JPS63288297A - Paper size composition and its production - Google Patents

Abstract

Aqueous rosin dispersion paper sizing compositions containing an ammonium salt or a precursor thereof, such as urea, a chemically-modified urea or a precursor of the latter.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to paper sizing compositions, methods for producing such compositions, methods for sizing paper products using these compositions, and the present compositions. This relates to products sized by . More particularly, the present invention provides aqueous paper size compositions, methods of making them, methods of using them, and compositions,
That is, it relates to sized products using the present composition in the form of a rosin dispersion.

[Conventional technology and issues]

Rosin consists of a complex mixture of cyclic terpene carboxylic acids and is relatively insoluble in water. In order to be usable in the form of an aqueous size composition, the rosin must either be taken into solution (as a rosin soap) or dispersed as fine droplets in water (as a rosin dispersion).

Rosin soap solutions consist of a system in which the azine acid functional groups are almost completely neutralized with base, thereby allowing insoluble rosin acid to be incorporated into the solution. In practice, the degree of neutralization used is 90% of the normally available acidity.
%, remaining unsaponified acid components and any neutral components present in the rosin are also retained in the soap structure. Rosin dispersions consist of fine particles of rosin and also contain stabilizers that serve to prevent destabilization of the dispersion. The stabilizer is usually a surfactant, which is a soap, especially a rosin soap, a protective colloid, or a mixture of both. Where a rosin soap is used, the dispersion contains about 1 to 10% of the total rosin acid present. It is made from a banko to neutralize it.

It has now been discovered that a rosin dispersion not previously reported or believed to have been made can be made and is highly suitable for use as a paper size composition.

It is known in the prior art that urea and various chemically modified derivatives of urea serve as precursors to ammonia or ammonium salts or as useful ingredients together with ammonia or ammonium salts in rosin soap size compositions. Are listed. For example, U.S. Pat.
No. 022,634 and ff.a, 895,77
No. 9 describes a size composition consisting of a rosin soap and a reaction product of urea with an acid selected from sulfamic acid, phosphoric acid, trichloroacetic acid, nitric acid, sulfuric acid, salt syrup, stearic acid and acetic acid. U.S. Patent No. 4,141,750
The publication describes similar compositions in which uric acid is reacted with a Lewis acid such as para-toluenesulfonic acid. U.S. Pat. No. 4,025,554 describes a size composition consisting of rosin soap and chemically modified urea.
Its preferred form is the product of reaction with urea sulfamino acids. U.S. Patent No. 4457.894
The publication describes a size composition consisting of a rosin soap and a product obtained by reacting urea with formic acid. U.S. Pat. No. 4,605,445 describes a size composition consisting of rosin soap and urea.

Ammonia or ammonium salt or its precursor,
It has already been found that it is advantageous to add it to the size composition of rosin dispersions. Not only do these compounds exhibit significant sizing activity when present in the sizing system of unstable dispersions (rather than, surprisingly, the dispersions become unstable as expected), In particular, the addition of these compounds has not hitherto been found to be beneficial, since they are stabilizing.

[Means to solve the problem]

According to one aspect of the invention, there is therefore provided a paper size composition consisting of an aqueous rosin dispersion, characterized in that it comprises ammonia or ammonium salts or precursors thereof.

Rosin is a solid resinous substance that occurs naturally in the oleoresin of pine trees. It consists of three main raw material sources: oleoresin exudate from living pine trees, oleoresin contained in the old stumps of pine trees, and oleoresin from tall oil produced as a by-product of the kraft paper industry. Obtained from one.

Besides the cyclic terpene carboxylic acids, rosin contains small amounts of non-acidic components.

The main component of rosin is abietic acid, which is a tricyclic,
It is a monocarboxylic acid with two unsaturated bonds. Abietic acid undergoes a Diels-Alder addition reaction with genophile. Rosin is therefore reacted with dienephilic carboxylic acids and derivatives thereof such as maleic acid, maleic anhydride and fumaric acid to form tetracyclic polycarboxylic acids. This reaction between rosin and genophile usually takes place in one fortifcation.
cation), and the reaction product is commonly referred to as Fortified 20 gin (hereinafter referred to as fortified rosin).

Dispersions of reinforced rosin are used as size compositions in the paper sizing industry. The 097 dispersion according to the invention is based on rosin or fortified rosin or a mixture of both. It is also possible to use fortified rosins that have been treated with formaldehyde to increase stability. Esterified or disproportionated rosins are also used in the compositions of the present invention. Esterified rosin is rosin that has been reacted with an alcohol, preferably a polyol such as glycerol. Disproportionated rosin is a rosin that is
It is a rosin treated by a catalytic process. Mixtures of any of these types of rosin may be used in the compositions of the present invention.

The preferred rosin used in the compositions of this invention is a backed rosin. Preferred fortified rosins are those in which the rosin has been reacted with genophile in an amount ranging from 5 to 50 wt% of the rosin, and generally about 10 wt%. The most preferred type of rosin is a 5-fortified tall oil rosin.

The rosin dispersion according to the invention I preferably contains from 2.5 to 80 wt% soap, which is preferably a rosin acid soap, and the total weight of solids in the dispersion. It is based on Rosin acid soaps are produced by saponifying rosin acid or strengthened rosin acid with an organic or inorganic base. Alternatively, the soap is generated in situ by neutralizing a portion of the total acidity of the rosin again with an organic or inorganic base. Preferably, such operations are performed at a concentration of 1 to 10 of the total acidity of the rosin acid.
%, more preferably in an amount in the range of 3 to 6%.

Rosin dispersions are made according to procedures using conventional techniques and ingredients known in the prior art.

In particular, a dispersion may contain, in addition to ammonia or ammonium salts or precursors thereof, one or more stabilizers. Various surfactants or emulsifiers may be mixed with other surfactants to stabilize the dispersion.
or with other known emulsifiers, or with other known auxiliary stabilizers. A preferred class of co-stabilizers are protective colloids such as casein.

Compositions comprising rosin, ammonia or ammonium salts or precursors thereof, stabilizers and protective colloids form a preferred aspect of the invention.

Anionic, nonionic, cationic or amphoteric surfactants are used as stabilizers in the dispersions of the invention. Generally, the anion is preferably a nonionic surfactant.

Examples of surfactants found for use in the compositions of the present invention include:

(1) General formula: (wherein, R1 represents a hydrocarbon residue having 4 to 18 carbon atoms, m is an integer with a value of 1 or 2, n is an integer with a value of 4 to 25, represents a hydrogen atom or a hydroxyl group, and M represents a monovalent cation); (1) General formula: (wherein R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; In the formula, A represents a straight chain or branched alkyl group having 2 to 3 carbon atoms, p (an integer having a value of 4 to 25, and Q is a monovalent cation), and U.S. Pat. Half ester salts of sulfonic acids including all such compounds described in US Pat. No. 509,588;
, No. 982.

[Wherein, R is a tricarbo/acid ester group of reinforced rosin acid, m is an average of 1.5 to 3, and n is an average of 4.5
The number is between 25 and 25. ] and European Published Patent No. 159,
A sulfosuccinic acid half ester of reinforced rosin containing all five compounds described in Publication No. 794.

(V) The following formula: % formula %] (wherein R represents an alkyl group containing 4 to 18 carbon atoms, R1 represents an alkyl group or alkenyl group containing 4 to 8 carbon atoms, and n is 4 is an integer with a value between 25 and 25).
A compound containing all the compounds described in Publication No. 67.

(wherein R represents an alkyl group containing 4 to 18 carbon atoms, and n is an integer with a value of 4 to 25) and is described in U.S. Pat. No. 4,203,776. These compounds include sulfosuccinate ester salts of condensates of ethylene oxide.

(v1〇 General formula: and mixtures thereof (wherein R represents an alkyl group, an alkylphenol group, an alkenyl group or an aralkyl group containing 5 to 20 carbon atoms, n has a value of 5 to 20, and X is Representing an inorganic or organic cation or hydrogen.Organic phosphate esters having the formula or other formulas of Examples of suitable materials include water-soluble polyaminopolyamide/shrimp chlorohydrin resin, water-soluble alkylene-polyamine/shrimp chlorohydrin resin, and poly(sialyl-amine)/shrimp chlorohydrin resin.

Although 7y-t-nia or ammonium salts may be used in the compositions of the present invention, it is preferred to use precursors thereof, such as urea, chemically modified ureas, or precursors thereof. Examples of compounds that are particularly useful in the compositions of the invention are:
Urea, thiourea, biuret, melamine, water-soluble urea/
Formaldehyde and melamine/formaldehyde resins and acid and Lewis acid derivatives of urea, U.S. Pat. Nos. 4,022,354 and 4,093,779
As described in this publication, the reaction product obtained by reacting urea with an acid selected from sulfamic acid, phosphoric acid, trichloroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, stearic acid and acetic acid, U.S. Pat. 4. Reaction products of urine X with Lewis acids such as p-)luenesulfonic acid, as described in U.S. Pat.
Reaction products of urea and sulfamic acid as described in US Pat. No. 554 and US Pat. No. 4,437,89
It includes the product obtained by the reaction of urea and formic acid as described in Publication No. 4.

A preferred source of ammonia or ammonium salts used in the compositions of the invention is the product obtained by the reaction of urea with a sulfamic acid/acid.

These products include those described in U.S. Pat. No. 4,025,354. These modified ureas are produced by combining urea with sulfamic acid and water. Ideally, the parts by weight of water are equal to the sum of the parts by weight of urea and sulfamic acid, but urea can also be treated with sulfamic acid with or without a large amount of water. A solution of urea-sulfamino acid has a pH of
for example, the pH is at least about 7.5.
It is heated to a temperature of 5 degrees.

With small amounts of water or when no water is used, the temperature that affects pH will be higher. However, in certain preferred embodiments, a 50% water-50% urea/sulfamino acid solution is used and about 100-113
°C (about 212-2ss'r'), preferably about 102-2ss'r'
It has been found that a temperature of 110°C (below about 215-260°C) increases the pH to at least about 7.91. Generally, the solution boils at a temperature that changes the pH, and heating should continue after boiling has stopped to prevent the pH change from reversing. Although the pH range is an important measure of reaction completion, a more important consideration is the acidity of the first stage product, measured in parts water (ppm).

When sulfamino acids are heated with urea, undefined reactions occur that not only raise the pH to basic values, but also affect the acidity of the solution. A desirable minimum acidity is at least 1.000 ppm, and a preferred minimum is 4,500 ppm. The actual amount of sulfamic acid most desirably used is probably as low as 0.1 wt% of urea, with preferred amounts ranging from 0.2 to 8.
It is in the range of 0wt. To achieve the desired results, the maximum amount of sulfamic acid required is generally 15 wt% up to 20 wt% of the urea. 50% (
7) When treated in a solution of urea and sulfamic acid in 150% water, 5% sulfamic acid has a pH ranging from 7.9 to 8.3.

It was found to produce an acidity of approximately 86,000 ppm. Thus, 0.25 wt% of sulfamic acid in urea yields a first stage product with an acidity of 4,500 ppm. As shown herein, the amount of sulfamic acid added to the solution is not as important as the final acidity to obtain the M1 stage product of the sizing composition of this embodiment.

The proportion of ammonia or ammonium salt (or in a preferred embodiment its precursor) to the rosin or fortified rosin desirably ranges from 5 to 60 wt%, preferably from 10 to 55 wt%.

The dispersions of the present invention are usually prepared as relatively concentrated compositions, which are diluted before use in the sizing process, or optionally added in concentrated form. In general, the dispersion advantageously contains a total of 20% of the rosin and ammonia, ammonium salt or precursor thereof.
The concentrate comprises from 60 wt% and more preferably and usually from 30 to 45 wt%.

The compositions of the present invention can be used as internal or surface sizes. Its use as an internal size is a preferred aspect of the invention. The internal sizing process consists of diluting the concentrated composition with water and adding this diluted composition to the suspension of pulp. Preferably, a flocculant such as paper sulfate, aluminum sulfate or polyaluminum chloride is added before, simultaneously with or after addition of the size composition. The amount of size composition used is generally
Based on the weight of the fibers in the pulp slurry upper (solid content: 0.1
The content ranges from 5.0 to 5.0 wt%. Compositions of the invention can also be made using phase inversion methods.

A rosin, preferably a fortified rosin, which has optionally been treated with paraformaldehyde in the presence of para-toluenesulfonic acid to prevent crystallization, and optionally it has been treated with concentrated sodium or potassium hydroxide, such as ammonia, etc. Although at least partially neutralized with a volatile base, the sled rosin is melted.

The mixture of sifting agents was then concentrated (e.g. 50 w
It is added as an aqueous solution containing t% solids.

To form a creamy water-in-oil emulsion,
Sufficient water (e.g. 20 to 4
0 wt%) is added and stirred. When diluted with water, this emulsion inverts to give a stable oil-in-water emulsion.

This typically ranges from 20 wt% to the highest achievable oil-in-water concentration (often about 80 wt% solids, preferably 30 to 50 wt% solids). The rosin content of the emulsion or dispersion usually comprises a small amount (90%) of unsaponified rosin acid. The emulsion is then mixed with ammonia, ammonium salts or precursors thereof.

This emulsion is used for sizing paper, including Meishun treated paper. The emulsion is a bactericide,
It may also contain at least one biocide such as slimicide and/or a fungicide and/or a diluent such as a wax.

Example 1 Tall oil rosin 350I treated with fumaric acid
Caustic Potassium 6.5 Casein 17 Sodium Tetraborate
The fortified rosin at 4160°C was cooled to 100°C and caustic potash was added with minimal water. A concentrated solution of casein and borate was added and the mixture was immediately inverted. This was mixed for 5 minutes and
It was diluted with water to a solids content of wt%.

The final product was mixed with a modified urea solution obtained by heating a solution of urea and sulfamic acid to boiling point and cooling the product.

Emulsion of rosin and modified urea solution is 25%
of the fortified rosin was mixed to replace the modified urea.

Example 2 Laboratory handmade paper has a Schopper-Reig value at 2-inch consistency.
ler Value) Manufactured from bleached sulfite pulp beaten to 40%. This pulp is prepared in a known amount of a preferred size or of a known industry standard dispersion size (Roscoll A&WLTDJ).
and treated with standard levels of aluminum sulfate, its p
H was adjusted to 4.9-5.0. The sheets were then made on a standard sheet forming machine and pressed and dried in a photo dryer set at 100°C.

After overnight conditioning, the sheets were tested for sizing using the Cobb test. Since the Copp value number is the number of grams of water absorbed per square meter under the test conditions, lower values represent improved sizing. The following results were obtained.

It can be seen that although the actual amount of rosin is less than the standard, the size effect is improved.

Example 3 The stability of a rosin dispersion was tested by an accelerated sedimentation test. This involves applying a large force of gravity to the product for a certain period of time and measuring the degree of sedimentation. This is a test that has been used for a long time and correlates well with storage under normal conditions.

The test results are shown in the table below.

The degree of settling refers to the degree of settling that would occur if the emulsion was normally stored for three months.

Claims (1)

[Claims] 1. In a paper size composition containing an aqueous rosin dispersion,
A paper size composition, characterized in that the composition also contains an ammonium salt or a precursor thereof. 2. The composition according to claim 1, wherein the dispersion comprises rosin, fortified rosin, formaldehyde-treated rosin, esterified rosin, disproportionated rosin, or a mixture thereof. 3. Claim 2, characterized in that the dispersion contains a fortified rosin, which rosin has been reacted with a dienophile in an amount ranging from 5 to 50 wt% of the weight of the rosin. Composition of. 4. Claim 2 or 3, characterized in that the dispersion contains reinforced tall oil rosin or gum rosin.
The composition described in Section. 5. The stabilizer according to claim 2 or 3, which contains one or more stabilizers selected from soaps, surfactants, emulsifiers, and protective colloids. Composition. 6. 2.5 to 8. based on the total weight of solids in the dispersion.
Composition according to claim 5, characterized in that rosin acid soap or other soap is present in an amount in the range 0 wt%. 7. Composition according to claim 6, characterized in that the soap is a rosin acid soap and that it is produced in situ by neutralization of a part of the total acidity of the rosin acid. thing. 8. Rosin acid soap has a total acidity of 1 to 1 of the total acidity of rosin acid.
Composition according to claim 7, characterized in that it is produced by neutralizing 0%. 9. The composition according to any one of claims 5 to 8, characterized in that casein is contained as a stabilizer. 10. Claims 5 to 9 contain one or more stabilizers selected from anionic, nonionic, cationic, and amphoteric surfactants.
The composition according to any of paragraphs. 11. Any one of claims 1 to 10, characterized in that it contains an ammonium salt or an ammonium salt precursor selected from urea, chemically modified urea, and its precursor. The composition according to crab. 12. Contains at least one of urea, thiourea, biuret, melamine, water-soluble urea/formaldehyde, melamine/formaldehyde resin, and urea derivatives obtained by reacting urea with an acid and a Lewis acid. 12. The composition according to claim 11. 13. The composition of claim 12, comprising the reaction product of urea and sulfamic acid with or without water. 14. The composition of claim 13, wherein the reaction product is made by heating urea and sulfamic acid to a temperature at which a change in pH occurs. 15. The composition according to any one of claims 1 to 14, wherein the proportion of ammonium salt or its precursor to rosin in the aqueous dispersion is in the range of 5 to 60 wt%. 16. The composition according to claim 15, wherein the amount of ammonium salt or its precursor is in the range of 10 to 35 wt%. 17. Claim 1 is in the form of a concentrate suitable for dilution before use and contains 25 to 60 wt% of the rosin and ammonium salt or its precursor together.
17. The composition according to any one of items 1 to 16. 18, 30 of rosin and ammonium salt or its precursor
18. A composition according to claim 17, comprising from 50 wt%. 19. The method according to claims 1 to 18, containing at least one bactericide, slimicide, fungicide or other biocide and/or at least one wax or other diluent. The composition according to any one of the above. 20. Melt the rosin, add at least one stabilizer, stir the mixture in the presence of a suitable amount of water to form a water-in-oil emulsion, and dilute the emulsion with water to form an oil-in-water emulsion. A method for producing a paper sizing composition comprising an aqueous dispersion of rosin prepared by inversion of a dispersion of rosin, characterized in that the dispersion is mixed with an ammonium salt or a precursor thereof. 21. The method of claim 20, wherein the dispersion comprises a fortified rosin in which the dienophile is in the range of 5 to 50 wt% of the weight of the rosin. 22. The method of claim 21, wherein the dispersion is made from rosin reacted with dienophile in an amount of about 10 wt% of the rosin. 23. Any of claims 20 to 22, wherein the rosin acid or other soap is present in an amount ranging from 2.5 to 8.0 wt%, based on the total weight of solids in the dispersion. Method described in Crab. 24. The method of claim 23, wherein the soap is a rosin acid soap and is formed in situ by neutralization of a portion of the total acidity of the rosin acid. 25. Rosin soap contains 3 to 6% of the total acidity of rosin acid.
Claim 2 formed by neutralizing
The method described in Section 4. 26. The method according to any one of claims 20 to 25, wherein the ammonium salt precursor is selected from urea, chemically modified urea, and precursors thereof. 27. The method of claim 26, wherein the reaction product of urea and sulfamic acid is added to the dispersion. 28. The method of claim 27, wherein the reaction product is produced by heating urea and sulfamic acid to a temperature at which a change in pH occurs. 29. A solution of 50% water and 50% urea/sulfamic acid was prepared at 100°C to 113°C (212° to 23°C).
5° F.) for a time sufficient to raise the pH to at least about 7.9.
The method described in Section 8. 30. The method of claim 29, wherein heating is continued until the solution boils and boils stop, resulting in a change in pH. 31, the reaction reduces the acidity of the resulting first stage product to 1
31. The method of claim 29 or 30, wherein the method is carried out for a sufficient period of time to reduce the amount to no less than ,000 ppm. 32. The method according to any one of claims 20 to 31, wherein the proportion of ammonium salt or its precursor to rosin in the aqueous dispersion is within the range of 5 to 60 wt%. 33. A paper size composition is added to the pulp suspension, optionally after dilution with water, a flocculant is added to the pulp suspension before, during, or after addition of the size composition, and the paper product is then In the method for producing a sized paper product, the paper sizing composition is a composition defined in any of claims 1 to 19, or claims 20 to 20. A method characterized in that it is produced by the method according to any of paragraph 32. 34, the size composition is 0 based on the weight of fibers in the pulp
．． used with solids content ranging from 1 to 5.0 wt%,
A method according to claim 33. 35. A method for producing a sized paper product in which a paper size composition is used as a surface size, wherein the paper size composition is a composition defined in any one of claims 1 to 19. or claim 2
A method characterized in that it is produced by the method according to any one of items 0 to 32. 36. A paper product manufactured by the method according to any one of claims 33 to 35.