CA2181495A1 - Water-based printing ink - Google Patents
Water-based printing inkInfo
- Publication number
- CA2181495A1 CA2181495A1 CA002181495A CA2181495A CA2181495A1 CA 2181495 A1 CA2181495 A1 CA 2181495A1 CA 002181495 A CA002181495 A CA 002181495A CA 2181495 A CA2181495 A CA 2181495A CA 2181495 A1 CA2181495 A1 CA 2181495A1
- Authority
- CA
- Canada
- Prior art keywords
- ink
- oil
- pigment
- group
- cyclodextrin
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
Abstract
The invention relates to a water-based oxidizing printing ink especially suited for flexographic printing.
The ink comprises an epoxy ester resin, an inorganic and/or organic pigment, a drier, a cyclodextrin and water. Preferably, the ink also includes a drier activator such as 2,2'-bipyridyl and a wax.
The ink comprises an epoxy ester resin, an inorganic and/or organic pigment, a drier, a cyclodextrin and water. Preferably, the ink also includes a drier activator such as 2,2'-bipyridyl and a wax.
Description
2181~95 lrATER-BA8ED PRINTI~G I~R
The invention relates to a water-based oxidizing printing ink. The ink has been found to be especially useful in flexographic printing processes.
Water-based printing inks are well-known. Although such inks are preferred over solvent-based inks from an environmental point o~F view, they are disadvantageous from the standpoint tllat they are slow-drying as compared to solvent-based inks For flexographic ]?rinting processes, oxidizing water-based printing inks generally require the use of driers such as a coba3Lt naphthenate. However, the incorporation of driers into water-based inks tends to destabilize the ink, particularly at the relatively high levels of driers which are required for flexographic printing processes. ~loreover, water-based inks containing the requisite levels of driers required for flexographic printing process~s have objectionable odors.
It has now been found that oxidizing water-based printing inks especially suitable for flexographic printing processes may be prepared with relatively low levels of driers, provided a cyclodextrin is incorporated in the ink. The resultant inks dry rapidly, are quite stable and have no objectionable odor.
The oxidizing water-based printing inks of the 3 0 invention comprise an epoxy ester resin; an inorganic and/or organic pigment; a drier; a cyclodextrin; and water.
-
The invention relates to a water-based oxidizing printing ink. The ink has been found to be especially useful in flexographic printing processes.
Water-based printing inks are well-known. Although such inks are preferred over solvent-based inks from an environmental point o~F view, they are disadvantageous from the standpoint tllat they are slow-drying as compared to solvent-based inks For flexographic ]?rinting processes, oxidizing water-based printing inks generally require the use of driers such as a coba3Lt naphthenate. However, the incorporation of driers into water-based inks tends to destabilize the ink, particularly at the relatively high levels of driers which are required for flexographic printing processes. ~loreover, water-based inks containing the requisite levels of driers required for flexographic printing process~s have objectionable odors.
It has now been found that oxidizing water-based printing inks especially suitable for flexographic printing processes may be prepared with relatively low levels of driers, provided a cyclodextrin is incorporated in the ink. The resultant inks dry rapidly, are quite stable and have no objectionable odor.
The oxidizing water-based printing inks of the 3 0 invention comprise an epoxy ester resin; an inorganic and/or organic pigment; a drier; a cyclodextrin; and water.
-
2 1 8 ~ 4 q~
Preferably, the epoxy ester resin is present in anamount of about 15-40 wt.%, preferably 20-35 wt.%, based on the weight of the ink, and comprises the reaction product of ( i) about 65-75 parts per hundred of the ester 5 obtained from the esterification of about 40-60 parts per hundred of an epoxy resin with about 60-40 parts per hundred of a drying oil partially conjugated unsaturated fatty acid having an iodine number of about 125-185, an acid number of about 180-210 and a degree of conjugation of about 20-25%, said ester having an acid number below about 10, and (ii) about 35-25 parts per hundred of a mixture of about 20-28% of one or more unsaturated monobasic acids having a polymerizable double bond and about 80-72~ of one or more reactive monomers having a polymerizable double bond, said epoxy resin comprising the c ~nd~nc~tion product of bisphenol A and epichloro-hydrin and having an ~3poxide equivalent weight of about 400 to 1100 and represented by the structure below wherein n has a value of 0 to about 8, preferably a value of about 2 . 2:
CHz-- CH2CH2---O~CH3 0cH2cHcH2--n -O~C~CH2CH-- CHz The epoxy ester resin is typically utilized in a neutral form. Such neutral form may be readily obtained by neutralization of about 94 parts of the resin with 6 25 parts of an amine such as 3 parts of triethanolamine and
Preferably, the epoxy ester resin is present in anamount of about 15-40 wt.%, preferably 20-35 wt.%, based on the weight of the ink, and comprises the reaction product of ( i) about 65-75 parts per hundred of the ester 5 obtained from the esterification of about 40-60 parts per hundred of an epoxy resin with about 60-40 parts per hundred of a drying oil partially conjugated unsaturated fatty acid having an iodine number of about 125-185, an acid number of about 180-210 and a degree of conjugation of about 20-25%, said ester having an acid number below about 10, and (ii) about 35-25 parts per hundred of a mixture of about 20-28% of one or more unsaturated monobasic acids having a polymerizable double bond and about 80-72~ of one or more reactive monomers having a polymerizable double bond, said epoxy resin comprising the c ~nd~nc~tion product of bisphenol A and epichloro-hydrin and having an ~3poxide equivalent weight of about 400 to 1100 and represented by the structure below wherein n has a value of 0 to about 8, preferably a value of about 2 . 2:
CHz-- CH2CH2---O~CH3 0cH2cHcH2--n -O~C~CH2CH-- CHz The epoxy ester resin is typically utilized in a neutral form. Such neutral form may be readily obtained by neutralization of about 94 parts of the resin with 6 25 parts of an amine such as 3 parts of triethanolamine and
3 parts of dimethylaminoethanol.
21~14q5 Preferably, the drying oil partially conjugated unsaturated fatty acid is obtained from an oil selected from the group consi~ting of safflower oil, sunflower oil, tung oil, canola oil, tall oil, dehydrated castor oil, soya bean oil, oiticica oil, plukenetia oil, perilla oil, h 3ee~ oil, walnut oil, tobacco seed oil and linseed oil. The monobasic acid is preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. The reactive monomer is preferably selected from the group consisting of styrene, vinyl toluene and the acrylic and methacrylic acid esters of Cl-C~0 alcohols.
Typically, 65-75 parts of the esterified epoxy resin i8 reacted with 35-25 parts of the mixture of unsaturated monobasic acids and reactive monomers. The reaction between the resin and such mixture is carried over a 2 hour period at 120-15~)C in the presence of about 1-6 wt96 of a peroxide catalyst such as di-tert. butyl peroxide, benzoyl peroxide, cumene peroxide, tertiary butyl perbenzoate, tertiary butyl hydroperoxide, and the like.
The resultant solution is then neutralized with an amine to a pH of about 5-9 to make it water dilutable.
Resins of the type employed in the water-based printing inks of the present invention are well known and are usually utilized in the form of a solution wherein organic solvents are generally present in an amount such that the solvent content will be in the range of about 3-15 wt%, based on the weight of the finished ink.
Useful organic solvents for dissolving the resin include glycol ethers and alcohols such as ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl etller, ethylene glycol monophenyl 21814~5 . ~
ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol n~phPnyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl 5 ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ethsr, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and mixtures thereof.
Epoxy ester resins useful for the present invention may be prepared in accordance with the t~a~hin~c of U.S.
Patent 4 ,166, 054 to Cllarles J. Meeske et al and assigned to Reichhold Chemicals, Inc., and incorporated herein by reference. These resins are commercially available; a useful example of SUCII resin is Reichhold Chemicals' Epotuf~ Epoxy Ester Resin 52-737 dissolved in a mixture of 15% ethylene glycol monobutyl ether, 6% ethylene glycol ~ yl ether and 9% sec-butyl alcohol. This ~;olution contains 70+:2% non-volatiles, an acid number of 54-60 and a Gardner-}ioldt viscosity of Z7-Z~.
The pigment is tyl?ically present in an amount of about 5-30 wt9~, preferably 10-20 wt.%, based on the weight of the ink. Suitable pigments include CI Pigment Yellow 12, CI Pigment Yellow 42, CI Pigment Black 7, CI Pigment Black 11, CI Pigment Red 9, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 57:1, CI Pigment Red 67, CI Pigment Red 146, CI Pigment Red 224, CI Pigment Green 7, CI Pigment Green 36, CI
Pigment Blue 15:3, CI Pigment Violet 23 and CI Pigment Violet 32.
2~8~95 The drier is present in an amount of about 0.1-5 wt.%, preferably 0.5--3 wt.%, based on the weight of the ink. Suitable driers comprise the octoates, resinates, naphthenates, n~o~ n~.ates, tallates and linoleates and 5 mixtures thereof of metals selected from the group consisting of calcium, cobalt, magnesium, r-nq~nr-ce, zinc, cerium, zirconium and mixtures thereof. Desirably, a drier activator such as 2, 2 ' -bipyridyl is incorporated in the ink in an amount of about 0 .1-1 wt. % .
The cyclodextrin is present in an amount of about 0.5-5 wt.%, preferably 1-3 wt.%, based on the weight of the ink. Suitable cyclodextrins comprise ~Y-cyclodextrin, ~-cyclodextrin, y-cyclodextrin and derivatives of such cyc1odextrins such as hy ILUXy~ PY1-~Y-CYC lodextrin, lly d~ VXy~L V~ 1 -,3 -CyC lodextr i n, hydroxyethyl -~-cyclodextrin, methyl-B-cyclodextrin, triacetyl-,B-cyclodextrin, maltoscyclodextrin, trimethyl-~-cyclodextrin, sulfate~-~-cyclodextrin, sulfated-~-cyclodextrin, sulfated-~y-cyclodextrin, carboxymethyl-,B-cyclodextrin, and t]he like. For the purposes of the present invention, the preferred cyclodextrin comprises ~y -cyclodextrin .
The printing ink of the invention desirably also contains a wax presenl_ in an amount of about 1-5 wt. %, based on the weight o f the ink. Such wax may be a polytetrafluoroethylene wax, polyethylene wax, Fischer-Tropsch wax, silicone fluid and mixtures thereof. It is also desirable to incorporate a defoamer in the ink in an amount of O. 1-0. 5 wt. 1., based on the weight of the ink.
The balance of the ink will consist of water.
Typically, the water ~ill be present in an amount of about 30-60 wt.%, based on the weight of the ink.
21~1495 .. --The water-based inks of the invention will typically have a viscosity of about 25 ~: 2 sec. as measured on a #2 Zahn cup at 20C and may be printed at speeds of up to 200 m/min. The inks dry rapidly - typically the imprinted substrate will be cured in ovens of 5-6 meters in length at temperatures of 80 to 180C and a residence time of 0.1 to 2 seconds. Thus a second color may be printed almost instantaneously upon a previously-printed color .
The following examples shall serve to illustrate the invention. Unless ot~erwise indicated, all parts and percentages are by weight.
TiXAMPT.~ 1 For comparative purposes, a conventional water-based printing ink was prepared from the components indicated in Table I below; this ink contained no driers.
TABLE ~
"Epotuf" 92--737, 70% ~:olids 28.6 Triethylamine 0 . 9 20 Dimethylaminoethanol 0 . 9 CI Pigment Red 17 15. 0 Polyethylene Wax 3 . 3 Silicone Emulsion 1. 3 Defoamer 0. 2 25 Water 49 . 8 100 . O
Printability : good Odor : standard pH 12 Solution Resistance : good 1% Aqueous Ammonia Res;istance: none Gloss : high Stability : good Incorporation of a drier in the ink would improve the formulation by crosslinking the epoxy ester resin and provide excellent resistance properties. However, metallic driers often hydrolyze in water; thus their use . . , , , = _ _ _ _ _ _ _ . , , would be altogether precluded or such usage would lead to instability problems or objectionable odors. Examples 2 and 3 set forth below illustrate the problems caused by the use of metallic driers in varying amounts.
r~AMPL~ 2 A water-based printing ink was prepared from the ,- ^nts indicated in Table II below; this ink contained the drier cobalt naphthenate and the drier activator 2, 2 ' -bipyridyl.
TAr~r r~ II
"Epotuf" 92-737, 7096 ~olids 28.6 Triethylamine 0 . 9 Dimethylaminoethanol 0 . 9 CI Pigment Red 17 15 . 0 15 Polyethylene Wax 3 . 3 Silicone Emulsion 1. 3 Defoamer 0 . 2 Cobalt Naphthenate, 59c 0.8 2, 2 ' -B ipyridyl, 3 0 % 0 . 3 2 0 Water 4 8 . 7 100. 0 Printability : good odor : heavy pH 12 Solution Resistance : very good 1~6 Aqueous Ammonia Resistance: very good Gloss : high Stability : unstable EXAMpT r.~ 3 A water-based printing ink was prepared from the components indicated in Table III below; this ink contained the drier cobalt naphthenate and the drier activator 2, 2 '-bipyridyl .
2l814q5 TABLE I I I
"Epotuf" 92--737, 70% solids 28.6 Triethylamine o . 9 Dimethylaminoethanol o . 9 5CI Pigment Red 17 15. 0 Polyethylene Wax 3 3 Silicone Emulsion 1. 3 Defoamer O . 2 Cobalt Naphthenate, 5~6 0.4 10 2,2'-Bipyridyl, 30% 0.3 Water 49. 1 100 . O
Printability : good Odor : moderate 15 pH 12 Solution Re6istance : very good 1~ Aqueous Ammonia ~esistance: weak Gloss : high Stability : unstable A water-based p~rinting ink was prepared from the ;D-~ts indicated in Table IV below; this ink contained the drier cobalt naphthenate, the drier activator 2, 2 ' -bipy]-idyl and ~y-cyclodextrin . Based on these results, it al?pears that cyclodextrins have the capability of formi]lg inclusion complexes with metallic driers thus "protec~ing" them from hydrolysis. The resulting water-based printing ink exhibited superior properties in respe~t to stability, odor and printability .
"Epotuf" 92--737, 7096 solids 28.6 Triethylamine O . 9 Dimethylaminoethanol O . 9 CI Pigment Red 17 15. 0 35Polyethylene Wax 3 3 Silicone Emulsion 1. 3 Def oamer O . 2 Cobalt Naphthenate, 5% 0 . 4 2, 2 ' -B ipyridyl, 3 0 ~ 0 . 3 40~-Cyclodextrin, 18% 1. 5 Water 47 . 6 100 . o ..... .
218~95 .' --g Printability : good Odor : slight pH 12 Solution Resisl~ance : very good 1% Aqueous Ammonia Resistance: excellent 5 Glos6 : high Stability : good The inks were tested by imprinting on a polyethylene polycoated board. Tlle drying cycle was 15 seconds in an oven at 80C.
The prints were tested after exposure to ambient temperature for 24 hours. Resistance to the high pH
reagents was evaluated as follows. The prints were placed on a flat surface. The appropriate solution was applied to the surface of the printed stock. After the 15 appropriate time had elapsed, the solutions were wiped 5 times in one directi~n with tissue paper using moderate .L e8~uL e in order to absorb bleed and loose pigment affected by the treatment solution.
21~14q5 Preferably, the drying oil partially conjugated unsaturated fatty acid is obtained from an oil selected from the group consi~ting of safflower oil, sunflower oil, tung oil, canola oil, tall oil, dehydrated castor oil, soya bean oil, oiticica oil, plukenetia oil, perilla oil, h 3ee~ oil, walnut oil, tobacco seed oil and linseed oil. The monobasic acid is preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. The reactive monomer is preferably selected from the group consisting of styrene, vinyl toluene and the acrylic and methacrylic acid esters of Cl-C~0 alcohols.
Typically, 65-75 parts of the esterified epoxy resin i8 reacted with 35-25 parts of the mixture of unsaturated monobasic acids and reactive monomers. The reaction between the resin and such mixture is carried over a 2 hour period at 120-15~)C in the presence of about 1-6 wt96 of a peroxide catalyst such as di-tert. butyl peroxide, benzoyl peroxide, cumene peroxide, tertiary butyl perbenzoate, tertiary butyl hydroperoxide, and the like.
The resultant solution is then neutralized with an amine to a pH of about 5-9 to make it water dilutable.
Resins of the type employed in the water-based printing inks of the present invention are well known and are usually utilized in the form of a solution wherein organic solvents are generally present in an amount such that the solvent content will be in the range of about 3-15 wt%, based on the weight of the finished ink.
Useful organic solvents for dissolving the resin include glycol ethers and alcohols such as ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl etller, ethylene glycol monophenyl 21814~5 . ~
ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol n~phPnyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl 5 ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ethsr, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and mixtures thereof.
Epoxy ester resins useful for the present invention may be prepared in accordance with the t~a~hin~c of U.S.
Patent 4 ,166, 054 to Cllarles J. Meeske et al and assigned to Reichhold Chemicals, Inc., and incorporated herein by reference. These resins are commercially available; a useful example of SUCII resin is Reichhold Chemicals' Epotuf~ Epoxy Ester Resin 52-737 dissolved in a mixture of 15% ethylene glycol monobutyl ether, 6% ethylene glycol ~ yl ether and 9% sec-butyl alcohol. This ~;olution contains 70+:2% non-volatiles, an acid number of 54-60 and a Gardner-}ioldt viscosity of Z7-Z~.
The pigment is tyl?ically present in an amount of about 5-30 wt9~, preferably 10-20 wt.%, based on the weight of the ink. Suitable pigments include CI Pigment Yellow 12, CI Pigment Yellow 42, CI Pigment Black 7, CI Pigment Black 11, CI Pigment Red 9, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 57:1, CI Pigment Red 67, CI Pigment Red 146, CI Pigment Red 224, CI Pigment Green 7, CI Pigment Green 36, CI
Pigment Blue 15:3, CI Pigment Violet 23 and CI Pigment Violet 32.
2~8~95 The drier is present in an amount of about 0.1-5 wt.%, preferably 0.5--3 wt.%, based on the weight of the ink. Suitable driers comprise the octoates, resinates, naphthenates, n~o~ n~.ates, tallates and linoleates and 5 mixtures thereof of metals selected from the group consisting of calcium, cobalt, magnesium, r-nq~nr-ce, zinc, cerium, zirconium and mixtures thereof. Desirably, a drier activator such as 2, 2 ' -bipyridyl is incorporated in the ink in an amount of about 0 .1-1 wt. % .
The cyclodextrin is present in an amount of about 0.5-5 wt.%, preferably 1-3 wt.%, based on the weight of the ink. Suitable cyclodextrins comprise ~Y-cyclodextrin, ~-cyclodextrin, y-cyclodextrin and derivatives of such cyc1odextrins such as hy ILUXy~ PY1-~Y-CYC lodextrin, lly d~ VXy~L V~ 1 -,3 -CyC lodextr i n, hydroxyethyl -~-cyclodextrin, methyl-B-cyclodextrin, triacetyl-,B-cyclodextrin, maltoscyclodextrin, trimethyl-~-cyclodextrin, sulfate~-~-cyclodextrin, sulfated-~-cyclodextrin, sulfated-~y-cyclodextrin, carboxymethyl-,B-cyclodextrin, and t]he like. For the purposes of the present invention, the preferred cyclodextrin comprises ~y -cyclodextrin .
The printing ink of the invention desirably also contains a wax presenl_ in an amount of about 1-5 wt. %, based on the weight o f the ink. Such wax may be a polytetrafluoroethylene wax, polyethylene wax, Fischer-Tropsch wax, silicone fluid and mixtures thereof. It is also desirable to incorporate a defoamer in the ink in an amount of O. 1-0. 5 wt. 1., based on the weight of the ink.
The balance of the ink will consist of water.
Typically, the water ~ill be present in an amount of about 30-60 wt.%, based on the weight of the ink.
21~1495 .. --The water-based inks of the invention will typically have a viscosity of about 25 ~: 2 sec. as measured on a #2 Zahn cup at 20C and may be printed at speeds of up to 200 m/min. The inks dry rapidly - typically the imprinted substrate will be cured in ovens of 5-6 meters in length at temperatures of 80 to 180C and a residence time of 0.1 to 2 seconds. Thus a second color may be printed almost instantaneously upon a previously-printed color .
The following examples shall serve to illustrate the invention. Unless ot~erwise indicated, all parts and percentages are by weight.
TiXAMPT.~ 1 For comparative purposes, a conventional water-based printing ink was prepared from the components indicated in Table I below; this ink contained no driers.
TABLE ~
"Epotuf" 92--737, 70% ~:olids 28.6 Triethylamine 0 . 9 20 Dimethylaminoethanol 0 . 9 CI Pigment Red 17 15. 0 Polyethylene Wax 3 . 3 Silicone Emulsion 1. 3 Defoamer 0. 2 25 Water 49 . 8 100 . O
Printability : good Odor : standard pH 12 Solution Resistance : good 1% Aqueous Ammonia Res;istance: none Gloss : high Stability : good Incorporation of a drier in the ink would improve the formulation by crosslinking the epoxy ester resin and provide excellent resistance properties. However, metallic driers often hydrolyze in water; thus their use . . , , , = _ _ _ _ _ _ _ . , , would be altogether precluded or such usage would lead to instability problems or objectionable odors. Examples 2 and 3 set forth below illustrate the problems caused by the use of metallic driers in varying amounts.
r~AMPL~ 2 A water-based printing ink was prepared from the ,- ^nts indicated in Table II below; this ink contained the drier cobalt naphthenate and the drier activator 2, 2 ' -bipyridyl.
TAr~r r~ II
"Epotuf" 92-737, 7096 ~olids 28.6 Triethylamine 0 . 9 Dimethylaminoethanol 0 . 9 CI Pigment Red 17 15 . 0 15 Polyethylene Wax 3 . 3 Silicone Emulsion 1. 3 Defoamer 0 . 2 Cobalt Naphthenate, 59c 0.8 2, 2 ' -B ipyridyl, 3 0 % 0 . 3 2 0 Water 4 8 . 7 100. 0 Printability : good odor : heavy pH 12 Solution Resistance : very good 1~6 Aqueous Ammonia Resistance: very good Gloss : high Stability : unstable EXAMpT r.~ 3 A water-based printing ink was prepared from the components indicated in Table III below; this ink contained the drier cobalt naphthenate and the drier activator 2, 2 '-bipyridyl .
2l814q5 TABLE I I I
"Epotuf" 92--737, 70% solids 28.6 Triethylamine o . 9 Dimethylaminoethanol o . 9 5CI Pigment Red 17 15. 0 Polyethylene Wax 3 3 Silicone Emulsion 1. 3 Defoamer O . 2 Cobalt Naphthenate, 5~6 0.4 10 2,2'-Bipyridyl, 30% 0.3 Water 49. 1 100 . O
Printability : good Odor : moderate 15 pH 12 Solution Re6istance : very good 1~ Aqueous Ammonia ~esistance: weak Gloss : high Stability : unstable A water-based p~rinting ink was prepared from the ;D-~ts indicated in Table IV below; this ink contained the drier cobalt naphthenate, the drier activator 2, 2 ' -bipy]-idyl and ~y-cyclodextrin . Based on these results, it al?pears that cyclodextrins have the capability of formi]lg inclusion complexes with metallic driers thus "protec~ing" them from hydrolysis. The resulting water-based printing ink exhibited superior properties in respe~t to stability, odor and printability .
"Epotuf" 92--737, 7096 solids 28.6 Triethylamine O . 9 Dimethylaminoethanol O . 9 CI Pigment Red 17 15. 0 35Polyethylene Wax 3 3 Silicone Emulsion 1. 3 Def oamer O . 2 Cobalt Naphthenate, 5% 0 . 4 2, 2 ' -B ipyridyl, 3 0 ~ 0 . 3 40~-Cyclodextrin, 18% 1. 5 Water 47 . 6 100 . o ..... .
218~95 .' --g Printability : good Odor : slight pH 12 Solution Resisl~ance : very good 1% Aqueous Ammonia Resistance: excellent 5 Glos6 : high Stability : good The inks were tested by imprinting on a polyethylene polycoated board. Tlle drying cycle was 15 seconds in an oven at 80C.
The prints were tested after exposure to ambient temperature for 24 hours. Resistance to the high pH
reagents was evaluated as follows. The prints were placed on a flat surface. The appropriate solution was applied to the surface of the printed stock. After the 15 appropriate time had elapsed, the solutions were wiped 5 times in one directi~n with tissue paper using moderate .L e8~uL e in order to absorb bleed and loose pigment affected by the treatment solution.
Claims (10)
1. A water-based oxidizing printing ink comprising:
(a) a resin;
(b) an inorganic and/or organic pigment;
(c) a drier; and (d) a cyclodextrin.
(a) a resin;
(b) an inorganic and/or organic pigment;
(c) a drier; and (d) a cyclodextrin.
2. The ink of claim 1 wherein the resin is present in an amount of about 15-40 wt.%, based on the weight of the ink, and comprises the reaction product of (i) about 65-75 parts per hundred of the ester obtained from the esterification of about 40-60 parts per hundred of an epoxy resin with about 60-40 parts per hundred of a drying oil partially conjugated unsaturated fatty acid having an iodine number of about 125-185, an acid number of about 180-210 and a degree of conjugation of about 20-25%, said ester having an acid number below about 10, and (ii) about 35-25 parts per hundred of a mixture of about 20-28% of one or more unsaturated monobasic acids having a polymerizable double bond and about 80-72% of one or more reactive monomers having a polymerizable double bond, said epoxy resin comprising the condensation product of bisphenol A and epichlorohydrin and having an epoxide equivalent weight of about 400 to 1100 and represented by the structure below wherein n has a value of 0 to about 8:
3. The ink of claim 2 wherein the drying oil partially conjugated unsaturated fatty acid is obtained from an oil selected from the group consisting of safflower oil, sunflower oil, tung oil, canola oil, tall oil, dehydrated castor oil, soya bean oil, oiticica oil, plukenetia oil, perilla oil, hemp-seed oil, walnut oil, tobacco seed oil and linseed oil.
4. The ink of claim 2 wherein the monobasic acid is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
5. The ink of claim 1 wherein the reactive monomer is selected from the group consisting of styrene, vinyl toluene and the acrylic and methacrylic acid esters of C1-C10 alcohols.
6. The ink of claim 1 wherein the pigment is present in an amount of about 5-30 wt%, based on the weight of the ink, and is selected from the group consisting of CI Pigment Yellow 12, CI Pigment Yellow 42, CI Pigment Black 7, CI Pigment Black 11, CI Pigment Red 9, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 57:1, CI Pigment Red 67, CI Pigment Red 146, CI Pigment Red 224, CI Pigment Green 7, CI
Pigment Green 3 6, CI Pigment Blue 15: 3, CI Pigment Violet 23 and CI Pigment Violet 32.
Pigment Green 3 6, CI Pigment Blue 15: 3, CI Pigment Violet 23 and CI Pigment Violet 32.
7. The ink of claim 1 wherein the drier is present is an amount of about 0.1-5 wt.%, based on the weight of the ink, and is selected from the group consisting of the octoates, resinates, naphthenates, neodecanoates, tallates and linoleates and mixtures thereof of metals selected from the group consisting of cobalt, magnesium, manganese, zinc, cerium, zirconium and mixtures thereof.
8. The ink of claim 1 including a drier activator comprising 2,2'-bipyridyl.
9. The ink of claim 1 wherein the cyclodextrin is present in an amount of about 0.5-5 wt.%, based on the weight of the ink, and is selected from the group consisting of .alpha.-cyclodextrin, .beta.-cyclodextrin, .gamma.-cyclodextrin and derivatives of such cyclodextrins.
10. The ink of claim 1 including a wax present in an amount of about 1-5 wt.%, based on the weight of the ink, said wax being selected from the group consisting of polytetrafluoroethylene waxes, polyethylene waxes, Fischer-Tropsch waxes, silicone fluids and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/503,791 | 1995-07-18 | ||
| US08/503,791 US5567747A (en) | 1995-07-18 | 1995-07-18 | Water-based printing ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2181495A1 true CA2181495A1 (en) | 1997-01-19 |
Family
ID=24003525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002181495A Abandoned CA2181495A1 (en) | 1995-07-18 | 1996-07-18 | Water-based printing ink |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5567747A (en) |
| EP (1) | EP0754729B1 (en) |
| JP (1) | JPH0931390A (en) |
| AT (1) | ATE184623T1 (en) |
| CA (1) | CA2181495A1 (en) |
| DE (1) | DE69604248T2 (en) |
| DK (1) | DK0754729T3 (en) |
| ES (1) | ES2136350T3 (en) |
| ZA (1) | ZA966078B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9458322B2 (en) | 2011-09-23 | 2016-10-04 | Emerald Hilton Davis, Llc | Self-assembled nano-structure particle and method for preparing |
| US10988618B2 (en) | 2011-09-23 | 2021-04-27 | Dystar Hilton Davis Corp. | Self-assembled nano-structured particle and methods for preparing |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1017801A (en) * | 1996-07-05 | 1998-01-20 | Fuji Xerox Co Ltd | Ink composition and image recording method |
| US6416829B2 (en) * | 1997-06-06 | 2002-07-09 | Fort James Corporation | Heat insulating paper cups |
| US6284816B1 (en) * | 1997-06-19 | 2001-09-04 | Sun Chemical Corporation | Energy curable flexographic inks incorporating grafted pigments |
| US6139665A (en) * | 1998-03-06 | 2000-10-31 | Fort James Corporation | Method for fabricating heat insulating paper cups |
| US6541560B1 (en) | 2000-03-15 | 2003-04-01 | Graphic Packaging Corporation | Control of volatile carbonyl compound in compositions used in printing, printing methods and resulting printed structure |
| DE10209013A1 (en) * | 2002-02-25 | 2003-10-23 | Carl Epple Druckfarbenfabrik G | Offset printing ink and method for producing an offset printing ink |
| US20060286325A1 (en) * | 2005-06-17 | 2006-12-21 | Fort James Corporation | Foam-paperboard laminates, articles incorporating same and methods of making the same |
| US8076397B2 (en) * | 2007-09-28 | 2011-12-13 | Graphix Essentials, Llc | Printing ink base material |
| EP2364215A4 (en) * | 2008-11-12 | 2012-05-30 | Lorama Inc | Stabilized drier for alkyd-based compositions |
| CN102781559B (en) | 2010-03-23 | 2014-12-17 | 东丽株式会社 | Separation membrane and method for producing same |
| EP2961616B1 (en) | 2013-02-27 | 2019-10-30 | Crayola, LLC | Rinsable inks and methods of making the same |
| KR101651418B1 (en) * | 2014-11-05 | 2016-09-05 | 대한잉크 주식회사 | Cyclodextrin-metal desiccant and printing ink composite for comprising the same |
| ES2679697B1 (en) | 2017-02-16 | 2019-06-21 | Kao Corp | Ink for flexographic printing |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166054A (en) * | 1976-02-25 | 1979-08-28 | Reichhold Chemicals, Inc. | Water dispersible epoxy resin copolymers and method of making the same |
| US4838938A (en) * | 1987-02-16 | 1989-06-13 | Canon Kabushiki Kaisha | Recording liquid and recording method by use thereof |
| US5108505A (en) * | 1990-05-16 | 1992-04-28 | Hewlett-Packard Company | Waterfast inks via cyclodextrin inclusion complex |
| US5177129A (en) * | 1991-04-22 | 1993-01-05 | The Valspar Corporation | Interior can coating compositions containing cyclodextrins |
| JPH05140498A (en) * | 1991-11-21 | 1993-06-08 | Sailor Pen Co Ltd:The | Water-base ink |
| US5367005A (en) * | 1993-10-29 | 1994-11-22 | Sun Chemical Corporation | Heatset security ink |
-
1995
- 1995-07-18 US US08/503,791 patent/US5567747A/en not_active Expired - Fee Related
-
1996
- 1996-07-16 JP JP8186328A patent/JPH0931390A/en not_active Withdrawn
- 1996-07-17 EP EP96111509A patent/EP0754729B1/en not_active Expired - Lifetime
- 1996-07-17 AT AT96111509T patent/ATE184623T1/en not_active IP Right Cessation
- 1996-07-17 DK DK96111509T patent/DK0754729T3/en active
- 1996-07-17 ES ES96111509T patent/ES2136350T3/en not_active Expired - Lifetime
- 1996-07-17 ZA ZA9606078A patent/ZA966078B/en unknown
- 1996-07-17 DE DE69604248T patent/DE69604248T2/en not_active Expired - Fee Related
- 1996-07-18 CA CA002181495A patent/CA2181495A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9458322B2 (en) | 2011-09-23 | 2016-10-04 | Emerald Hilton Davis, Llc | Self-assembled nano-structure particle and method for preparing |
| US10442932B2 (en) | 2011-09-23 | 2019-10-15 | Dystar Hilton Davis Corp. | Self-assembled nano-structure particle and method for preparing |
| US10988618B2 (en) | 2011-09-23 | 2021-04-27 | Dystar Hilton Davis Corp. | Self-assembled nano-structured particle and methods for preparing |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0754729B1 (en) | 1999-09-15 |
| ATE184623T1 (en) | 1999-10-15 |
| US5567747A (en) | 1996-10-22 |
| DE69604248D1 (en) | 1999-10-21 |
| DE69604248T2 (en) | 2000-05-11 |
| DK0754729T3 (en) | 2000-02-07 |
| JPH0931390A (en) | 1997-02-04 |
| EP0754729A1 (en) | 1997-01-22 |
| ES2136350T3 (en) | 1999-11-16 |
| ZA966078B (en) | 1997-02-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
Effective date: 20020718 |
|
| FZDE | Discontinued |
Effective date: 20020718 |