JP2002513102A - Paper manufacturing method - Google Patents

Abstract

The invention relates to a process for the production of paper from a suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension a drainage and/or retention aid comprising a cationic organic polymer, forming and dewatering the suspension on a wire, wherein the cationic organic polymer has an aromatic group and the suspension which is dewatered on the wire has a conductivity of at least 2.0 mS/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to papermaking, and more specifically, to a papermaking method in which a cationic organic polymer having a hydrophobic group and an anionic fine particle material are added to a papermaking raw material. The method improves draining and yield.

BACKGROUND OF THE INVENTION In the papermaking art, an aqueous suspension, called raw material, containing cellulose fibers and optional fillers and additives is supplied to a headbox, which places the raw material onto a forming wire mesh. Extrude. Water is drained from the raw material through a forming mesh, resulting in a wet web of paper on the mesh, which web is further dewatered and dried in the dryer section of the paper machine. The water, usually called white water, obtained by dehydration of this raw material, which contains fine particles, for example fine fibers, fillers and additives, is usually recycled in the papermaking process. Draining and retention aids are conventionally introduced into the feedstock to facilitate draining and increase the adsorption of fine particles on the cellulose fibers, such that these particles are retained by the fibers on the wire mesh. Cationic organic polymers such as cationic starch and cationic acrylamide-based polymers are widely used as drainage and retention aids. These polymers can be used alone, but more often they are used in combination with other polymers and / or anionic particulate materials such as, for example, anionic inorganic particles such as colloidal silica and bentonite. Can be

[0003] US Patent Nos. 4,980,025; 5,368,833; 5,603,805; 5,607,552; and 5,8
58,174; and International Patent Application WO 97/18351 disclose the use of cationic and amphoteric acrylamide-based polymers and anionic inorganic particles as raw material additives in papermaking. These additives are one of the most effective drainers and retention aids currently in use. A similar system is described in European Patent Application No. 80
No. 5,234.

SUMMARY OF THE INVENTION According to the present invention, improved drainage and yield can be obtained by using a drainer and retention aid comprising a cationic organic polymer having a hydrophobic group and an anionic particulate material. Was found. More specifically, the present invention relates to a method of producing paper from a suspension containing cellulosic fibers and optional fillers, the method comprising adding a cationic organic polymer and an anionic particulate material to the suspension; Molding and dewatering on a wire mesh, wherein the cationic organic polymer has non-aromatic hydrophobic groups. In a preferred aspect of the invention, the method further comprises shaping and dewatering said suspension on a wire mesh to obtain a wet web comprising cellulose fibers or paper and white water, recirculating said white water and optionally clear water To form a suspension comprising cellulose fibers which are dewatered to form paper and optional fillers, wherein the amount of fresh water introduced is less than 30 tons per ton of dry paper produced. The invention therefore relates to a method as further defined in the claims.

[0005] The method of the present invention results in improved draining and / or retention, which allows the present invention to increase the speed of the paper machine and reduce the amount of additives to provide a corresponding draining and retention effect. It allows the use of added amounts, thereby improving the papermaking process and leading to economic benefits. The process of the present invention is suitably used for the treatment of cellulosic suspensions in closed factories, wherein the white water is repeatedly recycled by introducing only a small amount of fresh water. The process is a papermaking process with a suspension of cellulose having a higher salt content and thus a higher conductivity level, for example a process with large white water recirculation and limited fresh water supply and / or Alternatively, it is suitably applied to a method of using fresh water having a high salt content.

The cationic organic polymers with hydrophobic groups according to the invention, also referred to here as “major polymers”, can be linear, branched or crosslinked, for example in the form of particulate material, and are preferably essentially Is linear. Preferably, the main polymer is water-soluble or water-dispersible. The hydrophobic groups of the main polymer are non-aromatic, which means that pendant groups attached to the backbone (backbone) of the polymer, or
Preferably, the heteroatom, for example nitrogen or oxygen, nitrogen is optionally charged,
The heteroatom can subsequently be attached to the polymer backbone, for example via a chain of atoms. The hydrophobic group has at least 2, usually at least 3 carbon atoms, suitably 3 to 12 and preferably 4 to 8 carbon atoms. This hydrophobic group is suitably a hydrocarbon chain. Examples of suitable hydrophobic groups are ethyl; propyl, such as n-propyl and isopropyl; butyl, such as n-butyl, isobutyl and t-butyl; pentyl, such as n-pentyl, neopentyl and isopentyl; hexyl, such as n-butyl Hexyl and cyclohexyl; heptyl, for example n-heptyl and cycloheptyl; octyl, for example n-octyl;
Nonyl, such as n-nonyl; decyl, such as n-decyl: undecyl, such as n
-Straight-chain, branched and cyclic alkyl groups such as -undecyl and dodecyl, for example n-dodecyl. Straight and branched chain alkyl groups are generally preferred.

[0007] The main polymer is selected from homopolymers and copolymers prepared from one or more monomers, including at least one monomer having a hydrophobic group, suitably an ethylenically unsaturated monomer, and the main polymer is preferably Is a vinyl addition polymer. As used herein, the term "vinyl addition polymer" refers to a polymer prepared by the addition polymerization of vinyl or ethylenically unsaturated monomers, including, for example, acrylamide-based and acrylate-based monomers.

According to a first embodiment of the present invention, suitable main polymers are cationic addition polymers obtained by polymerization of cationic monomers, having a monomer mixture comprising non-aromatic hydrophobic groups or cationic monomers. including. Preferably, the cationic monomer having a non-aromatic hydrophobic group is represented by the general formula (I):

[0009]

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Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or, preferably, 1
An alkyl group having from 1 to 3 carbon atoms, suitably from 1 to 2 carbon atoms;
Is O or NH; B is an alkylene or hydroxypropylene group of 2 to 8 carbon atoms, suitably 2 to 4 carbon atoms; R ₄ is a substituent comprising a hydrophobic group;
Suitably, is a non-aromatic hydrocarbon group containing at least 2 carbon atoms, suitably 3 to 12 carbon atoms and preferably 4 to 8 carbon atoms; and X ^- is an anionic counter ion, usually It is a halide such as chloride. This group R ₄ usually comprises and preferably is selected from any of the above-mentioned linear, branched or cyclic alkyl groups, the total number of carbon atoms of the groups R ₂ , R ₃ and R ₄ being:
Usually it is at least 4, suitably at least 5 and preferably at least 6. Examples of suitable cationic monomers having a non-aromatic hydrophobic group include (meth)
Acryloxyethyl-N, N-dimethyl-Nn-butylammonium chloride;
(Meth) acryloxyaminoethyl-N, N-dimethyl-NN-butylammonium chloride, (meth) acryloxypropyl-N, N-dimethyl-Nt-
Butyl ammonium chloride, (meth) acryloxyaminopropyl-N, N-dimethyl-Nt-butylammonium chloride, (meth) acryloxyaminopropyl-N, N-dimethyl-NN-hexylammonium chloride, (Meth) acryloxyethyl-N, N-dimethyl-Nn-hexyl ammonium chloride, (meth) acryloxyethyl-N, N-dimethyl-N-methylcyclohexyl ammonium chloride and (meth) acryloxyaminopropyl-N , N-dimethyl-N-methylcyclohexyl ammonium chloride.

The main polymer includes a homopolymer prepared from a cationic monomer having a non-aromatic hydrophobic group or a cationic monomer having a non-aromatic hydrophobic group and one or more copolymerizable monomers. , A copolymer prepared from a monomer mixture. Suitable copolymerizable nonionic monomers have the general formula (II)
Including the monomers represented by:

[0012]

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Wherein R 1 is H or CH ₃ ; A is O or NH; B is an alkylene or hydroxypropylene group of 2 to 8 carbon atoms, suitably 2 to 4 carbon atoms, or in, no both a and B, which by a single bond _{(O = C-NR 5 R} 6) are present between the C and N; substituents comprising R ₅ and R ₆ are H or a hydrophobic group, respectively Suitably a hydrocarbon group, preferably alkyl, from 1 to 6, suitably 1
To 4 and usually alkyl having 1 to 3 carbon atoms. Examples of suitable copolymerizable monomers of this type include (meth) acrylamide; N-alkyl (
Acrylamide-based monomers such as (meth) acrylamide and N, N-dialkyl (meth) acrylamide, for example Nn-propylacrylamide,
N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide and Nt-butyl (meth) acrylamide; and dialkylaminoalkyl (meth) acrylamide such as dimethylaminoethyl ( (Meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide; acrylate-based monomers such as dialkylaminoalkyl (meth) acrylate, for example, dimethylaminoethyl (meth) acrylate; Diethylaminoethyl (meth) acrylate, t
-Butylaminoethyl (meth) acrylate and dimethylaminohydroxypropyl acrylate; and vinylamides, such as N-vinylformamide and N-vinylacetamide. Preferred copolymerizable nonionic monomers include acrylamide and methacrylamide, ie, (meth) acrylamide, and the main polymer is preferably an acrylamide-based polymer.

Suitable copolymerizable cationic monomers include those represented by the following general formula (III):

[0015]

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Wherein R ₇ is H or CH ₃ ; R ₂ and R ₃ are each H or an alkyl group having preferably 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms; O
Or NH; B is an alkylene or hydroxypropylene group from 2 to 8 carbon atoms, suitably 2 to 4 carbon atoms; R ₇ is H, 1 to 3 carbon atoms, suitably 1 A hydrocarbon group, preferably an alkyl group having from 2 to 2 carbon atoms, or an aromatic group, suitably phenyl or an alkylene group, usually having 1 to 3 carbon atoms, suitably 1 to 2 carbon atoms. substituents include phenyl, substituted capable of binding to, for example, a benzyl group (-CH ₂ -C ₆ H ₅₎ or a phenyl group _{(-CH 2 -CH 2 -C 6 H} 5); and X ^- is an anionic counterion , Usually a halide such as methyl sulfate or chloride. Examples of suitable cationically copolymerizable monomers include the acid addition and quaternary ammonium salts of dialkylaminoalkyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylate described above, which are usually HCl, H ₂ SO 4 Prepared with acids such as ₄ , or quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, and the like; and diallylalkylammonium halides, such as diallyldimethylammonium chloride. Copolymerizable anionic monomers, such as acrylic acid, methacrylic acid, various sulfonated vinyl addition monomers, and the like, can also be used, preferably in small amounts.

According to a second embodiment of the present invention, suitable main polymers comprise non-aromatic hydrophobic groups and at least one ethylenically unsaturated monomer, non-aromatic hydrophobic as defined above. A cationic vinyl addition polymer obtained by polymerizing a monomer mixture comprising at least one non-cationic ethylenically unsaturated monomer, and the invention further comprises a non-aromatic compound as further defined in the claims. Cationic vinyl addition polymer having aromatic group of hydrophobic group, relates to its preparation and use. Suitable non-cationic monomers having a non-aromatic hydrophobic group include non-ionic monomers, preferably non-ionic monomers of general formula (IV):

[0018]

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Wherein R 1 is H or CH ₃ ; A is O or NH; B is an alkylene or hydroxypropylene group from 2 to 8 carbon atoms, suitably from 2 to 4 carbon atoms, or substitutions comprising R ₈ and R ₉ are H or a hydrophobic group, respectively; alternatively, no both a and B, which by a single bond _{(O = C-NR 8 R} 9) is present between the C and N A group, suitably a hydrocarbon group, preferably alkyl, having 1 to 6 carbon atoms, wherein at least one of R ₈ and R ₉ is a substituent comprising a hydrophobic group, suitably 2 to 6 and preferably Is an alkyl group having 3 to 4 carbon atoms. The total number of carbon atoms of the radicals R ₈ and R ₉ is usually at least 2, suitably at least 3 and especially 3
From 6. Examples of suitable copolymerizable monomers of this type include acrylamide-based polymers such as N-alkyl (meth) acrylamide, e.g.
-Ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide,
N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide and N-iso N-alkylaminoalkyl (meth) acrylamide; N, N-dialkylaminoalkyl (meth) acrylamide, and N-alkylaminoalkyl (meth) acrylate and N, N-dialkylaminoalkyl (meth) acrylate And acrylate-based monomers such as t-butylamino-2-ethyl (meth) acrylate.

Further suitable non-cationic monomers having a non-aromatic hydrophobic group are those of the general formula (V
Including non-ionic monomers represented by:

[0021]

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Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene group of 2 to 4 carbon atoms, suitably 2 to 3 carbon atoms, preferably ethylene (—CH ₂
—CH ₂ —) or propylene (—CH ₂ —CH (CH ₃ ) — or —CH (CH ₃ ) —CH ₂ —); n is an integer of at least 1, suitably 2 to 40 and preferably 3 To 20; R ₁₀ is suitably an alkyl substituent having a hydrophobic group and is an alkyl having at least 2 carbon atoms, suitably 3 to 12, preferably 4 to 8 carbon atoms. . Examples of suitable copolymerizable monomers of this type include alkyl (mono-, di- and polyethylene glycol) (meth) acrylates and alkyl (mono-, di- and polypropylene glycol) (meth)
Acrylates, such as ethyl triglycol (meth) acrylate and butyl diglycol (meth) acrylate.

The cationic monomer can be selected from any of the cationic monomers described above, including those of the general formulas (I) and (III), as well as diallyldialkylammonium such as diallyldimethylammonium chloride. Contains halide. The monomer mixture according to the second embodiment can also comprise other copolymerizable monomers, such as, for example, non-ionic monomers of the general formula (II) above, It may be free of hydrophobic groups, suitably acrylamide and methacrylamide, and the anionic monomers mentioned above.

The main polymers according to the invention are usually from 1 to 99 mol%, suitably from 2 to 50 mol% and preferably from 5 to 25 mol% of monomers having non-aromatic hydrophobic groups,
It contains 99 to 1 mol%, suitably 98 to 50 mol%, preferably 95 to 75 mol% of other copolymerizable monomers, which are preferably acrylamide or methacrylamide ((meth) acrylamide) The monomer mixture suitably comprises 98 to 50 mol%, preferably 95 to 75 mol%, of (meth) acrylamide, the sum of the percentages being 100. According to a first embodiment of the present invention, the monomer having a non-aromatic hydrophobic group is cationic. According to a second embodiment of the present invention, the monomer having a non-aromatic hydrophobic group is non-cationic, and the monomer mixture thus also comprises a copolymerizable cationic monomer,
It is suitably present in an amount of 2 to 50 mol%, preferably 5 to 25 mol%.

The main polymer according to the invention can be prepared by polymerization of monomers in a known manner,
The polymerization is suitably carried out in the aqueous or inverse emulsion phase. The monomers used, including the monomers having hydrophobic groups described above, are preferably at least partially soluble in the aqueous phase. Polymerization methods are generally known in the art and are described in the Ecyclopedia of
See Polymer Science and Engineering, Vol. 1-18, John Wiley & Sons, 1985, which is incorporated herein by reference. The polymerization is initiated in an aqueous phase containing monomers, a conventional radical polymerization initiator and optionally a chain transfer agent for molecular weight control of the polymer, suitably in an inert gas atmosphere, for example in nitrogen, in the absence of oxygen. It is performed. The polymerization is suitably carried out with stirring at a temperature between 20 and 100 ° C, preferably between 40 and 90 ° C.

Typically, the charge density of the main polymer is between 0.2 and 5.0 per gram of dry polymer.
meqv, suitably 0.6 to 3.0 meqv / g of dry polymer. The weight average molecular weight of the synthetic main polymer is usually at least about 500,000, suitably about 1,0
More than 00,000 and preferably more than about 2,000,000. This upper limit is not important;
This can be about 30,000,000, usually 25,000,000 and suitably 20,000,000.

The main polymer of the present invention is, for example, in a solid form, for example, in a powder or liquid form,
Any agglomerates such as, for example, solutions, emulsions, dispersions including salt dispersions and the like may be used. When added to the raw material, the main polymer is suitably in liquid form, for example in the form of an aqueous solution or dispersion.

The anionic particulate material according to the present invention can be selected from inorganic and organic particles.
Anionic inorganic particles that can be used in accordance with the present invention include anionic silica-based particles and smectite-type clay. The anionic inorganic particles preferably have a particle size in a colloidal range. Anionic silica-based particles, ie particles based on SiO ₂ or silicic acid, are preferably used and are usually supplied in the form of an aqueous colloidal dispersion, a so-called sol. Examples of suitable silica-based sols include different types of colloidal silica and polysilicic acid. The silica-based sol can also be modified and contain other elements, such as aluminum and / or boron, which can be present in the aqueous phase and / or in the silica-based particles. Suitable silica-based particles of this type include colloidal aluminum-modified silica and aluminum silicate. Mixtures of such suitable silica-based particles can also be used. Draining and retention aids containing suitable anionic silica-based particles are disclosed in US Patent Nos. 4,388,150; 4,927,498;
, 954,220; 4,961,825; 4,980,025; 5,127,994; 5,176,891; 5,368,833; 5,447,6
04; 5,470,435; 5,543,014; 5,571,494; 5,573,674; 5,584,966; 5,603,805; 5,
688,482; and 5,707,493; which are incorporated herein by reference.

The anionic silica-based particles suitably have a particle size of less than about 50 nm, preferably about 2 nm.
It has an average particle size of less than 0 nm, more preferably in the range of about 1 to about 10 nm. As is customary in silica chemistry, the particle size refers to the average size of the primary particles, which may or may not be agglomerated. The specific surface area of the silica-based particles is suitably above 50 m ² / g, preferably above 100 m ² / g. In general, this specific surface area can be up to about 1700 m ² / g, preferably up to 1000 m ² / g. This specific surface area can be measured by titration with NaOH in a known manner, for example by Sears Analytical Chemistry 28 (1956): 12, 1981-.
1983 and US Patent No. 5,176,891. Therefore,
The given area represents the average specific surface area of the particles.

In a preferred embodiment of the present invention, the anionic inorganic particles comprise 50 to 1
Silica-based particles having a specific surface area in the range of 000 m ² / g, preferably 100 to 950 m ² / g. These types of silica-based sols also include modified sols such as aluminum-containing silica-based sols and boron-containing silica-based sols. Preferably, the silica-based particles are present in a sol having an S-value ranging from 8 to 45%, preferably from 10 to 30%, and from 300 to 1
000 m ² / g, suitably silica-based particles having a specific surface area in the range of 500 to 950 m ² / g and preferably 750 to 950 m ² / g, the sol comprising aluminum and / or boron as described above. Can be modified. For example, these particles can be surface modified with aluminum to a degree of 2 to 25% silicon atom substitution. This S-value was determined by Iler and Dalton in J. Phys. Chem. 60 (1956), 955.
Can be measured and calculated as described in -957. This S-value indicates the degree of aggregation or microgel formation, while a low S-value indicates a high degree of aggregation.

In yet another preferred embodiment of the invention, the silica-based particles are selected from polysilicic acids having a large specific surface area and modified polysilicic acids, suitably greater than about 1000 m ² / g. Its specific surface area is from 1000 to 1700 m ² / g
, Preferably in the range of 1050 to 1600 m ² / g. The modified polysilicic acid sol may contain other elements, such as aluminum and / or boron, which may be present in the aqueous phase and / or in the silica-based particles. In the present technology, polysilicic acid is also referred to as silicic acid polymer, polysilicic acid microgel, polysilicate and polysilicate microgel, all of which are encompassed by the term polysilicic acid as used herein. Aluminum-containing compounds of this type are also commonly referred to as polyaluminosilicates and polyaluminosilicate microgels, both of which are encompassed by the terms colloidal aluminum-modified silica and aluminum silicate as used herein.

[0032] Smectite-type clays that can be used in the method of the present invention are known in the art and include naturally occurring, synthetic and chemically treated materials. Examples of suitable smectite clays include montmorillonite / bentonite, hectorite, beidellite, nontronite and saponite, preferably bentonite, especially bentonite having a surface area of preferably from 400 to 800 m ² / g after swelling. Suitable clays are disclosed in US Patent Nos. 4,753,710; 5,07
1,512 and 5,607,552, which are incorporated herein by reference.

The anionic organic particles which can be used according to the invention are highly crosslinked anionic vinyl addition polymers, suitably anionic, such as acrylic acid, methacrylic acid and sulfonated or phosphonated vinyl addition monomers. And copolymers containing non-ionic monomers such as (meth) acrylamide, alkyl (meth) acrylate, and the like. Useful anionic organic particles also include anionic condensation polymers, such as melamine-sulfonic acid sols.

In addition to the cationic organic polymer with hydrophobic groups and the anionic particulate material, the drainage and retention aids (drugs) according to the invention can also be used, for example, as low molecular weight cationic organic polymers and / or aluminum compounds. , May contain further components. As used herein, the term "draining and retention aid" refers to two or more components (auxiliaries, agents or additives) which, when added to the raw material, are greater than those obtained without these components. Also show good drainage and yield.

[0035] Low molecular weight (hereinafter LMW) cationic organic polymers that can be used are commonly referred to as anionic debris traps (ATC) and are used. ATC is known in the art as a neutralizing and / or fixing agent for harmful anionic substances present in the feedstock, and its use in combination with drainage and / or retention aids often involves drainage and / or retention. Further improve the yield. The LMW cationic organic polymer can be derived from natural or synthetic sources and is preferably a synthetic polymer of LMW. Suitable organic polymers of this type include the highly charged cationic organic polymers of LMW, which include homopolymers and copolymers based on polyamines, polyamidoamines, polyethyleneimines, diallyldimethylammonium chloride, (meth) acrylamide and (meth) acrylamide. ) Like acrylate. In relation to the molecular weight of the main polymer, the molecular weight of the LMW cationic organic polymer is usually low; suitably at least 2000, preferably at least 10
, 000. The upper limit for this molecular weight is usually about 700,000, suitably about 500,000, preferably about 200,000.

The aluminum compounds which can be used according to the invention are alum, aluminates, aluminum chloride, aluminum nitrate as well as polyaluminum chloride, polyaluminum sulphate, polyaluminum compounds having both chloride and sulphate ions, polyaluminum silicides And polyaluminum compounds such as acid salts-sulphates and mixtures thereof. These polyaluminum compounds may also contain anions other than chloride ions, for example from organic acids such as sulfuric acid, phosphoric acid, citric acid and oxalic acid.

The components of the draining and retention aid according to the invention can be added to the raw materials in any conventional manner and in any order. It is preferred that the main polymer be added to the raw material before adding the anionic particulate material, even if the reverse order can be used. Before the shearing phase selected from pumping, mixing, washing, etc., this main polymer,
More preferably, the anionic particles are added after this shearing step. L
When using a MW cationic organic polymer and / or an aluminum compound,
Such components are preferably introduced into the feedstock before the introduction of the main polymer and the anionic particulate material. Alternatively, the LMW cationic organic polymer and the main polymer can be introduced into the raw material substantially simultaneously, separately or in a mixture, for example, as disclosed in US Patent No. 5,858,174, which is hereby incorporated by reference. Add with reference.

The components of the drainage and retention aids are added to the raw material to be dehydrated,
Type and number, furnish type, filler content, filler type, location of addition, salt
It is added in an amount that can be varied within a wide range depending on the content and the like. Generally this
These components have better drainage and retention than would be obtained without each component added.
It is added in such an amount as to show a ball. The main polymer is based on a dry
Usually at least 0.001% by weight, often at least 0.005% by weight.
The upper limit is usually 3% by weight, suitably 1.5% by weight. The anion
The particulate material is usually at least 0.001% by weight, often at least 0.001% by weight.
5% by weight, based on the dry matter of the raw material, the upper limit is usually 1.0% by weight
, Suitably 0.6% by weight. When using anionic silica-based particles,
The total amount of addition is SiO_Two, Based on the dry raw material, suitably 0.
005 to 0.5% by weight, preferably 0.01 to 0.2% by weight.
When using the LMW cationic organic polymer in the present method, this
It can be added in an amount of at least 0.05% by weight, based on the dry substance. Suitably, this
Is in the range of 0.07 to 0.5% by weight, preferably 0.1 to 0.35% by weight.
Range. When using an aluminum compound in this method,
The total amount charged depends on the type of aluminum compound used and any other
Depends on the effect. For example, aluminum compounds can be used in rosin-based sizing agents.
Use as a precipitant is well known in the art. The total amount of this addition is Al _Two O_ThreeAnd usually at least 0.05% by weight, based on the dry raw material
You. Suitably, this amount will be in the range 0.5 to 3.0% by weight, preferably 0.1 to 3.0%.
The range is 2.0% by weight.

The process of the present invention is preferably carried out with cellulosic fibers, optionally with high electrical conductivity,
Used in the manufacture of paper from suspensions containing fillers. Raw materials that are usually dehydrated on wire mesh
Has a conductivity of at least 0.75 mS / cm, suitably at least 2.0 mS / c.
m, preferably at least 3.5 mS / cm. Very good results, 5.
Also observed at conductivity levels above 0 mS / cm and above 7.5 mS / cm.
Was. The conductivity can be measured, for example, by WTW LF 5 supplied by Christian Berner.
It can be measured with standard equipment such as 39 instruments. The values mentioned above are properly
Is supplied to or present in the head box of the paper machine.
By measuring the conductivity of the suspension of Lurose or, alternatively, this suspension
It is determined by measuring the conductivity of white water obtained by dehydration of the liquid. High guidance
Electrical level refers to a high content of salt (electrolyte), where various salts are
Metal, for example N⁺And K⁺, Alkaline earths such as Ca²⁺And Mg²⁺,aluminum
Ions such as Al³⁺, Al (OH)²⁺And like poly aluminum ions
Monovalent, divalent and polyvalent cations and halides such as Cl^-, Sulfate, SO_Four ^2- And HSO_Four ^-, Carbonates such as CO_Three ^2-And HCO_Three ^-, Silicate and lower organic
It can be based on monovalent, divalent and polyvalent anions such as acids. The present invention is particularly applicable to 2
Useful in the production of paper from raw materials with high content of salts of monovalent and polyvalent cations
Usually this content is at least 200 ppm, suitably at least 30 ppm.
0 ppm and preferably at least 400 ppm. These salts are especially
A concentrated aqueous fiber suspension from a pulp mill is usually mixed with water to produce paper at a paper mill.
Used to form raw materials in an integrated factory that produces a suitable diluted suspension
It can be derived from existing cellulose fibers and fillers. This salt was also introduced into the raw material
From various additives, such as fresh water supplied to this method or carefully added fresh water
May be derived from Furthermore, the content of this salt usually means that white water is recycled on a large scale
High in the process, this leads to considerable accumulation of salts in the circulation of water in this way.
Can get.

Thus, the present invention is furthermore suitable for use in papermaking processes in which white water is recycled (recycled) on a large scale, that is to say with a high degree of confinement of white water, for example 0% per ton of dry paper produced. From 30 tons of fresh water, usually less than 20 tons per ton of regular paper,
Suitably less than 15 tonnes, preferably less than 10 tonnes, especially less than 5 tonnes of fresh water are used. The recirculation of the white water obtained by the present method suitably comprises converting the white water to cellulose fibers and / or
Or mixing with optional fillers to form a suspension to be dewatered; preferably, this involves mixing white water with cellulose fibers and optional fillers before the suspension enters the forming wire mesh for dewatering. And mixing with a suspension containing This white water can be mixed with the suspension before, during or after the introduction of the drainage and retention aid. Fresh water can be introduced into the process at any stage; for example, fresh water can be mixed with cellulosic fibers to form a suspension, and fresh water can be mixed with a cellulose fiber-containing suspension to form a dewatered suspension. To dilute the liquor and it, it can be mixed before or after mixing the raw materials with the white water and before, during or after the introduction of the drainage and retention aid.

Further additives customary in papermaking can of course also be used in combination with the additives according to the invention, such as, for example, dry strength agents, wet strength agents, sizing agents such as rosin, ketene dimer and acids. Such as those based on anhydrides, optical brighteners, dyes and the like. The suspension or raw material of the cellulose may also be of conventional type, such as kaolin, clay, titanium dioxide, gypsum, talc and chalk, natural and synthetic calcium carbonate such as ground marble and precipitated calcium carbonate. Mineral fillers can be included.

The method of the present invention is used for producing paper. The term "paper" as used herein, of course, includes not only paper and its products, but also other sheet or web-like products, such as, for example, cardboard and paperboard and its products. The method can be used for the production of paper from different types of suspensions of cellulose-containing fibers, the suspension comprising:
Suitably it should contain at least 25% by weight of such fibers, preferably at least 50% by weight, based on dry matter. This suspension is made of chemical pulp, such as sulphate, sulphite and organic solvent pulp, from both hardwood and softwood.
It can be based on fibers from mechanical pulp such as thermomechanical pulp, chemical thermomechanical pulp, refiner pulp and groundwood pulp, and also on recycled fibers, optionally from deinked pulp, and mixtures thereof. Can be based on

The present invention is further described in the following examples, however, the invention is not intended to be limited to these examples. Unless otherwise specified, parts and% represent parts by weight and% by weight, respectively.

Example 1 A cationic polymer was prepared by polymerization of a monomer mixture by the following general procedure : Monomer and initiator, 2,2'-azobis (2-amidinopropane) dihydrochloride (
Wako V-50) was added to the aqueous phase and the polymerization was carried out for about 24 hours at 45 ° C. with stirring under a nitrogen atmosphere. The cationic polymer obtained as a transparent gel was dissolved in water and used as a 0.1% aqueous solution.

The polymers according to the invention, ie P1 to P5, and the polymers intended for comparison purposes, ie Ref. 1 and Ref. 2, was prepared from the indicated amounts of the indicated monomers: P1: acrylamide (90 mol%), and acryloxyethyldimethyl n-butyl ammonium chloride (10 mol%)
P2: acrylamide (90 mol%) and acryloxyethyldimethylmethylcyclohexyl ammonium chloride (10 mol%); P3: acrylamide (90 mol%), methacryloxyaminopropyltrimethylammonium chloride (5 mol%), and meta Acryloxyethyl t-butylamine (5 mol%); P4; acrylamide (90 mol%), methacryloxyaminopropyltrimethylammonium chloride (5 mol%), and N-isopropylacrylamide (5 mol%); P5; acrylamide ( 90 mol%), methacryloxyaminopropyltrimethylammonium chloride (5 mol%), and Nt-butylacrylamide (5 mol%); Ref. 1: Acrylamide (90 mol%), and acryloxyethyltrimethylammonium chloride (10 mol%). Ref. 2: Acrylamide (95 mol%), and acryloxyethyltrimethylammonium chloride (5 mol%).

Example 2 Draining and yield performance was evaluated with a Dynamic Drainage Analyzer (DDA) available from Akribi, Sweden, where the plug was removed and the vacuum was reversed from the side where the material was present. When applied to the side of the wire mesh, through the wire mesh,
Measure the time for a fixed volume of raw material to drain. The yield of the first pass was evaluated by a turbidimeter by measuring the turbidity of the filtrate and white water obtained by draining the raw material.

The furnish used was TMP / SGW (80/80) bleached with 56% by weight of peroxide.
20) Pulp, 14% by weight bleached birch / pine sulphate pulp (60/40) purified to 200 ° CSF, based on 30% by weight clay. To this raw material, S
The bleached water from Mill C was filtered through a 5 μm sieve, concentrated on a UF filter, and 40 g / l of a colloidal fraction cut off 200,000 was added.
The volume of the raw material was 800 ml, the consistency was 0.14%, and the pH was 7.0. The conductivity was adjusted to about 2.5 mS / cm by adding calcium chloride (400 ppm Ca).

The raw material was stirred in a baffled jar at a speed of 1500 rpm throughout the test and the addition was carried out as follows: i) 30 seconds of stirring following the addition of the cationic polymer to the raw material, ii ) Stirring for 15 seconds following addition of the inorganic particles to the raw material;
iii) Draining of the raw material while automatically recording the draining time.

The cationic polymers tested in this example were P1 and Re according to Example 1.
f. It was one. The anionic fine particle material used in this example is a US Patent No.
Sol of silica-based particles of the type disclosed in US Pat. The sol had an S-value of about 25% and contained silica particles having a specific surface area of about 900 m ² / g, which particles were surface modified with aluminum to the extent of 5%. This silica-based sol was calculated as SiO ₂ and added to the raw material in an amount of 1.5 kg / ton based on the dry raw material system. Table 1 shows P calculated as dry polymer for dry feed system (kg / ton).
1 and Ref. 1 shows values of drainage time and yield at various addition amounts of 1.

[0050]

[Table 1]

Example 3 In this series of tests, drainage and retention performance was evaluated according to the procedure described in Example 2. This furnish was the same as that used in Example 2. Raw material volume is 800
ml, pH is about 7, and the conductivity was adjusted to 7.0 mS / cm by the addition of calcium chloride (1300 ppm Ca), thus simulating a high electrolyte content and a high degree of white water confinement.

The anionic inorganic material according to Example 2 was used in this example as well, calculated as SiO ₂ , and added in an amount of 1.5 kg / ton based on the dry raw material system. The polymers used in this example are P1, P2 and Ref. 1
Met. Table 2 shows P1, P, calculated as dry polymer for dry feed system.
2 and Ref. 1 shows the dehydration and yield effects at various addition amounts of 1.

[0053]

[Table 2]

Example 4 In this series of tests, the dewatering and retention performance was evaluated according to the procedure described in Example 2. The raw materials used in this example are the same as the raw materials used in Example 3, and are about 7.0.
It had a conductivity of mS / cm (1300 ppm Ca). The anionic inorganic material according to Example 2 was calculated as SiO _{2 and} added in an amount of 1.5 kg / ton based on the dry raw material system. The polymers used were P3 according to Example 1 and Ref. It was one. Table 3 shows P3 and Ref. Calculated as dry polymer for the dry feed system. 1
The results of the dehydration test at various addition amounts of are shown.

[0055]

[Table 3]

Example 5 In this series of tests, the dewatering performance was evaluated according to the procedure described in Example 2. The raw materials used in this series of tests were the same as those in Example 2, and about 2.
It had a conductivity of 5 mS / cm. The polymers used were P4, P5 according to Example 1.
And Ref. 2, which were calculated as dry polymer relative to the dry feed system and were added in an amount of 2 kg / ton. The anionic inorganic material according to Example 2 was likewise used in this series of tests. Table 4 shows the results of the dehydration tests at various loadings of anionic inorganic material, calculated as SiO ₂ and based on the dry raw material system.

[0057]

[Table 4]

Example 6 In this series of tests, the dewatering and retention performance was evaluated according to the procedure described in Example 2. This furnish was identical to that used in Example 2. Raw material volume is 800ml
, PH was about 7. Sodium chloride (550 ppm Na) and calcium chloride are added to the raw material, and the conductivity is adjusted to 5.0 mS / cm (400 ppm Ca).
And 7.0 mS / cm (1300 ppm Ca).

The polymers P2, P3, Ref. 1 and anionic microparticles were also used in this series of tests in combination with a low molecular weight cationic polymer. This polyamine was added to the above raw materials, and after stirring for 30 seconds, a cationic acrylamide-based polymer was added. This polyamine was added in an amount of 3 kg / ton, calculated as dry polymer to dry feed system. The main polymer, ie P2, P
3 and Ref. 1 was calculated as the dry polymer for the dry feed system, and
An amount of 5 kg / ton was added. Table 5 was calculated as a different conductivity SiO _2, based on dry stock system, shows the dewatering and retention effect of the addition amount of the silica-based particles.

[0060]

[Table 5]

Example 7 In this series of tests, the dehydration and yield effects were evaluated according to the procedure described in Example 2. This furnish was identical to that used in Example 2. Raw material volume is 800ml
, PH was about 7. Various amounts of sodium chloride were added to the raw material, and the conductivity was adjusted to 2.5 mS / cm (550 ppm Na) (serial test numbers 1-3), 5.0 m
S / cm (1470 ppm Na) (serial test numbers 4 to 6) and 10.0 mS
/ Cm (3320 ppm Na) (series test numbers 7 to 9).

The cationic polymers used were P1 to P3 according to Example 1 and Ref. 1
Met. The anionic particulate material used was a hydrated suspension of powdered sodium bentonite in water.

Table 6 shows the dewatering and retention effects at various loadings of polymer calculated as dry polymer for the dry feed system and bentonite calculated as dry for the dry feed system.

[0064]

[Table 6]

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] May 17, 2000 (2000.5.17)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or an alkyl group having 1 to 3 carbon atoms ; A is O or NH; B is an alkylene group having 2 to 8 carbon atoms or hydroxypropylene; A group wherein R ₄ contains 3 to 12 carbon atoms
A substituent containing an aromatic hydrophobic group; and X ⁻ is an anionic counter ion; (ii) a nonionic monomer having a non-aromatic hydrophobic group represented by the general formula (IV) :

Embedded image Wherein R ₁ is H or CH _3; A is O or NH; B is an alkylene group or a hydroxy propylene group charcoal atom of 2 to 8, or alternatively, no both A and B , thereby C and N single bond _{(O = C-NR 8 R} 9) is exist between; a non-aromatic hydrophobic group having R ₈ and R ₉ carbon atoms from H or 1 6, respectively And at least one of R ₈ and R ₉ is a substituent comprising a hydrophobic group having 2 to 6 carbon atoms ; and (iii) a non-aromatic hydrophobic group represented by the general formula (V). Nonionic monomer having a group :

Embedded image Wherein R ₁ is H or CH _3; a hydrophobic group having R ₁₀ are at least two carbon atoms; A is O or NH; B is from 2 4 Al Killen group carbon atoms; n is integer of at least 1 Is a substituent.

3. The cationic organic polymer is a vinyl addition polymer containing at least one non-cationic monomer having a non-aromatic hydrophobic group and at least one cationic monomer in a polymerized form. the method of claim 1 or 2 and.

Embedded image R ₁ is H or CH ₃ ; R ₂ and R ₃ are each an alkyl group having 1 to 2 carbon atoms; A is O or NH; B is an alkylene group or a hydroxypropylene group having 2 to 4 carbon atoms; the method according to any one of claims 1 6, characterized in that is anionic counterion ^- and X; substituent containing an alkyl group R ₄ contains a carbon atom of from 4 to 8.

Embedded image Wherein R ₁ is H or CH _3; A is O or be NH; is an alkylene group or a hydroxy propylene group of B is 2 to 8 4 carbon atoms, or alternatively, no both A and B This by a single bond _{(O = C-NR 8 R} 9) exists between the C and N; a substituent comprising an alkyl group having R ₈ and R ₉ carbon atoms from H or 1 6, respectively a method according to any one of claims 1 to 7, wherein at least one of R ₈ and R ₉ are a substituent containing an alkyl group having carbon atoms of 3 to 4.

Embedded image Wherein R ₁ is H or CH ₃ ; A is O; B is an alkylene group of 2 to 4 carbon atoms;
The method according to any one of claims 1 8, characterized in that an alkyl having R ₁₀ is at least 2 carbon atoms; n is integer of at least 1.

18. bound to the non-aromatic hydrophobic group is nitrogen or oxygen, which subsequently, cations of claim 16 or 17, characterized in that it is bonded via a chain of atoms to the polymer backbone Vinyl addition polymer.

19. The non-aromatic hydrophobic group is cationic vinyl addition polymer according to claim 16, 17 or 18, characterized in that an alkyl group containing 3 to 12 carbon atoms.

Embedded image Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene or hydroxypropylene group of 2 to 4 carbon atoms, or alternatively,
No A and B, thereby a single bond between C and _{N (O = C-NR 8} R 9) are present;
R ₈ and R ₉ are each H or a substituent containing an alkyl group having 1 to 6 carbon atoms, and at least one of R ₈ and R ₉ is a substituent containing an alkyl group having 2 to 6 carbon atoms. 20. The cationic vinyl addition polymer according to claim 16, 17, 18, or 19.

Embedded image Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene group of 2 to 4 carbon atoms; n is an integer of at least 1; and R ₁₀ is alkyl having at least 2 carbon atoms. 21. The cationic vinyl addition polymer according to any one of claims 16 to 20, characterized in that:

23. The cationic vinyl addition polymer comprises, in polymerized form, a cationic monomer of general formula (I):

Embedded image Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or an alkyl group having 1 to 3 carbon atoms; A is O or NH; B is an alkylene group having 2 to 4 carbon atoms or hydroxypropylene; 23. A cation according to claim 16, wherein R ₄ is a non-aromatic hydrocarbon group containing 4 to 8 carbon atoms; and X ⁻ is an anionic counterion. Vinyl addition polymer.

24. The cationic vinyl addition polymer, in polymerized form, of a cationic monomer represented by the general formula (III):

Embedded image Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or 1 to 3 carbon atoms;
A is O or NH;; B is 2 to 8 carbon atoms, suitable from 2 4 alkylene or hydroxypropylene group having a carbon; suitable alkyl group having 1 to 2 carbon atoms R ₇ is H , alkyl group, benzyl group or phenylethyl group containing 1 to 3 carbon atoms; and X ^- cationic claimed in any one of claims 16 to 23, is characterized in that it is an anionic counterion Vinyl addition polymer.

25. The thione vinyl addition polymer, prepared from a monomer mixture comprising from 5 to 25 mole% nonionic monomer and 95 having a non-aromatic hydrophobic group 75 mole% of other copolymerizable monomers 25. A cationic vinyl addition polymer according to any one of claims 16 to 24, characterized in that:

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) D21H 21:10 D21H 21:10 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, G B, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG , MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Sikkal Rein Sweden, S-448 34 Froda, Wessleschen 2F Term (Reference) 4J100 AL08P AL08Q AM14P AM14Q AM17P AN04P BA03P BA08P BA13P BA14P BA30P BA31P BA33Q BC04Q CA03 DA56 EA03 JA13 4L055 AG18 AG25 AG73 AG99 AH18 EA30 EA32 EA34 FA10 FA22

Claims (24)

[Claims] Claims: 1. A method of adding a drainage and retention aid comprising a cationic organic polymer and an anionic particulate material to a suspension, shaping the suspension on a wire mesh and dewatering the cellulose fibers. A method for producing paper from a suspension containing the filler according to claim 1, wherein the cationic organic polymer has a non-aromatic hydrophobic group. 2. The method according to claim 1, wherein the cationic organic polymer is a vinyl addition polymer containing at least one monomer containing at least one cationic monomer having a non-aromatic hydrophobic group in a polymerized form. The method of claim 1, wherein 3. The cationic organic polymer is a vinyl addition polymer containing at least one non-cationic monomer having a non-aromatic hydrophobic group and at least one cationic monomer in a polymerized form. The method according to claim 1 or 2, wherein 4. The method according to claim 1, wherein the hydrophobic group is bonded to nitrogen or oxygen, which is subsequently bonded to the polymer main chain by a chain of atoms. the method of. 5. The method according to claim 1, wherein the hydrophobic group is an alkyl group containing 3 to 12 carbon atoms. 6. The method according to claim 1, wherein the cationic organic polymer is an acrylamide-based polymer. 7. The polymer represented by the general formula (I), wherein the cationic organic polymer is polymerized.
And a cationic monomer having a non-aromatic hydrophobic group represented by the following formula: R ₁ is H or CH ₃ ; R ₂ and R ₃ are each an alkyl group having 1 to 2 carbon atoms; A is O or NH; B is an alkylene group or a hydroxypropylene group having 2 to 8 carbon atoms; the method according to any one of claims 1 6, characterized in that is anionic counterion ^- and X; substituent containing an alkyl group R ₄ contains a carbon atom of from 4 to 8. 8. The polymer represented by the general formula (I), wherein the cationic organic polymer is polymerized.
Including a non-ionic monomer having a non-aromatic hydrophobic group represented by V): Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene or hydroxypropylene group of 2 to 8 carbon atoms, or alternatively, A and B
Without both of which by a single bond between C and _{N (O = C-NR 8} R 9) are present;
R ₈ and R ₉ are each H or a substituent containing an alkyl group having 1 to 6 carbon atoms, and at least one of R ₈ and R ₉ is a substituent containing an alkyl group having 2 to 6 carbon atoms. The method according to claim 1, wherein the method comprises: 9. The polymer represented by the general formula (V), wherein the cationic organic polymer is polymerized.
And a nonionic monomer having a non-aromatic hydrophobic group represented by the following formula: Wherein R ₁ is H or CH ₃ ; A is O; B is an alkylene group of 2 to 4 carbon atoms;
The method according to any one of claims 1 8, characterized in that an alkyl having R ₁₀ is at least 2 carbon atoms; n is integer of at least 1. 10. The cationic organic polymer is prepared from a monomer mixture comprising 5 to 25 mol% of monomers having non-aromatic hydrophobic groups and 95 to 75 mol% of other copolymerizable monomers. The method according to any one of claims 1 to 9, wherein the method is a vinyl addition polymer. 11. The method according to claim 1, wherein the at least one anionic particulate material is selected from silica-based particles and bentonite. 12. The method according to claim 1, wherein the drainage and retention aid further comprises a low molecular weight cationic organic polymer. 13. The method according to claim 13, wherein the suspension to be dewatered on a wire mesh is at least 2.0 mS
A method according to any of the preceding claims, having a conductivity of / cm. 14. The method further comprises dewatering the suspension on a wire mesh to obtain a wet web of paper and white water, recirculating the white water and optionally introducing fresh water to the cellulose fibers to be dewatered. 2. A suspension comprising an optional filler, wherein the amount of fresh water introduced is less than 30 tonnes per ton of dry paper produced.
The method according to any one of claims 3 to 7. 15. The process according to claim 1, wherein less than 10 tons of fresh water per ton of dry paper to be produced is introduced into the process. 16. A cationic vinyl addition polymer comprising at least one non-cationic monomer in polymerized form having a non-aromatic hydrophobic group and at least one cationic monomer. 17. The cationic vinyl addition polymer of claim 16, wherein the hydrophobic group is attached to nitrogen or oxygen, which is subsequently attached to the polymer backbone via a chain of atoms. 18. The cationic vinyl addition polymer according to claim 16, wherein the hydrophobic group is an alkyl group containing 3 to 12 carbon atoms. 19. The cationic vinyl addition polymer according to claim 16, 17 or 18, wherein the cationic vinyl addition polymer is an acrylamide-based polymer. 20. The cationic vinyl addition polymer, in polymerized form, comprises a nonionic monomer having a non-aromatic hydrophobic group of general formula (IV): Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene or hydroxypropylene group of 2 to 8 carbon atoms, or alternatively,
No A and B, thereby a single bond between C and _{N (O = C-NR 8} R 9) are present;
R ₈ and R ₉ are each a substituent containing H or an alkyl group having 1 to 6 carbon atoms, and at least one of R ₈ and R ₉ is a substituent containing an alkyl group having 2 to 6 carbon atoms. 20. The cationic vinyl addition polymer according to claim 16, 17, 18, or 19. 21. The cationic vinyl addition polymer, in polymerized form, comprises a nonionic monomer having a non-aromatic hydrophobic group of general formula (V): Wherein R ₁ is H or CH ₃ ; A is O or NH; B is an alkylene group of 2 to 4 carbon atoms; n is an integer of at least 1; and R ₁₀ is alkyl having at least 2 carbon atoms. 21. The cationic vinyl addition polymer according to any one of claims 16 to 20, characterized in that: 22. The cationic vinyl addition polymer, in polymerized form, comprises a cationic monomer of general formula (I): Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or an alkyl group having 1 to 3 carbon atoms; A is O or NH; B is an alkylene group having 2 to 4 carbon atoms or hydroxypropylene; group; non-aromatic hydrocarbon radical R ₄ contains a carbon atom of from 4 to 8; and wherein X ^- cations according to any one of claims 16 21, characterized in that an anionic counterion Vinyl addition polymer. 23. The cationic vinyl addition polymer, in polymerized form, comprises a cationic monomer of general formula (III): Wherein R ₁ is H or CH ₃ ; R ₂ and R ₃ are each H or 1 to 3 carbon atoms;
A is O or NH;; B is 2 to 8 carbon atoms, suitable from 2 4 alkylene or hydroxypropylene group having a carbon; suitable alkyl group having 1 to 2 carbon atoms R ₇ is H 23. Cationic as claimed in any one of claims 16 to 22, characterized in that: an alkyl group containing 1 to 3 carbon atoms, a benzyl group or a phenylethyl group; and X ^- is an anionic counterion. Vinyl addition polymer. 24. The cationic vinyl addition polymer as set forth in claim 1, wherein said cationic vinyl addition polymer comprises a monomer mixture comprising 5 to 25 mol% of a nonionic monomer having a non-aromatic hydrophobic group and 95 to 75 mol% of another copolymerizable monomer. 24. A cationic vinyl addition polymer according to any one of claims 16 to 23, characterized in that it is prepared.