JP2003517104A - Method of using hydrophobic associative polymer in production of cellulosic fiber composition, and cellulosic fiber composition incorporating hydrophobic associative polymer - Google Patents

Abstract

  (57) [Summary] A water-soluble copolymer produced from a monomer comprising a hydrophobic ethylenically unsaturated monomer and one or more of a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer and an anionic ethylenically unsaturated monomer. Papermaking method and composition using a hydrophobic associative polymer as a dehydration accelerator.

Description

Detailed Description of the Invention

[0001] cross-reference 1 of the background related application of the invention. FIELD OF THE INVENTION The present invention relates to the use of hydrophobically modified water-soluble polymers, hereinafter also referred to as hydrophobic associative polymers or HAPs, in the manufacture of cellulosic fiber compositions. The invention further relates to cellulosic fiber compositions incorporating HAP, such as paper and paperboard.

2. DESCRIPTION OF BACKGROUND AND OTHER INFORMATION The production of cellulosic fibrous sheets-particularly paper and paperboard-has the following steps: a step of producing an aqueous slurry of cellulosic fibers which may also contain inorganic mineral extenders or pigments; Depositing on a moving papermaking wire or fabric; and forming a sheet from the solid components of the slurry by draining.

Following the above steps, the sheet is squeezed, dried and further water removed. Organic and inorganic chemicals are often added prior to the sheet forming process to make the papermaking process cheaper or faster, or to impart specific properties to the final paper product.

The paper industry is constantly striving to improve the quality of paper, increase productivity and reduce manufacturing costs. To improve the drainage / dewatering and solids retention of the process, chemicals are often added to the fiber slurry before it reaches the papermaking wire or fabric; these chemicals are called dehydration promoters / retention aids. .

With respect to improving drainage / dewatering, drainage or dewatering of fiber slurries on papermaking wires or fabrics is often a rate limiting step to obtain faster process speeds.
(limiting step). Improved dewatering results in drier sheets in the press and dryer sections, reducing steam consumption. Furthermore, this is also a step in the papermaking process that determines many sheet end properties.

With respect to solids retention, papermaking retention aids are used to increase the yield of fine furnish solids in the web during the turbulent flow process of dewatering, forming a paper web. Without sufficient yield of fines solids, fines furnish solids are either lost as effluent from the process or accumulated at high levels in the recirculating white water loop, resulting in fouling deposits, May damage the drainage of the paper machine. In addition, insufficient retention of fine solids adds to the cost of the papermaker by the loss of additives intended to be adsorbed on the fiber to impart paper opacity, strength or sizing properties, respectively.

High molecular weight water-soluble polymers having either a cationic or anionic charge have traditionally been used as retention and dehydration promoters. Recent developments of inorganic microparticles, known as retention and dehydration promoters in combination with high molecular weight water soluble polymers, have demonstrated superior retention and dehydration efficiency over conventional high molecular weight water soluble polymers. U.S. Pat. Nos. 4,294,885 and 4,388,150 teach the combined use of starch polymers and colloidal silica. US Pat. No. 4,753
No. 710 teaches that a pulp furnish is agglomerated with a high molecular weight cationic flocculant, shear is induced in the agglomerated furnish, and then bentonite clay is introduced into the furnish. US Pat. Nos. 5,274,055 and 5,167,766 disclose the use of chemically crosslinked organic particulates or micropolymers as retention and dehydration promoters in the papermaking process.

Hydrophobically modified water-soluble polymers, also referred to hereinbelow as hydrophobic associative polymers or HAPs, are known to those skilled in the art, for example Encyclope.
dia of Polymer Science and Engineeri
ng, 2nd edition, 17, 772-779. U.S. Pat. No. 4,432,8
No. 81 and No. 4,861,499 and as thickeners for paint formulations, such as drilling mud formulations, fracturing fluids, liquid flow modifiers, lubricants, hydraulic fluids and lubricants. Discloses the use of these polymers for use in oil recovery processes. These patents do not teach or suggest the use of polymers in cellulosic compositions such as, for example, paper, or in methods of making these cellulosic compositions.

US Pat. No. 4,305,860 discloses the preparation of stable, pumpable, solvent-free polyampholyte lattices (colloidal dispersions of solid polymers in water). This polyampholyte lattice is characterized by their colloidal nature, their high solids content and low bulk viscosity coefficient. This lattice comprises about 10-30 mol% of at least one cationic monomer, 5-30 mol% of at least one anionic monomer, and 15-35%.
Mol% of at least one hydrophobic monomer and 5-70 mol% of at least 1
It is prepared by polymerizing a class of non-ionic hydrophilic monomers in the presence of water, a free-radical initiator and optionally a chelating agent at a total monomer percentage of 100 mol%. The lattice is taught to be particularly useful as a pigment retention and dewatering accelerator in the manufacture of paper, which is used to remove pulp from pulp when it is in a headbox, beater, hydropulper or stock chest. Can be added to. The high hydrophobic group content (> 15 mol%) renders the disclosed polymer insoluble in aqueous solution, which clearly distinguishes it from the HAP polymers disclosed in this invention.

EP 0896966A1 discloses the preparation of associative polymers by the inverse emulsion method using pendant acrylate hydrophobic chains extended by polyoxyethylene groups. The associative acrylic polymer comprises at least one monomer 95-9 selected from neutral ethylene, anionic or cationic monomers.
9.95 mol%, 0.05-5 mol% of at least one kind of acrylic monomer containing radical 2,4,6-triphenoethylbenzene, and at least one kind of polyunsaturated monomer 0-0.2 mol% Including and The associative polymer is 0.5 to
It is preferable to contain 5 mol% of polyoxyethylene 2,4,6-triphenoethylbenzene methacrylate. These polymers can be used in various areas such as paints, glues and adhesives, construction, textile fibers and papers. This composition is claimed for use as a thickener, flocculant and / or charge retention agent; no data or other details are given regarding this use.

SUMMARY OF THE INVENTION The present invention relates to cellulosic fiber compositions, and in particular cellulosic sheets such as, for example, paper or paperboard. The invention also relates to a method of making the composition.

The present invention relates to a method for producing a cellulosic fiber composition that includes adding HAP to a cellulosic pulp slurry, and to a cellulosic fiber composition that includes an aqueous slurry of cellulosic pulp and HAP. HAP is preferably a copolymer containing hydrophobic groups capable of forming a physical network structure through hydrophobic association, the nonionic ethylenically unsaturated monomer, the cationic ethylenically unsaturated monomer or the anionic ethylenically unsaturated monomer. It has at least one monomer selected from the group consisting of saturated monomers.

HAPs are highly associative and aqueous solutions, as evidenced by lower tan δ values than similar polymers without hydrophobic modification, as measured by viscoelastic characterization of 0.5% solutions. Form a network structure in. The addition of HAP to pulp furnishes provides significant improvements in retention and drainage activity while maintaining satisfactory sheet formation, which is a unique property that conventional flocculants could not achieve. Is. HAP is usually water soluble.

HAP is present in an amount of from about 0.001 mol% to about 10 mol%, at least one hydrophobic ethylenically unsaturated monomer, a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer. At least one monomer selected from monomers or anionic ethylenically unsaturated monomers, provided that the at least one hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-triphenoethylbenzene, Can be included.

[0015]   At least one hydrophobic ethylenically unsaturated monomer has the general structure:

[0016]

[Chemical 1]

Can be an ethylenically unsaturated monomer having at least one hydrophobic side group of
In the above formula, R ₁ is hydrogen or methyl; R ₂ when present is —CH ₂ —
, -C (O) -O -, - O-C (O) -, - C (O) -NR 6 -, - NR 6 -C (
O) - or -O- and is; is R ₃ when present _{- (- CH 2 -CHR 1 -O-} ) n -, a C ₁ -C ₂₀ alkyl or C ₁ -C ₂₀ hydroxyalkyl, these In which n is equal to 1-40 and R ₁ is as defined above; R ₄ when present is —NR ₆ — or —N ⁺ (R ₆ ) ₂ —; R ₅ is C ₄ -C ₂₀ alkyl, C ₄ -C _{2 0} cycloalkyl, polynuclear aromatic hydrocarbon group, alkyl alkaryl (alkaryl) having one or more carbon, or one or more haloalkyl having 4 or more carbon A hydrophobic side group selected; R ₆ when present is hydrogen, methyl, CH ₂ ═CR ₁ —CH ₂ —, identical or similar to the hydrophobic side groups R ₅ mentioned above, or mixtures thereof. by and; R ₄ is ^{_{-N + (R 6) 2 -}} Z is present when a is a conjugate base of an acid; however , R ₅ is provided that is not a 2,4,6-phenol ethylbenzene.

The polynuclear aromatic hydrocarbon group can be a naphthyl group. Haloalkyl having 4 or more carbons, preferably be a perfluoroalkyl selected from one or more of _{C 4 F 9 ~C 20 F 41} . Hydrophobic side groups are polyalkyleneoxy groups (wherein alkylene is propylene or higher alkylene and at least 1 per hydrophobic moiety).
Or can be a number alkyleneoxy units are present), or from one or more C ₄ -C _{2 0} alkyl group, or preferably may be selected from one or more C ₈ -C ₂₀ alkyl group.

Preferably, the hydrophobic ethylenically unsaturated monomer shown in Formula 1 is one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts, N-alkylethylenically unsaturated amides, α- Olefin, vinyl ester, vinyl ether, N
It may be selected from vinylamide, alkylstyrene, alkylpolyethylene glycol acrylate, alkylpolyethylene glycol methacrylate, or N-alkylethylenically unsaturated cationic monomers. Ethylenically unsaturated carboxylic acids preferably from C ₁₀ -C ₂₀ alkyl esters of acrylic and methacrylic acid, may more preferably be selected from dodecyl acrylate or dodecyl methacrylate. The ethylenically unsaturated amide may preferably be selected from N-octadecyl acrylamide, N-octadecyl methacrylamide or N, N-dioctyl acrylamide. The α-olefin may preferably be selected from 1-octene, 1-decene, 1-dodecene or 1-hexadecene. The vinyl ester may preferably be vinyl laurate or vinyl stearate. The vinyl alkyl ether may preferably be dodecyl vinyl ether or hexadecyl vinyl ether. The N-vinyl amide is preferably N-vinyl lauamide.
ramide) or N-vinyl stearamide. The alkyl styrene may preferably be t-butyl styrene. The alkyl polyethylene glycol acrylate, alkyl polyethylene glycol methacrylate may preferably be selected from lauryl polyethoxy (23) methacrylate. N
-Alkylethylenically unsaturated cationic monomers are preferably methyldiallylamine, N, N-dimethylaminoalkyl acrylate, N, N-dimethylaminoalkyl methacrylate, and N, N-dialkylaminoalkylacrylamide and N, N-dialkylamino. may be selected from each of C ₁₀ -C ₂₀ alkyl halide quaternary salts of alkyl methacrylamide.

At least one nonionic ethylenically unsaturated monomer is acrylamide, methacrylamide, N-alkylacrylamide, N, N-dialkylacrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N
It can be one or more of: vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate or N-vinylpyrrolidone. The N-alkyl acrylamide is preferably N-methyl acrylamide and the N, N-dialkyl acrylamide is preferably N, N-dimethyl acrylamide. The at least one nonionic ethylenically unsaturated monomer is preferably one or more of acrylamide, methacrylamide or N-methylacrylamide, more preferably acrylamide.

At least one anionic ethylenically unsaturated monomer is acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl sulfonic acid, styrene sulfonic acid, maleic acid. It may be one or more of an acid or a salt thereof, preferably one or more of acrylic acid, methacrylic acid or a salt thereof, more preferably one or more of a sodium or ammonium salt of acrylic acid.

At least one type of cationic ethylenically unsaturated monomer is diallylamine, acrylate of dialkylaminoalkyl compound, methacrylate of dialkylaminoalkyl compound, acrylamide of dialkylaminoalkyl compound,
Methacrylamides of dialkylaminoalkyl compounds, N-vinylamine hydrolysis products of N-vinylformamide and their salts and quaternaries
Can be selected from one or more of The quaternary salt of diallylamine may preferably be diallyldimethylammonium chloride. The dialkylaminoalkylacrylamide and the alkylaminoalkylmethacrylamide may preferably be N, N-dimethylaminopropylacrylamide and the acid or quaternary salt thereof is preferably N, N, N-trimethylaminopropylacrylamide chloride. be able to. The dialkylaminoalkyl acrylate and dialkylaminoalkyl methacrylate may preferably be N, N-dimethylaminoethyl acrylate and the acid or quaternary salt thereof is preferably N, N, N-trimethylaminoethyl acrylate chloride. You can The at least one cationic ethylenically unsaturated monomer further has the general formula:

[0023]

[Chemical 2]

Wherein R ₁ is hydrogen or methyl, R ₂ , R ₃ and R ₄ are hydrogen, C ₁ -C ₃ alkyl or hydroxyethyl, R ₂ and R ₃ , or R ₂ and R ₄ can together form a cyclic ring containing one or more heteroatoms, Z is a conjugate base of an acid, X is oxygen or NR ₁ , where R ₁ is as defined above. As defined,
And A is a C ₁ -C ₁₂ alkylene group]; or

[0025]

[Chemical 3]

Wherein R ₅ and R ₆ are hydrogen or methyl, R ₇ and R ₈ are hydrogen, C ₁ -C ₃ alkyl or hydroxyethyl, and Z is as defined above. The indicated compound; or

[0027]

[Chemical 4]

N-vinyl represented by a repeating unit of the formula: wherein R ₁ , R ₂ and R ₃ are each H or C ₁ -C ₃ alkyl and Z is as defined above. It can also be selected from one or more of formamide and related hydrolysates.

The cationic ethylenically unsaturated monomer whose description of the hydrophobic ethylenically unsaturated monomer is shown in Formulas 2 to 6 [in this case, for example, R ₂ of Formulas _{2, 4 to 5} and R ₇ of Formula 3 is Substituted by the pendant hydrophobic moiety R ₅ of Formula 1].

Dynamic vibrational frequency sweep in which HAP according to the invention (0.5% aqueous solution of HAP) at 0.0068 Hz is smaller than a similar polymer in the absence of hydrophobic ethylenically unsaturated monomers, most preferably smaller than 1. (dynamic oscillation frequen
cy sweep) tan δ value. At least one hydrophobic ethylenically unsaturated monomer group is present in an amount of about 0.01 mol% to about 10 mol%, more preferably about 0.1 mol% to about 5.0 mol%. Is also preferable.

The HAP used in the present invention can be an anionic, nonionic, cationic or amphoteric electrolyte copolymer, preferably an anionic copolymer. The anionic copolymer can include at least one hydrophobic ethylenically unsaturated monomer and at least one anionic ethylenically unsaturated monomer, and further includes at least one nonionic ethylenically unsaturated monomer. be able to.

The anionic copolymer comprises about 0.001 mol% to about 10 mol% of at least one hydrophobic ethylenically unsaturated monomer, about 1 mol% to about 99.999 mol% of at least one anionic ethylene. Unsaturated monomers, and about 1 mol% to about 9
9.999 mol% of at least one nonionic ethylenically unsaturated monomer can be included; preferably about 0.01 mol% to about 5 mol% of at least one.
Hydrophobic ethylenically unsaturated monomers, about 10 mol% to about 90 mol% of at least one anionic ethylenically unsaturated monomer, and about 10 mol% to about 90 mol%
Mol% of at least one nonionic ethylenically unsaturated monomer may be included; more preferably from about 0.1 mol% to about 2.0 mol% of at least one hydrophobic ethylenically unsaturated monomer. , About 30 mol% to about 70 mol% of at least one anionic ethylenically unsaturated monomer, and about 50 mol% to about 70 mol% of at least one nonionic ethylenically unsaturated monomer. You can

The cellulosic pulp slurries of the present invention containing HAP may further comprise, as desired by the skilled operator, for example at least one flocculant, at least one starch, at least one inorganic or organic coagulant, Alternatively, other ingredients such as at least one filler may be included.

[0034]   The invention also includes a cellulosic sheet produced by the method of the invention.
It The cellulosic sheet may include paper and paperboard incorporating HAP.   The present invention also includes adding HAP to the cellulosic pulp slurry.
A method for producing a cellulosic fiber composition, which comprises water of cellulosic pulp and HAP
Of a cellulosic fiber composition comprising a neutral slurry, wherein the HAP is about 0.001.
C of acrylic acid and methacrylic acid present in an amount of from about 10 mol% to about 10 mol%_Ten~ C ₂₀ At least one hydrophobic ethyl ester selected from one or more of alkyl esters
Unsaturated monomers and (a) about 1 mol% to about 99.999 mol% of acrylic.
Amide, methacrylamide, N-alkyl acrylamide, N, N-dialkyl
Acrylamide, methyl acrylate, methyl methacrylate, acrylonitri
, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate
Or at least one selected from one or more of N-vinylpyrrolidone
Nonionic ethylenically unsaturated monomer; (b) about 1 mol% to about 99.999 mol.
%, Acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane
Sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl
From one or more of sulfonic acid, styrenesulfonic acid, maleic acid or their salts
At least one anionic ethylenically unsaturated monomer selected; or (c
) About 1 mol% to about 99.999 mol% of diallylamine, dialkylamino acid
Acrylate of alkyl compound, Methacrylate of dialkylaminoalkyl compound
Acrylamide of dialkylaminoalkyl compounds, dialkylaminoalkyl compounds
Addition of methacrylamide as a kill compound and N-vinylamine as an N-vinylformamide
At least selected from water degradation products and one or more of their salts and quaternary salts
At least one selected from one kind of cationic ethylenically unsaturated monomer;
And a monomer of the same class.

The HAP is preferably at least one selected from one or more C ₁₀ -C ₂₀ alkyl esters of acrylic and methacrylic acid present in an amount of about 0.001 mol% to about 10 mol%. Hydrophobic ethylenically unsaturated monomer, (a) about 1 mol%
To about 99.999 mol% of at least one nonionic ethylenically unsaturated monomer selected from one or more of acrylamide, methacrylamide, or N-alkylacrylamide; (b) about 1 mol% to about 99. 999 mol% of at least one anionic ethylenically unsaturated monomer selected from one or more of acrylic acid, methacrylic acid or salts thereof; or (c) from about 1 mol% to about 99.999.
Mol% of at least one cationic ethylenically unsaturated monomer selected from one or more of N, N-dialkylaminoalkyl acrylates, N, N-dialkylaminoalkylmethacrylates, acids or salts thereof; And at least one monomer. Preferably, the at least one hydrophobic ethylenically unsaturated monomer may be selected from one or more of dodecyl acrylate or dodecyl methacrylate and the nonionic ethylenically unsaturated monomer may be acrylamide. The at least one anionic ethylenically unsaturated monomer may be selected from one or more of sodium or ammonium salts of acrylic acid, the cationic ethylenically unsaturated monomer being N, N-dimethylaminoethyl acrylate. Can be a quaternary salt of methyl chloride.

The above-mentioned pulp slurry containing HAP is added to the above-mentioned pulp slurry, if desired by a skilled worker, such as at least one flocculant, at least one starch, at least one coagulant or at least one filler. , Additional ingredients can be added.

The invention also relates to a method of making a cellulosic fiber composition comprising adding anionic HAP to a cellulosic pulp slurry, the cellulosic comprising an aqueous slurry of cellulosic pulp and anionic HAP. A fiber composition, wherein said anionic HAP is preferably at least one hydrophobic ethylenically unsaturated monomer selected from one or more of lauryl acrylate or lauryl methacrylate, at least one non-ionic which is acrylamide The present invention relates to the above cellulose-based fiber composition containing an ethylenically unsaturated monomer and at least one anionic ethylenically unsaturated monomer which is acrylic acid. To the above pulp slurry containing HAP, at the option of a skilled worker, for example at least 1
Flocculants of the type, at least one starch, at least one inorganic or organic coagulant or at least one filler can be added. The invention also relates to a cellulosic sheet produced from the above composition by the above method. The cellulosic sheet may include paper and paperboard incorporating HAP.

The cellulosic fiber composition of the present invention comprises HAP and its viscoelastic properties, as described above. Preferred cellulosic fiber compositions include paper. DESCRIPTION OF THE INVENTION 1. Definitions As used herein, the term "HAP" means the hydrophobic associative polymer of the present invention.

As used herein, the term “hydrocarbon” refers to “aliphatic,” “cycloaliphatic (cyclo).
The terms “aliphatic” and “alicyclic” refer to “alkyl”, “alkenyl”, “alkynyl” and “cycloalkyl” unless otherwise specified. The term "aromatic" is understood to include
This is also understood to include "aryl", "aralkyl" and "alkaryl" unless otherwise specified.

Hydrocarbon radicals are understood to include both unsubstituted and substituted hydrocarbon radicals, the latter meaning hydrocarbon moieties having additional substituents in addition to carbon and hydrogen. Similarly, an aliphatic group, an alicyclic group and an aromatic group are both an unsubstituted aliphatic group, an alicyclic group and an aromatic group-substituted aliphatic group, an alicyclic group and an aromatic group. The latter is understood as embracing, the latter meaning aliphatic, cycloaliphatic and aromatic radicals having additional substituents in addition to carbon and hydrogen.

Further, as referred to herein, a copolymer includes a polymer consisting of two different monomer units, or consisting essentially of two different monomer units or consisting essentially of two different monomer units. Understood as what to do.
Copolymers further include polymers that incorporate three or more different monomer units,
For example, it is understood to include terpolymers.

2. The Method of the Invention The present invention comprises a method for making cellulosic fiber compositions-in particular cellulosic fiber webs, more particularly cellulosic fiber sheets, and even more particularly paper and paperboard. This process involves the addition of at least one HA to a suitable furnish-for example cellulosic fiber pulp or cellulosic material, in particular cellulosic wood fiber or stock.
Including adding P.

Preferably, this polymer is added to a slurry containing an aqueous suspension of furnish. Furthermore, as a matter of preference, cellulosic webs-specifically sheets, more specifically paper or paperboard-are formed from this slurry.

The method of the present invention comprises providing a furnish consisting of cellulosic fibers with or without additional mineral filler suspended in water, and depositing the furnish on a papermaking wire or fabric. And a step of dehydrating the slurry to form a sheet from solid components, the method comprising at least one HAP
Are added at one or more points during this method. Preferably, this polymer is introduced into the fiber slurry prior to the series of dewatering steps.

[0045] HAP serves to increase particulate retention and / or improve fiber dehydration. This polymer is used as a filler when used and cellulosic fiber fine powder (cellu
It is particularly effective for improving yields both with losic fiber fines), and these fines are generated from the fibers during the process of the invention. It is hypothesized that HAPs form physical network structures through hydrophobic groups in aqueous solution, as demonstrated by their viscoelastic behavior. Since the three-dimensional structure of HAP is less likely to be absorbed on the surface of the particles, better crosslinks are formed between the particles, which leads to better retention and drainage activity.

Rheology: Principles, discussed herein.
Measurements and Applications, C.I. W. Ma
cosko, Wiley, New York, NY. ) Means a time-dependent reaction to deformation, i.e. for a short time the material is hard and glassy, but after a longer time it becomes rubbery or viscous. A common method of measuring this phenomenon is by stress relaxation, in which a momentary strain is applied to the material and the resulting stress relaxation recorded over time. Pure viscous materials exhibit zero stress once the strain is constant, whereas elastic solids do not exhibit stress relaxation. Viscoelastic materials exhibit stress relaxation between these two extremes; thus exhibiting combined elastic and viscous reactions, viscoelasticity.

Dynamic vibrational characterization of HAP materials to characterize viscoelastic properties,
In this case, the sample deforms like a sinusoid. The test is performed by a stress sweep that gives a constant frequency while increasing the stress (amplitude) or, conversely, by a frequency sweep that gives a constant stress while changing the frequency. The measured strain of the elastic component of the material is in phase with the applied stress, while the viscous component of the material is 90 ° out of phase. Tan δ is the ratio of the viscous component to the elastic component of a substance and characterizes the substance as exhibiting greater viscous or greater elastic properties. Thus, substances with a tan δ greater than 1 at a particular frequency exhibit predominantly viscous behavior and substances with tan δ less than 1 exhibit predominantly elastic behavior.

HAP can be used as the sole retention / dehydration promoter. Alternatively, the polymer can be used in combination with conventional papermaking flocculants-for example, at least one flocculant, such as a high molecular weight cationic, anionic or nonionic flocculant.

The method of the present invention can be carried out using a papermaking apparatus or system as described herein. It is emphasized that the method of the present invention is not limited to this particular apparatus or system, which is only given as a typical example which can be used.

Handbook for Pulp and Paper Technology
origins (GA Smook, TAPPI Press, Atlanta)
, GA), the pulp components are usually metered into the stock chest of the apparatus at a consistency level of 2.8-3.2% by weight. Equipment stock chests usually contain the final mixture, but in some cases low concentrations of additives can be added just before the headbox. The equipment chest stock is usually circulated in a constant head tank (stuff box) which feeds the stock through a control valve (basis weight valve) to the inflow device of the paper machine.

At the heart of this inflow device is a fan pump, which serves to mix the white water with the stock and deliver this blend to the headbox. Here, the stock is mixed with circulating white water from the wire pit and the consistency is reduced to the level required for the headbox (usually about 0.5% to about 1.0% by weight). .

White water, which typically has a solids concentration of about 0.1 wt% or less, is a liquid that results from the dehydration of the pulp slurry on the papermaking wire and flows into the wire pit. After fan pumping, the pulp slurry typically passes through a centrifugal cleaner and then through a pressure screen to the headbox.

Centrifugal cleaners remove debris such as binding fibers and debris, and pressure screens remove coarse impurities and loosen fibers. A headbox serves to dispense stock onto the endless moving papermaking wire or fabric; it can be a Fourdriner wire or a two wire former.

On a moving papermaking wire or fabric, the slurry is dewatered; the resulting liquid is white water, as described above, which drains from the slurry into the wire pits. This drainage causes the slurry to form into a sheet as it is carried to the press section over the wire or fabric.

As it passes through the press section, the sheet is squeezed between the rollers and thereby undergoes further dewatering. From the press section, the sheet then enters a dryer section, where it is further dried. From the drying section, the sheet subsequently passes through a calendar stack. In the calender stack, the sheets are squeezed between metal rollers to reduce their thickness and smooth the surface.

From this calendar stack, the sheets are wound on reels. The resulting paper may further be surface coated with a sizing or coating material.

The materials used in the method of the present invention include cellulosic pulp and at least one HA.
Includes P. It is also possible to use one or more additional substances, including at least one starch, at least one filler, at least one inorganic or organic coagulant and at least one conventional flocculant.

When a flocculant is used, the flocculant and HAP are simultaneously or at different points in the process, without intermittent shear points between their respective additions, or at different points in the process. , Can be added including intermittent shear points between their respective additions. Preferably, the flocculant and HAP are continuously added during the method of the invention,
That is, they are introduced at different points or time points. Flocculants can be added before or after HAP.

Shear can be added to the stock between the addition of the flocculant and the addition of HAP when added continuously. The devices or systems described herein provide high shear in fan pumps, centrifugal cleaners and presses.

Consistent with the above, it is preferred to equip the apparatus or system with suitable feed points for adding said substances such as flocculants and HAP. In this regard, a flocculant and / or
Or HAP at the feed point before the fan pump (eg, between the basis weight valve and the fan pump) and / or at the feed point before the centrifugal cleaner (eg, between the fan pump and centrifugal cleaner), and / or It can be added at the feed point before the pressure screen (eg between the centrifugal cleaner and the pressure screen).

With respect to other material feed points, starch, fillers or coagulants can be added at many points during the process, as known to those skilled in the art. The order of introducing the different substances during the method of the invention is not limited to the order given above and is generally based on the practicality and performance for each particular application.

3. Materials used a. Cellulosic Pulp Cellulosic fibrous pulp suitable for the process of the present invention includes conventional papermaking stocks, such as traditional chemical pulp. For example, bleached and unbleached sulfuric and sulfite pulps, mechanical pulps such as groundwood pulp, thermomechanical pulps, chemical-thermomechanical pulps, such as used corrugated containers, newsprint, office waste, magazine paper and other non-ink. Drainage waste, recycled pulp such as deinking waste, and mixtures thereof can be used.

B. Starch Starch adds strength properties, especially dry strength, to the cellulosic products obtained from the process of the present invention. Specifically, starch enhances the interfiber bonding in the stock. Starch also affects drainage properties.

Starches that can be used in the method of the present invention include cationic starch and amphoteric electrolyte starch. Suitable starches include those derived from corn, potato, wheat, rice, tapioca and the like.

Cationicity is imparted by the introduction of a cationic group, and further introduction of an anionic group imparts an ampholytic property. For example, cationic starch can be obtained by reacting starch with a tertiary amine or quaternary ammonium compound, such as dimethylaminoethanol or 3-chloro-2-hydroxypropyltrimethylammonium chloride. The cationic starch preferably has a degree of cation substitution (DS of about 0.01 to about 1.0, more preferably about 0.01 to about 0.10, and still more preferably about 0.02 to 0.04). ) -That is, the average number of substituted cation groups instead of hydroxyl groups per anhydroglucose unit.

Amphoteric electrolyte starches can be produced by the introduction of a variety of different anionic groups. A preferred ampholyte starch is an ampholyte starch having a net cationic character. Examples include phosphate or phosphate etherifying reagents.
Anionic phosphate groups can be introduced into the cationic starch by reaction with a reagent). When the cationic starch starting material is starch diethylaminoethyl ether, the amount of phosphate reagent used for this modification is that which yields about 0.07 to 0.18 moles of anionic groups per mole of cationic groups.

Other amphoteric electrolytes that can be used are those prepared by the introduction of sulfosuccinate groups into cationic starch. This modification is accomplished by adding a maleic acid half ester group to the cationic starch and reacting the maleate double bond with sodium bisulfite.

As a further additional example, the cationic starch can be etherified with 3-chloro-2-sulfopropionic acid and the carboxyl group in the starch by reaction with sodium chloroacetate or by hypochlorite oxidation. Can be introduced to
Propane sultone can be used to treat cationic starch to provide amphoteric properties.

Other useful ampholyte starches can be obtained by xanthogenic oxidation of diethylaminoethyl- and 2- (hydroxypropyl) trimethylammonium starch ethers.

Furthermore, the modification is extended by the introduction of nonionic or hydroxyalkyl groups from the treatment with ethylene oxide or propylene oxide.
)be able to.

Starch is preferably used in the process of the present invention at a rate of from about 1 pound per ton to about 100 pounds per ton of cellulosic pulp, based on the dry weight of the pulp. The starch concentration is more preferably about 2.5 pounds per ton of pulp to about 50 pounds per ton, and even more preferably about 5 pounds per ton of pulp to about 25 pounds per ton.

C. Fillers Fillers impart optical properties to cellulosic products. The filler imparts opacity and brightness to the finished sheet and improves its printing properties. Suitable fillers include calcium carbonate (both naturally occurring heavy carbonate and synthetically produced precipitated carbonate), titanium oxide, talc, clay and gypsum.
The amount of filler used can be an amount that yields a cellulosic product of up to about 50% by weight filler, based on the dry weight of the pulp.

D. Coagulants In addition to coagulants and HAPs, coagulants are used to enhance retention and drainage. The coagulant used may be either inorganic or organic.

The most common inorganic coagulants are alumina species. Suitable examples are technical grade aluminum sulphate (alum), polyaluminum chloride
, Polyhydroxy aluminum chloride, polyhydroxy aluminum sulfate, sodium aluminate and the like.

The organic coagulant is typically a synthetic polymeric material. Suitable examples include polyamine, poly (amidoamine), polyDADMAC, polyethyleneimine, N-vinylformamide polymer and copolymer hydrolysates and quaternized hydrolysates.
ized hydrolyzate) and the like.

In the method of the present invention, the coagulant is preferably used at a rate of from about 0.01 pounds per ton of cellulosic pulp to about 50 pounds per ton based on the dry weight of the pulp. The coagulant concentration is more preferably from about 0.05 pounds per ton of pulp to about 20 pounds per ton, and even more preferably from about 0.1 pounds per ton of pulp to about 10 pounds per ton.

E. Flocculants The ionic flocculants customary in the papermaking field are suitable as flocculants for the process according to the invention. Cationic, anionic, nonionic and amphoteric electrolyte flocculant-
In particular, cationic, anionic, nonionic and amphoteric electrolyte polymers can be used.

Polymers suitable as flocculants for the method of the present invention include homopolymers of nonionic ethylenically unsaturated monomers. As well as copolymers of monomers containing at least one nonionic ethylenically unsaturated monomer and at least one cationic ethylenically unsaturated monomer and / or at least one anionic ethylenically unsaturated monomer can be used In addition, copolymers of monomers containing two or more nonionic ethylenically unsaturated monomers can also be used.

The nonionic, cationic and anionic ethylenically unsaturated monomers which can be used are those mentioned herein above as being suitable for at least one HAP according to the invention.

Suitable nonionic ethylenically unsaturated monomers are acrylamide, methacrylamide, N-alkylacrylamides such as N-methylacrylamide,
For example, N, N-dialkylacrylamide such as N, N-dimethylacrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate, N-vinylpyrrolidone such as hydroxyethyl acrylate, Included are hydroxyalkyl methacrylates such as hydroxyethyl methacrylate or hydroxypropyl acrylate or hydroxypropyl methacrylate, hydroxyalkyl methacrylates, mixtures of any of the above, and the like. Of the above, acrylamide, methacrylamide and N-alkyl acrylamide are preferred, and acrylamide is particularly preferred.

Cationic ethylenically unsaturated monomers that can be used include diallylamine, acrylates of dialkylaminoalkyl compounds, methacrylates of dialkylaminoalkyl compounds, acrylamides of dialkylaminoalkyl compounds, methacrylamides of dialkylaminoalkyl compounds, N- Included are N-vinylamine hydrolysis products of vinylformamide, and salts and quaternary salts thereof.
N, N-Dialkylaminoalkyl acrylates and methacrylates, and their acid and quaternary salts are preferred, with the methyl chloride quaternary salt of N, N-dimethylaminoethyl acrylate being particularly preferred. Further regarding the cationic monomer,
A suitable example is the following general formula:

[0082]

[Chemical 5]

[Wherein R ₁ is hydrogen or methyl, R ₂ is hydrogen or C ₁ -C ₄ lower alkyl, R ₃ and / or R ₄ is hydrogen, C ₁ -C ₁₂ alkyl, aryl or Hydroxyethyl, R ₂ and R ₃ , or R ₂ and R ₄ can be taken together to form a cyclic ring containing one or more heteroatoms, Z is a conjugate base of the acid, X is oxygen or NR ₁ , where R ₁ is as defined above, A is a C ₁ -C ₁₂ alkylene group]; or

[0084]

[Chemical 6]

Wherein R ₅ and R ₆ are hydrogen or methyl, R ₇ is hydrogen or C ₁ -C ₁₂ alkyl, R ₈ is hydrogen, C ₁ -C ₁₂ alkyl, benzyl or hydroxyethyl. Yes,
Z is as defined above], or

[0086]

[Chemical 7]

N-vinylformamide and related hydrolysates represented by repeating units of [R ₁ , R ₂ and R ₃ are each H or C ₁ -C ₃ alkyl and Z is as defined above] Includes.

Suitable anionic ethylenically unsaturated monomers include acrylic acid, methacrylic acid and their salts; 2-acrylamido-2-methyl-propane sulfonate; sulfoethyl acrylate, sulfoethyl methacrylate; vinyl sulfonic acid; styrene sulfonic acid. And maleic acid and other dibasic acids and their salts. Acrylic acid, methacrylic acid and salts thereof are preferred, and sodium and ammonium salts of acrylic acid are particularly preferred.

These monomers can be polymerized into polymers by a number of initiator systems, including free radical (thermal and redox methods), cationic and anionic synthetic methods. Flocculant polymers can be made by many commercial means, including bulk polymerization, solution polymerization, dispersion polymerization and emulsion / inverse emulsion polymerization.
The resulting polymer can be provided for end use in many physical forms, including aqueous solutions, dry solid powders, dispersions and emulsion forms.

Flocculants can be nonionic, cationic, anionic or ampholytes. The nonionic polymer flocculant contains one or more of the above nonionic monomers. Cationic polymer flocculants contain one or more of the above cationic monomers. The level of total cationic monomer, based on molarity, ranges from about 1 to about 99%, preferably about 2 to about 50%, and even more preferably about 5 to about 40 mole% cationic monomer, with the balance being The monomer is any of the above nonionic monomers.

Anionic polymer flocculants contain one or more of the above anionic monomers. The level of total anionic monomer, based on molarity, ranges from about 1 to about 99%, preferably from about 2 to about 50%, and even more preferably from about 5 to about 40 mole% cationic monomer with the balance remaining. The monomer is any of the above nonionic monomers.

Amphoteric electrolyte polymer flocculants contain a combination of one or more of the aforementioned cationic and anionic monomers. Any combination of cationic and anionic monomers (single or multiple) is preferred, provided that at least one cationic monomer and one anionic monomer are used. The polymer can contain excess cationic monomer, excess anionic monomer, or equal amounts of both cationic and anionic monomers. The level of total ionic monomer, which is the total amount of both cationic and anionic monomers, based on molarity, is from about 1 to about 99%, preferably from about 2 to about 80%, and even more preferably from about 5%.
It is in the range of about 40 mol% cationic monomer with the remaining monomers being any of the above nonionic monomers.

A flocculant may be used in the process of the present invention in an amount of about 0.01 pounds per ton of cellulosic pulp to about 10 pounds per ton, based on the weight of the active polymer and the dry weight of the pulp.
It is preferably used at a rate of up to pounds. The flocculant concentration is more preferably about 0.05 pounds per ton of pulp to about 5 pounds per ton, and even more preferably about 0.1 pounds per ton of pulp to about 1 pound per ton.

F. Hydrophobic Associative Polymer (HAP) The present invention comprises at least one HAP. Suitable HAPs of the present invention are copolymers containing at least one hydrophobic ethylenically unsaturated monomer, provided that the at least one hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-triphenoethylbenzene. Includes. These copolymers further comprise at least one nonionic ethylenically unsaturated monomer, and / or at least one.
Includes types of cationic ethylenically unsaturated monomers, and / or at least one type of anionic ethylenically unsaturated monomer.

The hydrophobic ethylenically unsaturated monomer includes a water-insoluble hydrophobic ethylenically unsaturated monomer. Further with respect to hydrophobic ethylenically unsaturated monomers, these include ethylenically unsaturated monomers having hydrophobic groups, especially water-insoluble monomers and monomer surfactants. Hydrophobic groups include, for example: aliphatic hydrocarbon groups having at least 4 carbons such as C _{4 to} C ₂₀ alkyl and cycloalkyl; polynuclear aromatic hydrocarbon groups such as benzyl, substituted benzyl and naphthyl,
However, the substituted benzyl group is not 2,4,6-triphenoethylbenzene; alkaryl whose alkyl has one or more carbons; haloalkyl having four or more carbons, preferably perfluoroalkyl; alkylene is propylene or higher. Alkylene, including hydrophobic organic groups, such as organic groups having a hydrophobicity comparable to any of the polyalkyleneoxy groups in which there is at least one alkyleneoxy unit per hydrophobic moiety. Preferred hydrophobic groups are those having at least 4 carbons or more per hydrocarbon group, such as C _{4 to} C ₂₀ alkyl, or at least 4 carbons per perfluorocarbon group, such as C ₄ F _{9 to} C ₂₀ F _41. It includes a hydrophobic group having the above. C ₄ -C ₂₀ alkyl group is particularly preferred.

Suitable hydrocarbon group-containing ethylenically unsaturated monomers include esters or amides of C ₄ and higher alkyl groups. Particularly suitable esters are dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecyl acrylate,
It includes tetradecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, nonyl-α-phenyl acrylate, nonyl-α-phenyl methacrylate, dodecyl-α-phenyl acrylate and dodecyl-α-phenyl methacrylate.

C ₁₀ -C ₂₀ alkyl esters of acrylic acid and methacrylic acid are preferred. Of these, dodecyl acrylate and dodecyl methacrylate are particularly preferable. In addition, the following hydrocarbon group-containing ethylenically unsaturated monomers can be used: N-alkyl ethylenically unsaturated amides, such as N-octadecyl acrylamide, N-octadecyl methacrylamide, N, N-dioctyl acrylamide and the like. Derivatives of α-olefins such as 1-octene, 1-decene, 1-dodecene and 1-hexadecene; Vinyl esters where the ester has at least 8 carbons such as vinyl laurate and vinyl stearate; Vinyl ethers such as dodecyl. Vinyl ethers and hexadecyl vinyl ethers; N-vinyl amides such as N-vinyl lauramide and N-vinyl stearamide; alkyl styrenes such as t-butyl styrene; alkyl polyethylene glycol acrylates Alkylpolyethylene glycol methacrylate, such as lauryl polyethoxy (23) methacrylate; and N-alkylethylenically unsaturated cationic monomers, such as methyldiallylamine, N, N-dimethylaminoalkyl acrylate, N, N-dimethylaminoalkyl methacrylate and N. , N- dialkylaminoalkyl acrylamide, N, C ₁₀ ~C ₂₀ alkyl halide quaternary salts of N- dialkylaminoalkyl methacrylamide.

Suitable nonionic ethylenically unsaturated monomers are acrylamide; methacrylamide; N-alkylacrylamides, such as N-methylacrylamide; N, N-dialkylacrylamides, such as N, N-dimethylacrylamide. Methyl acrylate; Methyl methacrylate; Acrylonitrile; N
-Vinylmethylacetamide; N-vinylmethylformamide; Vinyl acetate; N
-Vinylpyrrolidone; including any mixture of the above. Of the above, acrylamide, methacrylamide and N-alkylmethacrylamide are preferred, and acrylamide is particularly preferred.

Among the cationic ethylenically unsaturated monomers that can be used are diallylamine, acrylates of dialkylaminoalkyl compounds, methacrylates of dialkylaminoalkyl compounds, acrylamides of dialkylaminoalkyl compounds, methacrylamides of dialkylaminoalkyl compounds, Included are N-vinylamine hydrolysis products of N-vinylformamide and their salts and quaternary salts.
N, N-Dialkylaminoalkyl acrylates and methacrylates, and their acid and quaternary salts are preferred, with the methyl chloride quaternary salt of N, N-dimethylaminoethyl acrylate being particularly preferred.

[0100]   Further suitable examples of cationic monomers include the following general formula:

[0101]

[Chemical 8]

Wherein R ₁ is hydrogen or methyl; R ₂ , R ₃ and R ₄ are hydrogen, C ₁ -C ₃ alkyl or hydroxyethyl; R ₂ and R ₃ , or R ₂ and R ₄ can together form a cyclic ring containing one or more heteroatoms; Z is a conjugated base of an acid; X is oxygen or NR ₁ , where R ₁ is as defined above. As defined;
A is C ₁ -C ₁₂ alkylene group; or

[0103]

[Chemical 9]

Wherein R ₅ and R ₆ are hydrogen or methyl, R ₇ and R ₈ are hydrogen, C ₁ -C ₃ alkyl or hydroxyethyl; Z is as defined above. The indicated monomer; or

[0105]

[Chemical 10]

N-vinylformamide and related hydrolysis products represented by repeat units of [R ₁ , R ₂ and R ₃ are each H or C ₁ -C ₃ alkyl and Z is as defined above] Includes.

Suitable anionic ethylenically unsaturated monomers include acrylic acid, methacrylic acid and their salts; 2-acrylamido-2-methyl-propane sulfonate; sulfoethyl acrylate, sulfoethyl methacrylate; vinyl sulfonic acid; styrene sulfonic acid. And maleic acid and other dibasic acids and their salts. Acrylic acid, methacrylic acid and salts thereof are preferred, and sodium and ammonium salts of acrylic acid are particularly preferred.

As a matter of preference, the hydrophobic ethylenically unsaturated monomers in HAP are
It is within the range that renders the polymer hydrophobically associative-that is, the concentration of hydrophobic monomers is low enough that the polymer is still water soluble or dispersible, yet provide the associativity as described herein. Is enough for. In this regard, the at least one HAP is preferably about 0.001 mol% to about 10 mol% -more preferably about 0.
． 01 mol% to about 5 mol%, and even more preferably about 0.1 mol% to about 2.
0 mol% -containing at least one hydrophobic ethylenically unsaturated monomer.

The HAPs used in the present invention include anionic, nonionic and cationic and ampholyte copolymers. Of these, anionic copolymers are preferred.

The anionic copolymer comprises at least one hydrophobic ethylenically unsaturated monomer and at least one anionic ethylenically unsaturated monomer. Preferably, the anionic copolymer further comprises at least one nonionic ethylenically unsaturated monomer. Consisting of, consisting essentially of, or consisting essentially of at least one hydrophobic ethylenically unsaturated monomer, at least one anionic ethylenically unsaturated monomer and at least one nonionic ethylenically unsaturated monomer. Terpolymers are especially preferred.

For the anionic copolymers, the preferred hydrophobic ethylenically unsaturated monomers are the hydrocarbon esters of α, β-ethylenically unsaturated carboxylic acids and their salts, dodecyl acrylate and dodecyl methacrylate being particularly preferred. Preferred nonionic ethylenically unsaturated monomers are acrylamide and methacrylamide. Preferred anionic ethylenically unsaturated monomers are acrylic acid and methacrylic acid.

The anionic copolymer is preferably about 0.001 mol% to about 10 mol% hydrophobic ethylenically unsaturated monomer, about 1 mol% to about 99.999 mol% nonionic ethylenically unsaturated monomer, And about 1 mol% to about 99.999 mol% of at least one anionic ethylenically unsaturated monomer. More preferably, these are from about 0.01 mol% to about 5 mol% of at least one hydrophobic ethylenically unsaturated monomer, from about 10 mol% to about 90 mol% of at least one nonionic ethylenic unsaturated monomer. Saturated monomer, and from about 10 mol% to about 90 mol% of at least one anionic ethylenically unsaturated monomer. Even more preferably, they are from about 0.1 mol% to about 2.0 mol% of at least one hydrophobic ethylenically unsaturated monomer, from about 50 mol% to about 70 mol% of at least one nonionic. It comprises an ethylenically unsaturated monomer and about 30 mol% to about 70 mol% of at least one anionic ethylenically unsaturated monomer.

These monomers can be polymerized to HAP polymers by a number of initiator systems, including free radical (thermal and redox methods), cationic and anionic synthetic methods. HAP can be produced by many commercial means, including bulk polymerization, solution polymerization, micellar solution polymerization, dispersion polymerization and emulsion / inverse emulsion polymerization. The resulting polymer can be provided for end use in many physical forms, including aqueous solutions, dry solid powders, dispersions and emulsion forms.

HAP is preferably used in the process of the present invention at a rate of from about 0.01 pounds per ton to about 10 pounds per ton of cellulosic pulp, based on the dry weight of the pulp. More preferably, the concentration of HAP is from about 0.05 pounds per ton of pulp to about 5 pounds per ton, and even more preferably from about 0.1 pounds per ton of pulp to about 1 pound per ton.

G. Other Additives The process of the present invention can still further include the customary additives used in their usual proportions for their usual purpose. Suitable examples include sizing agents, promoters, strength improvers, dye fixatives, polymeric coagulants and the like. The paper produced can also be surface-treated with surface sizes or coating substances.

4. Composition of the Invention A factor affecting the HAP concentration in the cellulosic composition of the invention is the proportion of polymer added during the manufacturing process. The cellulosic composition of the present invention, which is preferably a cellulosic sheet, more preferably paperboard or paper, is preferably from about 0.01 to about 10 pounds per ton, based on the dry weight of the composition. Preferably from about 0.05 to about 5 pounds per ton, and even more preferably from about 0.1 wt% to about 1 pound / ton-of HAP.

EXPERIMENTAL PART The invention is illustrated by the following procedures and tests; they are provided by way of illustration and should not be construed as limiting the scope of the invention. Unless otherwise specified, all percentages, parts, etc. are by weight.

1. Preparation of Flocculant HAP of the Invention and Control (a) Solution Polymerization HAP, anionic copolymers II, III and V-VII used in the invention are acrylamide (AM), acrylic acid (AA) and lauryl acrylate (LA).
). The control polymers, anionic copolymers I and IV, are prepared without the hydrophobically modified monomers lauryl acrylate-ie acrylamide and acrylic acid only.

Polymers I-VII are all prepared by solution polymerization. The proportions of the monomers used in each case are shown below.

[0120]

[Table 1]

In the case of Polymers II and III, 2.75 parts of acrylamide, 0.
17 parts (1 mol% of the monomers) lauryl acrylate, 2.25 parts acrylic acid, 1 part nonionic surfactant (Tergitol 15-S-9) and 10
Deoxygenate by sparging with a solution of 0 parts deionized water at room temperature with nitrogen for 45 minutes with stirring. Add 0.5 parts of 2 mg KBrO ₃ solution and add 10 parts of 0
． Inject 03% NaS ₂ O ₅ by syringe pump over 60 minutes.
The copolymer is obtained by precipitating the polymerization solution in acetone, which is dried under vacuum at 50 ° C. overnight.

Polymers V, VI and VII are prepared in the same way except for the proportions of the monomers. For Polymer V, the monomer ratio is 3.4 parts acrylamide, 0.1 parts (0.5 mol% of monomer) lauryl acrylate, and 1.
5 parts acrylic acid. For Polymer VI, the monomer ratio is 3
． 4 parts acrylamide, 0.19 parts (1 mol% of monomer) lauryl acrylate, and 1.5 parts acrylic acid. For Polymer VII, the monomer ratio was 3.4 parts acrylamide, 0.38 parts (2 mol% of the monomer.
) Lauryl acrylate and 1.5 parts acrylic acid.

Polymer I is a Polymer I except that it does not contain lauryl acrylate.
Prepare using the same methods and proportions as for ymer II and III. Pol
ymer IV is prepared in the same manner as polymer I, except that the monomer ratio is 3.5 parts acrylamide and 1.5 parts acrylic acid in Polymer IV.

For each of Polymers I, II and III, the resulting dried product is redissolved in deionized water to give a 0.5% polymer solution for which viscosity characterization is performed.

(B) Dispersion Polymerization A hydrophobic associative polymer is prepared by dispersion polymerization.

[0126]

[Table 2]

2. Viscosity Characterization (a) Solution Polymerization The viscosity of each 0.5% solution is measured by a Brookfield viscometer at 12 rpm and room temperature. The results are shown in Table 3 below. The molecular weights of HAP II and III and unassociated Polymer I are assumed to be similar as they are prepared under substantially the same synthetic conditions. A 20-fold increase in the 0.5% solution viscosities of HAP II and III compared to the Polymer I control sample was obtained from Polymer
Qualitative demonstration of the incorporation of hydrophobic monomers into r II and III. Pol
The extremely high 0.5% solution viscosities of ymer II and III also demonstrate that the HAPs of the invention are strongly associative in aqueous solution.

[0128]

[Table 3]

Further viscosity and rheological characterizations are performed on Samples IV-VII to demonstrate the associative properties of the modified samples relative to the unmodified control. The test is performed on a 0.5% aqueous solution. As shown in Table 3 above, Brook at 12 rpm
A field viscosity measurement is performed on the sample, which is a hydrophobic substance.
There is a marked increase in apparent viscosity with increasing levels. The highest levels of hydrophobic material show a 10-fold increase in Brookfield viscosity due to associative interactions. Additional studies are further performed by a controlled stress rheometer with a cone and slab morphology with a 60 mm diameter cone and a fixed angle of 2 degrees. The apparent viscosity of a 0.5% solids content polymer sample is measured at a constant shear rate of 10 s ^-1 , with a 10-fold increase in viscosity observed by the highest level of hydrophobic material, Brookf.
Similar results to those with the field viscometer are observed, demonstrating strong associative behavior. The stress sweep is performed in 20 log steps at a constant 1 Hz frequency and a stress range of 0.1-10.0 Pa with the instrument in dynamic stress oscillatuon mode. G'storage modulus is given as an equilibrium value in the linear viscoelastic region, which is defined as: G '= (τ ₀ / γ ₀ ) cos δ where τ ₀ is the stress amplitude. Yes, γ ₀ is the maximum strain amplitude (maximum s
train amplitude) and δ is the phase angle shift between the stress and the strain produced.
The G'storage modulus, also called the gel modulus, is considered an indicator of the degree and strength of network structure, as measured by intermolecular / intramolecular hydrophobic association. At equivalent stresses, materials with high G'values distort and deform less, thus exhibiting a stronger gel complex or network structure. These data show a linear relationship between hydrophobe concentration and G'storage modulus, with increasing hydrophobe levels increasing the modulus, with the highest G for the highest level of hydrophobic substitution. 'Indicates elastic modulus. Unmodified Polymer IV shows a storage modulus of 2 Pa, whereas modified Polymer VII containing 2 mol% lauryl acrylate is 25.6 Pa.
Shows the storage elastic modulus of.

Subsequently, a frequency sweep in the dynamic vibration mode was performed by a device in the dynamic vibration mode, with a constant stress of 0.1 Pa and a frequency of 0.0068 Hz to 10 Hz during a linear viscoelastic retention period. In the range, 3 readings per frequency 10 are performed. tan δ is the ratio of loss (viscosity) modulus to storage (elasticity) modulus and is calculated by the formula: tan δ = loss modulus / storage modulus = G ″ / G ′ A material with a high tan δ value is more Greater viscous properties, lower tan δ, greater elastic properties At low frequencies, for example 0.0068 Hz, the rate of stress on the sample is such that the linear polymer relaxes and the viscous type reaction or It is possible to exhibit a high tan δ.Polymers consisting of chemical or physical networks exhibit a pronounced polymer chain structure.These network structured materials are mechanically stable and within the time frame and frequency of this experiment. No relaxation, these materials show low tan δ values and are therefore more elastic, as shown in Table 4, 0 for the unmodified control polymer. Tan δ 20 at .0068 Hz
Is observed, the highest level of hydrophobic material gives a tan δ of 0.224. 6
． Low levels of tan δ are observed with high levels of hydrophobic substitution over a wide range of frequencies up to 8 Hz. This clearly demonstrates the strong associative behavior of HAP, which is consistent with the viscosity data above.

[0131]

[Table 4]

(B) Dispersion Polymerization Solution The dispersion polymer is characterized by a method equivalent to that described for the polymer. The data shown in Table 5 demonstrate similar results to those with solution polymerization products. It is observed that the apparent viscosity of the 0.5% solution increases with the introduction of the hydrophobic monomer. The stress sweep study in the dynamic vibration mode was performed on the unmodified control sample VIII.
Demonstrates increased G'storage modulus with Samples IX and XI compared to. Frequency sweep studies in the dynamic vibrational mode demonstrate the low tan δ of the hydrophobic associative polymer compared to the unmodified control.

[0133]

[Table 5]

Table 5 Dilute solution viscosity characteristics of HAP samples were measured in various concentrations of NaCl in aqueous solutions to give Polyflex CP. 3. Commercial polyacrylamide dehydration accelerator (Cytec Industries, West Patterson, NJ)
s, Inc. ) And Polymer E, commercial high molecular weight anionic polyacrylamide flocculants. The data are shown in Table 5.1. L. H. Sperlin
Induction to Physical Polymer by g
As discussed in Science (Wiley Interscience, 1992), this dilute solution property provides a relative indication of polymer molecular weight. In this experiment, the solvent viscosity η ₀ is compared to the polymer solution viscosity η. The relative viscosity is the unitless ratio of both: η _rel = η / η _{0 The} specific viscosity is the relative viscosity minus 1: η _sp = η _rel −1 Below, the reduced specific viscosity called RSV is g Polymer concentration (C
) Divided by: RSV = η _sp / C The unit of RSV is deciliter / gram (dl / g) and, as such, the hydrodynamic volume of the polymer in solution (hydrodynamic volume) ( HDV). Therefore, a high RSV demonstrates a large HDV in solution and a high molecular weight compared to conventional polymers. This experiment is performed in the dilute regime so that polymer coil overlap does not occur. The RSV value can be known by measuring the outflow time or the apparent viscosity of both the solvent and the polymer solution respectively by capillary or rotational viscometer method. The data shown in Table 5.1 was measured by a Brookfield rotational viscometer equipped with an ultra low (UL) adapter that can measure the viscosity of low viscosity solutions. These data show that polyelectrolyte R by varying salt concentration is well known to those skilled in the art.
Demonstrate the effect on SV. The HAP product of the present invention exhibits higher RSV in 1M NaCl additionally containing 0.1% nonylphenol ethoxylate (NPE) surfactant than in 1M NaCl alone. "RSV Rati
This phenomenon, called "o", is a dilute solution property specific to associative polymers containing hydrophobic substances and does not occur with linear, crosslinked or branched polymers. This RSV Ratio A dramatic increase was observed at higher levels of hydrophobic monomer, a control polymer, Polyflex CP.3.
Or it does not occur with Polymer E. This phenomenon is well established in the literature and is described as the hydrophobic domain binding to the surfactant, increasing the dilute solution viscosity or RSV.

[0135]

[Equation 1]

3. Yield and drainage tests A first series of Britt Jar retention tests and Canadian Standard Freeness (CSF) drainage tests were performed to demonstrate the performance of the HAPs of the invention as follows: non-hydrophobic associative polymer; conventional anionic polyacrylamide. Flocculants; and compare the performance of inorganic and organic dehydration promoters commonly referred to in the art as "microparticles" or "micropolymers".

Brit Jar (Paper Research, Gig Harbor, WA)
ch Materials, Inc. ) Yield testing is known in the art. The Britt Jar Yield Test mixes specific amounts of furnish under dynamic conditions and drains an aliquot of furnish through the bottom screen of the jar to quantify the level of fines retained. To be able to. The Britt jar used in this experiment was equipped with three vanes on a cylindrical wall to induce turbulent mixing and a 76μ screen was used for the lower plate.

CSF device used to measure relative drainage or dewatering rates (Lorentzen & Wettre, Code, Stockholm, Sweden)
30) is also known in the art (TAPPI Test Proc).
edure T-227). The CSF device includes a drainage chamber and a velocity measuring funnel, both of which are mounted on suitable supports. The drainage chamber is cylindrical and comprises a perforated screen plate and a hinged plate on the bottom and a vacuum-tight hinged lid on the top. The velocity measuring funnel has a bottom orifice and a side overflow orifice.

The CSF test is typically carried out by placing 1 liter of 0.3% strength furnish in a draining chamber, closing the top lid and immediately opening the bottom plate. The water is allowed to drain freely into the velocity measuring funnel; water flow beyond that defined by the bottom orifice overflows the side orifice and is collected in the graduated cylinder. The values obtained are expressed in ml of filtrate; higher quantitative values indicate higher dehydration levels.

The furnish used in this first series of experiments is a synthetic alkaline furnish.
This furnish is prepared from hardwood and softwood dry market wrap pulp and water and other materials. First, hardwood and softwood dry market wrap pulp was tested in a laboratory Valley beater (Voi, Appleton, Wisconsin).
In th), refining separately. These pulps are then added to the aqueous medium.

The aqueous medium used to prepare the furnish is a local hard water to a typical hardness.
d water) and deionized water. Inorganic salts are added to the medium in such amounts as to give it a typical alkalinity and total conductivity.

To prepare the furnish, hardwood and softwood are dispersed in an aqueous medium in a typical weight ratio of hardwood and softwood. Precipitated calcium carbonate (PCC) was added to the furnish, 8
It is introduced at 25% by weight, based on the combined dry weight of the pulp, to produce the final furnish containing 0% fiber and 20% PCC filler.

This first series of tests is described below: Polymer II, a hydrophobic associative anionic polyacrylamide of the invention, as described herein; Polymer.
I, unmodified anionic polyacrylamide control polymer as described herein, Polymer E, high molecular weight commercial anionic flocculant; Polyflex.
CP. 3. Commercial polyacrylamide dehydration accelerator (Cytec Industries, Inc., West Patterson, NJ); and bentonite clay, also commonly used in the art as a drainage and retention aid.

The Britt jar yield test in this first series is carried out with 500 ml of synthetic furnish with a typical solids concentration of 0.5%. The test is
Consistent with the sequence shown in Table 2, the following parameters; starch addition, mixing; alum addition, mixing; polymer flocculant addition, mixing; dehydration accelerator addition, mixing; carry out.

The cationic potato starch used was Stalok 600 (AE Staley, Decatur, IL), and alum was aluminum sulfate 18-hydrate (Delta Delta, Baltimore, MD) available as a 50% solution.
Chemical Corporation). The cationic flocculant used, called CRAMP-P, is 90/10 mol% acrylamide / N, N-
Dimethylaminoethyl acrylate methyl chloride quat; this material is commercially available as a self-inverting water-in-oil emulsion.

The yield value reported in Table 2 is the fines retention, in which case 500 ml of furnish was washed with 10 liters of water under mixing conditions to obtain B
The total fines in the furnish is first measured by taking out all of the fine particles, which are defined as particles smaller than the ritt jar 76μ screen. Next, 100 ml of the filtrate is drained after the above addition sequence, and then the filtrate is passed through a pre-weighed 1.5 μ filter paper to measure the fine powder yield for each treatment. The fines yield is calculated by the following formula: Fines yield% = (filtrate weight-fines weight) / filtrate weight In the equation, the weights of both filtrate and fines are standardized to 100 ml. Yield values represent the average of two replicate runs.

The CSF drainage test is carried out with 1 l of furnish with a solids concentration of 0.30%. The furnish for the above treatment was prepared externally from the CSF device using similar speeds as described for the Britt jar test in a square beaker,
Prepare by mixing several times to produce turbulent mixing. Upon completion of the additive addition and mixing sequence, the treated furnish is injected into the top of the CSF device to perform the test.

In both the Britt jar yield test and the CSF drain test, high quantitative values demonstrate high activity and a greater and more desirable response. The data shown in Table 6 compare the results obtained with the unmodified control Polymer I and the conventional anionic flocculant Polymer E to the Polymer of the invention.
It illustrates that r II results in superior activity. In addition, the polymers of the present invention are equivalent in activity to bentonite clays and are compatible with Polyflex CP. An activity similar to that of 3 is produced. All doses of the above substances are based on product activity unless otherwise stated.

[0149]

[Table 6]

A series of yield and drainage tests are performed using a pulsed drainer (PDD). Test substrates, test conditions and related chemical additives are the same as those used in Table 6.

The PDD has a rotating hydrofoil and a vacuum capability (vacuum capabili
ty) and. This is an instrument developed domestically (as described in US Pat. No. 5,314,581) as a reasonable simulation of actual yield, drainage and sheet forming operations. During the operation of this experiment, a vacuum is applied to the fibrous slurry to help form a fibrous mat and the vacuum is continued until a steady state equilibrium vacuum is obtained.

Various measurements can be performed using this PDD. For example, the PDD can be used to measure first pass yield, peak vacuum, equilibrium vacuum, peak to equilibrium vacuum ratio (PEVR) and vacuum dehydration time.

The first pass fines yield includes the weight of the final sheet, the total mass introduced into the PDD, and the total fines fraction of the stock defined as the fraction of the stock having a particle size of less than 76μ. It is calculated by the mass balance calculation. As with the Britt jar fines yield, higher values demonstrate a desirable response.

The peak vacuum is the total vacuum required during mat formation before air is drawn through the formed mat and the vacuum is broken. Equilibrium vacuum is a steady state vacuum drawn through the formed sheet. Hg for both peak and equilibrium vacuum
Measured in inches of pillar. The low quantitative value of peak vacuum demonstrates a fibrous matrix that is susceptible to dewatering.

The peak-to-equilibrium vacuum ratio (PEVR) is the unitless ratio of both of these outputs.
Studies have demonstrated that this parameter is useful as an indicator of sheet formation, with lower PEVR values demonstrating greater desirable or greater uniform sheet formation.

Vacuum dehydration time is the time to peak vacuum and is measured by the instrument in units of seconds. This reaction is believed to be similar to the wet-line on a paper machine, where the water is drained enough that the sheet loses its gloss or visible free water. Wet-line position is commonly monitored as an indicator of paper machine drainage. The desired response to the vacuum drainage (dehydration) parameter is a reduced (low) value, demonstrating improved drainage.

A second series of water drainage tests using PDD is performed with the same dehydration promoter as the first series except that bentonite is not present. The relevant starch, alum and cationic flocculant are as described above. The results in Table 7 show the values obtained for the above measurements from performing PDD measurements.

These results indicate that Polymer II of the present invention is critical for the depletion dose response (d
osage response). Specifically, as the dose is increased, gravity dehydration, peak vacuum and vacuum dehydration time are correspondingly improved.

It is noted that the unmodified control Polymer I and the conventional flocculant Polymer E do not show a dose response. In this regard, the yield response and associated drainage response do not increase or decrease as the dose of these polymers increases.

Compared to the activity of the control Polymer I and Polymer E, the Polymer
The improved drainage activity of er II is also clearly demonstrated by the Table 7 data.
Polymer II is based on Polyflex CP. Yielding a finer powder yield higher than that of Polymer III, Polymer II at 1.0 lb / ton Polymer II at 0.5 lb / ton Polymerflex CP. 3 results in a water drainage approximately equal to 3, so that Polyflex CP. It is close to the drainage activity of 3. At these equal drainage times, Polymer II was added to Polyflex CP. It is observed that PEVR values lower than 3, improved sheet uniformity or indications of sheet formation.

[0161]

[Table 7]

A series of Brit jar yield and CSF tests is given below: Polymer
III, a hydrophobic associative anionic polyacrylamide of the invention described herein; Polymer V-VII, a hydrophobic associative polymer of the invention showing progressively increasing levels of hydrophobic modification; Polymer IV, herein. Unmodified anionic polyacrylamide control polymer described in Polymer; Polymer E; and Pol.
yflex CP. It carries out by 3. The test is carried out according to the method described above. Data are for Polymer II compared to unmodified control Polymer IV.
Demonstrate the superior activity of the present invention caused by I and Polymer VII. An increase in yield and drainage activity was observed with increasing levels of hydrophobic substitution, Polymer VII was used in Polyflex CP. It is close to the activity of 3. The data are shown in Table 8.

[0163]

[Table 8]

Another series of retention and drainage tests is performed by PDD as in the second test. Conditions and materials include dehydration promoters as described below: Polymer III of the present invention and Polyflex CP. 3; Polymer M
, A commercially available high molecular weight polyacrylamide emulsion flocculant; and bentonite clay, the same as that used in the series.

Polymeric materials were evaluated at 0.5, 0.75, and 1.0 lbs / ton effective polymer, bentonite clays at 2, 4, and 6 lbs / ton according to the typically used mill dose levels. evaluate.

The Table 9 data illustrates the activity of polymers of the invention. Polyflex CP.
3. Bentonite clay and Polymer III all show a clear dose-response activity, Polymer M is not dose active. Polyme
r III produces comparable to greater retention and drainage activity compared to bentonite clay.

Further, regarding the comparative activities shown in Table 9, Polymer M was
Yield and drainage equal to r III yield and drainage, but at significantly higher PEVR; this reduction in sheet uniformity / formation at equal drainage is undesirable. 1.0 lb / ton Polymer III is 0.5
Pound / ton Polyflex CP. Since it is close to the water drainage of 3, Poly
The water draining activity of mer III was confirmed by Polyflex CP. It is close to the drainage activity of 3. At these equal drainage times, the PEVR of the polymer of the invention is Po
lyflex CP. It was again observed to be below the PEVR of 3, which is an indication of improved sheet uniformity / formation.

[0168]

[Table 9]

Another series of Brit Jar Yield and CSF Drainage tests are available from Polym.
er III and Polyflex CP. Carried out according to No. 3, which uses a high level of CPAM-P coagulant and an additional coagulant, polyvinylamine (PVAm). PVAm is an aqueous solution polymerization of N-vinylformamide monomer, followed by
Prepared by subsequent hydrolysis of the polymer to give N-vinylamine. The subject polymer is 90% hydrolyzed, so the resulting copolymer is 90 mol% N-vinylamine / 10 mol% N-vinylformamide; the polymer is 5% solids, 3 dl in 1M NaCl. / G intrinsic viscosity (intrinsic
viscosity). The data in Table 10 demonstrate the utility of HAP at high levels of CPAM-P flocculant and the activity with PVAm flocculant.

[0170]

[Table 10]

Another series of PDD experiments, as shown in Table 11, was performed in the same manner as described above, using Poly
mer III, Polyflex CP. 3 and 2 additional Polyfl
ex products, Polyflex CS and Polyflex CP. 2 (These are also C
ytec Industries, Inc. (Available from).
The data in Table 11 shows that Polymer III of the present invention is Polyflex CP.
． 2 improved yield and drainage activity, equal activity of Polyflex CS, and Polyflex CP. It is demonstrated that an activity close to 3 is produced.

[0172]

[Table 11]

A series of studies on Britt jar yield and CSF drainage are performed with the brine dispersion polymer described above. These studies, shown in Table 12,
r IX and X, polymers of the process of the invention modified with lauryl methacrylate; Polymer XI and XII, polymers of the process of the invention modified with lauryl acrylate; Polymer VIII, prepared under the same conditions as the hydrophobic associative polymer. Control polymer, but containing no hydrophobic substitution; Po
lyflex CP. 3 and Polymer A, a conventional high molecular weight anionic polyacrylamide powder flocculant. The additives associated with the test conditions are the same as described above, except that the cationic flocculant used is CPAM-N; CPAM-N is the CPAM previously used in composition and physical form.
-Equal to P. Anionic polyacrylamide flocculant (APAM) is also used. This material is a 30 mol% sodium acrylate / 70 mol% acrylamide copolymer commercially available as a self-inverting emulsion. The data in Table 12 demonstrate the improved activity of the substances of the invention. Polymers IX and XI show higher retention and drainage activity compared to dehydration promoter bentonite clay, control Polymer VIII and conventional flocculant Polymer A. This improved activity is observed with the CPAM flocculant, with the APAM flocculant and without the flocculant.

[0174]

[Table 12]

[0175]

[0176]

A series of evaluations is performed on the PDD using the same methods described in Table 12. The studies shown in Table 13 are Polymers IX and X, polymers of the method of the invention modified by lauryl methacrylate; Polymer XI and XII, polymers of the method of the invention modified by lauryl acrylate; Polymer.
VII, a control polymer prepared under the same conditions as the hydrophobic associative polymer, but containing no hydrophobic substitution; and Polyflex CP. It carries out by 3.
The data in Table 13 shows that Polym compared to the unmodified control Polymer VIII.
er IX, X and XI demonstrate a pronounced drainage activity. Polymer IX
, X and XI also show a clear dose activity at low PEVR and the unmodified control shows no significant dose response.

[0178]

[Table 13]

It will be appreciated that the above examples are provided for illustration only and should not be construed as limiting the invention in any way. Although the present invention has been described in relation to exemplary embodiments, it is understood that the words that have been used herein are words of description and illustration, rather than words of limitation. Changes may be made, within the purview of the appended claims, as presently stated and as amended, without departing from the scope and spirit of the invention in its aspects. Although the present invention has been described herein with reference to particular means, materials and embodiments, it is not intended that the invention be limited to the details disclosed herein; rather, the present invention is, for example, a patent. It extends to all functionally equivalent structures, methods and uses, such as are within the scope of the claims.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE, TR), OA (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, B Z, CA, CH, CN, CR, CU, CZ, DE, DK , DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, J P, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, R O, RU, SD, SE, SG, SI, SK, SL, TJ , TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW (72) Inventor Tsuhan, Huashi Tee             California, USA 91007,             Acadia, Acadia Avenue               756, Number C F-term (reference) 4J002 AA012 AB011 AB043 BG042                       BG052 FD01 FD20 FD34                       GK00 GK01 GK03 GK04                 4L055 AG64 AG71 AG72 AG73 AG74                       AG89 AH17 EA30 EA32 FA08                       FA10

Claims (37)

[Claims] 1. The cellulosic pulp slurry contains from about 0.001 mol% to about 1.
A repeating unit of at least one hydrophobic ethylenically unsaturated monomer present in an amount of 0 mol% and selected from nonionic ethylenically unsaturated monomers, cationic ethylenically unsaturated monomers or anionic ethylenically unsaturated monomers A hydrophobic associative polymer comprising at least one hydrophobic ethylenically unsaturated monomer containing no 2,4,6-triphenoethylbenzene from the repeating unit of at least one monomer A method for producing a cellulosic fiber composition, comprising: 2. The method of claim 1, wherein the hydrophobic ethylenically unsaturated monomer comprises an ethylenically unsaturated monomer having at least one hydrophobic side group. 3. The hydrophobic side group is C _{4 to} C ₂₀ alkyl, C _{4 to} C ₂₀ cycloalkyl, polynuclear aromatic hydrocarbon group, alkylaryl in which alkyl has 1 or more carbons; 4 or more carbons. 3. The method of claim 2, wherein the method is selected from one or more of a haloalkyl having a, or a polyalkyleneoxy group. 4. The method of claim 3, wherein the hydrophobic group is selected from one or more of C _{4 to} C ₂₀ alkyl. 5. The method of claim 3, wherein the hydrophobic group is selected from one or more of C _{8 to} C ₂₀ alkyl. 6. The method of claim 1, wherein the hydrophobic ethylenically unsaturated monomer is selected from one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts. 7. The method of claim 1, wherein the hydrophobic ethylenically unsaturated monomer is selected from one or more of C _{10 to} C ₂₀ alkyl esters of acrylic acid and methacrylic acid. 8. The nonionic ethylenically unsaturated monomer is acrylamide, methacrylamide, N-alkylacrylamide, N, N-dialkylacrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide. , Vinyl acetate or N-
The method of claim 1, wherein the method is selected from one or more of vinylpyrrolidone. 9. The method of claim 8, wherein the N-alkyl acrylamide is N-methyl acrylamide. 10. The method for producing a cellulosic fiber composition according to claim 8, wherein the at least one nonionic ethylenically unsaturated monomer is selected from one or more of acrylamide, methacrylamide, or N-alkylacrylamide. 11. The method for producing a cellulosic fiber composition according to claim 8, wherein the at least one nonionic ethylenically unsaturated monomer is acrylamide. 12. At least one anionic ethylenically unsaturated monomer is acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl sulfonic acid, styrene sulfonic acid, The method for producing a cellulosic fiber composition according to claim 1, which is selected from one or more of maleic acid and salts thereof. 13. The method for producing a cellulosic fiber composition according to claim 12, wherein the at least one anionic ethylenically unsaturated monomer is selected from one or more of acrylic acid, methacrylic acid, or salts thereof. 14. The method for producing a cellulosic fiber composition according to claim 13, wherein the at least one anionic ethylenically unsaturated monomer is selected from one or more of sodium salt or ammonium salt of acrylic acid. 15. The method of making a cellulosic fiber composition according to claim 1, wherein the at least one hydrophobic ethylenically unsaturated monomer group is present in an amount of about 0.01 mol% to about 1 mol%. 16. A cellulose pulp slurry, present in an amount of from about 0.001 mole percent to about 10 mole%, is selected from one or more of C ₁₀ -C ₂₀ alkyl esters of acrylic and methacrylic acid, at least Repeating unit of one kind of hydrophobic ethylenically unsaturated monomer; acrylamide, methacrylamide, N-alkylacrylamide, N, N-
At least one nonionic ethylenic unsaturation selected from one or more of dialkylacrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinylmethylacetamide, N-vinylmethylformamide, vinyl acetate or N-vinylpyrrolidone. Repeating units of monomers; and from one or more of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or salts thereof. A method of making a cellulosic fiber composition, comprising adding a water-soluble hydrophobic associative polymer comprising repeating units of at least one anionic ethylenically unsaturated monomer selected. 17. A water-soluble hydrophobic associative polymer is selected from one or more of C ₁₀ -C ₂₀ alkyl esters of acrylic acid and methacrylic acid present in an amount of about 0.001 mol% to about 10 mol%. A repeating unit of at least one hydrophobic ethylenically unsaturated monomer; a repeating unit of at least one nonionic ethylenically unsaturated monomer selected from one or more of acrylamide, methacrylamide or N-alkylacrylamide. And a repeating unit of at least one type of anionic ethylenically unsaturated monomer selected from one or more of acrylic acid, methacrylic acid, or salts thereof. . 18. A water-soluble hydrophobic associative anion containing at least one hydrophobic ethylenically unsaturated monomer selected from one or more of lauryl acrylate or lauryl methacrylate, acrylamide and acrylic acid in a cellulosic pulp slurry. Of a cellulosic fiber composition, which comprises adding a water-soluble polymer. 19. The method of claim 18, wherein the hydrophobic ethylenically unsaturated monomer is lauryl acrylate. 20. The method of claim 18, wherein the hydrophobic ethylenically unsaturated monomer is lauryl methacrylate. 21. A cellulosic fiber composition comprising an aqueous slurry of cellulosic pulp and a water soluble hydrophobic associative polymer, wherein the polymer is present in an amount from about 0.001 mol% to about 10 mol%. Of at least one kind of hydrophobic ethylenically unsaturated monomer repeating unit, and at least one kind selected from nonionic ethylenically unsaturated monomer, cationic ethylenically unsaturated monomer or anionic ethylenically unsaturated monomer The cellulosic fiber composition, which comprises a repeating unit of the monomer (1), provided that the at least one hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-triphenoethylbenzene. 22. At least one hydrophobic ethylenically unsaturated monomer comprises:
22. The cellulosic fiber composition of claim 21, comprising an ethylenically unsaturated monomer having at least one hydrophobic side group. 23. The hydrophobic side group is C ₄ -C ₂₀ alkyl, C ₄ -C ₂₀ cycloalkyl, polynuclear aromatic hydrocarbon group, alkaryl in which alkyl has one or more carbon atoms;
23. The cellulosic fiber composition of claim 22, selected from one or more of a haloalkyl having 4 or more carbons, or a polyalkyleneoxy group. 24. The cellulosic fiber composition of claim 23, wherein the at least one hydrophobic group is selected from one or more of C _{4 to} C ₂₀ alkyl groups. 25. The cellulosic fiber composition of claim 24, wherein the at least one hydrophobic group is selected from one or more of C _{8 to} C ₂₀ alkyl groups. 26. The cellulosic fiber composition of claim 21, wherein the at least one hydrophobic ethylenically unsaturated monomer is selected from one or more hydrocarbon esters of ethylenically unsaturated carboxylic acids and their salts. . 27. The cellulosic fiber composition of claim 26, wherein the at least one hydrophobic ethylenically unsaturated monomer is selected from one or more of C _{10 to} C ₂₀ alkyl esters of acrylic acid and methacrylic acid. 28. The at least one nonionic ethylenically unsaturated monomer is acrylamide, methacrylamide, N-alkylacrylamide, N, N-.
22. One selected from one or more of dialkyl acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methyl acetamide, N-vinyl methyl formamide, vinyl acetate or N-vinyl pyrrolidone.
The described cellulosic fiber composition. 29. The cellulosic fiber composition of claim 28, wherein the at least one nonionic ethylenically unsaturated monomer is acrylamide. 30. At least one anionic ethylenically unsaturated monomer is acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl sulfonic acid, styrene sulfonic acid, 22. The cellulosic fiber composition of claim 21, selected from one or more of maleic acid or salts thereof. 31. The cellulosic fiber composition of claim 30, wherein the at least one anionic ethylenically unsaturated monomer is selected from one or more of sodium or ammonium salts of acrylic acid. 32. The cellulosic fiber composition of claim 21, wherein the at least one hydrophobic ethylenically unsaturated monomer group is present in an amount of about 0.01 mol% to about 1 mol%. 33. A cellulosic fiber composition comprising an aqueous slurry of cellulosic pulp and a water soluble hydrophobic associative polymer, wherein the polymer is present in an amount from about 0.001 mol% to about 10 mol%. to, at least one repeating unit of the hydrophobic ethylenically unsaturated monomers are selected from one or more of C ₁₀ -C ₂₀ alkyl esters of acrylic acid and methacrylic acid; acrylamide, methacrylamide, N- alkylacrylamide, N, N-dialkyl acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methyl acetamide, N-vinyl methyl formamide,
At least one selected from one or more of vinyl acetate or N-vinylpyrrolidone
Repeating units of a class of nonionic ethylenically unsaturated monomers; and acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-propane sulfonate, sulfoethyl acrylate, sulfoethyl methacrylate, vinyl sulfonic acid, styrene sulfonic acid, maleic acid. Alternatively, the cellulosic fiber composition comprising repeating units of at least one anionic ethylenically unsaturated monomer selected from one or more of their salts. 34. The water-soluble hydrophobic associative polymer is selected from one or more of dodecyl acrylate or dodecyl methacrylate.
At least one kind of hydrophobic ethylenic unsaturated monomer, at least one kind of nonionic ethylenic unsaturated monomer which is acrylamide, and at least one kind of sodium salt or ammonium salt of acrylic acid; 34. The cellulosic fiber composition of claim 33, comprising an anionic ethylenically unsaturated monomer. 35. The cellulosic sheet of claim 33, which comprises paper. 36. A cellulosic fiber composition comprising an aqueous slurry of cellulosic pulp and a water soluble hydrophobic associative polymer, wherein the polymer is a hydrophobic selected from one or more of lauryl acrylate or lauryl methacrylate. The cellulosic fiber composition, comprising repeating units of an ethylenically unsaturated monomer, repeating units of a nonionic ethylenically unsaturated monomer that is acrylamide, and repeating units of an anionic ethylenically unsaturated monomer that is acrylic acid. 37. The cellulosic fiber composition according to claim 36, which is in the form of paper.