Aqueous solutions of optical brighteners

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

 

This invention relates to aqueous solutions of optical brighteners with polyvinyl alcohols which can be used directly by the paper manufacturers, and which provide a coated paper with high whiteness.

It is well known that white and therefore attractiveness of the covered securities can be enhanced by the introduction of optical brighteners in the composition of the coating. To satisfy the demand in covered securities high whiteness, requires more effective optical Brightener.

Although it is known that polyvinyl alcohol (PVOH) can improve the characteristic of the optical brighteners in pigmented coating compositions in acting as a carrier (see, for example, page 164 of “Surface Application of Paper Chemicals by Brander (Springer, 1977)), manufacturer of paper if you wish to use the polyvinyl alcohol enters separately in the coating composition is usually in the form of an aqueous solution obtained by high water content in the composition of the coating and, consequently, a prolonged drying time. Remains the problem of providing a manufacturer of paper completely satisfying means of the use of PVOH as a carrier for optical brighteners.

WO 2005/056658 provides a solution to the consideration of the method of obtaining water concentrate optionscollection/PVOH, containing successive stages: (a) providing water compositions clarifier comprising water and an active ingredient of an optical Brightener, in which the active ingredient of the optical brighteners are usually present in the aqueous compositions of the clarifier in the amount of from about 10% to about 25%; (b) mixing the polyvinyl alcohol resin with a specified composition of the optical Brightener in an amount of about 1 h the resin of polyvinyl alcohol 0.25-10 wt. including water composition clarifier with providing emerging aqueous concentrate of the polyvinyl alcohol resin and optical Brightener; and (C) boiling water concentrate with the dissolution of solid substances (i.e., obtaining an aqueous solution containing optical brighteners and 9.1-80% polyvinyl alcohol). The method allows to obtain a pigmented coating composition with low water content without compromising the degree of whiteness and color.

WO 2005/056658, however, does not provide a satisfactory solution for a manufacturer of paper, which usually wishes to dispense the solution of the optical Brightener/PVOH directly into the coating composition; aqueous solutions containing optical brighteners and more than 9% PVOH, are usually of such high viscosity that they can be supplied by the pump only with difficulty, if not to go. Manufacturers of paper is usually not FPIC is BNY to use a fluid with a viscosity of more than 1000 MPa·s not only because of the difficulty of the feed pump, but also because of the "shock" of thickening, when the liquid is of such high viscosity is introduced into the coating composition.

There remains a need to address the problem of providing an aqueous solution of the optical Brightener/PVOH, which combines good ability of clarification with low viscosity.

It was found that it is possible to obtain the solution of the optical Brightener/PVOH low viscosity, which can be used directly by the paper manufacturer, so that they can be dosed by a pump directly into the coating composition, and which provide a coated paper amazingly high brightness.

The present invention therefore provides aqueous solutions of optical brighteners consisting essentially of:

(a) from 10 to 50 wt.%, at least one optical Brightener of formula (1):

in which

M represents hydrogen, alkali metal atom, ammonium or a cation derived from an amine, preferably hydrogen or sodium, most preferably, sodium,

R1represents hydrogen, C1-C4-alkyl or C2-C4-hydroxyalkyl, and

R2represents a C1-C4-alkyl which may be substituted by-CN or-CONH2group, or With2-C4-hydroxyalkyl,

or R1and R2together with the atom is the monk closes morpholino-ring;

(b) from 0.5 to 9 wt.% polyvinyl alcohol having a degree of hydrolysis of from 60 to 85%; and

(C) water.

NR1R2represents, preferably, N(CH2CH2OH)2N(CH2CH(CH3)OH)2N(CH2CH2OH)CH2CH2CONH2or N(CH2CH(CH3)OH)CH2CH2CONH2and, most preferably, N(CH2CH2OH)2or N(CH2CH(CH3)OH)2.

Aqueous solutions can contain up to 10 wt.% salt, usually sodium chloride formed as a byproduct in the preparation of optical brighteners.

Aqueous solutions may contain one or more antifreeze, pesticides, complexing agents, or other additives, and organic by-products formed during the preparation of optical brighteners. Aqueous solutions can contain other media, such as polyethylene glycol.

Polyvinyl alcohol preferably has a degree of hydrolysis of from 65 to 80% and a viscosity according to Brookfield 2-40 MPa·s (4% aqueous solution at 20°C). More preferably, the polyvinyl alcohol has a degree of hydrolysis of from 65 to 80% and a viscosity according to Brookfield 2-20 MPa·s (4% aqueous solution at 20°C).

Preferably, the content of polyvinyl alcohol in the solution lies in the range of 1-5%, more preferably in the range of 1.5 to 4 wt.% by weight of solution.

Konzentrat the I optical Brightener solution is, preferably, in the range of 15-40 wt.%, more preferably, in the range of 18-35 wt.% by weight of solution.

The solution of the optical Brightener/PVOH is usually obtained from the introduction of polyvinyl alcohol as solids in the mixed solution of the optical Brightener in water and heated at 90-95°C until a clear solution is formed.

The aqueous solution has a pH of, preferably, from neutral to distinctly alkaline, in particular in the range from pH 7 to pH 10. If necessary, the pH can be adjusted by the introduction of M-relevant bases, such as hydroxides or carbonates of alkali metal, ammonia or amines.

The solution of the optical Brightener/PVOH invention are stable during storage and can be used directly as such in the sense that they can be dosed by a pump directly into the coating composition. Thus, another objective of the present invention is the introduction of the solution of the optical Brightener/PVOH in the composition of the coating to obtain a coated and optically brightened paper.

Thus, the present invention also provides a method of obtaining a coated paper, i.e. optically brightened, at least in the coating in which the coating composition, as described above, is applied to the paper after formation of the sheet.

Composition of coating pre what are essentially aqueous composition, which contain at least one binder and a white pigment, in particular, opaque white pigment, and can optionally contain other additives, such as dispersants, antifoams and synthetic thickeners.

Despite the fact that it is possible to obtain a coating composition that does not contain white pigments, the best white substrate for printing is obtained using opaque coating compositions that contain 10-70 wt.% white pigment. These white pigments are typically inorganic pigments, such as aluminosilicate (kaolin, otherwise known as China clay), calcium carbonate (chalk), titanium dioxide, aluminum hydroxide, barium carbonate, barium sulfate or calcium sulfate (gypsum).

The binder can be any of the binders commonly used in the paper industry to obtain coating compositions and binder may consist of a single binder or a mixture of primary and secondary binders. The only, or primary, the binder is preferably a synthetic latex, usually, styrene-butadiene, vinyl acetate, styrene-acrylic, venerability or ethylenevinylacetate polymer. The secondary binder may be, for example, starch, carboxymethylcellulose, casein, soy polymers, polyvinyl alcohol or a mixture of any of them.

Unity is Noah, or primary binder is used in an amount typically in the range of 5-25 wt.% by weight of white pigment. The secondary binder is used in an amount typically in the range of 0.1 to 10 wt.% by weight of white pigment.

Optical Brightener of formula (1) is used in an amount typically in the range of 0.01-1 wt.% by weight of white pigment, preferably in the range of 0.05-0.5 wt.% by weight of white pigment.

Examples

The following examples explain the invention in more detail. Unless otherwise specified, "%" and "parts" are by weight, the viscosity measured using Brookfield viscometer.

Sample preparation 1

The solution of the optical Brightener 1 is produced by mixing together the 25.9 wt. including optical Brightener of the formula (2),

72.0 wt. including water and

2.1 wt. including polyvinyl alcohol having a degree of hydrolysis of 71% and a viscosity according to Brookfield 5,4 MPa·s (4% aqueous solution at 20°C).

Viscosity by Brookfield 5,4 MPa·s (4% aqueous solution at 20°C) receive when heated to 90-95°C to obtain a clear solution which remains stable after cooling to room temperature. the pH of the solution adjusted to 9.0 with sodium hydroxide.

The viscosity of the solution is 97 MPa·s at 20°C and 211 MPa·s at 10°C.

Example preparation of 2

Comparative example (without polyvinyl with the IRTA)

The solution of the optical Brightener 2 is produced by mixing together the 25.9 wt. including optical Brightener of the formula (2) and 74,1 wt. including water. the pH of the solution adjusted to 9.0 with sodium hydroxide.

Application example

Receive a coating composition containing 500 wt. including chalk (commercially available under the trade name Hydrocarb 90 from OMYA), 500 wt. including clay (commercially available under the trademark of SPS Kaolin from IMERYS), 470 wt. including water, 6 wt. including dispersant (sodium salt of polyacrylic acid, commercially available under the trademark Polysalz S from BASF), 200 wt. including 50% of latex (copolymer of styrene-butadiene, commercially available under the trademark DL 921 from Dow) and 50 wt. including a 10% solution of carboxymethyl cellulose (commercially available under the trademark Finnfix 5,0 from Noviant) in water. The solids content is adjusted to 60% by addition of water and the pH adjusted to 8-9 with sodium hydroxide.

Solutions of optical brighteners 1 and 2, obtained as described in preparation examples 1 and 2, respectively, is injected in the concentration range from 0.4 to 1.0 wt.% solids in the mixed composition of the coating. Clarified the composition of the coating then is applied to the sheet of commercial 75 g/cm white paper base with a neutral sizing using automatic wire applicator with standard speed and standard load provolo the hydrated applicator. Coated paper is then dried for 5 min in a stream of hot air. Provide air-dried paper, and then determine the ice (CIE)-white on the calibrated Elrefo-spectrophotometer.

Table 1
The concentration of the active optical Brightener solution by weight of dry matter (%)The concentration of the active optical brighteners (2) by weight of dry matter (%)The ice-white using a solution of 1The ice-white using a solution of 2 (comparative)
0,40.104 g88,786,9
0,60,155to 89.988,2
0,80,20791,8of 89.1
1,00,259of 92.788,5

These results clearly show the surprising superiority of whiteness of coated papers obtained using data solutions that contain only 2.1 wt.% polyvinyl alcohol.

Examples preparation 3-5

Solutions of optical brighteners 3-5, containing 12.3% of active clarifier, is produced by mixing together

12.3 wt. including optical Brightener of the formula (2),

(87,7-x) wt. including water and

x wt. including polyvinyl alcohol having a degree of hydrolysis of 85.2% and a viscosity according to Brookfield at 3.7 MPa·s (4% aqueous solution at 20 °C)

when heated to 90-95°C to obtain a clear solution which remains stable after cooling to room temperature. the pH of the solution adjusted to 9.0 with sodium hydroxide.

The viscosity of each solution are presented in table 2.

Table 2
Number exampleThe concentration by weight PVOH solution (%)Viscosity
(20°C)
Viscosity
(10°C)
33,221,634,4
46,3123,5figure of € 256.4
5 (Example from WO 2005/056658)9,542695089

These results clearly show the pre is the data gives solutions in terms of low viscosity and, thus, the ability to go pump.

1. Aqueous solutions of optical brighteners consisting essentially of (a) from 10 to 50 wt.%, at least one optical Brightener of the formula (I):

in which
M represents hydrogen, alkali metal atom, ammonium or a cation derived from an amine,
R1represents hydrogen, C1-C4-alkyl or C2-C4-hydroxyalkyl, and
R2represents a C1-C4-alkyl which may be substituted by-CN or-CONH2group, or With2-C4-hydroxyalkyl,
or R1and R together with the nitrogen atom complete morpholino-ring;
(b) from 0.5 to 9 wt.% polyvinyl alcohol having a degree of hydrolysis of from 71 up to 85.2% and a viscosity according to Brookfield from 3 to 5.4 MPa·s; and
(c) water.

2. The solutions according to claim 1, in which
M represents sodium,
NR1R2represents N(CH2CH2OH)2N(CH2CH(CH3)OH)2N(CH2CH2OH)CH2CH2CONH2or N(CH2CH(CH3)OH)CH2CH2CONH2and
in which polyvinyl alcohol has a degree of hydrolysis of from 71 to 80% and a viscosity according to Brookfield 3-5,4 MPa·S.

3. The solutions according to claim 1, in which
M represents sodium,
NR1R2represents N(CH2CH2OH)2N(CH2CH(CH3/sub> )OH)2and
in which polyvinyl alcohol has a degree of hydrolysis of from 71 to 75% and a viscosity according to Brookfield 3-5,4 MPa·S.

4. The solutions according to claim 1, in which the concentration of polyvinyl alcohol is from 1 to 5 wt.% and in which the concentration of the optical Brightener is from 15 to 40 wt.%.

5. The solution according to claim 4, in which the concentration of polyvinyl alcohol is from 1.5 to 4 wt.% and in which the concentration of the optical Brightener is from 18 to 35 wt.%.

6. The application of the solution according to any one of claims 1 to 5 for coating compositions for paper.

7. A method of obtaining a coated paper in which a coating composition containing solution according to any one of claims 1 to 5, is applied to the paper after formation of the sheet.

8. The method according to claim 7, in which the coating composition contains from 10 to 70 wt.% one or more white pigments.

9. The method according to claim 7, in which the coating composition contains a primary binder based synthetic latex selected from styrene-butadiene, vinyl acetate, styrene-acrylic, vinylgroover or ethylene-vinyl acetate polymer, or optionally the secondary binder is selected from starch, carboxymethyl cellulose, casein, soy polymers or polyvinyl alcohol or a mixture of any of them.

10. The method according to claim 7, in which the primary binder is used in an amount of 5 to 25 wt.% from the mass of white pigment is a, in which the secondary binder is used in an amount of from 0.1 to 10 wt.% by weight of white pigment and in which the optical Brightener of formula (1) is used in an amount of from 0.01 to 1 wt.% by weight of white pigment, preferably from 0.05 to 0.5 wt.% by weight of white pigment.



 

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