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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
• • 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
  • D21H17/63—Inorganic compounds
  • D21H17/65—Acid compounds
• • 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
  • D21H17/63—Inorganic compounds
  • D21H17/66—Salts, e.g. alums
• • 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
  • D21H21/18—Reinforcing agents

Definitions

• the present invention provides a composition whose solution in aqueous or aqueous solutions of mucilages, starches and starch derivatives and / or polyvinyl alcohols gives papers high dimensional stability without the disadvantages of the prior art, such as the use of synthetic fibers or the use of mineral Fiber materials in the form of glass fibers in purchasing.
• papers impregnated with the formulation according to the invention can also be produced in a hydrophobized version.
• the invention provides a composition comprising the mineral epsomite and the potassium salt of sorbic acid which is solubilized as a mixture in water or in aqueous solutions of plant slimes, locust bean gum, starches, starch derivatives and / or polyvinyl alcohols.
• the solution is rendered hydrophobic by addition of a copolymer of acrylic ester and styrene.
• the impregnating fleets are used in the production of wallpaper papers, poster papers, affiche papers, map papers and dimensionally stable printing papers.
• nonwoven papers In order to achieve improved dimensional stability, it has been proposed to blend synthetic fibers into the paper to produce so-called nonwoven papers. Since synthetic fibers have low wet transverse elongation, the paper is stabilized against wet-transverse elongation. However, a major disadvantage of nonwoven papers is the high production costs. To "spin" the synthetic fibers, the synthetic fibers must be heavily diluted with water. In addition, synthetic fibers tend to form dust and are generally not biodegradable.
• EP 1914087 A1 also relates to a paper substrate for wallpaper comprising a nonwoven fabric having up to 50% by weight of synthetic fibers. Again, the use of synthetic fibers is disadvantageous, as described above.
• JP 2009096108 A discloses a paper substrate comprising a layer of expanded resin.
• papers having a surface coating with an expanded resin can be used only for limited applications and have therefore disadvantages. So coated papers are usually not suitable for the production of wallpaper.
• EP 98971 A2 refers to a textured wallpaper with a visible surface, which is relief-like and can be painted over.
• the wallpaper consists of an embossed wallpaper base with an embossing on both sides, on the back of the embossed wallpaper a smooth paper, eg waste paper, is glued.
• a water-insoluble and water-impermeable adhesive areas are created that can not absorb water and therefore can not swell or expand.
• a disadvantage of such a wallpaper is that the wallpaper base necessarily has an embossment, whereby the applicability of this base is limited to wallpaper and the possibilities for additional modifications are further limited. Also, the manufacturing process is rather tedious.
• WO 2005095712 A1 discloses a wallpaper that is preferably free of synthetic fibers.
• the wallpaper consists of a number of layers wherein a hydrophobic barrier layer is intended to separate the remaining layers of the wallpaper from a hydrophilic layer intended for adhering the wallpaper to a wall.
• the water absorption and wet transverse strain should be limited to the hydrophilic layer. Disadvantages of this wallpaper are the complex manufacturing process and the increased tendency of the resulting wallpaper to curl.
• EP 2 682 522 A1 discloses a dimensionally stable paper comprising a base paper which has been treated on at least one surface with an impregnating liquor comprising a sugar alcohol, urea and at least one compound selected from polyalkylene glycol and glycerine.
• an impregnating liquor comprising a sugar alcohol, urea and at least one compound selected from polyalkylene glycol and glycerine.
• the fundamental disadvantages of in EP 2 682 522 A1 In the case of the paper papers disclosed, the wallpaper papers impregnated with the liquor formulation described therein can not be rendered hydrophobic and, in addition, a loss of strength due to the impregnation must be accepted.
• WO 2012115626 A1 relates to a method of producing papers for ink jet printers.
• the manufacturing method comprises dissolving epsomite in a coating solution containing at least one additive for surface sizing of papers and coating at least one side of the paper with the coating solution.
• the epsomite in this surface coating is mainly used by the Improvement of the adhesion and retention of the printing inks on the paper surface.
• surface sizing does not allow the epsomite to penetrate the paper structure and therefore can not contribute to dimensional stability improvement.
• WO2010148156 A1 relates to paper products or paper substrates for use as a reinforcing tape (also known as drywall tape or joint tape).
• the paper products contain a sizing agent, an antimicrobial agent and other optional ingredients, including a binder.
• the cellulosic fibers may be contacted with the sizing agent, antimicrobial agent, and optional ingredients at any point in the papermaking process.
• Potassium sorbate is used as a potential antimicrobial substance in these paper products.
• the invention relates to a dry mixture of epsomite and potassium sorbate and an impregnating liquor, which is prepared from this dry mixture by dissolving the mixture in water or in already existing aqueous solutions and serves for the impregnation of papers and nonwoven hybrids. As a result of this impregnation, these papers or nonwoven hybrids are given high dimensional stability.
• the present invention permits a paper or nonwoven hybrid production in which the impregnating liquor can be adjusted both hydrophobicizing and non-hydrophobicizing without the effect of improving the wet cross-stretching being impaired.
• the invention provides a mixture of the mineral epsomite and the potassium salt of sorbic acid in the ratio of their dry weights of from 20: 1 to 5: 1, preferably from 12: 1 to 8: 1.
• the invention provides a mixture of the mineral epsomite and the potassium salt of sorbic acid to improve the dimensional stability of papers or nonwoven hybrids, and their solution in water or in aqueous solutions of locust bean gum, mucilages, starches and derivatives and / or polyvinyl alcohol ,
• the mixture comprises 15.5 to 30% by weight of epsomite and 1.3 to 4% by weight of potassium sorbate.
• the aqueous solution of the mixture can additionally Copolymers are added.
• the copolymers are preferably selected from a copolymer consisting of the monomers acrylic acid and acrylamide and a copolymer consisting of the monomers acrylic ester and styrene.
• 10 to 20% by weight of a copolymer consisting of the monomers acrylic acid and acrylamide and / or 3.2 to 5.4% by weight of a copolymer consisting of the monomers acrylic ester and styrene are added to the aqueous solution of the mixture.
• the mixture of epsomite and potassium sorbate has a dry matter content of 85 to 90% by weight in the mixture.
• the copolymer of acrylic acid and acrylamide is preferably present in a concentration of 20% and the copolymer of acrylic acid ester and styrene is preferably present in a concentration of 50%.
• the values given for the dry matter content or the concentrations relate to the starting materials which are used to prepare the impregnating liquor according to the invention.
• the invention further provides a process for producing an impregnating liquor which comprises the mixture according to the invention of epsomite and potassium sorbate and optionally further components.
• the invention provides a process for the impregnation of papers with the mixture of epsomite and potassium sorbate according to the invention or the impregnation liquors prepared therefrom.
• the invention further relates to the inventive mixture of epsomite and potassium sorbate or the impregnating liquors impregnated therefrom impregnated papers.
• the papers are preferably selected from wallpaper papers, poster papers, affiche papers, map papers, and dimensionally stable printing papers.
• Nonwoven hybrids in the sense of the present invention are wallpaper substrates produced on long-screen paper machines, which consist of 80% by weight of native fibrous materials and 20% by weight of polyester fiber short-cut. When less than 20% by weight of polyester fiber short cut is used, the dimensional stability also increasingly suffers from nonwoven hybrids. In particular, the native fibers swell in thickness upon contact with moisture and shrink again when they dry again. The associated changes in the dimensions of the papers and nonwoven hybrids are known as disturbing.
• the fibers In papers or nonwoven hybrids made on a fourdrinier paper machine, the fibers preferably orientate longitudinally and thus the dimensional change is concentrated on the transverse direction of the paper and nonwoven hybrid webs.
• the change in the dimensions of map paper, poster paper and affiche paper is particularly disturbing. Poor print retention and poor dimensional stability in the processing of the printed products are in the foreground.
• the native fibers swell in thickness upon contact with moisture and shrink again when they dry again.
• the associated changes in the dimensions of the papers and nonwoven hybrids containing less than 20 wt.% Polyester fiber short cut are known to be disturbing.
• the fibers In papers or nonwoven hybrids made on a fourdrinier paper machine, the fibers preferably orientate longitudinally and thus the dimensional change is concentrated on the transverse direction of the paper and nonwoven hybrid webs.
• the change in the dimensions of map paper, poster paper and affiche paper is particularly disturbing. Poor print retention and poor dimensional stability in the processing of the printed products are in the foreground.
• the object of the invention is to provide a means for improving the dimensional stability of papers and nonwoven hybrids while overcoming the disadvantages of the means known from the prior art. Since nonwoven hybrids already have a high dimensional stability, the object of the invention in this case is to be able to significantly lower the generally recognized in the art polyester fiber content of 20%.
• the dimensional stability is defined as the dimensional change of a paper between standard climate (22 ° C / 50% relative humidity) and complete swelling of the fibers after storage in the water.
• the object is achieved by providing a dry mixture from which an impregnating liquor can be prepared by dissolving in water or in aqueous solutions comprising starches, polyvinyl alcohols, galactomannans, locust bean gum or mixtures thereof, containing one or more inorganic salts and / or or organic salts.
• the anionic dry strength agent is preferably a copolymer which is composed of the monomers acrylic acid and acrylamide. It is further preferred for the anionic dry strength agent to have a viscosity of 50 to 700 mPas, preferably 150 to 500 mPas, particularly preferably 200 to 400 mPas (as measured, for example, with a Brookfield RVT viscometer at 20 rpm and 20 ° C.).
• the hydrophobizing agent is preferably a copolymer based on acrylic acid ester and styrene.
• the acrylic ester is methyl, ethyl or butyl acid ester.
• the minimum film-forming temperature of this copolymer is in the range from 0 ° C to 80 ° C, preferably between 10 ° C and 40 ° C.
• the water-soluble inorganic salts are preferably selected from epsomite (magnesium sulfate heptahydrate), sodium chloride and mixtures thereof.
• the water-soluble organic salt is preferably potassium sorbate.
• the polyvinyl alcohol preferably has an average viscosity and a high degree of saponification.
• the polyvinyl alcohol according to the invention preferably has a viscosity in the range from 10 to 40 mPas, more preferably in the range from 15 to 35 mPas.
• the degree of saponification of the polyvinyl alcohol according to the invention is preferably 88 mol%, particularly preferably 98 mol%, very particularly preferably or 99 mol%.
• Starches of any type and origin are basically suitable for use in the impregnating liquor according to the invention.
• Potato starch, corn starch, wheat starch, rice starch or peanut starch is preferably used. Particularly preferred is the use of potato starch or wheat starch.
• Further suitable for use in the impregnating liquor according to the invention are starch esters.
• the starch esters according to the invention are preferably selected from starch phosphates such as monostarch phosphate, distarch phosphate, phosphated distarch phosphate and acetylated distarch phosphate; and esters of starch with organic acids, such as acetylated starch or starch acetate, esters of starch with C 6 -C 26 fatty acids, succinic acid, adipic acid and citric acid or salts thereof.
• starch phosphates such as monostarch phosphate, distarch phosphate, phosphated distarch phosphate and acetylated distarch phosphate
• esters of starch with organic acids such as acetylated starch or starch acetate, esters of starch with C 6 -C 26 fatty acids, succinic acid, adipic acid and citric acid or salts thereof.
• the use of the inorganic salts, such as epsomite and / or sodium chloride, and the organic salts, such as preferably potassium sorbate, contributes in particular to improving the dimensional stability of papers and nonwoven hybrids.
• Potassium sorbate additionally causes rapid wetting and rapid penetration of the impregnating liquor into the raw papers or raw nonwoven hybrids.
• locust bean gum ensures a good water retention capacity of the impregnating liquor when the impregnating liquor comprises a hydrophobizing agent, such as, for example, the copolymer of monomers of acrylic ester and styrene.
• the anionic dry strength agent such as the copolymer of monomers of acrylic acid and acrylamide, or the starches or the galactomannans or polyvinyl alcohol, contribute to maintaining the strength of the impregnated papers and nonwoven hybrids.
• the dimensional stability of the impregnated papers and nonwoven hybrids does not deteriorate due to the addition of the hydrophobic copolymer of acrylate and styrene, although this would have been expected as a result of the indirectly effective reduction in the quantity of epsomite / potassium sorbate.
• the impregnating liquor according to the invention (including component 5) according to Table 1 has the following chemical-physical parameters: Concentration of the solution of the dry mixture: 34 to 38% PH value: 7.0 to 7.2 Charge: anionic Flow behavior: aqueous; Newtonian fluid Penetration time in unsized base paper: 0.5 sec. At 35 ° C
• the stated concentration of the dry mixture according to the invention in the aqueous impregnating liquor is 10 to 38%, preferably 15 to 38%, particularly preferably 30 to 38%.
• other additives such as solutions of starches, polyvinyl alcohols can lead to concentrations below 38%.
• the base papers to be impregnated with the impregnating liquor according to the invention are preferably hydrophilic, ie unsized. Mass-glued base papers absorb too little substance during the impregnation process and thus the desired effect of dimensional stabilization can not develop.
• Preferred according to the invention are base papers having a basis weight in the range of 40 to 130 g / m 2 , more preferably in the range of 50 g / m 2 to 110 g / m 2 .
• the formulation according to the invention can be introduced into the respective base papers both inside and outside of conventional paper machines in off-line coating systems by means of size press, film press, blade coaters or blade coaters.
• size press film press
• blade coaters blade coaters
• blade coaters especially to be preferred are the Equipment size press and film press, because here the liquor is introduced into the base paper with pressure.
• Table 2 shows various embodiments of the impregnating liquors according to the invention.
• Table 2 Variants of the impregnating liquors ⁇ / b> according to the invention component Concentration / dry content 1 , wt .% Parts by weight 2 , wt.% Preferred parts by weight 2 , wt .% Particularly preferred parts by weight 2 , wt .% water - 44.3 70.3 to 40 63.7 to 45 Mixture off 85 ...
• the invention further provides a method of making an impregnating liquor comprising dissolving the dry mixture of epsomite and potassium sorbate in water.
• concentration of the mixture in the solution after dissolution is 8 to 38%, preferably 15 to 30%.
• locust bean gum preferably from 0.1 to 0.3% by weight, based on the dry matter of the impregnating liquor, of the solution thus prepared can be added.
• the impregnating liquor 10 to 20 wt .-%, preferably 10.5 to 19 wt .-% solids of the dry strength acrylic acid-acrylamide copolymer can be added.
• the addition of the dry strength acrylic acid-acrylamide copolymer takes place in the form of a solution of the dry strength agent in water.
• the solution is dissolved in aqueous solutions which already comprise starches, degraded starches, starch esters, polyvinyl alcohols and / or galactomannans or mixtures thereof.
• the hydrophobing agent acrylic acid ester-styrene copolymer, based on the solids of the impregnating liquor, can be added to the impregnating liquor.
• the hydrophobizing agent is admixed with acrylic acid ester-styrene copolymer of the impregnating liquor in the form of a dispersion in water.
• a base paper having a basis weight of 86 g / m 2 and a filler content of 15% was prepared by the generally accepted state of the art.
• the pulp composition consisted of 28% elementary chlorine-free bleached pine sulphate pulp, 68% elemental chlorine-free bleached aspen pulp and 4% own pulp.
• the fibrous materials were ground in an upstream grinding mill to 25 to 28 ° SR. Under ° SR understands the Professional the degree of milling treatment of the fibers, indicated in the Schopper-Riegler degree.
• the fiber mixture dispersed in water was added with calcium carbonate as a filler, cationic epichlorohydrin resin as a wet strength agent, succinic anhydride dispersed in cationic starch, as a water repellent, and polyaluminum chloride as a precipitant.
• the total mixture was then applied continuously in a concentration of 0.9 to 1.0% via a headbox on the wire, which moved at a speed of about 600 m / min. With simultaneous dehydration to a dry content of about 16 to 20%, the paper web formed, which was later mechanically pressed and thermally dried.
• the base paper web reached the size press, where it received a surface treatment with a 7% solution composed of 93 parts water, 4 parts enzymatically degraded wheat starch and 3 parts potato starch ester.
• the coating weight was 3.5 g / m 2 of oven-dry coating spread on both sides of the paper. After drying the paper in the so-called after-dryer section of the paper machine to 93 to 94% final dry content, the paper, which now had a final surface weight of 89 to 91 g / m 2 , was smoothed in a machine calender.
• the resulting map paper is wet-strength, hydrophobic, printable by offset and has a wet transverse elongation of 2.3%, with 2.5 to 2.9% being determined in both edge regions of the paper web.
• Example 2 Map paper according to the invention
• the base paper was wet strength with epichlorohydrin resin and filled with 18% titanium dioxide based on the dry weight of the base paper. In contrast to Example 1 was added during the preparation of the raw paper no water repellent.
• the pulp mixture consisted of 23% elementary chlorine-free bleached pine sulphate pulp, 73% elementary chlorine-free bleached eucalyptus sulphate pulp and 4% own pulp.
• the pulp mixture was ground to 36 ° SR.
• A4 sheets prepared from the raw paper were impregnated with the liquor of the invention, which consisted of 150 g of water, 0.05 g of carob gum, 39 g of dry mixture consisting of 35 g epsomite and 4 g potassium sorbate, 15 g of anionic 20% copolymer consisting of the monomers acrylic acid and acrylamide and 5 g of 50% copolymer consisting of the monomers acrylic ester and styrene.
• the individual components were dissolved in the order mentioned at a temperature in the range of 20 to 35 ° C. Following the impregnation process, the sheets were dried on a photo-dryer at 75 to 80 ° C.
• the impregnated paper is hydrophobic and printable in offset printing.
• the improvement of the wet transverse strain amounts to 1.3% absolute, compared to raw paper.
• Example 2 In contrast to Example 1, however, no sizing agent and no water repellent had been added to the Simplextapetenpapier in the preparation of the raw paper.
• the base paper had a basis weight of 72 g / m 2 .
• the air-dry substance entries based on the liquor composition according to Table 1 are introduced by at least 10% based on the air-dry base paper, but preferably 12 to 30% by weight and particularly preferably 14 to 20% by weight ,
• the amount of substance input is determined by the liquor concentration, using a concentration of at most 38%.

Landscapes

• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Paper (AREA)

Priority Applications (2)

Applications Claiming Priority (1)

Publications (1)

Family

ID=50842099

Family Applications (1)

Country Status (2)

Citations (13)

• 2014
  • 2014-05-27 EP EP14170039.3A patent/EP2949812A1/fr not_active Withdrawn
• 2015
  • 2015-05-26 WO PCT/EP2015/061523 patent/WO2015181129A1/fr active Application Filing

Patent Citations (13)

Also Published As

Similar Documents

Legal Events