GB2489321A - An ink composition - Google Patents

An ink composition Download PDF

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Publication number
GB2489321A
GB2489321A GB1204957.3A GB201204957A GB2489321A GB 2489321 A GB2489321 A GB 2489321A GB 201204957 A GB201204957 A GB 201204957A GB 2489321 A GB2489321 A GB 2489321A
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parts
composition according
acrylate
optionally substituted
meth
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GB201204957D0 (en
GB2489321B (en
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Kevin Burns
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Sericol Ltd
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Sericol Ltd
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides

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

Abstract

An ink composition comprising (a) 57.75 to 96.7 parts in total of ethylenically unsaturated compounds, such as (meth) acrylamide, (2(2-ethoxyethoxy ethyl acrylate), (2-phenoxy ethyl acrylate), cyclic trimethylolpropane formal acrylate, caprolactone acrylate, dicyclopentadienyl methacrylate or isobornyl acrylate; (b) 2 to 15 parts of optionally substituted acyldiphenylphosphine oxide; (c) 0.3 to 5 parts of optionally substituted thioxanthone; (d) 0.5 to 10 parts of optionally substituted thiochroman-4-one; and (e) 0.5 to 12 parts of colourant; wherein all parts are by weight. The inks are particularly suitable for ink jet printing flexible substrates. They can be cured rapidly using a low irradiation dose and provide prints having a low degree of post-cure colour shift.

Description

COMPOSITIONS
This invention relates to compositions and to their use in ink jet printing.
Ink jet printing is a commonly used technique for printing substrates with an ink composition. The compositions used vary depending on the properties required for the printed substrate. Water-based, solvent-based and radiation-curable compositions for ink jet printing are commercially available.
Some radiation-curable compositions suffer from the problem of slow cure, reducing the rate at which printed substrates can be produced. The dose of radiation used to cure the composition can be increased, but this also increases the printing cost because more power is then used by the radiation source.
Furthermore, many radiation-curable compositions suffer from the problem of colour shift after curing. In other words, the colour of the cured composition changes to an undesirable extent post-curing.
There exists a need for compositions which can be cured rapidly using a low irradiation dose and provide prints having a low degree of post-cure colour shift.
According to the present invention there is provided a composition comprising: (a) 57.75 to 96.7 parts in total of ethylenically unsaturated compounds; (b) 2 to 15 parts of optionally substituted acyldiphenylphosphine oxide; (c) 0.3 to 5 parts of optionally substituted thioxanthone; (d) 0.5 to 10 parts of optionally substituted thiochroman-4-one; and (e) 0.5 to 12 parts of colorant; wherein all parts are by weight.
In this specification (including its claims), the verb "comprise' and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. In addition, reference to a feature by the indefinite article "a" or "an" does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements. For example "having one" means having one and only one (not including two or more). The indefinite article "a" or "an" thus usually means "at least one".
Component (a) preferably comprises (i) a compound having one (i.e. only one and not more than one) ethylenically unsaturated group; and (ii) a compound having more than one ethylenically unsaturated group. Compounds having one ethylenically unsaturated group may provide flexibility to a polymeric film formed after the composition has been cured. Compounds having more than one ethylenically unsaturated group may provide the film with good mechanical strength through providing crosslinking. The weight ratio of (i):(ii) depends on the properties desired for any film produced from the composition. Typically, however, the weight ratio of (i):(ii) is greater than 1:1, preferably greater than 2:1, more preferably greater than 3:1. The ratio of (i):(ii) is preferably c 100:1, more preferably c 50:1, especially c 20:1.
The compounds having one or more than one ethylenically unsaturated group are optionally monomeric, oligomeric or polymeric, with monomeric compounds being preferred.
Preferred ethylenically unsaturated groups are vinyl groups, (meth)acrylic groups, especially (meth)acrylate and (meth)acrylamide groups. Examples of ethylenically unsaturated groups include acrylamide (H2C=CHCONc) groups, methacrylamide (H2C=C(CH3)CONc) groups, acrylate (H2C=CHCO2) groups and methacrylate (H2C=C(CH3)C02-) groups.
As examples of compounds having one ethylenically unsaturated group there may be mentioned (meth)acrylamide, (meth)acryloylmorpholine, isobutoxymethyl(meth)acrylam ide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyld iethylene glycol (meth)acrylate, t-octyl (meth)acrylamide, diacetone (meth)acrylamide, lauryl (meth)acrylate, d icyclopentad iene (meth)acrylate, d icyclopentenyloxyethyl (meth)acrylate, d icyclopentenyl (meth)acrylate, N5N-di methyl(meth)acrylam ide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurluryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tn bromophenyl (meth)acrylate, 2-tn bromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hyd roxypropyl (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, bornyl (meth)acrylate and methyltriethylene diglycol (meth)acrylate and mixtures comprising two or more thereof.
Commercially available compounds having one ethylenically unsaturated group include: SR256 (2(2-ethoxyethoxy ethyl acrylate), SR339 (2-phenoxy ethyl acrylate), SR531 (cyclic trimethylolpropane formal acrylate), SR495B (caprolactone acrylate), SR535 (dicyclopentadienyl methacrylate), SR 506D (isobornyl acrylate), 5R423 (isobornyl methacrylate), SR 313A, 313B and 313D (C12-C14 alkyl (meth)acrylates), all available from Sartomer Co. Inc. and Ciba Ageflex FM6 (n-hexyl (meth)acrylate available from Ciba Specialty Chemicals).
As examples of compounds having more than one ethylenically unsaturated group there may be mentioned ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol d i(meth)acrylate, tricyclodecaned iyld imethylene d i(meth)acrylate, tris(2-hyd roxyethyl)isocya n urate d i(meth)acrylate, tris(2-hyd roxyethyl)isocya n u rate tri(meth)acrylate, caprolactone-mod ified tris(2-hyd roxyethyl)isocyanurate tri(meth)acrylate, trimethyloipropane tri(meth)acrylate, E0-modified trimethyloipropane tri(meth)acrylate, P0-modified trimethyloipropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester d i(meth)acrylate, polyethylene glycol d i(meth)acrylate, d ipentaerythritol penta(meth)acrylate, d ipentaeryth ritol tetra(meth)acrylate, caprolactone-mod ified d ipentaerythritol hexa(meth)acrylate, caprolactone-mod ified d ipentaerythritol penta(meth)acrylate, d itrimethylolpropane tetra(meth)acrylate, E0-mod ified bisphenol A di(meth)acrylate, P0-modified bisphenol A di(meth)acrylate, E0-modified hydrogenated bisphenol A d i(meth)acrylate, P0-modified hydrogenated bisphenol A di(meth)acrylate, E0-modified bisphenol F di(meth)acrylate and mixtures comprising two or more thereof.
Commercially available compounds having more than one ethylenically unsaturated group include: SR 295 (pentaerythritol tetracrylate); SR 350 (trimethylolpropane trimethacrylate); SR 351 (trimethylolpropane triacrylate); SR 367 (tetramethylolmethane tetramethacrylate); SR 368 (tris(2-acryloxy ethyl) isocyanurate triacrylate); SR 399 (dipentaerythritol pentaacrylate); SR 444 (pentaerythritol triacrylate); SR 454 (ethoxylated (3) trimethylolpropane triacrylate); SR 833S (tricyclodecane dimethanol diacrylate), SR 833S (a diacrylate), SR 9041 (dipentaerythritol pentaacrylate ester) and CN964A85, available from Sartomer Co Inc. The number of parts of component (a) is preferably 60 to 96, more preferably 65 to 95, especially 73.25 to 94.34.
The composition optionally comprises a urethane acrylate oligomer. Where such a monomer contains one or more ethylenically unsaturated groups it is part of component (a). The urethane acrylate oligomer is preferably an aliphatic urethane oligomer Examples of commercially available aliphatic urethane oligomers include: CN 934 CN 934X50, CN 944B85, CN 945A60, CN 945B85, CN 953B70, CN 961 E75, CN 961 H81, CN 962, CN 963A80, CN 963B80, CN 963E75, CN 963E80, CN 963J85, CN 964, CN 964A85, CN 964B85, CN 964H90, CN 964E75, CN 965, CN 965A80, CN 966A80, CN 966B85, CN 966H90, CN 966180, CN 966J75, CN 966R60, CN 968, CN 982E75, CN 982P90, CN 983, CN 983B88, CN 984 and CN 985B88, all available from Sartomer, and mixtures comprising two or more thereof.
Examples of commercially available aromatic urethane oligomers include CN 970A60, CN 970E60, CN 970H75, CN 971 A80, CN 972, CN 973A80, CN 973H85, CN 973J75, CN 975, CN 977C70, CN 978, CN 980, CN 980M50, CN 981, CN 981 A75, CN 981 B88, CN 982A75 and CN 982B88, all from Sartomer, and mixtures comprising two or more thereof.
When a urethane acrylate oligomer is included in the composition the amount is typically 0.25 to 6 wt%, especially I to Swt%, relative to the total weight of components (a) to (e).
The optionally substituted acyldiphenylphosphine oxide is preferably an optionally substituted benzoyl diphenylphosphine oxide.
The optional substituents which may be present on the optionally substituted acyldiphenylphosphine oxide are preferably selected from C14-alkyl, C14-alkoxy and halo (especially chloro), more preferably C14-alkyl, especially methyl.
As examples of optionally substituted acyldiphenylphosphine there may be mentioned isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-i -cyclohexanoyl-diphenylphosphine oxide, 2-ethylhexanoyl- diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, o-toluyld iphenylphosph me oxide, 3-pyridylcarbonyl-d iphenylphosphine oxide, acryloyldiphenylphosphine oxide, benzoyl-diphenylenephosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adi poyl-bis-d iphenylphosph me oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and mixtures comprising two or more thereof. 2,4,6-Trimethylbenzoyldiphenylphosphine oxide is particularly preferred.
Optionally substituted acyldiphenylphosphine oxides may be prepared by the general method described in US 4,324,744.
The number of parts of component (b) is preferably 3 to 14, more preferably 3 to 13, especially 3 to 10.
The optional substituents which may be present on the optionally substituted thioxanthone are preferably selected from alkyl (e.g. C14-alkyl), alkoxy (e.g. Ci..4-alkoxy) and halo (e.g. chloro) groups.
The optionally substituted thioxanthone is preferably of the Formula (1): (R2)n Formula (1) wherein: each R1 and each R2 independently is a substituent other than hydrogen; m has a value of 0, 1, 2, 3 or 4; and n has avalue of 0,1 or2.
Each R1 and each R2 independently is preferably C14-alkyl, C14-alkoxy or halo (especially chloro). In a particularly preferred embodiment, m has a value of 0, each R2 independently is C14-alkyl (especially isopropyl) and n has a value of I 012.
The optionally substituted thioxanthones may be prepared by general methods known in the art, for example by the cyclisation of 2-phenylthiobenzoic acid derivatives. The preparation can be performed in one step, e.g. by reacting a 2,2'-dithiodibenzoic acid compound with an aromatic compound in sulphuric acid.
Typical of the methods for preparing thioxanthones are those described in US 4,101,558 and US patent application Publication No. 2003229233.
As examples of optionally substituted thioxanthones there may be mentioned thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1- methoxycarbonylth ioxanthone, 2-ethoxycarbonylth ioxanthone, 3-(2- methoxyethoxycarbonyl) th ioxanthone, 4-butoxycarbonylth ioxanthone, 3- butoxycarbonyl-7-methylth ioxanthone, 1 -cyano-3-chloroth ioxanthone, 1- ethoxycarbonyl-3-chloroth ioxanthone, I -ethoxycarbonyl-3-ethoxyth ioxanthone, 1- ethoxycarbonyl-3-aminoth ioxanthone, 1 -ethoxycarbonyl-3-ph enylsudfu rylth ioxa nthone, 3,4-d i-[2-(2-methoxyethoxy) ethoxycarbonyl] th ioxanthone, 1 -ethoxycarbonyl-3-(1 -methyl-I -morpholinoethyl) th ioxanthone, 2-methyl -6-d imethoxymethylth ioxanthone, 2-methyl-6-(I, 1 -d imethoxybenzyl) th ioxanthone, 2-morpholinomethylth ioxanthone, 2-methyl-6-morpholinomethyl th ioxanthone, n-allylth ioxanthone-3,4-d icarboxim ide, n-octylth ioxanthone-3,4- dicarboximide, N-(1,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboximide, 1- phenoxyth ioxanthone, 6-ethoxycarbonyl-2-methoxyth ioxanthone, 6-ethoxycarbonyl-2-methylth ioxanthone and th ioxanthone-2-polyethylene glycol ester and mixtures comprising two or more thereof.
As examples of commercially available optionally substituted thioxanthones there may be mentioned isopropyl thioxanthone (available as Speedcure TM ITX), 2,4-diethyl thioxanthone, 2-t butyl thioxanthone, 2-chlorothioxanthone, l-chloro-4-propoxyth ioxanthone (CPTX) and 2-propoxy th ioxanthone. Isopropyl th ioxanthone is particularly preferred.
The number of parts of component (c) is preferably 0.4 to 4.5, more preferably 0.4 to 4, especially 0.4 to 3.
The optional substituents which may be present on the optionally substituted thiochroman-4-one are preferably selected from alkyl (e.g. C14-alkyl, especially methyl), alkoxy (e.g. C14-alkoxy, especially methoxy) and halo (especially chloro) groups.
Preferably the thiochroman-4-one has a C1..4-alkyl group (especially methyl) and a halo group (especially chloro).
The optionally substituted thiochroman-4-one is preferably of Formula (2): (R3)p-(R4)q Formula (2) wherein: each R3 and each R4 independently is a substituent other than hydrogen; and p has a value of 0, 1, 2, 3 or 4; and q has a value of 0, 1 or 2.
Preferably each R3 independently is halo, R4 is C14-alkyl, p has a value of 1 or 2 and q has a value of 1.
The number of parts of component (d) is preferably 0.5 to 8, more preferably 0.6 to 7, especially 0.7 to 5, more especially 0.8 to 3.
Thiochroman-4-ones may be prepared by methods known in the art, for example as described in "Thiochroman-4-ones: synthesis and reactions" by S. Bondock; M. A. Metwally, Journal of Sulfur Chemistry, 1741-6000, volume 29, Issue 6, 2008, pages 623-653. S.W. Schneller also provides synthetic methods in the article entitled "Thiochromanones and Related Compounds", Advances in Heterocyclic Chemistry, volume 18, 1975, pages 59-97.
The colorant is preferably an oil-soluble dye or, more preferably, a pigment.
The pigment which can be used as colorant is not particularly limited, for example it can be an organic or inorganic pigment or a mixture thereof. Numerous commercially available pigments are listed in the Colour Index International.
Examples of red or magenta pigments include C.I. Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226 and 257; C.I. Pigment Violet 3, 19, 23, 29, 30, 37, 50 and 88; and C.I. Pigment Orange 13, 16, 20 and 36.
Examples of blue or cyan pigments include CI. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1,22,27,28,29,36 and 60.
Examples of green pigments include C.I. Pigment Green 7, 26, 36 and 50.
Examples of yellow pigments include C.l. Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185 and 193.
Examples of black pigments include carbon blacks and C.I. Pigment Black 7, 28 and 26.
Examples of white pigments include titanium dioxide and CI. Pigment White6, 18 and 21.
The oil-soluble dye is preferably substantially insoluble in water (e.g. a water-solubility of below lwt% at 25°C) and soluble in the remaining components of the composition (solubility above lwt% at 25°C).
Examples of preferred oil-soluble dyes include: the C.I. solvent dyes mentioned below: C.I. Solvent: Black 3, 7, 27, 29 and 34; Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; Red 1, 3,8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; Violet 3; Blue 2, 11, 25, 35, 38, 67 and 70; Green 3 and 7; and Orange 2; and the C.l disperse dyes mentioned below: CI. Disperse: Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184:1, 186, 198, 199, 201, 204, 224 and 237; Orange 13, 29, 31:1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 11.1, 126, 127, 134,135,143,145,152,153,154,159,164,167:1,177,181,204,206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; Violet 33; Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165:1, 165:2, 176, 183, 185, 197, 198, 201, 214, 224, 225, 257, 266, 267, 287, 354, 358, 365 and 368; and Green 6:1 and 9.
When the composition is to be cured by irradiation, one will usually select a colorant which will not absorb all of the curing radiation.
Typically the colorant is dispersed with the other ingredients of the composition using a dispersing device, for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet type jet mill, a paint shaker or the like.
It is also possible to include a dispersant in the composition, especially when the colorant comprises a pigment. Although the type of dispersant is not particularly limited, it is preferred to use a high-molecular weight dispersant.
Examples of the high-molecular weight dispersant include the SolsperseTM hyperdispersants. It is also possible to use a synergist with the dispersant. In the present invention, the dispersant (when included) is preferably added in an amount of from I to 50 parts by weight per 100 parts by weight of colorant.
The colorant may be a single component or a combination of two or more components (e.g. 2 or more pigments).
When the colorant comprises a pigment it preferably has an average particle size below 0.5 pm, more preferably below 0.3 pm. This is for storage stability advantages, and also because larger particles could block the fine nozzles of an ink jet printer if the composition is used in such a printer.
The number of parts of component (e) is preferably 0.5 to 10, more preferably 0.6 to 7, especially 0.8 to 5, more especially 1.5 to 3.5.
When calculating the number of parts of component (e), the weight of any additional ingredients (e.g. dispersant, diluent, liquid vehicle etc.) are not included.
In view of the foregoing, a preferred composition according to the invention comprises: 73.25 to 94.34 parts of component (a); 3 to 10 parts of component (b); 0.4 to 3 parts of component (c); 0.7 to 5 parts of component (d); and 1.5 to 3.5 parts of component (e); wherein all parts are by weight.
In this preferred composition, component (a) preferably comprises the aforementioned ingredients (i):(ii) in a weight ratio of (i):(ii) greater than 1:1, preferably greater than 2:1, more preferably greater than 3:1, especially 4:1 to 40:1.
Preferably the total number of parts by weight of components (a) to (e) adds up to 100. When the total number of parts by weight of components (a) to (e) adds up to 100 this does not rule out the presence of further components, it merely further defines the total amount of components (a) to (e).
If desired further ingredients may be included in the composition, e.g. an antioxidant, a UV stabiliser, a surfactant etc. When the composition contains an antioxidant, the preferred antioxidant is a sterically hindered tertiary or secondary amine. Examples of such amines include N,N-diphenylamine, N-nitroso-diphenylamine, nitrosodiethylaniline, p- phenylenediamine, an N,N'-di(C1..4) alkyl-p-phenylenediamine such as N,N'-di-isobutyl-p-phenylenediamine, or N,N'-di-isopropyl-p-phenylenediamine, lrganoxTM 5057 (produced by Firma Ciba Spezialitaetenchemie), N-phenyl-p- phenylened iam me, N, N'-d iphenyl-p-phenylened iam i, N-isopropyl-N-phenyl-p-phenylenediamine, N,N'-di-s-butyl-p-phenylenediamine (KerobitTM BPD produced by BASF Aktiengesellschaft), N-phenyl-N'-isopropyl-p-phenylened iamine (VulkanoxTM 4010 produced by Bayer A C), N-(1,3-dimethylbutyl)-N'-phenyl-p- phenylened iamine, N-phenyl-2-naphthylamine, iminod ibenzyl, N, N'- diphenylbenzidine, N-phenyltetraaniline, acridone, 3-bydroxydiphenylamine, 4-hydroxydiphenylamine and mixtures comprising two or more thereof When an antioxidant is included in the composition the amount is typically 0.01 to 0.25wt%, relative to the total weight of components (a) to (e).
UV stabilizers may be included in the composition to reduce or prevent premature polymerization during the manufacture and storage of the composition.
Examples of suitable stabilisers include AdditolTM S100, SilO and 5120 from Cytec, FlorstabTM UV1, UV5, UV8, UV11 and UV12 from Kromachem; and TinuvinTM 328, 384, 1130, 400, 123, 292 and 5151 from Ciba.
When the composition contains a UV stabiliser, the amount present is selected so as not to unduly interfere with the process for radiation curing the composition in normal use. Typically 0.1 to lwt% of the UV stabiliser (e.g. an aluminium salt) is used, relative to the total weight of components (a) to (e).
When a surfactant is included in the composition the amount is typically 0.1 to 2.5wt% surfactant, relative to the total weight of components (a) to (e).
Preferably the composition has a viscosity of from 15 to 30 cP, more preferably 18 to 27 cP, when measured at 25°C.
Preferably the composition has a surface tension of from 20 to 40 mNIm, more preferably 25 to 35 mNIm, when measured at 2500.
The composition according to the invention may also be referred to as an ink, e.g. an ink jet printing ink.
According to a second aspect of the present invention there is provided a process for printing a substrate comprising applying thereto a composition according to any one of the preceding claims and curing the composition. The composition is applied to the substrate by means of an ink jet printer.
Is Preferably the curing is performed using ultra violet light, especially using a light emitting diode which emits ultraviolet light (UV-LED).
Printed substrates carrying a cured composition form a further feature of the present invention. Preferred substrates are metal, plastic, ceramic, glass, wood and papers.
The invention in further illustrated by the following examples in which all parts and percentages are by weight unless otherwise stated.
Example 1 and Comparative Examples 1 to 3 The compositions described in Table 1 were prepared by mixing the indicated number of parts by weight of the specified ingredients in a Silverson mixer for 30 minutes at a speed of 4000 rpm.
Table I
Ingredient Comp Ex I Comp Ex 2 Ex 1 Comp Ex 3 ((c) ((c) missing) ((d) missing) missing) Component (a) N-vinyl 29.53 25.18 14.81 15.17 caprolactam ___________ _____________ ________ ___________ Compound having Phenoxy ethyl 36.10 30.77 35.14 35.57 one ethylenically acrylate ___________ _____________ ________ ___________ unsaturated group Isobornyl 0 0 15.23 15.23 __________________ acrylate ___________ _____________ ________ ____________ Component (a) Ethoxylated 11.42 11.42 11.27 11.27 pentaerythritol Compound having tetraacrylate ___________ ____________ _______ ___________ more than one CN964A85 2.34 2.34 2.31 2.31 ethylenically unsaturated group ________________ ___________ _____________ ________ ____________ Component (b) LucirinTM TPO 9.52 6.0 9.4 9.4 Component (c) SpeedcureTM ITX 0 0 0.79 1.58 Component(d) 2-Methyl-6-1.6 8.8 01.58 0 chloro-thio- _________________ chroman-4-one ____________ ___________ Colorant (e) Cl. Pigment 8.64 8.64 8.53 8.53 dispersion Blue 15:4 __________________ dispersion ___________ _____________ ________ ___________ Other components UV12 0.32 0.32 0.32 0.32 (N,N'-di-sec.-0 0 0.09 0.09 butyl-p-phenylene diamine) ___________ _____________ ________ ____________ BYK-307 0.03 0.03 0.03 0.03 TegoradTM 2100 0.5 0.5 0.5 0.5 lrgacureTM 819 0 4.0 0 0 _______________ lrgacureTM 907 0 2.0 0 0 Total 100 100 100 100
Notes to Table 1:
1) The colorant (e) dispersion consisted of 3Owt% of Cl. Pigment Blue 15:4 in ii a liquid vehicle comprising a dispersant. Therefore the amount of colorant present was 30% of the amount indicated in Table 1.
2) UV12 was a 3Owt% suspension of an aluminium tris (N-hydroxy-N-nitroso phenylaminato-0-0' salt in phenoxy ethyl acrylate. Therefore 0.32 parts of UV12 consisted of 0.096 parts of an aluminium tris (N-hydroxy-N-nitroso phenylaminato- 0-0' salt and 0.224 parts of phenoxy ethyl acrylate having one acrylate group.
3) BYK-307 is a polyether modified polydimethylsiloxane available from BYK USA Inc..
4) TegoradTM 2100 is a silicone acrylate wetting agent available from Evonik Tego Chemie GmbH.
5) LucirinTM TPO is 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
6) lrgacureTM 819 is bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.
7) lrgacureTM 907 is 2-Methyl-i [4-(methylthio)phenyl]-2-morpholinopropan-i -one.
8) SpeedcureTM ITX is isopropyl thioxanthone.
9) CN964A85 is an aliphatic polyester based urethane diacrylate oligomer blended with 15% 5R306, tripropylene glycol diacrylate, obtained from Sartomer.
Results The compositions described in Table 1 above were coated onto a substrate (Mactac Imagin JT5929P gloss white self-adhesive PVC) using a 12 micron wire- wound bar. The coated substrates were then cured by passing them under a UV-LED irradiation source (a Baldwin 8W 395nm LED lamp) at a speed of 60 metres/minute enough times to produce a tack-free film. The dose required to produce this tack-free film was determined using a PowerMap UV output radiometer.
The L*a*b* values of the coated substrates immediately after curing and again 24 hours later were measured using a GretagMacbeth SpectroEye spectrophotometer. The colour shift, expressed as the LiE value, was calculated according to the equation: LiE = SORT [(L*2 -L*i)2 + (a*2 -a*1)2 + (b*2 -b*i)2J wherein: SORT means square root; L*i, a*i and b*i respectively mean the L*, a* and b* values immediately after curing; and L*2, a*2 and b*2 respectively mean the L*, a* and b* values 24 hours after curing.
The results are shown in Table 2.
Table 2
CompExi CompEx2 Exi CompEx3 ______________ ((c) missing) ((c) missing) ______________ ((d) missing) LED-UV dose >300mJIcm2 >300mJ/cm2 c200mJIcm2 <200mJ/cm2 required to produce a tack-free 12 micron film L*a*b* values immediately after curing ______________ _____________ L*1 46.93 45.80 49.20 48.39 a*1 -19.09 -19.67 -24.61 -25.88 b*1 -55.52 -54.45 -51.67 -50.17 L*a*b* values 24 hrs after curing _______________ _______________ _______________ L* 2 47.92 46.60 49.63 49.19 a*2 -20.40 -21.06 -23.90 -24.09 b*2 -55.53 -54.46 -52.94 -52.59 Colourshift 1.64 1.60 1.52 3.12 LiE __________ __________ __________ __________ In Tables I and 2 "Comp" means "comparative" and "Ex" means "Example".
Table 2 shows that a lower dose of UV light was required to produce a tack-free film for the composition of Example 1 compared to the Comparative Examples.
Furthermore, Example 1 demonstrated less colour shift than the Comparative
Examples.

Claims (18)

  1. CLAIMS1. A composition comprising: (a) 57.75 to 96.7 parts in total of ethylenically unsaturated compounds; (b) 2 to 15 parts of optionally substituted acyldiphenylphosphine oxide; (c) 0.3 to 5 parts of optionally substituted thioxanthone; (d) 0.5 to 10 parts of optionally substituted thiochroman-4-one; and (e) 0.5 to 12 parts of colorant; wherein all parts are by weight.
  2. 2. A composition according to claim 1 wherein component (a) comprises (i) a compound having one ethylenically unsaturated group; and (ii) a compound having more than one ethylenically unsaturated group.
    Is
  3. 3. A composition according to any one of the preceding claims wherein component (a) further comprises a urethane acrylate oligomer.
  4. 4. A composition according to any one of the preceding claims wherein the optionally substituted acyldiphenylphosphine oxide comprises an optionally substituted benzoyldiphenylphosphine oxide.
  5. 5. A composition according to any one of the preceding claims wherein the optionally substituted thioxanthone is of Formula (1): (R2)n Formula (1) wherein: each R1 and each R2 independently is a substituent other than hydrogen; m has a value of 0, 1, 2, 3 or 4; and nhasavalueofo,lor2.
  6. 6. A composition according to claim 5 wherein m has a value of 0, each R2 independently is C14-alkyl and n has a value of 1 or 2.
  7. 7. A composition according to any one of the preceding claims wherein the optionally substituted thiochroman-4-one is of Formula (2): (R3)p-(R4)q Formula (2) wherein: each R3 and each R4 independently is a substituent other than hydrogen; and p has a value of 0, 1, 2, 3 or 4; and q has a value of 0, 1 or 2.
  8. 8. A composition according to claim 7 wherein each R3 independently is halo, R4 is C14-alkyl, p has a value of 1 or 2 and q has a value of 1.
  9. 9. A composition according to any one of the preceding claims which comprises: 73.25 to 94.34 parts of component (a); 3 to 10 parts of component (b); 0.4 to 3 parts of component (c); 0.7 to 5 parts of component (d); and 1.5 to 3.5 parts of component (e); wherein all parts are by weight.
  10. 10. A composition according to any one of the preceding claims wherein component (a) comprises: (i) a compound having one ethylenically unsaturated group; and (ii) a compound having more than one ethylenically unsaturated group wherein the weight ratio of (i):(ii) is greater than 1:1.
  11. 11. A composition according to any one of the preceding claims which further comprises 0.1 to lwt% aluminium salt, relative to the total weight of components (a) to (e).
  12. 12. A composition according to any one of the preceding claims which further comprises 0.1 to 2.Swt% surfactant, relative to the total weight of components (a) to(e).
  13. 13. A composition according to any one of the preceding claims having a viscosity of from 15 to 30 cP when measured at 25°C.
  14. 14. A composition according to any one of the preceding claims having a surface tension of from 20 to 40 mN/m when measured at 25°C.
  15. 15. A process for printing a substrate comprising applying thereto a composition according to any one of the preceding claims and curing the composition.
  16. 16. The process of claim 15 wherein the composition is applied to the substrate by means of an ink jet printer.
  17. 17. The process of claim 15 or 16 wherein the curing is performed using a light emitting diode which emits ultraviolet light.
  18. 18. A printed substrate carrying a cured composition according to any one of claims Ito 14.
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CN103232754A (en) * 2013-04-25 2013-08-07 深圳市美丽华油墨涂料有限公司 UV (ultraviolet) curing ink and application thereof
EP2949710A1 (en) * 2014-05-30 2015-12-02 Fujifilm Corporation Radiation-curable ink composition, ink set, inkjet recording method, decorative sheet, decorative sheet molded product, process for producing in-mold molded article, and in-mold molded article

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EP2192163A1 (en) * 2008-11-27 2010-06-02 Fujifilm Corporation Ink composition and inkjet recording method

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EP2192163A1 (en) * 2008-11-27 2010-06-02 Fujifilm Corporation Ink composition and inkjet recording method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232754A (en) * 2013-04-25 2013-08-07 深圳市美丽华油墨涂料有限公司 UV (ultraviolet) curing ink and application thereof
EP2949710A1 (en) * 2014-05-30 2015-12-02 Fujifilm Corporation Radiation-curable ink composition, ink set, inkjet recording method, decorative sheet, decorative sheet molded product, process for producing in-mold molded article, and in-mold molded article
JP2015224340A (en) * 2014-05-30 2015-12-14 富士フイルム株式会社 Active ray-curable ink composition, ink set, inkjet recording method, decorative sheet, decorative sheet molded article, manufacturing method of in-mold molded article and in-mold molded article

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