the chloride ions of other metals of group II, such as calcium chloride, even have a negative effect on the bleaching effect of the optical Brightener.

Table 1
The compound of formula (21) (g/l)Magnesium chloride (g/l)Calcium chloride (g/l)White on CIE
000104,6
080104,7
008104,8
2,500122,3
2,580a 126.7
2,508123,4
5,000128,3
5,080133,1
5,008USD 128.0
7,500129,8
7,580133,7
7,508of 128.6
10,000RB 131.1
10,080134,5
10,008128,2
12,500to 130.6
12,580134,2
12,508RUB 127.3

Example 2

Solutions for sizing receive, adding an optical Brightener of the formula (22) in such a quantity to achieve a final concentration of optical Brightener in the range from 2.0 to 10.0 g/l, to a mixed aqueous solution of magnesium chloride (final concentration is 8 g/l) and anionic oxidized potato starch (Perfectamyi A4692 from AVEBE, VA) (final concentration is 50 g/l) at 60°C.

The solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates. The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Eirepho".

the example is repeated, and in the absence of magnesium chloride, i.e. in the presence of only sodium salts of optical Brightener, and replacing magnesium chloride an equivalent amount of calcium chloride.

The results are summarized in table 2 and convincingly demonstrate the advantages of using magnesium chloride to achieve high degrees of whiteness compared with the optical bleach only in the form of sodium salt.

Table 2
The compound of formula (22) (g/l)Magnesium chloride (g/l)Calcium chloride (g/l)White on CIE
000104,6
080104,7
008104,8
2,000119,2
2,080122,5
2,008121,5
4,000127,2
4,080RB 131.1
4,008127,9
6,000RB 131.1
6,080135,4
6,008humidity 131.6
8,000133,7
8,080138,1
8,008133,5
10,000136,0
10,080139,7
10,008134,7

Example 3

Compositions for sizing receive, adding an optical Brightener of the formula (22) in such amount to achieve a final concentration of optical Brightener in the interval from 0 to 12.5 g/l, to a mixed aqueous solution of magnesium chloride (final concentration is 6, 25 and 12.5 g/l) and anionic oxidized corn starch (Penford Starch 260) (final concentration is 50 g/l) at 60°C.

Each solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates. The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Auto Eirepho".

The results are shown in table 3.

Example 4

Compositions for sizing prepared by adding an optical Brightener of the formula (22) in such amount to achieve a final concentration of optical Brightener in the interval from a to 12.5 g/l, to mix aqueous solutions of uranyl magnesium thiosulfate (final concentration is 10 and 20 g/l) and anionic oxidized corn starch (final concentration is 50 g/l) (Penford Starch 260) at 60°C. the Solution sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates. The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Eirepho".

The results are shown in table 3.

Table 3
White on CIE
The compound of formula (22) (g/l)Salt Mg is absent, i.e. only salt NaAdded salt magnesium
Magnesium chloride (g/l) (example 3)The uranyl magnesium thiosulfate (g/l) (example 4)
6,2512,5 10,020,0
0102,8102,9103,5102,2102,7
2,5119,6122,4output reached 125.5125,1123,6
5,0128,9RB 131.1132,5132,9132,7
7,5135,1136,3137,9137,7137,9
10,0139,2140,9141,4141,1141,0
12,5141,1142,3of 142.8142,4142,4

The results convincingly demonstrate the advantages of using magnesium chloride or magnesium thiosulfate to achieve high degrees of whiteness. the tion with the optical bleach only in the form of sodium salt.

Example 5

Monosodium salt of aniline-2,5 disulfonate (115,6 parts) was added to 74,5 parts of the acid chloride cyanuric acid in 400 parts of ice and 300 parts of water.

Maintain pH of the reaction mixture approximately 4-5 by adding dropwise a 30% aqueous NaOH solution, at the same time the temperature is kept lower than 10°C using a bath of ice/water. After completion of the reaction, the temperature is gradually raised to 30°C, using an external heating system, and 74.1 parts of 4,4'-diaminostilbene-2,2'-disulfonate. The resulting mixture was heated to 50-60°C, maintaining a pH of approximately 5-7 by adding dropwise a 30% aqueous NaOH solution until completion of the reaction. Then add 63,8 part of aspartic acid, then add 89.8 parts of magnesium hydroxide, and the resulting suspension heated at 90-95°C to complete the reaction. The temperature is gradually reduced to room temperature and filtered off the insoluble substances. The final concentration adjusted to 0.125 mol of compound of the formula (3) per kg of solution, for this purpose, or add water or remove water by distillation. In this case, M consists of a mixture of cations of sodium and magnesium.

Example 6

Monosodium salt of aniline-2,5 disulfonate (115,6 parts) was added to 74,5 parts of the acid chloride cyanuric acid in 400 parts of ice and 300 parts of water. Add 26.8 parts of magnesium hydroxide, aderiva temperature 10°C using a bath of ice/water. After completion of the reaction, the temperature is gradually raised to 30°C using external heating. Add 25.7 parts of magnesium hydroxide, then 74,1 parts of 4,4'-diaminostilbene-2,2'-disulfonate. The resulting mixture was heated to 50-60°C to complete the reaction. Then add 63,8 part of aspartic acid and 100 parts of water, then add 89.8 parts of hydroxyl magnesium, and the resulting suspension heated at 90-95°C to complete the reaction. The temperature is gradually reduced to room temperature and filtered off the insoluble substances. The final concentration adjusted to 0.125 mol of compound of the formula (3) per kg of solution using UV-spectroscopy. In this case, M consists of a mixture of cations of sodium and magnesium.

Comparative example 7

Comparative solution 7 for optical bleaching is obtained by dissolving the compound of formula (22) in water to a final concentration of 0.125 mol/kg

Example 8

Compositions for sizing receive, adding an aqueous solution of optical Brightener obtained according to example 5, in such a quantity to achieve a final concentration of optical Brightener in the interval from 0 to 80 g/l in aqueous solution, obtained by the method of example 5 to a stirred aqueous solution of anionic oxidized potato starch (Perfectamyi A4692 from AVEBE, VA) (final concentration is 50 g/l) at 60°C. b the th solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates.

The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Auto Eirepho".

The results are shown in table 4.

Example 9

Compositions for sizing receive, adding an aqueous solution of optical Brightener obtained according to the method of example 6, in such a quantity to achieve a final concentration of optical Brightener in the interval from 0 to 80 g/l in aqueous solution, obtained by the method of example 6, to a mixed aqueous solution of anionic oxidized potato starch (Perfectamyi A4692 from AVEBE, VA) (final concentration is 50 g/l) at 60°C. Each solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates.

The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Auto irepho".

The results are shown in table 4.

Comparative example 10

Compositions for sizing receive, adding an aqueous solution of optical Brightener obtained according to the method of example 7, in such a quantity to achieve a final concentration of optical Brightener in the interval from 0 to 80 g/l in aqueous solution, obtained by the method of example 7 to a stirred aqueous solution of anionic oxidized potato starch (Perfectamyi A4692 from AVEBE, VA) (final concentration is 50 g/l) at 60°C. Each solution for sizing is allowed to cool, then pour on the moving rollers of a laboratory size press and put on a taped commercial 75 g/m2AKD (dimer of alkylbetaine), discolored sheet of base paper. The treated paper is dried for 5 minutes at 70°C in the dryer with flat plates.

The dried paper is brought to the required condition, then measure the brightness CIE on the calibrated spectrophotometer Auto Eirepho".

The results are shown in table 4.

Table 4
White on SA
The concentration of the solution for optical bleaching (g/l)Example 8P the emer 9 Comparative example 10
0of 101.5of 101.5of 101.5
10119,5119,6119,2
20127,4128,4a 126.7
40133,6135,0to 132.6
60137,1138,6br135.8
80138.2140,2136,8

The results convincingly demonstrate the advantage of using mixed salts of optical Brightener containing a cation of magnesium.

1. The compound of formula (1)

where R1denotes hydrogen orSO3-,
R2denotes hydrogen orSO3-,
R3 denotes hydrogen orCH2CO2-,
R4indicatesCH2CO2-,CH(CO2-)CH2CO2-orCH(CO2-)CH2CH2CO2-and where
M denotes the stoichiometric cation equivalent, required to balance the anionic charge in the formula (1) and is a combination of Mg2+with at least 1, preferably 1, 2, 3, 4, 5, or 6, more preferably 1, 2 or 3, more preferably 1 or 2, additional cations, and more cations selected from the group consisting of H+, cation of an alkali metal, alkaline earth cation IU is Alla, other than Mg2+, ammonium, mono-C1-C4-alkyl-di-C2-C3hydroxyethylamine, di-C1-C4-alkyl-mono-C2-C3hydroxyethylamine, ammonium, mono-, di - or triamese2-C3hydroxyalkyl radical, and mixtures thereof.

2. The method of obtaining the compounds of formula (1)as defined in claim 1, characterized by A reaction, followed by reaction, followed by reaction C,
where in the reaction of A compound of formula (10) is subjected to interaction with the compound of the formula (11), obtaining the compound of formula (12)

in reaction B, the compound of formula (12) is subjected to interaction with the compound of the formula (13), obtaining the compound of formula (14)


in reaction C, the compound of formula (14) is subjected to interaction with the compound of the formula (15), obtaining the compound of formula (1)

where R1, R2, R3and R4defined in claim 1;
M1 are the same or different in formulas (13) and (14), and M1 denotes the stoichiometric cation equivalent, required to balance the anionic charge in the above formula, and represents at least 1 cation selected from the group consisting of H+, cation saloon the first metal, the cation of the alkaline earth metal other than Mg2+, ammonium, mono-C1-C4-alkyl-di-C2-C3hydroxyethylamine, di-C1-C4-alkyl-mono-C2-C3hydroxyethylamine, ammonium, mono-, di - or triamese2-C3hydroxyalkyl radical, and mixtures thereof.
M2 independently of one another can be identical or different in formulas (10) and (12), and M2 represents a cationic stoichiometric equivalent required to balance the anionic charge in the above formulas when or R1or R2or as R1and R2are SO3and is defined as M1,
provided that at least one of the reactions A, B or C is carried out in the presence of cation CAT, and cation CAT represents Mg2+.

3. The method of obtaining the compounds of formula (1) as defined in claim 1, characterized by mixing the compounds of formula (20) with component b), which is a salt of magnesium MS2, in the aquatic environment,

where R1, R2, R3and R4defined in claim 1;
T balances anionic charge and indicates the desired stoichiometric equivalent of a cation selected from the group consisting of H+, cation of an alkali metal, ammonium, mono-C1-C4-alkyl-di-C2-C3 hydroxyethylamine, di-C1-C4-alkyl-mono-C2-C3hydroxyethylamine, ammonium, mono-, di - or triamese2-C3hydroxyalkyl radical, and mixtures thereof.

4. The method according to claim 3, where salt is magnesium MS2 selected from the group consisting of magnesium acetate, magnesium bromide, magnesium chloride, magnesium formate, magnesium iodide, magnesium nitrate, magnesium sulfate and magnesium thiosulfate.

5. The method according to claim 3 or 4, where the mixing is carried out in aqueous solution.

6. The use of the compounds of formula (20) as defined in section 3 to obtain the compounds of formula (1) as defined in claim 1.

7. The use of the compounds of formula (1) as defined in claim 1 in compositions for sizing for whitening paper.

8. Method of optical bleaching of paper, which includes stages
a) applying the composition for sizing containing a compound of formula (1) according to claim 1, on paper,
b) drying the treated paper.



 

Same patents:

FIELD: textiles, paper.

SUBSTANCE: in one of the aspects, the invention is directed to a method which enables mainly to maintain (or even increase) the brightness and/or whiteness of paper with increased degree of grinding the cellulose pulp, where the said method comprises grinding of the cellulose pulp till the freeness value of about 100 CSF and adding the composition OVA and a polymeric carrier to the paper surface in the size press in amounts sufficient to increase brightness and/or whiteness of the paper obtained. In another aspect, the invention is directed to a method of making paper from grinded cellulose pulp, which comprises grinding the suspension of cellulosic fiber to reduce the freeness up to about 100 CSF and mixing the cellulosic fiber with at least one optical bleaching agent (OBA) during or after the grinding stage and prior to adding any additional chemical ingredients of the wet stage of production.

EFFECT: effective maintenance or increase of brightness and whiteness of paper from the grinded cellulose pulp.

13 cl, 14 tbl, 34 dwg

FIELD: textiles, paper.

SUBSTANCE: method comprises the following steps: a) adding a known amount of one or more surface additives to a papermaking process in a known proportion with a known amount of one or more inert fluorescent markers, and the inert fluorescent markers are selected from the group consisting of fluorescein or derivatives of fluorescein and rhodamine, or derivatives of rhodamine, b) measuring the fluorescence of one or more inert fluorescent markers in the point after adding the surface additives and after the web formation, at that fluorescence is measured with a fluorometer of reflective type, c) establishing the correlation between the fluorescence value of the inert fluorescent markers on the web and the concentration of surface additives in the coating on the web and/or coating thickness on the web.

EFFECT: use of the proposed method enables paper machine to control the rate of adding at very low levels, with ability to assess quickly and regulate statically rate of adding beyond the technical specifications.

17 cl, 1 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: described is an aqueous solution of an optical brightener, containing (a) 10-50 wt % optical brightener of formula (I): where: M is hydrogen, an alkali metal atom, ammonia or an amine cation; R1 is hydrogen, C1-C4-alkyl or C2-C4-hydroxyalkyl; R2 - C1-C4-alkyl which can be substituted with -CN- or -CONH2-group or C2-C4-hydroxyalkyl; or R1 and R2 together with a nitrogen atom close a morpholine ring; (b) 0.5-9 wt % polyvinyl alcohol, having degree of hydrolysis 71-85.2% and Brookfield viscosity 3-5.4 mPa·s; and (c) water. The invention also describes use of said solution in a coating composition for paper and a method of obtaining paper coated with said coating composition.

EFFECT: disclosed aqueous solutions of optical brighteners have low viscosity, can be used directly by paper manufacturers and can be fed by a pump directly into the coating composition to provide a coating on paper with high whiteness.

10 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: water-soluble composition contains a) at least one water-soluble optical bleaching agent, b) a polymer obtained from an ethylenically unsaturated monomer or a monomer mixture, characterised by that at least one monomer is an acrylamide and the water-soluble polymer has average (weight-average) molecular weight between 500 and 49000, optionally c) polyethylene glycol with weight-average molecular weight between 500 and 6000, and d) water. Said composition is used to optically bleach paper.

EFFECT: high degree of bleaching while preserving rheological properties.

7 cl, 7 tbl, 70 ex

FIELD: textile, paper.

SUBSTANCE: full bleaching/extraction of craft cellulose fibres is carried out with a chorine agent. Afterwards fibres are washed and exposed to contact in solution with at least one optical bleach (OB) upstream the mixing box and the discharge box of the machine. Fibres in solution have consistency from 7 to 15%, pH of solution in process of contact of fibres with OB makes from 3.5 to 5.5, temperature of contact makes from 60 to 80°C, and time of contact is from 0.5 to 6 hours. Additional contact of OB with fibres is carried out in the device for coating application or in the gluing press. Contact may be carried out at the stage of storage, both at high density and low density of the craft-cellulose fibres, and also at the stage of refinement.

EFFECT: improved whiteness and brightness of fibres when using lower quantity of OB.

19 cl, 11 dwg, 12 tbl, 6 ex

FIELD: textile, paper.

SUBSTANCE: method concerns reducing speed of photoyellowing of paper containing mechanical pulp. The method includes coating the surface of a paper sheet during papermaking of aqueous solution containing an effective amount of one or more salts of thiocyanic acid.

EFFECT: improvement of stability to photoyellowing of paper and cost-effective way while reducing its toxicity.

16 cl, 10 tbl

FIELD: textile, paper.

SUBSTANCE: method includes formation of composition, containing water, raw starch and powder optical refining agent. Boiling of composition. Application of finished composition, at least on one surface of paper or cardboard base in coating press. Then base is dried. In another version of method composition is boiled at the temperature up to 299°F inclusive.

EFFECT: improved brightness of paper and cardboard.

7 cl, 4 dwg, 8 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention describes an aqueous dispersion of an optical bleaching agent which is stable during storage, does not contain dispersants and stabilisers and contains 20-40% active substance in form of one or more optical bleaching agents obtained through successive reaction of cyanuric chloride with 4,4'-diamino-2,2'- stilbene sulphonic acid, amine and a product of reacting monoethanol amine with acrylamide.

EFFECT: disclosed dispersion of optical bleaching agent does not require dispersants or other stabilising additives to prevent settling during storage and has excellent properties for bleaching paper and other cellulose materials.

8 cl, 2 tbl, 4 ex

FIELD: paper industry.

SUBSTANCE: methods refer to manufacturing of bleached cellulose material, prevention of yellowing and loss of whiteness in bleached craft-cellulose, and manufacturing of paper goods. In process of bleached cellulose material manufacturing, bleached craft-cellulose is produced and exposed to contact with sufficient amount of more or several reducing agents. Additionally bleached craft-cellulose is exposed to contact with one or several optical bleach, with one or more chelating agent. Method for prevention of yellowing and loss of whiteness of bleached craft-cellulose in storage includes addition of efficient amount of one or more reducing agent into bleached cellulose and possibly one or more chelating agent, one or more polycarboxylate or their combinations. Method for production of paper goods includes production of bleached craft-cellulose, formation of initial water suspension from it, water drainage with formation of sheet and sheet drying. Besides efficient amount of one or more reducing agent is added into bleached craft-cellulose, initial suspension or sheet. Additionally one or more chelating agent is added there, one or more optical bleach, one or more polycarboxylate, or their combination.

EFFECT: improved quality of paper goods, increased stabilisation of whiteness and increased resistance to yellowing in process of paper production and to thermal yellowing, improved colour pattern.

17 cl, 33 tbl

FIELD: textile, paper.

SUBSTANCE: procedure refers to production of wood pulp and can be implemented in pulp-and-paper industry. The procedure consists in whitening fibres of sulphate pulp with a whitening agent on base of chlorine and in washing whitened fibres of sulphate pulp. Upon washing fibres of sulphate pulp are subject to interaction with at least one optic whitener before mixing ponds. Interacting is carried out in solution at pH from 3.5 to 8.0 and temperature from 60 to 80°C during 0.5-6 hours. The invention also refers to wood pulp produced by the said procedure.

EFFECT: increased whiteness and optic brightness of paper at decreased utilisation of optic whitener.

22 cl, 11 dwg, 11 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing an alkenyl-substituted cyclic anhydride, comprising the following steps: isomerising one or more olefinically unsaturated C6-C28 hydrocarbons, from which at least 30 wt % is alpha-olefin, by contacting said hydrocarbons with a catalyst which contains an alkali metal on a support, and reacting the formed isomerised C6-C28 olefin hydrocarbons with a cyclic anhydride of an unsaturated dicarboxylic acid to form an alkenyl-substituted cyclic anhydride.

EFFECT: invention relates to use of said compound as a paper sizing additive and a method of producing said additive based on the obtained alkenyl-substituted cyclic anhydride.

20 cl, 2 tbl, 4 ex

Packing laminate // 2455169

FIELD: process engineering.

SUBSTANCE: invention relates to production and application of packing laminate and to food and drink package made therefrom. Laminate comprises, at least, one main layer of paper or cardboard and, at least, one barrier layer for fluid and, preferably, at least one barrier layer for gas. Paper or cardboard is impregnated with composition containing adhesive selected from the group including ketene dimers and multimers, succinic anhydride, colophony and mixes thereof, as well as acrylamide-based polymer.

EFFECT: higher water resistance.

15 cl, 10 tbl, 8 ex

FIELD: textiles, paper.

SUBSTANCE: paper base is intended for internal and external sizing, which has high dimensional stability, and can be used in pulp and paper industry. Paper base contains cellulose fibers, at least one filler, and sizing agent. At that the paper base has a coefficient of hygroextension from 0.6 to 1.5%. The Scott internal constraint in the transverse direction is not greater than 300 J/m2, and/or Scott internal constraint in the longitudinal direction is not greater than 300 J/m2. Also a method of manufacturing the paper base and versions of paper base are proposed.

EFFECT: increased dimensional stability and durability of the surface of the paper base.

26 cl, 24 dwg, 15 tbl, 5 ex

Paper sizing // 2429323

FIELD: textile, paper.

SUBSTANCE: invention relates to a water dispersion (its version) of a cellulose-active gluing substance (its version), a method to produce the water dispersion (its version), application of the water dispersion and a method of paper making. The water dispersion of the cellulose-active gluing substance contains an acid anhydride, an anion polyelectrolyte and a nitrogen-containing organic compound, which is an amine or a corresponding quaternary ammonia compound, having the molecular weight of less than 180 or having one or several hydroxyl groups. The method to produce the water dispersion of the cellulose-active gluing substance and its version includes dispersion of the acid anhydride in the water phase in presence of the anion polyelectrolyte and the nitrogen-containing organic compound, which is the amine or the corresponding quaternary ammonia compound, having the molecular weight of less than 180 or having one or several hydroxyl groups. The above specified water dispersions of the cellulose-active gluing substance may be used for sizing in mass or for surface sizing in paper making. The method of paper making includes addition of the above-specified water dispersions of the cellulose-active gluing substance to the water suspension of cellulose with subsequent dehydration of the produced suspension on a net of a paper-making machine or by application of these dispersions onto a surface of a cellulose sheet.

EFFECT: improved stability of the gluing water dispersion and efficiency of sizing, energy and capital cost saving.

41 cl, 13 tbl, 7 ex

FIELD: textile, paper.

SUBSTANCE: ground paper contains a certain amount of cellulose fibres and a gluing substance, besides, ground paper has a coefficient of hygro-expansion from 0.6 to 1.5%, inner link of Scott in cross direction not more than 130 J/m2 and/or inner link of Scott in longitudinal direction of not more than 130 J/m2.

EFFECT: increased stability of dimensions and strength of ground paper surface.

28 cl, 28 dwg, 12 tbl, 5 ex

FIELD: textile, paper.

SUBSTANCE: emulsion contains anhydrides of fatty acids, which are produced from unsaturated or saturated fatty acids or their mixtures with length of chain from 12 to 24 carbon atoms and are preserved as liquid at the temperature below 50°C. If necessary, emulsion for paper sizing additionally contains a reactive or a non-reactive agent for sizing and/or a fixator with aluminium ions content. Emulsion for paper sizing is produced by emulsification of fatty acids in water phase by means of shearing forces or intense mixing. Emulsifiers are used to form emulsion. Emulsion is used for continuous sizing of paper mass or to treat paper surface in sizing press. Emulsion is used to produce paper.

EFFECT: eliminates formation of sediments with sticky consistency with regular indices of pH in process of paper making and reduced duration of contact with water system.

16 cl, 4 tbl, 5 ex

FIELD: construction.

SUBSTANCE: ground contains cation water-fast additive, alkaline glueing agent and anion activator in specified amount. Anion activator it contains is a component selected from group, including polyacrylate, sulfonate, carboxymethylcellulose and galactomannan hemicellulose. Ground paper has pH from approximately 7.0 to approximately 10, and strength of internal link from approximately 25 to approximately 350 millifeet per pound per square inch. This ground paper is produced by contact of a certain amount of cellulose fibres with water-fast additive, alkaline gluing agent and anion activator, serially and/or simultaneously.

EFFECT: improved physical properties of ground paper and expanded assortment of paper tapes to cover joints.

22 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: substrate has a paper base containing cellulose fibre from deciduous wood with particle size smaller than 200 mcm after grinding in amount of not more than 45 wt % and average fibre length between 0.4 and 0.8 mm and filler in amount of 5-40 wt %, particularly 10-25 wt % in terms of the weight of cellulose.The substrate at least contains one polymer layer lying at least on one side of the paper base. There is a layer with a binding agent between the polymer layer and the paper base. The binding agent is a hydrophilic film-forming polymer made from hydroxypropylated starch and/or thermally modified starch. This layer may contain a pigment in form of calcium carbonate, kaolin, talc, titanium dioxide and/or barium sulphate.

EFFECT: reduced limpness and obtaining pure-bred production wastes.

27 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: adhesive contains a basic component in form of brewer's or distiller's yeast which is a waste from the brewing or distillation industry. The residue of brewer's or distiller's yeast is treated with 2% sodium hydroxide solution in ratio of 1:1. The adhesive composition contains the treated residue of brewer's yeast, glycerin and boric acid. Components of the composition are in the following ratio, pts. wt: residue of brewer's or distiller's yeast treated with 2% sodium hydroxide solution in ratio of 1:1 96.0-98.0; glycerin 1.9-3.7; boric acid 0.1-0.3.

EFFECT: adhesive composition has high adhesive capacity and low cost.

2 tbl

Paper making method // 2384661

FIELD: textile, paper.

SUBSTANCE: method relates to paper production and can be used in pulp-and-paper industry. Method involves the use of cellulose suspension from cellulose fibres and fillers (optional), dehydration of cellulose suspension on grid or sieve so that a sheet can be formed. Then the sheet is dried. In this method there used is polymeric addition which includes ethylenically unsaturated monomer soluble in water or potentially soluble in water, and ethylenically unsaturated monomer containing a reactive group. The latter represents an epoxy group. The polymeric addition used has molar weight which is less than one million. Polymer is obtained from mixture of monomers, which includes acrylamide and glycidyl methacrylate. Thus, the obtained polymer is used as an addition for increase of paper durability in dry condition, in wet condition, as reagent for internal paper sizing and for surface sizing.

EFFECT: increasing paper durability.

17 cl, 2 tbl, 3 ex

FIELD: chemistry; textiles; paper.

SUBSTANCE: preparation method of polysilicate containing aqueous composition representing homogeneous liquid at 25°C, includes stages as follows: I) preparation of aqueous liquid containing silicate, II) reducing pH of the liquid to 2-10.5, III) ensured polymerisation time to actual completion resulted in making product containing gelled substance, IV) processing gelled substance with sufficient shearing to produce homogeneous liquid. Aqueous composition is prepared by the presented method. Aqueous composition contains polysilicate. This composition represents homogeneous liquid at 25°C. The composition develops viscosity at least 200 mPa·s when evaluated at concentration 2 wt % and at 25°C with using Brookfield viscosimeter at 20 rpm with shaft №2, with polysilicate of specific surface area not exceeding 2000 m2/g and S-value below 5%. Paper or carton making process includes preparation of cellulose suspension, with aqueous composition added, water drainage from suspension thus shaping wet paper web thereafter dried. Paper or carton making process includes preparation of cellulose suspension, added with mineral filler and exposed to drainage and containment system procedure, followed with water drainage from suspension thus shaping wet paper web thereafter dried. Mineral filler is aqueous composition. Before drainage and containment system is enabled, the suspension is exposed to at least, one shearing. This system implies adding aqueous composition to cellulose suspension, while shearing stage is specified from stirring, clarification and pumping.

EFFECT: improved quality of paper and carton.

46 cl, 16 tbl, 6 ex, 2 dwg

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