WO2007061326A1 - Method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone - Google Patents

Method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone Download PDF

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Publication number
WO2007061326A1
WO2007061326A1 PCT/PL2006/000083 PL2006000083W WO2007061326A1 WO 2007061326 A1 WO2007061326 A1 WO 2007061326A1 PL 2006000083 W PL2006000083 W PL 2006000083W WO 2007061326 A1 WO2007061326 A1 WO 2007061326A1
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WO
WIPO (PCT)
Prior art keywords
derivatives
modifiers
materials
water
carbonic acid
Prior art date
Application number
PCT/PL2006/000083
Other languages
French (fr)
Inventor
Dariusz Stachura
Wieslaw Zadecki
Witold Rams
Original Assignee
Termo Organika Sp. Z O.O.
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 Termo Organika Sp. Z O.O. filed Critical Termo Organika Sp. Z O.O.
Priority to EP06824404A priority Critical patent/EP1951797A1/en
Publication of WO2007061326A1 publication Critical patent/WO2007061326A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/68—Triazinylamino stilbenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to a method of preparation and modification the materials protecting them against the harmful effects of ultraviolet radiation and ozone and reducing local tensions and looseness, thus improving their thermal resistance through increasing the flash point.
  • the prepared materials are thermosetting and chemo-hardening thermoplastics in the block form, in the form of foamable and foamed granulates, such as expanded polystyrene and polyurethanes, rubbers and natural rubber as well as cement, sulphur, polymer and asphalt concrete.
  • the main component used in the method according to the invention are compounds of stslbene and in particular its derivatives, especially in the form of 4,4'-bis(s- triazynylo-)diamino-2,2'-disulphostilbene derivatives whose method of obtaining is described in polish patent application P. 313640.
  • Patent description P. 328843 disclosures a method of marking paper, plastic mass and non-organic glass by adding, during the manufacture, in whole or in certain places, of substances containing a marker being a luminophore in which the matrix is made of fluorides, preferably LaF 3 or KYF 4 with admixtures of ions of rare earths metals, preferably Yb, Er, Ho or Tm.
  • a marker being a luminophore in which the matrix is made of fluorides, preferably LaF 3 or KYF 4 with admixtures of ions of rare earths metals, preferably Yb, Er, Ho or Tm.
  • Such materials may be added as components directly to paper, plastic or glass or in some of its places in the form of other materials of saturated luminophores - strips of paper (confetti), cloth, plastic, glass, etc.
  • European patent application EP728749 describes the use of stilbene compounds in the form of 4,4-di-(triazynyloamino)-stilbeno-2,4'-disulphone acid as agents partially absorbing ultraviolet radiation (UVA) and the usability of such compounds themselves in improving the sun protection factor (SPF) of textile fabrics.
  • UVA ultraviolet radiation
  • SPF sun protection factor
  • the aim of the invention is to eliminate the negative effects of ultraviolet radiation and ozone on the surfaces of materials used mainly in construction and exposed to all kinds of atmospheric impacts through buffer processing of energy streams.
  • the nature of the invention is a method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone in which a solution of stilbene derivatives are prepared and then, according to the invention the derivatives are grafted, at the temperature of up to 55 0 C in the presence of water - with carbonic acid diamide, of between 0.5 and 55 parts by weight in relation to the mass of the said derivatives and subsequently the material, like plastics, cement or concrete, is being directly treated with the so prepared modifiers and/or the active radicals of the said modifiers are built-in the surface of these materials and/or are introduced through monomers or the reacting components during chemical hardening, foaming, polymerization or condensation.
  • stilbene derivatives can be grafted with solid carbonic acid diamide with grain size below 40 ⁇ m at the temperature of up to 55 0 C without the presence of water, through the crushing of the modifiers in a mill and homogenization in ambient temperature for over 4 hours, with the quantity of carbonic acid diamide in relation to the solid stilbene derivatives of between 0.1 and 45 parts by weight.
  • the stilbene derivatives are 4,4'-bis(s- triazynylo-)diamino-2,2'-disulphostilbene derivatives.
  • the modifiers are preferably stilbene derivatives such as 4 I 4'-bis(s-triazynylo-)diamino-2,2'-disulphostilbene derivatives and/or water solutions of such derivatives which are grafted with carbonic acid diamide at the temperature of up to 55 0 C.
  • the modifiers are preferably solid, soluble and/or non- soluble in water, with grain size as determined by the conditions and as required and being between 4.5 mm and 1.0 ⁇ rn, or are liquids soluble and/or non-soluble in water.
  • modifiers which are soluble in water, through cement and/or mixing water.
  • the effect of the modifiers according to the invention indicate, by using of non-invasive tests, to the distribution of selected components in the mass of the material generated, e.g. expanded polystyrene, polyurethane, concrete, upon their prior introduction in the base material on its surface and/or in the mass of such material.
  • selected components e.g. expanded polystyrene, polyurethane, concrete
  • the modification and preparation, according to the invention, of the materials such as for instance sulphur concretes, result in structural orientation of the binding agent and adhesive activation with the filling agents which increases the homogenization of the mixtures thus enhancing the (mechanical and technological) efficiencies with considerable lowering of the system of anisotropy.
  • plastics using the method according to the invention especially foamed and foamable plastics such as expanded polystyrene, polyurethanes, olefines or urea-formaldehyde or resol resins, results in reduced anisotropy, improved resistance to ultraviolet radiation, surface neutralization, reduced of a surface tension and increased surface adhesion which is important in process of joining surfaces (gluing, etc.).
  • foamed and foamable plastics such as expanded polystyrene, polyurethanes, olefines or urea-formaldehyde or resol resins
  • Protection of the materials prepared using the method according to the invention, against the effects of ultraviolet radiation and ozone, consists in energy transformations of UV streams in the surface layer of the material into radiation within a range detectible by the human eye thus eliminating the aggressive impact of UV radiation on the material prepared according to the invention.
  • styrene polymer to be foamed e.g. commercially available Styropor® by BASF
  • a 4 I 4"-bis(s-tria ⁇ yny!o-)diamino-2,2 ⁇ - disulphostilbene derivative previously grafted, at the temperature of up to 55 0 C, with carbonic acid diamide in the presence of water, with the proportions of water to diamide in parts by weight of 5:1 , and with the quantity of the carbonic acid diamide in relation to the derivative of 0.6 parts by weight.
  • the mixing machine is started with the rotation speed of 0.1 m/s for 40 minutes. After the mixing machine is emptied, the material is homogenized further at the temperature of 20 ° C for 10 hours, obtaining the modification and preparation properties as per invention and is suitable for foaming using the well-known method.
  • the entirety is homogenized at the temperature of 20 0 C for 4 hours until homogenization is obtained suitable for making the working composition and then the hardening agent is added in the form of stoichiometric mixture of lsocyanates (component B) of 110 parts by weight, thus obtaining a material prepared according to the invention with the density of 40 kg/m 3 in the solid form.
  • component B stoichiometric mixture of lsocyanates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention relates to a method of preparation and modification of materials which are used mainly in the construction industry and which are exposed to aggressive atmospheric conditions, protecting them against the harmful effects of ultraviolet radiation and ozone. The method consists in preparing a solution of stilbene derivatives and, according to the invention, the stiibene derivatives are grafted, at the temperature of up to 55°C in the presence of water - with carbonic acid diamide, and subsequently the material, like plastics, cement or concrete, is being directly treated with the so prepared modifiers and/or the active radicals of the said modifiers are built-in the surface of these materials and/or are introduced through monomers or the reacting components during chemical hardening, foaming, polymerization or condensation.

Description

Title: METHOD OF PREPARATION THE MATERIALS PROTECTING THEM AGAINST THE EFFECTS OF ULTRAVIOLET RADIATfON AND OZONE
The present invention relates to a method of preparation and modification the materials protecting them against the harmful effects of ultraviolet radiation and ozone and reducing local tensions and looseness, thus improving their thermal resistance through increasing the flash point. The prepared materials are thermosetting and chemo-hardening thermoplastics in the block form, in the form of foamable and foamed granulates, such as expanded polystyrene and polyurethanes, rubbers and natural rubber as well as cement, sulphur, polymer and asphalt concrete.
Such modified materials are widely applied in the construction industry, economy and transport.
The main component used in the method according to the invention are compounds of stslbene and in particular its derivatives, especially in the form of 4,4'-bis(s- triazynylo-)diamino-2,2'-disulphostilbene derivatives whose method of obtaining is described in polish patent application P. 313640.
Method of using the stilbene derivatives (obtained with various methods) is known in the manufacturing of paper, fabric and detergent washing agents or for removing stains on photographic material, as described in patent descriptions PL 163456; PL 190110; PL 172872; PL 188490 and in the patent applications, e.g. P.342469; P. 353873.
Patent description P. 328843 disclosures a method of marking paper, plastic mass and non-organic glass by adding, during the manufacture, in whole or in certain places, of substances containing a marker being a luminophore in which the matrix is made of fluorides, preferably LaF3 or KYF4 with admixtures of ions of rare earths metals, preferably Yb, Er, Ho or Tm. Such materials may be added as components directly to paper, plastic or glass or in some of its places in the form of other materials of saturated luminophores - strips of paper (confetti), cloth, plastic, glass, etc. European patent application EP728749 describes the use of stilbene compounds in the form of 4,4-di-(triazynyloamino)-stilbeno-2,4'-disulphone acid as agents partially absorbing ultraviolet radiation (UVA) and the usability of such compounds themselves in improving the sun protection factor (SPF) of textile fabrics.
In the case of materials used in construction, their exposure to ultraviolet radiation and atmospheric ozone results in destruction of basic bonds in the materials and their depolimerϊsation leading to significant changes in their resistance parameters and changes in the colour and smoothness of the surface which causes additional negative consequences in the form of increased surface area, increased generation of electrostatic charges causing nucleuses of endogenic fire radicals which result in exogenic fires in this material.
The aim of the invention is to eliminate the negative effects of ultraviolet radiation and ozone on the surfaces of materials used mainly in construction and exposed to all kinds of atmospheric impacts through buffer processing of energy streams.
The nature of the invention is a method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone in which a solution of stilbene derivatives are prepared and then, according to the invention the derivatives are grafted, at the temperature of up to 550C in the presence of water - with carbonic acid diamide, of between 0.5 and 55 parts by weight in relation to the mass of the said derivatives and subsequently the material, like plastics, cement or concrete, is being directly treated with the so prepared modifiers and/or the active radicals of the said modifiers are built-in the surface of these materials and/or are introduced through monomers or the reacting components during chemical hardening, foaming, polymerization or condensation.
Preferably, according to the invention, stilbene derivatives can be grafted with solid carbonic acid diamide with grain size below 40 μm at the temperature of up to 550C without the presence of water, through the crushing of the modifiers in a mill and homogenization in ambient temperature for over 4 hours, with the quantity of carbonic acid diamide in relation to the solid stilbene derivatives of between 0.1 and 45 parts by weight. Preferably, according to the invention, the stilbene derivatives are 4,4'-bis(s- triazynylo-)diamino-2,2'-disulphostilbene derivatives.
The modifiers, according to the invention, are preferably stilbene derivatives such as 4I4'-bis(s-triazynylo-)diamino-2,2'-disulphostilbene derivatives and/or water solutions of such derivatives which are grafted with carbonic acid diamide at the temperature of up to 550C.
The modifiers, according to the invention, are preferably solid, soluble and/or non- soluble in water, with grain size as determined by the conditions and as required and being between 4.5 mm and 1.0 μrn, or are liquids soluble and/or non-soluble in water.
In the case of preparation of cement materials, it is preferable to introduce modifiers which are soluble in water, through cement and/or mixing water.
It was unexpectedly found that the effect of the modifiers according to the invention indicate, by using of non-invasive tests, to the distribution of selected components in the mass of the material generated, e.g. expanded polystyrene, polyurethane, concrete, upon their prior introduction in the base material on its surface and/or in the mass of such material.
The modification and preparation, according to the invention, of the materials such as for instance sulphur concretes, result in structural orientation of the binding agent and adhesive activation with the filling agents which increases the homogenization of the mixtures thus enhancing the (mechanical and technological) efficiencies with considerable lowering of the system of anisotropy.
Furthermore, the preparation of plastics using the method according to the invention, especially foamed and foamable plastics such as expanded polystyrene, polyurethanes, olefines or urea-formaldehyde or resol resins, results in reduced anisotropy, improved resistance to ultraviolet radiation, surface neutralization, reduced of a surface tension and increased surface adhesion which is important in process of joining surfaces (gluing, etc.). - A -
Protection of the materials prepared using the method according to the invention, against the effects of ultraviolet radiation and ozone, consists in energy transformations of UV streams in the surface layer of the material into radiation within a range detectible by the human eye thus eliminating the aggressive impact of UV radiation on the material prepared according to the invention.
The subject of the invention is presented in more detail in the preferable manufacturing examples:
Example 1
The following are put in the mixing machine:
100 parts by weight of styrene polymer to be foamed (e.g. commercially available Styropor® by BASF) and 0.5 parts by weight of a 4I4"-bis(s-tria∑yny!o-)diamino-2,2ϊ- disulphostilbene derivative previously grafted, at the temperature of up to 550C, with carbonic acid diamide in the presence of water, with the proportions of water to diamide in parts by weight of 5:1 , and with the quantity of the carbonic acid diamide in relation to the derivative of 0.6 parts by weight.
Then the mixing machine is started with the rotation speed of 0.1 m/s for 40 minutes. After the mixing machine is emptied, the material is homogenized further at the temperature of 20°C for 10 hours, obtaining the modification and preparation properties as per invention and is suitable for foaming using the well-known method.
Example 2
0.8 parts by weight of 4,4l-bis(s-triazynylo-)diamino-2,2'-disulphostilbene derivatives which were prior homogenized to grain size of 0.15 mm with carbonic acid diamide of 1.1 parts by weight are added to 100 parts by weight of a styrene polymer to be foamed (e.g. commercially available Owipian® by Dwory Oswiφcim Poland). Then the entirety is homogenized at the temperature of 20°C for 4 hours until surface diffusion anchorage is obtained on the Owipian® grain which is suitable for foaming using the well-known method.
Example 3
0.8 parts by weight of 4,4'-bis(s-triazynylo-)diamino-2,2'-disulphostilbene derivatives which were prior homogenized to grain size of 0.15 mm with carbonic acid diamide of 1.1 parts by weight are added to 100 parts by weight of 35 Portland cement. Then the entirety is homogenized at the temperature of 20°C for 4 hours until homogenization is obtained suitable for making mortars and cement concretes using the well-known method.
Example 4
1 part by weight of 4,4'-bis(s-triazynylo-)diamino-2,2'-disulphostilbene derivative which was prior homogenized to grain size of 0.15 mm with carbonic acid diamide of 1.1 parts by weight is added to 100 parts by weight of polyol (component A).
Then the entirety is homogenized at the temperature of 200C for 4 hours until homogenization is obtained suitable for making the working composition and then the hardening agent is added in the form of stoichiometric mixture of lsocyanates (component B) of 110 parts by weight, thus obtaining a material prepared according to the invention with the density of 40 kg/m3 in the solid form.

Claims

- D -What is claimed is:
1. Method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone in which a solution of stilbene derivatives are prepared wherein the derivatives are grafted, at the temperature of up to 550C in the presence of water - with carbonic acid diamide, of between 0.5 and 55 parts by weight in relation to the mass of the said derivatives and subsequently the material, like plastics, cement or concrete, is being directly treated with the so prepared modifiers and/or the active radicals of the said modifiers are built-in the surface of these materials and/or are introduced through monomers or the reacting components during chemical hardening, foaming, polymerization or condensation.
2. Method according to claim 1 wherein stilbene derivatives are grafted with solid carbonic acid diamide with grain size below 40 μm at the temperature of up to 550C without the presence of water, through the crushing of the modifiers in a mill and homogenization in ambient temperature for over 4 hours, with the quantity of carbonic acid diamide in relation to the solid stilbene derivatives of between 0.1 and 45 parts by weight.
3. Method according to claim 1 or 2 wherein the stilbene derivatives are 4,4'- bis(s-triazynylo-)diamino~2,2'-disuJphostilbene derivatives.
4. Method according to claim 1 wherein modifiers soluble in water are introduced through cement and/or mixing water.
PCT/PL2006/000083 2005-11-24 2006-11-21 Method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone WO2007061326A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06824404A EP1951797A1 (en) 2005-11-24 2006-11-21 Method of preparation the materials protecting them against the effects of ultraviolet radiation and ozone

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.378142 2005-11-24
PL378142A PL209690B1 (en) 2005-11-24 2005-11-24 Method for the treatment of plastics to proof them against UV radiation and ozone

Publications (1)

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WO2007061326A1 true WO2007061326A1 (en) 2007-05-31

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EP (1) EP1951797A1 (en)
PL (1) PL209690B1 (en)
RU (1) RU2406738C2 (en)
UA (1) UA93891C2 (en)
WO (1) WO2007061326A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL212057B1 (en) 2006-05-09 2012-08-31 Termo Organika Społka Z Ograniczoną Odpowiedzialnością Modified foaming and foamed materials and the manner of obtaining it
PL219515B1 (en) 2010-05-10 2015-05-29 Termo Organika Spółka Z Ograniczoną Odpowiedzialnością Agent for modifying foaming and foamed plastics and modified foaming and foamed plastics
RU2448139C1 (en) * 2010-11-26 2012-04-20 Государственное образовательное учреждение высшего профессионального образования "Тихоокеанский государственный университет" Method of protecting polymer materials from ultraviolet radiation
RU2471838C1 (en) * 2011-10-07 2013-01-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тихоокеанский государственный университет" Method of protecting polymer materials from ultraviolet radiation

Citations (16)

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GB573236A (en) * 1944-05-01 1945-11-12 British Cellophane Ltd Improvements in or relating to the production of sheet wrapping materials
DE1108231B (en) * 1955-03-28 1961-06-08 Bayer Ag Process for the preparation of derivatives of 1-stilbyl-1,3,5-triazine
FR1426425A (en) * 1965-01-12 1966-01-28 Leuna Werke Veb Process for the manufacture of hot-moldable plastic masses, and products conforming to those obtained by the present process or similar process
GB1059777A (en) * 1964-12-11 1967-02-22 Monsanto Chemicals Foamed or foamable vinylaromatic polymer compositions
GB1239818A (en) * 1967-08-03 1971-07-21 Geigy Ag J R Polysulfonated bis-s-triazinylamino-stilbene-2,2'-disulfonic acids
GB1428975A (en) * 1972-08-02 1976-03-24 Ici Ltd Colouration process
PL163456B1 (en) 1991-05-06 1994-03-31 Inst Przemyslu Organiczego Method of obtaining optical brightening agents constituting derivatives of 4,4'-bis-(4"-/2,5-disulfoaniline/-s-triazinyl-2")-diaminostilbeno-2,2'-disulfonic acid
EP0728749A2 (en) 1995-02-22 1996-08-28 Ciba-Geigy Ag Triazine derivatives, their preparation and use
PL313640A1 (en) 1996-04-03 1997-10-13 Zachem Zaklady Chem Organika Method of obtaining optical brighteners constituting derivatives of 4,4'-bis(s-triazinyl-)diamino-2,2'-disulphostibene
PL172872B1 (en) 1993-10-29 1997-12-31 Inst Przemyslu Organiczego Method of obtaining optical brighteners constituting compounds of bis-/s-triazinyl/diamino disulfo stilbene derivatives or mixtures of such compounds
PL328843A1 (en) 1998-09-23 2000-03-27 Laser Secura Sp Z Oo Method of marking paper, plastic materials and inorganic glass
PL342469A1 (en) 1998-02-20 2001-06-04 Ciba Sc Holding Ag Method of obtaining stilbenic compounds
WO2003044275A1 (en) * 2001-11-21 2003-05-30 Clariant International Ltd Improvements relating to optical brighteners
PL353873A1 (en) 1999-09-10 2003-12-01 Ciba Specialty Chemicals Holding Inc.Ciba Specialty Chemicals Holding Inc. Triazinylaminostilbene derivative as fluorescent whitening agents
PL188490B1 (en) 2000-03-30 2005-02-28 Inst Przemyslu Organiczego Brightening agent belonging to a group of the derivatives of bis-(s-triazinyl)-diaminodisulphostilbene
PL190110B1 (en) 1997-05-23 2005-10-31 Ciba Sc Holding Ag Triazinylamino stilbene compounds

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB573236A (en) * 1944-05-01 1945-11-12 British Cellophane Ltd Improvements in or relating to the production of sheet wrapping materials
DE1108231B (en) * 1955-03-28 1961-06-08 Bayer Ag Process for the preparation of derivatives of 1-stilbyl-1,3,5-triazine
GB1059777A (en) * 1964-12-11 1967-02-22 Monsanto Chemicals Foamed or foamable vinylaromatic polymer compositions
FR1426425A (en) * 1965-01-12 1966-01-28 Leuna Werke Veb Process for the manufacture of hot-moldable plastic masses, and products conforming to those obtained by the present process or similar process
GB1239818A (en) * 1967-08-03 1971-07-21 Geigy Ag J R Polysulfonated bis-s-triazinylamino-stilbene-2,2'-disulfonic acids
GB1428975A (en) * 1972-08-02 1976-03-24 Ici Ltd Colouration process
PL163456B1 (en) 1991-05-06 1994-03-31 Inst Przemyslu Organiczego Method of obtaining optical brightening agents constituting derivatives of 4,4'-bis-(4"-/2,5-disulfoaniline/-s-triazinyl-2")-diaminostilbeno-2,2'-disulfonic acid
PL172872B1 (en) 1993-10-29 1997-12-31 Inst Przemyslu Organiczego Method of obtaining optical brighteners constituting compounds of bis-/s-triazinyl/diamino disulfo stilbene derivatives or mixtures of such compounds
EP0728749A2 (en) 1995-02-22 1996-08-28 Ciba-Geigy Ag Triazine derivatives, their preparation and use
PL313640A1 (en) 1996-04-03 1997-10-13 Zachem Zaklady Chem Organika Method of obtaining optical brighteners constituting derivatives of 4,4'-bis(s-triazinyl-)diamino-2,2'-disulphostibene
PL190110B1 (en) 1997-05-23 2005-10-31 Ciba Sc Holding Ag Triazinylamino stilbene compounds
PL342469A1 (en) 1998-02-20 2001-06-04 Ciba Sc Holding Ag Method of obtaining stilbenic compounds
PL328843A1 (en) 1998-09-23 2000-03-27 Laser Secura Sp Z Oo Method of marking paper, plastic materials and inorganic glass
PL353873A1 (en) 1999-09-10 2003-12-01 Ciba Specialty Chemicals Holding Inc.Ciba Specialty Chemicals Holding Inc. Triazinylaminostilbene derivative as fluorescent whitening agents
PL188490B1 (en) 2000-03-30 2005-02-28 Inst Przemyslu Organiczego Brightening agent belonging to a group of the derivatives of bis-(s-triazinyl)-diaminodisulphostilbene
WO2003044275A1 (en) * 2001-11-21 2003-05-30 Clariant International Ltd Improvements relating to optical brighteners

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RU2406738C2 (en) 2010-12-20
RU2008120100A (en) 2009-11-27
PL378142A1 (en) 2007-05-28
UA93891C2 (en) 2011-03-25
EP1951797A1 (en) 2008-08-06
PL209690B1 (en) 2011-10-31

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