WO2001014442A1 - Compositions de polyurethane pour encres a laminer - Google Patents

Compositions de polyurethane pour encres a laminer Download PDF

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Publication number
WO2001014442A1
WO2001014442A1 PCT/US2000/022471 US0022471W WO0114442A1 WO 2001014442 A1 WO2001014442 A1 WO 2001014442A1 US 0022471 W US0022471 W US 0022471W WO 0114442 A1 WO0114442 A1 WO 0114442A1
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WO
WIPO (PCT)
Prior art keywords
alcohol
grams
polyurethane resin
percent
soluble
Prior art date
Application number
PCT/US2000/022471
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English (en)
Inventor
Ramesh Narayan
Douglas Rhubright
Timothy Vogel
Shailesh Shah
Sobhy El-Hefnawi
Original Assignee
Cognis Corporation
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 Cognis Corporation filed Critical Cognis Corporation
Priority to BR0013434-1A priority Critical patent/BR0013434A/pt
Priority to EP00955595A priority patent/EP1208127A1/fr
Priority to JP2001518770A priority patent/JP2004513977A/ja
Priority to AU67774/00A priority patent/AU6777400A/en
Publication of WO2001014442A1 publication Critical patent/WO2001014442A1/fr

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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Definitions

  • This invention relates to a polyurethane resin, its preparation, an ink composition, in particular, a flexographic packaging printing ink, containing the resin and a laminate prepared with the resin.
  • Flexographic packaging printing inks are liquid inks applied by cylinders or plates to a variety of flexible substrates, e.g., plastic film materials such as cellophane, polypropylene and polyethylene, aluminum foils, nylon, paper, which in turn, are utilized, inter alia, to wrap products such as boxed chocolates, toys, cookies, cigarettes, meat, etc. Where used between two films, the ink provides both visual indicia and adhesive properties. In this application, such ink compositions are commonly known as laminating inks.
  • Flexographic packaging printing inks are typically formulated from a solvent, a pigment, a resin binder and other additives.
  • the resin binder is utilized as a delivery vehicle in printing inks and provides the ink with one or more useful characteristics such as, for example, pigment wetting, abrasion resistance, gloss and adhesion to the substrate.
  • Various alcohol-soluble polymers have been utilized as resin binders for printing ink formulations, e.g., polyamides, cellulosics, acrylic and methacrylic esters, and rosin esters.
  • Certain polyurethanes have also been utilized in printing ink formulations. However, because of inconsistencies in adhesion properties to different substrates, this particular use of polyurethanes has been limited.
  • a given polyurethane may exhibit good adhesion to a polyolefin substrate, that same polyurethane might exhibit poor adhesion to polyesters. Poor solubility of many polyurethanes in solvents commonly used in flexographic packaging printing inks (e.g., alcohols) also discourages the use of polyurethanes in such inks.
  • solvents commonly used in flexographic packaging printing inks e.g., alcohols
  • polyurethane compositions which are soluble in the solvents commonly used in flexographic packaging printing inks and which exhibit good adhesion to a variety of substrates.
  • a polyurethane composition exhibiting this combination of properties would be particularly useful as laminating resin binders in printing ink formulations.
  • Z is an aliphatic, cycloaliphatic, aromatic or alkylaromatic group
  • R is a C 2 to C 8 straight chain or branched hydrocarbon group, the oligomeric reaction product of a C 2 to C 36 diol with a C 2 to C 36 diacid, or combinations thereof
  • R' is an amine or alcohol radical
  • X is the residue of a diamine
  • n is a number from 1 to 200
  • x is a number from 1 to 50
  • y is a number from 1 to 30, the polyurethane resin being soluble in a solvent containing an aliphatic alcohol to a level of at least 10 weight percent solids.
  • a method of preparing the foregoing polyurethane resin includes a) reacting an excess of an aliphatic, cycloaliphatic, aromatic, or alkylaromatic diisocyanate with a polymeric diol selected from the group consisting one or more polyether diols, one or more polyester diols, and mixtures thereof, to form an isocyanate-terminated prepolymer, b) reacting the prepolymer with a diamine, and then c) optionally endcapping any free isocyanate groups of the compound formed by step (b) with an amine or alcohol, to form a polyurethane resin which is soluble in a solvent containing an aliphatic alcohol to a level of at least 10 percent by weight solids.
  • the polyurethane resin exhibits desirable properties that render it especially useful in compositions, ink formulations, adhesives and varnishes.
  • the resin possesses cohesive strength, good alcohol solubility, good viscosity, and blocking resistance which are functions of both molecular and the percentage of hard segments present.
  • Polyurethane resins are described herein which are useful as binders in formulating printing inks, as adhesives for preparing laminates, and as clear varnishes.
  • Adhesives typically include a solution of a resin in a solvent, and are useful in binding laminae (layers of substrates) together to form laminates as described in more detail below.
  • Varnishes typically include resins dissolved in oils, alcohol, etc. used to provide a hard, glossy surface to wood, metals and other materials.
  • Z is an aliphatic, cycloaliphatic, aromatic or alkylaromatic group
  • R is a C 2 to C 8 straight chain or branched hydrocarbon group, the oligomeric reaction product of a C 2 to C 36 diol with a C, to C 36 diacid, or mixtures thereof
  • R 1 is an amine or alcohol radical
  • X is the residue of a diamine
  • n is a number from 1 to 200
  • x is a number from 1 to 50
  • y is a number from 1 to 30, the polyurethane resin being soluble in a solvent containing an aliphatic alcohol to a level of at least 10 percent by weight solids.
  • n is a number from 1 to 70 and x is a number from 1 to 30.
  • the polyurethane resin is prepared by reacting an aliphatic, cycloaliphatic, aromatic or alkylaromatic diisocyanate with a polymeric diol to provide an isocyanate-terminated polyurethane prepolymer. The prepolymer is then chain extended using a diamine to form urea linkages, and any free-isocyanate groups of the resulting polymer are optionally endcapped with an amine or alcohol to form the polyurethane resin.
  • the resulting polyurethane resin has a number average molecular weight of from 5,000 to 70,000 and preferably from 15,000 to 40,000.
  • Any diisocyanate of the formula: OCN-Z-NCO wherein Z is an aliphatic, cycloaliphatic, aromatic, or alkylaromatic group can be reacted with a polyether diol, polyester diol, or combinations therof to prepare the isocyanate-terminated polyurethane prepolymer.
  • diisocyanates include, but are not limited to, 1 ,4-diisocyanatobutane, 1 ,6-diisocyanatohexane, 1 ,5- diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-l, 6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1 ,4-diiso-cyanatocyclo-hexane, 1 -isocyanato-5- isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), 2,3- 2,4- and 2,6-diisocyanato-l -methyl cyclohexane, 4,4'- and 2,4'- diisocyanatodicyclohexylmethane, 1 -isocyanato-3(4)-isocyanatomethyl- 1 -methyl-methyl
  • Useful polymeric diols include one or more polyether diols, one or more polyester diols, and mixtures thereof.
  • Useful polyether diols include those represented by the formula:
  • R is a C 2 to C 8 straight chain or branched hydrocarbon group.
  • R is a C 2 to C 4 alkylene group.
  • particularly useful polyether diols include, but are not limited to, poly(ethylene ether) glycols, poly(propylene) ether glycols and poly(tetramethylene ether) glycols, with poly(tetramethylene ether) glycols being preferred.
  • the number average molecular weight of the polyether diol typically ranges from 250 to 10,000, preferably from 1000 to 2500, and more preferably from 1250 to 2000.
  • the polyether diols can also contain a minor percentage by weight, e.g., up to about 40 weight percent, of ester units. These diols can be obtained, e.g., by reacting one or more of the aforesaid polyether diols with a lactone such as e- caprolactone.
  • Useful polyester diols include those represented by the formula:
  • R 2 is the residue of a diol HOR 2 OH
  • Y is -OC R 3 COOR 2 0 in which R 2 has the aforestated meaning and R 3 is the residue of a dicarboxylic acid HOOCR 3 COOH or anhydride*— ⁇ * " thereof
  • p and q independently is from about 0 to about 600 and preferably from about 1 to about 100, the sum of p + q being from about 1 to about 1200 and preferably from about 1 to about 250, or Y is -OCR 4 O - in which R 4 is the residue of a lactone E 222 or an ⁇ , ⁇ - hydroxycarboxylic acid HOR 4 COOH and p, q and the sum of p + q have the aforestated values.
  • Diols HOR 2 OH, carboxylic acids HOOCR 3 COOH, anhydrides E_£_2_ ⁇ f (0) , lactones B ⁇ S and ⁇ , ⁇ - hydroxycarboxylic acids HOR 4 COOH that can be used herein include any of those known for preparing polyester diols.
  • Suitable diols include ethylene glycol, propylene glycol, 1 , 4-butane diol, neopentyl diol, hexanediol, diethylene glycol, dipropylene glycol, and the like.
  • Suitable dicarboxylic acids and anhydrides include adipic acid, phthalic acid, phthalic anhydride, and the like.
  • Suitable lactones and ⁇ , ⁇ - hydroxycarboxylic acids include butyrolactone, caprolactone, ⁇ , ⁇ - hydroxycaproic acid and the like.
  • polyester diols include, but are not limited to, poly(caprolactone) diols, poly(diethylene glycol-co-ortho-phthalic acid), poly(l ,6 hexane diol-co-ortho-phthalic acid), poly(neopentyl glycol-co-adipatic acid), poly(ethylene glycol-co-adipic acid) and poly(caprolactone) diols.
  • the number average molecular weight of the polyester diol typically ranges from 250 to 10,000, preferably from 500 to 2500, and more preferably from 1000 to 2000.
  • the polyester diols can also contain a minor percentage by weight, e.g., up to about 40 weight percent thereof, of ether units. These diols can be obtained, e.g., by reacting one or more of the aforesaid polyester diols with one or more 1,2-alkylene oxides such as ethylene oxide, propylene oxide, etc.
  • Polyether diols are desirable in terms of the product polyurethane resin having greater solubility in aliphatic alcohol solvents compared with polyester diols.
  • polyester diols impart greater tensile strength to the resin. Therefore, depending on the choice of polymeric diol, the polyurethane resin obtained in accordance with the invention can vary from those resins possessing high solubility and relatively low tensile strength, i.e., those made entirely from polyether diol to those of relatively low solubility and relatively high tensile strength made entirely from polyester diol, and all of the combinations of solubility and tensile strength properties in between as would be the case where mixtures of polyether and polyester diols are employed. Optimum proportion of solubility and strength can be obtained through routine testing.
  • the polymeric diol and diisocyanate are reacted under conditions which are well known to those skilled in the art.
  • the reaction is carried out in the presence of a solvent, which is a solvent that is ultimately used in compositions formulated using the resin such as the solvent system of an ink formulation.
  • suitable solvents in which the diisocyanate and polymeric diol can be reacted include, but are not limited to alkyl (1-5 carbon) acetates such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and pentyl acetate, with propyl acetate being particularly preferred if the resin is to be used in packaging inks or coatings applications.
  • the total amount of solvent used for preparation of the isocyanate- terminated prepolymer typically ranges from 0 to 90 percent by weight of the total solution, preferably ranges from 10 to 70 percent by weight of the total solution, and more preferably ranges from 25 to 60 percent by weight of the total solution.
  • a catalyst may be advantageously employed to accelerate the reaction of diisocyanate with diol.
  • Suitable catalysts include, but are not limited to, stannous octylate, stannous oxalate, dibutyltin dilaurate and triethylamine, with dibutyltin dilaurate being preferred.
  • the ratio of diisocyanate to polymeric diol is chosen to obtain a desired molecular weight as well as a desired level of urethane and urea segments. An excess of diisocyanate is used to ensure that the prepolymer is isocyanate terminated.
  • the equivalent ratio of diisocyanate to diol generally ranges from 1.01 : 1 to 5 : 1, preferably ranges from 1.1 : 1 to 3 : 1 , and more preferably ranges from 1.3 : 1 to 2.1 : 1.
  • Formation of the isocyanate-terminated prepolymer is generally carried out at a temperature ranging from 0 to 130°C, preferably ranging from 50 to 90°C.
  • the time of the reaction generally ranges from a period of from 1 to 12 hours, preferably from 3 to 4 hours.
  • the isocyanate-terminated prepolymer is then chain extended with a diamine to form a polyurethane resin.
  • the diamine can be any aliphatic, cycloaliphatic, aromatic, or heterocyclic diamine in which each of the amine groups possesses at least one labile hydrogen atom.
  • diamines ethylene diamine, 1 ,2-diaminopropane, 1,3-diaminopropane, hydrazine, diaminobutane, hexamethylene diamine, 1 ,4-diaminocyclohexane, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (isophorone diamine), 1,3- bis(aminomethyl)cyclohexane, 1,3 bis(aminomethyl)benzene, 2-(aminomethyl)-3,3,5- trimethylcyclopentylamine, bis-(4-aminocyclo-hexyl)-methane, bis-(4-amino-3- methylcyclohexyl)-methane, l-amino-l-methyl-3(4)-aminomethyl-cyclohexane, bis- (4-amino-3,5-diethylcyclohexyl)-methane, bis-a
  • the conditions under which the diamine is reacted with the prepolymer are not critical and are within the purview of one skilled in the art.
  • the reaction is carried out in the solvent or in a component of the solvent system ultimately used in the final composition formulated from the ink resin as described.
  • the amount of solvent utilized in the chain extension reaction generally ranges from 0 to 90 percent by weight, and preferably from 35 to 60 percent by weight.
  • the ratio of isocyanate end groups of the prepolymer to amines from the diamine monomer determines the final polymer molecular weight of the resin as well as the level of urea groups.
  • the mole ratio of diisocyanate to diamine is from 6: 1 to 1:5, preferably from 4: 1 to 1 :4.
  • the chain extension reaction with diamine is generally carried out at a temperature ranging from 0 to 90°C, and preferably ranging Following the chain extension reaction with diamine, if unreacted isocyanate groups exist some or all of the remaining isocyanate groups are preferably endcapped with an amine or alcohol to terminate the foregoing poly(urethane-urea) resin.
  • Suitable amines are monamines and diamines including, but not limited to butylamine, dibutylamine, aminopropylmorpholine, aminoethylpiperazine, dimethylaminopropylamine, di(isopropanol)amine, aminoethoxyethanol, aminoundecanoic acid, ethanolamine, dimethanolamine,4-aminophenol, isophoronediamine, dimer diamine, oleyl amine, hydrazine, Jeffamine brand mono or bis (aminopropyl) polypropyleneoxides.
  • suitable alcohols include, but are not limited to, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, ethanol, oleyl alcohol, 12-hydroxystearic acid, N-(hydroxyethyl)stearamide, ethoxylated nonylphenol, propoxylated nonylphenol, glycolic acid, or 6- hydroxycaproic acid.
  • the endcapping reaction of any remaining free isocyanate groups is carried out under conditions which are well known to those skilled in the art. Preferably, this reaction is carried out in the presence of a solvent or in a component of the solvent system ultimately used in the final composition formulated from the ink resin as described above.
  • the total amount of solvent utilized to endcap the free isocyanate groups generally ranges from 0 to 90 percent by weight, preferably ranges from 25 to 75 percent by weight.
  • the temperature of the endcapping reaction generally ranges from 0 to 100°C, and preferably ranges from 25 to 75°C.
  • the time of the endcapping reaction generally ranges from a period of from 0.1 to 6 hours, and preferably from 0.25 to 1 hours.
  • the NCO- equivalent ratio of the chain-extended resin to amine or alcohol generally ranges from 5:1 to 1:5, and preferably ranges from 1 :2 to 2:1.
  • a particularly preferred polyurethane resin prepared as described above is one wherein Z is an isophorone group, R is a C 4 hydrocarbon group, R 1 is an aminopropylmorpholine radical, X is the residue of isophorone diamine, n is 20, x is 6, and y is 1.75.
  • the polyurethane resin described herein is soluble in solvents such as alcohol to provide a clear solution.
  • solvents such as alcohol
  • an alcohol solvent can be added to reach a final dilution of 10 to 90 percent by weight solids, and preferably from 20 to 60 percent by weight solids, and more preferably 30 to 45 percent by weight solids at a temperature of about 20 °C.
  • suitable alcohol solvents include, but are not limited to, aliphatic alcohols, preferably short chain aliphatic alcohols having from 1 to 8 carbon atoms, and more preferably short chain aliphatic alcohols having from 1 to 4 carbon atoms, e.g., methanol, ethanol, 1-propanol, 2- propanol, 1-butanol, pentanol, hexanol, 2-ethyl hexanol and octanol.
  • the ratio of alkyl acetate to alcohol solvent ranges from about 1 :10 to about 10:1 by weight in the resin solution as supplied for making printing inks.
  • flexographic printing inks require at least 80% alcohol solvent to prevent swelling of the flexible printing plates that are based on either rubber or photopolymer.
  • the resulting clear solution of polyurethane resin in solvent can be used directly, without other additives, as a binder for packaging inks.
  • Other chemicals can be added to the clear polyurethane solution to formulate for a particular application, e.g., use of fillers, thickeners, other co-resins, waxes, etc.
  • the foregoing polyurethane solution can be combined with a pigment to form a printing ink composition.
  • One common technique is expected to use a pigment dispersion in nitrocellulose and solvent that is modified with the polyurethane resins from this invention. Such inks are expected to be suitable for surface printing and laminations.
  • the printing inks in general, contain three main components: 1) a pigment which imparts a color to the printing ink, 2) a binder which efficiently disperses the pigment and provides gloss, chemical resistance, toughness, etc. to the printed ink, and 3) a solvent which provides a medium to disperse/dissolve the pigment and binder.
  • the printing ink can also contain other minor additives such as fillers, surfactants, wax and the like to suit a variety of printing needs.
  • pigment is specifically used in this specification in that it is intended to refer to both pigments and dyes which impart a distinct color to the printing ink composition.
  • the purpose of any pigment is to provide contrast between the color of a printable substrate and the color of ink in order to provide a visually identifiable indicia on the substrate.
  • the pigment may be any of those which are typically used in flexographic inks such as monoazo yellows (e.g. CI Pigment Yellows 3, 5, 98); diarylide yellows (e.g. CI Pigment Yellows 12, 13, 14); Pyrazolone Orange, Permanent Red 2G, Lithol Rubine 4B, Rubine 2B, Red Lake C, Lithol Red, Permanent Red R, Phthalocyanine Green, Phthalocyanine Blue, Permanent Violet, titanium dioxide, carbon black, etc.
  • the pigment is employed in amounts of from 10 to 45 percent by weight, based on the weight of the ink composition.
  • the pigment is combined with the binder resin solution by any convenient method.
  • the pigment can be added to the binder resin solution and, at a properly adjusted viscosity, dispersed therein with ball mill, sand mill, horizontal media mill, high-shear fluid flow mill, Cowles Dissolver®, Kady Mill®, or the like.
  • the viscosity and printing characteristics of the printing ink composition may be modified further by addition of conventional addditives such as, plasticizers, sequestered wax, surfactants and the like to suit the particular printing needs.
  • the printing processes most advantageously used with the foregoing printing ink are the flexographic and/or gravure printing processes.
  • One characteristic of such printing processes is that the printing ink composition is applied to a surface of a printable substrate by a hydrophilic cylindrical transfer roll.
  • Printing processes are described, e.g., by T. Sulzberg et al., "Printing Ink Vehicles", Encyclopedia of Polymer Science and Engineering, Vol. 13, pp. 368-398 (John Wiley & Sons, Inc., N.Y., N.Y. 1988), the contents of which are incorporated by reference herein.
  • a method of printing which includes applying the foregoing printing ink composition to a printing surface having minute depressions therein which carry the composition, and contacting the printing surface with a printable substrate.
  • This method may be a letterpress printing method (wherein the minute depressions on the printing surface define raised portions of the surface which carry the composition to the substrate, e.g., flexography) or a gravure printing method (wherein the depressions carry the composition to the substrate).
  • the printing ink composition is applied to a flexible plate mounted on a plate cylinder.
  • the flexible plate is then contacted with a printable substrate by rotation of the plate cylinder.
  • the printing ink composition is applied to the flexible plate with a cylindrical transfer roll which is rotated to successively take up and then apply successive portions of the composition.
  • the laminates may contain laminae (layers of substrates) of a wide variety of flexible materials.
  • suitable laminae include films of polyethylene and polypropylene generally treated for adhesion promotion; also polyester such as polyethylene terephthalate, cellophane and polyamide which may or may not be coated with PVDC for improved barrier properties.
  • dissimilar laminae are used where films, for example, of corona treated polypropylene or polyethylene are bonded to polyester, polyamide or PVDC coated cellophane or PVDC coated polyester, or paper.
  • laminates prepared with woven and non- woven fabrics where the fibers are of cotton, polyester, polyolefin, polyamide, polyimide and the like; metallic foils such as aluminum foil; metallized films; paper and paperboard; and cellular flexible sheet material such as polyethylene foam, polyurethane foam and sponge and foam rubber.
  • the laminae will be translucent to visible light and, more typically, transparent. Such translucency or transparency will allow the colorant to present a hue and or resolvable image through that substrate.
  • the other laminate may also be translucent or transparent, but need not be, for example, when an opaque inner liner is desired.
  • any of the conventionally used solvent-borne or aqueous adhesives may be employed in the printing process.
  • Adhesives are discussed in "Adhesive Compositions", Encyclopedia of Polymer Science and Engineering, Vol. 1, pp. 547- 577 (John Wiley & Sons, Inc. N.Y., N.Y., 1985), the disclosure of which is incorporated by reference herein.
  • a solvent-borne adhesive a moisture curable polyurethane in a polar organic solvent is typically used.
  • an aqueous adhesive an aqueous emulsion of a flexible adhesive polymer is typically used.
  • the adhesive In forming the laminates, conventional techniques known per se are employed to apply the adhesive to the film substrate. Thus, these adhesives may be applied by use of an extrusion process or any mechanical coating process such as air knife, trailing blade, knife coater, reverse roll or gravure coating technique. Most commonly, the adhesive is coated over the ink on the substrate and allowed to dry. A second substrate is then applied to the adhesive layer under conditions of elevated temperature which activate the adhesive while in contact with the substrate, for example, a corona treated polyethylene or polypropylene film or other lamina. The following examples are meant to illustrate but not to limit the invention.
  • Example 1 180.01 Grams of Terathane 1400 (DuPont product) and 0.07 grams of dibutyltindilaurate were charged to a reaction vessel under nitrogen and heated to 60°C. Over 0.5 hour, 43.11 grams of isophorone diisocyanate was added to the Terathane solution followed by 99.88 grams n-propylacetate. The temperature was increased to 85°C and held for 2 hours. After cooling the reaction to 35°C and adding an additional 48.92 grams propylacetate to the vessel, a solution of 7.71 grams isophorone diamine, 4.06 grams diethanol amine in 102.03 grams 1-propanol was added from an addition funnel over 10 minutes. The mixture was held at 45°C for 30 minutes before adding 297.90 grams 1-propanol. After addition of the alcohol, the temperature was held at 85°C for 1 hour. The resulting resin had a molecular weight of 35,200.
  • the mixture was held at 50°C for 30 minutes before adding 6.57 grams diethanol amine and 220.68 grams 1- propanol. After addition of the alcohol, the temperature was held at 85°C for 1 hour.
  • the resulting resin had a molecular weight of 35,200.
  • Example 5 200.10 Grams of Terathane 1400 (DuPont product) and 0.19 grams of dibutyltindilaurate were charged to a reaction vessel under nitrogen and heated to 65°C. Over 0.5 hour, 44.50 grams of isophorone diisocyanate was added to the Terathane solution followed by 205.77 grams n-propylacetate. The temperature was increased to 85°C and held for 2.25 hours. After cooling the reaction to 35°C and adding an additional 223.3 grams propylacetate to the vessel, a solution of 4.15 grams isophorone diamine and 3.67 grams diethanol amine in 90.40 grams propylacetate was added from an addition funnel over 30 minutes. The solution was heated to reflux and 235.67 grams of distillate removed. The mixture was held at 90°C while adding 142.0 grams 1-propanol. The resulting resin had a molecular weight of 55,100.
  • Example 6 190.90 Grams of Terathane 1400 (DuPont product) and 0.18 grams of dibutyltindilaurate were charged to a reaction vessel under nitrogen and heated to 65°C. Over 0.5 hour, 40.68 grams of isophorone diisocyanate was added to the Terathane solution followed by 207.87 grams n-propylacetate. The temperature was increased to 85°C and held for 2.25 hours. After cooling the reaction to 35°C and adding an additional 89.02 grams propylacetate to the vessel, a solution of 4.07 grams isophorone diamine and 3.41 grams diethanol amine in 82.73 grams propylacetate was added from an addition funnel over 30 minutes. The solution was heated to reflux and 238.92 grams of distillate removed. The mixture was held at 80°C while adding 299.56 grams 1-propanol. The resulting resin had a molecular weight of 37,400.
  • Example 7 35.74 Grams of isophorone diisocyanate and 0.09 grams of dibutyltindilaurate in 145.62 grams propylacetate were charged to a reaction vessel under nitrogen and heated to 60°C. Over 1 hour, 166.40 grams of Terathane 1400 (DuPont product) was added to the isocyanate solution followed by another 36.0 grams n-propylacetate. The temperature was increased to 85°C and held for 2.25 hours. After cooling the reaction to 35°C, a solution of 3.07 grams isophorone diamine in 120.0 grams propylacetate was added from an addition funnel over 15 minutes. A solution of 2.85 grams diethanolamine in 85.84 grams propylacetate was added over 15 minutes. The solution was heated to reflux and 297.16 grams of distillate removed. The mixture was held at 90°C while adding 226.05 grams 1- propanol and 69.55 grams propylacetate. The resulting resin had a molecular weight of 33,200.
  • Example 8 180.41 Grams of Terathane 1400 (DuPont product) and 0.12 grams of dibutyltindilaurate in 100.54 grams propylacetate were charged to a reaction vessel under nitrogen and heated to 65°C. Over 1 hour, 47.32 grams of 1,3 bis(isocyanato-l- methylethylbenzene) (also known as TMXDI or tetramethylxylene diisocyanate) was added to the Terathane solution. The temperature was increased to 85°C and held for 3 hours.
  • 1,3 bis(isocyanato-l- methylethylbenzene) also known as TMXDI or tetramethylxylene diisocyanate
  • Example 9 32.05 Grams of isophorone diisocyanate and 0.09 grams of dibutyltindilaurate in 100.46 grams propylacetate were charged to a reaction vessel under nitrogen and heated to 60°C. Over 1 hour, 147.98 grams of Terathane 1400 (DuPont product) was added to the isocyanate solution followed by another 60.89 grams n-propylacetate. The temperature was increased to 85°C and held for 2.25 hours. After cooling the reaction to 35°C, a solution of 1.80 grams isophorone diamine in 107.31 grams propylacetate was added from an addition funnel over 15 minutes. A solution of 2.64 grams diethanolamine in 83.68 grams propylacetate was added over 15 minutes. The solution was heated to reflux and 250.76 grams of distillate removed. The mixture was held at 90°C while adding 204.02 grams 1- propanol and 28.79 grams propylacetate. The resulting resin had a molecular weight of 27,900.
  • Example 10 32.05 Grams of
  • Example 11 59.79 Grams of isophorone diisocyanate and 0.24 grams of dibutyltindilaurate in 70.51 grams propylacetate were charged to a reaction vessel under nitrogen and heated to 60°C. Over 1 hour, 250.91 grams of Terathane 1400 (DuPont product) was added to the isocyanate solution. The temperature was increased to 85°C and held for 2 hours. After cooling the reaction to 35°C and adding an additional 94.65 grams propylacetate to the vessel, a solution of 11.44 grams isophorone diamine in 49.60 grams propylacetate was added from an addition funnel over 15 minutes. A solution of 4.75 grams diethanolamine in 99.04 grams 2- propanol was added over 15 minutes. The solution was heated to 55°C while adding 270.75 grams 2-propanol. The resin solution was then heated to 85°C and held for 1 hour. The resulting resin had a molecular weight of 68,100.
  • Stepan Corporation (a polyester diol from orthophthalic acid and diethylene glycol) was added to the isocyanate solution followed by an additional 28.53 grams propylacetate. The temperature was increased to 85°C and held for 2 hours. After cooling the reaction to 55°C and adding an additional 104.75 grams propylacetate to the vessel, a solution of 6.62 grams isophorone diamine in 80.25 grams propylacetate was added from an addition funnel over 2 hours. The solution was heated to 60°C while adding 112.51 grams 1-propanol. The resin solution was then heated to 85°C and held for 1 hour. The resulting resin had a molecular weight of 136,000.
  • the temperature was raised to 65°C and held for 1 hour.
  • the polyurethane solution was 35% resin, 42.7% propylacetate, and 22.3% 1- propanol.
  • the resulting resin had a molecular weight of 32,000.
  • Example 21 120.02 Grams of isophorone diisocyanate, 0.06 grams of dibutyltindilaurate, and 216.71 grams n-propylacetate were charged to a reaction vessel under nitrogen and heated to 70°C. Over 1 hour, 154.82 grams of Acclaim 2220N poly(propylene oxide) diol from Lyondell and 227.12 grams of Stepanpol PN- 110 (a polyester diol from orthophthalic acid and neopentyl glycol) were added to the warm isocyanate solution. The temperature was increased to 85°C and held for 3 hours.
  • Stepanpol PN- 110 a polyester diol from orthophthalic acid and neopentyl glycol
  • Example 22 83.72 Grams of isophorone diisocyanate, 0.04 grams of dibutyltindilaurate, and 219.04 grams n-propylacetate were charged to a reaction vessel under nitrogen and heated to 70°C. Over 1 hour, 389.31 grams of Terathane 2000 (DuPont product) was added to the warm isocyanate solution. The temperature was increased to 85°C and held for 3 hours. After cooling the reaction to 45°C the vessel contents were pumped via an FMI Lab Pump over 1.5 hours to another vessel containing 42.14 grams isophorone diamine in 406.79 grams propylacetate. The mixture was held at 55°C for 30 minutes before adding 330.89 grams 1-propanol.
  • Terathane 2000 DuPont product
  • the temperature was raised to 65°C and held for 1 hour.
  • the polyurethane solution was 35% resin, 42.5% propylacetate, and 22.5% 1- propanol.
  • the resulting resin had a molecular weight of 31 ,000.
  • Lamination ink compositions are prepared using the components listed in Table 1 below.
  • each white ink composition add 30g of 4mm glass beads then grind 20 minutes on shaker and dilute to 60.0 centipoise with 80/20 solvent blend n-propanol ethyl acetate.
  • Extrusion Laminates are identified by the number corresponding to the foregoing polyurethane preparation examples.
  • Extrusion Laminates are identified by the number corresponding to the foregoing polyurethane preparation examples.
  • Adhesive Laminates are identified by the number corresponding to the foregoing polyurethane preparation examples.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une résine de polyuréthane obtenue par réaction d'un diol polymérique tel qu'un diol de polyéther, un diol de polyester, ou des mélanges de ceux-ci, avec un diisocyanate pour former un prépolymère à terminaison d'isocyanate. On procède alors à la réaction du prépolymère avec une diamine, celle-ci pouvant être suivie d'une réaction avec une autre amine ou un alcool. Des solutions claires de résine de polyuréthane sont utilisées dans la formulation de compositions d'encre d'imprimerie, d'adhésifs, et de vernis clairs.
PCT/US2000/022471 1999-08-20 2000-08-17 Compositions de polyurethane pour encres a laminer WO2001014442A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR0013434-1A BR0013434A (pt) 1999-08-20 2000-08-17 Resina de poliuretano, solução clara, método de preparação de uma resina de poliuretano, composição de tinta, método de preparação da mesma, laminado, e, método de preparação do mesmo
EP00955595A EP1208127A1 (fr) 1999-08-20 2000-08-17 Compositions de polyurethane pour encres a laminer
JP2001518770A JP2004513977A (ja) 1999-08-20 2000-08-17 ラミネート用インキに用いるポリウレタン組成物
AU67774/00A AU6777400A (en) 1999-08-20 2000-08-17 Polyurethane compositions for laminating inks

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15000599P 1999-08-20 1999-08-20
US60/150,005 1999-08-20
US63792900A 2000-08-14 2000-08-14
US09,637,929 2000-08-14

Publications (1)

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WO2001014442A1 true WO2001014442A1 (fr) 2001-03-01

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002038643A2 (fr) * 2000-11-13 2002-05-16 Sun Chemical Corporation Resines de poly(urethane/uree) solubles dans un solvant
EP1357141A1 (fr) * 2002-04-25 2003-10-29 Sicpa Holding S.A. Résine de polyuréthane dérivée de composés polyol hydrophiliques
WO2003091307A1 (fr) * 2002-04-25 2003-11-06 Sicpa Holding S.A. Resine polyurethanne derivee de resines polyhydroxylees
EP1496072A1 (fr) * 2003-07-11 2005-01-12 Sicpa Holding S.A. Résine de polyuréthane pour les encres blanches
WO2007006586A1 (fr) 2005-07-14 2007-01-18 Dsm Ip Assets B.V. Procede de preparation de polyurethanne a base de solvant
WO2009052973A1 (fr) * 2007-10-23 2009-04-30 Cognis Ip Management Gmbh Résines de polyuréthane pour encres pour pelliculage

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294129A (ja) * 2001-03-29 2002-10-09 Dainippon Ink & Chem Inc ラミネート缶用印刷インキバインダー
WO2007056660A1 (fr) * 2005-11-02 2007-05-18 Sun Chemical Corporation Encres d’impression flexographiques et a gravure pour substrats non tisses
JP2011504521A (ja) * 2007-10-31 2011-02-10 サン・ケミカル・コーポレーション 不織布基体のためのフレキソ印刷およびグラビア印刷インキ
JP6107384B2 (ja) * 2013-04-26 2017-04-05 東洋インキＳｃホールディングス株式会社 軟包装用ラミネートインキ組成物
JP6571710B2 (ja) * 2017-03-24 2019-09-04 三洋化成工業株式会社 印刷インキ用バインダー及びこれを用いた印刷インキ

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242674A (ja) * 1988-03-24 1989-09-27 Kuraray Co Ltd 印刷インキ用組成物
JPH05222333A (ja) * 1991-03-06 1993-08-31 Arakawa Chem Ind Co Ltd 印刷インキ用バインダーおよび印刷インキ組成物
JPH05331400A (ja) * 1992-05-28 1993-12-14 Arakawa Chem Ind Co Ltd 印刷インキ用バインダー
EP0604890A1 (fr) * 1992-12-28 1994-07-06 Sakata Inx Corporation Résine polyuréthanne, son procédé de préparation et encre d'impression pour produits stratifiés la contenant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242674A (ja) * 1988-03-24 1989-09-27 Kuraray Co Ltd 印刷インキ用組成物
JPH05222333A (ja) * 1991-03-06 1993-08-31 Arakawa Chem Ind Co Ltd 印刷インキ用バインダーおよび印刷インキ組成物
JPH05331400A (ja) * 1992-05-28 1993-12-14 Arakawa Chem Ind Co Ltd 印刷インキ用バインダー
EP0604890A1 (fr) * 1992-12-28 1994-07-06 Sakata Inx Corporation Résine polyuréthanne, son procédé de préparation et encre d'impression pour produits stratifiés la contenant

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198945, Derwent World Patents Index; Class A25, AN 1989-327740, XP002153577 *
DATABASE WPI Section Ch Week 199339, Derwent World Patents Index; Class A25, AN 1993-309340, XP002153575 *
DATABASE WPI Section Ch Week 199403, Derwent World Patents Index; Class A25, AN 1994-023061, XP002153576 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723820B1 (en) 2000-11-13 2004-04-20 Sun Chemical Corporation Solvent soluble poly(urethane/urea) resins
WO2002038643A3 (fr) * 2000-11-13 2002-10-03 Sun Chemical Corp Resines de poly(urethane/uree) solubles dans un solvant
WO2002038643A2 (fr) * 2000-11-13 2002-05-16 Sun Chemical Corporation Resines de poly(urethane/uree) solubles dans un solvant
US7067607B2 (en) 2002-04-25 2006-06-27 Sicpa Holding S.A. Polyurethane resin derived from hydrophilic polyol components
EP1361236A1 (fr) * 2002-04-25 2003-11-12 Sicpa Holding S.A. Résine de polyuréthane dérivée de résines polyhydroxylées
WO2003091307A1 (fr) * 2002-04-25 2003-11-06 Sicpa Holding S.A. Resine polyurethanne derivee de resines polyhydroxylees
EP1357141A1 (fr) * 2002-04-25 2003-10-29 Sicpa Holding S.A. Résine de polyuréthane dérivée de composés polyol hydrophiliques
CN1307228C (zh) * 2002-04-25 2007-03-28 盛威科比荷卢有限公司 由多羟基化树脂得到的聚氨酯树脂
EP1496072A1 (fr) * 2003-07-11 2005-01-12 Sicpa Holding S.A. Résine de polyuréthane pour les encres blanches
WO2005005508A1 (fr) * 2003-07-11 2005-01-20 Siegwerk Benelux Nv Resine polyurethanne pour encres blanches
WO2007006586A1 (fr) 2005-07-14 2007-01-18 Dsm Ip Assets B.V. Procede de preparation de polyurethanne a base de solvant
WO2007006583A1 (fr) * 2005-07-14 2007-01-18 Dsm Ip Assets B.V. Composition de polyurethanne supportee par un solvant
CN101238159B (zh) * 2005-07-14 2012-06-20 帝斯曼知识产权资产管理有限公司 制备溶剂型聚氨酯的方法
US8492458B2 (en) 2005-07-14 2013-07-23 Dsm Ip Assets B.V. Solvent borne polyurethane composition
CN101223203B (zh) * 2005-07-14 2013-08-14 帝斯曼知识产权资产管理有限公司 溶剂型聚氨酯组合物
WO2009052973A1 (fr) * 2007-10-23 2009-04-30 Cognis Ip Management Gmbh Résines de polyuréthane pour encres pour pelliculage

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JP2004513977A (ja) 2004-05-13
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AU6777400A (en) 2001-03-19

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