US3464886A - Das-triazine brighteners and paper made therewith - Google Patents

Das-triazine brighteners and paper made therewith Download PDF

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Publication number
US3464886A
US3464886A US546166A US3464886DA US3464886A US 3464886 A US3464886 A US 3464886A US 546166 A US546166 A US 546166A US 3464886D A US3464886D A US 3464886DA US 3464886 A US3464886 A US 3464886A
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Prior art keywords
paper
brighteners
solution
mole
compound
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Expired - Lifetime
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US546166A
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English (en)
Inventor
Albert Peter Paul
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.)
Wyeth Holdings LLC
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American Cyanamid Co
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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
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

Definitions

  • This invention relates generally to new brighteners or optical bleaching agents for paper and to an improved method for whitening paper by the use therewith during some stage of its manufacture, and more particularly, it relates to novel, selected bis-triazinylamino-stilbene compounds containing at least one iminobispropionamide radical (or bis-(2-carbamoylethyl) amino group).
  • the prospective brighteners may have other physical deficencies such as poor solubility or dispersibility and the like, tending to cause feathering and so forth.
  • the brighteners of this invention are an improvement over brighteners of related types previously known in the art in that they give distinctive reddish-blue shades of fluorescence which makes paper appear much Whiter. They are strongly fluorescent and give a strong clear whitening effect when applied to cellulose materials and especially when used in connection with paper. They are soluble and stable under acid conditions and can be used throughout the pH range which is standard for paper manufacture. They are especially good at low pH where some other brighteners either break down or show reduced efficacy. They have aflinity for cellulose and are non-yellowing and non-feathering. They are compatible with other paper chemicals, rosin, alum, fillers, softeners, wet strength resins, dyes and the like. They can also be used to brighten or intensitfy the color of dyed papers.
  • These compounds are useful for whitening paper when applied to paper pulp during beater operations and in finishing by tub sizing using a size press or by calendering or coating.
  • the new compounds or brighteners which are the subject matter of this invention can be prepared by reacting in any order of succession, 2 moles of cyanuric chloride with 2 moles of methanol, 1 mole of 4,4-diaminostilbene-2,2'-disulfonic acid or a salt thereof, and 2 moles of an iminobis-propionamide salt.
  • 2 moles of cyanuric chloride are reacted with 1 mole of 4,4-diaminostilbene-2,2'-disulfonic acid or a salt thereof and 4 moles of an iminobispropionamide salt.
  • the methanol if used, should be allowed to react first.
  • the whitening of paper may be achieved by using 0.01 to 2% of the brightener by weight of the paper or paper pulp, but either smaller or greater concentrations may be used to give corresponding lesser or greater brightening effects as desired.
  • the brighteners When the brighteners are used in beater application, a good white is obtained with 0.080.5% of brightener by weight of paper pulp.
  • These novel brighteners can be added before or after the alum. They are compatible with wood rosins, fillers, such as titanium dioxide, barium sulfate, zinc sufide, calcium carbonate, silicon dioxide, starches and clay, with wet strength resins, or with softeners ad dyes. Adjustment of the pH is made with alum normally used on the basis of about 4% by weight of the paper. In conventional practice, the pH of the paper pulp mixture is adjusted to 7, or below, before the paper is formed and finished.
  • the brighteners of this invention may also be used in sizing operations of the paper, such as tub size or size press, in which they may be employed in starch solutions in 0.51% concentration or in other aqueous sizing formulations.
  • the brighteners of this invention may be used in calendering with just the brightener present in water in a concentration of 0.05 to 1% or more.
  • the completed paper is treated with the solution of brightener to produce a clear white paper.
  • the brighteners of this invention may be used in coating paper in the usual aqueous coating formulations which include clay-casein, clay-starch or clay-caseinstarch.
  • the concentration of brightner may be 0.05-03% on the weight of the solids (clay, etc.).
  • the new brighteners of this invention may be converted to methylolated reactive brighteners which can react with cellulose fibers including cotton and paper, as well as other fibers having reactive hydrogen, such as silk, wool and nylon.
  • the brighteners are methylolated in aqueous solution with at least two moles of formaldehyde for each mole of iminobispropionamide group at temperatures of 2090 C., and a pH above neutrality, about pH 7.2 to 10, until methylolation is complete.
  • Such methylol groups remain active if further methylated or acetylated.
  • the methylolated brightener may be applied from an aqueous pad bath at pH 4-7 containing an acid catalyst, such as magnesium or ammonium chloride, ammonium sulfate or triethanolamine hydrochloride, in an amount 10-40% by weight of the brightener.
  • an acid catalyst such as magnesium or ammonium chloride, ammonium sulfate or triethanolamine hydrochloride.
  • the fabric thus padded is dried and cured at 300375 F. until fixation of the dye to the fabric is complete.
  • the fabric is then soaped, rinsed and dried.
  • the brightener is thus chemically linked to the fiber molecules of the fabric.
  • the fabric is brightened.
  • EXAMPLE 2 SO Na To a mixture of 9.30 g. (0.025 mole) of 99.5% 4,4- diamino-stilbene disulfonic acid, 150ml. water, and 50 ml. acetone, there is added, with warming and stirring, 10 ml. (0.05 mole) 5 N sodium hydroxide. The resulting solution is then cooled to 0 C., and a cold solution of 9.23 g. (0.05 mole) cyanuric chloride in 125 ml. acetone added. After stirring 10 minutes at 05 C., the pH is adjusted to about 5 with 16 ml. (0.05 mole) 5 N sodium hydroxide solution. There is then added a solution of 25.73 g.
  • EXAMPLE 3 Beater dyeing of paper pulp To 4 g. bleached sulfite paper pulp in ml. Water is added 0.5 ml. of a 4% solution of alum. The pH is adjusted to 4.5 with 4% alum solution, if necessary.
  • An 0.1% solution of the brightener is added as follows, based on the absorptivity (k) values of the products of Examples 1 and 2, respectively: (a) 3.3 ml. of a 0.1% solution of the product of Example 1 or ('b) 3.5 ml. of a 0.1% solution of the product of Example 2.
  • the pulp mixture is formed into a sheet on a Williams mold, using water adjusted to, pH 4.5.
  • the sheet is pressed at 18-20 lb. per square inch, for 30 seconds. It is dried on a drum dryer at 230240 F., for 5 minutes and conditioned at least 30 minutes at ambient humidity.
  • Each sheet is observed under ultraviolet light, (U.V. light) and the amount of fluorescence and chroma noted.
  • the compounds of Examples 1 and 2 both show strong blue-white fluorescence compared to little or no fluorescence of untreated paper. In addition, both show good chroma.
  • Example 1 Each sheet is then observed under north daylight. Under such light a hue difference is discernible to the trained eye.
  • the sheet of Example 1 is redder than the sheet of Example 2.
  • Both brighteners are redder than the brighteners of the art shown in Table I below. This redness is especially desirable in paper. Both sheets show a 6 clean and bright white compared to untreated paper, What is claimed is: which by contrast appears as a dull yellowish tint. 1.
  • Unsized Mohawk offset paper is coated by uniform 4.
  • a process of brightening paper which comprises drawdown using a No. 12 wire wound equalizer rod.
  • the applying to said paper an aqueous composition containcoated paper is dried at 200 F., for one minute and kept ing a compound of claim 1 and thereafter drying the at constant humidity for one-half hour. paper.
  • Paper consisting of cellulosic fibers containing from Example 1 is very slightly redder than the coating of the 0.001 to 0.1% by Weight of a compound of the formula:
  • Paper according to claim 6 having from 0.001 to brighteners of this invention perform well at pH 5.5 and 1% b i h f the compound wherein R is a methoxy do not have these faults.
  • group A C0IT1PafiI1 0f the P p d y thls Procedure, 8. Paper according to claim 6 having from 0.001 to With tWO P Q CQITIPOImdS slmllafly P p 011 0.1% by weight of the compound wherein both R and R equal k'vallle 1S glven in Table 5 are bis(2-carbamoylethyl) amino groups.

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US546166A 1966-04-29 1966-04-29 Das-triazine brighteners and paper made therewith Expired - Lifetime US3464886A (en)

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US54616666A 1966-04-29 1966-04-29

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US (1) US3464886A (enrdf_load_stackoverflow)
BE (1) BE697789A (enrdf_load_stackoverflow)
NL (1) NL6706055A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892675A (en) * 1973-01-23 1975-07-01 Ici Ltd Coating compositions
US3956283A (en) * 1973-05-22 1976-05-11 Sandoz Ltd. Bis-(triazinylamino)-stillene derivatives

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH508641A (de) * 1968-08-06 1971-06-15 Sandoz Ag Verfahren zur Herstellung neuer fluoreszierender Verbindungen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840557A (en) * 1958-06-24 Oo-nhj
GB814579A (en) * 1956-06-14 1959-06-10 Cassella Farbwerke Mainkur Ag Optical bleaching agents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840557A (en) * 1958-06-24 Oo-nhj
GB814579A (en) * 1956-06-14 1959-06-10 Cassella Farbwerke Mainkur Ag Optical bleaching agents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892675A (en) * 1973-01-23 1975-07-01 Ici Ltd Coating compositions
US3956283A (en) * 1973-05-22 1976-05-11 Sandoz Ltd. Bis-(triazinylamino)-stillene derivatives

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Publication number Publication date
NL6706055A (enrdf_load_stackoverflow) 1967-10-30
BE697789A (enrdf_load_stackoverflow) 1967-10-30

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