AU2017270305A1 - Binder for water-based liquid inks, water-based liquid ink, and printed matter - Google Patents

Binder for water-based liquid inks, water-based liquid ink, and printed matter Download PDF

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AU2017270305A1
AU2017270305A1 AU2017270305A AU2017270305A AU2017270305A1 AU 2017270305 A1 AU2017270305 A1 AU 2017270305A1 AU 2017270305 A AU2017270305 A AU 2017270305A AU 2017270305 A AU2017270305 A AU 2017270305A AU 2017270305 A1 AU2017270305 A1 AU 2017270305A1
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water
based liquid
binder
parts
mass
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AU2017270305B2 (en
Inventor
Toshinori Ishibashi
Sadamu Nagahama
Katsurou Oda
Yasutaka Oka
Rikei Sasaka
Naoto Satake
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DIC Graphics Corp
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DIC Graphics Corp
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    • 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

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

Abstract

Provided are: a binder for water-based liquid inks, which is usable in water-based liquid inks excellent in terms of adhesion to substrates, blocking resistance, and ink redissolution; and a water-based liquid ink composition including the binder. This binder for water-based liquid inks comprises: a urethane resin (A) that is a product of the reaction of polyols (a1) comprising an acid-group-containing polyol (a1-1) and a polyether polyol (a1-2) other than the polyol (a1-1) with a polyisocyanate (a2); and an aqueous medium (B). Said binder is characterized in that the urethane resin (A) has an acid group that has been neutralized with a metal salt, and the urethane resin (A) includes an alicyclic structure in an amount in the range of 1,000-5,000 mmol/kg with respect to the entire urethane resin (A).

Description

DESCRIPTION
Title of Invention: BINDER FOR WATER-BASED LIQUID INKS, WATER-BASED LIQUID INK, AND PRINTED ARTICLE
Technical Field [0001]
The present invention relates to a resin binder for water-based liquid inks that is able to be used in waterbased gravure printing and water-based flexography, and also to a water-based liquid ink composition.
Background Art [0002]
Water-based gravure printing and water-based flexography have been widely used to give the printed matter esthetics and functionality.
In recent years, the printing ink industry has witnessed a shift toward post-petroleum resources rooted in the sustainability perspective that emerged against a background of global spread, including an aggravation of air pollution and global warming, caused by VOCs contained in solvent-based printing inks as well as because of occupational safety and hygiene, plus the compounds’ flammability and explosibility. As a result, restrictions on the use of organic solvents have been becoming increasingly tight.
[0003]
The consumption of film packages, however, is in an upward trend worldwide because of population growth, increased income levels, and changes in distribution systems. Accordingly, the production of inks for packaging is increasing from year to year.
In film package printing, the standard practice has been to use solvent-based flexographic or gravure inks, but in recent years, water-based inks, which use water instead of organic solvents, have been developed because of the above change in the industry’s environmental mindset. Researchers are undertaking the development and improvement of water-based liquid inks of higher quality.
[0004]
When compared with solvent-based liquid inks, however, water-based liquid inks need to be further improved in performance in terms of adhesion to film, anti-blocking properties involving setoff of the printed image, and ink resolubility’’ for reducing filling-up scum, which occurs when ink dries on the printing plate during long-run printing. The current fact is that without this improvement, water-based liquid inks cannot gain sufficient recognition, and a faster expansion of them is hopeless. [0005]
An existing example of a water-based ink composition for surface printing on packaging is the invention of using a water-based polyurethane resin as a binder. This resin is obtained by reacting an isocyanate-containing polymer with a polyhydrazide compound and a polyamine compound other than the polyhydrazide compound to give a polyrethane resin and then making the resin water-based by neutralizing an organic solvent solution of the resin with a deionized water containing aqueous ammonia. Such an ink composition may admittedly retain adhesiveness to film and anti-blocking properties but is by no means sufficient in resolubility and, notably, cannot withstand long-run printing (e.g., PTL 1: Japanese Unexamined Patent Application Publication No. 8053641).
[0006]
Another existing invention is a water-based printing ink composition for lamination that uses a water-based polyurethane resin. This resin is obtained by reacting an organic diisocyanate compound with a polymeric diol compound containing a particular polycarbonate diol and with a chain extender to give and making it water-based by adding water and trimethylamine. This invention, however, is by no means one that considers the prevention of blocking and resolubility (e.g., PTL 2: Japanese Unexamined Patent Application Publication No. 5-171091).
[0007]
To further popularize water-based liquid inks as an option that chooses one in terms of the global environment, occupational environments, and cost, a binder of higher quality for water-based liquid inks needs to be developed that overcomes the tradeoff between improved prevention of blocking and improved resolubility without compromising adhesion to a substrate.
Citation List
Patent Literature [0008]
PTL 1: Japanese Unexamined Patent Application
Publication No. 8-053641
PTL 2: Japanese Unexamined Patent Application
Publication No. 5-171091
Summary of Invention
Technical Problem [0009]
An object of the present invention is to provide a binder for water-based liquid inks that is able to be used in a water-based liquid ink that is good in adhesion to a substrate, the prevention of blocking, and resolubility. A water-based liquid ink composition containing this binder is also provided.
Solution to Problem [0010]
After extensive research to solve the above problem, the inventors have found that the problem can be solved by using a binder for water-based liquid inks that contains a urethane resin that has acid groups and whose acid groups have been neutralized with a metal salt. The present invention was completed on the basis of these findings. [0011]
That is, the present invention relates to a binder for water-based liquid inks that contains a urethane resin (A) that is the product of reaction of polyols (al) including a polyol (al-1) having an acid group and a polyether polyol (al-2) other than the polyol (al-1) with a polyisocyanate (a2) ; and an aqueous medium (B) . The acid groups of the urethane resin (A) have been neutralized with a metal salt, and the urethane resin (A) contains alicyclic structures within the range of 1000 to 5000 mmol/kg based on the whole urethane resin (A). The present invention also relates to a water-based liquid ink composition containing this binder.
[0012]
The present invention also relates to the binder for water-based liquid inks in which the acid value of the urethane resin (A) is in the range of 10 to 50.
[0013]
The present invention also relates to the binder for water-based liquid inks in which the polyols (al) further include 0% to 20% by mass polyol (al-3) having an alicyclic structure .
[0014]
The present invention further relates to a water-based liquid ink that contains the above binder for water-based liquid inks, a pigment, and water. The surface tension at 25°C of the ink is between 25 and 50 mN/m.
[0015]
The present invention, moreover, relates to a printed article produced by performing flexographic printing with the above water-based liquid ink.
[0016]
The present invention even provides a printed article produced by performing gravure printing with the above water-based liquid ink.
Advantageous Effects of Invention [0017]
With a binder according to the present invention for water-based liquid inks, a water-based liquid ink can be obtained that is good in adhesion to a substrate, the prevention of blocking, and resolubility.
Description of Embodiments [0018]
A binder according to the present invention for waterbased liquid inks contains a urethane resin (A) and an aqueous medium (B).
[0019]
The urethane resin (A) can be, for example, one obtained by reacting polyols (al) including a polyol (al-1) having an acid group and a polyether polyol (al-2) other than the polyol (al-1) with a polyisocyanate (a2).
[0020]
Examples of polyols (al-1) having an acid group include polyols having a carboxyl group and polyols having a sulfonic acid group.
[0021]
Examples of polyols having a carboxyl group include 2r 2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. In particular, 2,2dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, satisfactory in dispersion stability, are preferred. Polyester polyols having a carboxyl group can also be used that are obtained by reacting a polyol having a carboxyl group with polycarboxylic acids. These polyols having a carboxyl group can be used alone or in combinations of two or more.
[0022]
Examples of polyols having a sulfonic acid group include polyester polyols obtained by reacting dicarboxylic acids, such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5-(4- 8 sulfophenoxy)isophthalic acid, or their salts with lowmolecular-weight polyols, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol. These polyols having a sulfonic acid group can be used alone or in combinations of two or more. [0023]
The polyol (al-1) having an acid group is preferably used within a range that makes the acid value of the urethane resin (A) between 10 and 50, more preferably between 10 and 35. It is to be noted that an acid value as mentioned in the present invention is a theoretical value calculated based on the amount used of the polyol (al-1) having an acid group and other acid-group-containing compounds used to produce the urethane resin (A).
[0024]
For the acid group, it is preferred that some or all of the groups have been neutralized into a metal salt with metal ions, such as sodium, potassium, calcium, copper, or lithium, to develop good dispersibility in water. The percentage neutralization is preferably in the range of 30% to 130%, more preferably 50% to 100%.
[0025]
The metal ions that can be used when neutralizing the acid groups, such as sodium, potassium, calcium, copper, and lithium, can be obtained from, for example, a metal hydroxide, such as sodium hydroxide, potassium hydroxide, or lithium hydroxide, a metal chloride, such as sodium chloride or potassium chloride, or a metal sulfide, such as copper sulfide .
[0026]
The polyether polyol (al-2) can be, for example, one that results from an addition polymerization of an alkylene oxide performed using one or two or more compounds having two or more active hydrogen atoms as the initiator(s). [0027]
Examples of initiators include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6hexanediol, bisphenol A, glycerol, trimethylolethane, and trimethylolpropane .
[0028]
Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
[0029]
The polyether polyol is preferably one having a numberaverage molecular weight of 500 to 3000 because such a polyether polyol is highly compatible with the pigment, for example, used in the ink.
[0030]
The polyols (al) may include, besides the polyols described above, a polyol (al-3) having an alicyclic structure .
[0031]
Examples of polyols (al-3) having an alicyclic structure include alicyclic-structure-containing polyols of low molecular weights, roughly 100 to 500, such as cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, dicyclohexanediol, butylcyclohexanediol, 1,1’-bicyclohexylidenediol, cyclohexanetriol, hydrogenated bisphenol A, and 1,3adamantanediol. These polyols having an alicyclic structure can be used alone or in combinations of two or more.
[0032]
The polyol (al-3) is preferably used within the range of 0% to 20% by mass in the total amount of the polyols (al) because this will reduce blocking of printed articles.
[0033]
Examples of polyisocyanates (a2) that can react with the polyols (al) include aromatic polyisocyanates, such as 4,4’-diphenylmethane diisocyanate, 2,4’-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolyene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; aliphatic polyisocyanates, such as hexamethylene diisocyanate and lysine diisocyanate; and polyisocyanates that have an alicyclic structure, such as cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. These polyisocyanates (a2) can be used alone or in combinations of two or more. [0034]
Examples of methods for producing the urethane resin (A), the product of reaction of the polyols (al) with the polyisocyanate (a2), include methods in which the polyols (al) and the polyisocyanate (a2) are mixed together with or without the presence of an organic solvent and allowed to react within the range of reaction temperatures of approximately 50°C to 150°C.
[0035]
The reaction between the polyols (al) and the polyisocyanate (a2) is preferably performed with, for example, the relative number of equivalents of isocyanate groups in the polyisocyanate (a2) to hydroxy groups in the polyols (al) in the range of 0.8 to 2.5, more preferably 0.9 to 1.5.
[0036]
Moreover, the urethane resin (A) is preferably one that has alicyclic structures because this will reduce blocking of printed articles.
[0037]
Examples of alicyclic structures include cyclobutyl rings, cyclopentyl rings, cyclohexyl rings, cycloheptyl rings, cyclooctyl rings, propylcyclohexyl rings, tricyclo[5.2.1.0.2.6]decyl structures, bicyclo[4.3.0]-nonyl structures, tricyclo[5.3.1.1]dodecyl structures, propyltricyclo[5.3.1.1]dodecyl structures, norbornene structures, isobornyl structures, dicyclopentanyl structures, and adamantyl structures. In particular, cyclohexyl-ring structures are preferred.
[0038]
The alicyclic structures are preferably within the range of 1000 mmol/kg to 5000 mmol/kg with respect to the whole urethane resin (A) because this will reduce blocking of printed articles.
It is particularly preferred that the alicyclic structures be within the range of 1000 mmol/kg to 4000 mmol/kg. Being within the range of 1000 mmol/kg to 3000 mmol/kg would be more preferred because this results in an ink excellent in resolubility and blocking properties.
It is to be noted that the calculation method refers to the total moles of added alicyclic structures per kg solid urethane resin.
[0039]
The alicyclic structures preferably include ones that come from a polyol having an alicyclic structure, which can be employed as one of the polyols (al) used to produce the urethane resin (A), but not all of them need to be ones that come from a polyol having an alicyclic structure. It may be that some of the alicyclic structures are ones that come from an alicyclic-structure-containing polyisocyanate, such as isophorone diisocyanate.
[0040]
The proportion of alicyclic structures in the urethane resin (A) to the whole urethane resin (A) as mentioned in the present invention is a value calculated based on the total mass of the polyols (al), polyisocyanate (a2), and all other starting materials for the production of the urethane resin (A) and the amount of substance of the alicyclic structures possessed by the alicyclic-structure-containing compound(s) used to produce the urethane resin (A).
[0041]
When producing the urethane resin (A) , furthermore, a chain extender may optionally be used.
[0042]
Examples of chain extenders include polyamines, hydrazine compounds, and other compounds having an active hydrogen atom. These chain extenders can be used alone or in combinations of two or more.
[0043]
Examples of polyamines include, for example, diamines, such as ethylenediamine, 1,2-propanediamine, 1,6hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4’-dicyclohexylmethanediamine, 3,3’dimethyl-4,4’-dicyclohexylmethanediamine, and 1,4cyclohexanediamine; and N-hydroxymethylaminoethylamine, Nhydroxyethylaminoethylamine, Nhydroxypropylaminopropylamine, N-ethylaminoethylamine, Nmethylaminopropylamine, diethylenetriamine, dipropylenetriamine, and triethylenetetramine. In particular, ethylenediamine is preferred.
[0044]
Examples of hydrazine compounds include hydrazine, N,N’-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazidde, adipic dihydrazide, glutaric dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, β-semicarbazidopropionic hydrazide, 3-semicarbazido-propylcarbazate, and semicarbazido-3-semicarbazidomethyl-3,5,5trimethylcyclohexane.
[0045]
Examples of other compounds having an active hydrogen include glycols, such as ethylene glycol, diethylene lycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3 butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerol, and sorbitol; phenols, such as bisphenol A, 4,4’-dihydroxydiphenyl, 4,4’dihydroxydiphenyl ether, 4,4’-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; and water.
[0046]
When the chain extender is a polyamine by way of example, the relative number of equivalents of amino groups to isocyanate groups in the polyamine [amino groups/isocyanate groups] is preferably equal to or smaller than 1.2, more preferably in the range of 0.3 to 1.
[0047]
Examples of organic solvents that can be used when producing the urethane resin (A) include ketone solvents, such as acetone and methyl ethyl ketone; ether solvents, such as tetrahydrofuran and dioxane; acetate solvents, such as ethyl acetate and butyl acetate; nitrile solvents, such as acetonitrile; and amide solvents, such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combinations of two or more .
[0048]
As for the organic solvent, part or all of the organic solvent may be removed during or after the production of the urethane resin (A), for example by vacuum distillation, as an attempt for safety and to reduce environmental burdens.
[0049]
The urethane resin (A) obtained by the method described above is preferably one having a weight-average molecular weight in the range of 5,000 to 500,000 because this allows for the development of durability of printed articles. It is more preferred to use one having a weight-average molecular weight in the range of 5,000 to 200,000, more preferably 20,000 to 100,000.
It should be understood that the measurement of weightaverage molecular weights (polystyrene-equivalent) by GPC (gel permeation chromatography) in the present invention was performed under the following conditions using Tosoh Corp. HLC 8220 system.
Separation columns: Tosoh Corp. TSKgel GMHHR-N; four columns were used. Column temperature: 40°C. Mobile layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml/min. Sample concentration: 0.4% by mass. Injection volume: 100 microliters. Detector: A differential refractometer.
[0050]
When this weight-average molecular weight is less than 5,000, not only the durability of printed articles is low, but also problems such as blocking due to incomplete drying relatively likely to occur. When the molecular weight is more than 500,000, problems such as poor ink transfer and low resolubility easily occur.
[0051]
The process of making the urethane resin (A) produced by the method described above water-based can be performed by, for example, the following methods.
[0052] [Method 1] A method in which some or all of the acid groups of water-based urethane resin obtained by reacting the polyols (al) with the polyisocyanate (a2) are neutralized, an aqueous medium (B) is added to disperse the resin in water, and then the chains are extended using the aforementioned chain extender to disperse urethane resin (A) in water.
[0053] [Method 2] A method in which water-based urethane resin obtained by reacting the polyols (al) with the polyisocyanate (a2) and a chain extender as described above are put into a reaction vessel at one time or in portions, the chain-extending reaction is initiated to produce urethane resin (A), some or all of the acid groups of the resulting urethane resin (A) are neutralized, and then an aqueous medium (B) is added to disperse the resin in water. [0054]
In [Method 1] and [Method 2], an emulsifier may optionally be used. In the dissolution or dispersion in water, machines, such as a homogenizer, may optionally be used.
[0055]
Examples of aqueous media (B) include water, organic solvents miscible with water, and mixtures thereof.
Examples of organic solvents miscible with water include alcohol solvents, such as methanol, ethanol, n-propanol, and isopropanol; ketone solvents, such as acetone and methyl ethyl ketone; polyalkylene glycols, such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ethers of polyalkylene glycols; and lactam solvents, such as N-methyl2-pyrrolidone. In the present invention, water may be used alone, a mixture of water and an organic solvent miscible with water may be used, or an organic solvent miscible with water may be used alone.
[0056]
In terms of safety and environmental burdens, it is preferred that the aqueous medium (B) be water alone or a mixture of water and an organic solvent miscible with water, in particular water alone.
[0057]
Examples of emulsifiers include nonionic emulsifiers, such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylenepolyoxypropylene copolymers; anionic emulsifiers, such as sodium oleate and other fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonate, polyoxyethylenealkyl sulfates, sodium alkanesulfonates, and sodium salts of alkyl diphenyl ether sulfonic acids; and cationic emulsifiers, such as salts of alkylamines, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. In particular, anionic or nonionic emulsifiers are preferred in regard to maintaining the good storage stability of the water-based flexographic ink according to the present invention.
[0058]
The binder according to the present invention for water-based liquid inks, a dispersion of urethane resin (A) obtained by the method described above in an aqueous medium (B), is preferably one that contains the urethane resin (A) within the range of 20% to 75% by mass with respect to the total solids content of the water-based liquid ink and 10% to 50% by mass with respect to the total amount of the water-based liquid ink. Setting the amount of the urethane resin (A) within the range of 20% to 75% by mass with respect to the total solids content of the water-based liquid ink improves adhesion to a substrate, whereas setting it within the range of 10% to 50% by mass with respect to the total amount of the water-based liquid ink is preferred in terms of the resolubility of the water-based ink during printing, reducing blocking of printed articles, and improving the print density.
As for other resins that can be mixed in the binder according to the present invention for water-based liquid inks, aqueous or water-dispersible resins are preferred, in particular ones having an acid value of 5 to 150 mg KOH/g. Examples include acrylic resins, styrene-acrylic resins, maleic acid resins, styrene-maleic acid resins, ot-olefinmaleic acid resins, ester resins, sulfonic acid resins, and phosphoric acid resins. In particular, styrene-maleic acid copolymers are preferred. To list a styrene-maleic acid copolymer as an example, the amount added thereof is preferably between 1% and 10% by mass of the total amount of the liquid ink. A subset of the resins may serve as pigment dispersant (s) .
[0059]
Examples of pigments used in a water-based liquid ink that employs a binder according to the present invention for water-based liquid inks include an organic and inorganic pigments and dyes used in ordinary inks, paints, recording agents, and the like.
[0060]
Examples of organic pigments include pigments such as azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine-azo, diktopyrrolopyrrole, and isoindoline pigments. For a cyan ink, copper phthalocyanine is preferred, and for a transparent yellow ink, it is preferred to use C.I. Pigment No Yellow 83 in terms of cost and light fastness.
[0061]
Examples of inorganic pigments include carbon black, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, red iron oxide, aluminum, and mica. Shiny pigments composed of glass flakes or lump flakes as the base material and a metal or metal oxide coating thereon (Metashine; Nippon Sheet Glass Co., Ltd.) can also be used. For a white ink, it is preferred to use titanium oxide, for a black ink, it is preferred to use carbon black, for gold and silver inks, it is preferred to use aluminum, and for a pearl ink, it is preferred to use mica all in terms of cost and tinctorial strength. Aluminum is in powder or paste form, but preferably is used in paste form for ease of handling and safety. Whether to use leafing or non-leafing aluminum is selected as appropriate in terms of brightness felt and density. As for the total of pigments, it is preferred that pigment(s) be contained in an amount sufficient to ensure the density and tinctorial strength of the ink, i.e., at a percentage of 1% to 50% by mass with respect to the total weight of the ink. Coloring agents can be used alone or in combinations of two or more.
[0062]
In a water-based liquid ink using a binder according to the present invention for water-based liquid inks, solvent and other auxiliaries for specific purposes can further be used.
The solvent can be water alone or an organic solvent miscible with water. Examples of organic solvents include alcohols, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-propyl alcohol; polyhydric alcohols, such as propylene glycol and glycerol; and ethers, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and ethyl carbitol.
[0063]
As for other auxiliary components, it is also possible to use on an as-needed basis materials including waxes, such as paraffin waxes, polyethylene waxes, and carnauba wax, and fatty acid amides, such as oleic acid amide, stearic acid amide, and erucic acid amide, both for giving the ink qualities such as friction resistance and lubricity; silicone and non-silicone antifoams for reducing foaming during printing; and dispersants, which improve the wetting of the pigment(s).
[0064]
A water-based printing ink composition relating to the present invention is produced using machines commonly used in the manufacturing of gravure and flexo printing inks, such as an Eiger mill, a sand mill, a gamma mill, and an attritor.
For a water-based liquid ink obtained using a binder according to the present invention for water-based liquid inks, its viscosity when the ink is used as a water-based flexographic ink only needs to be between 7 and 25 seconds, more preferably between 10 and 20 seconds, at 25°C as measured using a Rigo Zahn cup #4. The surface tension at 25°C of the resulting water-based flexo printing ink is preferably between 25 and 50 mN/m, and it would be more preferred that it be between 33 and 43 mN/m. The wetting of the ink on the substrate, such as fil, improves with decreasing surface tension of the ink, but when the surface tension is lower than 25 mN/m, adjacent dots in halftone-dot areas relatively easily join together due to the wettability, which often causes the dirt on the print surface that is called dot bridging. When the surface tension is higher than 50 mN/m, low wetting of the ink on the substrate, such as film, often causes repellence.
When the ink is used as a water-based gravure ink, its viscosity only needs to be between 7 and 25 seconds, more preferably between 10 and 20 seconds, at 25°C as measured using a Rigo Zahn cup #3. As with a water-based flexographic ink, the surface tension at 25°C of the resulting water-based gravure ink is preferably between 25 and 50 mN/m, and it would be more preferred that it be between 33 and 43 mN/m. The wetting of the ink on the substrate, such as fil, improves with decreasing surface tension of the ink, but when the surface tension is lower than 25 mN/m, adjacent dots in halftone-dot areas relatively easily join together due to the wettability, which often causes the dirt on the print surface that is called dot bridging. When the surface tension is higher than 50 mN/m, low wetting of the ink on the substrate, such as film, often causes repellence.
[0065]
A water-based liquid ink obtained using a binder according to the present invention for water-based liquid inks is good in adhesion to various substrates and can be used for printing on materials such as paper, synthetic paper, thermoplastic resin film, plastic articles, and sheet steel.
Examples of substrate films include films made from polyamide resins, such as Ny 6, nylon 66, and nylon 46; polyester resins, such as PET, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate; polyhydroxycarboxylic acids, such as polylactic acid; biodegradable resins, typified by poly(ethylene succinate), poly(butylene succinate), and other aliphatic polyester resins; thermoplastic resins, such as PP, polyethylene, and other polyolefin resins, polyimide resins, polyarylate resins, or mixtures thereof, as well as a stack of such films, but in particular, film made from polyester, polyamide, polyethylene, or polypropylene is suitably used. These substrate films may be non-oriented or oriented films, and their production process is not critical. The thickness of the substrate film is not critical either, but usually only needs to be in the range of 1 to 500 pm.
The print surface of the substrate film has preferably been treated with a corona discharge. Silica or alumina, for example, may have been deposited.
[0066]
The following describes the present invention in more specific terms by providing examples and comparative examples .
[0067] (Synthesis Example 1: Preparation of Binder (1) for WaterBased Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 191 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 141 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylolpropionic acid, 28 parts by mass of 1,4cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 20 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 9.0 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (1) for water-based aqueous inks was obtained with a non-volatile content of 40% by mass.
For this binder (1) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 2067 mmol/kg, and the acid value was 28.
It is to be noted that the calculation method refers to the total moles of added alicyclic structures per kg solid urethane resin.
[0068] (Synthesis Example 2: Preparation of Binder (2) for WaterBased Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 256 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 102 parts by mass of isophorone diisocyanate, 23 parts by mass of 2,2-dimethylolpropionic acid, 6.5 parts by mass of neopentyl glycol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 18 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 6.5 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (2) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (2) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 1150 mmol/kg, and the acid value was 25. [0069] (Synthesis Example 3: Preparation of Binder (3) for WaterBased Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 263 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 98 parts by mass of isophorone diisocyanate, 22 parts by mass of 2,2-dimethylolpropionic acid, 5.6 parts by mass of 1,4cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 17 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 6.2 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (3) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (3) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 1198 mmol/kg, and the acid value was 23. [0070] (Synthesis Example 4: Preparation of Binder (4) for WaterBased Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 250 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 109 parts by mass of isophorone diisocyanate, 8.6 parts by mass of 2,2-dimethylolpropionic acid, 26 parts by mass of 1,4cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 6.8 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 6.9 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (4) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (4) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 1671 mmol/kg, and the acid value was 9. [0071] (Synthesis Example 5: Preparation of Binder (5) for WaterBased Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 113 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 178 parts by mass of isophorone diisocyanate, 17 parts by mass of 2,2-dimethylolpropionic acid, 84 parts by mass of 1,4cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 13 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 2.2 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (5) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (5) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 3459 mmol/kg, and the acid value was 18. [0072] (Comparative Synthesis Example 1: Preparation of Binder (6) for Water-Based Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 196 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylolpropionic acid, 28 parts by mass of 1,4cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 19 parts by mass of triethylamine was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 9.2 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (6) for waterbased liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (6) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 2120 mmol/kg, and the acid value was 28. [0073] (Comparative Synthesis Example 2: Preparation of Binder (7) for Water-Based Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 291 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 80 parts by mass of isophorone diisocyanate, 16 parts by mass of 2r2-dimethylolpropionic acid, 4.9 parts by mass of neopentyl glycol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 13 parts by mass of a 50% aqueous solution of potassium hydroxide was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 3.4 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (7) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (7) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 901 mmol/kg, and the acid value was 17. [0074] (Comparative Synthesis Example 3: Preparation of Binder (8) for Water-Based Liquid Inks)
In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, reaction was initiated in the solvent mixture of 196 parts by mass of polyoxytetramethylene glycol (molecular weight, 2000), 145 parts by mass of isophorone diisocyanate, 26 parts by mass of 2,2-dimethylolpropionic acid, 28 parts by mass of 1,433 cyclohexanedimethanol, and 200 parts by mass of methyl ethyl ketone to give an organic solvent solution of a urethane prepolymer having a terminal isocyanate group.
Then 13 parts by mass of a 25% aqueous ammonia was added to neutralize some or all carboxyl groups of the urethane prepolymer, and the mixture was stirred sufficiently with 700 parts by mass of water and 9.2 parts by mass of an 80% aqueous solution of hydrazine, giving an aqueous dispersion of urethane resin. Then the dispersion was aged, and the solvent was eliminated. In this way, binder (8) for water-based liquid inks was obtained with a non-volatile content of 40% by mass.
For this binder (8) for water-based liquid inks, the aforementioned proportion of alicyclic structures in the urethane resin was 2120 mmol/kg, and the acid value was 28. [0075] [Production of Water-Based Flexographic Inks]
Using the binders for water-based liquid inks obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3, the flexo printing inks were stirred and mixed well according to the formula below and milled in a bead mill to give milled base inks. The milled base inks were additionally mixed with 10 parts of the water-based liquid ink binder and 4 parts of water. In this way, water-based blue flexo printing inks were produced. The viscosity of the resulting flexo printing inks was adjusted with water (q.s.) to be 16 seconds (25°C) as measured with a
Zahn cup #4 (Rigo).
Moreover, to check the surface tension of the resulting flexo printing inks, the surface tension at 25°C was measured.
The surface tension measurement was based on the
Whihelmy method and performed using Kyowa Interface Science Co., Ltd. DY-300 automatic surface tensiometer.
[0076] [Formulation of the Milled Base Inks]
FASTPGEN BLUE LA5380 cyan pigment (DIC) 15 parts Binder for water-based liquid inks 40 parts Nonionic pigment dispersant (BYK) 10 parts
Isopropyl alcohol 3 parts
Water 8 parts
Silicone antifoam (BYK) 0.2 parts [0077] [Total Amounts of the Finished Water-Based Blue Flexographic Inks (excluding water for viscosity adjustment)]
FASTPGEN BLUE LA5380 cyan pigment (DIC) 15 parts Binder for water-based liquid inks 50 parts
Nonionic pigment dispersant (BYK) 10 parts
Isopropyl alcohol 3 parts
Water 12 parts + q.s. (adjusted with a Zahn cup #4)
Silicone antifoam (BYK) 0.2 parts [0078]
Examples 1 to 5 and Comparative Examples 1 to 3, which were the above viscosity-adjusted blue flexo printing inks, were applied to the corona-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd. ESTER E5102; thickness, 12 pm) and corona-treated polypropylene (OPP) biaxially oriented film (Toyobo Co., Ltd. PYLEN P2161; thickness, 20 pm) specified in Table 1 using Flexoproof 100 test printer (Testing Machines, Inc.; anilox; 200 cells/inch) to print a 240-mm long x 80-mm wide solid image. The image was dried using a hair dryer. In this way, printed articles were obtained.
[0079] [Production of Water-Based Gravure Inks]
Using the binders for water-based liquid inks obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3, the gravure printing inks were stirred and mixed well according to the formula below and milled in a bead mill to give milled base inks. The milled base inks were additionally mixed with 10 parts of the water-based liquid ink binder and 9 parts of water. In this way, water-based blue gravure printing inks were produced. The viscosity of the resulting gravure printing inks was adjusted with water (q.s.) to be 16 seconds (25°C) as measured with a Zahn cup #3 (Rigo).
Moreover, to check the surface tension of the resulting gravure printing inks, the surface tension at 25°C was measured.
The surface tension measurement was based on the Whihelmy method and performed using Kyowa Interface Science Co., Ltd. DY-300 automatic surface tensiometer.
[0080] [Formulation of the Milled Base Inks]
FASTPGEN BLUE LA5380 cyan pigment (DIC) 15 parts
Binder for water-based liquid inks 40 parts
Nonionic pigment dispersant (BYK) 10 parts
Isopropyl alcohol 3 parts
Water 8 parts
Silicone antifoam (BYK) 0.2 parts [0081] [Total Amounts of the Finished Water-Based Blue Gravure Inks (excluding water for viscosity adjustment)]
FASTPGEN BLUE LA5380 cyan pigment (DIC) 15 parts
Binder for water-based liquid inks 50 parts
Nonionic pigment dispersant (BYK) 10 parts
Isopropyl alcohol 3 parts
Water 17 parts + q.s. (adjusted with a Zahn cup #3)
Silicone antifoam (BYK) 0.2 parts [0082]
Examples 6 to 10 and Comparative Examples 4 to 6 specified in Table 2, which were the above viscosityadjusted blue gravure printing inks, were applied to the same kinds of corona-treated polyethylene terephthalate (PET) film (Toyobo Co., Ltd. ESTER E5102; thickness, 12 pm) and corona-treated polypropylene (OPP) biaxially oriented film (Toyobo Co., Ltd. PYLEN P2161; thickness, 20 pm) as in Table 1 using a gravure proofer with a 25-pm deep gravure plate to print a 240-mm long by 80-mm wide solid image. The image was dried using a hair dryer. In this way, printed articles were obtained.
[0083]
The resulting flexo-printed and gravure-printed articles were evaluated for resolubility, anti-blocking properties, and adhesion to the substrate for each film. The ink transfer was checked by print density.
[0084] [Parameter 1: Resolubility]
A drop of distilled water was put on the ink-coated surface of the printed article with a dropper and wiped away with gauze quickly.
After the wiping, the time until the coating dissolved and disappeared was measured and evaluated.
Θ: After the drop is put, the coating dissolves less than 3 seconds.
Ο: After the drop is put, the coating dissolves within seconds and in less than 5 seconds.
Δ: After the drop is put, the coating dissolves in 5 seconds or more and 7 seconds or less.
x: It takes 7 seconds or more to dissolve the coating. [0085] [Parameter 2: Anti-bloking Properties]
The film was cut to a 4 cm x 4 cm size, and the cut pieces were put on top of one another with the printed surface of the printed article on the non-printed surface. After the stack was left under 40°C conditions for 12 hours under a load of 5 Kgf/cm2, a film was peeled away, and the ink transfer (setoff) to the non-printed surface was visually evaluated on the basis of the percentage area (%) of the setoff portion.
Θ: No transfer to the non-printed surface is observed.
O: Transfer caused by setoff is observed , although in
as small an area as less than 5%.
Δ: Transfer caused by setoff is observed in an area of
5% or more and less than 20%.
x: Transfer caused by setoff is observed in an area of
20 % or more.
[0086] [Parameter 3: Adhesion to the Substrate]
After the printed article was left for a day, adhesive tape (Nichiban, 12-mm wide) is attached to the printed surface, and an end of the tape was pulled off at right angles to the printed surface. The appearance was visually evaluated on the basis of the percentage, percentage area, of the remaining print coating.
Θ: No print coating was removed.
O: 80% or more and less than 90% of the print coating was left on the film.
Δ: 50% or more and less than 80% of the print coating was left on the film.
x: Only less than 50% of the print coating was left on the film.
[0087] [Parameter 4: Ink Transfer]
Ink transfer was evaluated by the solid density of the printed article using X-Rite SpectroEye densitometer.
O: The print suitability is good; the cyan density of the printed article is 1.9 or more.
Δ: The print suitability is intermediate; the cyan density of the printed article is 1.6 or more and less than 1.9.
x: The print suitability is poor; the cyan density of the printed article is less than 1.6.
[0088]
The evaluation results for the water-based blue flexographic inks are presented in Table 1.
[0089] [Table 1]
Table 1 Exampl e 1 Exampl e2 Exampl e3 Exampl e4 Exampl e5 Comparativ e Example 1 Comparativ e Example 2 Comparativ e Example 3
Binder (1) (2) (3) (4) (5) (6) (7) (8)
Surface tension mN/m of the waterbased blue flexographic ink (25°C) 35 37 38 42 37 32 40 44
3 <D CD C/5 Resolubilit y PET Θ Θ Θ Θ O X Θ X
OP P Θ Θ Θ Θ O X Θ X
Prevention of blocking PET Θ O O O Θ Θ X Θ
OP P Θ Θ Θ Θ Θ Θ Δ Θ
Adhesion PET Θ Θ Θ Θ Θ Θ Θ Θ
OP P Θ Θ Θ O O Θ O Θ
Ink transfer PET O O O O O O O Δ
OP P O O O O O O O X
[0090]
The evaluation results for the water-based blue gravure inks are presented in Table 2.
[0091] [Table 2]
Table 2 Exampl e6 Exampl e7 Exampl e8 Exampl e9 Exampl e 10 Comparativ e Example 4 Comparativ e Example 5 Comparativ e Example 6
Binder (1) (2) (3) (4) (5) (6) (7) (8)
Surface tension mN/m of the waterbased blue flexographic ink (25°C) 36 37 38 42 37 33 41 44
3 <D CD C/5 Resolubilit y PET Θ Θ Θ Θ O X Θ X
OP P Θ Θ Θ Θ O X Θ X
Prevention of blocking PET Θ O O O Θ Θ X Θ
OP P Θ Θ Θ Θ Θ Θ Δ Θ
Adhesion PET Θ Θ Θ Θ Θ Θ Θ Θ
OP P Θ Θ Θ O O Θ O Θ
Ink transfer PET O O O O O O O O
OP P O O O O O O O Δ
[0092]
With water-based liquid inks using a binder according to the present invention for water-based liquid inks, the prevention of blocking and ink resolubility can be achieved at the same time without compromising adhesion to a substrate and ink transfer, whether in flexographic or gravure printing, by adjusting the ink’s Zahn cup viscosity.

Claims (2)

  1. [Claim 1]
    A binder for water-based liquid inks, the binder comprising :
    a urethane resin (A) that is a product of reaction of polyols (al) including a polyol (al-1) having an acid group and a polyether polyol (al-2) other than the polyol (al-1) with a polyisocyanate (a2); and an aqueous medium (B), wherein the acid groups of the urethane resin (A) have been neutralized with a metal salt, and the urethane resin (A) contains alicyclic structures within a range of 1000 to 5000 mmol/kg based on the whole urethane resin (A).
  2. [Claim 2]
    The binder according to Claim 1 for water-based liquid inks, wherein an acid value of the urethane resin (A) is in a range of 10 to 50. [Claim 3] The binder according to Claim 1 for water-based liquid
    inks, wherein the polyols (al) further include 0% to 20% by mass polyol (al-3) having an alicyclic structure.
    [Claim 4]
    A water-based liquid ink comprising the binder according to any one of Claims 1 to 3 for water-based liquid inks, a pigment, and water, wherein a surface tension at 25°C of the ink is between 25 and 50 mN/m.
    [Claim 5]
    A printed article produced by performing flexographic printing with the water-based liquid ink according to Claim 4 .
    [Claim 6]
    A printed article produced by performing gravure printing with the water-based liquid ink according to Claim 4 .
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