The water composition sizing agent and method for producing paper

 

(57) Abstract:

The water composition sizing agent can be used to produce paper. The composition comprises a cyclic anhydride of dicarboxylic acid or alkylcatechols dimer, moremary polymer, which is amphoteric starch or amphoteric polymer based on acrylamide, and semi-aluminum compound. Amphoteric polymer is amphoteric starch, for example cationically potato starch. Semi-aluminum compound is polyaminoacid, solfataras polyaminoacid, polyaluminosilicate or mixture, or cocondensate cationic dicyanamide resin and semi-aluminum compounds. A sizing agent is alkylcatechols dimer. The method is designed to produce paper, cardboard or thin cardboard (thick paper) and can be used in the pulp and paper industry. The method is characterized by the fact that the sizing agent is added either in the mass or used as a surface sizing agent. As a sizing agent using the above aqueous composition. The use of water composition allows her small amount to get a very good about the lei. 2 C. and 8 C.p. f-crystals, 4 PL.

The invention relates to aqueous compositions sizing agent and method for producing paper.

The composition comprises a sizing agents, which are alkylbetaine the dimers or cyclic anhydrides of dicarboxylic acids, amphoteric polymer and semi-aluminum compound.

Alkylbetaine dimers (AAA=AAA) and the cyclic anhydrides of dicarboxylic acids, in particular alkenylamine anhydride (ACA=ASA), is widely used for sizing, waterproofing paper at neutral or alkaline pH. Compounds which are reactive toward cellulose and connect directly with the hydroxyl groups in cellulose. Commercially used products are usually stabilized cationic starch, which also contributes to the retention of a sizing agent. To increase retention and improve sizing also often use individual supplements retaining agents and other chemical substances and mixtures.

Known aqueous sizing composition based agent alkylating dimer, cationic starch and polychloride aluminum [1].

There is also known a method of obtaining a paper or bernotas sizing paper or paper-like product, moreover, as a sizing agent is used an aqueous solution of a mixture alkylating dimer and cyclic anhydride acid [2].

The lack of sizing compositions based alkylating dimer (AKD) is that they are relatively expensive because of the cost of AAA.

The technical result of the proposed water composition sizing agent, and the proposed method of producing paper, cardboard or thin cardboard (thick paper) is a good sizing of the small amounts of sizing agent, as the composition gives good retention and positively contributes to the overall retention of fibers and fillers and dehydration upon receipt paper.

This technical result is achieved by the fact that the water composition of the sizing agent according to the invention contains a cyclic anhydride of dicarboxylic acid or alkylcatechols dimer, amorphous polymer, which is amphoteric starch or amphoteric polymer based on acrylamide and poly-aluminum alloys connection.

Amphoteric polymer is amphoteric starch, which is the ratio of anionic and cationic groups in the range from 0.025:1 to 90:1.

tion is polyaminoacid, solfataras polyaminoacid, polyaluminosilicate or mixture, or cocondensate cationic dicyanamide resin and semi-aluminum compounds.

Semi-aluminum compound is present in an amount of from 0.1 to 10 wt.%, calculated as Al2O3on a sizing agent.

A sizing agent is alkylcatechols dimer.

Amphoteric polymer is present in an amount of from 1 to 35% relative to the weight of the ketone dimer.

Content metanovogo dimer is from about 5 to 30 wt.%.

This technical result is also achieved by the fact that in the method of producing paper, cardboard or thin cardboard (thick paper), according to which a sizing agent is added either in mass or as a surface sizing agent according to the invention as a sizing agent use water composition.

Two types of sizing agents are essentially well known. The cyclic anhydrides of dicarboxylic acids can be expressed with the General formula

,

in which

R2- dimetilan or trimethylene radical;

R1is a hydrocarbon group having more than 7 carbon atoms, Kotor is which are used serially to the fullest extent are the alkyl - and alkenyl-succinamide anhydrides (ASA), in particular isooctadecyl anhydride. Alkylbetaine dimers have the General formula

,

in which

R1and R2the hydrophobic hydrocarbon group having about 6 to 30 carbon atoms, which are usually alkyl groups having 12 to 20 carbon atoms, such as hexadecyl and octadecyl group.

Amphoteric polymer in the present compositions is amphoteric starch or amphoteric polymer based on acrylamide. The term "amphoteric" here refers to polymers containing both anionic and cationic groups. Amphoteric starch is preferred and for this purpose, the anionic group may, for example, be a phosphate, phosphonate, sulfate, sulfonate or carboxypropyl, and they are preferably phosphate groups are tertiary amino groups or Quaternary ammonium groups. The ratio of anionic and cationic groups in the starch may be in the range of from 0.025: 1 to 90:1 and preferably in the range from 0.4:1 to 40:1. Can be used any starch that contains these types of groups, and the starch can be made from potatoes, corn, wheat, tapioca, rice, oceanmale. Especially suitable for use is cationically potato starch, natural potato starch contains a sufficient amount of covalently bound phosphate monoatomic groups.

Amphoteric polymer may be a polymer based on acrylamide, which is a water-soluble polymer with acrylamide and/or methacrylamide as the main monomer unit. These polymers may have a molecular weight of about 10,000 to 1,500,000, suitable from approximately 300,000 to 800000. Amphoteric polymers based on acrylamide can be obtained by introduction of ionic groups in the polymer containing methacrylamide as the main component.

The cationic group can be introduced by various methods, such as the splitting of Hoffman and reaction manniche and anionic groups can be introduced, for example, by hydrolysis or reaction sulfotyrosine. Amphoteric polymers based on acrylamide can also be obtained by copolymerization of methacrylamide and a mixture of monomers containing both anionic and cationic monomers.

In these compositions is as amphoteric polymer and semi-aluminum compound. It is assumed that there is some interaction is good stabilization and good retention of the sizing agent in the mixture.

Ketone dimers are preferred sizing agents.

Water-AAA-dispersions which contain as amphoteric polymer, and poly-aluminum alloys connection, give a very good sizing small quantities of AAA, and the variance, in addition, have satisfactory stability and can be obtained with a sufficiently high content of dry residue for serial applications. The variance is also successfully used in the presence of restraint drying systems based on combinations of anionic inorganic colloids, such as colloids based on silica and cationic polymers. It was also shown that the variance can contribute to the improvement of dehydration and the General retention of fibers and optional fillers.

Semi-aluminum compounds contain aluminum, hydroxy-group and anions, they are called primary, and in aqueous solutions they are polynuclear complexes. Semi-aluminum complexes of the compounds as well as polyaluminium and polyaluminium containing sulfate are well known compounds and are used in combination with paper, among others, if the rosin sizing for fixing rosin in R the ut to be in the semi-aluminum compounds, having a General formula

,

in which

X is a negative ion, such as chloride or acetate;

n and m are positive integers, such that

3n-m>0.

Preferably X = Cl-and such semi-aluminum compounds known as polyaluminosilicate (GROIN = RACES). Polyaluminosilicate may also contain anions from faithful acid, phosphoric acid, chromic acid, dichromasy acid, silicic acid, citric acid, carboxylic acids or sulphonic acids.

The basicity of the semi-aluminum compounds of the above General formula is defined as the ratio m/3n100. The basicity of the fit is in the range from 10 to 90% and preferably in the range from 20 to 85%.

The most suitable semi-aluminum compounds in the present compositions are polyaluminosilicate, sulfadimidine polyaluminosilicate and polyaluminium sulfates. As examples of polyaluminosilicate may be given the compounds of General formula

[Al/OH/x(SO4)y/H2O/z]n,

in which

x has a value from 1.5 to 2.0;

Y has a value from 0.5 to 0.75;

x + 2y = 3;

z=1.5 to 4, suitable for 1.5 - 3.

Used here termininating compounds. Such products are considered in the description of European patent 320986.

An example of an industrial semi-aluminum compounds are Ecoflac (Ekoflock), produced by the famous company Eka Nobel AB. In this case, the basicity is about 25% and the content of sulfate and aluminum about 1.5 and 10 wt. % respectively, therefore, the aluminum content calculated as Al2O3. In aqueous solutions the predominant number is Al3(OH)+45which when diluted to a greater or lesser degree turns in Al13O4(OH)1724.

Other examples of commercially available compounds are without sulfate Sartoclear (Sachtoklar) supplied by the company Sachtleben Chemie (Germany), sulfacetamide WAC supplied by the company Atochemi (France), highly basic polyaluminosilicate connection Akron (Locron) supplied by the company HoechstAG (Germany), poly/hydroxylamine/ sulfate Omnicell (Omniklir) supplied by the company Omnikem (USA), Noprof (Niaproof), which is aluminumhydroxide supplied by the company Niacet (USA) and Altofts (Alzofix) based polyaluminosilicate and dicyanamide supplied by the company SKW Trostberg (Germany).

In ketenimine dispersions according to the iMER. Preferably, its content is from 5 to 20 wt.%. Semi-aluminum compound is present in relatively large quantities and suitable amount of from 0.1 to 10 wt.%, calculated as Al2O3on kamenova the dimer, and preferably, the number of the semi-aluminum compound is in the range from 1 to 6 wt.%. Despite the high content of aluminum compounds show good dispersion stability. The dispersions according to the invention may have a content of AAA from about 5 to 30 wt.%, and the content of AAA is suitable in the range from 10 to 20%.

Ketenimine dispersion according to the invention can be obtained by mixing an aqueous solution of amphoteric polymer with AKD-wax (paraffin) at a temperature of from about 55 to 95oC and homogenization at this temperature under a pressure of from about 50 to 500 bar. The emulsion obtained, which has a droplet size of from about 0.3 to 3 μm, and then quickly added during or after cooling. In addition to the above three main components in the dispersion can also be introduced by other components, for example anionic surfactants, such as matrilineality, fillers such as urea and its production is th temperature. In industrial ACA-products usually present emulsifier. Aqueous compositions of cyclic anhydrides of dicarboxylic acids are emulsions and compositions according to the invention can be obtained by mixing the liquid anhydride with a solution of an amphoteric polymer, so the solution is semi-aluminum compound. The solution should be maintained at a temperature of about 20oC. composition of cyclic anhydrides of dicarboxylic acids according to the invention contain suitable anhydride and an amphoteric polymer in a ratio by weight of from 1 : 1 to 1 : 4. Semi-aluminum compound is present in an appropriate amount with respect to the cyclic anhydride of dicarboxylic acid, as given for ketenimine dispersions. ASA emulsion usually get at a paper mill in terms of their use as a sizing agent in paper production. The anhydride content is from about 0.1 to 5% relative to the total mass.

Compositions according to the invention in the traditional way used in paper production. They can be used for surface sizing and sizing mass upon receipt paper, cardboard and thin cardboard (thick paper).

The invention is additionally illustrated by the following image, which do not limit the invention. Parts and percentages are by mass and mass%, unless otherwise noted.

Example 1. Ketenimine dispersion according to the invention is obtained as follows: 70 g of potato starch, cationizing to the degree of substitution 0,042, mixed with 450 g AAA-wax and approximately 2340 g of water containing 15 g matrilineality, at the 75oC, and the mixture is homogenized at this temperature under a pressure of 200 bar and quickly cooled. In the cooling process, add the semi-aluminum compound. For dispersion (1A) add 120 g of polyaluminosilicate containing sulphate Ecoflora from Eka Nobel AB. For dispersion (1b) add 168 g polyaluminosilicate of Omniclone from Omni Kem, USA, 2.8% of Al2O32O3.

Example 2. Sheets of paper are derived from the standard mass of bleached sulfate pulp (48% birch, 32% pine and 20% calcium carbonate) at pH 8.0 in accordance with the standard method SCAN - C23X for pilot production.

In table. 1 shows Saw-values determined in accordance with TAPPI standard T OS-63. In these tests the variance (1a) according to the invention compared with the dispersion Cf. (comparison) containing cationic starch from waxy maize and the same semi-aluminum compound, as in the dispersion (1a), and starch and semi-aluminum compound present in the same quantities as in dispersion (1a).

It is seen that the AAA-dispersion containing semi-aluminum compound, where the starch is amphoteric, are significantly more effective than the products in which the starch contains only cationic groups.

Example 3. Sizing effect dispersions (1b) and (1c) is investigated as in example 2, and the results of which are tabulated in table.2.

Example 4. In this example, for a 35% solution of H2O2examines the face value of permeability using the so-called tests mitilene. Tests are conducted on the mass of yomigana blagopoluchnaya resin and drying - restraint system on the basis of silicates and cationic starch are added to the mass separately from AAA-dispersion. A comparison between the dispersion (1a) according to the invention and standard AAA-dispersion containing cationic starch from maize waxy Cf. 1, and the variance of Cf. 2, corresponding to (1a), but containing semi-aluminum compound. The results are shown in table. 3.

It is seen that the dispersion according to the invention give improved sizing in comparison with the standard product. It also shows that this effect depends not only on the type of starch, but also from the combination of amphoteric starch and semi-aluminum compounds.

Example 5. For the same mass, as indicated above, tests dehydration in the presence of industrial restraint system Compozit, which contains silicasol (Si-Sol) and cationic starch (ACS), which add to the weight separately. Tests carried out with the use of this system in the presence of various ketenimine dispersions, and the drying effect is determined by using the "Canadian standard Freeness (CSF) Tester", which is the usual method to determine the dewatering or drainage capacity in accordance with SCAN-C21:65. For 0 - isogawa the capacity is 310 ml CFS. Tests carried out with the dispersions (1a) and (1b) according to the invention and the comparison is made with the dispersion of Comparison, the standard AAA-dispersion containing cationic maize starch waxy. The results are shown in table.4.

As you can see, the dispersions according to the invention give improved drying effect at that time, as the variance of the comparison produces a small decrease it.

1. The water composition sizing agent, characterized in that it contains a cyclic anhydride of dicarboxylic acid or alkilbetainy dimer, an amphoteric polymer, which is amphoteric starch or amphoteric polymer based on acrylamide and poly-aluminum alloys connection.

2. The composition according to p. 1, characterized in that the amphoteric polymer is amphoteric starch.

3. The composition according to p. 2, characterized in that the amphoteric starch is the ratio of anionic and cationic groups from 0.025 : 1 to 90 : 1.

4. Composition according to any one of paragraphs.1 to 3, characterized in that the amphoteric starch is cationically potato starch.

5. The composition according to p. 1, characterized in that the semi-aluminum compound is polyaminoacid, sulfidebearing connection.

6. The composition according to p. 5, characterized in that the semi-aluminum compound is present in an amount of 0.1 - 10 wt.%, calculated as Al2O3on a sizing agent.

7. Composition according to any one of paragraphs.1 - 6, characterized in that the sizing agent is alkylcatechols dimer.

8. The composition according to p. 7, characterized in that the amphoteric polymer is present in amounts of 1 to 35% relative to the weight of metanovogo dimer.

9. The composition according to PP.7 and 8, characterized in that the content metanovogo dimer is from about 5 to about 30 wt.%.

10. The method of producing paper, cardboard or thin cardboard (thick paper), in which a sizing agent is added either in the mass or used as a surface sizing agent, characterized in that as a sizing agent using the aqueous composition according to any one of paragraphs.1 to 9.

 

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