WO2014191408A1 - Polysaccharides cationiques modifiés et leurs utilisations dans la fabrication du papier - Google Patents

Polysaccharides cationiques modifiés et leurs utilisations dans la fabrication du papier Download PDF

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Publication number
WO2014191408A1
WO2014191408A1 PCT/EP2014/060947 EP2014060947W WO2014191408A1 WO 2014191408 A1 WO2014191408 A1 WO 2014191408A1 EP 2014060947 W EP2014060947 W EP 2014060947W WO 2014191408 A1 WO2014191408 A1 WO 2014191408A1
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Prior art keywords
cationic
modified
composition
galactomannan
polysaccharide
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PCT/EP2014/060947
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English (en)
Inventor
Karl Heinrich Oskar Tiefenthaler
Michael Maurer
Original Assignee
Dupont Nutrition Biosciences Aps
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Application filed by Dupont Nutrition Biosciences Aps filed Critical Dupont Nutrition Biosciences Aps
Priority to EP14726384.2A priority Critical patent/EP3004176A1/fr
Publication of WO2014191408A1 publication Critical patent/WO2014191408A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0093—Locust bean gum, i.e. carob bean gum, with (beta-1,4)-D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from the seeds of carob tree or Ceratonia siliqua; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • 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 relates to cationic modified polysaccharides, and uses thereof in papermaking.
  • modified polysaccharide as a paper additive is known to improve the properties of paper such as strength, drainage and pigment retention.
  • cationic modified guar gum is known for providing a denser surface to paper used for printing and imparts improved writing properties, better bonding strength and increased hardness. Due to the improved bonding strength guar gum also provides better breaking, mullen and folding strengths, and especially reduces dusting and linting problems in the printing process.
  • the pulp recipe for papermaking can be changed to cheaper fibres and/or higher filler content at the same level of paper strength.
  • starch which is also a known paper additive
  • guar gum is valuable in the papermaking process because of the possibility of applying lower dosages and its unique properties.
  • WO 00/31339 discloses a composition comprising cationic starch, cationic galactomannan gum (such as cationic guar, locust bean and fenugreek gum) and acid suitable as drainage aid and strength additive in papermaking.
  • cationic starch such as cationic guar, locust bean and fenugreek gum
  • acid suitable as drainage aid and strength additive in papermaking such as cationic guar, locust bean and fenugreek gum
  • US 5,554,745 discloses aldehydic, cationic derivatives of natural occurring galactose containing polysaccharides obtained by site-specific oxidizing the selected polysaccharide with the enzyme galactose oxidase providing a cation derivatized, enzyme oxidized product has an aldehyde function at a specific position of the polysaccharide disclosed as providing strength properties when used as a paper additive.
  • galactose containing polysaccharides mention is made of polygalactomannan gums such as locust bean gum and gear gum, as well as tamarind gum and gum arabic.
  • the use of native tamarind powder in the paper industry is mentioned in for example
  • Modified tamarind powder is known as an anionic modified product after conversion with sodium monochloroacetate and also as a cationic modified product for example known from S. Pal et. al., Int. J. Biological Macromolecules, 45, 2009, page 518-523 and US patent 5,554,745.
  • Cationization of tamarind in US patent 5,554,745 results in a modified polysaccharide which is cold water soluble in comparison to the starting material component tamarind powder, which is mainly soluble in hot water.
  • the preparation of cationized tamarind as described in for example said US patent 5,554,745 involves the use of isopropanol which is not desirable in an industrial process.
  • compositions such as a paper additive composition which may be used as an alternative paper additive to traditional paper additives such as guar gum. It is a further object of embodiments of the invention to provide a paper additive composition which is efficient and cold water soluble, and which may improve paper strength and ash retention. It is a further object of embodiments of the invention to provide a process for preparing said composition, preferably without the use of alcoholic solvents in a semidry process which makes the production safer and reduces energy consumption. It is a further object of embodiments of the invention to provide a method for preparing paper having an acceptable paper strength and ash retention. It is a further object to provide a paper having an acceptable paper strength and ash content compared to traditional paper.
  • the herein disclosed composition comprising a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the weight ratio of the first cationic-modified polysaccharide and the cationic-modified galactomannan is from 15:85 to 85 : 15 is advantageous.
  • the present inventors have found that by combining said first polysaccharide and said galactomannan, a composition having desirable properties relating to paper strength, filler retention and paper printability when added in a
  • the papermaking process may be prepared. Furthermore, the present inventors have found that the combination of the two types of cationic-modified polysaccharides may enable the use of a process without the need for alcohols, the use of which is disadvantageous in an industrial process, and which is commonly used when preparing cationic-modified tamarind.
  • the cost of the raw material guar gum which is an example of a galactomannan and which is commonly used for the same purpose as the paper additive composition disclosed herein, is higher than the price of the raw material tamarind which is an example of a polysaccharide from the genus Tamarindus.
  • the paper additive composition disclosed herein is thus economically advantageous.
  • the present invention relates to a composition
  • a composition comprising
  • the invention relates to a process for the preparation of a composition
  • a composition comprising
  • a cationic-modified galactomannan wherein the weight ratio of the first cationic-modified polysaccharide and the cationic- modified galactomannan is from 15 : 85 to 85: 15, the process comprising the steps of cationization of a polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus and a galactomannan in a semidry and alkaline mixture to obtain said compositions.
  • the invention also provides compositions obtainable by said process.
  • the invention relates to the use of a composition as described herein as a paper additive.
  • the invention relates to the use of (a) a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and (b) a cationic-modified galactomannan, wherein the weight ratio of the first cationic-modified polysaccharide and the cationic-modified galactomannan is from 15:85 to 85 : 15 as a paper additive.
  • the invention relates to a method for preparing paper by adding the composition or the paper additive as disclosed herein.
  • the invention relates to a paper comprising the composition or the paper additive as disclosed herein.
  • Fig. 1 shows the improvement of the relative breaking length (N) and ash content (% (w/w)) of letter printing paper measured as described in example 1 of different composition samples as further described in example 1 herein in comparison to no addition of additive (denoted “ohne") and addition of cationic guar gum (Guar Gum Meypro Bond 109) alone denoted "Mbl09".
  • Fig. 2 shows the relative breaking length (N) and ash content (% (w/w)) of newsprint paper measured as described in example 1.
  • Mb 109 denotes addition of cationic guar gum alone as additive and "ohne” means that no additive was added.
  • the remaining columns show the results obtained with a composition as disclosed herein, and further described in example 1, table 1.
  • Fig. 3 shows dewatering measured as described in example 1 of letter printing paper of different paper additives as described in example 1, table 1.
  • "63a”, “63b”, “62b” and “62a” show the results obtained with a composition as disclosed herein, and further described in example 1.
  • "Mb 109” denotes addition of cationic guar gum alone as additive and "ohne” means that no additive was added.
  • Fig. 4 shows the relative breaking length (N) of laboratory paper sheets made out of pure virgin fibre pulp as a mixture of 50% (w/w) short fibre and 50% (w/w) long fibre pulp without addition of additive as denoted with "ohne” and with addition of cationic modified Guar Gum Meypro Bond 109 (denoted “Mb 109").
  • CT109 and “43e” show the results obtained with a composition as disclosed herein, and further described in example 1.
  • paper as used herein includes sheet-like masses and molded products made from cellulosic materials which may be derived from natural sources as well as from synthetics such as polyamides, polyesters and polyacrylic resins and from mineral fibres such as asbestos and glass. In addition, papers made from combinations of cellulosic and synthetic materials are applicable herein. Paperboard is also included within the broad term “paper”.
  • polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and (b) the cationic-modified galactomannan are converted in a reaction with chemicals like in an alkaline solution such as an aqueous solution of a caustic reagent and cationization reagents in aqueous form.
  • a solvent is added, however, not in an amount higher than an amount ensuring that the reaction mixture still is semi-dry in a powdery form and does not form a suspension or a solution.
  • the moisture content of the semi-dry powder is in general below 45% (w/w) such as below 40% (w/w) or even below 35% (w/w).
  • the moisture content are primarily from non-alcoholic solvents such as water.
  • the aqueous solvent is a non-alcholic solvent, such as an aqueous solvent comprising less than 20 % (w/w) alchohol, less than 10 % (w/w), such as less than 5 % (w/w) alchohol or non alcholic solvent.
  • alkaline means in the present context that the pH of the mentioned reaction mixtures or chemicals is between pH 8 and 14.
  • non-alcoholic solvents means in the present context a solvent such as water comprising none or less than 20 % (w/w) such as less than 10 % (w/w), such as preferably less than 5 % (w/w) alcoholic solvent like e.g. ethanol or isopropanol.
  • the semi-dry and alkaline reaction mixture is performed in a non-alcoholic environment.
  • cationic-modified or cationic in connection with a polysaccharide such as a "cationic- modified” or a “cationic” tamarind or galactomannan means in the present context that a cationic charge is introduced in the polysaccharide for example by reaction with quaternary ammonia reagents as described in example 1.
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus
  • Tamarindus and a cationic-modified galactomannan, wherein the first cationic-modified polysaccharide is present in a weight percentage of 15-85% (w/w), preferably 20-80% (w/w), more preferably 25-75% (w/w), and more preferably 45-75% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic-modified galactomannan.
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the first cationic- modified polysaccharide is present in a weight percentage of about 70% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic-modified galactomannan.
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the first cationic- modified polysaccharide is present in an amount of more than 50% (w/w) or more than 60% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic-modified galactomannan.
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the cationic-modified galactomannan is present in a weight percentage of 15-85% (w/w), preferably 20-80% (w/w), more preferably 25-75% (w/w), and more preferably 25-55% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic-modified galactomannan.
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the cationic-modified galactomannan is present in a weight percentage of about 30% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic-modified
  • the herein disclosed composition comprises a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and a cationic-modified galactomannan, wherein the cationic-modified galactomannan is present in an amount of less than 50% (w/w), or less than 40% (w/w) based on the total amount of the first cationic-modified polysaccharide and the cationic- modified galactomannan.
  • the weight ratio between the first cationic-modified polysaccharide and the cationic-modified galactomannan is from 15 : 85 to 85 : 15, such as from 20 : 80 to 80 : 20, such as from 25 : 75 to 75 : 25, or such as from 45 : 55 to 55 : 45, such as a weight ratio of 50: 50, 60 : 40, and 70: 30.
  • the first cationic-modified polysaccharide is selected from the group consisting of polysaccharides from the genus Tamarindus.
  • the first cationic-modified polysaccharide is a cationic-modified tamarind such as a cationic- modified de-oiled tamarind.
  • the oil and fat content in de-oiled tamarind is approximately 2 % (w/w) or less.
  • Tamarind Kernel Powder is derived from the plant Tamarindus Indica, which is an evergreen tree. The polysaccharides contained in deoiled Tamarind kernel powder are described as a mixture of the sugars D-Galactose, D-Xylose and D-Glucose in the molar ratio of 1 : 2 : 3 and small amounts of other sugars.
  • the cationic-modified galactomannan is selected from the group consisting of cationic-modified guar gum, cationic-modified locust bean gum (LBG), cationic- modified tara gum and cationic-modified cassia gum.
  • the cationic-modified galactomannan is cationic-modified guar gum.
  • a free flowing agent is added in order to improve the free flowing properties of the powder.
  • About 0.1% (w/w) silica can be mentioned as an example of a free flowing agent.
  • an anti-dusting additive like an oil may be added.
  • the composition disclosed herein is preferably in powder form .
  • the particle size of said powder may be measured by sieving or screening through specified screens.
  • the powder is sieved using a vibratory sieve, such as a Retsch vibratory sieve, with an appropriate screen depending on which fraction of powder it is desired to measure, and the fractions are weighed after shaking of the sieve for 20 minutes.
  • the particle size of said powder is such that less than 1 % (w/w) is finer than 75 ⁇ or such that more than 99 % (w/w) are finer than 75 ⁇ , preferably such that less than 2 % (w/w) is coarser than 300 ⁇ and more than 60 % (w/w) are finer than 75 ⁇ .
  • the powder could furthermore be agglomerated.
  • a composition is considered "water soluble" when a thickening effect respectively a viscosity increase of water comprising a composition or additive as disclosed herein is determined such as for example determined by measurement of the viscosity with a Brookfield RVF, 20 rpm, with addition of 2% (w/w) to the aqueous solution, 25 °C, 24 h : appr. 150 mPa.s.
  • the range of viscosity is from 50 to 10000 mPa.s at 2% (w/w).
  • the composition is water soluble at room temperature because then no heating needs to be applied on customer site before usage.
  • water soluble after heating and ccoling means in the present context that a composition or additive as described herein causes a thickening and viscosity increasing effect on water in such a way that the viscosity (measured with a Brookfield RVF viscometer of a 2% (w/w) aqueous solution at 25 °C with rotation speed of 20 rpm) of the additive in an aqueous solution after 24 hours of swelling time at room temperature such as 25 °C is substantial identical with the viscosity measured after heating of the solution up to 95 °C and keeping it at 95 °C for 15 min and cooling to room temperature such as 25 °C afterwards for 15 min in a water bath.
  • room temperature means in the present context a temperature in the interval of 20-25 °C.
  • the herein disclosed composition is water soluble (means causing a thickening and viscosity increasing effect) at room temperature such as at 25 °C for example measured as described above.
  • a process for the preparation of a composition comprising a) a first cationic-modified polysaccharide selected from the group consisting of the genus Tamarindus, and b) a cationic-modified galactomannan, wherein the weight ratio of the first cationic-modified polysaccharide and the cationic-modified galactomannan is from 15: 85 to 85 : 15, the process comprising the steps of: cationization of a polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus and a galactomannan in a semidry, and alkaline, and preferably non-alcoholic mixture.
  • the cationization is performed by addition of water and aqueous chemicals in a semidry process under alkaline conditions where non-alcoholic solvents are applied for dispersing the powders. It is an advantage by the present process that it may be performed as a "semidry" process. This is due to environmental reasons and because usage of alcoholic solvents requires explosive protection at the plant.
  • said first polysaccharide and said galactomannan have been mixed before said cationization step in a weight ratio of from 15 :85 to 85: 15.
  • said first polysaccharide and said galactomannan have been mixed and then alkaline, semidry conditions are created by addition of an alkaline solution selected from the group consisting of sodium hydroxide, sodium carbonate and other usual alkaline bulk chemicals having a pH of approximately 12 to 14 before said cationization step. Further water is added for better distribution of the chemicals.
  • the alkaline solution is a caustic solvent such as 50% (w/w) sodium hydroxide.
  • said first polysaccharide and said galactomannan are added separately in any order, and the chemicals for perfoming the cationization is added in portions for example such that said galactomannan is added, then part of the chemicals and then said first polysaccharide, whereafter the remaining chemicals are added.
  • reagents and chemicals may be added to the process in order for the reaction to proceed more readily and resulting in an even better dispersible finished product.
  • reagents are borax or boric acid as a dry chemical or as aqueous solution which may be added to the mixture of polysaccharides or by making a premix with one of the polysaccharides and adding the second polysaccharide afterwards.
  • said cationization step comprises addition of a cationization agent.
  • the cationization agent is a quaternary ammonium compound.
  • a suitable cationization agent is for example 3-chloro-2-hydroxypropyltrimethylammonium chloride (such as sold under the name Reagens S, Sachem) and the corresponding epoxy- compound, the 2,3- epoxypropyltrimethylammonium chloride.
  • said cationization agent is 3-chloro-2-hydroxypropyltrimethylammonium chloride.
  • the number of cationic substituents on the polysaccharide can be varied and generally a degree of substitution (D.S.) between 0.005 to 1.5 and preferably between 0.01 to 0.5 will be used, such as between 0.01-0.2. While larger amounts of cationic substituents or higher degrees of substitution (D.S.) could be used, they are more costly and difficult to make and therefore not economically attractive.
  • degree of substitution D.S. as used herein is meant the average number of sites or substituent groups per anhydrohexose or anhydropentose units.
  • the cationization is performed at a temperature between 50°C and 95°C, such as between 70°C and 90°C, such as at 80°C. In most cases, this ensures a good conversion of the cationization reagent in the given the reaction time.
  • the cationized mixture may be kept between 50°C and 95°C for 30-120 minutes, such as between 70°C and 90°C for 30-105 minutes, such as at 80°C for 60 minutes in order for full conversion of cationization reagent to take place. In one embodiment, it may be
  • the process comprises a further step of neutralization of the cationized composition. This may be achieved by addition of an acid such as acetic acid.
  • the neutralisation is performed at a pH from 6 to 7.5.
  • the process comprises a further step of acidification to pH 4.5 or a further step of partly neutralization to pH 9 to 10.
  • the embodiment, wherein the pH is sligthly alkaline is especially useful when for example borax or boric acid is applied to the reaction mixture.
  • the process may further comprise a step where the cationized composition is dried, and optionally ground to a particulate powder providing a powder for example with a particle size wherein less than 2 % (w/w) is coarser than 300 ⁇ and more than 60 % (w/w) are finer than 75 ⁇ .
  • the particle size of said powder is such that less than 1 % (w/w) is finer than 75 ⁇ or such that more than 99 % (w/w) are finer than 75 ⁇ , preferably such that less than 2 % (w/w) is coarser than 300 ⁇ and more than 60 % (w/w) are finer than 75 ⁇ .
  • the powder could furthermore be agglomerated.
  • the particle size of said powder may be measured by sieving or screening through specified screens.
  • the powder is sieved using a vibratory sieve, such as a Retsch vibratory sieve, with an appropriate screen depending on which fraction of powder it is desired to measure, and the fractions are weighed after shaking of the sieve for 20 minutes.
  • composition obtained and/or obtainable by the process as disclosed herein may be used as a paper additive.
  • the composition or the paper additive as disclosed herein is added in a method for preparing paper, the composition could be added over the whole process of papermaking starting form addition into the pulper to the thick stock till the thin stock before headbox or as well be sprayed onto the paper web or between paper layers.
  • paper comprising the composition as disclosed herein or the paper additive as disclosed herein are provided.
  • the paper as disclosed herein treated with the composition or the paper additive as disclosed herein has a higher ash content but also good strength properties whilst higher ash content in general are expected to lower strength properties of paper.
  • compositions are useful as paper additives particularly to improve dry and initial wet strength properties, to improve ash retention and reduce dusting and linting problems.
  • the herein disclosed compositions may be used as beater additives, although their addition to the pulp may occur at any point in the paper-making process prior to the ultimate conversion of the wet pulp into a dry web or sheet. Thus, for example they may be added to the pulp while the latter is in the hydropulper, beater, various stock chests or headbox.
  • the herein disclosed compositions may also be sprayed onto the wet web.
  • compositions may be used for addition to pulp prepared from any type of cellulosic fibres, synthetic fibres, or combination thereof.
  • cellulose materials which may be used are bleached and unbleached sulfite, bleached and unbleached soda, neutral sulfite, semi-chemical ground wood, ground wood or any combination of these fibres.
  • fibres of the viscous rayon or regenerated cellulose type may be used.
  • any desired inert mineral fillers may be added to the pulp which is to be modified with the herein disclosed compositions.
  • Such materials include clay, titanium dioxide, talc, calcium carbonate, calcium sulfate and diatomaceous earths. Rosin or synthetic internal size may also be present, if desired.
  • the proportion of the herein disclosed compositions to be incorporated into the paper pulp may vary in accordance with the particular pulp involved and the properties desired (e.g., wet strength, temporary wet strength or dry strength). In general, it is preferred to use about 0.01 to 7% (w/w) and more preferably about 0.1 to 2.5% (w/w) of the herein disclosed compositions based on the dry weight of the pulp. The exact amount used will depend upon the type of pulp being used, the specific operating conditions, the particular end use for which the paper is intended, and the particular property to be imparted. The use of amounts greater than 2.5% (w/w) is not precluded, but is ordinarily unnecessary in order to achieve the desired results.
  • Embodiment 3 The composition according to embodiment 2, wherein the first cationic-modified polysaccharide is a cationic-modified de-oiled tamarind.
  • Embodiment 4 The composition according to embodiment 1, wherein the cationic- modified galactomannan is selected from the group consisting of cationic-modified guar gum, cationic-modified locust bean gum (LBG), cationic-modified tara gum and cationic-modified cassia gum.
  • the cationic- modified galactomannan is selected from the group consisting of cationic-modified guar gum, cationic-modified locust bean gum (LBG), cationic-modified tara gum and cationic-modified cassia gum.
  • Embodiment 5 The composition according to any one of embodiments 1-4, wherein the weight ratio between the first cationic-modified polysaccharide and the cationic- modified galactomannan is from 15 : 85 to 85 : 15, such as from 20 : 80 to 80: 20, such as from 25 : 75 to 75 : 25, such as a weight ratio of 50 : 50, 60 : 40, 70 : 30.
  • Embodiment 6 The composition according to any one of embodiments 1-5, wherein the composition is in powder form with a particle size of less than 2 % (w/w) is coarser than 300 ⁇ and more than 60 % (w/w) are finer than 75 ⁇ .
  • Embodiment 7 The composition according to any one of embodiments 1-6, wherein the composition is water soluble at room temperature.
  • Embodiment 8 A process for the preparation of a composition comprising
  • cationization step comprises addition of a cationization agent such as a quaternary ammonia compound.
  • Embodiment 10 The process according to any one of embodiments 8-9, wherein said quaternary ammonia compound is selected from the group consisting of 3-chloro-2- hydroxypropyltrimethylammonium chloride and the corresponding epoxy-compound, the 2,3- epoxypropyltrimethylammonium chloride.
  • Embodiment 11 The process according to any one of embodiments 8-10, wherein the semi-dry and alkaline reaction mixture is primarily non-alcoholic.
  • Embodiment 12 The process according to any one of embodiments 8-11, wherein said first polysaccharide and galactomannan is mixed before said cationization step in a weight ratio of from 15:85 to 85: 15.
  • Embodiment 13 The process according to any one of embodiments 8-12, wherein said mixed first polysaccharide and said galactomannan is moisturized by addition of an alkaline solution before said cationization step.
  • Embodiment 14 The process according to any one of embodiments 8-13, wherein said alkaline solution is provided by addition of an aqueous solution of a caustic solvent.
  • Embodiment 15 The process according to any one of embodiments 8-14, wherein the aqueous solution of caustic solvent is selected from the group consisting of sodium hydroxide, sodium carbonate or other alkaline bulk chemicals having a pH of approximately 12 to 14, such as sodium hydroxide 50% (w/w).
  • the aqueous solution of caustic solvent is selected from the group consisting of sodium hydroxide, sodium carbonate or other alkaline bulk chemicals having a pH of approximately 12 to 14, such as sodium hydroxide 50% (w/w).
  • Embodiment 16 The process according to any one of embodiments 8-15, wherein the pH of the mixed and moisturized solution of said first polysaccharide and said
  • galactomannan is between pH 8 and 14.
  • Embodiment 17 The process according to any one of embodiments 8-16, wherein the process comprises a further step of neutralization of the cationized composition.
  • Embodiment 18 The process according to embodiment 17, wherein the neutralization is achieved by addition of an acid.
  • Embodiment 19 The process according to embodiment 18, wherein the acid is acetic acid.
  • Embodiment 20 The process according to any one of embodiments 8- 19, wherein the process comprises a further step where the cationized composition is dried, optionally ground to a particulate powder with a particle size in which less than 2 % (w/w) is coarser than 300 ⁇ and more than 60 % (w/w) are finer than 75 ⁇ .
  • Embodiment 21 The process according to embodiment 8, wherein the first polysaccharide is tamarind kernel powder.
  • Embodiment 22 The process according to embodiment 8, wherein the
  • galactomannan is selected from the group consisting of cationic-modified guar gum, cationic- modified locust bean gum (LBG), cationic-modified tara gum and cationic-modified cassia gum.
  • Embodiment 23 The process according to any one of embodiments 8-22, wherein said cationization is performed at a temperature between 50°C and 95°C, such as between 70°C and 90°C, such as 80°C.
  • Embodiment 24 The process according to any one of embodiments 8-23, wherein the cationized mixture is kept between 50°C and 95°C for 30-120 minutes, such as between 70°C and 90°C for 30-105 minutes, such as at 80°C for 60 minutes.
  • Embodiment 25 A composition obtained by the process according to any one of embodiments 8-24.
  • Embodiment 26 A composition obtainable by the process according to any one of embodiments 8-24.
  • Embodiment 27 Use of the composition as described in any one of embodiments 1-
  • Embodiment 28 Use of (a) a first cationic-modified polysaccharide selected from the group consisting of polysaccharides from the genus Tamarindus, and (b) a cationic- modified galactomannan, wherein the weight ratio of the first cationic-modified
  • polysaccharide and the cationic-modified galactomannan is from 15: 85 to 85: 15 as a paper additive.
  • Embodiment 29. A paper additive comprising the composition according to any one of embodiments 1-7, or the composition according to any one of embodiments 25-26.
  • Embodiment 30. 27 A method for preparing paper by adding the composition according to any one of embodiments 1-7 or the composition according to any one of embodiments 25-26 or the paper additive according to embodiment 29.
  • EXAMPLE 1 First a blend of deoiled tamarind kernel powder (70 parts) and guar gum powder (30 parts) is prepared in a Nauta-Blender (or comparable suitable blending unit) . From this blend 400 kg are transferred to the reactor. Mixing is started and continued during the whole modification process. As the first component 52 I of Caustic (50% (w/w)) is added. After 10 min of homogenization 103 I of Reagens S (available from Sachem) is added and after 10 min of mixing 100 I water is dosed. The reaction mixture is homogenized for 10 min and then heated up to 80 °C in 20 min. The temperature level of 80 °C is kept for 60 min.
  • a Nauta-Blender or comparable suitable blending unit
  • reaction mixture is neutralized by addition of 41 I acetic acid (70% (w/w)) and homogenization is continued for at least additional 5 min. Afterwards the product is dried during grinding resulting in a fine brownish beige coloured powder. To improve the free flowing properties, about 0.1% (w/w) silica as free flowing agent is added in a fast blender.
  • the quality parameters for the product are :
  • Viscosity (Brookfield, 2% (w/w), 25°C, 60 min, spindle 1, 20 rpm) : about 150 mPa .
  • Viscosity (Brookfield, 2% (w/w), 25°C, 24 h, spindle 1, 20 rpm) : about 150 mPa.s pH (2% (w/w) solution) 6 - 7.5
  • Particle size is ⁇ 1 % (w/w) + 180 ⁇ ⁇ and > 90 % (w/w) - 75 ⁇ .
  • Fractions of powder are measured by sieving using a Retsch vibratory sieve with a timer and the fractions are weighed using a 100 mg precision balance.
  • a cationic modified guar gum additive cationic modified Guar Gum Meypro Bond 109, sold by DuPont
  • Lab sheets are prepared according to DIN 54358 part 1 on a "Frank"- lab sheet former. 0.3% (w/w) of aqueous product solution (0.1% (w/w) concentration) is added to a pulp mixture (having about 1% (w/w) consistency, i.e. a suspension of about 1 g fibres and filler in 99 g water) and after 60 sec. reaction time the paper sheet is formed in the "Frank"-lab sheet former.
  • the paper sheets are dried and afterwards conditioned to room temperature and atmospheric moisture, afterwards the breaking length and ash content are determined (if the sheet contains filler like newsprint paper and letterpress printing paper). Additionally the dewatering properties are measured from the samples. Comparing the breaking length figures of the herein disclosed cationic tamarind/guar gum based additive with the pure cationic modified guar gum (denoted Mbl09) it is seen in Fig 1 and 2 that the levels are comparable, perhaps slightly lower for the tamarind/guar gum based additive. In fig. 1 and 2 it is also seen that the ash content of the paper sheets prepared with the tamarind/guar gum based additive is remarkably high. It is significant that breaking strength values are still good. As regards the dewatering properties; these are better with the tamarind/guar gum based additive as seen in Fig. 3 than with the pure cationic guar gum additive. The dewatering of the blank sample without any cationic additive is slowest.
  • breaking length figures are determined according to DIN ISO 1924- 2: 2009-05 without full climatization but after drying the lab sheets are conditioned to room conditions for 4 hours and then measured with a Lloyd Instruments 500 tensile tester in direct comparision.
  • the above mentioned ash content of the paper sheets prepared is determined by heating the sample in a porcelain crucible at 500 °C for two hours. Amount of sample is approximately 1.5 g. The determination is performed according to DIN ISO 54370: 2007-06.
  • the above mentioned dewatering properties of the pulp suspension containing the composition is done with a Schopper-Riegler Freeness Tester according to DIN ISO 5267- 1 :2000-10. Measurement of viscosity of a given aqueous solution of a composition as disclosed herein, the result of which is shown in table 1, is performed using a Brookfield RVF viscometer at 25 °C with a rotation speed of 20 rpm after 24 hours of swelling time at room temperature. Selected control samples were subsequently examined by heating of the solution up to 95 °C and keeping it at 95 °C for 15 min and cooling to room temperature such as 25 °C afterwards for 15 min in a water bath and viscosity compared to the one which was achieved at 24 hours swelling time at 25°C.
  • Table 1 shows results with different samples prepared as described above under different reaction conditions.

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Abstract

La présente invention concerne des polysaccharides cationiques modifiés et leurs utilisations dans la fabrication du papier.
PCT/EP2014/060947 2013-05-27 2014-05-27 Polysaccharides cationiques modifiés et leurs utilisations dans la fabrication du papier WO2014191408A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITUB20150203A1 (it) * 2015-02-17 2016-08-17 Lamberti Spa Inibitori di scisti
CN105884923A (zh) * 2014-12-24 2016-08-24 江南大学 一种新型改性阳离子决明胶的制备方法
CN114315469A (zh) * 2022-01-25 2022-04-12 武汉绿农瑞益生物科技有限公司 一种微生物复合菌肥及其制备方法

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Publication number Priority date Publication date Assignee Title
EP0027316A1 (fr) * 1979-09-17 1981-04-22 Merck & Co. Inc. Mélange contenant des alginates, du TKP et de la gomme de guar et compositions pigmentées pour revêtir le papier contenant ce mélange
US5554745A (en) * 1992-05-14 1996-09-10 National Starch And Chemical Investment Holding Corporation Aldehyde cationic derivatives of galactose containing polysaccharides used as paper strength additives
WO2000031339A1 (fr) * 1998-11-23 2000-06-02 Hercules Incorporated Melanges de gomme galactomannane cationique/amidon cationique utilises comme additifs de drainage et de resistance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027316A1 (fr) * 1979-09-17 1981-04-22 Merck & Co. Inc. Mélange contenant des alginates, du TKP et de la gomme de guar et compositions pigmentées pour revêtir le papier contenant ce mélange
US5554745A (en) * 1992-05-14 1996-09-10 National Starch And Chemical Investment Holding Corporation Aldehyde cationic derivatives of galactose containing polysaccharides used as paper strength additives
WO2000031339A1 (fr) * 1998-11-23 2000-06-02 Hercules Incorporated Melanges de gomme galactomannane cationique/amidon cationique utilises comme additifs de drainage et de resistance

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105884923A (zh) * 2014-12-24 2016-08-24 江南大学 一种新型改性阳离子决明胶的制备方法
ITUB20150203A1 (it) * 2015-02-17 2016-08-17 Lamberti Spa Inibitori di scisti
WO2016131762A1 (fr) * 2015-02-17 2016-08-25 Lamberti Spa Inhibiteurs de schiste à base de gomme de tamarin cationique, et fluide de forage comprenant l'inhibiteur de schiste
RU2710575C2 (ru) * 2015-02-17 2019-12-27 Ламберти Спа Ингибиторы сланцев на основе катионной тамариндовой камеди и буровой раствор, содержащий ингибитор сланцев
US10787598B2 (en) 2015-02-17 2020-09-29 Lamberti Spa Shale inhibitors based on cationic tamarind gum, and drilling fluid comprising the shale inhibitor
CN114315469A (zh) * 2022-01-25 2022-04-12 武汉绿农瑞益生物科技有限公司 一种微生物复合菌肥及其制备方法

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