EP2748237A1 - Revêtements de film de polyalkylèneimine époxylée - Google Patents

Revêtements de film de polyalkylèneimine époxylée

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Publication number
EP2748237A1
EP2748237A1 EP13702855.1A EP13702855A EP2748237A1 EP 2748237 A1 EP2748237 A1 EP 2748237A1 EP 13702855 A EP13702855 A EP 13702855A EP 2748237 A1 EP2748237 A1 EP 2748237A1
Authority
EP
European Patent Office
Prior art keywords
film
thermoplastic film
coated
coated thermoplastic
compound
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13702855.1A
Other languages
German (de)
English (en)
Inventor
Dennis E. Mcgee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jindal Films Americas LLC
Original Assignee
Jindal Films Americas LLC
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
Priority claimed from PCT/US2012/035977 external-priority patent/WO2013048576A1/fr
Application filed by Jindal Films Americas LLC filed Critical Jindal Films Americas LLC
Publication of EP2748237A1 publication Critical patent/EP2748237A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/06—Epoxy-capping
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines

Definitions

  • the present invention(s) relate to film coatings to improve printability, and more particularly to epoxide or glycidyl-modified polyalkyleneimines and its use as a coating on at least one side of a polyolefm film.
  • US 6,893,722 discloses the use of an amine functional styrenated polyacrylate-based coatings with unsaturation to enhance cross-linking that demonstrates improved printability on polypropylene films.
  • WO 2012-134695 describes film coatings that retain some essential elements of US 6,893,722 that yield excellent UV printability and print durability (isopropyl alcohol resistance, pasteurization resistance, etc.) but without VOCs and without the need of a complex polymerization process (and the associated equipment constraints).
  • a key element taught in WO 2012-134695 is modification of a polyalkyleneimine (PAI) backbone in such a way to yield a dry coating that contained moieties of ethenic unsaturation from the group consisting of acrylic, methacrylic, and enamine.
  • PAI polyalkyleneimine
  • the present disclosure is to a different kind of modification of PAI polymers by reacting glycidyl ethers of ethoxylated long-chain alcohols and other such modifiers with primary and secondary amines in the PAI backbone.
  • thermoplastic films wherein at least one side of the film is coated with a coating composition, the coating composition comprising the reaction product of a PAI having at least primary amine, and an epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (Mw) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; or within a range of from 200 or 300 g/mole to 600 or 800 or 1000 g/mole.
  • a coating composition comprising the reaction product of a PAI having at least primary amine, and an epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (Mw) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; or within a range of from 200 or 300 g/mole to 600 or 800 or 1000 g/mole.
  • coated thermoplastic films having a coating composition on at least one side of the film, the coating composition comprising a substituted PAI having at least primary amines:
  • each R is independently a hydrogen or an epoxide-derived group having at least one epoxide moiety and a weight average molecular weight (M w ) of at least 500 or 800 or 1000 g/mole; each R" is selected from divalent Ci to C 4 or C 6 or C 10 alkylene groups; and wherein n is a value within the range of from 50 to 100 or 400 or 600 or 800 or 1000 or 2000 or 3000 or 4000, wherein the degree and type of branching along the polymer backbone is variable, this formula represents only one of several types of branching that can occur.
  • a method for making a coated film comprising: combining in water a PAI having at least primary amines, and an epoxide compound having at least one epoxide moiety and a weight average molecular weight (M w ) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole, forming a reaction product; diluting the aqueous reaction product to a solids level within the range of from 0.1 or 0.25 or 0.5 or 1 or 2 or 4% to 5 or 10 or 15 or 20%; applying the diluted reaction product evenly to at least one surface of a thermoplastic film; drying the reaction product on the at least one film surface to form a dried coating composition at a temperature within the range of from 70 or 80°C to 120 or 130 or 140°C; wherein the weight of the dried coating compound on each side of the film is within the range from 0.005 or 0.010 or 0.015 g/m 2 to 0.035 or 0.040 or 0.050 or 0.075 or 0.
  • Figure 1 is a photograph of an acrylate-polyethyleneimine coated film that has been exposed to silicon from a liner, then having been corona treated below the line drawn half-way down the length of the film, followed by treatment with printing ink (blue);
  • Figure 2 is a photograph of a similarly coated and treated film as in Figure 1 , but with higher coating weight of the acrylate-polyethyleneimine coating;
  • Figure 3 is a photograph of a similarly treated film, where the silicon has been cleaned from the central strip of the film using adhesive tape, demonstrating that the ink beads up and does not adhere where the silicon remained and was exposed to coronal treatment;
  • Figure 4 are graphical representations of how RID is influenced by various parameters shown in Table 1, where "NGR" is the inventive sample of Table 1, where the heading of each graph represents the y-axis;
  • Figure 5 are graphical representations of how the viscosity of the inventive and prior art coatings are influenced by various levels of ingredients, where "NGR" is the inventive sample of Table 1, where the heading of each graph represents the y-axis;
  • Figure 6 is a graphical representation of the viscosity on day 1 as a function of the level of DenacolTM in the reaction mixture
  • Figure 7 is a graphical representation of the viscosity on day 7 as a function of the level of DenacolTM in the reaction mixture
  • Figure 8 is a graphical representation of the %INK-W 0-2 as a function of the level of Denacol (glycidyl ether) added;
  • Figure 9 is a graphical representation of the %INK-W 0-2 as a function of the level of Denacol (glycidyl ether) (phr) added to the reaction mixture for various coating weights on the film; and
  • Figure 10 is a graphical representation of the RID as a function of the level of Denacol (glycidyl ether) added to the reaction mixture at various coating weights on the film.
  • Denacol glycol ether
  • the invention(s) disclosed herein include a novel film coating comprising the reaction product of a PAI and an epoxide or glycidyl-type compound, preferably a higher molecular weight glycidyl ether.
  • a novel film coating comprising the reaction product of a PAI and an epoxide or glycidyl-type compound, preferably a higher molecular weight glycidyl ether.
  • Such modification of the PAI backbone improves print performance after the print surface has been in contact with silicone-based release liners.
  • the inventor has found that ethenic unsaturation, as taught in US 6,893,722 and WO 2012-134695, is actually detrimental to print performance of the coating when the print surface has been contaminated with silicone.
  • the "coating composition” described herein comprises (or consists essentially of, or consists of) at least the substituted PAI, but may also include some unreacted species (PAI and/or epoxide) and may include processing additives as described furtherer herein.
  • PAI and/or epoxide unreacted species
  • processing additives as described furtherer herein.
  • PAI polyalkyleneimine
  • (R-NH)x is a polymeric or monomeric unit where R contains from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms, and most preferably from 1 to 4 carbon atoms; x is an integer from 1 to 500,000. More particularly, the PAI may be represented by the following general formula: (-NHCI3 ⁇ 4CH2-)m[- N(CH 2 CH 2 NH 2 )CH 2 CH 2 -] thread, wherein m is from 10 to 20,000, and n is from 20 to 2,000, preferably from 50 to 2000.
  • Useful PAIs may also comprise secondary amines, and may also comprise tertiary amines, thus, most desirably, useful PAIs have a combination of primary, secondary and tertiary amines.
  • the PAIs preferably have a level of secondary amines within the range of from 20 or 30 or 40% to 60 or 70 or 80% relative to all the nitrogens on the PAI.
  • the PAIs preferably have, independently, a level of primary and tertiary amines within the range of from 5 or 10 or 15% to 30 or 35 or 40 or 50% relative to all the nitrogens on the PAI.
  • the PAIs that are useful herein have a weight average molecular weight (M w ) of from 10,000 or 20,000 g/mole to 80,000 or 100,000 or 200,000 or 500,000 or 800,000 or 1,000,000 g/mole.
  • M w weight average molecular weight
  • desirable commercial PAIs include LupasolTM FG, G20, G35, G100, HF, and P from BASF, and EpominTM SP012, SP018, SP200, and P1050 from Nippon Shokubai.
  • the "epoxide compounds” described herein are compounds that have at least one epoxide moiety, preferably only one epoxide moiety, and possesses a weight average molecular weight (Mw) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; or within a range of from 200 or 300 g/mole to 600 or 800 or 1000 g/mole.
  • Mw weight average molecular weight
  • An "epoxide-derived group” is simply an epoxide compound that has reacted via an epoxide carbon, either the alpha or beta, to form a substitution compound with an amine of the PAI.
  • Preferable epoxide compounds are sel (III):
  • R is hydrogen or another epoxide compound (the same or different), a fatty acid, a C 10 to C50 alkyl; a C 6 or Cg to C22 or C50 alkoxy, alcohol or ethoxylated alcohols; C 6 to C40 phenyls or aryls and alkyl-substituted versions thereof, and combinations of any two or more of these groups.
  • Highly desirable epoxide compounds are glycidyl compounds selected from mono- functional glycidyl ethers of ethoxylated primary, secondary, and tertiary alcohols having a weight average molecular weight (M w ) of at least 200 or 300 or 400 or 500 or 600 g/mole, or within a range of from 200 or 300 g/mole to 500 or 800 or 1000 g/mole.
  • M w weight average molecular weight
  • the epoxide compound is a mono-functional such as described in (II) or (III), water-soluble glycidyl ether having greater than or equal to 12 or 14 or 16 or 18 or 20 moles of ethoxylation; or within a range from 10 or 12 or 14 moles to 18 or 20 or 24 moles of ethoxylation.
  • Examples of potentially suitable epoxide compounds are mono-functional glycidyl ethers such as DenacolTM EX192, EX171 (based on primary long-chain alcohols, Denacol EX191 is the glycidyl ether of a primary alcohol containing a mixture of C 12 and C 13 carbon chains and no ethoxylation; Denacol EX171 is the glycidyl ether of an ethoxylated (15 moles) primary Ci 2 alcohol) and Denacol FCA-364-9, FCA-364-12, FCA-364-15, and FCA-364-20 (based on secondary long-chain alcohols having a mixture of Cn to C 15 carbon chains and 9, 12, 15, or 20 moles of ethoxylation, respectively).
  • DenacolTM EX192, EX171 based on primary long-chain alcohols, Denacol EX191 is the glycidyl ether of a primary alcohol containing a mixture of C 12 and C 13 carbon chains and no eth
  • Mono-functional, water-soluble glycidyl ethers having greater than or equal to 10 or 12 or 14 moles of ethoxylation are most preferable, or within a range of from 8 or 10 moles to 14 or 16 or 18 or 20 moles.
  • Other water-soluble mono- functional glycidyl ethers like ethylene oxide, (R)-(+)-Glycidol, (S)-(-)-Glycidol, or racemic glycidol could be used alone or in conjunction with the ethoxylated, long-chain glycidyl ethers already described.
  • poly-functional glycidyl ethers like Denacol EX811, Denacol EX821, Denacol EX-314, or Denacol EX622 could be used alone or in conjunction with the ethoxylated, long-chain glycidyl ethers to boost molecular weight, although excessive cross-linking may create issues with viscosity and printability.
  • the epoxide compound is chosen so that there is little or no cross-linking of the coating on the surface of the film.
  • the present invention is directed in part to a coating composition
  • a coating composition comprising an epoxide-substituted PAI (or "substituted PAI"), that is the reaction product of a PAI having at least primary amine, and an epoxide compound having at least one epoxide moiety and a weight average molecular weight (Mw) of at least 100 or 150 or 200 or 250 g/mole.
  • the coating composition comprises (or consists essentially of, or consists of) a substituted PAI that may be represented by the formula (I):
  • each R is independently a hydrogen or an epoxide-derived group having at least one epoxide moiety and a weight average molecular weight (M w ) of at least 500 or 800 or 1000 g/mole; each R" is selected from divalent Ci to C 4 or C 6 or C 10 alkylene groups; and wherein n is a value within the range of from 50 to 100 or 400 or 600 or 800 or 1000 or 2000 or 3000 or 4000, or 5,000 or 10,000 or 15,000 or 20,000 wherein the degree and type of branching along the polymer backbone is variable, this formula representative of only several types of branching that can occur.
  • ethenic unsaturation is substantially absent from the coating composition, meaning that no measurable amount of unsaturation is present.
  • the invention is also directed in part to a coated thermoplastic film, wherein at least one side of the film is coated with a coating composition, the coating composition comprising the reaction product of the PAI having at least primary amine, and the epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (M w ) of at least 200 g/mole.
  • the coating composition comprising the reaction product of the PAI having at least primary amine, and the epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (M w ) of at least 200 g/mole.
  • M w weight average molecular weight
  • the coating composition is the reaction product with the additional component of an acetoacetoxy compound.
  • the dry coating weight of the coating on the film may be within the range from 0.05 or 0.10 or 0.15 g/m 2 to 0.35 or 0.40 or 0.50 or 0.75 or 1.00 g/m 2 ; otherwise, the weight of the dried coating compound on one or each side of the film is preferably within the range from 0.005 or 0.010 or 0.015 g/m 2 to 0.035 or 0.040 or 0.050 or 0.075 or 0.100 g/m 2 .
  • the coating composition may be the reaction product with the additional component of ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; preferably ethylene oxide.
  • the acetoacetoxy compound is preferably selected from: wherein R' is an acrylate or methacrylate moiety, a Ci to C 2 o alkyl or alkylene, a Ci to C 2 o alkoxy or hydroxide or alkyl-substituted versions thereof.
  • the invention(s) also include a method for making the coated film comprising combining in aqueous medium of at least 60 wt% (vole%) water, preferably consisting of water, a PAI as described above and an epoxide compound as described, forming a reaction product; diluting the aqueous reaction product to a solids level within the range of from 0.1 or 0.25 or 0.5 or 1 or 2 or 4% to 5 or 10 or 15 or 20%.
  • the diluted reaction product is applied evenly to at least one surface of a thermoplastic film.
  • the reaction product is dried on at least one film surface to form a dried coating composition at a temperature within the range of from 70 or 80°C to 120 or 130 or 140°C.
  • the weight of the dried coating compound on one or each side of the film is within the range from 0.005 or 0.010 or 0.015 g/m 2 to 0.035 or 0.040 or 0.050 or 0.075 or 0.100 g/m 2 .
  • Any desirable method can be used to apply the suspension of reaction product (substituted PAI), such as a gravure roll, spray, etc., as is known in the art.
  • the composition of the aqueous coatings are such that the viscosity (25°C) is less than 1000 or 800 or 500 or 400 cP, or within a range of from 10 or 20 or 50 cP to 500 or 800 or 1000 cP.
  • the presence of some acetoacetoxy moieties can be used to adjust the viscosity, and/or dilution of the reaction product with water or an alcohol (esp. methanol, ethanol or isopropanol).
  • the PAI reaction product, or coating composition may include other processing additives known in the art to facilitate processing or adjust the viscosity of the composition such as anti-foaming agents, including insoluble oils, dimethyl polysiloxanes and other silicones, certain alcohols, stearates and glycols such as ethylene glycol monohexyl ether (commercially available as Hexyl CellosolveTM from Dow Chemicals) or DowanolTM PM (also from Dow Chemical); wetting agents such as ionic and non-ionic surfactants; and particulates such as particles of alumina, silica, calcium carbonate, titanium dioxide, clays, magnesium silicate, aluminum silicate, calcium phosphate, PMMA, and other particulates, preferably having an average diameter of from 1 to 50 or 100 microns.
  • the aqueous coating formulation can comprise from 0.2 wt% up to 5 or 8 or 10 wt% by weight of the coating composition (including solvent) of processing additives.
  • the epoxide compound is preferably reacted with the PAI in an amount to bind to between 10 or 20 or 30 or 40 or 50% to 60 or 70 or 80 or 90 or 95 or 100% of the primary amines of the polymer.
  • the epoxy equivalent weight (EEW) for the mono-functional glycidyl ether in this example is preferably within a range from 800 or 850 to 1000 or 1100 EEW and the PAI having an amine value within the range from 12 or 14 to 20 or 22 or 24 mmol/g solid and from 40 to 60% secondary amine content relative to all amines in the polymer.
  • the thermoplastic film which is preferably flexible in that it can conform to round or otherwise irregularly-shaped objects, comprises at least one layer of a polymer selected from the group consisting of polypropylenes, polyethylenes, polyesters, nylons, and mixtures thereof.
  • the thermoplastic film comprises polypropylene as the primary component, even if it is not the only component, as the film may comprise any number of layers commonly known in the art, with polypropylene at the core.
  • the thermoplastic film is an oriented polypropylene film.
  • the flexible thermoplastic films that are useful for the inventive coated films can be of most any structure but preferably have at least a SCS structure, where "C” is the core polypropylene layer, and “S” is a sealable or otherwise coatable skin layer.
  • the "C” and “S” layers are most preferably co-extruded polymeric materials, the core layer having a thickness within the range of from 10 or 15 ⁇ to 25 or 30 or 40 or 60 ⁇ ; the overall film preferably has a thickness within the range of from 20 or 30 ⁇ to 40 or 50 or 60 or 80 or 100 ⁇ .
  • a flexible film may have any number of other tie-layers "T” and skin layers "S", each of which may be the same composition or different, as is known in the art, and thus may have an overall structure such as STCTS, STCS, SCTS, STCTSS, STCTS, SCTSS, etc.
  • the structure is one of P C CS, P C SCTS, P C STCTS, etc., where "P c " is the printable coating which may include at least one primer layer against the film side as is known in the art.
  • the coated film may or may not be "energy treated” as by using heat, corona, plasma, e-beam, or other ionizing radiation imparted to at least part of the film surface, such treatment also including oxygen and/or mixed with inert gases such as nitrogen or argon.
  • the coated side of the film is not energy-treated (heat, corona, plasma, e-beam) prior to rolling and storage.
  • the inventive films are useful for labels and thus may comprise printing upon the coated side of the film.
  • the films may have incidental silicone (Si) on the coated surface as the result of being in contact with adjacent film layers in a roll or through other incidental contact or removable layer (e.g., such layers comprising release agents such as, or including, silicone), and thus the coated side of the film may have within the range from 2 or 3 or 5 mol% to 10 or 15 mol% silicon on its surface, based on the relative elemental abundance of all silicon-containing species detected by ESCA.
  • Si incidental silicone
  • This first comparative example is a description of a lab-scale method to quantify the problem being solved and an Example demonstrating the problem.
  • RID Relative Ink Density
  • Step 1 Preparation of Silicone Solution. Chloroform was used to create a 0.2% (2000 ppm) solution of XiameterTM PMX-200 Silicone Fluid 60,000 cS. Once the silicone fluid had completely dissolved, nine parts of anhydrous isopropyl alcohol were added to the solution for every part of chloroform solution. The result was a clear solution containing 200 ppm silicone fluid that was roughly 90% IPA and 10% chloroform. This is used to coat a test film to mimic the effects of exposure to a liner containing silicon.
  • Step 2 Apply Silicone to Test Sample.
  • the sample that was to be printed with the print surface facing up was placed on a K Control Coater and clipped into place. Two pieces of unwrinkled brown paper with a total thickness of about 150 microns were placed under the test sample. The #2 red-handled Meier rod was locked into place. Care was taken that the weights were free to apply pressure to both ends of the Meier rod. Enough of the silicone solution was applied in front of the rod to ensure that the entire surface of the test sample was covered when the K Control Coater moved the bar across the sample: a wet spot on the paper at the edges and end of the sample was a good indicator of adequate coverage.
  • the drawdown speed setting was at ' 10' (maximum).
  • the excess silicone solution was wiped off of the Meier rod and then the rod was cleaned with ethyl acetate.
  • the silicone solution has completely evaporated off of the test sample by the time that the operator has cleaned the rod, but care was taken that the silicone solution was completely evaporated before performing the next step.
  • the sample was air dried and not heated. Measurements made by ESCA showed that the Si level on a sample prepared in this way was about 2 mol% (mole percent), or between 2 and 15 mol% if coarser rods or more concentrated silicone solutions were used.
  • the ESCA measurements were made on a PHI 5600 ESCA system, following the procedure for using that instrument.
  • Step 3 Corona Treat the Silicone-Treated Sample before Printing.
  • the silicone-treated sample was corona treated prior to printing in order to reproduce typical procedures followed in commercial film printing processes. However, part of the sample was left untreated, as explained below. Since the de-wetting phenomenon usually only occurs after corona treatment, only part of the sample film was protected from exposure to the corona so that there was a basis for comparing the ink density in the treated portion to ink density in the untreated portion. This was accomplished by covering the top half of the sample with a piece of uncoated 2-mil base OPP film like 196 MC550. Tape was used to affix the protective cover to the test sample.
  • the power setting reading was set between 43 and 48% power when the treater was on. This was a normal fluctuation range. If sporadic readings are seen below 40%> or above 50%, then the treater power was adjusted accordingly until stable.
  • the test was developed with OPPaLyteTM 350 TW film as the carrier web, but almost any carrier web with a thickness of 25-50 microns is suitable.
  • the web was stopped before the printable surface contacted any other rolls.
  • the sample was removed from the carrier web, and the treatment cover (which can be used again) was removed from the sample.
  • Step 4 Print Samples on the Little Joe Proofing Press.
  • IGT Printability Tester Fl made by IGT Testing Systems (The Netherlands).
  • reproducible responses were obtained using a Little Joe proofing press.
  • the ink-transfer mechanism is different for these two pieces of equipment.
  • the IGT Tester transfers ink from an anilox roll to a supported piece of film attached to a roller; the Little Joe transfers ink from a blanket to a flat piece of film held in place on a flat surface. Absolute ink densities are more variable off of the Little Joe unless all parts are cleaned after every drawdown.
  • Samples were printed on the Little Joe proofing press. The sample was taped to a single sheet of white copy paper and then mounted in the clips in the center of the Little Joe on the sample stage. No other paper or spacers were on the sample stage.
  • the blanket Prior to applying the ink to the sample, the blanket was rapidly worked over the platen seven times with the seventh pass continuing directly over the sample. The blanket was lifted on the return stroke so that the blanket only contacts the print surface one time.
  • the rate of ink de- wetting can differ from sample to sample, so it is preferred to wait for 10 seconds or until all visual movement of the ink has stopped before passing the printed sample through the Fusion UV unit to cure the ink. Two passes were used to cure the ink when printed on the Little Joe.
  • Step 5 Measuring Ink Density.
  • An XiRiteTM 500 Series Spectrodensitometer was used for measuring ink density. Samples were tested over a stack of at least 50 sheets of white paper to ensure that the countertop color did not affect the reading. Two measurements were made in the untreated area, which was fairly uniform. If the ink laydown appeared poor in both treated and untreated zones, the sample was unsuitable for printing and the RID not measured or recorded. Two measurement locations were selected that appeared to be representative of the entire untreated zone (away from the contact location of the silicone bead, plus possible defects due to backside treatment and any obvious anomalies related to the drawdown). The location of the measurement was marked after making the measurement for future reference.
  • Ink densities for the untreated area should be between about 1.5 and 2.4 when using the cyan Gemini FlexocureTM ink. Based on a few test cases, the RID value will trend slightly higher if the untreated ink density was higher. If the ink was too thick, then the de-wetting effect was totally obscured.
  • Step 6 Calculation of the RID.
  • the RID calculation was performed as follows: an average of two density measurements in the untreated area and five density measurements in the treated area were made. The treated average was divided by the untreated average and the raw RID result was reported as a percentage. Replicate tests were generally within 10 to 15%. To compare results from one sample set to the next, it was preferable to normalize the raw RID results to a commercial benchmark like 50 LL534II. The raw RID average for an experimental sample was divided by the raw RID result for 50 LL534II tested on the same day with the same treatment conditions and the same silicone solution. The normalized RID value was reported as a percentage.
  • ScotchTM 610 tape was used to remove surface silicone from the print face of a sample laminated to a silicone release liner. As described above, the sample was passed through the treater with the upper portion covered prior to printing. After printing, ink adhesion was then tested with Scotch 600 tape (shown in angled lanes outlined in black) as shown in Figure 3. Catastrophic ink de-wetting (low ink density) was seen in zones exposed to corona treatment without having surface silicone removed by tape. Ink adhesion and ink density were excellent in all untreated zones (cleaned or not).
  • TC means “top coat” or simply “coating.”
  • Coating compositions prepared in this experiment all contained some level of 4-methoxyphenol (MEHQ). This material was added to prevent possible polymerization of AAEM during the substitution reaction.
  • MEHQ 4-methoxyphenol
  • a log-linear set of levels was chosen: 1 , 10, 100, and 1000 ppm with log values of 0, 1 , 2, and 3, respectively.
  • the Type 1 coating compositions in the above table contained enough AcAc compounds (acetoacetoxyethyl methacrylate [AAEM] and/or ethyl acetoacetate [EtOAcAc]) to react stoichiometrically with all the available primary amines in Epomin PI 050.
  • the highest levels of AAEM (125 phr) and EtOAcAc (75 phr) correspond to the stoichiometric amount of AcAc material needed to react with the primary amines to form enamines.
  • Denacol EX171 which has one epoxide moiety, was chosen to be stoichiometrically equivalent to the number of available secondary amines in Epomin PI 050 that could react with the glycidyl ether.
  • Coatings were applied using a 550-Quad gravure cylinder on a lab-scale coater.
  • samples were prepared by coating 5 -inch wide film on a TalboysTM lab coater
  • a 550-Quad gravure cylinder with a flooded nip is used to apply coatings to the desired side of the film after in-line corona treatment.
  • the coating is held in a stainless steel pan that can be raised and lowered to ensure that the gravure cylinder remains wet.
  • Coating consumption can be estimated by weighing the pan and the coating before and after coating a known amount of film.
  • the line speed is typically 35-40 feet/min (10.7-12.2 m/min), and the coatings are dried by passing through a four-foot oven set at the desired temperature. Rolls are wound onto cardboard cores that are three inches in diameter.
  • Table 2 (“AcAc” is acetylacetone) describes the formulations for the sixteen coating compositions that were tested in this example.
  • a 20% aqueous solution of Epomin PI 050 was used to facilitate faster dispersion of the viscous polymer.
  • Denacol EX171 which is a waxy solid at room temperature, was melted at about 53°C prior to mixing with the other ingredients. The indicated ingredients were mixed at ambient temperature with a magnetic stirring bar for about eight days before they were coated on a clear, 2-mil base film manufactured by ExxonMobil
  • y-axis units are in the headings of each graph: "log 10 MEHQ” is the concentration of MEHQ in the wet coating; “AAEM” is the phr of AAEM used in the polymer synthesis; “NGR Type” means that EtOAcAc was used to compensate for reduction in the acetoacetoxy functionality (or not) as the AAEM level was changed; “% Solids” describes the solids content of the coating formulation when it was applied and since the same gravure cylinder is used for the entire experiment the dry coating weight will change roughly in proportion to the solids content of the coating; “T°C” is the drying temperature in °C that was used to dry the coating in the oven.
  • gravure cylinders and process equipment can be designed to handle a very wide range of viscosities
  • coatings with viscosities that are less than 500 cP are preferred, more preferably less than 100 cP, and very commonly less than 20 cP (25°C).
  • All Type 1 polymers (theoretically having all primary amines capped with an AcAc compound) had viscosities that were less than 30 cP.
  • the mean viscosity for the Type 2 coating compositions was less than 400 cP.
  • Including as little as 45-phr AAEM in the formulation was enough to lower the mean viscosity from about 1100 cP to less than 50 cP.
  • Example 3
  • phase differentiation causes large variations in viscosity versus Denacol loading; coating composition viscosity passes through a minimum at 1150 phr Denacol EX171 per 100 phr Epomin PI 050.
  • Coating compositions can also be synthesized at lower solids content (for example, 3% or 5% solids) if the polymer dispersion turns out to be too viscous at higher solids.
  • Use of a PAI with lower molecular weights can help to reduce dispersion viscosities and allow coating compositions to be produced at solids levels of at least 10% solids.
  • This Example demonstrates the effect of the level of substitution of the coating composition on print durability after exposure to water.
  • samples were printed with ink on test surfaces that had no prior exposure to UV light followed by two passes under the UV lamp to cure the ink. This is the "O-Ink-2" curing protocol.
  • the effect of too much Denacol was visible in samples cured with the O-Ink-2 printing protocol.
  • Each pass under the UV lamp typically exposed the sample to an energy equivalent that was between 0.09 and 0.12 Joules/cm 2 .
  • Samples were prepared containing between 10 phr and 1000 phr Denacol EX171 and applied at a variety of coating weights to determine a range of compositions and coatings weights that had the best print durability after exposure to water.
  • the same set of samples was also tested for relative ink density after contact with silicone (RID).
  • the plots in Figures 9 and 10 show the outcome.
  • compositions that offer the most latitude with respect to print durability as a function of coating weight comprise between 100 phr and 600 phr Denacol EX171 per 100 phr Epomin PI 050.
  • RID values were also at least 95% in this range, which was quite acceptable. However, due to the viscosities described in Example 3, coating compositions having a Denacol EX171/Epomin P1050 ratio between about 4 and 6 are generally preferred. If emulsions in this range are prepared at between 5 and 8% solids, then desirable emulsion viscosities of less than 500 cP were obtained. These emulsions can then be easily diluted to achieve coating weights between about 0.01 and 0.03 g/m 2 , which will yield excellent printability and print durability, even after being exposed to silicone-based release liners.
  • Epomin PI 050 According to data published by Nippon Shokubai (www.shokubai.co.jp/en/products/functionality/epomin2), Epomin PI 050 has 25% primary and tertiary amines and 50% secondary amines. Therefore, the average amine hydrogen equivalent weight was 43 g/eq. According to the certificate of analysis provided by Nagase, the lot of Denacol EX171 used in this experiment had an epoxy equivalent weight (EEW) of 990 g/eq. Though Epomin PI 050 has an equal number of primary and secondary amine hydrogens initially (primary amines have two reactive hydrogens and secondary amines only have one), once a primary amine reacts a first time, it becomes a secondary amine.
  • one-third of the amines on Epomin PI 050 can behave as primary amines, and two- thirds can behave as secondary amines. Since primary amines are more reactive that secondary amines, the reaction between the glycidyl ether of the ethoxylated alcohol will be with the primary amines in the PAI polymer.
  • the preferred level of epoxide compound of the coating compositions should contain enough glycidyl ether, of the type described in this invention, to react with between 10 and 100% of the available primary amine hydrogens. Factoring in issues with emulsion viscosity, more preferred coating compositions would contain enough glycidyl ether to consume between 40 and 100% of the available primary amine hydrogens. Most preferred formulations would contain enough glycidyl ether to consume between 50 and 90%> or even between 60 and 80%> of the available primary amines.
  • This example distinguishes blocking (the adhesion of the film to itself or another similar film) tendencies between ethoxylated PAI, which does not contain glycidyl ethers with a hydrophobic chain, and a coating composition prepared according to this invention.
  • Polymer 1 Polyethylene imine, 80% ethoxylated (weight average molecular weight (M w ) 70,000) was purchased from Sigma-Aldrich as a 37.8% aqueous solution. This polymer was the reaction product of polyethylene imine and ethylene oxide (C 2 H 4 O) such that about 80% of the primary and secondary amines become hydroxyethylated (R 2 NCH 2 CH 2 OH, where "R" is the polymer backbone).
  • Coated Structures Three coated structures were prepared using the above polymer solutions. Both polymers were diluted to 0.5%> solids with deionized water and applied to 196 MC550 film obtained from ExxonMobil Chemical Co. using a 130-Quad gravure cylinder at 40 fpm, as described in an earlier example. The base film was corona treated in line, as described in another example, to facilitate coating laydown. The coatings were dried at 100°C, which yielded an approximate coating weight of 0.03 g/m 2 .
  • Roll #1 A roll was prepared in which both sides of the substrate were coated with Polymer 1. After coating one side of the substrate with Polymer 1 , the roll was sent through the coater again, such that the second side of the substrate was also coated with Polymer 1 under the same conditions. The finished roll had about 100 wraps (or layers) of film on the roll (approximately 90 to 100 linear feet).
  • Roll #2 A roll was prepared in which only one side of the substrate was coated with Polymer 1, but the second side was corona treated at the same level that was used during the coating step. Some roll stock laminators prefer to have an uncoated, but treated surface on the adhesive- receiving side. This sample was prepared by corona treating one side of the film during the first pass through the small coater (without engaging the coating station). When the film was sent through the coater again, the second side was corona treated and coated with Polymer 1. The finished roll also had about 100 wraps (or layers) of film on the roll (approximately 90 to 100 linear feet). Roll #3: During the first pass through the coater, Polymer 1 was applied to the substrate. On the second pass through the coater, Polymer 2 was applied to the opposite side.
  • This finished roll also had about 100 wraps (or layers) of film on the roll (approximately 90 to 100 linear feet).
  • Blocking Results All three rolls were kept at ambient conditions (about 23°C, about 40-50% RH) for twelve days. After that time, it was attempted to unwind the small rolls using the unwinding and rewinding stations on the coater (no coatings were in the station and the oven was off). Ideally, the coated rolls should unwind all the way down to the core without affecting the clarity of the coated surfaces. The number of wraps taken off each roll was recorded as a way to quantify the blocking response and summarized in Table 3.
  • Results from this example show that polymers prepared according to this invention have excellent block resistance, even if paired against a coating with very strong blocking tendencies.
  • Ethoxylated PEI was very printable and resistant to solvents (when thin layers are applied to treated polyolefin films). It could make a useful coating for the print surface or the adhesive-receiving surface. However, the blocking tendencies of ethoxylated PEI limit its utility in structures that require a treated surface or a coated surface on the opposite side of the film. However, a blend of ethoxylated PEI with substitution polymers from this invention can be used to fine tune the balance of coating properties, since Polymer 1 was water soluble (hydrophilic) and Polymer 2 was not water soluble (hydrophobic). Example 6
  • Coating Formulation The following ingredients were mixed in a 2-gallon pail liner using a football-shaped magnetic stirrer to make sample coating compositions. When all the components were dissolved after about 30 minutes of mixing, the contents were transferred to two half-gallon plastic jugs and placed in a hot room (53°C) for about 24 hours:
  • Epomin P 1050 (diluted to 20% solids, 100 parts) 169.0 g
  • TCI yielded an approximate coating weight of 0.03 g/m 2 on a pilot-scale coater equipped with a pre-coat station and oven and a reverse-direct gravure topcoat station and oven:
  • Roll 2-1 was coated on one side, with no coating or treatment on the second side.
  • Roll 2-2 was symmetrically treated and coated with TCI on both sides.
  • Roll 2-3 was coated with TCI on one side and corona treated, but not coated, on the second side. Note, with no coating stations closed on the second pass (used to corona treated the uncoated surface), Roll 2-3 had some wrinkles wound into the roll, because tension control was difficult.
  • Each 26-inch wide roll was slit into one 15-inch wide roll and two rolls that were 4.75 inches wide. During the slitting operation, rolls were wound so that the coated surface intended for printing ended up on the outside of the slit roll. A Dusenbery ribbon slitter was used.
  • the static field was also measured on the unwinding roll with a Simco Hand-E-Stat electrostatic field meter. Haze values of film near the core of the conditioned slit roll were compared with haze measured in the slab that was taken right off of the master roll when it was first prepared on the pilot-scale coater. [0087] To get a general idea of the blocking force near the core, the end of the film was secured, and the core (with layers of film amounting to less than 0.25 inches remaining on the core) was dropped into a barrel. The qualitative rate at which the core drops (not at all, slow, moderate, fast, or very fast) was taken as a factor in assessing the blocking rating.
  • film can be rolled off of the core merely by rotating the core: Such samples would have a '0' blocking rating (“R" value).
  • R '0' blocking rating
  • Table 5 Ambient conditions during rewinding were used: 73 ⁇ 1°F, 44% RH.
  • coating compositions prepared according to this invention do not block strongly to themselves or to uncoated surfaces (with or without corona treatment). Besides low unwinding force, coating haze was not adversely affected near the core of conditioned slit rolls, and the coated surfaces were free of mottling.
  • Example 6 Certain samples from Example 6 were laminated and printed upon to demonstrate their utility.
  • the 15 -inch wide wrinkle-free samples from Additional Example 6 were laminated to a pre-siliconized liner coated with a permanent adhesive from Hexion Chemical Company (SynthebondTM 7701) by Polymeric Converting.
  • a permanent adhesive from Hexion Chemical Company (SynthebondTM 7701) by Polymeric Converting.
  • the uncoated adhesive -receiving surface was corona treated immediately prior to coming in contact with the permanent adhesive. Since Roll 2-2 was symmetrically coated, no on-line corona treatment of the label face stock was necessary.
  • the coating weight for the adhesive was about 15 g/m 2 .
  • Pressure at the laminating nip was kept at 30-35 psi. Winding tension was kept between 8-10 lbs for the 15-inch web.
  • Comparative Examples 8 and 9 are used to compare to inventive Example 10 to demonstrate the usefulness of the invention when a film has been in contact with silicone.
  • High- performance label films in the industry usually have one side designated as the printable surface and the opposite side designated as the adhesive -receiving surface (examples from ExxonMobil Chemical Co.: Label-LyteTM 50LL539, Label-LyteTM 50LL534 II; RayofaceTM CPA).
  • examples from ExxonMobil Chemical Co.: Label-LyteTM 50LL539, Label-LyteTM 50LL534 II; RayofaceTM CPA examples from ExxonMobil Chemical Co.
  • roll stock laminators will apply the pressure-sensitive adhesive to the wrong side of the film due to improper labeling of the input film or improperly mounting the roll on the line. The result is wasted material that is unsuitable for printing.
  • This example demonstrates a print face coating similar to that taught in US 6,893,722; and having an adhesive-receiving side according to US 2007/0248810 Al, the adhesive coating called, for short, an "acrylic-ionomer blend".
  • an adhesive-ionomer blend Using a custom-built pilot-scale coater having a station to apply and dry a primer via an offset roll and a topcoat station that applies coating via reverse direct gravure, a structure was prepared in which a block-resistant adhesive-receiving "acrylic-ionomer blend" was applied at 0.30 g/m 2 to one side of primed Label-Lyte 196 LL B2 from ExxonMobil Chemical Co.
  • the primer beneath the adhesive-receiving coating was Mica H760A (a polyethyleneimine dispersion in water) applied at a thickness that yielded an optical density of between 0.060 and 0.065 when measured at 510 nm with a Radiachromic Reader (Far West Technology, Inc.) after a piece of Label-Lyte 196 LL B2 coated only with the primer was immersed for 30 seconds in a 0.83 g/L methanolic solution of the potassium salt of ethyl eosin (Sigma- Aldrich) that was rinsed with water and patted dry with a tissue. The eosin dye binds to amines and the water rinse removes unbound dye.
  • Mica H760A a polyethyleneimine dispersion in water
  • Optical density can be correlated with coating weight: thicker coatings yield a darker pink color after staining than thinner coatings.
  • the primer was dried at 175°F (about 80°C).
  • Line speed was set at 175 fpm and the film was treated with a bare-roll treater (from Pillar) with a power setting of 1.0 kW.
  • the primer station contained a 200-Quad gravure cylinder that transferred the acrylic- based coating to an offset roll, which applied the coating to the film.
  • the topcoat station was equipped with a 330-lpi ceramic gravure cylinder used as a kiss coater to apply the acrylic-based coating to the film while rotating at the same speed but in the direction opposite to that of the moving web.
  • the printable coating comprised 100 parts R1117 XL (an amine functional styrenated polyacrylate from Owensboro Specialty Polymers, LLC), 30 parts Ludox CLP, 5 parts acetoacetoxy ethyl methacrylate (Sigma- Aldrich), 1 part MichemEmulsionTM 09730 (Michelman, Inc.), and 0.5 parts TospearlTM 120 (Momentive Performance Materials Japan LLC).
  • the coating weight for the printable surface was about 0.13 g/m 2 and was applied at 12% solids. The coating weights for this example were determined by weighing about 0.023 m 2 of coated film before and after the coatings were removed by hand extraction with methyl ethyl ketone.
  • the 26-wide roll was slit into smaller rolls on a Dusenbery ribbon slitter.
  • a slit roll that was 43 ⁇ 4 inches wide and 1500 to 1700 feet long on a 31 ⁇ 2-inch outside diameter (“OD") cardboard core was placed into a conditioning cabinet (Model 518 from Electro-tech System, Inc.) set at 50°C/50% RH for one week. After removing the roll from the conditioning cabinet, a small slab of film was taken from the outer portion of the roll for printing tests (see table), and the remainder of the roll was moved to ambient storage conditions.
  • This Example demonstrates the coating disclosed in WO 2012-134695 on a clear film substrate.
  • a two-sided coated roll was prepared, slit, and conditioned as described in Example 8 with the following differences.
  • Mica H760A was applied in the pre-coat station such that the optical density at 510 nm after staining the dried primer (without a topcoat) with eosin dye was between 0.103 and 0.111 OD.
  • the same topcoat (applied over the top of the dried primer) was used on both sides of the film, which comprised 100 parts of the Mica/AAEM coating composition [prepared at 10% theoretical solids containing 100 phr Mica H760A and 200 phr AAEM, as described in Example 2 of WO 2012-134695 (Blend 19)] and 100 parts Ludox CLP.
  • the calculated average coating weight (based on the total amount of topcoat used after coating both sides) was applied at 3% solids to achieve a calculated coating weight of 0.0459 g/m 2 .
  • this roll was noticeably more yellow than the roll in Example 8; however, the difference was not discernible to the eye when looking at only a few sheets.
  • This roll unwound with less noise than Example 8. Initially this sample showed no hissing when it was unwound after conditioning for a week at 50°C/50% RH. Toward the middle of the roll and down to the core, very light hissing was heard periodically (perhaps due to slight variations in the coating weight). This conditioned roll was unwound to the core without tearing.
  • This Example demonstrates the inventive coatings on a clear substrate.
  • a two-side coated film roll was prepared, slit, and conditioned as described in Examples 8 and 9 with the following differences. No coatings were used in the pre-coat station on either pass.
  • the topcoat station was equipped with a 120-lpi ceramic gravure cylinder, which was used to apply a coating composition comprising 100 phr Epomin PI 050, 600 phr Denacol EX171, and 10 phr Imicure EMI-24, which, after initial mixing, was allowed to react for 22 hours at 53°C before being diluted to 0.6% solids prior to coating.
  • the coating weight on each side was about 0.030 g/m 2 .
  • the oven temperature for the topcoat oven was about 100°C. After conditioning for a week at 50°C/50% RH, the slit roll unwound to the core with no hissing or other signs of blocking. The conditioned roll had much less color than Example 9.
  • Table 7 show RID values for samples printed as described in Example 1 with the O-Ink-2 printing protocol. Ink adhesion (initially and after immersion in water) was essentially perfect for all three samples. Only samples prepared according to this invention were tested for RID after being conditioned for a week at 50°C/50% RH. This Example 10 had both sides of the slit film tested (identified as outside and inside).
  • Example 9 prints equally well on both sides, but the relative ink density (RID) after being in contact with silicone was unacceptably low (less than 80%, similar to the lower portion of the sample in Figure 3 that was not cleaned with tape prior to corona treatment in the RID test).
  • a coated thermoplastic film wherein at least one side of the film is coated with a coating composition, the coating composition comprising the reaction product of a PAI having at least primary amine, and an epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (M w ) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; or within a range of from 200 or 300 g/mole to 600 or 800 or 1000 g/mole.
  • a coating composition comprising the reaction product of a PAI having at least primary amine, and an epoxide compound having at least one epoxide moiety, preferably one epoxide moiety, and a weight average molecular weight (M w ) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; or within a range of from 200 or 300 g/mole to 600 or 800 or 1000 g/mole.
  • each R is independently a hydrogen or an epoxide-derived group having at least one epoxide moiety, preferably one, and a weight average molecular weight (M w ) of at least 200 or 300 or 400 or 500 or 800 or 1000 g/mole; each R" is selected from divalent Ci to C 4 or C 6 or C 10 alkylene groups; and wherein n is a value within the range of from 50 to 100 or 400 or 600 or 800 or 1000 or 2000 or 3000 or 4000, or 8,000 or 10,000 or 15,000 or 20,000 wherein the degree and type of branching along the polymer backbone is variable, this formula representative of only several types of branching that can occur.
  • the coated thermoplastic film of numbered paragraphs 1 and 2, wherein the PAI also comprises secondary amines.
  • thermoplastic film of any one of the previous numbered paragraphs wherein the thermoplastic film comprises at least one layer of a polymer selected from the group consisting of polypropylenes, polyethylenes, polyesters, nylons, and mixtures thereof.
  • thermoplastic film of any one of the previous numbered paragraphs wherein the thermoplastic film comprises oriented polypropylene as its primary film layer.
  • coating composition is the reaction product with the additional component of an acetoacetoxy compound; wherein the coating weight of the coating on the film is within the range from 0.05 or 0.10 or 0.15 g/m 2 to 0.35 or 0.40 or 0.50 or 0.75 or 1.00 g/m 2 .
  • R is hydrogen or another epoxide compound (the same or different), a fatty acid, a Cio to C50 alkyl; a C 6 or Cg to C22 or C50 alkoxy, alcohol or ethoxylated alcohols; C 6 to C 40 phenyls or aryls and alkyl-substituted versions thereof, and combinations of any two or more of these groups, wherein "derivation” assumes a substitution reaction with either the alpha or beta carbon of the ethoxide group.
  • R is hydrogen or another glycidyl compound (the same or different), a fatty acid, a Cio to C50 alkyl; a C 6 or Cg to C22 or C50 alkoxy, alcohol or ethoxylated alcohols; C 6 to C40 phenyls or aryls and alkyl-substituted versions thereof, and combinations of any two or more of these groups, wherein "derivation” assumes a substitution reaction with either the alpha or beta carbon of the ethoxide group.
  • M w weight average molecular weight
  • thermoplastic film of numbered paragraph 7, wherein the acetoacetoxy compound is selected from:
  • R' is an acrylate or methacrylate moiety, a Ci to C 2 o alkyl or alkylene, a Ci to C 2 o alkoxy or hydroxide or alkyl-substituted versions thereof.
  • the coated thermoplastic film of any one of the previous numbered paragraphs wherein the weight of the dried coating compound on each side of the film is within the range from 0.005 or 0.010 or 0.015 g/m 2 to 0.035 or 0.040 or 0.050 or 0.075 or 0.100 g/m 2 .
  • the coated thermoplastic film of any one of the previous numbered paragraphs wherein the coated film is not energy-treated (e.g., heat, corona, plasma, e-beam) prior to rolling and storage.
  • thermoplastic film of numbered paragraph 19 wherein the coated side of the film has within the range from 2 or 3 or 5 mol% to 10 or 15 mol% silicon on its surface, based on the relative elemental abundance of all silicon-containing species detected by ESCA.
  • thermoplastic film of any one of the previous numbered paragraphs, wherein ethenic unsaturation is substantially absent from the coating composition is substantially absent from the coating composition.
  • thermoplastic film of any one of the previous numbered paragraphs wherein the epoxide compound is reacted with the PAI in an amount to bind to between 10 or 20 or 30 or 40 or 50% to 60 or 70 or 80 or 90 or 95 or 100% of the primary amines of the polymer.
  • a method for making the coated film of any of the previous numbered paragraphs comprising:
  • a reaction product combining in water a PAI having at least primary amines, the epoxide compound having at least one epoxide moiety, preferably one, and a weight average molecular weight (M w ) of at least 200 or 400 or 500 or 800 or 1000 g/mole, forming a reaction product;
  • aqueous reaction product diluting or otherwise adjusting the aqueous reaction product to a solids level within the range of from 0.1 or 0.25 or 0.5 or 1 or 2 or 4% to 5 or 10 or 15 or 20%; in the alternative, adjusting the reaction product viscosity (25°C) to a level of less than 1000 or 800 or 500 or 400 cP, or within a range of from 10 or 20 or 50 cP to 500 or 800 or 1000 cP by the addition of water or an alcohol and/or the addition of some processing agent;
  • thermoplastic film applying the diluted/adjusted reaction product evenly to at least one surface of a thermoplastic film
  • thermoplastic film of any one of the previous numbered paragraphs.
  • thermoplastic film as a label, the coated thermoplastic film formed from the coated film of any one of the previous numbered paragraphs.

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Abstract

L'invention concerne un film thermoplastique revêtu et un procédé de fabrication de film revêtu, dans lequel au moins un côté du film est revêtu par une composition de revêtement, la composition de revêtement comprenant le produit de réaction d'une polyalkylèneimine ayant des azotes au moins primaires, et d'un composé époxyde ayant au moins une fraction époxyde et une masse moléculaire moyenne en poids (Mw) d'au moins 200 g/mol. Le poids du composé de revêtement séché sur chaque côté du film se situe à l'intérieur de la plage de 0,005 g/m2 à 0,100 g/m2, et est notamment utile dans le revêtement de film pour permettre une aptitude à l'impression lorsque la surface du film sera exposée à des taux élevés de silicium qui pourrait provenir, par exemple, de papier/films anti-adhésifs.
EP13702855.1A 2012-05-01 2013-01-18 Revêtements de film de polyalkylèneimine époxylée Withdrawn EP2748237A1 (fr)

Applications Claiming Priority (2)

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PCT/US2012/035977 WO2013048576A1 (fr) 2011-09-29 2012-05-01 Film mat garni d'un produit de condensation de polyalkylimine imprimable
PCT/US2013/022074 WO2013165486A1 (fr) 2012-05-01 2013-01-18 Revêtements de film de polyalkylèneimine époxylée

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EP3393783A4 (fr) * 2015-12-21 2019-10-23 Jindal Films Americas LLC Revêtements imprimables pour films et étiquettes

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