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
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/14—Carboxylic acids; Derivatives thereof
  • D21H17/15—Polycarboxylic acids, e.g. maleic acid
  • D21H17/16—Addition products thereof with hydrocarbons
• • 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
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/17—Ketenes, e.g. ketene dimers
• • 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
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
  • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]

Definitions

• the invention relates to a method for producing impregnated papers inside or outside the paper machine, according to which the papers are given a high resistance to penetration against fats and oils.
• a method is known according to which a paper web consisting of cellulose fibers is passed through a hot, aqueous zinc chloride solution or through a sulfuric acid bath and a high fat density is achieved by partial hydrolysis of the cellulose. Paper made with this high resistance to grease and oil penetration is no longer recyclable. Methods are also known in which chromium salts of the fatty acids are used to generate a high penetration resistance to fats and oils. Papers treated with these processes contain chromium as a heavy metal and are therefore considered to be harmful to health if they are used to pack food.
• this packaging material is a food or animal feed
• these organic fluorine compounds enter the food chain.
• they since they are not broken down by human or animal metabolism, they remain in the body. They are suspected of damaging human and animal biological genes.
• these papers are regularly made wet-resistant and are used for this purpose
• Epichlorohydrin resins are used, which contain the harmful substances monochloropropanediol (MCPD) and dichloropropanol (DCP).
• MCPD monochloropropanediol
• DCP dichloropropanol
• a paper produced by such a method has only a low fat density, tested according to generally recognized and standardized test methods.
• EP 1 170 418 AI describes a coating for grease-resistant paper with a special hydrophobically modified starch.
• the aim of the invention is to provide paper with a high level of penetration resistance to fats and oils by means of a new design of chemical technology, while remaining recyclable, printable and not harmful to health, such as heavy metals, fluorocarbon compounds, monochloropropanediol, Contains dichloropropanol or formaldehyde due to the recipe.
• the invention has for its object to provide a paper which has a high penetration resistance to fats and oils, which is easy to recycle, can be printed well and is free from the above-mentioned harmful substances, and to specify a method for producing such a paper , According to the invention the object is achieved by a paper according to claim 1 and a method according to claim 12.
• the degree of grinding is determined as a Schopper-Riegler number (° SR) according to ISO 5267-1. According to the invention, a value of 65-90 ° SR, in particular 78-82 ° SR, is preferred. It is also possible to use low-quality papers (cardboard) with a freeness of 15 - 65 ° SR, in particular 30 to 65 ° SR.
• ASA alkenyl succinic anhydride
• ALD alkyl ketene dimers
• tree resin resin glue
• the alkenylsuccinic anhydride (ASA) used for sizing is, for example, a reaction product of maleic anhydride and ⁇ -olefins with 16 to 20 carbon atoms. According to the invention, it is preferably used in an amount of 0.05 to 0.3% by mass, preferably 0.1% by mass, based on the dry paper. For this purpose, it is emulsified using a protective colloid, for example cationic starch.
• ASA alkenylsuccinic anhydride
• the treatment with the aqueous impregnation liquor can be carried out both in the paper machine and outside of it.
• the liquor can also contain other auxiliary substances such as crosslinking agents, complexing agents, etc.
• the binder system consists of water-soluble binders and possibly water-insoluble polymers.
• Water-insoluble polymers are preferably polyacrylonitriles, polyacrylates, polyvinyl acetates and polystyrene-polyacrylate copolymers. Their proportion should not be so large that the paper can no longer be recycled and, according to the invention, is at most 20% by mass.
• water-soluble binders are preferably polyvinyl alcohols, carboxyl group-containing polyvinyl alcohols (vinyl alcohol-carboxylic acid copolymers), ethylene-vinyl alcohol copolymers, acetalized ethylene-vinyl alcohol copolymers, acetalized polyvinyl alcohols, polyvinyl butyrals, silanol groups-containing, silanol groups-containing acetal-modified polyvinyl , acetalized cationically modified polyvinyl alcohols, acetalized carboxyl group-containing polyvinyl alcohols, gelatin, galactomannans, alginates, carboxymethyl cellulose and starches as well as mixtures of several binders selected from these classes of substances.
• the binder system particularly preferably comprises polyvinyl alcohol and gelatin.
• Gelatin is preferred in which the aqueous solution with 0.1% by mass at 24 ° C. has a surface tension of less than 42 rriN / m.
• a combination of these components with carboxyl-containing polyvinyl alcohol and / or at least one compound from the group consisting of ethylene-vinyl alcohol copolymer, acetalized ethylene-vinyl alcohol copolymer, acetalized polyvinyl alcohol, acetalized silanol group-containing, acetalized cationically modified polyvinyl alcohols and / or polyvinyl butane al is advantageous.
• the polyvinyl alcohol content of the is also preferred Binder system realized by a mixture of at least two different polyvinyl alcohols, of which at least one has a viscosity of less, the other or the other one of more than 35 mPa.s.
• the viscosity of polyvinyl alcohol is understood to mean the viscosity measured in accordance with DIN 53015 on an aqueous solution with 4% by mass at 20 ° C.
• the impregnation liquor for producing the paper sheet according to the invention preferably contains a crosslinking agent, particularly preferably glyoxal, in a concentration of 2 to 15 percent by mass, based on the total amount of binder and crosslinker.
• a crosslinking agent particularly preferably glyoxal
• the concentration of the impregnation liquor is advantageously between 2 and 15, preferably between 5 and 7.5 percent by mass of dry substance.
• the application weight of the impregnation liquor, calculated as dry substance, is advantageously between 0.3 and 1.5 g / m each side.
• the process for the production of the paper sheet according to the invention comprises the production of a base paper from cellulose, wood pulp or recycled waste paper with the aforementioned grinding degrees, the sizing of this paper in bulk, in particular with alkenylsuccinic anhydride (ASA), and the impregnation of the sized base paper with an impregnation liquor contains a binder system comprising 80 to 100 parts by weight of water-soluble binders and 20 to 0 parts by weight of water-insoluble polymers in dispersion.
• ASA alkenylsuccinic anhydride
• the impregnation can take place both in the paper machine and outside it. Common devices, e.g. B. size presses, film presses etc. can be used for this.
• the raw paper is preferably dried to: a dry matter content of 95 to 99%.
• a drying process to the desired final moisture level also follows.
• Polyvinyl alcohol (PVA) due to the viscosity (in mPa.s) determined in accordance with DIN 53015 on an aqueous solution with 4% by mass at 20 ° C and the degree of hydrolysis, expressed in% of hydrolyzed vinyl acetate groups.
• Suitable products are sold, for example, under the Mowiol and Poval brands by Kuraray Specialties Europe.
• Polyvinyl alcohol (PVA-C) containing carboxyl groups also by viscosity and degree of hydrolysis as above.
• Suitable products are types KL-318 and KL-506 from Kuraray Specialties Europe.
• PVA-K Cationically modified polyvinyl alcohol
• CM-318, C-118 and C-506 from Kuraray Specialties Europe.
• Polyvinyl alcohol (PVA-R) containing silanol groups also by viscosity and degree of hydrolysis as above.
• Suitable products are e.g. the type R-1130 from Kuraray Specialties Europe.
• PEVA Ethylene-vinyl alcohol copolymer also by viscosity and degree of hydrolysis. Suitable products are sold under the Exceval brand by Kuraray Specialties Europe, for example the type HR-3010. PEVA can be obtained through copolymerization of vinyl acetate and ethylene as well as subsequent ones Hydrolysis of the vinyl acetate to vinyl alcohol units.
• Acetalized polyvinyl alcohols such as polyvinyl butyral (PVB) are also characterized by viscosity, degree of hydrolysis and degree of acetalization. To maintain water solubility, the degree of acetalization is at most 30 mol%.
• the acetalized polyvinyl alcohols which can be used according to the invention are obtained by acetalizing a polyvinyl acetate prepared by hydrolysis.
• Homopolymers of vinyl acetate as well as copolymers of olefins such as ethylene, propylene or other V-olefins with vinyl acetate can be used as polyvinyl acetate.
• the polymers obtained after hydrolysis contain 0 to 15 mol% of olefin units, 50 to 99.9 mol%, preferably 75 to 99.9 mol%, particularly preferably 85 to 99.9 mol% of vinyl alcohol units and 0.1 to 50 mol%, preferably 0.1 to 25 mol%, particularly preferably 0.1 to 15 mol% of vinyl acetate units.
• the acetalization with the aldehydes mentioned takes place up to a degree of acetalization of 1 to 30 mol%, preferably 1 to 20 mol%.
• the described silanol group-containing, carboxyl group-containing and cationically modified polyvinyl alcohols can be acetalized analogously.
• Suitable products are the types GELITA Imagel MA (39 mN / m) and GELITA Imagel BP (56 mN / m, brands of Stoess AG).
• Carboxymethyl cellulose can be used in a commercially available form.
• Alginate can be used as sodium alginate, for example available from Kimica Corp., Japan.
• the recipes listed in Table 1 include proportions by mass of the dry matter of the impregnated liquor, which also contains essentially only water.
• the dry content of the liquor can be between 2 and 15% by mass, preferably between 5 and 7.5% by mass. In addition to the appropriate quantity ranges, preferred values are given for each component.
• the impregnating liquors according to the invention can be prepared by dissolving the constituents in water at 90 to 95 ° C., if appropriate after swelling some of the dry constituents in cold water.
• the impregnation liquors thus produced are applied to a raw paper made of cellulose with a freeness of 65 to 90 ° SR, preferably 78-82 ° SR, which has been mass-sized with alkylene succinic acid, inside or outside the paper machine on one or on both sides.
• a preferred range of application weight is between 0.3 and 1.5 g / m per side, calculated as dry matter in the liquor.
• the paper web is impregnated using L0 one of the generally known application methods inside or outside the paper machine and subsequent drying of the web on drying cylinders or contactless, e.g. in floating dryers.
• the invention can be carried out in a wide range of basis weights of the base paper. Papers or with 28-350 g / m 2 are preferred.
• 20 paper web produced according to the invention has a high penetration resistance to fats and oils, measured according to generally recognized and standardized test methods as in Examples 1 to 3, although the individual components polyvinyl alcohol or gelatin or CMC or ethylene-25 vinyl alcohol copolymer or alginates or galactomannans or Starch derivatives only develop low-value penetration resistances against oils and fats.
• Examples 4 to 14 relate to polymers which can be used according to the invention
• Examples 15 to 30 relate to the papers impregnated with these polymers.
• Example 2 The relevant test results determined on the finished paper are shown in Table 2.
• the impregnation media described in the examples were applied with a size press to unsized raw paper (examples 1 and 2 - state of the art), while in example 3 the impregnation liquor was applied with a size press to alkenylsuccinic anhydride gel-based raw paper (according to the invention).
• All of the base papers mentioned in Examples 1, 2 and 3 are produced from cellulose which has been given a freeness of 78 ⁇ SR to 82 ° SR.
• the impregnation takes place at a paper web speed of approx. 600 m / min.
• the application takes place on both sides of the paper web. Drying after impregnation is first carried out contactlessly in an infrared dryer and then with drying cylinders.
• a paper web is made from fibrous materials as described above. 2%, based on the paper, of a 12% epichlorohydrin resin solution is added to this fibrous suspension in order to give the paper a desired wet strength.
• the pre-dried paper web is impregnated with a dry content of 95 to 99% in a size press with an impregnation liquor which is determined from 2 parts by mass of complexing agent solution, 10 parts by weight of polyvinyl alcohol with a viscosity of 28 mPa.s, as described above !, and a degree of hydrolysis of 99%, 6.5 parts by weight of CMC with a medium viscosity, 6.5 parts by weight of a galactomannan, 65 parts by weight of a potato starch ester with film-forming properties (Perfectamyl 150A - Avebe), 10 parts by weight of a glyoxal solution of 40% concentration and 25 parts by weight a 33% solution of fluorocarbons (Cartafluor UHC - Clar
• the impregnation liquor has a pH value of 7.0 to 7.3, a viscosity of 27 to 30 s flow time from the Ford cup, 4 mm nozzle, at 20 ° C and a dry matter concentration of 6.4 to 6.5% ,
• the application weight on the base paper is 0.9 g / m 2 per side, i.e. a total of 1.8 g / m 2 .
• the paper web is dried again to a final dry content of 93%.
• Fat density according to DIN 53116 level V no permeability level IV: no permeability level III: no permeability level II: 2 breakthroughs stage I: 30 breakthroughs, 10 of them larger than 1 mm 2
• red-colored palm kernel fat is applied to the test specimen on an area of 50 cm using a template.
• Level V indicates the carbon copies after 10 minutes, which are counted on an underlying white paper sheet.
• Stage IV is also determined after a test period of 10 minutes, but the palm kernel fat was loaded with a pressure of 20 N / cm 2 . The same load is applied to levels III, II and I, but the test duration is then 60 min (level III); 24 hours (level II) and 36 hours (level I). Fat density according to Tappi T454: t> 1800 s.
• a time of 1800 s corresponds to a high penetration resistance against greases and oils.
• the paper Due to the use of epichlorohydrin resins for wet strengthening, the paper contains the critical substances monochloropropanediol and dichloropropanol in a legally permissible amount. It also contains organically bound fluorine, which is suspected of damaging the genome.
• a paper web is made from fibrous materials as described in Example 1. As in Example 1, 0.5 to 2%, based on the paper, of a 12% epichlorohydrin resin solution is also added to this fibrous suspension in order to impart a desired wet strength to the paper.
• the pre-dried paper web is now impregnated with a dry content of 95 to 99% in a size press with an impregnation liquor, which consists of 12 parts by weight of polyvinyl alcohol with a viscosity of 28 mPa.s, as above, and a degree of hydrolysis of 99%, 7 parts by weight of CMC an average viscosity, 7 parts by weight of a galactomannan, 70 parts by weight of a potato starch ester with film-forming properties and 10 parts by weight of a 40% glyoxal solution and water consists .
• an impregnation liquor which consists of 12 parts by weight of polyvinyl alcohol with a viscosity of 28 mPa.s, as above, and a degree of hydrolysis of 99%, 7 parts by weight of CMC an average viscosity, 7 parts by weight of a galactomannan, 70 parts by weight of a potato starch ester with film-forming properties and 10 parts by weight of a 40%
• the impregnation liquor contains no fluorocarbon compounds. It has a pH value of 6.2 - 6.8, a viscosity of 24 to 27 s flow time from the Ford cup, 4 mm nozzle, and a dry matter concentration of 6.1 to 6.3%.
• the application weight on the base paper is 0.6 g / m 2 per side, that is 1.2 g / m 2 in total. After impregnation, the paper web is dried again to a final dry content of 93%.
• Fat density according to DIN 53116 level V no permeability level IV: 65 breakthroughs, 16 of which are larger than 2 mm level III, II, I: large area breakthroughs
• the paper Due to the use of epichlorohydrin resins for wet strengthening, the paper contains monochloropropanediol and dichloropropanol in a legally permitted amount. However, it has little penetration resistance to greases and oils.
• a paper web is made from fibrous materials as described in Example 1. No epichlorohydrin resin is added to the fiber suspension, but 0.1% alkenyl succinic anhydride (Baysize 18 - Bayer) and 0.9% cationic potato starch (HI-CAT 145 - Roquette Freres), based on paper added.
• the pre-dried paper web is now impregnated with a dry content of 96 to 99% in the size press with an impregnation liquor which is composed of 7 parts by weight of a polyvinyl alcohol with a viscosity of 15 mPa.s, determined as above, and a degree of hydrolysis of 79%, 25 Parts by weight of a polyvinyl alcohol with a viscosity of 28 mPa.s and a degree of hydrolysis of 99%, 12 parts by weight of a polyvinyl alcohol with a viscosity of 40 mPa.s and a degree of hydrolysis of 88%, 15 parts by weight of a polyvinyl alcohol with a viscosity of 56 mPa.s and a degree of hydrolysis of 88%, 15 parts by weight of a carboxyl group-containing polyvinyl alcohol with a viscosity of 18 mPa.s and a degree of hydrolysis of 84%, 17 parts by weight of a gelatin with a
• the impregnation liquor has a pH value of 6.4 to 6.9, a viscosity of 30 to 32 s flow time from the Ford cup and nozzle
• Dry application was 1.2 g / m 2; per page.
• GD means large-area breakthroughs; with numerous breakthroughs, the number of breakthroughs greater than 1 mm 2 is given after the slash.
• the paper produced according to example 3 according to the invention has a high penetration resistance to fats and oils, is free from organically bound halogen including epichlorohydrin resin and fluorocarbon compounds, is free from heavy metals, is recyclable, can be printed with printing inks on both water and solvent bases and is inside the paper machine was created as part of the manufacturing process.
• Example 6 1440 grams of polyvinyl alcohol Mowiol ® 4-98 are dissolved in 5760 ml of water. After 172.02 g of n-butyraldehyde have been introduced, the pH is adjusted to about 1 using 20% hydrochloric acid. The solution is stirred for 2 hours at the adjusted pH. The solution is then adjusted to a pH of 6-8 with 10% sodium hydroxide solution and stirred for 1 hour.
• the Höppler viscosity according to DIN 53015 is 5 mPas for a 4% by weight solution in water and 21 mPa s for an 8% by weight solution in water.
• the solutions are already cloudy at room temperature. If you heat them up, they fail at approx. 30 ° C.
• the glass point (Tg) determined by DSC measurement is 79 ° C.
• Example 10 1062.5 g of polyvinyl alcohol Exceval RS-2117 are dissolved in 7437.5 ml of water. After 41.57 g of n-butyraldehyde have been introduced, the pH is adjusted to about 1 using 20% hydrochloric acid. The solution is stirred for 2 hours at the adjusted pH. The solution is then adjusted to a pH of 6-8 with 10% sodium hydroxide solution and stirred for 1 hour.
• the Höppler viscosity according to DIN 53015 is 19 mPas for a 4% by weight solution in water and 261 mPa s for an 8% by weight solution in water.
• the solutions become cloudy at approx. 41 ° C. If you heat them up further, they fail at approx. 48 ° C.
• the glass point (Tg) determined by DSC measurement is 77 ° C.
• Table 4 shows the penetration resistances of these papers.

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• 2004
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• 2005
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