EP0232196B1 - Latex de diuréthanne comme agent de collage en industrie papetière, son procédé de fabrication - Google Patents

Latex de diuréthanne comme agent de collage en industrie papetière, son procédé de fabrication Download PDF

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Publication number
EP0232196B1
EP0232196B1 EP87400086A EP87400086A EP0232196B1 EP 0232196 B1 EP0232196 B1 EP 0232196B1 EP 87400086 A EP87400086 A EP 87400086A EP 87400086 A EP87400086 A EP 87400086A EP 0232196 B1 EP0232196 B1 EP 0232196B1
Authority
EP
European Patent Office
Prior art keywords
diurethane
latex
solvent
process according
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87400086A
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German (de)
English (en)
French (fr)
Other versions
EP0232196A1 (fr
Inventor
Catherine Beuzelin
Claude Senez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
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 Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT87400086T priority Critical patent/ATE46377T1/de
Publication of EP0232196A1 publication Critical patent/EP0232196A1/fr
Application granted granted Critical
Publication of EP0232196B1 publication Critical patent/EP0232196B1/fr
Expired legal-status Critical Current

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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
    • 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

Definitions

  • the present invention relates to a new agent for bonding in the paper industry, more particularly paper and cardboard, consisting of a cationic diurethane dispersed in an aqueous medium, in the form of latex, and its preparation process.
  • Cationic urethanes used as bonding agents for the paper industry, are already the subject of patents. They are always polyurethanes or cationic oligourethanes. It is for example known to prepare a quaternary ammonium compound, from an NCO-terminated prepolymer, obtained by addition of a polyisocyanate on an aliphatic dihydroxylated monomer compound, elongated by an aliphatic diol containing a salifiable tertiary nitrogen and / or quaternizable. This is the case, for example, of French patent n ° 2 256 937.
  • shorter molecules namely diurethanes, used in the form of latex
  • Bonding of the paper in the mass consists in incorporating during the formation of the sheet, organic products intended to reduce or even eliminate the hydrophilicity of the papers to make them suitable for printing and writing.
  • the invention therefore relates to products for bonding paper, consisting of diurethanes carrying quaternary ammonium groups, capable of adsorbing on the cellulose fiber, and thus made water-dispersible to form a latex ready for use.
  • This cationic diurethane comprises at least one aliphatic chain of at least 7 carbons, giving a hydrophobic character specific to the effectiveness of the bonding.
  • the invention further comprises the process for obtaining these latexes from toluene diisocyanate or diphenylmethane diisocyanate and N-dialkylalkanolamines.
  • the invention thus comprises a method for bonding paper and cardboard, characterized in that these bonding products can be used in a neutral medium. It is understood that the term bonding relates as well to a bonding in the mass as a bonding to the surface.
  • the diurethanes used according to the invention are reaction products of an organic polyisocyanate, in this case toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), with two identical or different N-dialkylalkanolamines, at least one of the alkanolamines being N substituted by at least one aliphatic chain comprising at least 7 carbon atoms and preferably at least 14 carbon atoms.
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • the N-dialkylalkanolamine is preferably modified to quaternary ammonium before reacting with the polyisocyanate, but the timing of the quaternization of the tertiary N-dialkylalkanolamine does not affect the level of effectiveness of diurethane as a bonding agent for paper.
  • the quaternization rate is such that the diurethane can be self-dispersing, without however altering the hydrophobic power of the product.
  • the products of the invention are therefore cationic diurethanes, having a hydrophobic power, dispersible in water, to form stable latexes capable of adsorbing on the cellulose fibers and therefore usable for the bonding of paper.
  • the diisocyanates of 2 - 4 or 2 - 6 of toluene, as well as their mixture (TDI), and the diphenylmethane diisocyanate (MDI) are used as polyisocyanates.
  • N-dialkylalkanolamines organic compounds containing two aliphatic chains each linked to nitrogen and a hydroxy group also linked to nitrogen by a linear or branched aliphatic chain comprising 2 to 4 carbons, or by a polyoxyalkylene chain of degree polycondensation between 1 and 4.
  • N-dialkylalkanolamines being used according to the invention it is necessary that at least one of the two aliphatic chains of at least one of these N-dialkylalkanolamines is not too short, because it is not possible under the conditions of the invention, by reaction of two N-dialkylalkanolamines with short chains with TDI or MDI, according to the operating method described below, to obtain latexes effective for bonding paper. It is however not excluded to use the same N-dialkylalkanolamine having at least one aliphatic chain at C, minimum.
  • Suitable quaternizing agents are in principle all quaternizing substances. Mention will preferably be made of compounds containing an activated halogen such as, for example, chloride, bromide or methyl iodide, benzyl chloride, allyl chloride, or else epichlorohydrin or active esters such as for example sulfate dimethyl.
  • the reaction between the polyisocyanate, in this case TDI or MDI, and the optionally quaternized N-dialkylalkanolamine (s), can be carried out in the solvent phase, or in the absence of solvent, depending on the nature of the diurethane, symmetrical or asymmetrical, desired.
  • the solvents used When the reaction takes place in an organic solvent medium, the solvents used must not contain active hydrogen atoms capable of reacting with the isocyanate groups.
  • the solvents used must also have a low boiling point, so that they can be easily removed from the final latex. These solvents must also facilitate the dispersion of the dimer in water.
  • the reaction can be accelerated using various catalysts such as organometallic compounds such as, for example, stannous octanoate, lead octanoate or dibutyltin dilaurate.
  • organometallic compounds such as, for example, stannous octanoate, lead octanoate or dibutyltin dilaurate.
  • the quaternization of N-dialkylalkanolamine is carried out between 25 ° C and 100 ° C by an appropriate quaternizing agent, defined above.
  • the quaternization rate is preferably between 10 and 50% relative to the quaternizable nitrogen. Too high a quaternization affects the effectiveness of the final product since it contributes to exaggerating its hydrophilic nature. Too little quaternization does not allow the adduct to be dispersed correctly. It is noted that dimethyl sulfate is one of the most suitable quaternizing agents since its action is very rapid.
  • the partially quaternized final diurethane can be produced from a mixture of two diurethanes, one partially or not cationized, the other partially or 100% quaternized, in a ratio such that the desired final quaternization rate is obtained. . It is also possible to directly obtain the desired cationicity rate by quaternizing the number of tertiary nitrogen required for the N-dialkylalkanolamine (s).
  • the symmetrical diurethane carrying quaternized nitrogen atoms is generally obtained with stirring by progressive addition of TDI or MDI to the quaternized N-dialkylalkanolamine diluted or not in a solvent organic, in the presence or absence of a catalyst.
  • the dilution is such that a dry extract of the diurethane of between 20 and 75% is obtained; the addition reaction being exothermic, the temperature is limited by the reflux of the solvent.
  • the asymmetric diurethane is more generally obtained, with stirring, by slow addition of one of the two dialkylalkanolamines, diluted in an organic solvent, on the polyisocyanate, preferably in an organic solvent medium.
  • the other dialkylalkanolamine is then added more quickly.
  • the final diurethane is obtained by mixing two diurethanes, for example one weakly or not quaternized, the other strongly or 100% cationic, it is preferable to work in a solvent medium to carry out the synthesis of the two diurethanes.
  • the desired cationicity level is obtained by direct quaternization of the tertiary nitrogen, it is not necessary to work in a solvent medium, provided that this cationicity rate does not exceed 30%.
  • the organic solution of cationic diurethane is emulsified in water.
  • the cationic diurethane is advantageously diluted in an appropriate solvent, such as methylene chloride or ethyl acetate, so as to have a dry extract. between 20 and 60%.
  • an appropriate solvent such as methylene chloride or ethyl acetate
  • the emulsion in water of the diurethane, in solution in the solvent is facilitated by the use of a third solvent.
  • the purpose of this solvent is to homogenize all of the three constituents of the mixture: the diurethane, the solubilizing solvent and the water. For example, the association of acetone with methylene chloride, two solvents whose behavior is completely opposite with respect to water, favors obtaining fine and stable dispersions.
  • the quantity of third solvent necessary for optimizing the fineness of the dispersion is a function of the quantity of solvent in which the diurethane is dissolved.
  • the particle size is greater than 0.4 lm I, which leads eventually to settling phenomena.
  • the amount of water required for dispersing must be above a threshold, determined by the total amount of solvents, below which it is impossible to obtain a stable and effective latex.
  • the mixing of the aqueous phase and the organic phase, in the presence of a third solvent can be carried out by means of a conventional mixing device with high shearing power and making it possible to work under high pressures.
  • the procedure is preferably carried out as follows: the diurethane previously dissolved in an appropriate organic medium, ethyl acetate being one of the preferred solvents, is put into aqueous emulsion by means of a homogenizer; the use of a third solvent is not excluded. The solvent (s) are then removed by distillation.
  • cationic diurethane latexes are obtained with dry matter contents varying from 7 to 30% by weight.
  • the particle size does not generally exceed 0.2 ⁇ m, which gives the latex excellent stability.
  • aqueous dispersion of the diurethane is carried out using either an ultrasonic probe or a homogenizer with high shearing action operating under pressure from 400 to 700 bars.
  • a latex is obtained, the dry matter content of which is 9.2% by weight and the particle size of 0.15 ⁇ m.
  • Example 4 Using the same equipment as in Example 4, to 71 parts of an ethyl acetate solution containing 55% by weight of toluene diisocyanate, 216 parts of a CH 3 CO 2 C solution are added very slowly 2 H 5 containing 35% by weight of methylstearylaminomethyl-1-ethanol quaternized at 17%. Then 94.1 parts of didodecylethanolamine having the same cationicity rate as the first disubstituted alkanolamine, diluted in 120 parts of ethyl acetate, are introduced more quickly.
  • Example 2 The procedure is as in Example 2, replacing the distearylethanolamine by a dialkylethanolamine derived from coconut oil and having fatty chains in C l o (10%), C 12 (45%), C 14 (16 - 20%) , C 16 (10-20%), C 18 (15%).
  • this cationic diurethane solution To 25 parts of this cationic diurethane solution, 55 parts of acetone are added. The mixture is emulsified in 150 parts of water, with an ultrasonic probe. After removing the solvents, the latex contains 8.7% by weight of dry matter and the particle size is 0.13 ⁇ m.
  • the product is put into aqueous dispersion, in the absence of solvent, using a homogenizer.
  • a latex is obtained, the dry matter content of which is 12.3% by weight and the particle size of which is 0.3 ⁇ m.
  • diurethane To 25 parts of diurethane is added 37.5 parts of ethyl acetate. 180 parts of water are then added and the mixture is emulsified using an ultrosonic probe. After removal of the solvents by distillation, a 20% quaternized diurethane latex is obtained, the dry matter content of which is 11.8% by weight and the particle size of which is 0.14 ⁇ m.
  • ethyl acetate To 40 parts of the cationic diurethane thus obtained, 50 parts of ethyl acetate are added. This mixture is then emulsified in 300 parts of water, using a homogenizer. After removing the solvent by distillation, a latex is obtained, the dry matter content of which is 11.3% by weight and the particle size of which is 0.1 ⁇ m.
  • the product is put into aqueous dispersion, in the absence of solvent, using a homogenizer.
  • a latex is obtained, the dry matter content of which is 12.3% by weight and the particle size of which is 0.35 ⁇ m.
  • the COBB is determined in accordance with standard AFNOR Q 03.018. According to this standard, the quantity of water that can be absorbed by paper or cardboard during a given time is determined. The weight of water retained per unit area is measured for a fixed period. The lower the water absorption, the better the bonding effect.
  • the COBB determination is carried out on a circular sample of 100 cm 2 of surface. The contact time between the water and the paper sample is 50 seconds (COBB 60 ).
  • the level of bonding agent is given as a percentage. by weight of active substance compared to dry pulp.
  • tests 1 to 6 and tests 7 to 14 Two series of tests (tests 1 to 6 and tests 7 to 14) are carried out to determine the properties of the latexes prepared in the examples and used as agents for bonding paper in the mass, in neutral medium .
  • a 65 g / m 2 paper is prepared, under conditions akin to industrial manufacture, from a pulp of long fiber cellulose bleached and refined at 24 ° SR at which the bonding agent is added at different rates. Paper fillers such as calcium carbonate and retention agents are optionally introduced into the pulp. Forms of paper are drawn on the laboratory machine, known under the name of "Formette Franck", dried under vacuum at 90 ° C for 5 minutes then passed in the oven for 45 min at 130 ° C. The determination of COBB 60 is carried out 3 hours after placing in ambient atmosphere. The particular conditions of each test are given below.
  • the latex prepared according to the method of Example 1, is introduced into the pulp diluted in demineralized water (8 g of cellulose per liter of water), in the absence of any paper filler at the dose of 0, 5% by weight of dry diurethane relative to the dry paste.
  • the latex is introduced, prepared according to the method of Example 1, at a dose of 0.8% of dry diurethane compared to dry paste.
  • a cationic starch corn wax is also added at a dose of 0.3%, always compared to the dry paste.
  • the latex prepared according to the method of Example 2 is introduced, at a dose of 0.3% of diurethane dry compared to the dry pulp, as well as a cationic starch at a dose of 0.3% and a moderately cationic polyacrylamide, commonly used in the paper industry, at a dose of 0.03%.
  • the latex prepared according to the method of Example 4 is introduced, at a dose of 0.5% dry diurethane relative to the dry paste, as well as a starch and a polyacrylamide both cationic, respectively at the dose of 0.25% and 0.04% relative to the dry paste.
  • diluted paste having the same composition as that of test n ° 3, 0.8% of latex prepared according to the method of example 5 is introduced, as well as the two retention agents used in test n ° 3, at a dose of 0.3% and 0.03% respectively.
  • the latex prepared according to the method of Example 6 is introduced, at a dose of 1% dry diurethane relative to the dry paste, as well as a cationic corn wax at a dose of 0.28% and a polyacrylamide modified at a dose of 0.03%.

Landscapes

  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Indole Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP87400086A 1986-01-24 1987-01-15 Latex de diuréthanne comme agent de collage en industrie papetière, son procédé de fabrication Expired EP0232196B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87400086T ATE46377T1 (de) 1986-01-24 1987-01-15 Diurethan-latex als leimungsmittel in der papierindustrie und dessen herstellungsverfahren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8600997A FR2593839B1 (fr) 1986-01-24 1986-01-24 Latex de diurethanne comme agent de collage en industrie papetiere, son procede de fabrication
FR8600997 1986-01-24

Publications (2)

Publication Number Publication Date
EP0232196A1 EP0232196A1 (fr) 1987-08-12
EP0232196B1 true EP0232196B1 (fr) 1989-09-13

Family

ID=9331449

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87400086A Expired EP0232196B1 (fr) 1986-01-24 1987-01-15 Latex de diuréthanne comme agent de collage en industrie papetière, son procédé de fabrication

Country Status (12)

Country Link
US (2) US4786330A (th)
EP (1) EP0232196B1 (th)
JP (1) JPS62177298A (th)
AT (1) ATE46377T1 (th)
CA (1) CA1263489A (th)
DE (1) DE3760562D1 (th)
ES (1) ES2012084B3 (th)
FI (1) FI870305A7 (th)
FR (1) FR2593839B1 (th)
GR (1) GR3000184T3 (th)
NO (1) NO865129L (th)
PT (1) PT84192B (th)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4211480A1 (de) * 1992-04-06 1993-10-07 Bayer Ag Verfahren zur Naßverfestigung von Papier
ES2098602T5 (es) * 1992-08-07 2000-12-01 Bayer Ag Resinas multifuncionales exentas de cloro para el acabado del papel.
US5736008A (en) * 1993-04-08 1998-04-07 Congoleum Corporation Fibrous-reinforced sheet
US5512618A (en) * 1993-05-07 1996-04-30 Enviro-Chem, Inc. Suspension-enhancing adhesive additive for paper manufacturing, liquid adhesive composition using same, and method of preparing liquid adhesive composition
DE19516405A1 (de) * 1995-05-04 1996-11-07 Bayer Ag Verfahren zur Herstellung strukturfester Papiere
WO1996036432A1 (en) * 1995-05-17 1996-11-21 Betzdearborn Inc. Post-treatment process and product
US8647471B2 (en) * 2010-12-22 2014-02-11 Bayer Materialscience Llc Process for the production of sized and/or wet-strength papers, paperboards and cardboards

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1164190A (fr) * 1953-06-23 1958-10-07 Chemie Linz Ag Procédé de production d'esters de l'acide polyméthylène-, ou phénylène-bis-carbamique
US2878279A (en) * 1953-06-23 1959-03-17 Oesterreischische Stickstoffwe Process of making bis-carbamic acid ester compounds
NL104700C (th) * 1955-08-12
US3081310A (en) * 1956-12-24 1963-03-12 Searle & Co Bis(aminoalkylcarbamates)
US3873484A (en) * 1972-12-06 1975-03-25 Whitco Chemical Corp Latex of quaternized polyether-dialkanolamine polyisocyanate prepolymer chain extended with water with ethoxylated phenol, and cured products
DE2537653B2 (de) * 1975-08-23 1977-10-27 Bayer Ag, 5090 Leverkusen Papierleimungsmittel und verfahren zur papierleimung
FR2565267B1 (fr) * 1984-06-05 1987-10-23 Atochem Latex de polyurethanne comme agent de collage en industrie papetiere, son procede de fabrication

Also Published As

Publication number Publication date
PT84192B (pt) 1989-09-14
FI870305A0 (fi) 1987-01-23
EP0232196A1 (fr) 1987-08-12
JPH0372759B2 (th) 1991-11-19
NO865129L (no) 1987-07-27
GR3000184T3 (en) 1990-12-31
US4892620A (en) 1990-01-09
PT84192A (fr) 1987-02-01
NO865129D0 (no) 1986-12-17
FR2593839A1 (fr) 1987-08-07
ES2012084B3 (es) 1990-03-01
CA1263489A (fr) 1989-11-28
FI870305A7 (fi) 1987-07-25
US4786330A (en) 1988-11-22
JPS62177298A (ja) 1987-08-04
ATE46377T1 (de) 1989-09-15
FR2593839B1 (fr) 1988-04-29
DE3760562D1 (en) 1989-10-19

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