Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/54—Nitrogen-containing linkages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

• composition containing low VOC aminoalkyl-functional silicon compounds for coating paper or film
• the present invention relates to the use of a low-VOC aminoalkyl-functional silicon compounds coating composition for the treatment of paper or film for ink-jet applications, a corresponding composition as such and their preparation.
• VOC volatile organic compounds
• Aminosilanes are known as water-soluble adhesion promoters, for example as so-called size or primers in the glass fiber industry.
• a number of other application areas for amino-functional silanes or siloxanes are: The use in coating systems, in the field of corrosion protection, for the biocidal finishing of surfaces, in wood treatment, in the production of electrophotographic toner (EP 0 992 857 B1), in the paper industry (EP 1 559 750 A2, EP 1 408 155 A1, EP 1 413 451 B1), as a constituent in aminosilicone fluids (US Pat. No.
• Oligo-silylated alkylamines such as bis (trialkoxysilyl-alkyl) amine or tris (3-triethoxysilyl-propyl) amine, or mixtures thereof, are not completely soluble in water even with addition of acid.
• such solutions are usually not long lasting. They tend to gel or particle formation, which can lead to increased blockage of nozzles and thus to the loss of production and longer downtime when applied. Furthermore, significant amounts of hydrolysis alcohol are released.
• WO 05/014741 discloses alcoholic aminosilane or aminosiloxane-containing d. H. VOC-rich compositions and their use for paints and coatings and for the treatment of fillers and pigments.
• VOC volatile organic compounds
• PVA polyvinyl alcohol
• the invention had the object of providing a low-VOC composition on the basis of aminosilanes for the production of coating colors.
• the concern was to use such coating colors for the treatment of special paper or film for ink-jet applications, without degrading the properties.
• a volatile or substantially VOC-free composition can be produced in a simple and economical manner and advantageously, since environmentally friendly in coating colors, in particular for the treatment of paper or film for ink. Jet applications, said composition is based at least partially on one or more partially or fully hydrolyzed and optionally condensed or co-condensed aminoalkyl and oligo-silylated aminoalkyl, alkoxy or hydroxy-functional silicon compounds and the alcohol the composition is at least partially removed.
• compositions to be used in the context of the present invention can advantageously be prepared by initially introducing or mixing the amino-functional, hydrolyzable silane feedstock;
• solvents or diluents preferably the preferred Further, one may optionally add an organic or inorganic acid, suitably a degree of neutralization of the mono-silylated aminoalkyl or oligo-silylated aminoalkyl groups from 0 to 125%, preferably from 0.01 to 120%, especially preferably 70 to 115%, very particularly preferably 75 to 110%, is set, the preferred alkoxysilanes used by the addition of a defined amount of water selectively partially or completely hydrolyzed, being in total from 0.01 to 1000 mol, preferably 0, From 1 to 500 mol, particularly preferably from 0.2 to 250 mol, very particularly preferably from 0.3 to 100 mol, in particular from 0.5 to 10 mol of water per mol of Si of the silanes used here, it is possible to optionally condense and co-condensate the hydrolyzate, wherein corresponding organosiloxanes may be formed as condensates or cocondensates of the silicon compounds used here, and the proportion
• the content of volatile organic compounds (VOC) under ambient conditions, in particular of alcohols such as methanol, ethanol or isopropanol, in the composition to a content of less than or equal to 1 wt .-%, in particular less than or equal to 0.5 wt. %, ie up to the detection limit (water determination, for example, according to Karl Fischer or by GC analysis), based on the composition set.
• VOC volatile organic compounds
• water determination for example, according to Karl Fischer or by GC analysis
• VOC-poor ie essentially VOC-free, composition which can be used according to the invention and advantageously use it as a base for a coating color, wherein such a coating composition based on a composition according to the invention is excellently suitable for treating paper or film, in particular for Ink -Jet applications, can use.
• the present invention therefore provides for the use of a composition which is low in volatile organic compounds (VOC) or substantially free of VOCs in coating colors, the composition being based at least proportionally on one or more partially or completely hydrolyzed and optionally condensed or cocondensed aminoalkyl groups. and oligo-silylated aminoalkyl-, alkoxy- or hydroxy-functional silicon compounds based and the alcohol is at least partially removed from the composition.
• the present invention further provides a process for the preparation of a composition which can be used according to the invention by
• R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
• Y is a bivalent alkylene group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 J 3 - or - [CH 2 CH (CH 3 ) CH 2 ] -, x is 0, 1 or 2 and n is 0 or
• R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched one
• R and R are the same or different and each represents a hydrogen atom or a linear or branched one
• Y is independently a bivalent alkylene group from the series -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 - or - [CH 2 CH (CH 3 ) CH 2 ] - and n is independently 0 or 1,
• mono-silylated amines are to be understood as meaning those of the formulas I.
• oligo-silylated amines are in particular those which carry two and more than two silyl groups on an amino group or alkylamine, for example according to formula II (bis-silylated) or formula III (tris-silylated) and / or corresponding compounds which may also be cyclized.
• aminoalkylalkoxysilanes of the general formula I used are preferably H 2 N (CH 2 ) 3 Si (OCH 3 ) 3 (AMMO),
• component (A) from the series AMMO, AMEO, DAMO, TRIAMO, 3- (N-alkylamino) propyltrialkoxysilane, wherein alkyl is methyl, ethyl, n-propyl or n-butyl and Alkoxy is methoxy or ethoxy
• component (B) can be from the series Bis-AMMO, bis-AMEO, bis-DAMO, bis-TRIAMO
• component (C) from the series Tris-AMMO, Tris-AMEO.
• mixtures containing compounds of the general formulas I, II, and / or III can advantageously be used in the process according to the invention.
• Such mixtures which can be used according to the invention may also comprise so-called condensation products of said aminoalkoxysilanes.
• Condensation products or reaction products of aminoalkoxysilanes of the general formulas I, II and / or III suitably mean those dimeric, trimeric, tetrameric or higher oligomeric products which are generally obtained by condensation or cocondensation and / or prehydrolysis of the respective monomers with elimination of Alcohol is produced.
• the educt components are thus linked via Si-O-Si bonds.
• the present invention also provides a composition which can be used according to the invention, wherein aminoalkyl- or oligo-silylated-aminoalkyl-, hydroxy- and optionally alkoxy-functional silicon compounds which are contained in the composition comprise a reaction product from the reaction, ie. H. the partial or complete hydrolysis and optionally condensation or cocondensation of
• R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
• Y is a bivalent alkylene group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 J 3 - or - [CH 2 CH (CH 3 ) CH 2 ] -, x is 0, 1 or 2 and n is 0 or 1, or
• groups R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
• groups Y are the same or different and Y is a bivalent alkylene group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 ) S- or - [CH 2 CH (CH 3 ) CH 2 ] -
• y and z are independently 0, 1 or 2 and m and n are independently the same 0 or 1, or
• R and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 C atoms
• Y is independently a bivalent alkylene group selected from the group -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 - or - [CH 2 CH (CH 3 ) CH 2 ] - and n is independently 0 or 1, or
• (D) represent at least two of the aforementioned silylated alkylamines of the general formula I, II and III and the content of free alcohol in the composition is less than or equal to 1 wt .-%, preferably less than 0.5 wt .-%, based on the Composition, is.
• compositions in which corresponding aminofunctional silicon compounds are present each fully hydrolyzed, d. H. carry substantially no more alkoxy groups, so that in the presence of water hydrolysis alcohol is released.
• the reaction in particular hydrolysis and condensation or cocondensation, at a temperature ⁇ 100 0 C, preferably from 10 to 80 0 C, particularly preferably from 15 to 60 0 C, in particular from 20 to 50 0 C, through.
• a temperature ⁇ 100 0 C preferably from 10 to 80 0 C, particularly preferably from 15 to 60 0 C, in particular from 20 to 50 0 C, through.
• an organic or inorganic acid it is advantageous to use hydrochloric acid (HCl or aqueous hydrochloric acid) or aqueous acetic acid or aqueous formic acid, wherein the proportion of water introduced thereby is at the same time attributable to the amount of water to be introduced according to the invention for the controlled hydrolysis of the alkoxysilanes.
• an addition of acid can also be carried out after the preparation of the present composition, it being preferred to adjust to a pH of from 2 to 6, in particular from 3 to 5.
• a distillative work-up of the product mixture from the reaction, d. H. from the resulting product mixture is preferably distilled under mild heating and under reduced pressure, the otherwise readily volatile under ambient conditions, in particular the hydrolysis alcohol and optionally added solvent or diluent, at least partially from. Possibly. In doing so, it is possible to replace the amount of volatiles removed from the system by the same volume of water and / or acid.
• composition of the invention may preferably have a content of organic or inorganic acid, suitably a
• Neutralization degree of the aminoalkyl and oligo-silylated aminoalkyl groups from 0 to 125%, preferably 0.1 to 120%, more preferably 70 to 115%, most preferably 75 to 110%, based on the amine number, is present.
• Determination of the amine number can generally be carried out in accordance with DIN 32 625 (potentiographic titration with HCl).
• the acid used is an inorganic or organic acid, in particular hydrochloric acid, acetic acid or formic acid, wherein the aminoalkyl- and oligo-silylated-amionalkyl-functional silicon compounds in the present composition according to chemical understanding at least partially present as a cationic amine mixture, ie that a composition used according to the invention preferably has a content of acid and / or a corresponding salt of acid and one of the present amino-functional compounds.
• the pH of a composition used according to the invention is preferably in the range from 2 to 11, particularly preferably between 2.5 and 6.5, very particularly preferably in the range from 3.0 to 6.0, in particular between 3.5 and 5.0.
• compositions according to the invention are generally distinguished by a viscosity of from 2 to 1000 mPa s, preferably from 3 to 500 mPa s, more preferably from 4 to 250 mPa s, the viscosity being able to be determined, for example, in accordance with DIN 53 015.
• compositions which can be used according to the invention are distinguished by particularly good water solubility.
• composition in which at least one silicon compound of the aminoalkyl- or oligo-silylated-aminoalkyl-, hydroxy- and optionally alkoxy-functional silicon compounds present in the composition comprises a reaction product from the reaction, ie. H. the partial or complete hydrolysis and optionally condensation or cocondensation of
• R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
• Y is a bivalent alkylene group from the series -CH 2 -, - (CH 2 ) 2 -, - (CH 2 J 3 - or - [CH 2 CH (CH 3 ) CH 2 ] -, x is 0, 1 or 2 and n is 0 or
• groups R, R 'and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms
• groups Y are the same or different and Y is a bivalent alkylene group from the series -CH 2 -, - (CH 2 J 2 -, - (CH 2 ) S- or - [CH 2 CH (CH 3 ) CH 2 ] -
• y and z are independently 0, 1 or 2 and m and n are independently the same 0 or 1 are, or
• R and R are the same or different and each represents a hydrogen atom or a linear or branched alkyl
• Y is independently a bivalent alkylene group from the group -CH 2 -, - (CH 2 ) 2 -, - (CH 2 ) 3 - or -
• n is independently 0 or 1, or
• (D) represents at least two of the aforementioned silylated alkylamines of the general formula I, II and III.
• composition which has a content of at least one at least partially hydrolyzed silicon compound of from 0.1 to 99.5% by weight, based on the composition.
• compositions which can be used according to the invention have, in particular, an active ingredient content of cationic amino-functional silicon compounds or said reaction products from 0.1 to 95 wt .-%, preferably 1 to 80% by weight, particularly preferably 5 to 60 wt .-%, most preferably 10 to 50 wt .-%, based on the composition on.
• the composition used according to the invention may have a water content of from 99.9 to 0.5% by weight, based on the composition, all components in the composition resulting in a total of 100% by weight.
• a composition of the invention is advantageously the basis for a coating color, which usually further components such as binders, z. B.
• Processing aids such as defoamers, surfaces active substances, just to name a few contains.
• at least one metal oxide preferably fumed silica
• having an average particle size of less than 1 ⁇ m in particular from 50 to 400 nm, particularly preferably from 90 to 200 nm (median value, for example with static light scattering ) and in an amount of 5 to 50 wt .-%, in particular from 10 to 30 wt .-%, based on the composition.
• a coating color used in the context of the present invention advantageously contains at least partially hydrolyzed amino-functional silicon compounds in an amount of from 1 to 10% by weight, preferably from 2 to 7% by weight, particularly preferably from 4 to 6%. , based on the coating pigment (metal oxide) used in the coating color.
• the present coating composition is used for the coating of paper or film, wherein the coating color is advantageously applied to the surface of a film or a paper, in particular one modified with polyethylene (PE) Special paper, applies and dries or hardens.
• PE polyethylene
• At least one of the said aminosilanes according to (A), (B) or (C) can initially be added, optionally mixed with the addition of alcohol and / or acid, water can be added in a controlled manner and, under temperature control and good mixing, the present composition Alkoxysilanes at least partially hydrolyze or condense or co-condensate.
• VOC components in particular alcohol, are then removed from a composition to be used according to the invention by distillation.
• water which is optionally acidified and may contain alcohol, and doses the desired aminosilane or Aminosilangemisch under temperature control and thorough mixing.
• the volatile constituents in particular alcohol, are preferably distilled off at least proportionally and, if necessary, the pH can be adjusted by adding acid.
• the preparation of a said composition can usually be done under protective gas coverage.
• a composition thus obtained can advantageously form the basis for the preparation of a metal oxide dispersion, in particular a dispersion of fumed silica.
• the composition can be gradually added to a dispersion of the metal oxide, for example a dispersion of fumed silica, and it is appropriate to ensure that the pH is preferably from about 3 to 6, especially at approx. pH 4 remains.
• This can be done by adding mineral acids, such as HCl, but also organic acids, such as acetic acid or formic acid.
• the preparation is allowed to react at elevated temperature and optionally assisted by ultrasound with stirring.
• the dispersion can then be filtered to remove unwanted coarse fractions.
• the dispersion thus obtained can advantageously be used as the basis for the production of a coating color.
• the dispersion with stirring to a solution of the binder, z.
• PVA and other coating color additives, such as crosslinkers, z.
• the coating color can by means of known coating technologies, such as doctor blade, contact coating, z. B. Blade coating, as well as contactless casting technologies, eg. B.
• Slide Coating, Curtain Coating curtain coating, applied to paper or foil and dried accordingly.
• This can be, preferably with an optimized ratio of binder and coating pigment, a microporous
• the surface of the coating pigments which has been positively charged by the aminosilane component may be the negatively charged ink dyes or
• Pigments bind particularly well and thus leads to waterproof prints.
• compositions used according to the invention are distinguished in the application and application of appropriately treated paper in the case of ink jet printing.
• the solids content of the aqueous silane systems is determined as follows:
• Constant weight dried in a drying oven Constant weight dried in a drying oven.
• the filter is dried in a platinum crucible, ashed and annealed for 1 hour at 800 0 C in a muffle furnace.
• the residue is smoked after weighing with hydrofluoric acid, the crucible is annealed by means of a fan burner and optionally annealed again at 800 0 C and weighed after cooling.
• the difference between the two weighings corresponds to the content of SiO 2 .
• D x 100 / E wt.% SiO 2
• Alcohol determination is by GC.
• Example 1 Composition with reduced VOC content
• Dynasylan ® 1189 [N- (n-butyl) -3-aminopropytri- methoxysilane, Manufacturer: Degussa GmbH] presented and 80.0 g of methanol.
• the temperature rose from 28 0 C to 50 0 C. It was stirred for 3 hours at 60 0 C.
• 208.89 g of methanol was distilled off at about 200 mbar.
• the weight of the residue / product was 394.87 g.
• Rotor-Stator-System (Ultra-Turrax) double jacket pot 3 liters
• Dissolver for stirring in the AEROSIL ® 200 Polytron (Rotor-Stator) dispersing unit Stirrer, 2 dropping funnels for dropwise addition of the silane solution and the HCl solution Heatable ultrasonic bath (40 W ultrasonic power) 500 ⁇ m sieve
• the viscosity of the dispersions thus prepared was measured after 24 hours with a Brookfield viscometer.
• These coating colors were applied to a photobase paper (300 micrometers thick) using a profiled metering rod.
• the wet film thickness of the coating was 110 microns.
• the coating was dried at 105 ° C. for 8 minutes.
• composition or dispersion / coating color according to the invention it is thus possible to provide a coating which, despite a significant reduction in the VOC content, achieves an equally good printout with an ink-jet printer.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
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• 2007
  • 2007-08-28 DE DE102007040802A patent/DE102007040802A1/de not_active Withdrawn
• 2008
  • 2008-07-04 US US12/674,601 patent/US20110259240A1/en not_active Abandoned
  • 2008-07-04 JP JP2010522276A patent/JP5523319B2/ja active Active
  • 2008-07-04 WO PCT/EP2008/058684 patent/WO2009037015A1/de not_active Ceased
  • 2008-07-04 EP EP08774775A patent/EP2181140A1/de not_active Withdrawn
  • 2008-08-27 CN CNA2008101463804A patent/CN101376792A/zh active Pending
• 2018
  • 2018-06-23 US US16/016,571 patent/US20180305500A1/en not_active Abandoned
• 2021
  • 2021-03-15 US US17/202,175 patent/US20210230373A1/en not_active Abandoned

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