JPS60119298A - Sizing method and composition of cellulose fiber - Google Patents

Abstract

An aqueous sizing composition can be prepared by mixing into water a concentrate that comprises a substantially anhydrous dispersion of a polyelectrolyte in an organic liquid comprising a solution of a reactive size in a hydrophobic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the sizing of cellulose fibers, compositions for use therein and their manufacture.

During the papermaking process, it is necessary to make the naturally hydrophilic cellulose fibers hydrophobic to prevent aqueous liquid from penetrating into the resulting sheet, allowing it to be written on or printed on a notebook. This process, known as sizing, can be carried out by adding a sizing agent to the pulp slurry (usually
This is called internal sizing. ) or a sizing agent can be applied to the produced paper sort. The present invention relates to this internal sizing method.

There are two types of sizing agents commonly used. One of these is based on rosin, which is used in conjunction with alum. The rosin is added as a soap solution or as a top layer, and the rosin is then added directly to the sheet formation. The rosin is added and retained as fine particles.

The second type of size is a reactive size such as a ketene dimer or anhydride size that chemically reacts with the cellulose fibers. Preferably applied in combination with a polymer/electrolyte that helps retain size in the notebook.

The reactive size is generally applied to the pulp in the aqueous emulsion, generally the cationic state,
Be loved. Although the emulsion can be made in a mill, a mill with an emulsifying device is required, and the concentrated emulsion can be diluted and milled for further use. It would be even more convenient if it could be supplied to Unfortunately, reactive sizes tend to react with water, making aqueous emulsions rather unreliable.

Anhydrous salt sizes, such as alkenyl succinate anhydrous sizes, are so reactive that these emulsions must be milled immediately prior to use.

These sizes are typically fed to the mill with cationic starch, which generally must be pre-processed before emulsification, making it inconvenient for the emulsion to be produced in the mill.

Although ketene timer sizes are often supplied to the mill in the form of emulsions, these emulsions only limit longevity and the maximum concentration of ketene dimer in the emulsion is rather low, generally below 6%. , a very human-friendly emulsion must be supplied for paper manufacture.

Although emulsification of liquid ketene timers can be accomplished using conventional emulsification equipment, some of the preferred ketene timers are solid at ambient temperatures. U.S. Patent No.:

These emulsifications, as described in US Pat. Kazu is necessary. The typically important ketene dimer is the distearyl ketene dimer, which alone has a relatively low solubility in organic solvents, and the solution to be emulsified must be rather dilute. For example, we have determined that the timer is set to 40 during Hensen.
wt% (benzene:dimer weight ratio is 1:067), any solution in benzene is no longer possible.
It must be second thinner. This dimer is also less soluble in other organic solvents than in I\nozene.

As described in U.S. Pat. It is made by emulsifying the dimer in an aqueous solution of a cationic dispersant.

Although the emulsion can be made to any convenient solids content, it is stated that a solids content of 1 to 5% by weight can be used.

In each of the examples of U.S. Pat. No. 3,046,186, the initial composition that is made and contains both the size and the polyelectrolyte is extremely dilute. For example, in Example 1, the initial concentrate is approximately 9% sized based on the total composition.

As mentioned above, it is preferable to supply the polyelectrolyte together with the reactive size, but if the reactive size and the polyelectrolyte are supplied separately, there are disadvantages related to the supply emulsion of the reactive size and the polyelectrolyte. It is thought that some of the damage can be minimized. However, this introduces other disadvantages.

It would therefore be highly desirable to be able to provide a stable concentrated composition containing both a reactive size and a polyelectrolyte that can be easily diluted with water at the mill.

The concentrated composition according to the invention is characterized in that it consists of a substantially anhydrous dispersion of a polyelectrolyte in an organic liquid consisting of a solution of a hydrophobic solvent of reactive size.

The concentrated composition generally has a reactive size concentration of 20% or more, preferably at least 286%. The concentration of reactive sizes is often in the range of 30-60%. The amount may be large, for example up to 80% or 85%. All amounts of gore are based on Ichikawa's total amount of composition.

The weight ratio on a dry basis of polyelectrolyte:reactive size is generally from 1:1 to 1:10, preferably from 2 to 1:4 or 1:5.

In order for the condensate to be able to operate conveniently and to have a fairly high active content, the reactive size is
It is necessary to use a small amount (0.67 parts (40% solution) of organic solvent) based on the weight of the organic solvent.The weight ratio of organic solvent to reactive size is generally 1:10 to 1.067, preferably 11. ~l:3.

When using the most dilute reactive size solvent solution commonly used in the present invention (60 parts solvent to 40 parts reactive size), the lull of the polyelectrolyte is generally between 4 and 40 parts, and the reactivity A composition containing 83.3% reactive size can be prepared using, for example, 100 parts of reactive size, 10 parts of solvent, and 10 parts of polymer. It can be formed from 10 parts of electrolyte.

Preferred compositions have a reactive size of about 1 part solvent to 1 part solvent.
~3 parts (preferably about 2 parts) and about 0 polymer/electrolyte
5 to 2 parts (preferably about 1 part).

Concentrated compositions must be substantially anhydrous for the composition to be stable; in practice this means that if water is present, the amount of water is preferably less than 10% by weight of the composition. shall be 5% by weight or less.

Preferably the water content is less than 1%, mostly less than 2% by weight of the composition. The amount of water is generally inadequate to form a polyelectrolyte solution, and preferably the equilibrium water content of the polyelectrolyte (4-N, when exposed to the ambient atmosphere in dry powder form) The color is determined by not exceeding the water content of the electrolyte (m), most preferably the same or less.

The organic liquid in which the polyelectrolyte is dispersed is a solution in a hydrophobic solvent of reactive size. Suitable solvents are organic hydrocarbon liquids which are immiscible with water, such as l\\nene, quinolene, toluene, mineral oil, kerosene and vegetable oils.

In addition to being substantially free of water, the composition is preferably substantially free of any highly polar liquids with which reactive sizes tend to react. Preferably, the liquid phase of the composition consists essentially only of the hydrophobic solvent and the dissolved size.

Although any type of reactive size can be used in the present invention, ketene dimer reactive sizes or anhydrous reactive sizes are preferred.

Suitable ketene dimer reactive sizes that can be used include readily available commercial fats such as palmitic, stearic, oleic or myristic acids.
Contains dimers derived from acids or mixtures thereof. Of course, the ketene dimer must be soluble in the organic liquid selected for the polymer dispersion in 411. Suitable materials are known, for example as described in U.S. Pat.
, 046,186. The ketene dimer may be solid or liquid, but is generally most concentrated; this product can be obtained when the dimer is a liquid.

Suitable anhydride-reactive sizes for use include alkenyl-1-succinic anhydride sizes. Suitable materials are available from US special
'1'' No. 3.102.064.

Polyelectrolytes are generally water soluble, and an advantage of the present invention is that they can be made to any desired molecular weight, especially higher molecular weights than can conveniently occur in existing compositions. be. For example, true viscosity can typically range from 1 to 20, generally from 3 to 9.

Polyelectrolytes may be cationic, anionic or nonionic, with cationic polyelectrolytes generally being preferred.

Preferred cationic electrolytes are homopolymers or copolymers of diallylsialgyl (generally dimethyl)ammonium chloride, and 4-dialkyl amino acids, generally present as quartered acid addition salts or quaternary ammonium salts with methyl chloride or dimethyl sulfate. Alkyl acrylates and methacrylates (dimethylaminoethyl acrylate and methacrylate-1 are preferred)
jl. ) homopolymers and copolymers. Copolymers of these monomers can be formed with acrylamide or methacrylamide and typically contain at least 1% by weight of cationic monomer, usually at least 30 m m', 1%. Other cationic acrylamides and methacrylamide etc. can be used.

Other cationic monomers that can be used are polyamine epiha[J hydrin polymer O'], hynonoandhiami F'+
'511t! polyamines and polyimines, such as monomers and poly-tyreneimine.

Suitable 111-ion polymers include polyacrylamide.

Suitable anionic polymers include those formed from monomers containing carboxylic or sulfonic acid groups. These groups can be used as free acids or
Suitable acids include acrylic acid, methacrylic acid, and 2-acrylamido-2-methyl group [J Panosulponic acid. The anionic polymer may be a pomopolymer as described in 1-, or a mixture thereof, or a copolymer, for example with acrylamide. Suitable polymers are polyacrylamides containing up to 25% or more of acrylic acid groups. It is.

The concentrated composition is most commonly produced by adding a reactive size to a substantially anhydrous dispersion of a polyelectrolyte in a hydrophobic liquid and forming a size solution in the hydrophobic liquid every 4 degrees. Dispersions of polyelectrolytes in hydrophobic liquids are generally prepared by mechanically dispersing a powdered polyelectrolyte into a liquid, or by forming a dispersion in a hydrophobic liquid of an aqueous polymer, and further dispersing the dispersion. It can be produced by azeotropic dehydration. This dispersion is
The aqueous polymer solution may be dispersed in a hydrophobic liquid or prepared by, for example, reverse phase emulsion or suspension polymerization. The aqueous solution of monomers forming the polyelectrolyte can then be dispersed in the urawa and polymerized by supermulsion or suspension polymerization mechanisms to form aqueous polymer droplets dispersed in the urawa, followed by the Dry the composition. Any aqueous dispersion (such as described in British Patent No. 1,482,515)
It is preferred that it is formed in the presence of a polymerizable dispersion stabilizer, and also preferably a water-in-water emulsifying surfactant, and 411 which azeotropically promotes post-drying of the product.

The user composition is generally prepared by the user from a concentrated composition by adding the concentrated composition to water and dispersing the polyelectrolyte in the water without dissolving it to form a crystalline emulsion in water of a saw-sized solution. Manufactured by.

The formation of crystalline-in-water emulsions is promoted mechanically by the application of high U-shear and/or by the presence of an oil-in-water emulsifier such as ethoxylated nonylphenyl. The oil-in-water emulsifier may be contained in the concentrate or in the water in which the emulsion is formed.

The filtrate from which the emulsion is formed may be the water of the cellulose pulp suspension to be treated, but is preferably a concentrate or first converted to an aqueous emulsion, with a ~5%, preferably 0,05-1%
Is it possible to obtain a reactive size concentrate?

This emulsion can then be added to aqueous cellulose pulp and filter paper made therefrom in a conventional manner. The amount of reactive size in the aqueous pulp is generally from about 0.01 to about 1% by weight, based on the dry weight of the pulp. Upon addition to the pulp slurry, active size/7) IJ droplets are retained by the polymer on the fibers and the size reacts with the fibers. The sizes released from the emulsion in this way are at least as good as those obtained using conventional ketene dimer emulsions.

Thus, the present invention provides a storage-stable concentrated composition (1% You get the horns you give.

Examples of the present invention will be described below.

A substantially anhydrous dispersion of a copolymer of quartered methyl chloride and acrylamide of dimethylaminoethyl methacrylate (DMAHMA) is prepared by a reverse phase dispersion polymerization process. Acrylamide! J was supplied as a 57% aqueous solution, and the quarter-shin saw monomer was supplied as a 65% aqueous solution.

These solutions were prepared using the solvent Pearl Oil 1.50 and Park [J
[Furene]・In the mixture/) is contaminated.

Polymerization is initiated and completes completely, and the resulting no-product is distilled under reduced pressure and mixed with water.
Remove Dilene. polymer (and each dispersion A)
The true viscosity of the polymer with +:l in -H is in the range of 4 to 6.

In the process of 1-1, the ratio of I) MΔEMA nearacrylamide is 8020 parts by weight, and the resulting polymer dispersion (dispersion A) is 475 tonne weight percent of the active polymer.
Contains. A 1% solution of the polymer in water is IOr
Rotating at pm (4' spin), using Le No. 3, chamber 1M, IIV'l' block feel l' viscosity 6,40 Gcp
Don't do it.

In other experiments, the monomer proportions were the same and the molecular weight of the resulting polymer was 10' or higher. Here t'J
The dispersion is named dispersion B.

In other processes, Dispersion C and Nari (3D dispersion) are more broadly adhered to than those described in Dispersion I and are 50% active polymer dispersions in Mineral i+Ii.

In this process, the ratio of DMAEMA+acrylamide was 30 to 0 parts by weight, and the resulting dispersion was named ('-) dispersion 1) and contained 50% by weight of active polymer. The polymer in the dispersion is of low molecular weight with a true viscosity of 3.16@'4.

In another process, a substantially anhydrous dispersion of polyamine-epichlorohydrin condensate is prepared in a solvent pearl with a very small amount of emulsifier prior to distilling off the water under reduced pressure.
It is produced by emulsifying a polymer obtained by aqueous phase polymerization into a mixture of Oil 60 and 5BPII. The resulting polymer dispersion, designated Dispersion 1, contains 37.6% by weight of active polymer.

Examples 1-5 A series of concentrated compositions according to the invention are made by dissolving a reactive size in each dispersion A-E.

In Example 1, the size is hexadecenyl dimer, and 1.05 g of dispersion A, 4 g of hexadecenyl ketene dimer, and 1 g of oil-in-water emulsifier are concentrated to produce 64.
A 5% active sizing composition is obtained. The water content of the concentrate is 1
% or less. The product is into a concentrate.

In Example 2, the concentrate is prepared by mixing 2 m Jl of dispersion B with 2 mf of octadecenyl ketene dimer to form concentrate 1
Make 3 or more.

In Example 3, 61 parts by weight of the dispersion are mixed with 1 part by weight of alkenyl succinic anhydride reactive soybean to form Concentrate C 4'.

In Example 4, an aqueous condensate containing 2 g of dispersion 1), 5 g of alkenyl succinate anhydride, 2.25 g of mineral 71JI and 0.75 g of oil-in-water emulsifier was prepared by dissolving alkenyl succinate anhydride in a mixture of dispersion and mineral oil. is obtained as a 50% active Zaing concentrate 1) with a water content of less than 1%.

In Example 5, in the presence of an emulsifier, alkenyl succinate anhydride was dissolved in dispersion E, and 5 g of alkenyl succinate anhydride was added.
, 5.31 g of dispersion E and 1°28 g of oil-in-water emulsifier.
to form a 43.1% active size concentrate (43.1% active size concentrate).

14Ll of each concentrate A-1 is used to prepare the corresponding aqueous emulsion with an active size content of 1% by weight by stirring the appropriate amount of dispersion into water. Each of these 1% active emulsions also has an active size content of 0.
．． Diluted to 1% by weight, these 0.1% emulsions are named emulsions A-E (made from ~13 to concentrate, respectively).

The effectiveness of each emulsion in sizing cellulose fibers is determined by a one minute Cobb test. In each of these tests, a handsheet is created from the calcium carbonate-containing material on a standard laboratory note-taking machine, then the sort is dried and the Cobb value determined for 1 minute. For Emulsions A-D the material is bleached sulfate/bleached Bard material;
For Emulsion H it is bleached sulfate (Kraft).

In test A, the handsheet is 100 g, sm and the material contains 20% calcium carbonate and 0.5% constituent material. The emulsion is Emulsion 8 or, as a comparison, a commercially available superemulsion made from a 6% emulsion of ketene dimer in water stabilized with cationic starch. This is Emulsion F.

In test 13, the handsheet was tested with 50% bleached sulfate, 40% bleached birch and 52°S, R,
It is made from a raw material of roughly 7% calcium carbonate, roughly crushed II. The inventory was prepared by mixing 2 mi of the 50% dispersion of the polymer used to make Dispersion 13 into 196 mJij of deionized water and then rapidly stirring at maximum speed using a Silverson mixer to obtain octadecenyl. ketene 2
…! The resulting solution of emulsion I3-ζ.
, Yonoko is sized with emulsion G obtained as a comparison. The resulting 1% emulsion was diluted to 0.1% to form Emulsion G.

In test C, 50 parts of bleached sulfate, 40 parts of bleached birch wood, and 10 parts of calcium carbonate were used in an inventory of 7
0g5I11 hand notes are made and these are sized with Emulsion C or Comparative Emulsion H. This is produced as follows. A 12% aqueous dispersion of cationic starch is treated at 95° C. for 20 minutes with constant stirring. Cool the treated starch and dilute to 9% active. Two parts of alkenyl succinate anhydride are added to three parts of cationic starch with stirring. Continue high shear mixing using a rubber mixer to obtain a fine particle size emulsion.

Dilute this emulsion with water to 0.75% active size,
Further dilute to 0.1%.

In test D, 70 gm5 handsheets were made from raw materials of 50 parts bleached sulfate, 40 parts bleached birch wood and IO parts calcium carbonate crushed to 50°S, R, and after manufacturing the sheets were polished. Place it on the board, 3
．． 5kg/cm! Pressure was applied for 5 minutes at 110° C. and dried in a ring for 2 hours. Emulsion D is used to size each of these sheets.

In Test E, a 70 gm5 handrate is prepared in a conventional manner from bleached sulfate feedstock, dried and pressed as in Test D, and sheet sized using Emulsion E.

The formulations and Cobb values are shown in the table below. Preparations were recorded as percent active size based on paper dry weight.

The Cobb Index is the Cobb value for 1 minute.

Tess] Emulsion Dispensing Cobb Hehe 〇, 1527.4 A O, 225, 8 F O, 1533, 2 B B 0.2 26 G O, 265 CCOJ 21.2 CO, 4+94 It O, 321, 6 II O ,419,8 D 11 0.2 25.6 1) 0.3 17.0 1) 0.5 +, 4.3 1; , 8 to E can all give a sizing of 114 pairs. Test C has a result of +'K
2-Pack System 11 with 6J of manpower available on the market
Test B shows that the results are surprisingly better than those obtained by sequential formation of a single emulsion G. Test A shows that the results are better than those obtained with conventional emulsion systems. Similarly satisfactory results are obtained when the polymer is a polyacrylamide containing 10% monomer of acrylic acid groups (like the sodium salt), the stock containing alum and having a pt of 15.5.

In addition to these results, a significant benefit of the present invention to mill operators is that instead of obtaining or making large volumes of dilute emulsions that would be stored in the mill, mill operators can produce small volumes of highly concentrated emulsions. All you have to do is make the pottery saw you want and simply dilute it in the jug that you use when you need it.

Patent Applicant Allied Colloids Limited Agent
Person Patent attorney: 1 person (Continued from page 1) 0 Inventor: Normar Dennis Lowther

Claims (1)

[Claims] 1. Polyelectrolyte in an organic liquid consisting of a solution of a hydrophobic solvent of reactive size and suitable for dilution with water for the purpose of zynoning cell fibers. A concentrated composition characterized in that it consists of a substantially anhydrous dispersion. The concentration of the two reactive sizes is less than 1-1" in the total composition.
40 weight jj1 of the combined weight of size and solvent
% or more of -1-. The concentration of 3 reactive sizes is 30-85% by weight of the total composition.
and the weight ratio of O]R solvent:reactive size is 110
The composition according to claim 1, which has a molecular weight of 1.067 to 1.067. 4. The weight ratio of polymer-electrolyte reactive size is 1. :I-
5. The composition according to any one of the preceding claims, wherein the composition contains 1 part by weight of a solvent, 1 to 3 parts by weight of a reactive size, and 0.5 to 2 parts by weight of a polymer electrolyte. Claims 0
! The composition according to any one of Item 1. 6. A composition according to any of the preceding claims, wherein the reactive size is selected from ketene dimer and anhydrous reactive size. 7. A composition according to any of the preceding claims, wherein the polyelectrolyte is selected from water-soluble cationic, anionic and nonionic polymers. 8. Polyelectrolytes include dialkylaminoalkyl acrylates and methacrylates and their acid salts and their quaternary ammonium salts, noaryldialkylammonium chloride acrylamide, acrylic acid, methacrylic acid, and 2-acrylamido-2-methylpropanesulfone. Polymers formed from at least one monomer selected from acids and selected from polyamines and polyimine polymers riQ
The composition according to any one of item 4. 9. The composition according to any one of the preceding claims, which additionally contains an in-water emulsifier. 10. The composition of any of claims 011 prepared by adding a reactive size to a substantially anhydrous dispersion of a polyelectrolyte in a hydrophobic liquid. If, claims made by forming an aqueous dispersion of a polyelectrolyte in a hydrophobic liquid by reverse phase polymerization, dehydrating the dispersion azeotropically, and then adding a reactive size. 112. A composition according to any of paragraphs 111. 12 Diluted with water to size cellulose fibers 4
dispersing in a sufficient amount of water a concentrate consisting of a substantially anhydrous dispersion of a polyelectrolyte in an organic liquid consisting of a solution of a hydrophobic solvent of a reactive size;
An aqueous composition characterized in that a reactive size having a concentration in water of 0.01 to 5% by weight is obtained. 13. Consisting of a substantially anhydrous dispersion of a polyelectrolyte in an organic liquid suitable for dilution with water for sizing cellulose fibers and consisting of a solution of a reactive sized hydrophobic solvent. Disperse the concentrate in enough water to
A cellulose fiber characterized in that an aqueous cellulose pulp or a cellulose paper made from the pulp is treated with an aqueous composition obtained by obtaining a reactive size having a concentration of 0.01 to 5% by weight in water. How to size.