WO2001079605A2 - Inhibition du jaunissement des papiers - Google Patents

Inhibition du jaunissement des papiers Download PDF

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Publication number
WO2001079605A2
WO2001079605A2 PCT/CA2001/000543 CA0100543W WO0179605A2 WO 2001079605 A2 WO2001079605 A2 WO 2001079605A2 CA 0100543 W CA0100543 W CA 0100543W WO 0179605 A2 WO0179605 A2 WO 0179605A2
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WO
WIPO (PCT)
Prior art keywords
weight
paper
pulp
radical scavenger
titanium dioxide
Prior art date
Application number
PCT/CA2001/000543
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English (en)
Other versions
WO2001079605A3 (fr
Inventor
Zhirun Yuan
John Alois Schmidt
Peter Francis Mcgarry
Cyril Heitner
Original Assignee
Pulp And Paper Research Institute Of Canada
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 Pulp And Paper Research Institute Of Canada filed Critical Pulp And Paper Research Institute Of Canada
Priority to JP2001576985A priority Critical patent/JP2004504500A/ja
Priority to AU2001254542A priority patent/AU2001254542A1/en
Priority to CA002405662A priority patent/CA2405662A1/fr
Publication of WO2001079605A2 publication Critical patent/WO2001079605A2/fr
Publication of WO2001079605A3 publication Critical patent/WO2001079605A3/fr
Priority to SE0203040A priority patent/SE525893C2/sv
Priority to NO20024957A priority patent/NO20024957D0/no
Priority to FI20021862A priority patent/FI20021862A/fi

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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
    • D21H21/143—Agents preventing ageing of paper, e.g. radiation absorbing substances
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing 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
    • D21H17/675—Oxides, hydroxides or carbonates

Definitions

  • the present invention relates to light stable lignin-containing papers and to methods of rendering lignin-containing papers light stable; more especially the invention provides a method that can be used in paper mills to produce light stable lignin-containing papers by the application of titanium dioxide and a radical scavenger, which can be added to the base paper sheet or as a component of pigment coating formulations employed to coat the paper.
  • a radical scavenger which can be added to the base paper sheet or as a component of pigment coating formulations employed to coat the paper.
  • Pigmented coatings and fillers improve paper gloss, color, and printability. They can also improve brightness stability, depending on type and amount of the pigments used.
  • the pigments provide some brightness stability, either by scattering or absorbing incident UV light.
  • Clay and calcium carbonate provide brightness stability primarily by the scattering mechanism, since they have a high reflectance but a low absorption of UV light.
  • the present invention provides a method that can be used to produce light stable lignin-containing papers using Ti0 2 pigment and a radical scavenger. Light stable lignin-containing papers or paperboards can be produced with this method.
  • the invention also provides a light stable lignin-containing paper containing Ti0 2 , and a radical scavenger.
  • a light stable lignin-containing paper having a content of particulate titanium dioxide and a radical scavenger effective to inhibit yellowing of the paper.
  • a method of rendering a lignin-containing paper light stable comprising: a) incorporating in said paper a content of particulate titanium dioxide and a radical scavenger, in an amount effective to inhibit yellowing of the paper, or b) coating the paper with a coating formulation having a content of particulate titanium dioxide and a radical scavenger, in an amount effective to inhibit yellowing of the paper.
  • the lignin-containing papers of the invention are papers of high lignin content in which yellowing occurs as a result of modifications in the lignin in the paper.
  • High yield indicates high retention of lignin and these pulps typically have a lignin content (Klason lignin) of 15 to 35%, by weight, based on the weight of the pulp.
  • Lignin content varies as between hardwoods and softwoods and between species. In general these pulps derived from hardwoods have a lignin content of 15-25%, by weight, of the pulp and the pulps derived from softwoods have a lignin content of 20 to 35%, by weight of the pulp.
  • the pulp will be bleached, for example, with peroxide, the bleaching does not remove the lignin.
  • the paper may be formed from such bleached high yield pulp as the sole pulp component or the bleached high yield pulp may be co-mixed with a chemical pulp, for example, kraft pulp.
  • the high yield pulp will comprise more than 10%, by weight, and preferably more than 50%, more preferably 80% to 100%, by weight, of the pulp component of the paper.
  • Ti0 2 is the most efficient light-scattering pigment commercially available, due to its high refractive index. Thus, it is known in the art that
  • Ti0 2 can be used as a filler, usually together with other pigments such as clay or ground or precipitated calcium carbonate, to improve optical properties such as brightness and opacity.
  • Pigmented coatings in addition to enhancing optical properties, improve surface properties such as gloss, smoothness, color, printing detail, and brilliance.
  • the Ti0 2 may also be employed in pigmented coatings together with clay, calcium carbonate and other pigments.
  • Such coatings can be applied on or off machine with various kinds of equipment including, but not restricted to, blade, rod or airknife coaters, or film coating size presses. Surface application of chemicals and pigments provides close to 100% retention, which reduces wet-end deposits, wear of paper machine clothing and effluent loads.
  • Ti0 2 is a strong absorber of near UV light. Thus, Ti0 2 can stabilize paper brightness by both scattering and absorbing UV light.
  • Ti0 2 occurs in rutile and anatase crystal forms. While both forms have high scattering power and high near UV abso ⁇ tion, the rutile form is preferred in this invention. The rutile form is more stable with regard to outgassing and has a higher near UV absorption.
  • Ti0 2 The behaviour of Ti0 2 is strongly influenced by its average particle size.
  • the current invention exploits both UV absorbing and scattering properties of Ti0 2 .
  • Particle sizes from 0.01 to 1.5 microns are typically employed.
  • Particle sizes ranging from 0.1 to 1.5 microns are preferred due to their better scattering ability, and within this range, particle sizes from 0.16 to 0.28 microns are even more preferred.
  • the Ti0 2 is suitably employed in the paper in an amount of 0.05 to 10%, preferably 0.5 to 15% and more preferably 1 to 10%, by weight based on the oven dry weight of fibre.
  • Radical Scavengers are used in conjunction with the Ti0 2 either in the base sheet or in a coating, to improve the brightness stability of the lignin-containing papers. Both agents show better brightness stability as dosages are increased up to a limiting value. In accordance with the invention it has been found that combining these two agents provides better brightness stability than is possible using either agent alone.
  • Thiols, ascorbate and hindered amine compounds are radical scavengers that have some efficacy at reducing light-induced yellowing.
  • the hindered amine compounds such as described by Seltzer et al., McGarry et al. and Yuan et al. are preferred because of their superior thermal stability and lack of objectionable odor. (Seltzer et al (International publication WO 99/05108) McGarry et al, (J. Pulp Paper Sci., (2000), 26(2), 59-66) and Yuan et al (Proceedings: PAPTAC 87th Annual Meeting, Montreal, 2001, (PAPTAC) C43-C52).
  • pigments comprise as much as 40%, by weight, of total mass of the paper when used as a filler, and up to 50%, by weight, when applied as a coating. It is technically possible to use Ti0 2 as the only pigment. However, preferred methods use Ti0 2 loadings of 0.05% to 50%, more preferably 2 to 30%, by weight of the total pigments. Suitable pigments for use with Ti0 2 in the filler or coating include but are not restricted to clay and ground or precipitated calcium carbonate, as extenders.
  • Ri is selected from hydrogen, hydroxyl, primary, secondary, tertiary or quaternary amino, alkyl, alkoxy, aminoalkyl alkylene oxide of the general formula [-0-(CH2) n ] N where n is 1 to 4 and N is 1 to 20.
  • the alkyl or alkyl moiety in Rj has from 1 to 12 carbons, and may be straight chain or branched.
  • alkyl and alkyl moieties may be unsubstituted or substituted with hydroxyl (OH), carboxyl (COOH) or carboxylate (COO " r M + / c ) groups with M being a metal ion from the 1st, 2nd or 3rd group of the periodic table, or Zn, Cu, Ni or Co; or M is a group N + (R 6 ) 4 where R 6 is alkyl of 1 to 8 carbon atoms or benzyl, and r and z are each integers of 1 , 2 or 3;
  • R 2 and R 3 can be the same or different and are selected from hydrogen, hydroxyl (OH), carboxyl (COOH) or carboxylate (COO " r M * , ) groups with M being a metal ion from the 1st, 2nd or 3rd group of the periodic table, or Zn, Cu, Ni or Co; or M is a group N + (R 6 ) 4 where R 6 is alkyl of 1 to 8 carbon atoms or benzyl, and r and z are each integers of 1 , 2 or 3;
  • Y is oxyl or hydroxyl
  • X is an inorganic or organic anion, such as carbonate, borates, bicarbonate, chloride, bisulfate, sulfate, formate, acetate, citrate, oxalate, ascorbate, phosphonate, phosphate, nitrate, bromide, bisulfite, sulfite, benzoate, tartrate, acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate, polymethacrylate, a carboxylate of nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid or of diethylenetriaminepentaacetic acid, a diethylenetriaminepentamethylenephosphonate, an alkylsulfonate or an arylsulfonate and p is an integer of 1 to 20, preferably
  • an organic ultra violet absorber for example, o-hydroxybenzophenone or o-hydroxyphenylbenzotriazole is employed in addition to the titanium dioxide and the radical scavenger and this is found to further inhibit yellowing.
  • the UVA is suitably employed in an amount of 0.1 to 0.8%, preferably 0.1 to 0.4%, by wt. based on the weight of oven dry fibres.
  • FIG. 1 is a plot demonstrating the relationship between the PC number and the content of Ti0 2 , at different coating weights
  • FIG. 2 is a plot demonstrating the relationship between PC number and content of Ti0 2 at different contents of radical scavenger
  • FIG. 3 is a plot demonstrating the relationship between PC number and content of radical scavenger at different contents of Ti0 2 ;
  • FIG. 4 is a plot demonstrating the relationship between PC number and content of Ti0 2 at a fixed content of radical scavenger;
  • FIG. 5 is a plot demonstrating the relationship between PC number and accelerated exposure to light for different contents of Ti0 2 and Ti0 2 in combination with a radical scavenger in a coating; and FIG. 6 is a plot similar to Fig. 5 but employing the Ti0 2 as filler rather than in a coating.
  • Machine-made papers containing mechanical pulp were coated with pigmented formulations with or without Ti0 2 or a radical scavenger (RS).
  • RS radical scavenger
  • the citric acid salt of 4-hydroxy-2,2,6,6-tetramethyl-N-hydroxypiperidine was used as the radical scavenger.
  • Rutile Ti0 2 slurry was used in the experiments. Two different coating formulations were used. The effect of RS on the yellowing inhibition was tested by inco ⁇ orating the inhibitor as an additive in the formulation. The effect of Ti0 2 was examined by substituting it for a portion of the calcium carbonate in the coating formulations.
  • k and s are the abso ⁇ tion and scattering coefficients of the paper, respectively, and R ⁇ is the ISO brightness expressed as a fractional value.
  • PC number is directly proportional to the chromophores formed during light-induced yellowing. Therefore the smaller the PC number, the less the paper has yellowed.
  • the % of Ti0 2 , RS and UVA is by weight based on the weight of oven dried fibres.
  • the base sheet contained in wt. %, 97% alkaline peroxide bleached mechanical pulp (APMP) pulp and 3% kraft pulp.
  • the pigmented coating color contained, in wt. %, 55% clay, 45% ground calcium carbonate, starch, latex, and coating additives.
  • the initial ISO brightness varied from 74.5% to 81.0% depending on the total coat weight and amount of Ti0 2 inco ⁇ orated in the coating.
  • Figure 1 plots the PC number obtained after 12 days accelerated exposure as a function of Ti0 2 content for coat weights of 4, 9 and 14 g/m 2 /side. These weights correspond approximately to light, medium and heavy coating.
  • the different values of the intercepts for each line show that the clay/calcium carbonate coating itself, in the absence of Ti0 2 , affords some inhibition of yellowing, and that this inhibition improves with increasing coat weight. Adding Ti0 2 at any coat weight further improves the yellowing inhibition. Inhibition improves with increasing Ti0 2 addition up to a maximum between 5% to 6% on fiber. Although yellowing slows, it still occurs at these maximum levels of Ti0 2 .
  • a coated paper as described in Example 1 was prepared with a 9 g/m side coat weight. Samples containing Ti0 2 and the citric acid salt of 4- hydroxy-2,2,6,6-tetramethyl-N-hydroxypiperidine as radical scavenger were tested for light stability.
  • Figure 2 shows the resulting plot of PC number after 12 days accelerated exposure versus the amount of Ti0 2 added. As noted in Example 1 , when Ti0 2 alone is used, yellowing inhibition is maximized at a Ti0 2 content between 5% and 6%. Figure 2 also shows that adding radical scavenger to a coating color containing Ti0 2 enhances the yellowing inhibition. Figure 2 also shows that adding radical scavenger to the coating color improves yellowing inhibition under conditions where no additional benefit can be obtained by increasing the amount of Ti0 2 .
  • Figure 3 shows plots of PC number after 12 days exposure versus the amount of radical scavenger in the coating, at a coating weight of 9g/m 2 and different contents of Ti0 2 .
  • the yellowing inhibition achieved by adding radical scavenger alone reaches a maximum at an application of about 0.5%/side. This maximum level can be improved by including Ti0 2 in the coating.
  • Coated paper as described in Example 1 was prepared with a 14 g/m /side coat weight containing 0.3% of the radical scavenger 4-hydroxy- 2,2,6,6-tetramethyl-N-hydroxypiperidine citrate and various amounts of Ti0 2 .
  • the pigmented formulation consisted of 80% ground calcium carbonate and 20% delaminated clay, starch, latex, and some minor additives. As shown in Figure 5, replacing 12% of the CaC0 3 with Ti0 2 which corresponds to 1.15% Ti0 2 charge on fiber, increased the brightness stability. Doubling the amount of Ti0 2 to 2.3% provided no further improvement in brightness stability. Adding 1.0% of the radical scavenger together with 1.15% Ti0 2 gave a brightness stability better than that possible using Ti0 2 alone.
  • samples containing 0.6% Ti0 2 , 1 % radical scavenger and both 0.6% Ti0 2 and 1 % radical scavenger were irradiated for 12 days.
  • the PC number values are listed in Table 1. The data show that the effect of adding Ti0 2 and radical scavenger together at the indicated levels (smaller increase in PC number) is greater than the sum of their individual effects.
  • Coated paper using a 49 g/m 2 base sheet and 9 g/m 2 /side coating were prepared as described in Example 1.
  • Ti0 2 also improved the paper brightness stability when it was retained in the sheet as filler.
  • the radical scavenger improved the paper brightness stability, but a combination of Ti0 2 and radical scavenger offered much better yellowing inhibition.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

La présente invention permet de rendre des papiers contenant de la lignine stables à la lumière en leur ajoutant du TiO2 en combinaison avec un capteur de radicaux amine à encombrement stérique.
PCT/CA2001/000543 2000-04-19 2001-04-19 Inhibition du jaunissement des papiers WO2001079605A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2001576985A JP2004504500A (ja) 2000-04-19 2001-04-19 紙黄変の阻止
AU2001254542A AU2001254542A1 (en) 2000-04-19 2001-04-19 Inhibition of yellowing in papers
CA002405662A CA2405662A1 (fr) 2000-04-19 2001-04-19 Inhibition du jaunissement des papiers
SE0203040A SE525893C2 (sv) 2000-04-19 2002-10-15 Ljusstabilt lignininnehållande papper, metod för att göra papper ljusstabilt och användning av partikelformig titandioxid tillsammans med radikalomhändertagande för att hämma gulning i papper
NO20024957A NO20024957D0 (no) 2000-04-19 2002-10-15 Inhibering av gulning i papir
FI20021862A FI20021862A (fi) 2000-04-19 2002-10-18 Paperin kellastumisen estäminen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19844700P 2000-04-19 2000-04-19
US60/198,447 2000-04-19

Publications (2)

Publication Number Publication Date
WO2001079605A2 true WO2001079605A2 (fr) 2001-10-25
WO2001079605A3 WO2001079605A3 (fr) 2002-02-28

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PCT/CA2001/000543 WO2001079605A2 (fr) 2000-04-19 2001-04-19 Inhibition du jaunissement des papiers

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JP (1) JP2004504500A (fr)
AU (1) AU2001254542A1 (fr)
CA (1) CA2405662A1 (fr)
FI (1) FI20021862A (fr)
NO (1) NO20024957D0 (fr)
SE (1) SE525893C2 (fr)
WO (1) WO2001079605A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381756A (zh) * 2016-11-16 2017-02-08 中国林业科学研究院林产化学工业研究所 一种基于无机氧化物的抑制高得率浆返黄的加填浆料及其制备与应用
CN115029956A (zh) * 2022-06-10 2022-09-09 万国纸业太阳白卡纸有限公司 一种卡纸及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0280332A1 (fr) * 1987-02-27 1988-08-31 Mo Och Domsjö Aktiebolag Procédé pour la stabilisation du degré de blancheur de la pâte à papier blanchie contenant de la lignine
WO1999005108A1 (fr) * 1997-07-23 1999-02-04 Ciba Specialty Chemicals Holding Inc. Inhibition du jaunissement de pate et de papier via des oxydes nitres et autres co-additifs
US5998119A (en) * 1998-08-27 1999-12-07 Eastman Kodak Company Imaging element with a substrate containing low molecular weight hindered amine stabilizer
GB2340955A (en) * 1998-08-27 2000-03-01 Eastman Kodak Co Photographic support with at least two polymer layers over the support on the image side with a hindered amine stabilizer in at least one layer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0280332A1 (fr) * 1987-02-27 1988-08-31 Mo Och Domsjö Aktiebolag Procédé pour la stabilisation du degré de blancheur de la pâte à papier blanchie contenant de la lignine
WO1999005108A1 (fr) * 1997-07-23 1999-02-04 Ciba Specialty Chemicals Holding Inc. Inhibition du jaunissement de pate et de papier via des oxydes nitres et autres co-additifs
US5998119A (en) * 1998-08-27 1999-12-07 Eastman Kodak Company Imaging element with a substrate containing low molecular weight hindered amine stabilizer
GB2340955A (en) * 1998-08-27 2000-03-01 Eastman Kodak Co Photographic support with at least two polymer layers over the support on the image side with a hindered amine stabilizer in at least one layer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106381756A (zh) * 2016-11-16 2017-02-08 中国林业科学研究院林产化学工业研究所 一种基于无机氧化物的抑制高得率浆返黄的加填浆料及其制备与应用
CN106381756B (zh) * 2016-11-16 2018-02-02 中国林业科学研究院林产化学工业研究所 一种基于无机氧化物的抑制高得率浆返黄的加填浆料及其制备与应用
CN115029956A (zh) * 2022-06-10 2022-09-09 万国纸业太阳白卡纸有限公司 一种卡纸及其制备方法

Also Published As

Publication number Publication date
WO2001079605A3 (fr) 2002-02-28
NO20024957L (no) 2002-10-15
JP2004504500A (ja) 2004-02-12
CA2405662A1 (fr) 2001-10-25
NO20024957D0 (no) 2002-10-15
SE525893C2 (sv) 2005-05-24
SE0203040L (sv) 2002-10-31
SE0203040D0 (sv) 2002-10-15
AU2001254542A1 (en) 2001-10-30
FI20021862A (fi) 2002-10-18

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