Cellulose product, method of its production and application

FIELD: textile, paper.

SUBSTANCE: cellulose product comprises thermoplastic microspheres and a charged aromatic acrylamide polymer. The method to produce a cellulose product includes provision of an aqueous solution of suspension that contains cellulose fibres. Addition of thermoplastic microspheres and the charged aromatic acrylamide polymer into the suspension, and dehydration of the produced suspension. Thus made cellulose product may be used as a cardboard for liquid packing.

EFFECT: reduced porosity of a cellulose product as its volume increases and improved resistance of a wick edge to penetration of aqueous liquids for cellulose products.

25 cl, 3 tbl, 4 ex

 

Description

The technical field to which the invention relates

The present invention relates to cellulosic product containing thermoplastic microspheres, and to its preparation and application.

Background of invention

Cellulosic products containing thermoplastic microspheres, known in the art, see U.S. patent No. 3556934, 4133688 and 5125996 published patent application U.S. No. 2003/0152724, lined with Japanese application No. 2002-254532 and 2003-105693, Japanese application No. 2689787, published applications international patent No. 2001/54988, 2004/099499, 2004/113613 and 2006/068573 and C. Söderberg, World Pulp & Paper Technology 1995 / 1996, “The International Review for the Pulp & Paper Industry”, p.p. 143-145.

Thermoplastic microspheres can be entered in the pulp and products to provide paper products paper and paperboard of low density and high density, for example, insulating containers, such as, for example, paper cups, which can be used for serving hot and cold drinks. However, it is known from practice that the porosity of such cellulosic products may be too high, thus reducing the resistance to penetration of gases and aqueous liquids, especially correspondingly reduced resistance titledeko edge penetration of aqueous liquids for taped pulp products containing thermopla the quadratic microspheres.

It would be preferable to create cellulosic products containing thermoplastic microspheres, which show improved properties, in particular improved porosity and resistance titilayo edge.

Brief description of the invention

The present invention relates to cellulosic product containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer.

The present invention also relates to a method for producing cellulose product, which includes

(i) providing a water suspension containing pulp fibers;

(ii) introducing the slurry of thermoplastic microspheres and a charged aromatic acrylamidoethyl polymer; and

(iii) dewatering the obtained suspension.

The present invention also relates to the use of cellulosic product containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer, as a packaging carton for liquids.

Detailed description of the invention

Introduction thermoplastic microspheres in pulp products usually increases the porosity, increases the volume and decreases the density in comparison with cellulose products, not containing thermoplastic microspheres. It was found that according to the present invention, the zoom is the porosity may be less with a corresponding increase, and improved low porosity is obtained by using the cellulose products containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer. In this context, improved porosity is an indication of increased resistance to penetration of gases and/or aqueous liquids and improved resistance titledeko edge penetration of aqueous liquids for taped pulp products containing thermoplastic microspheres. Therefore, the present invention makes possible the creation of cellulosic products with improved properties.

The term "pulp products", as used here, refers to all types of cellulosic products, including bales of pulp and pulp products in the form of a sheet and a cloth, preferably of paper and paper Board. Cellulose product may contain several layers or sheets containing cellulose fibers, including single-layer and multi-layer paper and cardboard.

According to the present invention the cellulose product is produced in a way that provides an introduction thermoplastic microspheres and a charged aromatic acrylamidoethyl polymer in the aqueous pulp suspension, and then dehydrating the resulting suspension with a molded pulp product. In the preferred embodiment, this image is giving provides a single layer cellulosic product such as paper and paperboard, containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer, which preferably distributed throughout the cellulosic product, more preferably, essentially uniformly distributed throughout the cellulose product.

In another preferred embodiment, the invention provides multi-layer cellulosic product, such as paper and paperboard, containing cellulose fibers, where at least one of said two or more layers, or sheets, contains thermoplastic microspheres and charged aromatic acrylamidoethyl polymer. Preferably, thermoplastic microspheres and charged aromatic acrylamidoethyl polymer distributed throughout at least one of said two or more layers, more preferably essentially uniformly distributed throughout at least one of said two or more layers. Multilayer cellulose products according to the present invention can be obtained by forming at least one layer containing cellulose fibers, thermoplastic microspheres and charged aromatic acrylamidoethyl polymer, and attach the specified at least one layer to one or more layers containing cellulose is haunted fibers forming multilayer cellulose product. For example, multilayer cellulose product can be obtained by forming one or more individual layers separately in one or more metaproteomic intermediate products and then laying them together in the wet state. Examples of suitable types of laminated cellulose product of the present invention include varieties containing from three to seven layers or sheets containing cellulose fibers and at least one of the cellulose layers or sheets containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer. In multi-layer cellulosic products with three or more layers, preferably at least one of the middle layer contains a thermoplastic microspheres and charged aromatic acrylamidoethyl polymer.

Pulp products according to the present invention in the form of a sheet or Mat, including single-layer and multi-layer products such as paper and cardboard, preferably, have a lot of units of product from about 50 to about 500 g/m2most preferably, from about 100 to about 300 g/m2.

The term "paper cardboard", as used here, refers to various types of paper paperboard, containing cellulosic fibers, including solid cardboard, for example, solid paperboard of bleached sulphate is cellulose (SBS) and solid paperboard of unbleached sulphate pulp (SUS), cardboard, for example flexible box Board (FBB), flexible cardboard, cardboard for packaging liquids (LPB), including decorative, aseptic, block, seasations packaging and sterilizes cardboard, paperboard from waste paper with a white strip (WLC), the paperboard of unbleached Kraft paper, gray paperboard from waste paper and cardboard from recycled materials, packing cardboard and cardboard container, including white Kraft strip of sulphate pulp, Kraft strip of fully bleached pulp, the test strip, the white test strip from sulphate pulp, unbleached Kraft gasket, unbleached test strip and strip made from recycled materials, track and corrugated track. In a preferred variant of the invention, the cellulosic product is a cardboard for the packaging of liquids.

According to the present invention the pulp product and the suspension may contain various types of cellulosic fibers and, preferably, contain at least 25 wt.% and, more preferably, at least 50 wt.% such fibers relative to the dry substance. Pulp product and the suspension can be made of and contain pulp fibers of various types of pulp such as bleached and unbleached pulp based on the source and/or regenerated fibers. Cellulose can be based fibers from himicheskoi cellulose, such as sulphate, sulphite and organosilica pulp, mechanical pulp, such as thermomechanical pulp ((TMC)(TSR)), chemothermomechanic cellulose ((HTML) (STMR)), refined pulp and ground wood pulp from both hard wood and soft wood, and may be based on regenerated fibres, not necessarily from undyed cellulose(REC)(DIP)), and mixtures thereof. The cellulose product can also be made from fibers derived from annual plants, such as pennisetum red, bagasse, flax, straw, etc. Cellulose product may contain one or more layers of same or different types of pulp. Examples of multilayer combinations include the top of bleached chemical pulp/the middle of the REC, HTML or mechanical pulp/rear of bleached chemical pulp; the top of bleached chemical pulp/the middle of the REC, HTML or mechanical pulp/rear of mechanical pulp; the top of bleached chemical pulp/the middle of the REC, HTML or mechanical pulp/top of bleached chemical pulp pulp; and the top of bleached chemical pulp/rear of unbleached chemical pulp; the upper side is not necessarily covered, and the back side is not necessarily covered. The upper side refers to the thoronet, intended for facing the outside of the final product or the packaging.

According to the present invention the cellulose product contains thermoplastic microspheres, which may be foamed or nesperennub thermally expandable microspheres. Thermoplastic microspheres, preferably, foaming and introduced into the pulp slurry or the initial mixture, the method of obtaining a cellulose product or as podsilenie or as nevspahannye thermally expandable microspheres, which, preferably, foaming when heated in the method of obtaining a cellulose product, for example during the stage of drying, where heat is supplied or on the individual stage of the way, for example in a cylindrical heater or in the laminator. The microspheres may be expanded when the cellulose product is still wet or when the pulp product is completely or almost completely dried up. The microspheres preferably administered in the form of an aqueous suspension, which optionally may contain other additives desired for introduction into the pulp suspension.

Thermoplastic microspheres according to the present invention, preferably, contain a shell of thermoplastic polymer, kapsulirujushchej propellant. The propellant preferably is a liquid having a point is andsinging not higher than the softening temperature of the shell of thermoplastic polymer. When heated, thermally expandable microspheres of the propellant increases the internal pressure at the same time, when the shell softens, resulting in a significant expansion of the microspheres. As foaming and podsilenie thermoplastic microspheres are commercially available under the trademark Expancel (Akzo Nobel) and come in various forms, such as dry Svobodnoye particles, such as aqueous suspension or as a partially dewatered wet sediments. They are also well described in the literature, for example in U.S. patents№№ 3615972, 3945956, 4287308, 5536756, 6235800, 6235394 and 6509384, in published patent application U.S. No. 2005/0079352, in European patent No. 486080 and 1288272, in published application for international patent # WO 2004/072160 and lined with Japanese applications No. 1987-286534, 2005-213379 and 2005-272633, which therefore provided here as a reference.

Thermoplastic polymer shell of thermoplastic microspheres, preferably made of homopolymer or copolymer obtained by copolymerization of polymerizable monomers with ethylene unsaturation. Such monomers can be, for example, nitrosomonas monomers, such as Acrylonitrile, Methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylate, fumaronitrile or crotonates, complex acrylic esters such as methyl acrylate or acrylate, the false methacrylic esters, such as methylmethacrylat, isobornylacrylat or methacrylate, vinylchloride, such as vinyl chloride, complex, vinyl esters such as vinyl acetate, simple vinyl esters, such as simple alkylvinyl esters, such as simple metilidinovy ether or a simple ethylenically ether, and other vinyl monomers, such as vinylpyridine, vinylidenechloride, such as vinylidenechloride, styrene, such as styrene, halogenated styrene or α-methylsterols, or diene, such as butadiene, isoprene and chloroprene. You can also use any mixtures of the above monomers.

Propellant thermoplastic microspheres may contain hydrocarbons, such as propane, butane, isobutane, n-pentane, isopentane, neopentane, hexane, isohexane, neohexane, heptane, isoheptane, octane or isooctane, or mixtures thereof. In addition to these, you can also use other types of hydrocarbons such as petroleum ether or chlorinated or fluorinated hydrocarbons such as methyl chloride, methylene chloride, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, Trichlorofluoromethane, perfluorinated hydrocarbons, etc.

Expandable thermoplastic microspheres suitable for the invention, preferably, have a volumetric average diameter from about 1 to about 500 microns, more preferably, from about 5 to about 100 the km, most preferably, from about 10 to about 50 microns. The temperature at which it starts foaming, called Tstartthat is, preferably, from about 60 to about 150°C, most preferably from about 70 to about 100°C. the Temperature at which the maximum foaming, called Tmaxthat is, preferably, from about 90 to about 180°C, most preferably from about 115 to about 150°C.

Podsilenie thermoplastic microspheres suitable for the invention, preferably, have a volumetric average diameter from about 10 to about 120 microns, most preferably from about 20 to about 80 microns. Density preferably ranges from about 5 to about 150 g/DM3most preferably, from about 10 to about 100 g/DM3. Although podsilenie thermoplastic microspheres are commercially available as such, they can also get thermal unilateral foaming nesperennub expandable thermoplastic microspheres, for example, before they are introduced into the pulp suspension, which will be easier if expandable microspheres have Tstartbelow about 100°C, so that the heating medium can be used water vapor.

In the method of obtaining a cellulose product charged arene is political acrylamidoethyl polymer according to the present invention, preferably, acts as a restraint, drainage and/or hardening dry additive, optionally, in combination with other additives in the pulp suspension, such as silicon-containing material, coagulants and other organic polymers. The terms "retention and drainage additive"as used here, refers to one or more additives in the pulp suspension, which provide improved retention and/or drainage in the production method of the cellulose product. The term "hardening dry additive"as used here, refers to one or more additives in the pulp suspension, which give improved strength in the dry state cellulosic product.

Charged aromatic acrylamidoethyl polymer according to the present invention contains one or more charged or ionic groups of the same type or of different types. One or more charged groups can be anionic, cationic, or a combination of both anionic and cationic groups. In one embodiment of the invention, the polymer contains one or more cationic groups of the same type or of different types. Alternative or additionally, the polymer may contain one or more anionic groups of the same type or of different types. Charged aromatic acrylamidoethyl is OLIMAR maybe thus, selected from anionic, amphoteric and cationic organic polymers. Examples of suitable cationic groups include sulfonate and primary, secondary, tertiary and Quaternary ammonium groups, preferably Quaternary ammonium groups. Examples of suitable anionic groups include carboxylate, sulphonate, sulphate, phosphate and phosphonate groups.

Charged aromatic acrylamidoethyl polymer according to the present invention contains one or more aromatic groups of the same type or of different types. The aromatic group may be present in the polymeric base (main circuit) or in the group substituent, which is attached to the polymeric base. Examples of suitable aromatic groups include aryl-, aralkyl and alkaryl group, such as phenyl, phenylene, naphthyl, xylylene, benzyl and phenylethyl; nitrogen-containing aromatic (aryl) groups, such as pyridine and chinoline, as well as derivatives of these groups, such as benzyl.

Charged aromatic acrylamidoethyl polymer according to the present invention contains in polymerized form one or more polymerizable acrylamidoethyl monomers, i.e. acrylamide and/or substituted acrylamide, such as methacrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, dia is criminally(meth)acrylamide, N,N-methylene-bis(meth)acrylamide, N-vinyl(meth)acrylamide and N-methylallyl(meth)acrylamide. Examples of suitable charged aromatic acrylamidoethyl polymers according to the present invention include polymers obtained by the polymerization of Monomeric mixtures containing acrylamide or methacrylamide, i.e. the (meth)acrylamide, preferably acrylamide. The monomer mixture may also contain one or more copolymerizate cationic, anionic and/or nonionic monomers. According to a preferred variant implementation of the Monomeric mixture contains one or more charged aromatic monomers which can be cationic and/or anionic. Alternative or additional Monomeric mixture contains anionic and/or cationic monomers and non-ionic aromatic monomer.

Examples of suitable cationic aromatic monomers include monomers represented by the General structural formula (I)

in which

R3represents N or CH3,

R1and R2are each H or, preferably, a hydrocarbon group, suitably alkyl group having from 1 to 3 carbon atoms, preferably 1-2 carbon atoms,

And2represents O or NH,

In2represents an alkyl - or alkylene group having from 2 to 8 at narodnih atoms, suitably from 2 to 4 carbon atoms, or hydroxypropyl-group

Q represents a Deputy containing aromatic group, suitably a phenyl - or substituted phenyl group, which may be attached to the nitrogen through alkylene groups, typically with from 1 to 3 carbon atoms, suitably 1-2 carbon atoms, and, preferably, Q is a benzyl group (-CH2With6H5), and

X-is an anionic counterion, typically a halide, for example chloride.

Examples of suitable monomers represented by the General structural formula (I)include dimethylaminoethylacrylate Quaternary salt and dimethylaminoethylmethacrylate Quaternary salt. Examples of other suitable copolymerizate cationic monomers include acid additive salts and Quaternary salts of dimethylaminoethyl(meth)acrylate and diallyldimethylammoniumchloride and triethylammonium salt.

Examples of anionic monomers include monomers, which are anionic in aqueous solution. Examples of suitable anionic aromatic monomers include styrelseledamot and their salts, including salts of sodium and other alkali metals. Examples of other suitable copolymerizate anionic monomers include acrylic acid, methacryloylamido, ethylacrylate acid, crotonic acid, taconova acid and maleic acid and their salts, preferably their salts, including salts of sodium and other alkali metals.

Examples of suitable nonionic aromatic monomers include styrene, substituted styrene and divinylbenzene. Examples of other suitable copolymerizate non-ionic monomers include galatsaray monomers, such as dialkylaminoalkyl(meth)acrylates, polietilenglikoli(meth)acrylate, glycidyl(meth)acrylate and vinylamide.

The preferred examples of charged aromatic acrylamidoethyl polymers according to the present invention include cationic and amphoteric cationic polymers obtained by cationic polymerization of aromatic monomer or monomer mixture containing (meth)acrylamide and a cationic aromatic monomer represented by the General structural formula (I), usually in combination with an anionic monomer. Other examples include anionic and amphoteric polymers obtained by polymerization of a monomer mixture containing (meth)acrylamide and anionic aromatic monomer, for example styrelseledamot and their salts, optionally in combination with a cationic monomer.

Charged aromatic acrylamidoethyl polymers according to the present invention can be obtained Polimeri what situation monomer mixture, usually containing from 1 to 99 mol.%, preferably from 2 to 50 mol.% and, preferably, from 5 to 20 mol.%, monomer having an aromatic group, for example, a monomer having an aromatic and cationic or anionic groups, or a monomer having an aromatic group, and a monomer having a cationic or anionic group, respectively, and from 99 to 1 mol.%, preferably from 98 to 50 mole%, and preferably from 95 to 80 mol.% other copolymerizate monomers which preferably contain acrylamide or methacrylamide ((meth)acrylamide), monomer mixture, preferably containing from 98 to 50 mole% and preferably from 95 to 80 mol.% (meth)acrylamide, and the sum of the percentages is 100.

Charged aromatic acrylamidoethyl polymer according to the present invention may be unbranched, branched or crosslinked. Charged aromatic acrylamidoethyl polymer is suitably a water-soluble or swollen, preferably, water-soluble, and it is preferably introduced into the pulp suspension in the form of its aqueous solution or dispersion.

Charged aromatic acrylamidoethyl polymer according to the present invention may have a charge density from about 0.5 to about 10 mEq/g and, preferably, from about 1 to about 8 mEq/g Examples of aromatic polymers which can be used according to the present invention, include polymers discussed in WO 2002/12626, 2003/064767, 2006/068576 and 2006/123989, which therefore provided here as a reference.

Usually charged aromatic acrylamidoethyl polymer has srednevekovoy molecular weight of at least 50,000, or at least about 500000, or at least about 1000000. In most cases, preferably, srednevekovaja molecular weight is not more than about 50 million, especially not more than about 10 million, or approximately 5 million

Examples of suitable silicon-containing materials include anionic (silicon dioxide)containing particles and anionic clay smectite type. Preferably, the silicon-containing material has particles in the colloidal range of particle size. Preferably used anionic (silicon dioxide)containing particles, i.e. particles based on SiO2or silicic acid, and such particles are usually suspendered in the form of aqueous colloidal dispersions, the so-called sols. Examples of suitable silicon-containing materials include colloidal silicon dioxide, and various types of polysilicon acid or homopolymerization or copolymerizing. (Silicon dioxide)containing sols can be modified and can contain other elements, such as aluminum, boron, nitrogen, zirconium, gallium, titanium, etc., which may be present in the aqueous phase and/or (silicon dioxide)containing the particles. Examples of suitable (silicon dioxide)containing particles of this type include colloidal silicon dioxide, modified alumina, and aluminosilicates. Can also be used mixtures of such suitable (silicon dioxide)containing particles. Examples of suitable drainage and retention supplements containing anionic (silicon dioxide)containing particles include additives discussed in U.S. patent№№ 4388150, 4927498, 4954220, 4961825, 4980025, 5127994, 5176891, 5368833, 5447604, 5470435, 5543014, 5571494, 5573674, 5584966, 5603805, 5688482 and 5707493, which therefore provided here as a reference.

Examples of suitable anionic (silicon dioxide)containing particles include anionic (silicon dioxide)containing particles having an average particle size less than about 100 nm, preferably less than about 20 nm and most preferably in the range of from about 1 to about 10 nm. As conventional in the chemistry of silica, the particle size refers to the average size of the main particles, which can be aggregated or non-aggregated. Specific surface area (silicon dioxide)containing particles is suitably greater than 50 m2/g and, preferably, above 100 m2/, Usually the specific surface area can be up to about 1700 m2/g and predpochtitelno, up to 1000 m2/g Specific surface area is determined by NaOH titration is well known manner, for example, as described in the work G.W.Sears, Analytical Chemistry, 28 (1956): 12, 1981-1983 and in U.S. patent No. 5176981. This area, therefore, represents the average specific surface area of particles.

Preferably, anionic (silicon dioxide)containing particles have a specific surface area in the range from 50 to 1000 m2/g, more preferably from 100 to 950 to m2/, Sols (silicon dioxide)containing particles of these types also cover modifications, for example, any of the items listed above. Preferably, (silicon dioxide)containing particles are present in the ashes, having an S-value in the range from 8 to 50%, preferably from 10 to 40%, containing (silicon dioxide)containing particles with a specific surface area in the range from 300 to 1000 m2/g, suitably from 500 to 950 to m2/g, and preferably from 750 to 950 to m2/g, which sols can be modified, as described above. S-value can be measured and calculated as described in the work of Iler & Dalton, J. Phys. Chem., 60 (1956), 955-957. S-value indicates the degree of aggregation or formation of microgel, and a lower S-value indicates a higher degree of aggregation.

In still another preferred embodiment of the invention (dioxide to amnia)containing particles selected from polysilicon acid, or homopolymerization or copolymerizing having a high specific surface area above about 1000 m2/g Specific surface area can be in the range of from 1000 to 1700 m2/g and preferably from 1050 to 1600 m2/, Sols modified or copolymerizing polysilicon acids may contain other elements, as described above. In the technique of polysilicon acid is also known as the polymeric silicic acid, the microgel polysilicon acid polysilicate and the polysilicate microgel, which are all covered by the term "polysilicon acid", as used here. Aluminium-containing compounds of this type are also commonly referred to as polyaluminosilicate and the microgel of polyaluminosilicate, which are both covered by the term "silicon dioxide, modified aluminum" and "silicate"as used here.

Examples of suitable anionic clays smectite type include the montmorillonite/bentonite, hectorite, Badelt, nontronite, saponite, laponite, preferably bentonite. Examples of suitable anionic bentonite clays include clay, discussed in U.S. patent No. 4753710, 5071512 and 5607552, which therefore provided here as a reference.

Examples of suitable cationic coagulants (also known as traps waste or fixative) include himself a water-soluble organic polymer and inorganic coagulants coagulants. Cationic coagulants can be used separately or together, i.e. polymer coagulant may be used in combination with an inorganic coagulant. Examples of suitable water-soluble cationic organic polymer coagulants include cationic polyamine, polyamidoamine, polyethyleneamine, polymers, polycondensation dicyandiamide and polymers polymerization of water-soluble monomer with ethylene unsaturation or Monomeric mixture which is formed from 50 to 100 mol.% cationic monomer and 0-50 mol.% another monomer. The amount of cationic monomer is usually at least 80 mol.%, eligible 100%. Examples of suitable cationic monomers with ethylene unsaturation include dialkylaminoalkyl(meth)-acrylates and-acrylamide, preferably, in quaternionic form, and diallyldimethylammoniumchloride, such as diallyldimethylammoniumchloride ((DADMAC)(DADMAC)), preferably homopolymers and copolymers of DADMAC. Cationic organic polymer coagulants are usually srednevekovoy molecular weight in the range from 1,000 to 700,000, suitably from 10000 to 500000. Examples of suitable inorganic coagulants include aluminum compounds such as aluminum and semi-aluminum compounds, such as polyaluminosilicate, polyaluminosilicate, polyaluminosilicate and CME is I.

Examples of other organic polymers which can be used as drainage and retention additives include polymers of the above types, except that one or more aromatic groups present in the polymers. Examples of suitable organic polymers of the specified type include anionic, amphoteric and cationic polysaccharides, such as gargani and starches, anionic, amphoteric and cationic polymers of vinyl accession, such as acrylamidoethyl polymers, for example, essentially unbranched, branched and crosslinked anionic and cationic acrylamidoethyl polymers, preferably cationic starch and cationic and anionic polyacrylamide.

According to the present invention cellulose and preferably glued hydrophobic sizing agent, which is introduced into the initial mixture before dehydration and/or applied to the surface of the cellulose product, preferably at least create more gluing materials. In multilayer cellulose products, preferably prokleivayutsya one or more layers containing thermoplastic microspheres and the aromatic polymer. Taped pulp products according to the present invention show increased resistance to penetration of aqueous liquids, especially hydrocarbons is lichenous resistance to fitilieu edge. The preferred sizing agent include interacting with cellulose sizing agent, such as dimers or multimer of ketene, such as dimers alkyl - or alkenylamine (AKD), succinic anhydrides, for example alkyl - or alkenylamine anhydrides (ASA) and their mixtures. Others used a sizing agent include not interacting with cellulose sizing agent such as rosin, starch and other polymeric sizing agent, for example copolymers of styrene with vinyl monomers, such as maleic anhydride, acrylic acid and its alkalemia esters, acrylamide, etc. are the Same or different sizing agent can be used for different layers in the cellulosic product. For example, you can use AKD or ASA in one or more layers and rosin in one or more other layers.

Preferred ketene dimers have the General formula (II)

where R1and R2are the same or different saturated or unsaturated hydrocarbon group such as alkyl, alkenyl, cycloalkyl, aryl or aralkyl. The hydrocarbon group may be branched or unbranched and preferably have from 6 to 36 carbon atoms, most preferably from 12 to 20 carbon atoms. Examples of hydrocarbon g the SCP include branched or unbranched groups: octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl, cyclohexyl and hexadecyl. Depending on the hydrocarbon groups of the ketene dimer can be solid or liquid at room temperature (25°C). Examples of suitable sizing substances include a sizing agent, discussed in U.S. patent No. 5969011, 6165259, 6306255 and 6846384.

According to the present invention cellulose and, preferably, contains a hardening agent in the wet state, which is introduced into the initial mixture before dehydration. Suitable hardening agents in the wet state include tar: polyaminoamide, polyamideimides, polyaminopolycarboxylic, urea, mcevisualaid/formaldehyde, phenol-formaldehyde, condensation, polyacrylamidegel, polyvinylene, polyurethane, polyisocyanate, and mixtures thereof, of which particularly preferred is polyaminopolycarboxylic.

Especially preferred is that at least one sizing substance, preferably a dimer of ketene, and a hardening agent in the wet state, preferably polyaminopolycarboxylic are introduced into the initial mixture upon receipt of the paper or paper Board.

The cellulose product can which also contain other additives, usually used in obtaining paper and introduced into the pulp slurry prior to dewatering. Such additives may include one or more fillers, such as mineral fillers, such as kaolin, white clay, titanium dioxide, gypsum, talc, chalk, crushed marble, ground calcium carbonate and pre-precipitated calcium carbonate. Other commonly used additives may include colorants, optical brighteners, etc.

According to the present invention the cellulose product, such as single-layer and multi-layer paper and paper cardboard, may be subjected to additional stages of processing. Examples of suitable processing stages include a coating, such as coating of starch and coating pigment, printing and cutting. Accordingly, examples of suitable cellulosic product of the present invention include paper, cardboard, coated, for example coated with starch and/or pigment, paper and cardboard with printed.

Thermoplastic microspheres, charged aromatic acrylamidoethyl polymer and optionally other additives, such as silicon-containing materials, coagulants, and other organic polymers, sizing agent and a hardening agents in the wet state, can be introduced into the pulp suspend the Yu traditional way and in any order. Preferably thermoplastic microspheres in the pulp suspension, preferably, prior to the introduction of a charged aromatic acrylamidoethyl polymer, even if can also be used in the opposite order of introduction, and, preferably, prior to the introduction of silicon-containing materials, sizing substances and reinforcing agents in the wet state, if used. When using a silicon-containing material is preferably charged led aromatic acrylamidoethyl polymer in the suspension prior to or simultaneously with the introduction of the silicon-containing material. In addition, preferably the cationic polymer to phase shift, which can be selected from pumping, mixing, cleaning, etc. and enter the silicon-containing material after such a phase shift. When using a cationic coagulant it is preferable to introduce into the pulp suspension early in the method, preferably, prior to the introduction of a charged aromatic acrylamidoethyl polymer and silicon-containing material, if used. When using a sizing agent it is preferable to introduce into the pulp suspension early in the method, for example, before or after the introduction of thermoplastic microspheres. When using a hardening agent in the wet state it preferably is of contain in the pulp suspension early in the method, usually before the introduction of the sizing agent and either before or after the introduction of thermoplastic microspheres.

According to the present invention thermoplastic microspheres, charged aromatic acrylamidoethyl polymer and other optional additives can be incorporated in the pulp suspension and to be present in the cellulosic product in amounts which can vary within wide limits depending on (among other things) the type and number of additives, the type of pulp suspensions, filler content, type of filler, the moment of introduction, etc. the Amount of thermoplastic microspheres is suitably from about 1 to about 100, preferably from about 1 to about 50, and most preferably, from about 4 to about 40 kg/ton dry cellulosic suspension or product. The number of charged aromatic acrylamidoethyl polymer is suitably from about 0.01 to about 30 and preferably from about 0.1 to about 5 kg/ton dry cellulosic suspension or product. If used, the amount of siliceous material is suitably from about 0.01 to about 10 and preferably from about 0.1 to about 5 kg/ton dry cellulosic suspension or product. If used, the amount of cationic coagulant is suitably from about 0.01 to Primero and preferably, from about 1 to about 20 kg/ton dry cellulosic suspension or product. If used, the amount of other organic polymer is suitably from about 0.01 to about 30 and preferably from about 0.1 to about 5 kg/ton dry cellulosic suspension or product. If used, the amount of sizing agent is suitably from about 0.1 to about 10 and preferably from about 0.3 to about 5 kg/ton dry cellulosic suspension or product. If used, the amount of hardening agent in the wet state is, preferably, from about 0.1 to about 10 and preferably from about 0.5 to about 5 kg/ton dry cellulosic suspension or product.

The present invention is additionally illustrated by the following examples, which, however, is not intended to be limiting thereof. Parts and % are parts by weight and wt.%, accordingly, unless otherwise specified.

Example 1

The examples use the following products:

MS1:Nevspahannye microspheres with average particle size 16-24 μm (Expancel 820SL80).
MS2:Nevspahannye microspheres with average particle size of 6-9 μm (Expancel 461WU20).
MS3:Partially podsilenie microspheres with average particle size of 20-30 μm (Expancel 461WE20).
PL1:Cationic acrylamidoethyl the polymer obtained by the polymerization of acrylamide (90 mol.%) and acrylonitrilebutadiene (10 mol.%), moreover, the polymer has an average-weight molecular weight of about 6 million and a cationic charge of about 1.2 mEq/g
PL2:Cationic acrylamidoethyl the polymer obtained by the polymerization of acrylamide (90 mol.%) and acrylonitrilebutadienestyrene (10 mol.%), moreover, the polymer has srednevekovoy molecular weight of about 6 million and a cationic charge of about 1.2 mEq/g
PL3:Cationic acrylamidoethyl the polymer obtained by the polymerization of acrylamide (90 mol.%) and acrylonitrilebutadiene (10 mol.%), moreover, the polymer has srednevekovoy molecular weight of about 1 million and a cationic charge of about 1.2 mEq/g
PL4:Cationic acrylamidoethyl the polymer obtained by the polymerization of acrylamide (90 mol.%) and acrylonitrilebutadienestyrene (10 mol.%), moreover, the polymer has srednevekovoy molecular weight of about 1 million and is tinny charge of about 1.2 mEq/g

NP1:Anionic inorganic condensation polymer of silicic acid in the form of a Sol of colloidal silicon dioxide, modified aluminum, having an S-value of <35 and containing silicon dioxide)containing particles with a specific surface area of about 700 m2/year
ST1:Cationic starch-containing biopolymer modified 2,3-hydroxypropyltrimethylammonium to D.S. 0,042, and the polymer has a cationic charge density of about 0.28 mEq/g
SA1:Sizing substance AKD, stable PL3.

Example 2

The Central layer of cardboard for packaging liquid is obtained in the form of PFI-sheet with a unit weight of 200 g/see the Raw materials used in the experiment is a Kraft fibers of bleached soft wood. The consistency of the mixture is 1.8%. Conductivity is 0.2 MSM/see

Introduction in the initial mixture are performed at the following times (in seconds):

- 0, Expancel microspheres, MS1

- 15, cationic polymer, PL

- 30, anionic colloidal solution of silicon dioxide, NP1

- 45 c, dehydration.

The cardboard sheets are pressed and dried. In order to make mi is ropery MS to foam, use cylindrical dryer at 125°C.

The porosity is determined using an instrument Bendtsen Porosity Tester Model 5, supplied by the firm of Anderson & Sörensen, Denmark. The unit of measurement for this device for measuring the porosity is [ml/min] air. Volume, measured in [cm3/kg], is calculated by dividing the thickness [μm] specific weight [g/m2]. The thickness is determined by the device L&W Tester Type 5102 supplied by the company Lorentzen &Wettre, Sweden, and the unit weight of the product is determined using a standard scale to obtain the weight [g] for a given area [m2] sample paper or cardboard.

Table 1 shows the results of measurements of porosity and density at different levels of administration, calculated as dry product dry commodity system, except (silicon dioxide)containing particles, which were calculated as SiO2and on a dry commodity system.

Experiments No. 1-5 demonstrate methods using additives used for comparison (Ref.), and experiments No. 6-8 show the methods according to the present invention.

Table 1
No.
experiment
Microspheres MS1
Expancel
(kg/t)
Type
polymer
Polim the p
(kg/t)
Nanoparticles
NP1
(kg/t)
Volume (cm3/g)Porosity (ml/min)
1----2,1328
2---0,52,2385
310PL 10,50,52,4558
420PL 10,50,52,7742
540PL 3223,11010
610PL 20,5 0,52,4532
720PL 20,50,52,7703
840PL 4223,1933

As can be seen from table 1, when using PL2 and PL4 according to the present invention, the volume increases at a relatively low porosity compared using PL1 and PL3.

Example 3

The Central layer of cardboard for packaging liquid is obtained in the form of PFI-sheet in accordance with the General method of example 2, except that the conductivity was adjusted to 3.0 MS/cm by addition of CaCl2.

Table 2 shows the results of experiments No. 1-2 demonstrate methods using additives used for comparison (Ref.), as experiment No. 3 shows the method according to the present invention.

Table 2
No.
experiment
Microspheres MS1
Expancel
(kg/t)
Type
polymer
Polymer
(kg/t)
Nanoparticles
NP1
(kg/t)
Volume (cm3/g)Porosity (ml/min)
1----2,2337
220PL 320,52,6718
320PL 420,52,6668

As can be seen from table 2, the present invention provides a cellulose product with improved (lower) porosity.

Example 4

The Central layer of cardboard for packaging liquids get on a pilot paper machine (HRM) unit weight paperboard 120 g/see the Original raw materials used in the experiment is a 100% unbleached chemical thermomechanical pulp (HTMC). the pH is 8.0.

Introduction in the initial mixture perform the SJ in the following order:

cationic starch 1, ST1, 50%

- microspheres Expancel, MS

cationic starch 1, ST1, 50%

- sizing substance AKD, SA1

a cationic polymer, PL

- anionic colloidal solution of silicon dioxide, NP1.

Sample paper of Mat were dried at the exit of the car HRM (maximum drying temperature 100°C). Microspheres foaming at 140°C in a cylindrical dryer.

Table 3 shows the results of experiments No. 1-2 demonstrate methods using additives used for comparison (Ref.), and experiments No. 3-4 show the methods according to the present invention.

Table 3
No.
the Expo-
riment
Cation
starch
ST1
(kg/t)
Proclai-
living
substance
SA1
(kg/t)
Micro
sphere
Expancel
(kg/t)/
type
The polymer (kg/t)/
type
Nano
particles NP1 (kg/t)
Volume (cm3/g)Porosity (ml/min)
13+3240/MS 20,15/13 3,02458
23+3240/3 MS0,15/134,12625
33+3240/MS 20,15/233,02417
43+3240/3 MS0,15/234,12617

As can be seen from table 3, the present invention provides a cellulose product with improved (lower) porosity.

1. Cellulosic product containing thermoplastic microspheres and charged aromatic acrylamidoethyl polymer.

2. Cellulosic product according to claim 1, where thermoplastic microspheres are expanded.

3. Cellulosic product according to claim 1, where thermoplastic microspheres are nesperennub and thermally expanded.

4. Cellulosic product according to claim 1, where the charged aromatic acrylamide is holding the polymer is water-soluble.

5. Cellulosic product according to claim 1, where the charged aromatic acrylamidoethyl polymer is cationic.

6. Cellulosic product according to claim 4, where the charged aromatic acrylamidoethyl polymer is cationic.

7. Cellulosic product according to claim 1, where the charged aromatic acrylamidoethyl polymer is amphoteric.

8. Cellulosic product according to claim 1, where the charged aromatic acrylamidoethyl polymer contains Quaternary ammonium group.

9. Cellulosic product according to claim 1, where the charged aromatic acrylamidoethyl polymer obtained by cationic polymerization of aromatic monomer or Monomeric mixture containing a cationic aromatic monomer represented by the General structural formula (I):

in which R3represents N or CH3,
R1and R2are each H or altergroup having from 1 to 3 carbon atoms,
A2represents O or NH,
In2represents an alkyl-, or akilagpa having from 2 to 8 carbon atoms, or hydroxypropylamino,
Q represents benzerrou, and
X-is an anionic counterion.

10. Cellulosic product according to claim 1, where the charged aromatic acrylamidoethyl polymer is anionic.

11. Cellulose is the product according to claim 1, where the charged aromatic acrylamidoethyl polymer has srednevekovoy molecular weight of above 500000.

12. Cellulosic product according to claim 1 where the cellulose product is paper or paper Board.

13. Cellulosic product according to claim 1, in which in addition there is a sizing agent.

14. Cellulosic product according to claim 1, in which in addition there is a silicon-containing material.

15. Cellulosic product according to claim 1, in which in addition there is a hardening agent in the wet state.

16. Cellulosic product according to claim 1 where the cellulose product is a multi-layer paper carton.

17. Cellulosic product according to claim 1 where the cellulose product contains at least 50 wt.% cellulose fibers in relation to the dry substance.

18. Application of cellulose product according to any one of claims 1 to 17 as cardboard for the packaging of liquids.

19. A method of obtaining a cellulose product, which includes:
(i) providing a water suspension containing pulp fibers;
(ii) introducing the slurry of thermoplastic microspheres and a charged aromatic acrylamidoethyl polymer; and (iii) dewatering the obtained suspension.

20. The method according to claim 19, where thermoplastic microspheres are expanded.

21. The method according to claim 19, where thermoplastic microspheres are nesperennub and cat the ski foaming.

22. The method according to claim 19, where the charged aromatic acrylamidoethyl polymer is cationic.

23. The method according to claim 19, where the charged aromatic acrylamidoethyl polymer obtained by cationic polymerization of aromatic monomer or Monomeric mixture containing a cationic aromatic monomer represented by the General structural formula (I):

in which R3represents N or CH3,
R1and R2are each H or altergroup having from 1 to 3 carbon atoms,
A2represents O or NH,
In2represents an alkyl-, or akilagpa having from 2 to 8 carbon atoms, or hydroxypropylamino,
Q represents benzerrou, and
X-is an anionic counterion.

24. The method according to claim 19 which further includes
(i) introduction in the pulp suspension sizing agent;
(ii) coating the surface of the cellulose product sizing agent;
(iii) introduction in the pulp suspension silicon-containing material; or
(iiii) introduction in the pulp suspension hardening agent in the wet state.

25. The method according to claim 19, where the pulp product is a multi-layer paper carton.



 

Same patents:

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31 cl, 12 dwg

FIELD: textile, paper.

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20 cl, 9 dwg, 7 ex

FIELD: paper industry.

SUBSTANCE: cardboard contains at least two layers: the first layer made of raw materials having high density and high module of elasticity; and the second layer to provide voluminousness for cardboard, in which the second layer contains chemical-thermomechanical pulp (CTMP) of broadleaf wood, cellulose and/or CTMP of coniferous wood at the specified ratio of components. At the same time coherence by Scott is achieved, making at least 80 J/m2; index of bending resistance making at least 5 Nm6/kg3 and strength in direction z, making at least 200 kPa. Invention also relates to products made of cardboard.

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15 cl, 8 tbl

FIELD: process engineering.

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18 cl, 2 dwg

FIELD: textiles, paper.

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4 cl, 1 tbl, 3 ex

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26 cl, 4 tbl, 3 ex

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17 cl, 16 dwg, 1 tbl, 3 ex

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1 tbl, 5 ex

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11 cl, 3 tbl, 3 ex

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EFFECT: the invention ensures the manufacture of the barrier substance with the stable quality and the good barrier properties with respect to the gas and may be used for packaging, in particular, for the food products.

12 cl, 5 dwg, 4 tbl, 3 ex

FIELD: paper industry.

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32 cl, 2 dwg, 3 tbl, 3 ex

FIELD: textile; paper.

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EFFECT: production of paper material having good combination of optical, mechanical, tactile properties, evenness and volume including economical efficiency of the process.

10 cl, 6 dwg, 2 ex

FIELD: textile, paper.

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EFFECT: preventing skin cuts, improving flexibility and stiffness of paper material.

29 cl, 25 dwg, 14 tbl, 8 ex

FIELD: pulp-and-paper industry, in particular, paper sheet having surface feeling hash to the finger, and method for applying coating onto paper sheet.

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EFFECT: simplified method and improved quality of paper sheet.

17 cl, 16 dwg, 1 tbl, 3 ex

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EFFECT: improved quality of paper owing to preventing sliding thereof during separation of sheets in stacks, delamination of coating during printing process and, accordingly, elimination of paper dusting and formation of impure imprints.

7 cl, 2 dwg, 2 tbl, 13 ex

The invention relates to thermosensitive recording materials, in particular paper and taking into account the major area of application is the production of business and securities can be attributed to the means of their protection against forgery
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SUBSTANCE: ground contains cation water-fast additive, alkaline glueing agent and anion activator in specified amount. Anion activator it contains is a component selected from group, including polyacrylate, sulfonate, carboxymethylcellulose and galactomannan hemicellulose. Ground paper has pH from approximately 7.0 to approximately 10, and strength of internal link from approximately 25 to approximately 350 millifeet per pound per square inch. This ground paper is produced by contact of a certain amount of cellulose fibres with water-fast additive, alkaline gluing agent and anion activator, serially and/or simultaneously.

EFFECT: improved physical properties of ground paper and expanded assortment of paper tapes to cover joints.

22 cl, 1 dwg, 1 ex

Paper making method // 2384661

FIELD: textile, paper.

SUBSTANCE: method relates to paper production and can be used in pulp-and-paper industry. Method involves the use of cellulose suspension from cellulose fibres and fillers (optional), dehydration of cellulose suspension on grid or sieve so that a sheet can be formed. Then the sheet is dried. In this method there used is polymeric addition which includes ethylenically unsaturated monomer soluble in water or potentially soluble in water, and ethylenically unsaturated monomer containing a reactive group. The latter represents an epoxy group. The polymeric addition used has molar weight which is less than one million. Polymer is obtained from mixture of monomers, which includes acrylamide and glycidyl methacrylate. Thus, the obtained polymer is used as an addition for increase of paper durability in dry condition, in wet condition, as reagent for internal paper sizing and for surface sizing.

EFFECT: increasing paper durability.

17 cl, 2 tbl, 3 ex

FIELD: paper; chemistry.

SUBSTANCE: method of cellulose fiber modification is realised in the following manner. Suspension mass of cellulose fibers is prepared. In process of its bleaching cellulose derivative is added in at least one stage of acid bleaching. pH of suspension mass is in the interval from approximately 1 to approximately 4, and temperature - in interval from approximately 30 to approximately 95°C. As cellulose derivative carboxy-alkyl-cellulose is used, for instance, carboxy-methyl-cellulose. From this suspension of bleached fiber mass paper is produced by means of dehydration of this suspension on the mesh with formation of paper.

EFFECT: higher strength in wet condition and softness of paper.

42 cl, 2 dwg, 1 ex

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