EP0600801B1 - Latex-Bindemittel für Papierstreichmasse - Google Patents

Latex-Bindemittel für Papierstreichmasse Download PDF

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Publication number
EP0600801B1
EP0600801B1 EP93402931A EP93402931A EP0600801B1 EP 0600801 B1 EP0600801 B1 EP 0600801B1 EP 93402931 A EP93402931 A EP 93402931A EP 93402931 A EP93402931 A EP 93402931A EP 0600801 B1 EP0600801 B1 EP 0600801B1
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EP
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Prior art keywords
weight
epoxy resin
binder
coating composition
binder according
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Revoked
Application number
EP93402931A
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English (en)
French (fr)
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EP0600801A1 (de
Inventor
Philippe Larraillet
Jean-Pierre Lavallee
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
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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
    • 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
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • 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
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a latex binder for a paper coating composition comprising an aromatic epoxy resin emulsion.
  • composition for coating paper is generally meant an aqueous coating composition essentially containing a filler (pigment), a binder and possibly various adjuvants.
  • Such a composition is applied to the paper in order to modify the surface properties, in particular the whiteness, the gloss, the printability, etc. It is now in common use in the paper industry to use as essentially binding a latex of organic, synthetic, film-forming polymer, in the form of an aqueous emulsion.
  • wet peel resistance is of particular importance.
  • the offset printing process which is based on the repulsion of water by fatty inks, actually uses water. In four-color offset printing, we are therefore led to print the second, third or fourth color in a previously wet location. It is therefore important, in order to avoid the phenomena of peeling in the wet state, which result in fouling of the blanket of the offset presses, that the coated paper has sufficient wet peel resistance.
  • the improvement in the resistance to dry stripping (RAS) and / or wet (RAH) is unfortunately often accompanied by a degradation of the porosity in inks of the layer or a degradation of the storage stability of the binder. or a degradation of the storage stability of the coating composition.
  • the main aim of the present invention is precisely to provide an organic copolymer binder for coating composition giving the coating both a wet and dry peel resistance very improved in combination with good coating porosity and good stability to storage of the binder and the coating composition.
  • emulsion B If the content of emulsion B is less than 0.1%, the expected effect is not obtained in particular at the level of the RAH. If the content of B is greater than 3%, the binder obtained has too great an instability of the viscosity over time (in fact an increase) making it unsuitable for use in a coating composition.
  • the aromatic epoxy resin is preferably chosen from epoxy resins of the bisphenol type, in particular bisphenol A, epoxy resins of the novolak type and their mixtures.
  • Bisphenol A (2,2-bis (4'-hydroxyphenyl) propane) type epoxy resins is the product of the reaction of bisphenol A with epichlorohydrin. These resins are products commercially available in particular under the registered trademarks Epikote (Shell), DER (Dow Chemical), Araldite (Ciba) and ERL (UCC).
  • Novolak type epoxy resins are also commercially available products, in particular under the registered trademarks Epikote, DEN and EPN.
  • aromatic epoxy resins can be emulsified, generally without difficulty, using nonionic surfactants.
  • nonionic surfactants which can be used, mention may be made of polyethers such as polyethylene and / or polypropylene oxides, alkylaromatic ethers of polyethylene and / or polypropylene glycol.
  • Other usable surfactants are the polyoxyalkylene derivatives of hexitol including sorbitans and mannitans, some of which are marketed under the registered trademark "Tween” by Atlas Powder Company.
  • Other usable surfactants are adducts of polyoxyethylene glycol and of glycidyl polyethers of polyhydric phenols. It is recommended according to the invention to use from 1 to 20%, preferably from 3 to 10% by weight of surfactant relative to the weight of aromatic epoxy resin during the aqueous emulsion of said resin.
  • the preferred nonionic surfactants are polyoxyalkylene glycol, the straight or branched alkylene part of which has between 2 and 6 carbon atoms.
  • all or part of the polyoxyalkylene glycol, the straight or branched alkylene part of which comprises between two and six carbon atoms is grafted by means of a covalent bond onto the aromatic epoxy resin.
  • Compounds a) and b) of the epoxy resin may contain other substituents of the alkyl, aryl, sulfonyl and the like type.
  • the preferred compounds b) are bisphenol A (2,2'-bis (4'-hydroxyphenyl) propane) and bis (4-hydroxyphenylmethane).
  • the diglycidyl ethers a) are prepared by reaction of b) with an epoxy containing a halogen according to for example the teaching of patents US-A 2,582,985, US-A 2,615,007 and US-A 2,633,458.
  • the aqueous dispersion of epoxy resin is made stable by the incorporation into the resin of a diglycidyl ether of a polyoxyalkylene glycol.
  • Compound c) is prepared by reacting the epichlorohydrin with a polyoxyalkylene glycol in a molar ratio making it possible to obtain c).
  • the preferred polyoxyalkylene glycols are those prepared by reaction of ethylene oxide and / or propylene oxide with an aliphatic dialcohol such as glycol and having a molecular weight of between 5000 and 10000.
  • the aqueous dispersion B) generally comprises 30 80% dry matter, preferably 50-70%.
  • the epoxy resin in aqueous dispersion in B) preferably has a molecular weight of between 500 and 20,000.
  • this aqueous dispersion also comprises a stabilizing amount of a reactive diluent d) with a content in B) preferably between 1 and 25, preferably 5 to 20%, by weight relative to the weight of dry epoxy resin contained in B).
  • reactive diluents are unsaturated, epoxidized hydrocarbons and glycidyl ethers of C 8 -C 17 aliphatic alcohols such as 2-ethyl hexanol, dodecanol and eicosanol.
  • the emulsion may contain a crosslinking agent preferably chosen from alkylene polyamines such as ethylene diamine and diethylamine diamine and polyaminoamines.
  • a crosslinking agent preferably chosen from alkylene polyamines such as ethylene diamine and diethylamine diamine and polyaminoamines.
  • the presence of such a catalyst is not essential especially in the case where the aqueous latex dispersion comprises a polymer having in its chain organic groups capable of reacting with epoxy groups such as carboxylic groups and amine groups primary and secondary.
  • aqueous dispersions B) of epoxy resin which can be used in the context of the present invention are more particularly described in US Pat. No. 4,315,044 cited as reference.
  • the aqueous dispersion A) film-forming of a styrene / butadiene, styrene / acrylate and styrene / butadiene / acrylate latex copolymer can be any aqueous dispersion of this type known and usable as a binder in coating compositions for paper.
  • the polymerizable base monomers are chosen from, styrene, butadiene and acrylic esters, the copolymer always comprising styrene.
  • the styrene can be replaced in whole or in part by alphamethylstyrene or vinyltoluene.
  • acrylic esters we mean the esters of (meth) acrylic acid with C 1 -C 12 , preferably C 1 - alcohols C 8 such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate ).
  • Latex A is preferably a copolymer based on styrene / 1,3-butadiene. More particularly suitable are copolymers based on 25 to 60% by weight of butadiene, 40 to 75% by weight of styrene and 0 to 6% of ethylenically unsaturated monomers comprising at least one carboxylic acid function and their monoesters with an alkanol in C 1 - C 8 and from 0 to 3% of an ethylenically unsaturated monomer with a sulfate or sulfonate function, in particular metallylsulfonate and sulfoethylmethacrylate.
  • the latex of copolymer A is prepared in a manner known per se by polymerization in aqueous emulsion of butadiene and / or styrene and / or acrylate and optionally of at least one other monomer, in the presence of at least one initiator and d '' at least one emulsifying agent with a mixture concentration of the monomers in the reaction medium generally between 20 and 60% by weight.
  • the monomers used can be introduced as a mixture or separately and simultaneously into the reaction medium, either before the start of polymerization in one go, or during polymerization by successive fractions or continuously.
  • the conventional anionic agents are used, represented in particular by fatty acid salts, alkylsulfates, alkylsulfonates, arylsulfates, arylsulfonates, alkylarylsulfates, alkylarylsulfonates, sulfosuccinates, alkylphosphates alkaline, salts of abietic acid, hydrogenated or not. They are used in an amount of 0.01 to 5% by weight relative to the total weight of the monomers.
  • the initiator which is water-soluble, is more particularly represented by hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and by persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate. It is used in amounts of between 0.05 and 2% by weight relative to the total of the monomers.
  • a reducing agent such as sodium bisulfite or formaldehyde sulfoxylate, polyethyleneamines, sugars: dextrose, sucrose, metal salts.
  • the amounts of reducing agent used vary from 0 to 3% by weight relative to the total weight of the monomers.
  • the reaction temperature is generally between 0 and 100 ° C, and preferably between 30 and 70 ° C.
  • the transfer agent used in proportions ranging from 0 to 3% by weight relative to the monomer (s) is generally chosen from mercaptans such as N-dodecylmercaptan, tertiododecylmercaptan cyclohexene: halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride. It makes it possible to adjust the proportion of grafted polymer and the length of the grafted molecular chains. It is added to the reaction medium either before the polymerization, or during polymerization.
  • the latexes thus obtained can be used in particular as binders for the preparation of aqueous compositions for coating paper and more particularly paper for offset printing.
  • the binder according to the invention it is recommended to adjust the pH of the dispersion A) of latex and the emulsion B) of epoxy resin to a similar value before mixing, this value being preferably less than 7, preferably less than 6.
  • pigments are mixed with the binder and various additives are added.
  • the most commonly used pigment is mineral clay such as kaolin. It is also possible to use, alone or as a mixture with mineral clay, other pigments such as calcium carbonate, titanium oxide, white satin, hydrargillite, talc, barium sulphate and plaster.
  • These pigments are dispersed in water, generally in an alkaline medium and in the presence of dispersing agents, the most important of which are tetrasodium pyrophosphate, sodium hexametaphosphate, low molecular weight polyacrylates at levels between 0, 2 and 0.5% by weight relative to the pigments. These pigments are fixed to the paper by means of binders.
  • aqueous latexes of a synthetic polymer have already been proposed, used either alone or in admixture with natural binders such as starches, proteins, casein, or synthetics such as polyvinyl alcohols. It is also possible to associate with latex products capable of improving the water retention properties of coating compositions such as carboxymethylcelluloses or alginates, or a latex of an alkali-swelling or alkali-soluble polymer.
  • pigment at least 40% by weight of calcium carbonate Ca CO 3 relative to the total weight of pigment used.
  • the rest of the pigment is then chosen from the mineral pigments usually chosen for coating and, in particular, those mentioned above.
  • Preferably all the pigment consists of crushed Ca CO 3 and / or precipitation. It has indeed been surprisingly found that the beneficial effect of the use of an epoxy resin emulsion is even greater, in particular at the level of the RAH, in the case of the use of Ca CO 3 .
  • the coating compositions may finally contain other various ingredients such as in particular crosslinking agents, anti-foaming agents, slip agents, optical brighteners.
  • the coating of the paper using the coating compositions according to the invention is carried out by means of a bedding machine according to various techniques using various devices among which mention may be made of those known industrially under the following names: the blade d , the size press, the Champion coater, the roller coater, the trailing blade and the rotary bar. After coating, the paper undergoes a drying operation generally followed by a calendering operation.
  • the present invention therefore also relates to a process for coating paper, characterized in that at least one of the two faces of the paper is coated with 5 to 30 g / m 2 of coating composition according to the invention.
  • the mixture is heated to about 60 ° C for the duration of the reaction (about 12 h).
  • the conversion rate is around 98%.
  • the procedure is exactly as for A1 except that 1.5 parts of tert-dodecylmercaptan and 0.25 parts of ammonium lauryl sulfate are used.
  • the latex dispersion A2 thus obtained has the same properties as A1 except that the viscosity is 120 mPa.s and the average diameter of the joints is 170 nm.
  • the mixture is heated to 60 ° C during the reaction.
  • the conversion rate is around 97%.
  • the epoxy resin emulsion based on bisphenol A is used, sold by the company Hi-Tek Polymers: Louisville, USA under the trade name CMD W 60-3515.
  • This emulsion epoxy resin is the addition product of bisphenol A glycidyl ether, bisphenol A and diglycidyl ether of a copolymer of ethylene oxide and propylene oxide.
  • a mixture of 98% latex A1, A2 and A3 prepared under a) above is carried out in a propeller mixer at room temperature with 2% of emulsion B (B1, B2, B3 and B4 of epoxy resin defined under b ) above), the percentages being calculated on the basis of the weight of the dry extracts of A and B to assess the stability of the binder L 1 thus obtained, its viscosity is measured at time 0, at 2 days, 30 days and 78 days (Brooklfield viscosity at 50 rpm at 20 ° C). The results are collated in Table 1 below:
  • a control coating composition C1 (0) is prepared having exactly the same composition as C1 except that L1 (n) is replaced by dispersion A1 prepared in point a) above.
  • a layer of 20 g / m2, expressed as dry matter, is applied using an air layer coater, on one side of a 50 g / m2 SIBILLE® paper, on a DIPROMA® coating machine. .
  • the coated paper is dried in a tunnel oven at a temperature of 120 ° C and then undergoes calendering consisting of 8 successive passes between 2 cylinders under a force of 30 KN per meter.
  • the RAH is determined using a PRUFBAU® press under a printing force of 0.8 KN at a speed V of 0.5 m / s.
  • the IGT press was developed by the "Institut von Grafischetechnik” in Amsterdam (Netherlands).
  • optical density O.D.
  • composition of the coating bath and the properties of the coated papers are collated in Table 2 below.
  • control coating composition C2 (0) is the same as C1 (0) described in Example 1.
  • Example 2 To prepare C2, the procedure of Example 1 is followed except that a binder L2 is used which is a mixture of dispersion A1 with 2% (calculated as dry) of emulsion B2. The paper is coated and the properties of the coated papers are measured as described in Example 1 above. The results are collated in Table 3 below.
  • Composition C3 is prepared like compositions C1 or C2 except that one starts from the binder L3 which is a mixture of dispersion A2 with the emulsion B1.We also prepare a control coating composition C3 (0) having exactly the same composition as C3 , except that the binder is only formed by the dispersion A2 prepared in point a2) of Example 1 above.
  • compositions C3 and C3 (0) the paper is coated and the properties of the coated papers are measured as described in Example 1 above.
  • Example 2 The procedure is as in Example 1 except that a mixture of A2 with 2% of B2 is used as binder L4.
  • the control composition C4 (0) has as binder only A2.
  • Table 5 The results are collated in Table 5 below.
  • Example 2 The procedure is as in Example 1, except that one starts from a binder which is a mixture of dispersion A3 with emulsion B1 or B2.
  • the control composition C5 (0) has as a binder only A3.

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  • Chemical Kinetics & Catalysis (AREA)
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Claims (16)

  1. Bindemittel für eine Zusammensetzung zum Beschichten von Papier, dadurch gekennzeichnet, daß sie umfaßt:
    A) 97 bis 99,9%, vorzugsweise 97,5 bis 99,5% (berechnet auf Basis des Gewichts des Trockenauszugs) einer wäßrigen filmbildenden Dispersion eines Latex eines organischen Copolymers, ausgewählt aus einem Styrol/Butadien-, StyroVAcrylat- und Styrol/Butadien/Acrylat-Copolymer,
    B) 3 bis 0,1%, vorzugsweise 2,5 bis 0,5% (berechnet aufBasis des Gewichts des Trockenauszugs) einer wäßrigen Emulsion eines aromatischen Epoxyharzes und eines nichtionischen oberflächenaktiven Mittels.
  2. Bindemittel nach Anspruch 1,
    dadurch gekennzeichnet, daß das aromatische Epoxyharz aus den Epoxyharzen vom Bisphenoltyp, den Epoxyharzen vom Novolaktyp und deren Mischungen ausgewählt wird.
  3. Bindemittel nach Anspruch 1 oder 2,
    dadurch gekennzeichnet, daß die oberflächenaktiven Mittel der Emulsion B Polyoxyalkylenglykole sind, bei denen der geradkettige oder verzweigtkettige Alkylenbestandteil 2 bis 6 Kohlenstoffatome enthält, wobei die Gesamtheit oder ein Teil dieser Mittel auf das aromatische Epoxyharz gepfropft ist.
  4. Bindemittel nach einem der Ansprüche 1 bis 3,
    dadurch gekennzeichnet, daß das Epoxyharz eine Masse an Epoxyäquivalent zwischen 160 und 2000, vorzugsweise zwischen 180 und 300 hat.
  5. Bindemittel nach einem der Ansprüche 1 bis 4,
    dadurch gekennzeichnet, daß das Epoxyharz der Emulsion B ein selbstemulgierendes Epoxyharz ist, das das Additionsprodukt von Reaktionspartnern ist, die umfassen:
    a) einen Diglycidylether eines phenolischen dihydroxylierten Derivats,
    b) ein phenolisches dihydroxyliertes Derivat,
    c) einen Diglycidylether eines Polyoxyalkylenglykols.
  6. Bindemittel nach Anspruch 5,
    dadurch gekennzeichnet, daß das Epoxyharz das Additionsprodukt ist von:
    40 bis 90 Gewichtsteilen a),
    3 bis 35 Gewichtsteilen b) und
    1 bis 25 Gewichtsteilen c).
  7. Bindemittel nach Anspruch 5 oder 6,
    dadurch gekennzeichnet, daß die Verbindung b) aus Bisphenol A und Bis-(4-hydroxyphenylmethan) ausgewählt wird.
  8. Bindemittel nach einem der Ansprüche 5 bis 7,
    dadurch gekennzeichnet, daß die Verbindung c) das Produkt der Reaktion von Epichlorhydrin mit einem Polyoxyalkylenglykol mit einem Molekulargewicht zwischen 5000 und 10000 ist.
  9. Bindemittel nach einem der vorangegangenen Ansprüche,
    dadurch gekennzeichnet, daß die wäßrige Dispersion B) 30 bis 80% Trockensubstanz umfaßt.
  10. Bindemittel nach einem der Ansprüche 5 bis 8,
    dadurch gekennzeichnet, daß das Epoxyharz ein Molekulargewicht zwischen 500 und 20000 hat.
  11. Bindemittel nach einem der vorangegangenen Ansprüche,
    dadurch gekennzeichnet, daß die wäßrige Dispersion B) darüberhinaus 1 bis 25 Gew.-%, bezogen auf das Gewicht des trockenen Epoxyharzes, eines reaktiven Verdünnungsmittels, ausgewählt aus den epoxidierten Kohlenwasserstoffen und den Glycidylethern aliphatischer C8-C17-Alkohole, enthält.
  12. Bindemittel nach einem der vorangegangenen Ansprüche,
    dadurch gekennzeichnet, daß das Latex-Copolymer aus der Copolymerisation von:
    - 25 bis 60 Gew.-% Butadien,
    - 40 bis 75 Gew.-% Styrol,
    - 0 bis 6 % mindestens eines Monomers, ausgewählt aus den Monomeren mit ethylenischer Ungesättigtheit, die mindestens eine carboxylische Säurefunktion tragen, und deren Monoestern mit einem C1-C8-Alkanol,
    - 0 bis 3 % eines Monomers mit ethylenischer Ungesättigtheit und mit einer Sulfat- oder Sulfonatfunktion, insbesondere Methallylsulfonat und Sulfoethylmethacylat resultiert.
  13. Beschichtungszusammensetzung für Papier, die übliche Pigmente und übliche Zusatzstoffe enthält,
    dadurch gekennzeichnet,
    daß sie als Bindemittel ein Bindemittel, wie in einem der Ansprüche 1 bis 11 definiert, enthält.
  14. Beschichtungszusammensetzung nach Anspruch 13,
    dadurch gekennzeichnet, daß mindestens 40 Gew.-% des Pigments aus Calciumcarbonat bestehen.
  15. Beschichtungszusammensetzung,
    dadurch gekennzeichnet, daß sie 100 Gewichtsteile Pigment, 5 bis 25 Gewichtsteile Bindemittel, wie in einem der Ansprüche 1 bis 12 definiert, 1 bis 10 Gewichtsteile Zusatzstoffe enthält.
  16. Verfahren zum Beschichten von Papier,
    dadurch gekennzeichnet, daß man mindestens eine der Seiten des Papiers mit einer Beschichtungszusammensetzung, wie in einem der Ansprüche 13 bis 15 definiert, entsprechend einer Menge von 5 bis 30 g/m2 je Papierseite bestreicht.
EP93402931A 1992-12-04 1993-12-03 Latex-Bindemittel für Papierstreichmasse Revoked EP0600801B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9214621A FR2698892B1 (fr) 1992-12-04 1992-12-04 Liant latex composition pour couchage de papier.
FR9214621 1992-12-04

Publications (2)

Publication Number Publication Date
EP0600801A1 EP0600801A1 (de) 1994-06-08
EP0600801B1 true EP0600801B1 (de) 1997-03-12

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ID=9436233

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Application Number Title Priority Date Filing Date
EP93402931A Revoked EP0600801B1 (de) 1992-12-04 1993-12-03 Latex-Bindemittel für Papierstreichmasse

Country Status (5)

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EP (1) EP0600801B1 (de)
AT (1) ATE150117T1 (de)
BR (1) BR9304959A (de)
DE (1) DE69308766T2 (de)
FR (1) FR2698892B1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004505154A (ja) * 2000-08-01 2004-02-19 アンセル・ヘルスケア・プロダクツ・インコーポレーテッド ゴム手袋用新規コーティング
US6884468B1 (en) 2003-10-27 2005-04-26 Basf Ag Method of making a paper coating using a blend of a vinyl aromatic-acrylic polymer dispersion with a vinyl aromatic-diene polymer dispersion
WO2013061286A1 (en) * 2011-10-27 2013-05-02 Basf Se Paper coating compositions comprising a polymer dispersion from room temperature liquid and gaseous monomers

Also Published As

Publication number Publication date
DE69308766T2 (de) 1997-07-31
EP0600801A1 (de) 1994-06-08
BR9304959A (pt) 1994-07-05
FR2698892A1 (fr) 1994-06-10
FR2698892B1 (fr) 1995-01-20
DE69308766D1 (de) 1997-04-17
ATE150117T1 (de) 1997-03-15

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