US3869311A - Application of precipitates of methylene-ureas and products obtained - Google Patents

Application of precipitates of methylene-ureas and products obtained Download PDF

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Publication number
US3869311A
US3869311A US4137470A US3869311A US 3869311 A US3869311 A US 3869311A US 4137470 A US4137470 A US 4137470A US 3869311 A US3869311 A US 3869311A
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US
United States
Prior art keywords
paper
precipitate
urea
methylene
base
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Expired - Lifetime
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English (en)
Inventor
Guy Jacquelin
Solange Sangenis
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.)
Centre Technique de lIndustrie des Papiers Cartons et Celluloses
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Centre Technique de lIndustrie des Papiers Cartons et Celluloses
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    • 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
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/42—Coatings with pigments characterised by the pigments at least partly organic
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/50—Acyclic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • N 41,374 1 pp 0 A method of manufacture from a pre-determmed material, especially of a synthetic or fibrous type, of a 1 g" Appllcatlon y Data material, in particular a paper for reproduction, which June 3, 1969 France 69.18236 Combines superior qualities of whiteness, opacity, thermal stability, insolubility and lightness, said [52] US. Cl. 117/155 L, 117/33.5 T, 117/154 method consisting ofloading said material, throughout [51] Int.
  • the present invention relates to a method of preparation, from a pre-determined material, in particular synthetic or fibrous, of a substance which combines high qualities of whiteness, opacity in the visible spectrum, transparency to ultra-violet rays, stability to light and heat, insolubility and lightness. This method is more particularly intended to be applied to the manufacture of special papers: paper for reproduction, printing, absorbent papers.
  • the invention also relates to a material, in particular a paper, obtained by the above-mentioned method.
  • the condensation products of urea and formaldehyde have formed the subject of numerous studies, and theindustrial products manufactured from these reactants are also numerous: according to the relative proportions of urea and formol, and the conditions of reaction, there are obtained resins for moulding, adhesives, adjuvants for textiles, paper-making, etc.
  • the reactants are utilized in a slightly acid medium.
  • white precipitates of methylene-ureas having a low degree of polymerization known as Goldschmidt" products which are undesirable for these manufactures.
  • the method according to the invention consists of charging the said material, throughout its mass or superficially, with a filler product having a base of a precipitate of methylene-ureas having a low degree of polymerization, obtained by the reaction of urea on formaldehyde in an acid medium.
  • This filler product permits the above-mentioned characteristics to be given to the base material and produces a substance having advantageous qualities for various branches of the technical art, especially the branch of synthetic materials or paper-making products.
  • the filler product with a base of precipitate of methylene-ureas is particularly suitable to this latter case, due to its opacity to visible light and its transparency to ultra-violet rays.
  • certain special papers for reproduction necessitate good opacity to visible light, combined with maximum transparency to ultraviolet rays.
  • its physical characteristics per mit to be obtained in the paper, this appearance being desirable for certain printing papers.
  • the filler product is preferably applied in the form of a su-' perficial coating on a paper support and is composed of an aqueous suspension ofa precipitate of methyleneureas and the binders and adjuvants usually employed in coating compositions: dispersing agent, casein, latex of the styrene butadiene type or the like.
  • the material obtained is a printing paper which has especially qualities of opacity, whiteness and matt surface which are improved for a reduced weight as compared with standard papers, and in particular papers coated with compositions having a kaolin base.
  • the resistance to tearing of the coatings with a base of formol-urea precipitate is higher or equal to that of the coatings with a base of kaolin; for an equal volumetric concentration of pigment, this strength is greater in the case of coatings with a base of formolurea precipitate.
  • composition of a surface coating which may, amongst others, be applied on a paper AFNOR IV: parts of formolurea precipitate, 15 parts of casein, 10 parts of styrenebutadiene latex and 0.6 parts of dispersant in suspension in 293 parts of water.
  • the content of dry material in a composition of this kind is approximately equal to 30% and its Brookfield viscosity (axis No. l, 100 rpm.) is 80 centipoises.
  • the first method consists in carrying out the following operations in order to obtain 355.3 grams of precipitate:
  • the various values given for these methods of manufacture can be subject two modifications: in particular, the granular size of the product obtained can be regulated by acting on the concentrations, the temperature and the stirring of the medium at the moment of acidification.
  • the precipitate of methylene-ureas obtained especially by these methods of preparation appear in the form of small spheres exhibiting the optical phenomenon of the Maltese cross, similar to that which is observed on grains of native starch, with a stratified structure.
  • the physical characteristics of this precipitate are as follows:
  • Volume-mass comprised between 1.00 and 1.70
  • pH value of the isoelectric point comprised between 4 and 7;
  • Proportion of nitrogen (Kjeldahl) comprised between 30 and 38%.
  • the index of refraction of this precipitate is comprised between 1.4 and 1.6; the following Table gives the factor of diffuse reflection for two precipitates, one corresponding to a molar ratio of formaldehyde/urea of 0.95, the other to a ratio of 1.9.
  • the measurements were made by means of an Elrepho photometer calibrated with respect to MgO by taking 100% as the reflection factor for MgO.
  • the whiteness index measured under the same conditions with a filter R 457 is equal to 98.2 for the first precipitate and 96.4 for the second.
  • precipitates of methylene-ureas may also be obtained by more direct syntheses involving for example the use of a direct reaction of carbon monoxide on ammonia at high pressure in the presence of a catalyst.
  • the invention also relates to a paper, particularly intended for printing and manufactured by the method described above; according to the invention, this paper is charged with a superficial coating layer with a base of a methylene-ureas precipitate.
  • the support paper for the coating may be for example an AFNOR IV paper and the composition by weight of the surface coating is as follows:
  • FIG. 1 represents:
  • a curve B giving by way of comparison the whiteness of a non-calendered paper obtained by coating, on an identical paper support, with a standard composition with a base of kaolin having an equal proportion of binder by weight;
  • the calendering operations were carried out by three passes through the Ramisch calender (two tonnes).
  • FIG. 2 shows curves C, C D and D, giving the opacity on a white ground of the four cases of papers referred to above, as a function of the dry weight of coating deposited (in g/sq.m.).
  • the papers coated by a filler product with a base of formol-urea precipitate have a high microporosity, but also a macro-porosity which may be high.
  • the transparency to ultra-violet rays of this filler material makes it possible to obtain a high efficiency with optical blueing agents.
  • the coating composition maycomprise up to 1.5% of these agents by weight of the filler introduced.
  • the latter is fixed on the methylene-ureas at the time of manufacture of this latter.
  • FIG. 3 represents:
  • a curve E giving, as a function of the maximum wave-length, the diffused reflection factor of a paper coated with 13.5 of a coating with a base of formo1-urea precipitate, without optical blueing agent;
  • a curve E giving, as a function of the maximum wave-length, the diffuse reflection factor of a paper coated with the same weight of a coating with a base of formol-urea precipitate containing 0.87% of optical blueing agent with respect to the dry extract of the coating bath;
  • the optical blueing agent is more effective when the filler has a base of formolurea precipitate.
  • FIG. 4 represents:
  • a curve G14 giving, as a function of the proportion of optical blueing agent with respect to the dry mate rials of the coating baths, the diffuse reflection factor of a paper coated with 14 g/sq.m. of a coating with a base of formol-urea precipitate;
  • optical blueing agent is more effective in the case of a coating with a base of formol-urea precipitate, the difference being greater as the thickness of the coating is increased.
  • the formolurea precipitates are relatively economical materials. This ad vantage is accentuated, by reason of their low density in comparison with mineral fillers which are two or three times more dense; for equal weights, the effective surface coated by coatings with a base of formol-urea precipitate is greater. This factor is particularly advantageous for papers intended for printing, for which increased lightness is desired for a given opacity.
  • aldehyde may be partly substituted for the formaldehyde.
  • pH value of the isoelectric point between about 4 to 7
  • a percent of nitrogen between about 30 and 38%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
US05041374 1969-06-03 1970-05-28 Application of precipitates of methylene-ureas and products obtained Expired - Lifetime US3869311A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR6918236A FR2030524A5 (de) 1969-06-03 1969-06-03

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US05/517,413 Continuation-In-Part US3959570A (en) 1969-06-03 1974-10-24 Application of precipitates of methylene ureas and products obtained

Publications (1)

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US3869311A true US3869311A (en) 1975-03-04

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US05041374 Expired - Lifetime US3869311A (en) 1969-06-03 1970-05-28 Application of precipitates of methylene-ureas and products obtained

Country Status (7)

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US (1) US3869311A (de)
BE (1) BE809363Q (de)
CA (1) CA924196A (de)
DE (1) DE2026963B2 (de)
FR (1) FR2030524A5 (de)
GB (1) GB1319822A (de)
SE (1) SE385927B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960856A (en) * 1988-11-28 1990-10-02 Georgia-Pacific Corporation Urea-formaldehyde compositions and method of manufacture
US5110898A (en) * 1988-11-28 1992-05-05 Georgia-Pacific Corporation Method for manufacturing amino-aldehyde compositions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH606607A5 (de) * 1974-12-16 1978-11-15 Ciba Geigy Ag
US4452934A (en) * 1981-09-28 1984-06-05 Georgia-Pacific Corporation Aminoplast resin compositions
GB8826471D0 (en) * 1988-11-11 1988-12-14 Shaw Chemical Systems Ltd Flame retardant composition
US5080754A (en) * 1990-07-20 1992-01-14 The Research Foundation Of State University Of Ny Method for reducing brightness reversion in lignin-containing pulps and article of manufacture thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399489A (en) * 1943-10-06 1946-04-30 American Cyanamid Co Coating compositions for paper and the like
US2652374A (en) * 1951-01-31 1953-09-15 Calgon Inc Water resistant paper coatings and method of making same from ureaformaldehyde, ammonium metaphosphate, amylaceous material, and clay
US2851424A (en) * 1957-06-28 1958-09-09 Switzer Brothers Inc Fluorescent compositions
US2956898A (en) * 1960-10-18 Certification of correction
US3018287A (en) * 1958-11-05 1962-01-23 Fidelity Union Trust Company Optical brighteners for use with paper
US3181950A (en) * 1957-06-06 1965-05-04 Gevaert Photo Prod Nv Method for optical bleaching of coated photosensitive papers and resultant product

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2956898A (en) * 1960-10-18 Certification of correction
US2399489A (en) * 1943-10-06 1946-04-30 American Cyanamid Co Coating compositions for paper and the like
US2652374A (en) * 1951-01-31 1953-09-15 Calgon Inc Water resistant paper coatings and method of making same from ureaformaldehyde, ammonium metaphosphate, amylaceous material, and clay
US3181950A (en) * 1957-06-06 1965-05-04 Gevaert Photo Prod Nv Method for optical bleaching of coated photosensitive papers and resultant product
US2851424A (en) * 1957-06-28 1958-09-09 Switzer Brothers Inc Fluorescent compositions
US3018287A (en) * 1958-11-05 1962-01-23 Fidelity Union Trust Company Optical brighteners for use with paper

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960856A (en) * 1988-11-28 1990-10-02 Georgia-Pacific Corporation Urea-formaldehyde compositions and method of manufacture
US5110898A (en) * 1988-11-28 1992-05-05 Georgia-Pacific Corporation Method for manufacturing amino-aldehyde compositions

Also Published As

Publication number Publication date
SE385927B (sv) 1976-07-26
BE809363Q (fr) 1974-05-02
DE2026963A1 (de) 1970-12-10
CA924196A (en) 1973-04-10
DE2026963B2 (de) 1976-12-30
FR2030524A5 (de) 1970-11-13
GB1319822A (en) 1973-06-13

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