CA2406172A1 - Stock size for paper or board manufacture, method for preparation of size, use of size - Google Patents
Stock size for paper or board manufacture, method for preparation of size, use of size Download PDFInfo
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- CA2406172A1 CA2406172A1 CA002406172A CA2406172A CA2406172A1 CA 2406172 A1 CA2406172 A1 CA 2406172A1 CA 002406172 A CA002406172 A CA 002406172A CA 2406172 A CA2406172 A CA 2406172A CA 2406172 A1 CA2406172 A1 CA 2406172A1
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- Prior art keywords
- stock
- size
- maleic acid
- paper
- stock size
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic 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
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Abstract
A stock size intended to be added as a solution to the pulp stock in connection with the manufacture of paper or board in order to improve the characteristics of the paper or board, e.g. to reduce the absorption of liquids, to increase the dry strength and wet strength. The stock size contains a polymer, which is based on styrene maleic acid and stabilised with a polysaccharide, such as cationic starch. The stock size is advantageousl prepared in a steam jet cooker. The stock size is suitably used as a stock size in the manufacturing of liquid packaging board.
Description
Stock size for paper or board manufacture, method for preparation of size, use of size The present invention relates to a stock size, to a method for preparation of size, and to the use of size defined in the preambles of the independent claims presented be-low.
In the manufacture of paper and board sizing means a treatment which is mainly aimed at reducing the liquid absorption of paper or board and at increasing the strength of both dry and wet paper or board.
As cellulose fibres have a hydrophilic surface, and as the surface of the paper or board made of the fibres is porous by structure, the surface of paper and board is highly absorbent. In many paper or board products, such as liquid packaging board, fine paper, printing paper and base papers for coating, liquid absorption is a harmful property. The liquid absorption can be reduced by sizing the paper or board, either with stock size or surface size. The stock size is added to the fibre stock before the stock is supplied to the headbox of a paper machine or board machine. Surface size is used to coat the formed fibre web, for instance in the drying section at a, size press.
Paper sizing has traditionally used resin size which, is bonded to the cellulose fibres with the aid of alum. Therefore resin sizing can be used only at low pH
levels. The final sizing of the paper, i.e. the attachment of the resin to the fibres, occurs in the drying section of the paper machine, mainly at a temperature > 70 °C, and when the dry solids content has reached a level > 60 %.
Neutral or alkalic sizing uses synthetic sizes which do not necessarily require alum.
The most important synthetic sizing agents are the AKD sizing agents, i.e. the siz-ing agents based on alkyl ketene dimeter, and the ASA sizing agents, i.e. the sizing agents based on alkenyl succinic anhydride. It is assumed that esterification reac-tions occur between these sizing agents and the hydroxyl groups of the cellulose fi-bres, so that these reactions attach the sizing agent to the fibre.
The. reactions between the AKD sizing agents and the hydroxyl groups of the cel-lulose fibres take place very slowly. The final sizing of the paper is reached only after several hours after the papermaking is finished, which causes some disadvan-tages. Due to the long reaction time the paper or board sized with the ADK
sizing agent can not be directly supplied to its final use, but the paper or board must be stored on rolls, generally for at lea t one day, before the final sizing is obtained.
This requires extra storage space.
The ASA sizing agents are more reactive and they react with the cellulose more strongly and rapidly than the AKD sizing agents, i.e. generally already in the drying section of the paper machine. The reactive ASA sizing agents thereby react faster than other sizing agents also with water. The reactivity regarding water may cause sticking in the paper machine, if there is not a rapid retention of the size and a rapid reaction between the sizing agent and the fibres.
The market has seen different latex materials as the newest stock sizes, styrene acrylates being the most commonly used. The advantage of these sizing agents is that they do not form covalent bonds with the fibres, whereby the hydrophobic ef-fect can be found also during the formation of the paper web. Cationic latex materi-als are attached to the fibres due to their surface charge. However, as a result of the strong cationicity these products increase the paper's porosity by some amount.
It is known to use styrene malefic acid as such as the surface hydrophobic agent in the surface sizing agents in order to give a higher hydrophobicity to the surface of the paper or board. The salt of the styrene malefic acid is an anionic molecule, and therefore there will be no natural retention to anionic fibres and it is not suitable for the use as a stock size, The article "A new sizing agent; styrene-malefic anhydride copolymer with alum or iron mordants", T. Wang, J. Simonsen and C. Biermann, Tappi Journal Vol. 80, No.l, p. 277 - 281 proposes to use an SMA sizing agent, i.e. styrene malefic anhy-dride size, as the stock size. The arricle proposes the use of alum or iron chloride in order to provide retention of the size to the fibre. However, the article concludes that stock sizing of only unbleached paper will be successful with this sizing agent.
The object of the present invention is to provide an improved stock size and a method for preparation of size, where the above-mentioned. disadvantages are minimised.
In the manufacture of paper and board sizing means a treatment which is mainly aimed at reducing the liquid absorption of paper or board and at increasing the strength of both dry and wet paper or board.
As cellulose fibres have a hydrophilic surface, and as the surface of the paper or board made of the fibres is porous by structure, the surface of paper and board is highly absorbent. In many paper or board products, such as liquid packaging board, fine paper, printing paper and base papers for coating, liquid absorption is a harmful property. The liquid absorption can be reduced by sizing the paper or board, either with stock size or surface size. The stock size is added to the fibre stock before the stock is supplied to the headbox of a paper machine or board machine. Surface size is used to coat the formed fibre web, for instance in the drying section at a, size press.
Paper sizing has traditionally used resin size which, is bonded to the cellulose fibres with the aid of alum. Therefore resin sizing can be used only at low pH
levels. The final sizing of the paper, i.e. the attachment of the resin to the fibres, occurs in the drying section of the paper machine, mainly at a temperature > 70 °C, and when the dry solids content has reached a level > 60 %.
Neutral or alkalic sizing uses synthetic sizes which do not necessarily require alum.
The most important synthetic sizing agents are the AKD sizing agents, i.e. the siz-ing agents based on alkyl ketene dimeter, and the ASA sizing agents, i.e. the sizing agents based on alkenyl succinic anhydride. It is assumed that esterification reac-tions occur between these sizing agents and the hydroxyl groups of the cellulose fi-bres, so that these reactions attach the sizing agent to the fibre.
The. reactions between the AKD sizing agents and the hydroxyl groups of the cel-lulose fibres take place very slowly. The final sizing of the paper is reached only after several hours after the papermaking is finished, which causes some disadvan-tages. Due to the long reaction time the paper or board sized with the ADK
sizing agent can not be directly supplied to its final use, but the paper or board must be stored on rolls, generally for at lea t one day, before the final sizing is obtained.
This requires extra storage space.
The ASA sizing agents are more reactive and they react with the cellulose more strongly and rapidly than the AKD sizing agents, i.e. generally already in the drying section of the paper machine. The reactive ASA sizing agents thereby react faster than other sizing agents also with water. The reactivity regarding water may cause sticking in the paper machine, if there is not a rapid retention of the size and a rapid reaction between the sizing agent and the fibres.
The market has seen different latex materials as the newest stock sizes, styrene acrylates being the most commonly used. The advantage of these sizing agents is that they do not form covalent bonds with the fibres, whereby the hydrophobic ef-fect can be found also during the formation of the paper web. Cationic latex materi-als are attached to the fibres due to their surface charge. However, as a result of the strong cationicity these products increase the paper's porosity by some amount.
It is known to use styrene malefic acid as such as the surface hydrophobic agent in the surface sizing agents in order to give a higher hydrophobicity to the surface of the paper or board. The salt of the styrene malefic acid is an anionic molecule, and therefore there will be no natural retention to anionic fibres and it is not suitable for the use as a stock size, The article "A new sizing agent; styrene-malefic anhydride copolymer with alum or iron mordants", T. Wang, J. Simonsen and C. Biermann, Tappi Journal Vol. 80, No.l, p. 277 - 281 proposes to use an SMA sizing agent, i.e. styrene malefic anhy-dride size, as the stock size. The arricle proposes the use of alum or iron chloride in order to provide retention of the size to the fibre. However, the article concludes that stock sizing of only unbleached paper will be successful with this sizing agent.
The object of the present invention is to provide an improved stock size and a method for preparation of size, where the above-mentioned. disadvantages are minimised.
An object is then to provide a stable stock size, which is simple to prepare and ad-vantageous to use.
An object is also to provide a stock size, which can be widely used, for the sizing of both bleached and unbleached paper or board.
An object is further to provide a stock size, with which the sizing occurs already in the drying section of the paper machine.
In order to attain the above-mentioned objects the stock size, the method for prepar-ing it, and its use, are characterised in what is defined in the characterising parts of the independent claims presented below.
A typical stock size according to the invention comprises a polymer based on sty-rene malefic acid and stabilised with a polysaccharide, such as starch or mannan.
The polymer based on styrene malefic acid is a salt of styrene malefic acid, for in-stance ammonium salt of styrene malefic acid. The stock size according to the inven-tion comprises typically 1 to 99 %, advantageously 10 to 90 %, most advanta-geously 30 to 70 % of a polymer of styrene malefic acid, calculated as dry matter.
The polysaccharide used is typically oxidised and/or cationised starch, where the substitution level (DS) of the anionic and/or cationic groups is 0 to 2.
Advanta-geously the starch is cationised so, that the substitution level of the cationic groups is 0 to 1, preferably 0.01 to 0.2, most preferably 0.01 to 0.05. The stock size con-tams typically 10 to 90 % cationic starch, calculated as dry matter. The viscosity of the polysaccharide is advantageously over 5 mPas (5 %, 60 °C, Brookfield), more advantageously over 200 mPas, most advantageously over 400 mPas.
The polymer can be retained to the cellulose fibres with the aid of the polysaccha-ride part attached to the polymer. By using this polymer, which is stabilised by the polysaccharide, alum or other corresponding complex forming agent, such as polya-luminium chloride, is not required in such amounts as when using a polymer, which is not stabilised by polysaccharide. However, for instance alum, polyaluminium chloride and/or retention agent can be added to the stock in accordance with re-quirements. Alum or polyaluminium chloride can be added to the stock size in an amount of about 5 to 50 % of the stock size dry matter. A retention agent can be added in an amount of about 1 to 20 % of the stock size dry matter, when required.
An object is also to provide a stock size, which can be widely used, for the sizing of both bleached and unbleached paper or board.
An object is further to provide a stock size, with which the sizing occurs already in the drying section of the paper machine.
In order to attain the above-mentioned objects the stock size, the method for prepar-ing it, and its use, are characterised in what is defined in the characterising parts of the independent claims presented below.
A typical stock size according to the invention comprises a polymer based on sty-rene malefic acid and stabilised with a polysaccharide, such as starch or mannan.
The polymer based on styrene malefic acid is a salt of styrene malefic acid, for in-stance ammonium salt of styrene malefic acid. The stock size according to the inven-tion comprises typically 1 to 99 %, advantageously 10 to 90 %, most advanta-geously 30 to 70 % of a polymer of styrene malefic acid, calculated as dry matter.
The polysaccharide used is typically oxidised and/or cationised starch, where the substitution level (DS) of the anionic and/or cationic groups is 0 to 2.
Advanta-geously the starch is cationised so, that the substitution level of the cationic groups is 0 to 1, preferably 0.01 to 0.2, most preferably 0.01 to 0.05. The stock size con-tams typically 10 to 90 % cationic starch, calculated as dry matter. The viscosity of the polysaccharide is advantageously over 5 mPas (5 %, 60 °C, Brookfield), more advantageously over 200 mPas, most advantageously over 400 mPas.
The polymer can be retained to the cellulose fibres with the aid of the polysaccha-ride part attached to the polymer. By using this polymer, which is stabilised by the polysaccharide, alum or other corresponding complex forming agent, such as polya-luminium chloride, is not required in such amounts as when using a polymer, which is not stabilised by polysaccharide. However, for instance alum, polyaluminium chloride and/or retention agent can be added to the stock in accordance with re-quirements. Alum or polyaluminium chloride can be added to the stock size in an amount of about 5 to 50 % of the stock size dry matter. A retention agent can be added in an amount of about 1 to 20 % of the stock size dry matter, when required.
The salt of styrene malefic acid acting as the sizing agent component is advanta-geously an ammonium, sodium, potassium or calcium salt, or alternatively a combi-nation of said ion forms. A particularly advantageous salt is the ammonium salt of styrene malefic acid. The salt of styrene malefic acid may also contain other copoly-merised monomers, such as different acrylates, butadiene, acrylamides or acryloni-triles. The salt of styrene malefic acid may be partly in an amide and/or imide form.
The styrene share of the salt of styrene malefic acid according to the invention can vary between 25 and 90 %. A large amount of styrene is advantageous regarding this invention, because the hydrophobic properties of the sizing agent are particu-larly due to the styrene.
A sizing agent based on styrene malefic acid is typically stabilised so that starch flour in granule form or starch in solution is mixed into the size solution, and then the temperature of this mixture is raised, typically to 80 - 150 °C, in order to bring about the reactions between the sizing agent and the starch. In a stabilisation occur-ring at lower temperatures the sizing agent and the starch granules are mixed until the starch granules are dissolved, i.e. for about 1 hour. However, the preparation is advantageously made with the aid of pressure in a steam jet cooker, where the mix-ing temperature is rapidly raised to > 100 °C, typically to 120 - 150 °C. Then the reaction time is shortened to a few minutes. After the heating the solution is cooled to room temperature.
Another preparation manner is to add the starch already at the preparation stage of the salt of styrene malefic acid. Then starch, styrene malefic anhydride and a water solution of an alkali, such as ammonia, is mixed and heated, until a clear, brownish or yellowish olution is obtained.
One preparation manner according to the invention is to add 500 g starch flour in granule form to 5 kg of an ammonium salt solution of styrene malefic acid of 10 %
dry matter, whereby the starch flour has a nitrogen content of 0.4 % dry matter and a viscosity of 110 mPas at 60 °C as a 30 % solution. The pH of the starch should be at least 7. The starch is evenly suspended into the solution, and then the slurry is cooked at 140 °C in a high pressure steam jet cooker, which more generally is known by the name JET cooker. After the cooking the produced clear brownish so-lution is cooled to room temperature.
The size based on starch according to the invention presented above has a good re-tention to the fibre suspension, whereby it can be used as a stock size. The size is attached to the fibres already in the drying section of the paper machine, and it does not require extra storage. The solution form of the size is advantageous regarding 5 the even distribution of the size, -a.nd thus it provides an even effect in the finished paper web.
The starch-based salt of styrene malefic acid provides many advantages and new applications, in comparison to a form comprising of only salt. The size is suitably used as stock size without alum or corresponding other complex forming agent, such as polyaluminium chloride, or with only very small amounts of complex form-ing agents. The starch-based size has further an essentially lower tendency to foam than the agent comprising of only salt of styrene malefic acid, whereby it is easy to use. This lower foaming is particularly advantageous in surface sizing applications.
As a stock size the salt of styrene malefic acid based on starch is particularly suitable to be used in the manufacturing of liquid packaging board. In the liquid packaging board manufacture improvements in the resistance to different liquids can be ob-tained, which is necessary, for instance, if the actual coating is damaged. In addition the size gives a low porosity and a good stiffness to the board. Generally it can also be said that the stock size according to the invention gives a good wet strength and dry strength to paper.
The salt of styrene malefic acid stabilised by starch according to the invention is par-ticularly suitable as a stock size for base paper which is made for coating purposes.
The size increases the hydrophobicity and lowers the paper's porosity and prevents the coating from penetrating into the base paper at the coating stage.
The stock size stabilised by starch according to the invention is also very suitable as a stock size in printing paper or fine paper. This stock size will suitably reduce the penetration of ink into the paper. The stock size according to the invention is further particularly well suited for use in sizing fine paper, as an addition to another stock size, such as AKD size or ASA size. The size according to the invention can also be used as an additive to the surface size in surface sizing.
The stock size according to the invention is also suitably used as a protective col-loid for AKD, ASA and/or for a resin dispersion, which is to be added to the stock of paper or board, and also for the pre-treatment of filler; such as PCC, which is to be added to the stock. Typically the stock size according to the invention is added to the fibre stock before the fibre stock is supplied to the head box.
The feasibility of the invention is illustrated by the following examples.
Example 1 In this test the liquid absorption (Cobb60) of the salt of styrene malefic acid (SMA) and a corresponding starch-stabilised size (StSMA) at different pH values were compared. In the laboratory a 2 % mixture of fibre pulp which contained 60 %
birch pulp and 40 % pine pulp was made. Then the size was added as a IO % solution to the pulp, as an amount which was 3 % of the pulp. Alum was added as an 1 %
solu-Lion according to Table 1 below. A retention agent (BMA 590) was added as an amount of 0.02 % of the stock.
The size, the SMA or the starch stabilised SMA (St SMA) was added to the pulp, and the pulp was stirred for 30 seconds. Then in some cases alum was added.
Then the pulp was mixed another 1.5 minutes. The mixture was poured into a sheet mould, to which the retention agent was dispensed, as a 0.5 % solution. The sheets, 140 g/m2, made in this way were dried in a rapid dryer. The absorption of water was measured by a Cobb60 measurement. The test results are presented in Table 1.
Table 1 Test Alum PH SMA StSMA Cobb60 1 0.50% 7 3% - >100 2 0.50 % 7 - 3 % 20 3 1.00 % 5 3 % - > 100 4 1.00 % 5 - 3 % 23,6 In the table it can be seen that the liquid absorption Cobb60 is 20 and 23.6 for the sheet which is sized with the starch-stabilised salt of styrene malefic acid, and this is substantially lower than the liquid absorption for sheets which were sized with con-ventional salt of styrene malefic acid, the later being > 100. Thus the sheet sized with the starch-based salt of styrene malefic acid stabilised by starch according to the invention has a better sizing level and water resistance.
The styrene share of the salt of styrene malefic acid according to the invention can vary between 25 and 90 %. A large amount of styrene is advantageous regarding this invention, because the hydrophobic properties of the sizing agent are particu-larly due to the styrene.
A sizing agent based on styrene malefic acid is typically stabilised so that starch flour in granule form or starch in solution is mixed into the size solution, and then the temperature of this mixture is raised, typically to 80 - 150 °C, in order to bring about the reactions between the sizing agent and the starch. In a stabilisation occur-ring at lower temperatures the sizing agent and the starch granules are mixed until the starch granules are dissolved, i.e. for about 1 hour. However, the preparation is advantageously made with the aid of pressure in a steam jet cooker, where the mix-ing temperature is rapidly raised to > 100 °C, typically to 120 - 150 °C. Then the reaction time is shortened to a few minutes. After the heating the solution is cooled to room temperature.
Another preparation manner is to add the starch already at the preparation stage of the salt of styrene malefic acid. Then starch, styrene malefic anhydride and a water solution of an alkali, such as ammonia, is mixed and heated, until a clear, brownish or yellowish olution is obtained.
One preparation manner according to the invention is to add 500 g starch flour in granule form to 5 kg of an ammonium salt solution of styrene malefic acid of 10 %
dry matter, whereby the starch flour has a nitrogen content of 0.4 % dry matter and a viscosity of 110 mPas at 60 °C as a 30 % solution. The pH of the starch should be at least 7. The starch is evenly suspended into the solution, and then the slurry is cooked at 140 °C in a high pressure steam jet cooker, which more generally is known by the name JET cooker. After the cooking the produced clear brownish so-lution is cooled to room temperature.
The size based on starch according to the invention presented above has a good re-tention to the fibre suspension, whereby it can be used as a stock size. The size is attached to the fibres already in the drying section of the paper machine, and it does not require extra storage. The solution form of the size is advantageous regarding 5 the even distribution of the size, -a.nd thus it provides an even effect in the finished paper web.
The starch-based salt of styrene malefic acid provides many advantages and new applications, in comparison to a form comprising of only salt. The size is suitably used as stock size without alum or corresponding other complex forming agent, such as polyaluminium chloride, or with only very small amounts of complex form-ing agents. The starch-based size has further an essentially lower tendency to foam than the agent comprising of only salt of styrene malefic acid, whereby it is easy to use. This lower foaming is particularly advantageous in surface sizing applications.
As a stock size the salt of styrene malefic acid based on starch is particularly suitable to be used in the manufacturing of liquid packaging board. In the liquid packaging board manufacture improvements in the resistance to different liquids can be ob-tained, which is necessary, for instance, if the actual coating is damaged. In addition the size gives a low porosity and a good stiffness to the board. Generally it can also be said that the stock size according to the invention gives a good wet strength and dry strength to paper.
The salt of styrene malefic acid stabilised by starch according to the invention is par-ticularly suitable as a stock size for base paper which is made for coating purposes.
The size increases the hydrophobicity and lowers the paper's porosity and prevents the coating from penetrating into the base paper at the coating stage.
The stock size stabilised by starch according to the invention is also very suitable as a stock size in printing paper or fine paper. This stock size will suitably reduce the penetration of ink into the paper. The stock size according to the invention is further particularly well suited for use in sizing fine paper, as an addition to another stock size, such as AKD size or ASA size. The size according to the invention can also be used as an additive to the surface size in surface sizing.
The stock size according to the invention is also suitably used as a protective col-loid for AKD, ASA and/or for a resin dispersion, which is to be added to the stock of paper or board, and also for the pre-treatment of filler; such as PCC, which is to be added to the stock. Typically the stock size according to the invention is added to the fibre stock before the fibre stock is supplied to the head box.
The feasibility of the invention is illustrated by the following examples.
Example 1 In this test the liquid absorption (Cobb60) of the salt of styrene malefic acid (SMA) and a corresponding starch-stabilised size (StSMA) at different pH values were compared. In the laboratory a 2 % mixture of fibre pulp which contained 60 %
birch pulp and 40 % pine pulp was made. Then the size was added as a IO % solution to the pulp, as an amount which was 3 % of the pulp. Alum was added as an 1 %
solu-Lion according to Table 1 below. A retention agent (BMA 590) was added as an amount of 0.02 % of the stock.
The size, the SMA or the starch stabilised SMA (St SMA) was added to the pulp, and the pulp was stirred for 30 seconds. Then in some cases alum was added.
Then the pulp was mixed another 1.5 minutes. The mixture was poured into a sheet mould, to which the retention agent was dispensed, as a 0.5 % solution. The sheets, 140 g/m2, made in this way were dried in a rapid dryer. The absorption of water was measured by a Cobb60 measurement. The test results are presented in Table 1.
Table 1 Test Alum PH SMA StSMA Cobb60 1 0.50% 7 3% - >100 2 0.50 % 7 - 3 % 20 3 1.00 % 5 3 % - > 100 4 1.00 % 5 - 3 % 23,6 In the table it can be seen that the liquid absorption Cobb60 is 20 and 23.6 for the sheet which is sized with the starch-stabilised salt of styrene malefic acid, and this is substantially lower than the liquid absorption for sheets which were sized with con-ventional salt of styrene malefic acid, the later being > 100. Thus the sheet sized with the starch-based salt of styrene malefic acid stabilised by starch according to the invention has a better sizing level and water resistance.
7.
Example 2 In this test the characteristics obtained with a cationic styrene acrylate sizing agent were compared with the starch-stabilised salt of styrene malefic acid according to the invention.
In a test paper machine paper from a pulp of birch/pine (70/30) was manufactured, to which per produced paper ton was added Starch Raisamyl 135 sp . 7 kg/t Retention agent Percol 162 100 g/t Retention agent Hydrocol O 1.5 kg/t Filler material GCC 100 kg/t Grammage of paper 49.2 to 52.8 g/m2 Thickness of paper 62 to 65 ~.m As the sizing agent cationic styrene acrylate (acryl.) and the starch-based salt of sty-rene malefic acid (StSMA) according to the invention was used. In the tables 2 and 3 it is presented how these sizing agents affect the paper's porosity (Bendtsen;
ml/min), the strength in the z direction (Bonding; J/m2), tensile index (machine di rection and cross direction; Nm/g), tensile_ stiffness (machine direction and cross direction; MNmlkg), burst index (kPam2lkg), picking resistance (Dennison, surface and base), friction (static and kinetic), drop test (surface and base; s), and the absor bency (Cobb30, surface and base; glm3).
Example 2 In this test the characteristics obtained with a cationic styrene acrylate sizing agent were compared with the starch-stabilised salt of styrene malefic acid according to the invention.
In a test paper machine paper from a pulp of birch/pine (70/30) was manufactured, to which per produced paper ton was added Starch Raisamyl 135 sp . 7 kg/t Retention agent Percol 162 100 g/t Retention agent Hydrocol O 1.5 kg/t Filler material GCC 100 kg/t Grammage of paper 49.2 to 52.8 g/m2 Thickness of paper 62 to 65 ~.m As the sizing agent cationic styrene acrylate (acryl.) and the starch-based salt of sty-rene malefic acid (StSMA) according to the invention was used. In the tables 2 and 3 it is presented how these sizing agents affect the paper's porosity (Bendtsen;
ml/min), the strength in the z direction (Bonding; J/m2), tensile index (machine di rection and cross direction; Nm/g), tensile_ stiffness (machine direction and cross direction; MNmlkg), burst index (kPam2lkg), picking resistance (Dennison, surface and base), friction (static and kinetic), drop test (surface and base; s), and the absor bency (Cobb30, surface and base; glm3).
Table 2 Size Acryl. Acryl. Acryl. Acryl.
0.15% 0.3% 0.6% 1.0%
Bendtsen ml/min 1170 1460 1370 1295 Bonding 344 374 357 355 Tensile index, 57.49 58.53 60.11 59.94 and Tensile index, 32.5 32.97 33.45 33.71 cd Tensile stiffness,8.636 8.729 8.685 8.748 and Tensile stiffness,3.648 3.892 3.823 3.713 cd Burst index 2.55 2.63 2.66 2.52 Dennison, surf 10 9 11 11 Dennison, base 12 10 12 12 Friction, static 0.631 0.589 0.551 0.621 Friction, kinetic0.498 0.488 0.427 0.546 Dro test, surf 54.3 75.7 I I I.7 > I80 Dro test, base 65.3 68.7 111.7 > I80 Cobb30, surf 56.0 56.1 52.4 48.4 Cobb30, base 57.2 53.9 54.3 49.6 In addition Table 3 presents test results fxom a run where the stock size was not used.
0.15% 0.3% 0.6% 1.0%
Bendtsen ml/min 1170 1460 1370 1295 Bonding 344 374 357 355 Tensile index, 57.49 58.53 60.11 59.94 and Tensile index, 32.5 32.97 33.45 33.71 cd Tensile stiffness,8.636 8.729 8.685 8.748 and Tensile stiffness,3.648 3.892 3.823 3.713 cd Burst index 2.55 2.63 2.66 2.52 Dennison, surf 10 9 11 11 Dennison, base 12 10 12 12 Friction, static 0.631 0.589 0.551 0.621 Friction, kinetic0.498 0.488 0.427 0.546 Dro test, surf 54.3 75.7 I I I.7 > I80 Dro test, base 65.3 68.7 111.7 > I80 Cobb30, surf 56.0 56.1 52.4 48.4 Cobb30, base 57.2 53.9 54.3 49.6 In addition Table 3 presents test results fxom a run where the stock size was not used.
Table 3 Size - StSMA StSMA
0.15 % 0.3 alo Bendtsen (ml/min)1300 1095 765 Bonding 141 451 524 Tensile index, 55.5 67.42 70.51 and Tensile index, 27.77 36.18 38.56 cd Tensile stiffness,8.457 9.228 9.717 and Tensile stiffness,4.196 4.260 4.261 cd Burst index 2.47 2.99 2.98 Dennison, surf 6 11 12 Dennison, base 7 11 13 Friction, static 0.627 0.657 0.675 Friction, kinetic0.527 0.570 0.583 Dro test, surf 42.0 87.6 124.6 Dro test, base 47.6 80.0 136.0 Cobb30, surf 58.1 53.2 53.2 Cobb30, base 59.4 52.5 54.0 From the tests, it can be concluded that the size according to the invention provides a lower porosity (Bendtsen), the same hydrophobicity (drop test, Cobb), an im-proved stiffness (tensile stiffness) and strength than the cationic styrene acrylate.
0.15 % 0.3 alo Bendtsen (ml/min)1300 1095 765 Bonding 141 451 524 Tensile index, 55.5 67.42 70.51 and Tensile index, 27.77 36.18 38.56 cd Tensile stiffness,8.457 9.228 9.717 and Tensile stiffness,4.196 4.260 4.261 cd Burst index 2.47 2.99 2.98 Dennison, surf 6 11 12 Dennison, base 7 11 13 Friction, static 0.627 0.657 0.675 Friction, kinetic0.527 0.570 0.583 Dro test, surf 42.0 87.6 124.6 Dro test, base 47.6 80.0 136.0 Cobb30, surf 58.1 53.2 53.2 Cobb30, base 59.4 52.5 54.0 From the tests, it can be concluded that the size according to the invention provides a lower porosity (Bendtsen), the same hydrophobicity (drop test, Cobb), an im-proved stiffness (tensile stiffness) and strength than the cationic styrene acrylate.
Claims (21)
2. A stock size according to claim 1, characterised in that the polymer based on styrene maleic said is a salt of styrene maleic acid.
3. A stock size according to claim 1, characterised in that the polymer based on styrene maleic acid is ammonium salt of styrene maleic acid.
4. A stock size according to claim 1, characterised in that also other monomers are copolymerised in the polymer based on styrene maleic acid.
3. A stock size according to claim 1, characterised in that the stock size contains 1 to 99%, advantageously 10 to 90 %, most advantageously 30 to 70 % of a poly-mer of styrene maleic acid, calculated as dry matter.
6. A stock size according to claim 1, characterised in that the stock size contains to 90 % cationic starch, calculated as dry matter.
7. A stock size according to claim 1, characterised in that the stock size com-prises a polymer based on styrene maleic acid and stabilised with cationic starch, in a heat process, such as is a steam jet cooker or the like.
8. A stock size according to claim 1, characterised in that the stock size further contains a complex forming agent, such as alum or polyaluminium chloride, typi-cally 5 to 50 % of the stock size, calculated as dry matter.
9. A stock size according to claim 1, characterised in that the stock size further contains a retention agent, typically 1 to 20 % of the stock size, calculated as dry matter.
10. A method for preparing the size used in the making of paper or board, the size containing a polymer formed from a derivative of styrene maleic acid, character-ised in that - polysaccharide, such as cationic starch, is mixed to a polymer solution formed from a derivative of styrene maleic acid, and the polymer solution thus obtained is supplied to a heating device, such as a steam jet cooker, where the temperature of the polymer solution is raised to a temperature of> 100 °C and the mixture is allowed to react in order to form a stable cationic siz-ing product.
11. A method according to claim 10, characterised in that the derivative of sty-rene maleic acid is a salt of styrene maleic acid.
12. A method according to claim 10, characterised in that a cationic natural.
polymer, typically cationic starch, is supplied as a dispersion into the polymer solu-tion formed from the derivative of styrene maleic acid.
13. A method according to claim 10, characterised in that further alum, polyam-monium chloride and/or a retention agent is added to the sizing product.
14. The use of a sizing product prepared by a method according to claim 10 as stock size in the manufacturing of liquid packaging board.
15. The use of a sizing product prepared by a method according to claim 10 as stock size in the manufacturing of base paper intended for coating.
16. The use of a sizing product prepared by a method according to claim 10 as a protective colloid for an AKD, ASA and/or resin dispersion, which is to be added to paper or board stock.
17. The use of a sizing product prepared by a method according to claim 10 as a pre-treatment agent for a filler, such as PCC, which is to be added to paper or board stock.
18. A method for stock sizing of the fibre stock used in the manufacture of paper or board,characterised in that before the fibre stock is supplied to the headbox a size prepared according to claim 10 is added to the fibre stock.
19. A method for stock sizing of the fibre stock used in the manufacture of paper or board, characterised in that an AKD, ASA and/or resin dispersing treated with a size prepared according to claim 10 is added to the fibre stock.
20. The use of a sizing product prepared by a method according to claim 10 as an additive of the surface size is surface sizing.
21. A method according to claim 10, characterised in that the temperature of the polymer mixture is raised to a temperature of > 100°C in a steam jet cooker.
Claims
1. A stock size intended to be added as a solution to the pulp stock in connection with the manufacture of paper or board in order to improve the characteristics of the paper or board, e.g. to reduce the absorption of liquids, to increase the dry strength and wet strength, characterised in that the stock size contains a polymer, which is based on styrene maleic acid and stabi-lised with a polysaccharide, such as cationic starch.
2. A stock size according to claim 1, characterised in that the polymer based on styrene maleic acid is a salt of styrene maleic acid.
3. A stock size according to claim 1, characterised in that the polymer based on styrene maleic acid is ammonium salt of styrene maleic acid.
4. A stock size according to claim 1, characterised in that also other monomers are copolymerised in the polymer based on styrene maleic acid.
5. A stock size according to claim 1, characterised in that the stock size contains 1 to 99%, advantageously 10 to 90%, most advantageously 30 to 70% of a poly-mer of styrene maleic acid, calculated as dry matter.
6. A stock size according to claim 1, characterised in that the stock size contains to 90% cationic starch, calculated as dry matter.
7. A stock size according to claim 1, characterised in that the stock size com-prises a polymer based on styrene maleic acid and stabilised with cationic starch, is a heat process, such as in a steam jet cooker or the like.
8. A stock size according to claim 1, characterised in that the stock size further contains a complex forming agent, such as alum or polyaluminium chloride, typi-cally 5 to 50% of the stock size, calculated as dry matter.
9. A stock size according to claims 1, characterised in that the stock size further contains a retention agent, typically 1 to 20% of the stock size, calculated as dry matter.
10. A method for preparing the size used in the making of paper or board, the size containing a polymer formed from a derivative of styrene maleic acid, character-ised in that - polysaccharide, such as cationic starch, is mixed to a polymer solution formed from a derivative of styrene maleic acid, and - the polymer solution thus obtained is supplied to a heating device, such as a steam jet cooker, where the temperature of the polymer solution is raised to a temperature of > 100°C and the mixture is allowed to react in order to form a stable cationic siz-ing product.
11. A method according to claim 10, characterised in that the derivatives of sty-rene maleic acid is a salt of styrene maleic acid.
12. A method according to claim 10, characterised in that a cationic natural polymer, typically cationic starch, is supplied as a dispersion into the polymer solu-tion formed from the derivative of styrene maleic acid.
13. A method according to claim 10, characterised is that further alum, polyami monium chloride and/or a retention agent is added to the sizing product.
14. The use of a sizing product prepared by a method according to claim 10 as stock size is the manufacturing of liquid packaging board.
15. The use of a sizing product prepared by a method according to claim 10 as stock size in the manufacturing of base paper intended for coating.
16. The use of a sizing product prepared by a method accordions to claim 10 as a protective colloid for as AKD, ASA and/or resin dispersion, which is to be added to paper or board stock.
17. The use of a sizing product prepared by a method according to claim 10 as a pre-treatment agent for a filler, such as PCC, which is to be added to paper or board stock.
18. A method for stock sizing of the fibre stock used in the manufacture of paper or board, characterized in that before the fibre stock is supplied to the headbox a size prepared according to claim 10 is added to the fibre stock.
19. A method for stock sizing of the fibre stock used in the manufacture of paper or board, characterised in that an AKD, ASA and/or resin dispersion treated with a size prepared according to claim 10 is added to the fibre stock.
20. The use of a sizing product prepared by a method according to claim 10 as an additive of the surface size in surface sizing.
21. A method according to claim 10, characterised in that the temperature of the polymer mixture is raised to a temperature of > 100°C in a steam jet cooker.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20000928A FI117716B (en) | 2000-04-18 | 2000-04-18 | Method for pretreatment of filler, modified filler and its use |
| FI20000928 | 2000-04-18 | ||
| PCT/FI2001/000375 WO2001079607A1 (en) | 2000-04-18 | 2001-04-17 | Stock size for paper or board manufacture, method for preparation of size, use of size |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2406172A1 true CA2406172A1 (en) | 2001-10-25 |
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ID=8558240
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002405999A Expired - Fee Related CA2405999C (en) | 2000-04-18 | 2001-04-17 | Method for pretreatment of filler, modified filler with a hydrophobic polymer and use of the hydrophobic polymer |
| CA002406172A Abandoned CA2406172A1 (en) | 2000-04-18 | 2001-04-17 | Stock size for paper or board manufacture, method for preparation of size, use of size |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002405999A Expired - Fee Related CA2405999C (en) | 2000-04-18 | 2001-04-17 | Method for pretreatment of filler, modified filler with a hydrophobic polymer and use of the hydrophobic polymer |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US6939441B2 (en) |
| EP (2) | EP1276931B1 (en) |
| AT (1) | ATE450651T1 (en) |
| AU (2) | AU2001256379A1 (en) |
| CA (2) | CA2405999C (en) |
| DE (1) | DE60140665D1 (en) |
| ES (1) | ES2336424T3 (en) |
| FI (1) | FI117716B (en) |
| PT (1) | PT1276931E (en) |
| WO (2) | WO2001086067A1 (en) |
Families Citing this family (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6565646B1 (en) | 2001-11-02 | 2003-05-20 | Luzenac America, Inc. | Talc composition and use in paper products |
| DE10209448A1 (en) * | 2002-03-05 | 2003-09-18 | Basf Ag | Aqueous slurries of finely divided fillers, processes for their production and their use for the production of filler-containing papers |
| CA2671973C (en) * | 2002-04-09 | 2013-02-26 | Fpinnovations | Swollen starch compositions for use in papermaking |
| FI114231B (en) * | 2002-05-03 | 2004-09-15 | Raisio Chem Oy | Procedure for coating paper or cardboard |
| FI20022046A0 (en) * | 2002-11-18 | 2002-11-18 | Raisio Chem Oy | Improvement of paper or cardboard |
| NZ546773A (en) | 2003-10-08 | 2008-05-30 | Ciba Sc Holding Ag | Additive for reducing paper linting and dusting |
| US9156990B2 (en) * | 2003-12-22 | 2015-10-13 | Eka Chemicals Ab | Filler for papermaking process |
| US8252143B2 (en) * | 2004-06-22 | 2012-08-28 | Akzo Nobel N.V. | Filler for paper making process |
| CN1965128A (en) | 2004-06-22 | 2007-05-16 | 阿克佐诺贝尔公司 | Filler for paper making process |
| US7799169B2 (en) | 2004-09-01 | 2010-09-21 | Georgia-Pacific Consumer Products Lp | Multi-ply paper product with moisture strike through resistance and method of making the same |
| ES2554691T3 (en) | 2004-12-17 | 2015-12-22 | Basf Se | Papers with a high load content and high dry tensile strength |
| FR2881064A1 (en) * | 2005-01-26 | 2006-07-28 | Omya Development Ag | Disinfecting, conserving, reducing and/or controlling microbial contamination of aqueous dispersions and/or suspensions of mineral materials comprises increasing the concentration of hydroxyl ions and dispersing/crushing the suspensions |
| CN100336974C (en) * | 2005-06-16 | 2007-09-12 | 陕西科技大学 | Modifying method using talcum powder as paper filler and adhesive-applying agent |
| US7682438B2 (en) | 2005-11-01 | 2010-03-23 | International Paper Company | Paper substrate having enhanced print density |
| FI123223B (en) * | 2006-02-09 | 2012-12-31 | Upm Kymmene Corp | A method for treating a filler |
| GB0608126D0 (en) * | 2006-04-24 | 2006-06-07 | Imerys Minerals Ltd | Barrier compositions |
| US7964063B2 (en) | 2006-08-11 | 2011-06-21 | Georgia Tech Research Corporation | Methods and compositions for papermaking |
| US8557925B2 (en) * | 2007-03-01 | 2013-10-15 | Georgia-Pacific Chemicals Llc | Blends of anionic copolymers suitable for surface size and methods of making the same |
| FI123482B (en) * | 2007-06-01 | 2013-05-31 | Teknologian Tutkimuskeskus Vtt | Fiber Product and Method for Modifying the Printability Properties of a Fiber Product of Paper or Cardboard |
| ES2378425T5 (en) | 2007-07-05 | 2017-05-16 | Omya International Ag. | Aqueous suspensions of finely divided fillers, process for their preparation and use for the manufacture of papers with high content in fillers and high dry strength |
| CN103422395B (en) | 2012-05-15 | 2016-03-02 | 纳尔科公司 | The method of dehydration, scraps of paper wet web strength and wet strength is strengthened in papermaking |
| US9181657B2 (en) | 2007-09-12 | 2015-11-10 | Nalco Company | Method of increasing paper strength by using natural gums and dry strength agent in the wet end |
| US8088250B2 (en) | 2008-11-26 | 2012-01-03 | Nalco Company | Method of increasing filler content in papermaking |
| US9752283B2 (en) | 2007-09-12 | 2017-09-05 | Ecolab Usa Inc. | Anionic preflocculation of fillers used in papermaking |
| US8647472B2 (en) * | 2007-09-12 | 2014-02-11 | Nalco Company | Method of increasing filler content in papermaking |
| EP2075374A1 (en) | 2007-12-17 | 2009-07-01 | Omya Development AG | Method for manufacturing a coating slip including the use of an acrylic thickener with a water resistant chain and slip obtained |
| CA2710804C (en) | 2007-12-26 | 2013-07-02 | International Paper Company | A paper substrate containing a wetting agent and having improved print mottle |
| FR2928383B1 (en) | 2008-03-06 | 2010-12-31 | Georgia Pacific France | WAFER SHEET COMPRISING A PLY IN WATER SOLUBLE MATERIAL AND METHOD FOR PRODUCING SUCH SHEET |
| US8460511B2 (en) | 2008-10-01 | 2013-06-11 | International Paper Company | Paper substrate containing a wetting agent and having improved printability |
| CN102677535B (en) * | 2011-03-11 | 2015-12-16 | 纳尔科公司 | The method of dewatering efficiency, increase plate wet web strength, increase plate wet strength and raising filler confining force is improved in papermaking |
| TR201908012T4 (en) * | 2008-12-03 | 2019-06-21 | Omya Int Ag | Aqueous slurries of fine-grained fillers, method for its production and use for producing papers containing fillers. |
| EP2199462A1 (en) * | 2008-12-18 | 2010-06-23 | Coöperatie Avebe U.A. | A process for making paper |
| EP2357277A1 (en) | 2010-02-12 | 2011-08-17 | Rhodia Acetow GmbH | Photodegradable paper and its use |
| US9133583B2 (en) | 2011-04-05 | 2015-09-15 | P.H. Glatfelter Company | Process for making a stiffened paper |
| US8496784B2 (en) * | 2011-04-05 | 2013-07-30 | P.H. Glatfelter Company | Process for making a stiffened paper |
| CN110344282A (en) | 2011-09-15 | 2019-10-18 | 英默里斯颜料公司 | Kaolinic composition and correlation technique comprising the polymer treatment with styrene-based |
| MX366743B (en) * | 2012-04-13 | 2019-07-04 | Sigma Alimentos Sa De Cv | Hydrophobic paper or cardboard with self-assembled nanoparticles and method for the production thereof. |
| KR101289376B1 (en) * | 2012-04-23 | 2013-07-29 | 주식회사 삼양제넥스 | Starch-based liquid composition for pretreating filler, filler pretreated with the composition for making paper, and paper comprising the filler |
| CN102675918B (en) * | 2012-05-04 | 2014-06-18 | 安徽江东科技粉业有限公司 | Preparation method of low-yellowness antibacterial calcium carbonate functional composite powder for ventilated membrane |
| FR2992967B1 (en) | 2012-07-06 | 2016-01-22 | Roquette Freres | MIXTURES OF POLYVINYLAMINES AND COMPOSITIONS OF CATIONIC LIQUID AMYLACEOUS MATERIALS AS AGENTS FOR IMPROVING THE DRY RESISTANCE OF PAPERS AND CARTONS |
| CN105378179B (en) | 2013-06-17 | 2018-05-25 | 纳尔科公司 | Dehydration efficiency is improved in papermaking, scraps of paper wet web strength is improved, improves scraps of paper wet strength and the method for reinforcing filler retentivity |
| CN104746388B (en) * | 2013-12-25 | 2018-05-08 | 艺康美国股份有限公司 | A kind of method of the sizing efficiency for the ASA lotions for improving macromolecule emulsifier emulsification |
| WO2015116095A1 (en) | 2014-01-30 | 2015-08-06 | Hewlett-Packard Development Company, L.P. | Print media for inkjet printing |
| CN104031416B (en) * | 2014-05-20 | 2016-01-06 | 凤台精兴生物科技有限公司 | A kind of modified calcium carbonate and preparation method thereof that can be used as sound-absorbing filler |
| CN104059392B (en) * | 2014-05-27 | 2015-07-01 | 池州凯尔特纳米科技有限公司 | Porous material modified calcium carbonate and preparation method thereof |
| US9365979B2 (en) | 2014-08-27 | 2016-06-14 | Ecolab Usa Inc. | Method of increasing paper surface strength by using polyaluminum chloride in a size press formulation containing starch |
| CN104790263A (en) * | 2015-03-28 | 2015-07-22 | 桐城市福润包装材料有限公司 | Packaging paper production process |
| US11035076B2 (en) * | 2016-06-22 | 2021-06-15 | Performance Biofilaments Inc. | Surface-modified cellulosic materials and methods of producing the same |
| US10072381B2 (en) * | 2016-07-19 | 2018-09-11 | The United States Of America, As Represented By The Secretary Of Agriculture | Starch amine complexes for increased water resistance of paper |
| CN106433220A (en) * | 2016-08-22 | 2017-02-22 | 江西广源化工有限责任公司 | Preparation method of modified superfine calcium carbonate powder and product of preparation method |
| CN106366705A (en) * | 2016-08-22 | 2017-02-01 | 江西广源化工有限责任公司 | Preparation method of talcum powder used for ship anticorrosion coatings |
| CN106433224A (en) * | 2016-08-22 | 2017-02-22 | 江西广源化工有限责任公司 | Method for preparing black talc powder for wood-plastic composite material |
| CN110114400A (en) * | 2016-12-28 | 2019-08-09 | 日本瑞翁株式会社 | Bridging property rubber composition and rubber cross object |
| CN110180340A (en) * | 2019-06-19 | 2019-08-30 | 齐齐哈尔龙江阜丰生物科技有限公司 | A kind of low-temperature plasma emission-control equipment |
| CN111808443B (en) * | 2020-07-16 | 2021-11-30 | 江苏华力索菲新材料有限公司 | Preparation method of delustering agent for chemical fibers |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6500791A (en) * | 1964-02-17 | 1965-08-18 | ||
| US3404112A (en) * | 1965-03-31 | 1968-10-01 | Air Reduction | Paper coating composition containing vinyl acetate-ethylene-triallyl cyanurate terpolymers and coated product formed therefrom |
| US3632535A (en) * | 1967-09-20 | 1972-01-04 | Cpc International Inc | Emulsion polymerization method and resultant aqueous latex |
| US4115187A (en) * | 1970-03-31 | 1978-09-19 | Welwyn Hall Research Association | Agglomerated fillers used in paper |
| JPS49118915A (en) * | 1973-03-26 | 1974-11-13 | ||
| FR2264129B1 (en) * | 1974-03-14 | 1978-07-28 | Rhone Poulenc Ind | |
| GB1505641A (en) | 1974-04-19 | 1978-03-30 | Grace W R & Co | Process of preparing a filler composition for paper |
| US4436857A (en) * | 1978-08-07 | 1984-03-13 | The General Tire & Rubber Company | Coating rubber with a composition which resists removal by water |
| US4301107A (en) * | 1978-08-30 | 1981-11-17 | American Cyanamid Company | Melt-spinning a plurality of acrylonitrile polymer fibers |
| JPS5556178A (en) * | 1978-10-23 | 1980-04-24 | Kindai Kagaku Kogyo Kk | Preparation of aqueous emulsion for waterproof agent |
| SU779473A1 (en) | 1978-12-21 | 1980-11-15 | Центральный научно-исследовательский институт бумаги | Paper pulp production method |
| US4243564A (en) * | 1979-05-18 | 1981-01-06 | Moses Konigsberg | Reaction products of a hydrolyzed styrene-maleic anhydride copolymer and a dispersed high amylopectin starch product neutralized with a volatile alkali, method of making same, and coating compositions comprising same |
| AT365680B (en) * | 1979-09-25 | 1982-02-10 | Mobil Oil Austria | METHOD FOR PRODUCING LOW TO STRONG-SIZED PAPER OR CARDBOARD |
| US4301017A (en) * | 1980-04-28 | 1981-11-17 | Standard Brands Incorporated | Stable, liquid starch graft copolymer composition |
| SU962400A1 (en) | 1981-03-24 | 1982-09-30 | Центральный научно-исследовательский институт бумаги | Pulp composition |
| SU1263739A1 (en) | 1985-06-14 | 1986-10-15 | Центральный научно-исследовательский институт бумаги | Method of producing paper pulp |
| GB8531558D0 (en) * | 1985-12-21 | 1986-02-05 | Wiggins Teape Group Ltd | Loaded paper |
| DE3702712A1 (en) * | 1987-01-30 | 1988-08-11 | Basf Ag | SIZING AGENT FOR PAPER BASED ON FINE-PARTED AQUEOUS DISPERSIONS |
| US4892590A (en) * | 1988-06-03 | 1990-01-09 | Pfizer Inc. | Precipitated calcium carbonate-cationic starch binder as retention aid system for papermaking |
| CH678636A5 (en) * | 1989-01-11 | 1991-10-15 | Baerle & Cie Ag | Sizing of paper and board - by adding sizing agent comprising natural or synthetic resin contg. anionic or acid gps. and zeolite to fibre suspension |
| FR2678961B1 (en) * | 1991-07-12 | 1993-10-15 | Atochem | NEW PROCESS FOR THE MANUFACTURE OF PAPER AND THE PAPER THUS OBTAINED. |
| US5380361A (en) * | 1993-03-12 | 1995-01-10 | Minerals Technologies, Inc. | Modified filler material for alkaline paper and method of use thereof in alkaline paper making |
| US5824190A (en) * | 1995-08-25 | 1998-10-20 | Cytec Technology Corp. | Methods and agents for improving paper printability and strength |
| US5993604A (en) * | 1995-12-05 | 1999-11-30 | The Dow Chemical Company | Internally sized articles and method for making same |
| JP3767058B2 (en) | 1996-12-24 | 2006-04-19 | 星光Ｐｍｃ株式会社 | Paper surface treatment agent |
| US6162328A (en) * | 1997-09-30 | 2000-12-19 | Hercules Incorporated | Method for surface sizing paper with cellulose reactive and cellulose non-reactive sizes, and paper prepared thereby |
| US6156112A (en) * | 1998-02-12 | 2000-12-05 | Craig; Daniel H. | High solids aqueous dispersions of reactive hydrophobizing agents |
| DE19806745A1 (en) | 1998-02-18 | 1999-08-19 | Bayer Ag | Aqueous polymer dispersion useful as surface sizing agent for paper, cardboard etc. |
| US6126783A (en) | 1998-07-09 | 2000-10-03 | Minerals Technologies Inc. | Surface modified fillers for sizing paper |
| FI105565B (en) | 1999-02-05 | 2000-09-15 | Raisio Chem Oy | Polymer dispersion and process for its preparation |
| FI117717B (en) | 1999-07-09 | 2007-01-31 | Ciba Sc Holding Ag | Surface Adhesive Composition |
| US6210475B1 (en) * | 1999-09-03 | 2001-04-03 | Bayer Corporation | Use of hydroxyalkylated starches for improved emulsification of sizing agents |
-
2000
- 2000-04-18 FI FI20000928A patent/FI117716B/en not_active IP Right Cessation
-
2001
- 2001-04-17 EP EP01929673A patent/EP1276931B1/en not_active Expired - Lifetime
- 2001-04-17 AT AT01929673T patent/ATE450651T1/en active
- 2001-04-17 CA CA002405999A patent/CA2405999C/en not_active Expired - Fee Related
- 2001-04-17 PT PT01929673T patent/PT1276931E/en unknown
- 2001-04-17 WO PCT/FI2001/000376 patent/WO2001086067A1/en active Application Filing
- 2001-04-17 US US10/257,634 patent/US6939441B2/en not_active Expired - Fee Related
- 2001-04-17 WO PCT/FI2001/000375 patent/WO2001079607A1/en not_active Application Discontinuation
- 2001-04-17 AU AU2001256379A patent/AU2001256379A1/en not_active Abandoned
- 2001-04-17 ES ES01929673T patent/ES2336424T3/en not_active Expired - Lifetime
- 2001-04-17 AU AU56378/01A patent/AU5637801A/en not_active Abandoned
- 2001-04-17 EP EP01929672A patent/EP1276933A1/en not_active Withdrawn
- 2001-04-17 US US10/257,862 patent/US7211608B2/en not_active Expired - Fee Related
- 2001-04-17 DE DE60140665T patent/DE60140665D1/en not_active Expired - Lifetime
- 2001-04-17 CA CA002406172A patent/CA2406172A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001086067A1 (en) | 2001-11-15 |
| US6939441B2 (en) | 2005-09-06 |
| ES2336424T3 (en) | 2010-04-13 |
| FI20000928A (en) | 2001-10-19 |
| ATE450651T1 (en) | 2009-12-15 |
| CA2405999A1 (en) | 2001-11-15 |
| US20030121632A1 (en) | 2003-07-03 |
| US20030109617A1 (en) | 2003-06-12 |
| AU5637801A (en) | 2001-10-30 |
| WO2001079607A1 (en) | 2001-10-25 |
| FI20000928A0 (en) | 2000-04-18 |
| EP1276931B1 (en) | 2009-12-02 |
| FI117716B (en) | 2007-01-31 |
| CA2405999C (en) | 2009-12-29 |
| EP1276931A1 (en) | 2003-01-22 |
| AU2001256379A1 (en) | 2001-11-20 |
| EP1276933A1 (en) | 2003-01-22 |
| US7211608B2 (en) | 2007-05-01 |
| PT1276931E (en) | 2009-12-21 |
| DE60140665D1 (en) | 2010-01-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |