WO2005028533A1 - Resines de polyurethanes de faible poids moleculaire - Google Patents

Resines de polyurethanes de faible poids moleculaire Download PDF

Info

Publication number
WO2005028533A1
WO2005028533A1 PCT/US2003/026286 US0326286W WO2005028533A1 WO 2005028533 A1 WO2005028533 A1 WO 2005028533A1 US 0326286 W US0326286 W US 0326286W WO 2005028533 A1 WO2005028533 A1 WO 2005028533A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
diol compound
compound
polymer
ink
Prior art date
Application number
PCT/US2003/026286
Other languages
English (en)
Inventor
David Klein
William P. Keaveney
Robert Auerbach
Original Assignee
Sun Chemical 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 Sun Chemical Corporation filed Critical Sun Chemical Corporation
Priority to PCT/US2003/026286 priority Critical patent/WO2005028533A1/fr
Priority to AU2003265579A priority patent/AU2003265579A1/en
Publication of WO2005028533A1 publication Critical patent/WO2005028533A1/fr

Links

Classifications

    • 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
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Definitions

  • This invention relates to low molecular weight polyurethane resins for use in laminating inks displaying high lamination bond strength.
  • laminated flexible packagings are currently used since direct contact of the contents with inks must be avoided to ensure utmost hygiene while impressing consumers with the high quality of printing.
  • Lamination is carried out by two methods described hereunder: extrusion lamination which comprises printing an ink on various plastic film bases, applying a primer coat on the printed surface as required, and then laminating a molten layer of polyolefin or the like; and adhesive lamination which comprises applying an adhesive to the printed surface, and then laminating a plastic film.
  • extrusion lamination which comprises printing an ink on various plastic film bases, applying a primer coat on the printed surface as required, and then laminating a molten layer of polyolefin or the like
  • adhesive lamination which comprises applying an adhesive to the printed surface, and then laminating a plastic film. Whichever method is adopted, inks to be used on the various kinds of plastic films to be laminated are required to adhere strongly not only to the base film but also to the film to be laminated .
  • Solvent based inks represent the bulk of the laminating inks consumed for packaging.
  • the main resins used in solvent applications are acrylics, modified acrylics, polyamides, and urethanes. These soluble resins typically wet out and adhere to the film surfaces and laminated structures with superior bonds.
  • Water based inks are gaining in popularity as a way to reduce organic emissions and retained solvent in food packaging.
  • acrylics, and more recently urethanes have found utility and are of the solution and latex type.
  • water based inks suffer from wettability, adhesion, and bond strength limitations
  • Japanese Patent Application No. 354568/1991 discloses an aqueous laminating printing ink for use as a binder in an aqueous polyurethane resin containing a polycarbonate diol as a diol component and which was improved in adhesion to various plastic films and peel strength of laminates. Flexible packagings produced by using such aqueous laminating inks can be used to make bags for packaging dry foods .
  • Japanese Patent Application No. 317425/1992 discloses a method for improving the adhesion to various plastic films and the peel strength of laminates by using, as an ink binder resin, an acrylic copolymer that had functional groups capable of reaction with a hydrazine group or a hydrazide group introduced into the molecule, and hydrazine compounds as a crosslinking agent, said agent with those functional groups and carbonyl groups that developed on the film surface by subsequent surface treatment.
  • an ink binder resin an acrylic copolymer that had functional groups capable of reaction with a hydrazine group or a hydrazide group introduced into the molecule
  • hydrazine compounds as a crosslinking agent, said agent with those functional groups and carbonyl groups that developed on the film surface by subsequent surface treatment.
  • the binder resins will crosslink with the crosslinking agents to lower their fluidity and capability for redissolution.
  • U.S. patent 5,656,701 discloses polyurethane resins having at, least one group selected from hydrazine groups, hydrazide groups and semicarbazide groups (the group of these functional groups is described as HYD groups) , in the molecule, a process for producing the same, aqueous ink compositions for plastic film using the same as binders, aqueous adhesive agents for film lamination and a method of making laminates using said ink and/or adhesives . While the polyurethane resins described in this patent posses better than before physical properties, the extrusion lamination bond strength was still considered to be relatively weak.
  • the present invention provides a polyurethane resin having a number average molecular weight of up to 5,000, wherein the resin is prepared by: (a) reacting a diisocyanate compound with at least one monomer diol compound and optionally a polymer diol compound without a chain extendor to form a polymer, wherein the molar ratio of the monomer diol compound over the polymer diol compound when present is above 1; and (b) capping the polymer with a terminator.
  • the present invention also provides a method for preparing a polyurethane resin comprising: (a) reacting a diisocyanate compound with at least one monomer diol compound and optionally a polymer diol compound without a chain extendor to form a polymer, wherein the molar ratio of the monomer diol compound over the polymer diol compound when present is above 1; and (b) capping the polymer with a terminator.
  • polyurethane resins of the present invention can be used in laminating inks displaying high lamination bond strength when such resins have a number average molecular weight of up to 5,000 and prepared by reacting an isocyanate compound with at least one monomer diol compound and optionally a polymer diol compound without a chain extendor to form a polymer, wherein the molar ratio of the monomer diol compound over the polymer di ⁇ l compound when present is above: 1, followed by capping the polymer with a terminator.
  • the resin of the present invention have an average molecular weight of about 3,000 to 5,000.
  • the monomer diol compound is preferably dimethylol propionic acid, 2 -methyl-1, 3-propanediol , chloroglycerol, 1, 4-butanediol, 1, 6-hexanediol or neopentylglycol .
  • the organic diisocyanate may be any monomeric diisocyanate but is more preferably toluenediisocyanate.
  • the polymer diol may be one of any available examples but is preferably Terathane 650 or Tone 0200, and the terminator is a CI to C4 primary alcohol such as propanol, or Abitol, or hydroxylated surfactants such as Igepal C-720.
  • Table 1 illustrates the length of the various diols that can be used in preparing the resins of the present invention:
  • the molar ratio of the monomer diol compound over the polymer diol compound when present in the resin of the present invention is above 2.
  • the resin can also have acid number of 0 to about 300, preferably, of about 60 too 140, and more preferably about 120 to 135.
  • the formation of the polymer of the present invention prior to capping (or termination) is carried out in an organic solvent, followed by addition of water and a basic compound and removal of the organic solvent by azeotropic distillation.
  • the organic solvent is an aprotic compound having a boiling temperature of about 60 to 140°C, more preferably, methylethylketone.
  • the basic compound is ammonium hydroxide.
  • Example 1 - Resin Synthesis The urethane resins of the present invention were made by first adding the diols (see below for composition) and MEK [methyl ethyl ketone] to a flask, distilling off a few percent of solvent to remove residual water and then cooling to 40°C. The TDI [toluene diisocyanate] was added continually and after the initial exotherm subsided, the mixture was heated to 78-80°C. When the theoretical NCO limit was reached the reaction was quenched with n-propanol . MEK was stripped off until stirring was difficult and then water/ammonia was a : dded slowly. When the temperature reached 100-101°C the MEK had been removed and the urethane was completely dissolved in water. The resin solids level was 31-33% in water.
  • Polyurethane Resin Solution 1 [Toluenediisocyanate/Dimethylolpropionicacid (/2-methyl- 1,3 propanediol, Molar ratio (0.95/0.65/0.20)] Polyurethane Resin Solution 2
  • Polyurethane Resin Solution 3 [Toluenediisocyanate/Dimethylolpropionicacid/1 , 4 butanediol, Molar ratio (0.95/0.65/0.20)]
  • Polyurethane Resin Solution 4 [Toluenediisocyanate/Dimethylolpropionicacid/Terathane 650, Molar ratio (0.95/0.65/0.20)] .
  • Example 2 Procedure For Ink Preparation
  • White ink was prepared as follows: In a blender jar add resin, water, grind aid, and white pigment were added. The mixture was grinded at high speed 4 minutes or until the grind reaches 0/0 on the grind gauge. Then, surfactants were added as well as water to adjust viscosity to the proper specification.
  • Colored ink was prepared as follows: The appropriate solvents and defoamers were added to the resin with stirring to make a letdown varnish. The proper amount of pigment dispersion were weighed into a jar. While stirring the pigment dispersion, the appropriate amount of letdown varnish to the jar was added. Water was subsequently added to adjust the ink to the proper viscosity.
  • Example 3 - Ink formulation Water-based laminating inks were prepared by grinding pigment into, or letting down a commercial pigment dispersion with, a varnish made from the above described experimental polyurethane resins. . The following tables illustrate the various compositions of experimental Inks 1-5:
  • Table 2 - Ink 1 White water-based laminatin ink
  • Ink 1 was prepared by weighing in a blender jar Joncryl 62 (14 g) , water (25.8 g) , Tioxide R-HD6X (90 g) , urea (1.8 ⁇ g), and Surfynol CT-136 (2.0 g) . The mixture was blended at high speed for 4 minutes. Then, Joncryl 62 (11 g) , Rez 300 (8.4 g) , experimental polyurethane resin 1 (38 g) , Surfynol 104 PA (2 g) , Dapro DF-975 (0.2 g) , and water (6.8 g) were added. All ingredients were mixed for 15 seconds to make Ink 1.
  • Varnish 1 was made by weighing experimental polyurethane resin solution 1 (81.9 g), water (14.2 g) , n-pr ⁇ pylalcohol (2.8 g) , Surfynol 104PA (0.9 g), O.lg Nalco 2303, and Daypro DF-975. The ingredients blended at high speed for 5 minutes. Then, varnish (50 g) was
  • Joncryl 62 (14 g) , water (25.8 g) , Tioxide R-HD6X ⁇ 90 g) , urea (1.8 g) , and Surfynol CT-136 (2 g) were weighed in a blender jar and blended at high speed for 4 minutes. Then, Joncryl 62 (11 g) , Rez 300 (8.4 g) , experimental polurethane resin solution 3 (38 g) , Surfynol 104PA (2 g) , Daypro DF-975 (0.2 g) , and water (10 g) were added and mixed for 15 seconds to result in Ink 4.
  • Joncryl 62 (14 g) , water (25.8 g) , Tioxide -HD6X (90 g) , urea (1.8 g) , and Surfynol CT-136 (2 g) were weighed in a blender jar and blended at high speed for 4 minutes. Then, Joncryl 62 (11 g) , Rez 300 (8.4 g) , experimental polyurethane resin solution 4 (38 g) , Surfynol 104PA (2 g) , Daypro DF-975 (0.2 g) , water (2 g) were added and mixed for 15 seconds to result in Ink 5.
  • Joncryl 2610 (25 g) , water (25.8 g) , Tioxide R-HD6X (90 g) , urea (1.8 g) , and Surfynol CT-136 (2 g) were weighed in a blender jar and blended at high speed for 4 minutes. Then, add Joncryl 2610 (25 g) , Rez 300 (11 g) , Lucidene 351 (7 g) , TV94-5991 (6 g) , Surfynol 104 PA (2 g) , Dapro DF-975 (0.2 g) , Nalco 2303 (0.2 g) , and water (4 g) were added and mixed for 15 seconds to result in DPF-427 white ink.
  • Example 4 - Ink Testing Experimental inks were printed side-by- side with the standard ink using a 200-line anilox flexo roller on the appropriate film. Prints were dried for 10 seconds in an 80°C oven.
  • Extrusion lamination Prints were overprinted with a primer using a 360-line anilox roller. The prints . were dried for 15 seconds in an 80 °C oven. Extrusion lamination was modeled by placing the appropriate polyethylene film to the print and then running the . structure through the hot roll laminator set at 300°F. The structure was then immediately tested for bond strength. The bond strength was determined by pulling apart the laminated structure with the Instron Tensile Tester. This test determines the adhesive and cohesive properties of the laminated inks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention porte sur une résine de polyuréthane don't le poids moléculaire moyen au nombre s'élève à 5,000. On prépare cette résine en mettant à réagir un composé de diisocyanate avec au moins un composé diol monomère et éventuellement un composé diol polymère sans allongeur de chaîne de façon à former un polymère, le rapport molaire du composé diol monomère sur le composé diol polymère, s'il y a, étant supérieur à 1, et en coiffant ensuite le polymère avec un terminateur.
PCT/US2003/026286 2003-08-21 2003-08-21 Resines de polyurethanes de faible poids moleculaire WO2005028533A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2003/026286 WO2005028533A1 (fr) 2003-08-21 2003-08-21 Resines de polyurethanes de faible poids moleculaire
AU2003265579A AU2003265579A1 (en) 2003-08-21 2003-08-21 Low molecular weight polyurethane resins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2003/026286 WO2005028533A1 (fr) 2003-08-21 2003-08-21 Resines de polyurethanes de faible poids moleculaire

Publications (1)

Publication Number Publication Date
WO2005028533A1 true WO2005028533A1 (fr) 2005-03-31

Family

ID=34374763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/026286 WO2005028533A1 (fr) 2003-08-21 2003-08-21 Resines de polyurethanes de faible poids moleculaire

Country Status (2)

Country Link
AU (1) AU2003265579A1 (fr)
WO (1) WO2005028533A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1520940A (en) * 1977-06-16 1978-08-09 Ciba Geigy Ag Production of low molecular weight urethane polymer dispersions
US4163094A (en) * 1978-04-07 1979-07-31 Scm Corporation Heat curing water soluble homopolyurethanes
EP0590480A1 (fr) * 1992-09-29 1994-04-06 Basf Corporation Compostion de revêtement de polyuréthane à partir d'un polyol contenant une chaîne longue aliphatique
EP0835890A1 (fr) * 1996-10-11 1998-04-15 Canon Kabushiki Kaisha Polymère d'addition soluble à l'eau et encre aqueuse l'utilisant
WO1999041320A1 (fr) * 1998-02-17 1999-08-19 Minnesota Mining And Manufacturing Company Encre pour jet d'encre renfermant un dispersant a base de polyurethanne
WO2002012396A2 (fr) * 2000-08-09 2002-02-14 Dow Global Technologies Inc. Polyurethanne thermoplastique haute resistance a faible poids moleculaire et ses melanges

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1520940A (en) * 1977-06-16 1978-08-09 Ciba Geigy Ag Production of low molecular weight urethane polymer dispersions
US4163094A (en) * 1978-04-07 1979-07-31 Scm Corporation Heat curing water soluble homopolyurethanes
EP0590480A1 (fr) * 1992-09-29 1994-04-06 Basf Corporation Compostion de revêtement de polyuréthane à partir d'un polyol contenant une chaîne longue aliphatique
EP0835890A1 (fr) * 1996-10-11 1998-04-15 Canon Kabushiki Kaisha Polymère d'addition soluble à l'eau et encre aqueuse l'utilisant
WO1999041320A1 (fr) * 1998-02-17 1999-08-19 Minnesota Mining And Manufacturing Company Encre pour jet d'encre renfermant un dispersant a base de polyurethanne
WO2002012396A2 (fr) * 2000-08-09 2002-02-14 Dow Global Technologies Inc. Polyurethanne thermoplastique haute resistance a faible poids moleculaire et ses melanges

Also Published As

Publication number Publication date
AU2003265579A1 (en) 2005-04-11

Similar Documents

Publication Publication Date Title
EP1229090B1 (fr) Résine de polyuréthane et procédé pour sa préparation, composition de revêtement la contenant, son utilisation pour l'impression de substrats plastiques, et procédé pour la fabrication d'un laminé avec une image imprimée
CN108864807B (zh) 印刷油墨用粘合剂、印刷油墨及其应用以及印刷物
US6723820B1 (en) Solvent soluble poly(urethane/urea) resins
AU2002231758A1 (en) A polyurethane resin and method of producing it, a coating composition comprising a polyurethane resin, use of a polyurethane resin for printing plastic substrates
JP2018177854A (ja) リキッドインキ組成物、印刷物及びラミネート積層体
EP1361236B1 (fr) Résine de polyuréthane dérivée de résines cétoniques dures
EP1357141B1 (fr) Résine de polyuréthane dérivée de composés polyol hydrophiliques
US6624240B2 (en) Low molecular weight polyurethane resins
JP2004513977A (ja) ラミネート用インキに用いるポリウレタン組成物
JP7156796B2 (ja) 表刷り用リキッド印刷インキ組成物及び印刷物
JP3895035B2 (ja) 水性印刷インキ組成物
WO2005028533A1 (fr) Resines de polyurethanes de faible poids moleculaire
JP3791631B2 (ja) 水性印刷インキ組成物
JP2001002971A (ja) ラミネート用印刷インキ組成物、およびそれを用いたラミネート加工物。
AU2004255321A1 (en) A polyurethane resin for white inks
JP3237506B2 (ja) グラビア印刷インキ用バインダー
JPH05222332A (ja) 印刷インキ用バインダー
JPH0137427B2 (fr)
JPH06100817A (ja) フレキソ印刷インキ用バインダー
JPH10130561A (ja) 水性印刷インキ組成物
JPH02117974A (ja) 印刷インキ用バインダー
JPH07324179A (ja) ラミネート用溶剤系印刷インキ組成物
JPH07157706A (ja) 印刷インキ用バインダー
JPS6191268A (ja) プラスチック用印刷インキ組成物
JP2000273382A (ja) ラミネート用印刷インキ組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NI NO NZ OM PG PH PT RO RU SC SD SE SG SK SL SY TJ TN TR TT TZ UA UG US UZ VC VN ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR HU IE IT LU NL PT RO SE SI SK TR BF BJ CF CI CM GA GN GQ GW ML MR NE SN TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP