WO2023195877A1 - Composition for the surface treatment of paper - Google Patents
Composition for the surface treatment of paper Download PDFInfo
- Publication number
- WO2023195877A1 WO2023195877A1 PCT/RU2022/050411 RU2022050411W WO2023195877A1 WO 2023195877 A1 WO2023195877 A1 WO 2023195877A1 RU 2022050411 W RU2022050411 W RU 2022050411W WO 2023195877 A1 WO2023195877 A1 WO 2023195877A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paper
- composition
- surface treatment
- biocidal properties
- properties
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000004381 surface treatment Methods 0.000 title claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 11
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 5
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 abstract description 35
- 235000011187 glycerol Nutrition 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 17
- 230000000996 additive effect Effects 0.000 description 11
- 239000003139 biocide Substances 0.000 description 10
- 229920001131 Pulp (paper) Polymers 0.000 description 8
- 230000029918 bioluminescence Effects 0.000 description 6
- 238000005415 bioluminescence Methods 0.000 description 6
- -1 polyhexamethylene guanidine salts Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 244000000010 microbial pathogen Species 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000013642 negative control Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BXQNSPXDWSNUKE-UHFFFAOYSA-N 1,3-benzothiazole 1-oxide Chemical class C1=CC=C2S(=O)C=NC2=C1 BXQNSPXDWSNUKE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 206010007134 Candida infections Diseases 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 208000001528 Coronaviridae Infections Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 206010037637 Pyoderma streptococcal Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 201000003984 candidiasis Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 231100000283 hepatitis Toxicity 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline 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
- 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
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Definitions
- the invention relates to paper production, in particular, to the production of security paper with biocidal properties, for example, paper for making banknotes.
- banknotes change hands many times during their existence. At the same time, they accumulate contaminants and various pathogenic microorganisms (germs, bacteria, fungi, viruses), which are transmitted through contact from person to person and contribute to the spread of dangerous infectious diseases such as streptoderma, candidiasis, hepatitis, coronavirus infection, etc.
- banknote paper introducing compounds with biocidal properties into banknote paper, as well as giving the paper low adsorption properties.
- the latter is achieved, among other things, through surface treatment of paper polyurethane dispersion with the addition of a crosslinking agent. After this treatment, the paper becomes more resistant to contamination, and its absorbency to aqueous solutions, oils, and fats is also reduced.
- a composition with biocidal properties is known (patent RU 2436305 dated December 20, 2011), which contains an organic compound selected, among other things, from the group of isothiazolinones, as well as an inorganic compound selected from the group of metal oxides.
- a composition with biocidal properties is known (application US 2008227766 dated September 18, 2008), consisting of a combination of two components, one of which is selected from the group of benzothiazolinones, and the other from the group containing organic and inorganic silver compounds, including silver nanoparticles.
- a composition with biocidal properties is known (patent RU 2436561 dated December 20, 2011), which contains as one of the components a compound based on isothiazolinone, which, in particular, can be used as 2-methyl-4-isothiazolin-3-one.
- This composition allows one to achieve good biocidal properties with low consumption of components.
- Patent US 8592045 dated November 26, 2013 describes banknotes with antimicrobial properties, material and production method.
- the banknotes are coated with two different antimicrobial substances contained in composition of the polymer coating.
- an antimicrobial substance based on isothiazolinone is described. According to the authors, this technical solution is the closest to the claimed one.
- the problem solved by the invention is to impart biocidal properties to paper treated from the surface with a composition based on polyurethane dispersion while maintaining good physical and mechanical characteristics.
- composition for surface treatment of paper containing an isothiazolinone derivative has the following composition (wt.%): polyurethane dispersion (in terms of dry matter) 12-18
- biocidal properties in the invention means the ability to suppress the development of pathogenic microorganisms, such as microbes, bacteria, fungi, and viruses.
- this term means that paper treated with this chemical composition has fungicidal, antimicrobial and antiviral properties.
- the 2-methyl-4-isothiazolin-3-one used in the invention belongs to the group of isothiazolinones and is widely used as a preservative in cosmetics and paint and varnish production.
- this biocidal additive When preparing a composition for surface treatment of paper (hereinafter referred to as the composition), this biocidal additive must be used in the form of an aqueous solution with a concentration of 10-30%, or, more preferably, with a concentration of 10-20%.
- the invention uses aqueous dispersions of anionic type ionomer polyurethane, in which part of the polyol component is replaced by a polyfunctional monomer with carboxyl groups neutralized with ammonia or a tertiary amine.
- PUD polyurethane dispersions
- the concentration of PUD used in the manufacture of the composition should be in the range of 28-40%, or, more preferably, in the range of 28-32%.
- a crosslinking agent based on polyaziridine (hereinafter referred to as the crosslinking agent) is added to the composition in order to increase the wet strength and reduce the adsorption properties of the paper in relation to liquids.
- the amount of crosslinking agent in the composition should be in the range of 0.5-1.4%.
- the addition of less than 0.5% crosslinking agent does not allow achieving the required paper characteristics.
- adding more than 1.4% crosslinking agent does not improve paper performance and is not economically feasible.
- a product with the trade name CX-100, manufactured by DSM NeoResins is used as a cross-linking agent in the invention. If the properties match, products from other manufacturers can be used for this purpose.
- the introduction of glycerin into the composition helps to improve the migration of the biocide additive from a paper sheet treated with a polyurethane dispersion with a cross-linking agent.
- the presence of glycerol probably facilitates the transfer of the biocide additive from the surface of the paper into the liquid contaminant containing pathogenic microorganisms.
- the composition is prepared as follows. PUD with a concentration of 28-40% is pre-diluted with water to the required concentration and stirred for 5-30 minutes.
- a biocide additive in the form of an aqueous solution with a concentration of 10-30%, glycerin and a cross-linking agent based on polyaziridine.
- the entire process of preparing the composition is carried out at a temperature of 18-25 °C.
- the finished composition with a pH of 7.0 - 9.5 is used for processing paper within 8-12 hours from the moment of preparation. If necessary, colloidal silver particles with a size of 10-50 nm stabilized in an aqueous environment are also added to the composition in order to improve the biocidal properties.
- the paper is produced using well-known technology for the production of banknote paper.
- the fibrous raw material is ground and paper pulp is prepared.
- the following are added to the prepared paper pulp: fillers (titanium dioxide, chalk, kaolin, etc.), additives to increase the strength of paper in dry and wet states (sodium carboxymethylcellulose, polyamide (amine) epichlorohydrin resin, etc.), substances for internal and mass sizing of paper (alkyl ketene dimers, alkenyl succinic acids, etc.), dyes (direct, acid, etc.), etc.
- additives necessary for protection against counterfeiting are introduced into the paper pulp, such as dyed fibers, fibers with fluorescent and magnetic properties, etc.
- a paper web is formed on a round mesh or flat mesh papermaking machine (PM), which may contain watermarks, security threads built into the paper structure, etc.
- PM round mesh or flat mesh papermaking machine
- the formed and pre-dried paper web is processed with a composition in accordance with the invention on the PM (on-line ), using a size press, film press, impregnation bath, etc.
- the finished paper web is treated with a composition in accordance with the invention separately standing equipment (off-line).
- the temperature of the composition during processing of the paper web should not exceed 35 °C.
- a test method is used, which is based on determining changes in the intensity of bioluminescence of genetically engineered bacteria under the influence of biocidal additives contained in paper samples. Paper without biocidal additives is used as a negative control.
- a “Biotoke-10” luminometer with a set of cuvettes for measuring bioluminescence, as well as a biological indicator “Ecolum”, which is a non-pathogenic bioluminescent bacteria, is used.
- Ecolum biological indicator
- Bioluminescence measurement is then carried out. The greater the decrease in bioluminescence intensity (quenching), the better the biocidal properties of the paper.
- the fibrous raw material is ground and paper pulp is prepared.
- the composition of the paper pulp is 100% cotton fiber.
- the necessary additives are introduced into this paper pulp at different stages of preparation in accordance with the technology for manufacturing banknote paper.
- a paper web is formed on a paper machine, which, after preliminary drying, is treated in an impregnation bath with compositions containing a biocide additive (examples 2-12).
- a biocide additive for a negative control
- paper is made using a composition without a biocide additive (example 1).
- the paper treated with these compositions is finally dried, calendered and rolled.
- Formulations of compositions for processing paper are shown in Table 1.
- the addition of glycerin to the composition helps improve the biocidal properties of paper.
- a comparison of a composition without glycerin (example 2) with compositions containing glycerin (examples 5-7), with the same dosage of the biocide additive shows an increase in the quenching of bioluminescence due to the addition of glycerin. That is, at the same dosage, the effectiveness of the biocide additive in the presence of glycerol increases.
- compositions in accordance with the invention which reduce the consumption of biocidal additives, compared to compositions that do not contain glycerin (examples 2-4), while maintaining the good biocidal properties of paper.
- testing of paper made using compositions in accordance with the invention demonstrates the presence of good physical and mechanical characteristics.
- compositions in accordance with the invention makes it possible to produce paper with good biocidal properties while maintaining its physical and mechanical characteristics. This is achieved through a certain combination of components, as well as through the use of glycerin in the composition, which makes it possible to reduce the dosage of the biocide additive while maintaining its effectiveness.
Abstract
The invention relates to papermaking, and more particularly to the manufacture of a security paper with biocidal properties, for example paper for the manufacture of banknotes. Proposed is a composition for the surface treatment of paper, containing isothiazolinone and having the following proportions of ingredients: 12-18 wt% polyurethane dispersion (on a dry basis); 0.3-1.2 wt% 2-methyl-4-isothiazolin-3-one; 0.9-2.1 wt% glycerine; 0.5-1.4 wt% polyaziridine-based crosslinking agent; and the balance water. The technical result is that of imparting biocidal properties to paper that is surface-treated with the claimed polyurethane dispersion-based composition, while maintaining good physical and mechanical characteristics.
Description
КОМПОЗИЦИЯ ДЛЯ ПОВЕРХНОСТНОЙ ОБРАБОТКИ БУМАГИ COMPOSITION FOR SURFACE TREATMENT OF PAPER
Изобретение относится к бумажному производству, в частности, к области изготовления защищенной бумаги с биоцидными свойствами, например, бумаги для изготовления банкнот. The invention relates to paper production, in particular, to the production of security paper with biocidal properties, for example, paper for making banknotes.
Необходимость придания бумаге для изготовления банкнот биоцидных свойств диктуется тем обстоятельством, что, являясь основным платежным средством наличного денежного обращения, банкноты за время своего существования многократно переходят из рук в руки. При этом на них накапливаются загрязнения и различные патогенные микроорганизмы (микробы, бактерии, грибы, вирусы), которые передаются при контакте от человека к человеку и способствуют распространению опасных инфекционных заболеваний, таких как стрептодермия, кандидоз, гепатит, коронавирусная инфекция и т.д. The need to impart biocidal properties to paper for the production of banknotes is dictated by the fact that, being the main means of payment in cash circulation, banknotes change hands many times during their existence. At the same time, they accumulate contaminants and various pathogenic microorganisms (germs, bacteria, fungi, viruses), which are transmitted through contact from person to person and contribute to the spread of dangerous infectious diseases such as streptoderma, candidiasis, hepatitis, coronavirus infection, etc.
Введение в бумагу для изготовления банкнот различных соединений с биоцидными свойствами позволяет повысить безопасность банкнот в процессе обращения за счет снижения содержания на их поверхности патогенных микроорганизмов. Другим решением может быть придание бумаге низких адсорбционных свойств по отношению к жидким субстанциям, выделяемым телом человека (кожный жир, пот), так как эти субстанции могут быть потенциальными носителями патогенных микроорганизмов. The introduction of various compounds with biocidal properties into paper for the production of banknotes makes it possible to increase the safety of banknotes during circulation by reducing the content of pathogenic microorganisms on their surface. Another solution could be to give the paper low adsorption properties in relation to liquid substances secreted by the human body (sebum, sweat), since these substances can be potential carriers of pathogenic microorganisms.
Наилучшую защиту обеспечивает комбинация этих двух решений, то есть введение в бумагу для банкнот соединений с биоцидными свойствами, а также придание бумаге низких адсорбционных свойств. Последнее достигается, в том числе, за счет поверхностной обработки бумаги
полиуретановой дисперсией с добавкой сшивающего агента. После такой обработки бумага приобретает повышенную устойчивость к загрязнению, а также снижается её впитывающая способность к водным растворам, маслу, жирам. The best protection is provided by a combination of these two solutions, that is, introducing compounds with biocidal properties into banknote paper, as well as giving the paper low adsorption properties. The latter is achieved, among other things, through surface treatment of paper polyurethane dispersion with the addition of a crosslinking agent. After this treatment, the paper becomes more resistant to contamination, and its absorbency to aqueous solutions, oils, and fats is also reduced.
Из уровня техники известны соединения, которые можно применить для придания бумаге биоцидных свойств. Например, известен способ изготовления защищенной бумаги, который предполагает введение в бумагу водорастворимых солей полигексаметиленгуанидина (патент RU 2229547 от 27.05.2004). Однако, водорастворимые соли полигексаметиленгуанидина являются сильными коагулянтами и способны активно взаимодействовать со многими химическими соединениями и, в том числе, с полиуретановой дисперсией. По этой причине применять их совместно с полиуретановой дисперсией затруднительно. Compounds are known from the prior art that can be used to impart biocidal properties to paper. For example, there is a known method for producing security paper, which involves introducing water-soluble polyhexamethylene guanidine salts into the paper (patent RU 2229547 dated May 27, 2004). However, water-soluble salts of polyhexamethylene guanidine are strong coagulants and are capable of actively interacting with many chemical compounds, including polyurethane dispersion. For this reason, it is difficult to use them together with polyurethane dispersion.
Известна композиция с биоцидными свойствами (патент RU 2436305 от 20.12.2011), которая содержит органическое соединение, выбранное, в том числе, из группы изотиазолинонов, а также неорганическое соединение, выбранное из группы оксидов металлов. A composition with biocidal properties is known (patent RU 2436305 dated December 20, 2011), which contains an organic compound selected, among other things, from the group of isothiazolinones, as well as an inorganic compound selected from the group of metal oxides.
Известна композиция с биоцидными свойствами (заявка US 2008227766 от 18.09.2008), состоящая из комбинации двух компонентов, один из которых выбирают из группы бензотиазолинонов, а другой - из группы, содержащей органические и неорганические соединения серебра и, в том числе, наночастицы серебра. A composition with biocidal properties is known (application US 2008227766 dated September 18, 2008), consisting of a combination of two components, one of which is selected from the group of benzothiazolinones, and the other from the group containing organic and inorganic silver compounds, including silver nanoparticles.
Известна композиция с биоцидными свойствами (патент RU 2436561 от 20.12.2011), которая содержит одним из компонентов соединение на основе изотиазолинона, в качестве которого, в частности, может использоваться 2- метил-4-изотиазолин-З-он. Эта композиция позволяет достичь хороших биоцидных свойств при низком расходе компонентов. A composition with biocidal properties is known (patent RU 2436561 dated December 20, 2011), which contains as one of the components a compound based on isothiazolinone, which, in particular, can be used as 2-methyl-4-isothiazolin-3-one. This composition allows one to achieve good biocidal properties with low consumption of components.
В патенте US 8592045 от 26.11.2013 описаны банкноты с антимикробными свойствами, материал и способ получения. На поверхность банкнот нанесены два различных антимикробных вещества, содержащихся в
составе полимерного покрытия. В частности, описано антимикробное вещество на основе изотиазолинона. По мнению авторов, это техническое решение является наиболее близким к заявляемому. Patent US 8592045 dated November 26, 2013 describes banknotes with antimicrobial properties, material and production method. The banknotes are coated with two different antimicrobial substances contained in composition of the polymer coating. In particular, an antimicrobial substance based on isothiazolinone is described. According to the authors, this technical solution is the closest to the claimed one.
Задача, решаемая изобретением - придание бумаге, обрабатываемой с поверхности составом на основе полиуретановой дисперсии, биоцидных свойств при сохранении хороших физико-механических характеристик. The problem solved by the invention is to impart biocidal properties to paper treated from the surface with a composition based on polyurethane dispersion while maintaining good physical and mechanical characteristics.
Задача решается тем, что композиция для поверхностной обработки бумаги, содержащая производное изотиазолинона, согласно изобретению, имеет следующий состав (мае .%): полиуретановая дисперсия (в пересчете на сухое вещество) 12-18The problem is solved by the fact that the composition for surface treatment of paper containing an isothiazolinone derivative, according to the invention, has the following composition (wt.%): polyurethane dispersion (in terms of dry matter) 12-18
2-метил-4-изотиазолин-3-он 0,3- 1,2 глицерин 0,9-2, 1 сшивающий агент на основе полиазиридина 0,5- 1,4 вода остальное2-methyl-4-isothiazolin-3-one 0.3-1.2 glycerol 0.9-2, 1 polyaziridine-based crosslinking agent 0.5-1.4 water the rest
Поставленная задача решается также бумагой, изготовленной с применением композиции для поверхностной обработки, охарактеризованной совокупностью изложенных выше признаков. This problem is also solved by paper made using a composition for surface treatment, characterized by a combination of the characteristics described above.
Под термином «биоцидные свойства» в изобретении подразумевается способность подавлять развитие патогенных микроорганизмов, таких как микробы, бактерии, грибы, вирусы. Кроме того, под этим термином подразумевается наличие у обработанной этим химическим составом бумаги фунгицидных, антимикробных и антивирусных свойств. The term “biocidal properties” in the invention means the ability to suppress the development of pathogenic microorganisms, such as microbes, bacteria, fungi, and viruses. In addition, this term means that paper treated with this chemical composition has fungicidal, antimicrobial and antiviral properties.
Используемый в изобретении 2-метил-4-изотиазолин-3-он (далее - биоцидная добавка) относится к группе изотиазолинонов и находит широкое применение в качестве консерванта в косметике и лакокрасочном производстве. При изготовлении композиции для поверхностной обработки бумаги (далее - композиция) эту биоцидную добавку необходимо применять в виде водного раствора с концентрацией 10-30 %, или, что более предпочтительно, - с концентрацией 10-20 %.
В качестве полиуретановой дисперсии в изобретении применяют водные дисперсии иономерного полиуретана анионного типа, в которых часть полиольного компонента замещена полифункциональным мономером с карбоксильными группами, нейтрализованными аммиаком или третичным амином. Причем наиболее предпочтительно использовать полиуретановые дисперсии (далее - ПУД), изготовленные без использования органических растворителей, например, как это подробно описано в патенте RU 2554882 С1 от 27.06.2015. Концентрация ПУД, применяемой при изготовлении композиции, должна быть в диапазоне 28-40 %, или, что более предпочтительно, - в диапазоне 28-32 %. The 2-methyl-4-isothiazolin-3-one used in the invention (hereinafter referred to as the biocide additive) belongs to the group of isothiazolinones and is widely used as a preservative in cosmetics and paint and varnish production. When preparing a composition for surface treatment of paper (hereinafter referred to as the composition), this biocidal additive must be used in the form of an aqueous solution with a concentration of 10-30%, or, more preferably, with a concentration of 10-20%. As a polyurethane dispersion, the invention uses aqueous dispersions of anionic type ionomer polyurethane, in which part of the polyol component is replaced by a polyfunctional monomer with carboxyl groups neutralized with ammonia or a tertiary amine. Moreover, it is most preferable to use polyurethane dispersions (hereinafter referred to as PUD) made without the use of organic solvents, for example, as described in detail in patent RU 2554882 C1 dated June 27, 2015. The concentration of PUD used in the manufacture of the composition should be in the range of 28-40%, or, more preferably, in the range of 28-32%.
Сшивающий агент на основе полиазиридина (далее - сшивающий агент) добавляют в композицию с целью повышения влагопрочности и снижения адсорбционных свойств бумаги по отношению к жидкостям. Количество сшивающего агента в композиции должно быть в диапазоне 0,5-1, 4 %. Добавка менее 0,5 % сшивающего агента не позволяет достичь необходимых характеристик бумаги. В сравнении с этим, добавка более 1,4 % сшивающего агента не способствует улучшению характеристик бумаги и является экономически нецелесообразной. Например, в качестве сшивающего агента в изобретении используют продукт с торговым названием СХ-100, производимый компанией DSM NeoResins. При совпадении свойств с этой целью можно применить и продукты других изготовителей. A crosslinking agent based on polyaziridine (hereinafter referred to as the crosslinking agent) is added to the composition in order to increase the wet strength and reduce the adsorption properties of the paper in relation to liquids. The amount of crosslinking agent in the composition should be in the range of 0.5-1.4%. The addition of less than 0.5% crosslinking agent does not allow achieving the required paper characteristics. In comparison, adding more than 1.4% crosslinking agent does not improve paper performance and is not economically feasible. For example, a product with the trade name CX-100, manufactured by DSM NeoResins, is used as a cross-linking agent in the invention. If the properties match, products from other manufacturers can be used for this purpose.
Введение в композицию глицерина способствует улучшению миграции биоцидной добавки из бумажного листа, обработанного полиуретановой дисперсией со сшивающим агентом. Кроме того, наличие глицерина, вероятно, облегчает переход биоцидной добавки с поверхности бумаги в жидкую загрязняющую субстанцию, содержащую патогенные микроорганизмы. Отсутствие в композиции глицерина, при сравнимых дозировках биоцидной добавки, приводит к ухудшению биоцидных свойств бумаги.
Композицию изготавливают следующим образом. ПУД с концентрацией 28-40 % предварительно разбавляют водой до требуемой концентрации и перемешивают 5-30 минут. Затем в разбавленную ПУД при непрерывном перемешивании добавляют расчетные количества остальных компонентов: биоцидную добавку в виде водного раствора с концентрацией 10-30 %, глицерин и сшивающий агент на основе полиазиридина. Весь процесс приготовления композиции проводят при температуре 18-25 °C. Готовую композицию с pH 7,0 - 9,5 применяют для обработки бумаги в течение 8-12 часов с момента приготовления. При необходимости, в композицию также добавляют, с целью улучшения биоцидных свойств, стабилизированные в водной среде частицы коллоидного серебра размером 10-50 нм. The introduction of glycerin into the composition helps to improve the migration of the biocide additive from a paper sheet treated with a polyurethane dispersion with a cross-linking agent. In addition, the presence of glycerol probably facilitates the transfer of the biocide additive from the surface of the paper into the liquid contaminant containing pathogenic microorganisms. The absence of glycerol in the composition, at comparable dosages of the biocide additive, leads to a deterioration in the biocidal properties of the paper. The composition is prepared as follows. PUD with a concentration of 28-40% is pre-diluted with water to the required concentration and stirred for 5-30 minutes. Then the calculated amounts of the remaining components are added to the diluted PUD with continuous stirring: a biocide additive in the form of an aqueous solution with a concentration of 10-30%, glycerin and a cross-linking agent based on polyaziridine. The entire process of preparing the composition is carried out at a temperature of 18-25 °C. The finished composition with a pH of 7.0 - 9.5 is used for processing paper within 8-12 hours from the moment of preparation. If necessary, colloidal silver particles with a size of 10-50 nm stabilized in an aqueous environment are also added to the composition in order to improve the biocidal properties.
Бумагу изготавливают по известной технологии производства банкнотной бумаги. Для этого осуществляют размол волокнистого сырья и готовят бумажную массу. В приготовленную бумажную массу добавляют: наполнители (двуокись титана, мел, каолин и т.д.), добавки для повышения прочности бумаги в сухом и мокром состоянии (натриевая соль карбоксиметилцеллюлозы, полиамид(амин)эпихлоргидринная смола и т.д.), вещества для внутр имассной проклейки бумаги (димеры алкилкетена, алкенил янтарные кислоты и т.д.), красители (прямые, кислотные и т.д.) и др. Кроме того, в бумажную массу вводят добавки, необходимые для защиты от подделки, такие как окрашенные волокна, волокна с флуоресцентными и магнитными свойствами и др. The paper is produced using well-known technology for the production of banknote paper. To do this, the fibrous raw material is ground and paper pulp is prepared. The following are added to the prepared paper pulp: fillers (titanium dioxide, chalk, kaolin, etc.), additives to increase the strength of paper in dry and wet states (sodium carboxymethylcellulose, polyamide (amine) epichlorohydrin resin, etc.), substances for internal and mass sizing of paper (alkyl ketene dimers, alkenyl succinic acids, etc.), dyes (direct, acid, etc.), etc. In addition, additives necessary for protection against counterfeiting are introduced into the paper pulp, such as dyed fibers, fibers with fluorescent and magnetic properties, etc.
Из приготовленной бумажной массы на круглосеточной или плоскосеточной бумагоделательной машине (БДМ) формуют бумажное полотно, которое может содержать водяные знаки, встроенные в структуру бумаги защитные нити и др. Сформованное и предварительно подсушенное бумажное полотно обрабатывают композицией в соответствии с изобретением на БДМ (on-line), используя для этого клеильный пресс, пленочный пресс, пропиточную ванну и т.д. В частном случае, готовое бумажное полотно обрабатывают композицией в соответствии с изобретением на отдельно
стоящем оборудовании (off-line). Температура композиции в процессе обработки бумажного полотна не должна превышать 35 °C. From the prepared paper pulp, a paper web is formed on a round mesh or flat mesh papermaking machine (PM), which may contain watermarks, security threads built into the paper structure, etc. The formed and pre-dried paper web is processed with a composition in accordance with the invention on the PM (on-line ), using a size press, film press, impregnation bath, etc. In a particular case, the finished paper web is treated with a composition in accordance with the invention separately standing equipment (off-line). The temperature of the composition during processing of the paper web should not exceed 35 °C.
Для оценки биоцидных свойств бумаги используют метод испытания, который основан на определении изменения интенсивности биолюминесценции генно-инженерных бактерий под воздействием биоцидных добавок, содержащихся в образцах бумаги. В качестве отрицательного контроля применяют бумагу без биоцидных добавок. Для испытания используют люминометр «Биотоке- 10» с набором кювет для измерения биолюминесценции, а также биологический индикатор «Эколюм», который представляет собой непатогенные биолюминесцирующие бактерии. В процессе испытания образцы бумаги выдерживаются в водном растворе биологического индикатора «Эколюм» в течение 5 минут. Затем осуществляют измерение биолюминесценции. Чем больше снижение интенсивности биолюминесценции (гашение), тем лучше биоцидные свойства бумаги. To assess the biocidal properties of paper, a test method is used, which is based on determining changes in the intensity of bioluminescence of genetically engineered bacteria under the influence of biocidal additives contained in paper samples. Paper without biocidal additives is used as a negative control. For testing, a “Biotoke-10” luminometer with a set of cuvettes for measuring bioluminescence, as well as a biological indicator “Ecolum”, which is a non-pathogenic bioluminescent bacteria, is used. During testing, paper samples are kept in an aqueous solution of the biological indicator “Ecolum” for 5 minutes. Bioluminescence measurement is then carried out. The greater the decrease in bioluminescence intensity (quenching), the better the biocidal properties of the paper.
Далее заявленная композиция подробно объясняется на примерах. Next, the claimed composition is explained in detail using examples.
Примеры осуществления Examples of implementation
Осуществляют размол волокнистого сырья и приготавливают бумажную массу. Состав бумажной массы - 100 % хлопковое волокно. В эту бумажную массу на разных стадиях подготовки вводят необходимые добавки в соответствии с технологией изготовления банкнотной бумаги. Из приготовленной бумажной массы на БДМ формуют бумажное полотно, которое после предварительной сушки обрабатывают в пропиточной ванне композициями, содержащими биоцидную добавку (примеры 2-12). Для отрицательного контроля изготовляют бумагу, используя композицию без биоцидной добавки (пример 1). Бумагу, обработанную этими композициями, окончательно сушат, каландрируют и сматывают на накат. The fibrous raw material is ground and paper pulp is prepared. The composition of the paper pulp is 100% cotton fiber. The necessary additives are introduced into this paper pulp at different stages of preparation in accordance with the technology for manufacturing banknote paper. From the prepared paper pulp, a paper web is formed on a paper machine, which, after preliminary drying, is treated in an impregnation bath with compositions containing a biocide additive (examples 2-12). For a negative control, paper is made using a composition without a biocide additive (example 1). The paper treated with these compositions is finally dried, calendered and rolled.
Рецептуры композиций для обработки бумаги показаны в таблице 1.Formulations of compositions for processing paper are shown in Table 1.
Результаты оценки биоцидных свойств бумаги за счет снижения интенсивности биолюминесценции (гашения), по отношению к
отрицательному контролю (пример 1), показаны в таблице 2. Results of assessing the biocidal properties of paper by reducing the intensity of bioluminescence (quenching) in relation to negative control (example 1) are shown in table 2.
Как видно из результатов испытания, добавка в композицию глицерина способствует улучшению биоцидных свойств бумаги. Так, сравнение композиции без глицерина (пример 2) с композициями, содержащими глицерин (примеры 5-7), при одинаковой дозировке биоцидной добавки, показывает увеличение гашения биолюминесценции за счет добавки глицерина. То есть, при одинаковой дозировке эффективность действия биоцидной добавки в присутствии глицерина увеличивается. As can be seen from the test results, the addition of glycerin to the composition helps improve the biocidal properties of paper. Thus, a comparison of a composition without glycerin (example 2) with compositions containing glycerin (examples 5-7), with the same dosage of the biocide additive, shows an increase in the quenching of bioluminescence due to the addition of glycerin. That is, at the same dosage, the effectiveness of the biocide additive in the presence of glycerol increases.
Причем, наилучший результат достигается при применении композиций в соответствии с изобретением (примеры 8-11), которые позволяют снизить расход биоцидной добавки, по сравнению с композициями, не содержащими глицерин (примеры 2-4), при сохранении хороших биоцидных свойств бумаги. Кроме того, испытание бумаги, изготовленной с применением композиций в соответствии с изобретением (примеры 8-11), демонстрирует наличие хороших физико-механических характеристик. Moreover, the best result is achieved when using compositions in accordance with the invention (examples 8-11), which reduce the consumption of biocidal additives, compared to compositions that do not contain glycerin (examples 2-4), while maintaining the good biocidal properties of paper. In addition, testing of paper made using compositions in accordance with the invention (examples 8-11) demonstrates the presence of good physical and mechanical characteristics.
Таким образом, применение композиций в соответствии с изобретением позволяет изготовить бумагу с хорошими биоцидными свойствами при сохранении её физико-механических характеристик. Это достигается за счет определенного сочетания компонентов, а также за счет применения в композиции глицерина, который позволяет снизить дозировку биоцидной добавки при сохранении эффективности её действия.
Thus, the use of compositions in accordance with the invention makes it possible to produce paper with good biocidal properties while maintaining its physical and mechanical characteristics. This is achieved through a certain combination of components, as well as through the use of glycerin in the composition, which makes it possible to reduce the dosage of the biocide additive while maintaining its effectiveness.
Claims
1. Композиция для поверхностной обработки бумаги, содержащая производное изотиазолинона, имеющая следующий состав (мае .%): полиуретановая дисперсия (в пересчете на сухое вещество) 12-18 2-метил-4-изотиазолин-3-он 0,3 - 1 ,2 глицерин 0,9-2, 1 сшивающий агент на основе полиазиридина 0,5- 1,4 вода остальное.1. Composition for surface treatment of paper containing an isothiazolinone derivative, having the following composition (wt.%): polyurethane dispersion (in terms of dry matter) 12-18 2-methyl-4-isothiazolin-3-one 0.3 - 1, 2 glycerol 0.9-2, 1 cross-linking agent based on polyaziridine 0.5-1.4 water the rest.
2. Бумага, изготовленная с применением композиции для поверхностной обработки, охарактеризованной в п. 1. 2. Paper made using the surface treatment composition described in paragraph 1.
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Citations (4)
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RU2318942C1 (en) * | 2006-07-12 | 2008-03-10 | Федеральное Государственное Унитарное Предприятие "Гознак" (Фгуп "Гознак") | Composition for paper manufacturing |
EP2634309A1 (en) * | 2012-03-01 | 2013-09-04 | Giesecke & Devrient GmbH | Security paper |
US8592045B2 (en) * | 2007-02-09 | 2013-11-26 | Microban Products Company | Antimicrobial currency, material and method |
RU2651249C1 (en) * | 2016-11-10 | 2018-04-18 | Общество с ограниченной ответственностью "Бумага и Картон" (ООО "Бумага и Картон") | Method of producing paper with antimicrobial characteristics |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2318942C1 (en) * | 2006-07-12 | 2008-03-10 | Федеральное Государственное Унитарное Предприятие "Гознак" (Фгуп "Гознак") | Composition for paper manufacturing |
US8592045B2 (en) * | 2007-02-09 | 2013-11-26 | Microban Products Company | Antimicrobial currency, material and method |
EP2634309A1 (en) * | 2012-03-01 | 2013-09-04 | Giesecke & Devrient GmbH | Security paper |
RU2651249C1 (en) * | 2016-11-10 | 2018-04-18 | Общество с ограниченной ответственностью "Бумага и Картон" (ООО "Бумага и Картон") | Method of producing paper with antimicrobial characteristics |
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