CN101292069A - Reducing the water and water vapour absorbence and enhancing the dimensional stability of paper and paper products and use of coated paper products - Google Patents
Reducing the water and water vapour absorbence and enhancing the dimensional stability of paper and paper products and use of coated paper products Download PDFInfo
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- CN101292069A CN101292069A CNA2006800386759A CN200680038675A CN101292069A CN 101292069 A CN101292069 A CN 101292069A CN A2006800386759 A CNA2006800386759 A CN A2006800386759A CN 200680038675 A CN200680038675 A CN 200680038675A CN 101292069 A CN101292069 A CN 101292069A
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- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/24—Addition to the formed paper during paper manufacture
- D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
- D21H23/28—Addition before the dryer section, e.g. at the wet end or press section
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/48—Condensation polymers of aldehydes or ketones with phenols
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/52—Epoxy resins
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
Abstract
The invention concerns a process for reducing the water and water vapour absorbence and enhancing the dimensional stability of paper and paper products by treatment with an aqueous solution and/or dispersion of at least one reactive material capable of reacting with itself and/or with cellulose fibres by crosslinking, which comprises compressing cellulose fibres or a paper product obtained therefrom by dewatering on a wire, then contacting the compressed paper product with an aqueous solution and/or dispersion of the reactive material, decompressing under continued contact with the aqueous solution and/or dispersion, and drying and crosslinking the paper product; and also the use of the coated paper products thus obtainable and/or of the coated cellulose fibres obtainable therefrom by fibrization, in thermoplastics and thermosets.
Description
The method that the present invention relates to reduce paper and paper products suction and hygroscopicity and increase its DIMENSIONAL STABILITY, wherein with containing at least a can the processing with self and/or with the aqueous solution and/or dispersion liquid that cellulose fibre carries out crosslinked reactivity material, and the material after will handling is heated to and carries out drying and crosslinked temperature; The invention still further relates to the coated paper goods that obtained and/or by their coated fiber cellulose fibers through taking off fine process for producing as the additive of thermoplastic with as the Application of Additives of thermosetting plastics.
Publication is at Wood Science and Technology, 1993, the 347-355 page or leaf, being entitled as " timber is handled to improve its DIMENSIONAL STABILITY and durability through water-soluble dihydroxymethyl resin " sets forth: timber is after impregnating agent is handled, and its contraction and swelling behavior and antibiotic insect resistance capacity can be improved.Wherein, impregnating agent is formed by containing dihydroxymethyl dihydroxy ethylidene-urea (DMDHEU or 1,3-two (hydroxymethyl)-4, the aqueous solution of 5-dihydroxy imidazoline-2-ketone) and catalyst.Catalyst is slaine, citric acid, amine salt, can use separately or be used in combination.The concentration of the DMDHEU aqueous solution is 5% to 20%.The catalyst addition is based on 20% of DMDHEU meter.Dipping under reduced pressure carries out.At high temperature, DMDHEU id reaction and react with timber.This is reflected under the temperature of 80 ℃ or 100 ℃ and carried out in baking oven 1 hour.Through the wood sample of this processing, it shrinks and swelling behavior is improved, up to 75%.DMDHEU concentration be 20% o'clock also be like this.In this way, the wooden sample of experiment is of a size of 20mm * 20mm * 10mm.Because wooden product size is big, is easy to produce slight crack, so the method is only for being used in the little wooden product of size.
EP-B0891244 discloses suitably using decompression and/or add and has depressed, and uses the dipping method of the wooden product that contain solid wood that biodegradable polymer, natural resin and/or fatty acid ester carry out.Wherein, high temperature floods.Pore in wooden product major part at least is filled, thereby forms the mechanograph that contains wooden product and biodegradable polymer.Polymer does not react with timber.Handle through this, biological degradation function that timber is intrinsic and mechanical property be loss not.Its thermoplasticity increases.According to the ratio of the polymer of introducing, polymer enters the hardness that wood matrix can increase wood surface, thereby soft natural wood also can be used as high-quality floor.
SE-C 500 039 discloses with the harden method of timber of the mode of densification.Wherein, adopt suitable vacuum impregnation technology, use is carried out impregnation process based on the various monomers of the aminoplast of melamine and formaldehyde to untreated timber, and then, in squeezer, densification is carried out in drying and curing under the high temperature.The reagent of mentioning is: DMDHEU, dimethylol urea, dimethoxy methyl urea, dimethylol ethylene urea, dimethylol propylidene urea, dimethoxy-methyl alditol.This method shortcoming is, because the result of densification causes the loss of timber natural structure, and the formaldehyde emission of wooden product finished product is higher, and its degree depends on the crosslinking agent of use.
WO 04/033171 discloses the production method of the wooden product with high surface hardness and low burst size of methanal, and wherein untreated wooden product flood with the aqueous solution of following material:
A) impregnating agent comprises by C
1-51 of alcohol, polyalcohol or its mixture modification, 3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone and
B) catalyst, it is selected from ammonium or slaine, organic or inorganic acid and its mixture, and drying is at high temperature solidified then.
According to WO 041033170 disclosed method, working concentration is that the steep water solution of 1-50 weight % carries out impregnation process to wooden product, can improve DIMENSIONAL STABILITY, durability and the case hardness thereof of wooden product, wherein impregnating agent contains in A group material and/or at least a B group material and at least a C group material as catalyst, subsequently, for avoiding dry, under wet environment, the impregnating agent id reaction and with wooden product reaction.Suitable impregnating agent is dihydroxymethyl dihydroxy ethylidene-urea (DMDHEU) for example, urea-glyoxal adduct, melocol adduct.Appropriate catalyst is a magnesium chloride for example, zinc chloride, ammonium chloride; Or acids, as formic acid, maleic acid, hydrochloric acid or sulfuric acid.
WO 2004/025019 discloses the method and apparatus that contained liquid and other liquid exchange in the fiber.The method that it adopted is, the fiber cake is depressed into the degree that liquid that a great deal of is stored in fibrous inside enters space between the fiber, in the compression step process, other liquid that is used to replace first kind of liquid to the fiber cake weight feed of compression, like this, remove first kind of liquid from the space between the fiber, then, reduce pressure under the further effect of other liquid that is used to replace first kind of liquid, other replacement liquid is further absorbed.Liquid cleaning agent, chemical treatments, liquid acids or alkali, bleaching agent, delignification agent, catalyst, complexing agent, fluorescence indicator, metal ion, CATION or anionic polymer, colouring agent, inorganic matter can be used as replacement liquid.By this method, can from cellulose fibre, remove part lignin component at least, thus more even, the high-quality pulp of preparation.
Cellulose fibre of being produced and paper products, for example paper, paperboard and cardboard are easy to suction and absorb water vapour from air.The result is that the DIMENSIONAL STABILITY of cellulose fibre and paper products and mechanical property are reduced to disadvantageous degree.For reducing the water imbibition of paper products, can add wet strength agent, for example, can in producing described product process, add in the raw material.So-called wet strength agent is for example not only to increase wet also can increasing by force to do strong urea formaldehyde resin (referring to EP-A 0 123 196 and US3,275,605), and melamine resin (DE-B 10 90 078) and other commercial product are as commodity Luresin by name
(BASF AG) by the polyamide-based amine condensation product of epichlorohydrin cross-linked.
The purpose of this invention is to provide the water imbibition of a kind of reduction paper and paper products (such as paperboard and cardboard) and the method for hygroscopicity and its DIMENSIONAL STABILITY of increase.
According to the present invention, purpose of the present invention can realize by a kind of method that reduces the water imbibition and the hygroscopicity of paper and paper products and increase its DIMENSIONAL STABILITY, but wherein use and contain at least a id reaction and/or paper and paper products are handled with the aqueous solution and/or dispersion liquid that cellulose fibre carries out crosslinked reactivity material, then, the material of handling is heated to carries out dry and crosslinked temperature, if it is suitable, cellulose fibre or the paper products made through the silk screen draining by them are at first through overcompression, then, paper products after the compression contact with the aqueous solution and/or the dispersion liquid of reactivity material, eliminate pressure under the further effect of the described aqueous solution and/or dispersion liquid.The crosslinked of reactivity material taking place more than 30 ℃, and for example, temperature range is by 35 ℃ to 200 ℃.This method can carry out also can intermittently carrying out continuously.
Preferable methods is, contain the cellulose fibre of at least 50 weight % protofibres or obtain through the silk screen draining by them and moisture be the paper products of at least 0.7 gram water/every gram dry cellulosic fiber, under the pressure of 2.1MPa at least, compress earlier, then, paper products after the compression contact with the aqueous solution and/or the dispersion liquid of reactivity material, under the further effect of the described aqueous solution and/or dispersion liquid, eliminate pressure, dry then paper products, the temperature that is heated in the 70-200 ℃ of scope is carried out crosslinked.
For example, the aqueous solution and/or dispersion liquid contain at least a resinoid as the reactivity material, described adhesive is selected from: the melocol adduct, urea-glyoxal adduct, the carbamide adduct, the P-F adduct, one-component and two component system based on epoxy resin, polyurethane or polyisocyanate, polyacrylate, polymethacrylates, styrene-(methyl) acrylate copolymer dispersion liquid and/or styrene-butadiene-(methyl) acrylic copolymer dispersion liquid.Some occasion is used the mixture of at least two kinds of reactivity materials, and effect is better.For example, the mixture of melamine/melocol condensation product.The reactivity material exists as the aqueous solution or as aqueous dispersions.Therefore, can between solution and dispersion liquid, change.For example, as using dispersion liquid, the mean particle diameter that is dispersed in the polymer particle in the water is less than 1 μ m, preferably less than 500nm, usually between 10 to 100nm.
For example, the aqueous solution and/or dispersion liquid contain following reactivity, cross-linkable masses:
(i) at least a reactivity material that can form polymer,
(ii) as needing at least a C
1-5Pure, at least a polyalcohol or its mixture and
(iii) at least a catalyst.
The example that can form the reactivity material (i) of polymer is urea-glyoxal adduct and its derivative, for example, 1,3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone (below be called " DMDHEU ").In dipping process, it can use separately, also can with (ii) (at least a C
1-5Pure, at least a polyalcohol or its mixture) the common use.If, 1,3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone and alcohol and/or polyalcohol use jointly as impregnating agent, then form 1 of corresponding modification, 3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone (below be called " mDMDHEU ").For example, such compound is disclosed in US 4,396,391 and WO98/29393 in.These are 1,3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone and at least a C
1-5The product of pure, at least a polyalcohol or its mixture.
Group compound (ii) comprises C
1-5Alcohol, for example methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, the best is a methyl alcohol; Polyalcohol, for example ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butanediol, 1,3 butylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, and poly alkylene glycol, as polyethylene glycol, polypropylene glycol, the block polymer of ethylene glycol and propylene glycol.The molecular formula of polyethylene glycol is HO (CH
2CH
2O)
nH, wherein n is 3-20, the best is a diethylene glycol.
In order to prepare 1 of modification, 3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone (mDMDHEU), DMDHEU mixes with monohydric alcohol and/or polyalcohol, and wherein the consumption of monohydric alcohol and/or polyalcohol is based on the 0.1-0.2 molar equivalent of DMDHEU meter separately.The mixture of DMDHEU and monohydric alcohol and/or polyalcohol for example reacts under the condition of 1-2.5 with the pH value in temperature 20-70 ℃ scope, after the reaction pH value is transferred to 4-8.
The reactivity material that can form polymer of group (i) is interpreted as melocol adduct and urea-glyoxal adduct and their derivative.Relate to following compound in the example: dimethylol urea, two (methoxy) urea, tetramethylol acetylene diurea, methoxy urea, 1,3-dimethyl-4,5-dihydroxy imidazoline-2-ketone, 1,3-two (hydroxymethyl) imidazoline-2-ketone or its mixture.As needs, as impregnating agent, group (i) compound can be at (ii) at least a C of existence group
1-5Use under the situation of pure, at least a polyalcohol or its mixture.The alcohol that is fit to and mentioning more than the polyalcohol, the best is methyl alcohol, diethylene glycol and their mixture.
For example, it is 1-70 weight % that the aqueous solution of impregnating agent contains concentration, be preferably 10-60 weight %, particularly the group of 20-60 weight % (i) reactivity compound and group compound (ii).Impregnating agent preferably contains as 1 of group (i) compound, 3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone (DMDHEU).
Except that group (i) and optional group (ii) the material, impregnating agent always contains catalyst (iii).Appropriate catalyst (iii) is for example slaine, is selected from: metal halide, metal sulfate, metal nitrate, metal tetrafluoroborate, metal phosphate, or their mixture.Group instantiation (iii) is: magnesium chloride, magnesium sulfate, zinc chloride, lithium chloride, lithium bromide, boron trifluoride, aluminium chloride, aluminum sulfate, zinc nitrate, sodium tetrafluoroborate.The mentioned compound as catalyst can be used alone or as a mixture.
Other appropriate catalyst (iii) is an ammonium salt, for example ammonium chloride, ammonium sulfate, ammonium oxalate, Diammonium phosphate (DAP) or their mixture.In addition, also useful as catalysts of organic acid and/or inorganic acid.For example maleic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, oxalic acid, p-methyl benzenesulfonic acid, hydrochloric acid, sulfuric acid, boric acid or their mixture.
Preferred compound is in organizing (iii): magnesium chloride, zinc chloride, magnesium sulfate, aluminum sulfate or their mixture.Magnesium chloride is the most desirable.
Organizing (iii), catalyst concentration is for example to organize (i) to organizing the (iii) 0.1-10 weight % of the percentage of reactivity material gross weight, preferred 0.2-8 weight %, most preferably 0.3-5 weight %.
Above-described and contain in the product of formaldehyde of condensation unit form the special condensation product that uses low formaldehyde.Among the present invention, low formaldehyde is interpreted as that the reactivity material does not contain free formaldehyde substantially, even cellulose fibre after handling or paper products do not discharge formaldehyde substantially yet in dry and solidification process.Usually, such reactivity material contains＜formaldehyde of 100ppm.
Other can with self and/or to carry out crosslinked reactivity material with cellulose fibre be the resinoid that does not contain free formaldehyde.For example, such adhesive is set forth at following document, as content disclosed by the invention, with for referencial use.Promptly, US 4 076 917, and EP-A 0 445 578, and EP-A 0583086, EP-A 0 651 088, the 4th page of the 12nd row of WO 97/31036 be to the 12nd page of the 14th row, and the 2nd page of the 22nd row of WO97/31059 be to the 12nd page of the 5th row, 12 page of the 36th row of the 3rd page of eighth row to the of WO-A-97/31060,49 591 the 3rd page of the 5th row of DE-A-199 is to the 7th page of the 38th row, the 5th page of the 34th row of WO 01/27163, the 22 2nd row and patent DE-A199 17 965 disclosed radiation-curing binders.
Except that the adhesive of above-mentioned patent disclosure, the resinoid that is fit to all is the disclosed curing adhesive of this patent, for example, be used to strengthen nonwoven fabric and/or especially for this purpose resinoid, for example based on the resinoid of phenol and formaldehyde, based on the above-mentioned carbamide and the resinoid of urea-formaldehyde resins, urea-glyoxal resin, particularly, formaldehydeless one pack system and two component system based on epoxy resin, or polyurethane, polyacrylate, polymethacrylates, polyvinyl acetate, styrene-propene acid resin copolymer dispersion liquid, styrene-methacrylate copolymer dispersion liquid, styrene-butadiene-(methyl) acrylate copolymer dispersion liquid and above-mentioned dispersion liquid with as the polycarboxylic acid of linked and the mixture of polyol blends.
Desirable resinoid is the mixture of following component:
(a) polymer that obtains by radical polymerization, it contains the ethylenically unsaturated carboxylic acids acid anhydride of the 5-100 weight % that introduces with the polymerized unit form or the ethylenically unsaturated dicarboxylic that its carboxyl can form anhydride group.
(b) at least a alkanolamine contains at least two hydroxyls in its molecule, and/or at least a polyalcohol.
The object lesson of such mixture is: the aqueous solution and/or the dispersion of the copolymer of 80 weight % acrylic acid and 20 weight % maleic acids, about 40%-60 weight % that its solid content is, molar weight Mw is 15000-900000, this solution and/or dispersion liquid and triethanolamine combination or make up with mixture that the aqueous solution of the copolymer of 55 weight % acrylic acid and 45 weight % maleic acids and triethanolamine are formed.As needs, these adhesives can contain as the esterification catalyst of reaction promoter and/or contain the compound of bonding phosphorus, for example hypophosphorous acid.
Above-mentioned copolymer (a) for example can be made up of following:
Unsaturated list of at least a olefinic or the dicarboxylic acids of-50-99.5 weight %,
At least a alefinically unsaturated compounds of-0.5-50 weight % is selected from: monoesters and diester that the ester of olefinic unsaturated monocarboxylic, ethylenically unsaturated dicarboxylic and the amine with at least one hydroxyl form; With
Other monomer of-maximum 20 weight %.
Contain at least a copolymer (a) and at least a alkanolamine or high official can the beta-hydroxy alkylamine and/or the thermosetting Aquo-composition of at least a polyalcohol as can comprise at least a surfactant in addition when needing.
Other resinoid is based on the mixture of following material:
-polycarboxylic acids.For example, polyacrylic acid, polymethylacrylic acid, the copolymer of acrylic acid and maleic acid, the copolymer of methacrylic acid and maleic acid, the copolymer of ethene and maleic acid, the copolymer of styrene and maleic acid, or acrylic or methacrylic acid and the monohydric alcohol of 1 to 24 carbon atom and the synthetic copolymer of ester class of acrylic or methacrylic acid formation.The K value of polycarboxylic acids be 50 to 100 (according to H.The method of Fikentscher, in dimethyl formamide, 25 ℃, the concentration of polymer is under the condition of 1 weight %, measures unneutralized polycarboxylic acids) and
-polyalcohol.For example, trimethylolpropane, glycerol, 2-hydroxymethyl fourth-1,4-glycol, polyvinyl alcohol and/or polyfunctional amine and/or alkanolamine.
The consumption of polycarboxylic acids, polyalcohol, alkanolamine and polyfunctional amine preferably makes sour official quantity to equate with the sense sum of hydroxyl and amine, referring to EP-A 0445578.In addition, Mw is preferably 10 by molar weight, 000 or be less than 10,000 polycarboxylic acids (homopolymers or copolymer) and the crosslinkable material of forming such as the aqueous solution of the polyhydroxy-alcohol of triethanolamine are suitable, wherein the best equivalent proportion of hydroxyl and carboxyl is 0.4: 1 to 1.0: 1, referring to EP-A0990727.
The method according to this invention, BASF Aktiengesellschaft company commodity are called Acrodur
Serial adhesive be more suitable for as the reactivity thing.The example is through the cinnamic acrylic ester aqueous polymer dispersion of polycarboxylic acid's modification with as the polyalcohol of crosslinked component.It takes place crosslinked in the temperature that is low to moderate 130 ℃.But for reaching high production speed, the crosslinked 180-200 of being preferably in ℃ is carried out.Many formaldehydeless adhesives are arranged on the market, for example, the polycarboxylic acids of modification and the colourless transparent aqueous solution of forming as the polyhydroxy-alcohol of crosslinked component to little Huang.It is crosslinked to carry out between about 160 ℃-180 ℃ of baking temperature.
The formaldehydeless reactivity thing that contains at least a polycarboxylic acids and at least a polyalcohol and/or alkanolamine or polyfunctional amine is particularly preferred.As needs, the mixture of being made up of these reactive materials also can further comprise formaldehydeless polymer, and the BASFAktiengesellschaft company commodity of for example selling on the market are called Acrodur
Polyacrylate.Contain 1-70 weight %, 10-60 weight % most preferably as the aqueous solution of the reactivity thing of impregnating agent and/or dispersion, be generally the reactivity material of 30-50 weight %.
Among the present invention, paper products are interpreted as for example paper itself, paperboard and cardboard.Method of the present invention can particularly come from waste paper from from various cellulose fibres natural and regeneration, and it only mixes use with protofibre.Protofibre is interpreted as and is processed into paper products or the not dry cellulose fibre of crossing.In the mixture that contains protofibre and the fiber that comes from waste paper, the content of protofibre cellulose fiber for example is at least 50 weight %, preferably is at least 70 weight %.In the particularly preferred method, the paper pulp that contains 100% protofibre is as initiation material.Fiber that be fit to produce paper pulp is for being for example to be usually used in this purpose quality, for example, mechanical pulp, the chemical pulp of bleaching and non-bleaching reaches the paper pulp from annual plant.For example, mechanical pulp comprises wood fragments, hot mechanical pulp (TMP), chemi-mechanical pulp (CTMP), the wood fragments of compacting, semi-chemical pulp, high-yield pulp and refining mechanical pulp (RMP).For example sulfate, sulphite and sodium carbonate paper pulp are suitable as chemical pulp.The preferred chemical pulp that uses non-bleaching is also referred to as non-bleached kraft pulp.The suitable annual plant that is used to produce paper pulp raw material is for example paddy rice, wheat, sugarcane and mestha.
Compare with the cellulose fibre of drying, protofibre has high porosity.Referring to BioresourceTechnology, 87 phases (2003), 325-330 page or leaf (author: W.Grindl, F.Zargar-Yaghubi and R.Wimmer).Observe if get wet cellulose fibre, discovery water both had been present in and also had been present in cellulose fibre inside between the cellulose fibre.Referring to paper pulp and paper industry technological associations engineering conference file in 1993, second, the the 741st to 747 page (author: G.VLaivinsA. and M.Scallan), the aqueous slurry of cellulose fibre are squeezed the degree that is contained 0.7-1 gram water/every gram dry cellulosic fiber by its paper that forms that makes in the drainage procedure on the silk screen of paper-making machine.After the squeezing, for example by behind the size press, between the fiber and cellulose fibre inside still exists water.Because fiber has enough porositys, by the extrusion fiber structure, can remove the moisture content of fibrous inside.In the method for the invention, the product of draining is stressed so that the moisture content of fibrous inside is discharged on silk screen.This pressure is 2.1MPa at least, may be up to 50MPa.Be preferably between the 2.5-10MPa.Because 2.1MPa pressure is applied to mainly on the wet fiber product of being made up of the protofibre cellulose fiber at least, the water content of its paper products will be lower than 0.7 and restrain water/every gram dry cellulosic fiber.The moisture 0.3-0.5 gram of for example every gram dry cellulosic fiber.Be generally the 0.3-0.4 gram.
Fibre structure exerted pressure and with the aqueous solution of reactivity material fibre structure is handled to carry out continuously or can intermittently carry out.The 5th page of the 3rd row of patent WO2004/25019 to the 8th page of eighth row disclose a kind of with before the relevant continuous processing of technology.Explain in detail herein.Spinning cake on the silk screen or on the conveyer belt pushes through the roll gap between two pressure rollers.As a result, the moisture content in the cellulose fibre leaves cellulose fibre inside, enters between the compression spinning cake fiber, partly leaves spinning cake.Press conveyer belt rotates on a roller, forms roll gap with the squeezing spinning cake with another roller, and under the help of this press conveyer belt, the cellulosic fibrous structure of compression contacts with the aqueous solution of reactivity material under pressure.As a result, the moisture of cellulose fibre inside and the moisture between the fiber are replaced by the aqueous solution of reactivity material.After leaving roll gap, the gap of the aqueous solution of the cellulosic fibrous structures of compression by the reactivity material is housed.The cellulose fibre of compression begins to relax.As the sponge of compression, when discharging, the aqueous solution of cellulose fibre absorption reaction active material.Solution not only infiltrates in the interior space of paper products but also infiltrated fiber cellulose fiber inside.Like this, the reactivity material not only applies the independent cellulose fibre of paper products, and fibrous inside has been carried out applying to small part.After handling with the aqueous solution of reactivity material, paper products carry out drying and for example are heated to 70-120 ℃ temperature so that the reactivity material carries out cross-linking reaction.
According to the Batch Process technology of the inventive method, for example at first, the silk screen order of paper machine directly is 80-150 μ m, and secondly, the main raw material of producing paper is the protofibre cellulose fiber, and its basic weight is 50-500g/m
2, be generally 75-250g/m
2Its moisture is 50-80 weight %, and paper is put in the squeezer with porous pallet.Subsequently, be successively placed on the paper by the system paper felt of at least a reactivity material and aqueous solution dipping with such as polymethyl methacrylate, polystyrene or polyacrylic plastic paper.Piston enters in the squeezer formed stratiform thing is applied the pressure of 2.1MPa at least, makes from being forced to discharge by the porous pallet with the moisture content of fibrous inside and the unnecessary reactivity material aqueous solution in the cellulosic fibrous structures.When using the inventive method to carry out batch production, its pressure acting duration is 0.1-120 second, is preferably 0.5-20 second.During continous mode was produced, its pressure acting duration was 0.01-20 second, is preferably 0.02-1 second.After the compression, relax stage, paper can the further absorption reaction active material aqueous solution.Paper takes out in squeezer then, dry and be heated to 70-220 ℃, preferably 120-170 ℃ so that the reactivity material is crosslinked.
Adopt the size press method, under the situation of using aqueous solutions of polymers, polymer-coated amount is＜5g/m
2, be generally 1-3g/m
2And adopting method of the present invention, polymer-coated amount is＞5g/m
2, be generally 5.5-8g/m
2Compare with known coating method, use method of the present invention, the DIMENSIONAL STABILITY of paper and paper product is higher, and it absorbs water and hygroscopicity reduces.
The paper products that use the inventive method to make can be used to the suspension of produce cellulose fibers.For example in water, decompose paper and paper products.And then, can get by dehydration
Cellulose fibre, this fibrous inside contains part coatings at least.This cellulose fibre for example form of powder exists.
Use method of the present invention can produce writing paper, printing paper, wrapping paper, corrugated paper, wallpaper, cardboard is by the laminated paper that paperboard or paper and at least a thermoplastic paper or film are formed, building element.The mixture of following material particularly importantly: (i) paper products of making by the inventive method and/or take off fibrillation and handle the coated fiber cellulose fiber that obtains and (ii) thermoplastic or thermosetting plastics.Can be made into any mechanograph of wanting from such mixture.
Furthermore, the present invention relates to the coated paper or the coated paper goods that use the inventive method to make, and/or handle the coated fiber cellulose fiber that obtains through taking off fibrillation, as the Application of Additives of the additive and the thermosetting plastics of thermoplastic by them.
Such mixture contains 0.1-90 weight %, is preferably 1-70 weight %, is generally at least a component (i) of 2-50 weight %.Its composite for example is mixed and made into by at least a coating material and at least a thermoplasticity or thermosetting plastics.Mixing can for example be carried out with extruder, for example softening point range that at least a product that applies according to the present invention and thermoplastic are heated to thermoplastic or the temperature that is higher than its softening point, and extrusioning mixture.
The thermoplastic that is fit to for example is: polyolefin, as polyethylene from high pressure process, low-pressure polyethylene, polypropylene, poly-but-2-ene, poly-but-1-ene, polyisobutene, polystyrene; Polyamide, as polycaprolactam, or the condensation polymer of hexamethylenediamine and adipic acid; Polyester is as polyethylene terephthalate, polymethyl methacrylate, Merlon; And polyvinyl chloride.
The example of thermosetting plastics is top reactivity material of having set forth for paper and paper products coating, urea formaldehyde resin for example, melamine resin, one pack system and bicomponent system based on epoxy resin, polyurethane or polyisocyanate, crosslinkable polyacrylate and crosslinkable polymethyl methacrylate.
Component (i) and component mixture (ii) are suitable for producing mechanograph, particularly produce building element, for example, the wall insulating composite material, such as with sheet form as the wall clad can with exclusion of water steam, or as inner core and the cover layer of producing door; This material can be used for the furniture of production indoor and outdoor; This material can be used for producing the shell of electric equipment, such as dust catcher, kitchen equipment, TV, radio, stereo set, computer; This material can be used for producing auto parts machinery, for example, and the upholstery of door, instrument board, seat shelf; This material can be used for making the packing box of fresh flower, flowerpot, watering can, plant pot; This material can be used for the wall and the support of wayside pavilion; This material can be used for toy, can be used as packaging material.
Remove specified otherwise, the percentage among the embodiment is weight percentage.
Embodiment:
Absorptive mensuration
The pattern product that are of a size of 4cm * 4cm placed 20 ℃ of distilled water interior 30 minutes, took out, and blotted with absorbent cloth, weighed then.Weight increases with percentage (%) to be calculated.
The mensuration of DIMENSIONAL STABILITY
Place a week in 20 ℃ temperature above being of a size of the silica gel of pattern product in dry vessel of 4cm * 4cm, weigh then.Measure paper thickness (D in addition
1).Then, the pattern product in dry vessel water above place a week so that paper is by steam-laden.Weigh then, measure its thickness (D
2).DIMENSIONAL STABILITY is determined by following formula:
In the formula, D
1Be the thickness of dried paper, D
2Thickness for l Water Paper.
Hygroscopicity is measured
Place a week in 20 ℃ temperature above being of a size of the silica gel of pattern product in dry vessel of 4cm * 4cm.(W then weighs
1), the pattern product in dry vessel water above place a week so that paper is by steam-laden.(W again weighs
2).Hygroscopicity is determined by following formula:
Stiffness is measured:
According to German standard DIN53121, use the beam type method to measure its stiffness.For this purpose, downcut the pattern be of a size of 100 * 25.4mm, after the clamping, measure under the following conditions: measure length l=100mm, specimen width b=25.4mm, bend angles alpha=20 °.Guarantee that when maximum deflection, power Fmax reaches 15mN at least.Each sample in measurement 5 times.
Embodiment 1
By the paper pulp that 70% pine sulfate pulp of bleaching and 30% betulinic acid salt paper pulp mix, its degree Schopper-Riegler is 35 ° of SR (Schopper-Rieger), dewaters in fast rapid-result paper machine.The basis weight of paper is 80g/m
2Paper between filter paper by squeezed to moisture be 50%, flood then.The method of dipping is: at first paper is put into squeezer, the squeezer bottom directly is the papermaking-machine of 100 μ m for the silk screen order.Then the Kaurit that uses 50% concentration
The impregnated system paper of 210 (urea formaldehyde resin) aqueous solution felt is placed on the paper, covers poly methyl methacrylate plastic paper again.Impose the pressure of 2.1MPa, continued for 5 seconds.Like this, the aqueous solution of water in the paper and system paper felt floating coat material is discharged from the squeezer bottom.Subsequently, remove pressure, take out impregnated paper.Under 130 ℃ of temperature, with dry 4 hours of paper.With this understanding.Resin in the fiber and that be deposited on the fiber takes place crosslinked.Then, stiffness, DIMENSIONAL STABILITY and the water imbibition of this paper are tested.It the results are shown in Table.
Embodiment 2-6
Repeat embodiment 1, only different is to use the aqueous solution of the resinoid in the table 1 and/or dispersion liquid to replace Kaurit
210 aqueous solution.It the results are shown in Table 2.
Comparative Examples 1
Repeat embodiment 1, only different is to replace Kaurit with distilled water
210 aqueous solution flood system paper felt.It the results are shown in Table 2.
Table 1
Table 2
| Embodiment number | Stiffness (mN) | Water imbibition (%) | Hygroscopicity (%) | DIMENSIONAL STABILITY reduces (%) after the moisture absorption |
| 1 | 1700 | 100 | 15 | 3 |
| 2 | 2200 | 50 | 9 | 5 |
| 3 | 2000 | 270 | 20 | 6 |
| 4 | 3521 | 250 | 20 | 7 |
| 5 | 3000 | 110 | 15 | 4 |
| Comparative Examples number | ||||
| 1 | 254 | 475 | 22 | 8 |
Claims (12)
1. one kind is reduced the water imbibition of paper and paper products and the method for hygroscopicity and its DIMENSIONAL STABILITY of increase, wherein use and contain at least a can the processing with self and/or with the aqueous solution and/or dispersion liquid that cellulose fibre carries out crosslinked reactivity material, the material that to handle is heated to drying and the crosslinking temperature that carries out then, wherein cellulose fibre or the paper products made through the silk screen draining by them are at first through overcompression, then, paper products after the compression contact with the aqueous solution and/or the dispersion soln of reactivity material, under the further effect of the described aqueous solution and/or dispersion liquid, eliminate pressure, then paper products are carried out drying and crosslinked.
2. according to the method for claim 1, the cellulose fibre that wherein contains at least 50% weight protofibre, perhaps thus cellulose fibre make through the silk screen draining and contain at least 0.7 the gram water/every gram dry cellulosic fiber paper products, at first under the pressure of 2.1MPa at least, compress, paper products after the compression contact with the aqueous solution and/or the dispersion liquid of reactivity material then, under the further effect of the described aqueous solution and/or dispersion liquid, eliminate pressure, paper products are carried out drying and be heated to 70-200 ℃ of temperature carrying out cross-linking reaction.
3. according to the method for claim 1 or 2, wherein the aqueous solution and/or dispersion liquid contain at least a resinoid as the reactivity material, described adhesive is selected from the melocol adduct, urea-glyoxal adduct, the carbamide adduct, the P-F adduct, one-component and two component system based on epoxy resin, polyurethane or polyisocyanate, polyacrylate, polymethacrylates, styrene-(methyl) acrylate copolymer dispersion liquid and/or styrene-butadiene-(methyl) acrylic copolymer dispersion liquid.
4. according to each method of claim 1-3, wherein the aqueous solution and/or dispersion liquid contain the following component as the reactivity material:
(i) at least a reactivity material that can form polymer,
(ii) as needing at least a C
1-5Pure, at least a polyalcohol or its mixture and
(iii) at least a catalyst.
5. according to each method of claim 1-4, wherein the aqueous solution and/or dispersion liquid contain the following component as the reactivity material:
(i) at least a melocol adduct, urea-glyoxal adduct and/or carbamide adduct,
(ii) as needing at least a C
1-5Pure, at least a polyalcohol or its mixture and
(iii) at least a catalyst.
6. according to each method of claim 1-5, wherein the aqueous solution and/or dispersion liquid contain the following component as the reactivity material:
(i) 1,3-two (hydroxymethyl)-4,5-dihydroxy imidazoline-2-ketone.
7. according to each method of claim 1-5, wherein the aqueous solution and/or dispersion liquid contain the following component as the reactivity material:
(i) dimethylol urea, two (methoxy) urea, tetramethylol acetylene diurea, methylol methyl urea, 1,3-dimethyl-4,5-dihydroxy imidazoline-2-ketone, 1,3-two (hydroxymethyl) imidazoline-2-ketone, or their mixture,
(ii) as needing at least a C
1-5Pure, at least a polyalcohol or its mixture and
(iii) at least a catalyst.
8. according to each method of claim 1-7, wherein the aqueous solution of reactivity material and/or dispersion liquid contain at least a catalyst (iii), and it is selected from metal halides, metal sulfate, metal nitrate, metal tetrafluoroborate and metal phosphate.
9. according to each method of claim 4-7, wherein used catalyst is a magnesium chloride.
10. according to each method of claim 1-3, wherein used reactivity material is the mixture of following component:
(a) polymer that obtains by radical polymerization, its contain the ethylenically unsaturated carboxylic acids acid anhydride of the 5-100 weight % that introduces with the polymerized unit form or the unsaturated dicarboxyl acid of olefinic that its carboxyl can form anhydride group and
(b) contain the alkanolamine of at least two hydroxyls at least a its molecule, and/or at least a polyalcohol.
11. according to the method for claim 10, wherein the aqueous mixture of following component is used as the reactivity material:
-polycarboxylic acids and
-polyhydroxy-alcohol and/or polyfunctional amine and/or alkanolamine,
The amount of this mixture makes the quantity of sour official's energy equal the sum of alcoholic extract hydroxyl group and amine official energy.
12. coated paper of producing according to the method for claim 1-11 or paper products and/or by the Application of Additives of their coated fiber cellulose fibers as the additive and the thermosetting plastics of thermoplastic through taking off the fibrillation process for producing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005050658A DE102005050658A1 (en) | 2005-10-20 | 2005-10-20 | Process for reducing the absorption of water and water vapor and for increasing the dimensional stability of paper and paper products and use of coated paper products |
| DE102005050658.5 | 2005-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101292069A true CN101292069A (en) | 2008-10-22 |
Family
ID=37596227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800386759A Pending CN101292069A (en) | 2005-10-20 | 2006-10-12 | Reducing the water and water vapour absorbence and enhancing the dimensional stability of paper and paper products and use of coated paper products |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20080264587A1 (en) |
| EP (1) | EP1943385A1 (en) |
| CN (1) | CN101292069A (en) |
| BR (1) | BRPI0616932A2 (en) |
| CA (1) | CA2625075A1 (en) |
| DE (1) | DE102005050658A1 (en) |
| WO (1) | WO2007045587A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018393A (en) * | 2014-06-12 | 2014-09-03 | 苏州经贸职业技术学院 | Macromolecule sizing agent and preparation method thereof |
| CN105297421A (en) * | 2015-12-07 | 2016-02-03 | 常熟市华谊织造有限公司 | After-finishing process of dacron fabric |
| CN114341433A (en) * | 2019-09-06 | 2022-04-12 | 日本甜菜制糖株式会社 | Corrosion-resistant paper |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE529897C2 (en) | 2006-03-27 | 2007-12-27 | Rottneros Ab | Molded trough |
| JP5409356B2 (en) * | 2006-06-27 | 2014-02-05 | ビーエーエスエフ ソシエタス・ヨーロピア | Finishing method for paper and paper products |
| US20110174676A1 (en) * | 2007-07-20 | 2011-07-21 | Joakim Stockhaus | Disposable trays of fibre material coated with a removable film layer |
| FI20105456A (en) * | 2010-04-27 | 2011-10-28 | Helsingin Yliopisto | Process for making a material composition and material composition |
| US20180001321A1 (en) * | 2014-12-22 | 2018-01-04 | Evan Koslow | Reactor and process for producing nanofibers and method of using nanofibers in web-forming techniques |
| US10914036B2 (en) * | 2015-10-27 | 2021-02-09 | Hewlett-Packard Development Company, L.P. | Ink fixative solutions |
| CN105780172A (en) * | 2016-03-31 | 2016-07-20 | 华南理工大学 | Plant-based light-emitting fiber and preparation method thereof |
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|---|---|---|---|---|
| US2049469A (en) * | 1933-08-16 | 1936-08-04 | Raybestos Manhattan Inc | Manufacture of saturated fibrous products |
| US2309089A (en) * | 1938-10-06 | 1943-01-26 | Stein Hall Mfg Co | Method of making paper of improved wet strength |
| GB866103A (en) * | 1956-10-08 | 1961-04-26 | American Cyanamid Co | Improved melamine resin colloid and manufacture of wet-strength paper therewith |
| US2993828A (en) * | 1960-03-15 | 1961-07-25 | Texon Inc | Process and apparatus for forming an impregnated fiber product |
| US3275605A (en) * | 1964-11-24 | 1966-09-27 | Scott Paper Co | Amine-modified urea-formaldehyde resins and process of manufacture thereof |
| US4396391B2 (en) * | 1982-06-30 | 1993-03-16 | Treating cellulose textile fabrics with dimenthylol dihydroyethyleneuree-polyol | |
| DE3313726A1 (en) * | 1983-04-15 | 1984-10-18 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING WATER-SOLUBLE CATIONIC UREA-FORMALDEHYDE RESINS AND THE USE THEREOF IN PAPER PRODUCTION |
| FI831767L (en) * | 1983-05-19 | 1984-11-20 | Laennen Tehtaat Oy | CHEMISTRY OF PAPPER INNEHAOLLANDE SUBSTITUTES CELLULOSA. |
| ATE113307T1 (en) * | 1990-03-03 | 1994-11-15 | Basf Ag | MOLDING. |
| US5661213A (en) * | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
| CZ313698A3 (en) * | 1996-04-01 | 1999-01-13 | Markus Rettenbacher | Shaped body made of impregnated wood |
| US5753078A (en) * | 1996-06-07 | 1998-05-19 | Cartons St-Laurent, Inc./St. Laurent Paperboard, Inc. | Method of making surface coated or impregnated paper or paperboard |
| DE19654739A1 (en) * | 1996-12-30 | 1998-07-02 | Basf Ag | Mixed-alkylated or -hydroxyalkoxyalkylated methylolated 4,5-dihydroxy-imidazolidin-2-ones |
| SE0202733D0 (en) * | 2002-09-16 | 2002-09-16 | Skogsind Tekn Foskningsinst | Process and arrangement for replacing fluid in fibers with a replacement fluid |
| DE10246400A1 (en) * | 2002-10-04 | 2004-08-05 | Georg-August-Universität Göttingen | Process for improving the surface hardness of a wooden body with an aqueous solution of an impregnating agent |
| US20040118540A1 (en) * | 2002-12-20 | 2004-06-24 | Kimberly-Clark Worlwide, Inc. | Bicomponent strengtheninig system for paper |
-
2005
- 2005-10-20 DE DE102005050658A patent/DE102005050658A1/en not_active Withdrawn
-
2006
- 2006-10-12 WO PCT/EP2006/067304 patent/WO2007045587A1/en active Application Filing
- 2006-10-12 US US12/067,818 patent/US20080264587A1/en not_active Abandoned
- 2006-10-12 CA CA002625075A patent/CA2625075A1/en not_active Abandoned
- 2006-10-12 CN CNA2006800386759A patent/CN101292069A/en active Pending
- 2006-10-12 EP EP06807172A patent/EP1943385A1/en not_active Withdrawn
- 2006-10-12 BR BRPI0616932A patent/BRPI0616932A2/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018393A (en) * | 2014-06-12 | 2014-09-03 | 苏州经贸职业技术学院 | Macromolecule sizing agent and preparation method thereof |
| CN105297421A (en) * | 2015-12-07 | 2016-02-03 | 常熟市华谊织造有限公司 | After-finishing process of dacron fabric |
| CN114341433A (en) * | 2019-09-06 | 2022-04-12 | 日本甜菜制糖株式会社 | Corrosion-resistant paper |
| CN114341433B (en) * | 2019-09-06 | 2023-10-24 | 日本甜菜制糖株式会社 | Corrosion-resistant paper |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080264587A1 (en) | 2008-10-30 |
| CA2625075A1 (en) | 2007-04-26 |
| DE102005050658A1 (en) | 2007-04-26 |
| EP1943385A1 (en) | 2008-07-16 |
| BRPI0616932A2 (en) | 2016-11-08 |
| WO2007045587A1 (en) | 2007-04-26 |
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Open date: 20081022 |