WO2023055326A1 - Nouvel agent de revêtement de surface pour papier - Google Patents

Nouvel agent de revêtement de surface pour papier Download PDF

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Publication number
WO2023055326A1
WO2023055326A1 PCT/TR2022/051047 TR2022051047W WO2023055326A1 WO 2023055326 A1 WO2023055326 A1 WO 2023055326A1 TR 2022051047 W TR2022051047 W TR 2022051047W WO 2023055326 A1 WO2023055326 A1 WO 2023055326A1
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WO
WIPO (PCT)
Prior art keywords
cationic
acrylate
monomers
fluorocarbon
monomers containing
Prior art date
Application number
PCT/TR2022/051047
Other languages
English (en)
Inventor
Baris OKUYAN
Gokhan SENEL
Semih Durmus
Original Assignee
Akkim Kimya Sanayi Ve Ticaret Anonim Sirketi
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Akkim Kimya Sanayi Ve Ticaret Anonim Sirketi filed Critical Akkim Kimya Sanayi Ve Ticaret Anonim Sirketi
Publication of WO2023055326A1 publication Critical patent/WO2023055326A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons

Definitions

  • the invention generally relates to surface coating agents with water repellent properties for papers and their use.
  • the invention relates to cationic polymeric sizing agents for paper and the use thereof.
  • Paper fibers made of cellulose tend to absorb liquids. In paper products, it is preferred that the paper is resistant to liquid diffusion and absorption. Therefore, surface sizing processes are applied to give the paper a barrier against liquid, especially in the paper industry.
  • polymers that are mostly in the form of solutions or dispersions (emulsion polymers) are used as surface sizing agents.
  • emulsion polymers include styrene and maleic anhydride copolymers, methacrylate and acrylate monomer copolymers, styrene copolymers containing acrylate/methacrylate monomers, polyurethane dispersions or acrylonitrile copolymers, and graft polymers.
  • the common point of all these sizing agents is that they have a hydrophilic and a hydrophobic molecule section. Anionic, amphoteric, and cationic polymers can be used for this purpose.
  • the said polymer structures are used in various industrial areas such as dye, coating, and paper, but they are insufficient to meet the needs of paper producers. For these reasons, research on polymer-based surface sizing agents continues increasingly.
  • cationic styrene acrylate (styrene acrylic acid ester) polymer products are commonly used as surface gluing or surface coating (i.e. surface sizing) agents. By using these products, it is aimed to provide effects such as water repellency on paper and writability to surface texture, and not blurring in ink and paints applied to the paper surface. In the state of the art, there is a need to increase the water repellency of these products.
  • the patent application numbered US 2002/0096285 A1 discloses a surface sizing agent modified with cellulose.
  • the said surface sizing agent comprises a cationic polymer and bacterial cellulose and/or fine fibrous cellulose of plant origin.
  • the cationic polymer is an acrylic polymer, vinyl polymer, or allyl polymer, each having a quaternary amino group.
  • the patent application numbered US 2009/0068485 discloses a cationic surface sizing agent produced by quaternization of a copolymer obtained by polymerization of a monomer, (meth) acrylic acid with C4 to C18 alkyl ester and styrene or a derivative thereof, which contains certain proportions by weight of tertiary amino groups, developed to improve sizing performance.
  • SAE cationic styrene-acrylic acid ester emulsions
  • the present invention relates to surface coating agents suitable for use in textile, paper, and similar industries and their uses that meet the aforementioned requirements and bring some additional advantages.
  • the primary object of the invention is to provide a surface coating agent with improved performance for textile and paper products.
  • Another object of the invention is to provide a surface coating agent for improving water repellency on the surfaces of textile and paper products.
  • Another object of the invention is to provide a novel surface coating agent that is easy to prepare for textile and paper products.
  • Another object of the invention is to provide a process that improves the performance of cationic surface coating agents used in textile and paper products.
  • Another object of the invention is to provide a novel combination of surface coating agents that provides usability in the desired performance ranges with a variety of formulations in textile and paper products.
  • Another object of the invention is to provide a surface coating agent suitable for use in paper products for sizing the paper surface.
  • the present invention is a mixture for use as a surface coating agent comprising at least one cationic polymer emulsion and at least one fluorocarbon dispersion as a sizing agent, wherein the said cationic polymer emulsion is a cationic styrene acrylate copolymer emulsion.
  • the ratio by mass of the said cationic styrene acrylate copolymer emulsion to the said fluorocarbon polymer dispersion is 95:5 to 85:15.
  • the monomers preparing the said cationic styrene acrylate copolymer are selected from aromatic vinyl monomers such as styrene and methylstyrene; unsaturated monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl acrylate, dodecyl acrylate, isobutyl acrylate; unsaturated dicarboxylic acid esters such as itaconic acid and maleic acid esters; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; monomers containing the hydroxyl function such as 2-hydroxyl ethyl methacrylate; monomers containing the nitrile function such as acrylonitrile and methacrylonitrile; monomers containing the amino function such as 2-dimethyl
  • the cationic monomers for preparing the said cationic styrene acrylate copolymer are selected from monomers comprising quaternized amino groups such as methacryloyl aminopropyl trimethyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
  • the said fluorocarbon dispersion comprises water-based C6-C8 fluorocarbon.
  • it is a surface sizing agent for paper.
  • the present invention is the use of a mixture comprising at least one fluorocarbon dispersion together with at least one cationic polymer emulsion as the sizing agent as the surface sizing agent in papers, wherein the said cationic polymer emulsion is a cationic styrene acrylate copolymer emulsion
  • the ratio by weight of the said cationic styrene acrylate copolymer emulsion to the said fluorocarbon polymer emulsion is 95:5 to 85:15.
  • the monomers for preparing the said cationic styrene acrylate copolymer are selected from aromatic vinyl monomers such as styrene and methylstyrene; unsaturated monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl acrylate, dodecyl acrylate, isobutyl acrylate; unsaturated dicarboxylic acid esters such as itaconic acid and maleic acid esters; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; monomers containing the hydroxyl function such as 2-hydroxyl ethyl methacrylate; monomers containing the nitrile function such as acrylonitrile and methacrylonitrile; monomers containing the amino function such as 2-dimethyl
  • the cationic monomers for preparing the said cationic styrene acrylate copolymer are selected from monomers comprising quaternized amino groups such as methacryloyl aminopropyl trimethyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
  • the said fluorocarbon dispersion comprises water-based C6-C8 fluorocarbon.
  • a novel combination of products is provided as a surface coating agent.
  • This combination synergistically improves the performance of cationic styrene acrylate copolymers, a well-known surface sizing agent for paper in the state of the art, and consequently improves the water resistance, ink, and dye print quality on paper and similar surfaces.
  • the combination of the invention is a mixture comprising at least one cationic polymer emulsion and at least one fluorocarbon dispersion as a surface sizing agent.
  • the cationic polymer emulsion is a cationic styrene acrylate copolymer emulsion.
  • the said cationic acrylate copolymer includes styrene-based acrylic ester polymerization (copolymerization) products. These structures are obtained by providing a molecular sequence at low cationity with a polymerization based on styrene-based ester copolymer.
  • Cationic polymeric sizing agents used for papers are known. These products are commonly used in the paper industry as surface gluing or surface coating agents. These provide properties such as water repellency on paper and writability to surface texture, and no blurring of ink and paint applied to the paper surface. Fluorocarbon structures are generally known to benefit from water repellency.
  • the cationic styrene acrylate copolymer emulsion is obtained by adapting the cationic groups to the styrene-acrylic ester polymer system.
  • the cationic groups used are generally cationic starch and/or quaternized ammonium-containing structures.
  • the ionicity of the polymer obtained in this way is cationic.
  • Quaternized ammonium salts can continue to have a wide pH range of cationic charge and can be used for acid, alkaline, and neutral sizing, which is why they are preferred.
  • Any cationic styrene acrylate copolymer emulsion known as a surface sizing agent may be used in the mixture of the invention by a person skilled in the art.
  • a cationic styrene acrylate copolymer according to the invention is preferably an emulsion polymer.
  • Preferred monomers for the preparation of a cationic styrene acrylate copolymer according to the invention include aromatic vinyl monomers such as styrene and methylstyrene, more preferably styrene; unsaturated monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, cyclohexyl acrylate, dodecyl acrylate, isobutyl acrylate, more preferably methyl methacrylate, butyl acrylate; unsaturated dicarboxylic acid esters such as itaconic acid and maleic acid esters, more preferably maleic acid; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, more preferably acrylic acid; monomers containing the hydroxyl function such as 2-hydroxyl ethylmethacrylate, mono
  • Perglutin® K532 product sold commercially by Kurita Water Industries Ltd. and the Basoplast® 285S product sold by Badische Anilin- & Soda-Fabrik (BASF) are particularly suitable.
  • the fluorocarbon (FC) emulsion according to the invention may be any fluorocarbon-based water repellent known to a person skilled in the art.
  • the said fluorocarbon emulsion is preferably a water-based C6-C8 fluorocarbon-containing dispersion.
  • fluorocarbon compounds reduce the surface energy between the fabrics and the air and increase the surface tension between the liquid and the fabric. In this way, fabrics are given a good water repellency feature.
  • fluorocarbon compounds can be directly applied to the paper surface by combining with a cationic styrene acrylate copolymer, which is another agent that gives water repellency to the paper surfaces, and as a result of curing at certain temperatures, oil and water repellency properties are added to the paper surface.
  • a cationic styrene acrylate copolymer which is another agent that gives water repellency to the paper surfaces, and as a result of curing at certain temperatures, oil and water repellency properties are added to the paper surface.
  • AKEF FC 400 and AKEF FC 600 products sold by Akkim Kimya San. ve Tic. A. ⁇ . in the market Bioguard 420 and Bioguard C6RA Plus products sold by Biotex and Perfloro MRD products sold by Forniture Tessili Riunite
  • a mixture of at least one fluorocarbon polymer emulsion and at least one cationic polymer dispersion is prepared.
  • a more effective product is obtained and the amount of chemicals in paper applications is reduced and performance is increased.
  • a desired or better performance can be achieved by using a smaller amount of cationic styrene acrylate copolymer.
  • usability is provided in the desired performance ranges with formulation diversity.
  • the mixing ratio of the said cationic polymer dispersion to the said fluorocarbon polymer emulsion is preferably 95:5 to 85:15 by weight. It was found that technical difficulties such as stability problems, sediment formation, and performance reduction experienced due to the interactions of the components forming the mixture of the invention with the preferred rates were overcome. Desired results can be obtained in terms of the compatibility of the chemicals with each other and the regulatory requirements specific to the chemicals used in the formulation and their compatibility with each other.
  • the mixtures of the invention can be prepared in different formulations and used in different industries. It can be used in textile, paper, and similar industries, and it can be developed by increasing hydrophobic effects in different industries and used as an advanced chemical.
  • This resulting mixture can be used directly by dilution or without dilution. It is seen that the viscosity of the resulting mixture remains below 50 cps at 20°C. Therefore, there is no need to make a change in a general cationic polymer dispersion application.
  • the mixture of the invention can be applied to the paper surfaces as a surface sizing agent by a known method to the person skilled in the art.
  • the mixtures were obtained by mixing different types of fluorocarbon polymer emulsions with different types of styrene acrylate copolymer surface sizing agents at the rates of 5%, 10%, and 15% by mass.
  • the Cobb values of the resulting mixtures were measured and water repellents were tested on the paper surface.
  • Perglutin® K532 Kelta Water Industries Ltd.
  • Basoplast® 285S Basoplast® 285S
  • AKEF FC 400 amphoteric, C8 fluorocarbon dispersion
  • AKEF FC 600 weak cationic, C6 fluorocarbon dispersion
  • -Bioguard 420 weak cationic, C8 fluorocarbon dispersion
  • Bioguard C6RA Plus weak cationic, C6 fluorocarbon dispersion
  • Perfluoro MRD weak cationic, C8 fluorocarbon dispersion
  • the Cobb Test is used to measure the amount of water absorbed over a period of time while the prepared paper is held between a metal ring and a plate. During this process, 100 ml of water and paper are exposed. Before the test, the paper (12.5 x 12.5) cm is cut and weighed. For the tests here, water was kept on paper for 60 seconds. At the end of this period, excess water was discharged from the system, drying paper was placed on the leaf and excess water was disposed of. Then the paper was weighed and the Cobb value, which is the amount of water absorbed, was calculated as %.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

L'invention concerne un mélange destiné à être utilisé comme agent de revêtement de surface. Ledit mélange comprend au moins une émulsion fluorocarbonée conjointement avec au moins une émulsion polymère cationique en tant qu'agent d'encollage, ladite émulsion polymère cationique étant une émulsion copolymère styrène-acrylate cationique.
PCT/TR2022/051047 2021-09-28 2022-09-27 Nouvel agent de revêtement de surface pour papier WO2023055326A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2021/015103A TR2021015103A2 (tr) 2021-09-28 2021-09-28 Kağit i̇çi̇n yeni̇ bi̇r yüzey kaplama ajani
TR2021/015103 2021-09-28

Publications (1)

Publication Number Publication Date
WO2023055326A1 true WO2023055326A1 (fr) 2023-04-06

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PCT/TR2022/051047 WO2023055326A1 (fr) 2021-09-28 2022-09-27 Nouvel agent de revêtement de surface pour papier

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TR (1) TR2021015103A2 (fr)
WO (1) WO2023055326A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030678A (en) * 1989-08-08 1991-07-09 Ppg Industries, Inc. Cationic surface sizing emulsion
CN101768895A (zh) * 2009-01-07 2010-07-07 湖北大学 一种苯丙乳液型高效表面施胶剂及其制备方法
CN104805732A (zh) * 2015-05-15 2015-07-29 贺明波 一种苯丙乳液型高效表面施胶剂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5030678A (en) * 1989-08-08 1991-07-09 Ppg Industries, Inc. Cationic surface sizing emulsion
CN101768895A (zh) * 2009-01-07 2010-07-07 湖北大学 一种苯丙乳液型高效表面施胶剂及其制备方法
CN104805732A (zh) * 2015-05-15 2015-07-29 贺明波 一种苯丙乳液型高效表面施胶剂及其制备方法

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Publication number Publication date
TR2021015103A2 (tr) 2021-10-21

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