TW200530348A - Organic solvent-based printing inks - Google Patents

Abstract

An organic solvent-based printing ink composition is provided which comprises certain red and blue cationic dyestuffs of the azo and methine classes, an organic solvent, an organic acid which preferably is a resin acid, soluble in the organic solvent, and optionally an organic pigment. The cationic dyestuff is formed (in situ) from a dye precursor which is e.g. the corresponding carbinol of the dyestuff or its decomposable salt (by acid treatment). The compositions show e.g. high colour strength and excellent rheological properties and can be used in publication or packaging gravure flexographic, lithographic or letterpress printing processes.

Description

200530348 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an organic soluble composition, which contains basic (cationic) red and blue dyes as the sole coloring agent or toner (Tint 5 Reagents), mainly for inks based on colorants, which are used for, for example, photogravure printing of publications or gravure printing of packaging products, rotary printing of rubber plates, letterpress or lithographic printing methods. Solvent-based printing ink. Red and blue dyes, for example, azo (monoazo) or kagawa (polymethan) dyes, which are derived from dye precursors (which can be methanol 10 bases or salts of dyes (whose cationic structure is prone to acids) Intermediate decomposition)) is prepared by reacting with an organic acidic component before or during the method of manufacturing printing ink (in situ). [Previous technology] Use of certain color matrix (methanol) for the manufacture of organic solvents

15 Ink systems have been disclosed in, for example, FATITEC CONGRESS 1976, 13, 554, during which dyes and triarylmethane, diarylmethane, and related alcohols of the Gutton family and color pigment compositions containing so-called printing resins mixing. The use of azo or metagawa-type dyes and their precursors (methanol) is not mentioned. In addition, the efficacy (eg, color intensity) can only be added with organic soluble (methylbenzene soluble) 20 surfactants (eg, ten Diphenyl benzoic acid) and increase visually. Although the use of the dye precursors of the aforementioned pigment families is not entirely convincing, it has been found that by using basic red and blue dyes of special groups (made from dye precursors) for the production of organic solvents, Printing ink composition can achieve significant effects. 200530348 [Summary of the Invention] Therefore, the main object of the present invention is to provide the printing ink composition. Other objects of the present invention relate to a method of manufacturing such printing ink compositions and a method of using the same. 5 These and other objects of the invention are described below. Therefore, in a first aspect, an organic solvent-based printing ink composition is provided, including (1) a cationic dye of chemical formulas (1) to 4.

6 200530348

X2… (4) 2 = This individual system gas, substituted or unsubstituted alkynyl group, earthenyl group, square group, heteroaryl group or propylpropyl group, or r17 and r18 can be combined together to form a ring, _H ^ & 4 5 υ15, and r16 are each independently a halogen, aryl, nitro, 9 '10, 12, alkenyl, alkoxycarbonyl, aryl, fluorenyl, c alkenyl, 10 15 20 arylthio, fluorenylamino, alkynyl, arylcontinyl, and each -r6, R7, 4 Rl. , Rl2, R] 4, Ri5, or r] 6 any ^ muryl 'at the beginning to form a homocyclic or heterocyclic aromatic or non-aromatic ring, which can be combined with integers from 0 to 4, p and k Is an integer from 0 to 5, (is from 111 to 11 deducted and qw is an integer from 0 to 3, 2 is an integer from 0 to 4, 1 is a number, y and eight] are from resin acid organic anions, and & amp ... is an organic anion, (2) an organic solvent, (3) an acid or a salt soluble in an organic solvent, and (4) an optional colorant. In addition, the component (3) may It is a water carrier (binding agent), and then the dye component of rice component ， is, for example, a monoazo dye (the chemical formula is described as "represented." ) Dye. 1 (3)), and the substituted * RrRls of the chemical formulae (1) to (4) are each independently a substituted or unsubstituted alkyl or alkoxy group of 200530348, which contains 丨 to ⑼ carbon atoms Species (preferably 1 to 10 carbon atoms) can be linear or branched. Examples are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, dodecyl, hexadecane , Octadecyl and corresponding 5 isomers. The ethoxy species can be listed similarly. The lower alkyl / alkoxy (C "C4) species is preferred, and the methyl and Methoxy. As for substituted alkyl and alkoxy (preferably related to the above-mentioned chain length, one can be mentioned on the one hand is hydroxyalkyl, haloalkyl (fluorine-bromo-iodine), amine Alkyl, cyanoalkyl, and arylalkyl, wherein the aryl moiety 10 may be further substituted (e.g., lower alkyl and alkoxy, halo, hydroxy, cyano, amine, Carboxyl, carbaminyl), and on the other hand, for example, arylalkyloxy (aryl substituted with aryl as described above). Cycloalkyl may contain 5 to 10 ring carbon atoms, preferably * C5- C7 species, that is, cyclopentyl, cyclohexyl, and cycloheptyl, cyclohexyl are most preferred. The 15-energy substituents may be lower alkyl, preferably methyl and ethyl. Aryl may be Contains, for example, 6 to 10 carbon atoms, preferably phenyl or naphthyl, optionally with a hydroxyl group, a group (fluoro ... chlorine ... bromo_, iodine), an amino group, a cyano group, a carboxyl group, and a carbon atom Amine, Sulfur and Thioamino groups are substituted. Heteroaryl groups preferably contain 5 to 10 ring atoms, including one or more (example 20 such as' 1 to 3) nitrogen, oxygen or sulfur atoms. An example may be imidazole Oxazolyl, oxazolyl, thiazolyl, thienyl, pyrrolyl, pyrazolyl, triazolyl, pyridyl, pyridyl, pyrimidinyl, difluorenyl, benzimidazolyl, benzoxazolyl, and Fluoroxanyl, including isomers. For monocyclic groups, 5 or 6 ring atoms are preferred. 200530348 Substituents can be selected from, for example, hydroxyl, halogen, amine, and substituted moonyl Cyanoyl (including esters and acid amines) • Sulfur, thiosalamine, lower alkyl. Allyl can be optionally substituted with lower alkyl, halogen, or cyano. 5 ^ and 3 can be combined to form a 5 to 7 member homocyclic or heterocyclic ring, such as cyclopentane, cyclohexane or tetrahydrofuran. R4 and I can be combined with Rn and heart 8 to form a non-aromatic or aromatic ring of a heterocyclic ring or a 6-membered member, such as morphine, pyrene, or. Than slightly burned. Preferred substituents RrR are hydrogen, an alkyl group of 4 to 4 carbon atoms, and a hydroxyalkyl or cycloalkyl group having 1 to 4 carbon atoms in the alkanoyl moiety. Furthermore, the substituents R65, R7, R9, R10, Rl2, Ri4, Ri5, and Ri6 are each independently a southern element, a cyano group, a cyano group, an aryloxy group, a dilute group, an alkenyl group, an oxyoxy group, an aryloxyhydroxy group, Aryloxy, fluorenyl (RCO-), alkylthio, arylthio, fluorenylamino, including carboxyamino (carboamido) R_c0_NH_ (for example, example 15 hydrogen, alkyl Or phenyl) and sulfonylamino (thioamino) RrS02-NH- (Ri-based, for example, alkyl or phenyl), alkylsulfonyl, arylsulfonyl or thiol, Among them, the number of carbon atoms can be up to 10; depending on these groups, the lower limit can be 1 (carbo) or 6 (aryl). Any two R6 or any two R7 or any two R9 or any two or any two R »4 or any two R1S or any two R10 can be combined together to form a ring with which they are attached, a ring system that increases the ring, various Monocyclic or bicyclic ring like a ring or heterocyclic aromatic or non-aromatic ring. The ring-enhancing ring may contain 6 to _ ring atoms, and is preferably a 5- or 6-membered saturated or unsaturated homocyclic ring (benzyl, cyclobenzyl, cyclohexyl); or It may contain nitrogen, oxygen and / 200530348 or sulfur atom in the heterocyclic ring; examples are thienyl, furfuryl, pyrimidinyl, pyridyl or -o-ch2_o-ch2-yl. Substituents R6, R7, R9, Rio, Rl2, Rl4, Rl5, and Rl6 further preferably are halogens (individually), more preferably chlorine and molybdenum, cyano and 5nitro. The index η is an integer of 0 to 4, preferably 0 or 2, and the best is 0; the index m is an integer of 0 to 4, preferably 0 to 2, and the best is 0. The index p is an integer from 0 to 5, preferably from 0 to 3, and most preferably from 0 to 2. The index q is an integer of 0 to 4, preferably 0 to 2, and most preferably 0. 10 The index k is an integer from 0 to 5, preferably from 0 to 3, and most preferably from 0. The index t is an integer from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5, and most preferably from 2. The indices y and w are integers from 0 to 3, preferably from 0 to 2. The index z is an integer from 0 to 4, preferably from 0 to 2. 15 Furthermore, when the integers n, m, p, q, k, w, y, and z are applied, the specific R groups in the group represented by this integer need not be the same. For example, the symbol in which η is equal to 3 (^^ may represent a substituent gas, a fluorenyl group, and a nitro group, that is, the three R groups represented by (R) 3 are independent of each other. The anion system is derived from the following for the anion X2 A preferred embodiment is the resin acid described in Example 20. The anion X2 ... is generally derived from organic acids, such as fatty acids of 8 to 24 (preferably 8 to 18) carbon atoms, which are linear or branched, saturated Or unsaturated and contains octanoic acid (c8), nonanoic acid (c9), capric acid (c) 〇), lauric acid (c12), myristic acid (c14), palmitic acid (c16), stearic acid (CIS) , Monounsaturated oleic acid 10 200530348 (Ci8), diunsaturated linoleic acid (Ci8), triunsaturated linoleic acid (Ci8) 'and erucic acid (C22). The fatty acid may be unsubstituted, or Furthermore, it is substituted by, for example, a hydroxyl group or chlorine (preferably a hydroxyl group). Preferably, the carboxylic acid is unsubstituted. 5 Preferably, the fatty acid is saturated or monounsaturated. : 18 fatty acids.

Further acids may be 2- (2,4-di-tert-pentylphenoxy) -butanoic acid; phosphorus / phosphonic acid, such as monolauryl phosphate, dioctyl phosphate or dodecylphosphonic acid Benzyl acid; such as, hexadecyl:!: Carboxylic acid, benzoic acid substituted by alkyl group, such as p-benzophenic acid or p-octylbenzene-carboxylic acid; naphthyl acid or alkyl group Naphthalenesulfonic acid of 10; further phenolic acids such as 3,5-di-third-butylsalicylic acid; others are carboxylic acids having a C5-C7 cycloalkyl backbone which is unsubstituted or substituted with CrC4 alkyl For example, 4-cyclohexylbutanoic acid, 3-cyclohexylpropionic acid, cyclohexylacetic acid, cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, and cyclopentanecarboxylic acid. Preferably, the anionic X plant is derived from resin acid. The term "resinic acid" -15 In the context of the present invention-includes acidic species mainly derived from (cyclo) hydrocarbon resins, such as terpenes or terpene-based resins, such as the rosin family of rosin or abietic acid, Contains chemically modified rosin and di- and poly-polymerized rosin. Therefore, suitable examples of resin acids may be terpene-based carboxylic acids such as acyclic, monocyclic, or bicyclic (: 1 () terpenes) Alkenes, acyclic, monocyclic, bi20 ring or tricyclic C15 sesquiterpenes, acyclic, monocyclic or tricyclic C2G diterpenes, especially tricyclic C2G diterpenes, for example, abietic acid, Dihydro rosin acid and tetrahydro rosin acid. Preferred resin acids are rosin (main component of rosin acid), rosin acid and rosin-based resin and derivatives thereof, especially chemically modified rosin 200530348. Rosin acid contains, For example, gum rosin, wood rosin, tall oil rosin, and chemically modified species, such as halogenated, sulfonated, phosphinated, or nitrated rosin; further included are disproportionated, hydrogenated, dimerized, polymerized, or Partially polymerized rosin; and esters modified with rosin For example, 5 rosin 'pentaerythritol rosin esters of maleinization and phenolic resin modified by rosin. The anions X! ... and X2 ... are not derived from inorganic acids such as hydrochloric acid, sulfuric acid, etc. Chemical formulae (1) to (4 ) Chromophores of cationic (basic) dyes, such as' organized as the Society of Dyers and 10 colonsts and the American Society of Textile Chemists and Colorists

American

Association of Textile Chemists and Colorists) c.l. alkali dyes in the colorimetric index (C.I.) issued by households. Details of the dye are revealed in the meantime. Representative examples: For dyes of formula (1): CI test red 14, CI test purple 16 (CI number 48013); For dyes of chemical formula (2): cL basic red 12 (CI • No 48970) ;

20 The component (2) of the printing ink composition of the present invention is an organic solvent (including cyclic ether, diol bond,-and poly-acrylic group), S purpose, | all ranges from polar to non-polar organic solvents ), Which can be selected from the group consisting of selectively functionalized aliphatic hydrocarbons, selectively denatured aromatic hydrocarbons (preferably benzene series), dioxanyl and solubilizing ink carrier polyalkylene glycol, polyalkylene group Glycol ethers, alcohols (monohydric, nitrogen-containing heterocyclic compounds, ribs and ribs) ★ Rhyme 12 200530348 components and monomers (acrylate monomers) and their mixtures composed of monarch aliphatic hydrocarbons, For example, those having a boiling point in the range of 75 to 400. (: boiling point in the range; which has a boiling point in the range of about 75 to 180 ° C, even if the distillate has a higher fluorine point in the boiling point range of 180 to 400 ° C Can be applied.

Typical examples are general paraffins such as heptane, octane, nonane, etc., iso-chain burning smoke such as isooctane; crude gasoline, petrolatum, and refined gasoline, 1 heptene, 1-octene, 1-nonane Ene. Examples of higher boiling point distillates are those in the range of 240 to 270 ° C and 280 to 350 ° C, respectively. 10 15

20 Best of all, the fragrant Yagaki is a benzene series, especially benzene which is unsubstituted or substituted with Ci monoalkyl, such as benzene, dimethylbenzyl, and better toluene; the halogenated halogen of one step, such as chlorine Benzene (mono-, di- and tri-). As the dipeptone, there can be used, for example, ethylene glycol monomethyl and monoethyl ligand-propyl- ^, ethyl diethylene glycol, butyl diethylene glycol, or phenyl glycol. > Typical alcohols, for example, Ci-C, such as those with more polarities, such as formazan, ethanol, n-propanol, isopropanol, and ethoxypropanol, among which ethanol is the preferred species; And less polar ones, for example, C4_C8 alcohols, such as n-butanol, isobutanol, second butanol, third butanol, or n-hexanol, the corresponding isomers, and further Cyclohexanol and benzyl alcohol. Dialkyl ethers are, for example, methyl ethyl ether or diethyl ether, and examples of cyclic ethers are tetrahydrofuran and dioxane. Representative esters are acetates, such as, and preferably ethyl acetate. Propyl acetate or butyl acetate, suitable homologues of acetone, methyl ethyl ketone, ketol, cyclohexanone and acetophenone. Methyl isobutyl ketone, dipropylene 13 200530348 Preferred series of halogenated aliphatic hydrocarbons are dichloromethane, trichloromethane, tetrachloromethane, trigasethane, tetrachloroethane, trichloroethylene, tetrachloromethane Vinyl chloride. Nitrogen-containing heterocyclic compounds are, for example, N-methyl-2-pyrrolidone or 1,3-dimethyl-2-osalone. 5 Polyalkylene glycol, preferably a low molecular weight polyethylene glycol having a molecular weight of 100 to 800, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol 200 , Polyethylene glycol 300, polyethylene glycol 400, or polyethylene glycol 600, especially polypropylene glycols having a molecular weight of 150 to 400, or a low molecular weight, such as dipropylene glycol, tripropylene glycol. Polypropylene glycol P 400 or polypropylene glycol P 425. Polyalkylene glycol ether system, for example, CrC of polyphenylene glycol; alkyl ether, for example, diethylene glycol monobutyl ether, 2- (2-methoxyethoxy) ethanol, 2 -(2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, or 2- [2- (2-ethoxyethoxy) eth Oxy] ethanol. 15 Glycols or thiodiols, for example, C2-C6 alkylene glycols or sulfides

Alcohols such as ethylene glycol, propylene glycol, butanediol, 1,5-pentanediol, thiodiglycol, hexanediol. Polyhydroxy alcohols and ethers thereof, for example, glycerol or 1,2,6-hexanetriol, and CrC4 alkyl ethers such as 2-methoxyethanol or 1-methoxyprop-2-ol. 20 The monomers of UV-curable inks are also classified as solvents in this context. Typical examples are acrylate monomers, such as 1,4-butanediol acrylate, propoxylated glycerol tripropionate S, and pentaerythritol tripropionate S, but do not exclude others. Ink carrier components or excess organic acids can also be used as solvents for this reaction. 14 200530348 The preferred organic solvent is selected from the group consisting of selectively bleached aliphatic cigarettes, sexually halogenated aromatic hydrocarbons (preferably benzene series), di-, polar / polar) alcohols, Sat, ketones, and solubilizing inks. A group consisting of a mixture of Saki and Lai :: _. Preferably, the 5th substance contains an ethanol / ethyl acetate ratio of 99: 99-1 v / v).

10

The organic acid of the component ⑺ of the printing ink composition of the present invention is the anion X1 · •• of the dye of the chemical formula 虽, which is mentioned when it is derived from resin acid. Mixtures of acids can also be used. The acid used is preferably non-surface active in nature and is preferably compatible with ink solvents and binders (ink carriers). For the printing ink composition containing the dyes of the chemical formulae (to (4), the acid 'of the component (3) may include a non-resinic acid (' acidic species') in addition to the resin acid, which is selected from With 'for example, 6 to 36 (preferably 6 to 24) carbon atoms of the organic slow acid and organic Gu group, and it can be aliphatic (linear, branched, saturated, unsaturated) or aromatic Species. For example, the functional organic acids or anhydrides shown in US-A-4,605,441 are not used. 0 aliphatic carboxylic acids, preferably saturated or unsaturated aliphatic acids having 6 to 18 carbon atoms, may be unsubstituted. Or, moreover, it is substituted, for example, with a lower alkyl group than 20 (for example, ethyl ethylhexanoate); the aromatic acid may be substituted with chlorine, a lower alkyl group and / or a hydrocarbon group (for example, salicylic acid). And 3,5-di-tert-butylsalicylic acid) or may be a polyacid (eg, 1,2,3'-tricarboxylic acid). Further acids may be esters and amidines carrying acids (carrying carboxylic acid groups), including these monomers, dimers, polymers (terpolymers, etc.) and polymers, such as, 15 200530348 acrylic acid , Polyacrylic acid, polyaspartic acid and polyhydroxystearic acid. Preferably, the acid may be an aliphatic or fragrant acid of 6 to 24 carbon atoms, such as' carbyl lutein or optionally substituted benzene or cylic acid = Examples of acids are alkyl (C ^ C] 8) sulfonic acids, such as hexylsulfonic acid, decayl: luteinic acid or octadecanoic acid; courtyard-based (C1_C18) benzene, such as p-burn 2 lutein, p-xin n-dodecylbenzene or p-stearylbenzenesulfonic acid; and naphthalenesulfonic acid or alkyl (CrC8) naphthalenesulfonic acid. 10 yuan further acid can be contained in the motif part, for example, 8 to 18 carbon atoms of stone dance / phosphonic acid (part of _), such as' Gu's single laurel motif, linoleic acid or ten 'Two-octyl g purpose of mono-basic linolenic acid. 1. In addition, for the Indian water composition containing the dye of the chemical formula (4), the acid of the component (3) may include the aforementioned aliphatic or aromatic lutein acid. Component (4) of the composition of the present invention is preferably related to organic colorants, which include, for example, monoazo, diazo, naphthol, dioxan, acetone, azomethine, azo 15 condensation, metal wrong Compounds, nitro, purple ring ketones, fluorenone, allanone, benzimidone, iso-Sju flower, iso-pyridine g, isocyanate, mesitone, aminoenone, Pigments of allium pyrimidine, indanthrone, xanthone, scallion ketone, scallion ketone, isotope, diketopyrrolopyrrole, carbazole, osmium, indigo or thioindigo, but not excluded other. Mixtures of these colorants can also be used. 20 is preferably an organic colorant of the following chemical types: monoazo, diazo, azosulfonium, naphthalene, and metal complex colorant (eg, self-cyanine). Further details on the organic pigment literature are Industrial Organic Pigments, W. Herbst, K. Hunger, 2nd edition, VCH Verlagsgesellschaft, Weinlieim, 1997. 16 200530348 Optionally, organic pigments can be mixed with pigments containing oxide, pigments of iron oxide and iron hydroxide, pigments of chromium oxide, spinel-plastic entangled pigments, complex acid pigments, carbon black, and Prussia Blend of inorganic pigments in Zhiwangfeng Temple. A further object of the present invention is the aliphatic or aryl-acid salt of CI Chromatic Red 54 and CL Chromatic Blue 5 145 as described above, preferably dodecyl benzoate only @ 夂 盐, and q • Infrared red ^ is a slow acid salt as described above, which is more acid oil H ethylhexanoate and derivatized acid salt. These salts are produced, for example, by reacting the formazan precursor or decomposable salt of the dye with the corresponding acid or endogenous acid with the same molecular weight or residual acid. 1〇 / The printing ink composition of the invention can be manufactured by various methods, which is the further object of the present invention .... It is based on or disperses in the organic precursor of the so-called dysprosium dye, which is the precursor of the dye, methanol In the test, the 15-type carbonic acid chloric acid salt (acid or ... is mixed with _ sealing fatty acid dissolved in an organic solvent, and mixed with optional colorants. Starting in two or two steps, a kind of manufacturing A method of printing ink composition containing chemical formula ⑴ or (2), including the method of dissolving or dispersing the wood ⑷ seal in chemical formula (5) or 面

Dye precursors of N (5) 17 ^ 5 200530348

(6) where R] to R8, m and η have the meanings shown, and A is —〇r, _n (r) 2, -N ⑻ COR, -N (R) S〇2R5 -SR, -S (0) R, -〇2CR5 -N⑻CON (R) 2, -〇 CON (R) 2, -s〇2N (R) 2 or -n (R) COOR, where 5 R is R !, and ( b) Organic resin acids dissolved in organic solvents, and (c) selective colorants, mixed together. As for the preferred substituents and explanations, the definitions provided for those of the compounds of the formulae (1) and (2) are preferred. 10 as the best substituent A-oh. -When using a dye of the formula ⑹ In addition to the addition of an organic resin acid (as component ⑻), the non-resinic acidic species as described above can also be used to make a printing ink composition. This method can also be used for dye precursors of chemical formula (5), resulting in a known composition for transferring 15 ink ribbons (e.g. 698,49 °). However, the use of these compositions as printing inks is a further object of the present invention. -Further '-A method for manufacturing a printed black water composition containing a dye of the chemical formula (3) or (4), including chemical formula (3) or ( 4) The salt of the dye is mixed with the organic acid dissolved in the organic solvent and the colorant with the selectivity of 18 200530348 (C). Suitable dye salts for decomposition are, for example, bicarbonate (carbonic acid carbonate) (hco3 ...) and carbonate (C032 ...). -According to a further alternative, manufacturing can be carried out as follows: 5 This method comprises (a) dye precursors / decomposable salts of dyes of formulae (1) to (4), and (b) soluble in organic (polar Or non-polar) solvent of organic acid (preferably resin acid), evaporate the solvent (under reduced pressure) from the mixture until a dry mixture is obtained, and 10 make the dry mixture soluble again in the desired ink medium Compatible organic solvents (organic non-polar solvents) and (c) selective (organic) colorants.

The dye precursor (a) may include carbonates / acid carbonates of the species of the formulae (5) and (6) or compounds of the formulae (3) 15 and (4). "Decomposable salt" is decomposed by treatment with an organic acid as previously defined. The solvent of the solution (b) should be such that the starting material (methanol) / carbonate-acid carbonate / resinic acid) can be sufficiently dissolved and reacted. The organic solvents previously designated as better solvents are most suitable here, especially ketones (acetone), dialkyl ethers (diethyl 20 ether) and halogenated hydrocarbons (dichloromethane, chloroform). Furthermore, these solvents can be easily removed from the reaction mixture. The solvent used for the re-dissolving step needs to be selected from those referred to as ink solvents as preferred solvents such as aromatic hydrocarbons (benzene), aliphatic alcohols (ethanol, ethanol) and esters (ethyl acetate) or mixture. 19 200530348 Furthermore, the method of the present invention further comprises the use of so-called ink vehicles (or agents), such as resins, oils, celluloses, polyamides, polyolefin species (originally derived from vinyl- or acrylic Basic monomers) and rosin and rosin esters are mixed with dry or wet or mixed components (a), (b) and optionally (c). 5 10 15 20 These ink carriers, which are generally any known binders, contain resins, such as long oil, medium oil or short oil, alkyd resins, phenol modified alkyd resins, Phenolic resins, rosin-modified phenolic resins, metal resin salts, such as copper, zinc, or magnesium resin salts, petroleum resins, (cyclic) hydrogen tree moons, such as' @ or 箱-酉 分 酸酸 ， Acrylic, styrenic and vinyl polymer-based resins, melamine and epoxy resins, dimerization and polymerization of right incense, peak incense modified Malay, Fuma and secret resin and Malay resin; Oils, such as ^. Pore retorts and vegetable oils; Cellulose, such as continyl cellulose, cellulose acetol & △ ^ For example, polyvinyl butyral species, vinyl alcohol, polyethylene Glycolate, propylene, propylene propionate, and polygas for a long time. In addition, the method of the present invention can-gas dilute, gasification polylean. The acid (Yu Jingxianglang, and the components ⑷, organic (tree moon purpose)) is dissolved in the organ, more 隹-⑷, but this mixture is implemented together. &Quot; Non-polar organic solvents as defined by W, wet Blending (co-dissolved, further human purpose. This d-solution or concentrated type) is a dry mixture (0 /), organic (resin) acid and selectivity of the invention selected according to this alternative Only for further purposes. In addition, in the method of the present invention, eight L 3 dry mixed components (a), organic (resin) 20 200530348 2 (e) 'and ink carrier are optional, but in organic solvents, preferably non-polar organic solvents U ~ co-solubilization of component (C) used in accordance with the present invention, and Heihuan truncated Qicheng (scientific) acid 'and selective subtractive blending (co-solubilization X-Year's purpose. Step-Step Purpose. This compound-bath or Chinese-condensed form) is an alternative to the steps of the present invention. 10 (a), organic (resin) acids, and selective M methods "combine components into pre-formed In addition or with a dry mixture machine, 1 water-borne scraper. This method can be used to extrude the component ⑷, ink BL, and optionally ⑷㈣ or ㈣ mixture into a carrier 〶ID body dispersion , Solution or scale. Obtaining an extruded product according to this method is a further objective of the present invention. The organic / inorganic system is as previously defined.) 4 Processing can also be performed by applying shear and / or heat (if required) ) Make the organic tree = pre-filament in melted ink or ink carrier components. In W shell, the alcohol precursor is applied by shearing And / or heat (if needed)

In addition, both the alcohol precursor and the organic resin acid can be used together / individually in the ink vehicle in one step. Furthermore, the method of the present invention is carried out in which components (b) & (c) together constitute a resin salt colorant. The basic and selective components can be used by any known method using ball mills, sand mills, bead mills, attritors, continuous horizontal media dispersers, hoists * grinding cities, two-roller grinders, pressure Type kneader, or extruder 5 'further by the traditional method of manual or mechanical shaking, or by low or high shear 21 • 200530348 cutting and stirring the printing ink composition mainly composed of two steps and two colors I) Dissolve the ink vehicle in an organic solvent, and (II) Disperse the colorant in the dissolved ink vehicle. Step (II) generally requires far more than the step to produce a sudden cut of privacy and cause heat 10 15 20 It has been found that the manufacturing of the ink according to the present invention is exceptionally shown in the following manufacturing methods, all of which produce the same ink ： "-There is acid completely dissolved in organic solvents, and its precursors (A7 and therefore the dye solution is added to the ink prepared by the carrier _ vehicle dissolution 0 /-organic (resin) acid and precursor (methanol) They are dried and mixed together, but the organic solvent (a non-polar organic solvent) is added to the dye solution prepared in advance, and the ink solution is prepared in advance.-Organic (resin) acid, The precursor (methanol) and the ink carrier resin are dried and mixed together, and then 'co-dissolved in organic solvents (non-polar organic solvents). In all three cases, the required degree of shear is similar to that of general solvent-based ink carriers. Resin resin is required, and far less than that required to disperse colorants. Because of lower cutting, the heat generation in the ink is greatly reduced. Therefore, it can be used within the same regulations and is generally used to simply dissolve the ink. Agent resins are similar The finished colored ink is cut.. Due to the reaction order, many processing possibilities are now available. The manufacture of heart-colored ink can now be implemented on any equipment that can produce low shear. 22 200530348 For dispersion The traditional high-shear method of colorants is not required, even if the possibility of implementation is included. The mixing of precursor (methanol) and resin acid can be carried out in an extruder with an appropriate carrier. This carrier system can be a concentrate of a bath or an appropriate ink carrier. The reaction of the precursor (methanol) can be achieved during the extrusion process, even if this is not necessary, because the concentrate can be dispersed thereafter Occurs during the ink solvent. The precursor (methanol) coloring method can be used in combination with traditional coloring methods. Therefore, further possibilities for the processing of inks and colorants are unfolded. In general, many traditional solvent-based liquids The ink does not contain a high content of 10 rosin-based resin (resin acid) as part of its composition. These resins are commonly used in colorants that are designated for lithographic offset printing inks based on distillation or vegetable oil. . In addition to improving the performance of colorants in the ink system, the advantages of one step can also be obtained. Rosin-based resin treatment is used to reduce the aggregation of colorants during manufacturing and drying. Colorants containing rosin-based resins are generally available Manufactured more quickly and reproducibly, while also producing products with lower agglomeration. Therefore, the dispersibility and final properties of the products are generally superior. Traditionally, many solvent-based liquid inks (for example, toluene Photogravure printing inks for major publications) have not yet used rosin-based color buckets because the solution of this material in the ink vehicle will cause increased viscosity. 20 But 'because rosin-based resins are acidic in nature, there are existing Possibility of using this material as a conversion agent for the precursor of methanol dyes. Therefore, the colorant can be regarded as a carrier of the alcohol conversion agent. Methanol can also be considered as a resin salting agent that is reduced in the toluene system. Reagent for traditional problems. The south color intensity of the dye formation allows the use of lower colorants, thus reducing viscosity. Also exists 23 200530348 There is the possibility of improving gloss, so the binder content can be reduced equally. The composition of the present invention can be used in an amount effective for the intended purpose. In general, good results are based on components (by weight) containing 0.1-50%, 1-95% (preferably 5-95%) of component (2), 0.1-75% (preferred) The range is from 0 to 50%), 5 (3) and 0-50% (4). Preferably, the concentration may be: 15-40% of the component (1), 40-60% of the component (2), 20-50% of the component (3), and 0-50% of the component ( 4). • The composition can generally be implemented in the following two forms: (A) a composition containing components (1) to (3) but without color-this composition can be used as a printing ink by itself, for example, gravure printing or rubber plate Rotary printing ink (full pigment composition). (B) A composition containing the components (1) to (4), wherein the components (!) To (?) Are used for toning, coloring, and enhancing the printing ink mainly composed of the main colorant (4). Brilliant toner (partial pigment composition). 15 component (3) organic (resin) acid is reacted with (methanol precursor) excess acid, steep component. Although most experimental procedures require high levels of acidic components for the reaction to proceed, a 1: 1 molar reaction with methanol can be used. Therefore, component (3), /. Existence means that no excess acid is present in the ink composition; in this case, for example, an ink vehicle (as defined previously) may be used as the component (3). In addition, it may be a specific excess, which may be defined above about 0.01%. It has also been confirmed that excessive amounts of-夂 H can be used, and that it constitutes a major part of the binder resin composition (e.g., binder resin for photo printing, its towels, binder resin-general, resin acid, etc., such as , Metal resin salt), therefore, it can be up to 75% of the ML soil series 50%. Therefore, the excess component ⑺ can be defined as 0 "to 24 200530348 75%, preferably 0 to 500. . Furthermore, additives for printing inks can be used. Typical & 3-customary known to those skilled in the art i. 0 agent contains drying accelerator, drying inhibitor, uncolored extender, filler, surfactant, rheological impermeability Oxidants, ants, oils, shellfish, wetting agents, dispersing stabilizers, through-print suppression swords and anti-foaming agents; into the + + station's accelerators, crosslinking agents, plasticizers, first (before, Deodorant, fixing agent and chelating agent. 10 15 20 This = printed dark water composition can be used for flat substrate printing corresponding & plate °. And packaging gravure printing, lithographic printing, printing and rubber Rotary printing. These methods are a step forward in the present invention: These methods are used for the printing of 'for example' Zide, newspapers, miscellaneous supplements, headings, packaging materials, food packaging and containers, paper, film [Executive application method] Shuming will be further described with reference to its specific examples, but it should be understood that these examples are used for illustration purposes, "rabbits are" presented by sundial "and should not It is construed as a limitation on the scope of the invention as described herein. The content is expressed in parts by weight or weight percent. The temperature is expressed in Jane's degrees. All examples are performed at room temperature. The reaction time is used to achieve the complete king: liquid (which represents dye precursors and organic ( Resin) is defined as the complete% required. Generally, this reaction time is between 2 and 20 minutes, although iron can vary depending on the degree of agitation applied. 25 200530348 Examples: Example 1 1 〇 Gram of the CI test red 54 acid carbonate (bicarbonate) is mixed with 10 grams of dodecylbenzenesulfonic acid in 10 grams of ethanol. 70 grams of 31% solid 5nitrocellulose medium and the rest are rough A 5: 1 (v / v) blend of ethanol and ethyl acetate was added, followed by broken glass beads, and then mechanically shaken. A strong dark red ink was thus prepared. Example 2 1 g of oleic acid Mix with 0.5 g of CI · basic red 54 acid carbonate, mix gently and warm gently. Then, add toluene to show a complete solution of dark red. Example 3 2.25 g of 2-ethylhexanoic acid and 〖〇 g of CI. Basic red M acid carbonate is mixed And gentle warming. Once the complete solution was obtained, 5 grams of flat 15-plate printing thermosetting ink medium was added and allowed to produce a dark red ink. Example 4 L0 grams of dodecylbenzenesulfonate and 1.0 grams of CI · alkali The red 54 acid carbonate is mixed in 20 ml of ethanol and boiled until complete evaporation is achieved. 0.48 g of a 5G% dye mixture is mixed with 152 g of lithographic hot 20 curing varnish and stored at 7 (TC 30 minutes, and then disperse by a secondary glass plate dispersing device (25 series of 2 series, without adding handles). The ink of Gucheng is displayed with the traditional color ink (which is printed in lithography c) color material red 57 : 1 constitutes the master, and the money is made by making the pigment of gram and [π gram of varnish using 5 series of 75 revolutions, 2 kg mixed with no heat treatment 26 200530348) equal strength. Furthermore, dye inks show improved gloss and transparency. When Example 4 was repeated by using C.I. Basic Blue 145 Acid Carbonate, the same good results were obtained. 5 Example 5 5 grams of C.I. red 12 methanol was mixed with 5 grams of dodecaylbenzoxanthanic acid in 5 grams of ethanol. 35 grams of a 31% solid nitrocellulose medium, the remainder being a roughly 5: 1 blend of ethanol and ethyl acetate, was added and then glass beads were added, followed by mechanical shaking. Intense dark blue-red ink was thus made by 10. In Example 6, 2.5 g of polymerized rosin was dissolved in 10 ml of ethyl acetate, followed by 1.0 g of C.I. basic red 12-ol. The mixture was shaken until a complete solution was reached, then 5 grams of 31% solid nitrocellulose medium and the remaining 15 series of a roughly 5: 1 blend of ethanol and ethyl acetate were added. Printing this ink shows a strong bluish red with high gloss and transparency. Example 7 10 grams of CI · basic red bus 12 methanol and 20 grams of tall oil rosin in 28 5 grams of ethanol and 41 5 grams of 24% solid commercially available nitrocellulose ink 20 vehicle (remaining ethanol) mixing. The resulting mixture was shaken on a mechanical shaker for 45 minutes. The resulting ink appears intensely red. It is better in gloss and transparency than 10 grams of commercial CI · Colorant Red 57: 1 composition (instead of methanol and tall oil rosin). It is prepared by dispersing glass beads on a mechanical shaker for the same time. The major improvement of the ink was 27 200530348. The 50/50 blend of the above colorants and dye inks showed the same color intensity as pure colorants, plus significant improvements in gloss, transparency and purity, and reduced dichroism. 5 Furthermore, the pigment ink ratio of 70:30 to dye ink shows an advantage over the 5% strength of the individual pigment materials. Example 8 2.5 g of tall oil rosin was dissolved in 10 ml of toluene, followed by 10 g of C.I. test red 12-ol. The mixture was shaken until a complete solution was reached. After that, 5 g of a 50% solid metal resin salt medium was added, and the remainder was methylbenzene. This ink shows strong blue-red with high gloss and transparency. Example 9 11.0 grams of dodecylbenzenesulfonate and L0 grams of C.I. basic red 12% alcohol; 20 liters of literary essence were mixed and boiled until complete evaporation was achieved. 0.48 g formed at 50 ° /. Dye mixture with 152 g of lithographic thermosetting varnish This is stored at 70 C for 30 minutes, and then dispersed by a Muller glass plate dispersing device (25 revolutions of 2 series, without adding missing codes). The formed ink shows better than traditional color ink (it is mainly composed of lithographic CI · colorant red 57: 1 composition, by using 0.24 g of colorant and 1.76 g of 20 shi varnish using 75 revolutions of 5 series and It is made with 2 kg weights and mixed without heat treatment.) 10% strength. Furthermore, dye inks show improved gloss, transparency, and dispersibility. Example 10 0.12 g of C.I. Basic Red 14 Methanol and 0.12 g of dodecylbenzenesulfonic acid 28 200530348 The acid was mixed with 1.2 g of ethyl acetate. 1.0 g of a commercially available nitrocellulose ink vehicle (the remaining ethyl acetate) in 24% solids was added and shaken to produce a completely dark red solution. The resulting ink produces a dark, intense, shiny, and transparent red color during printing. 5 Example 11 0.5 g of C.I. Basic Red 14 Methanol and 0.5 g of dodecylbenzenesulfonic acid were dissolved in 4.85 g of ethanol. 4.15 grams of 24% solids of commercially available nitrocellulose ink vehicle (residual ethanol) was added, followed by 1.5 grams of ethyl acetate and shaken to produce a completely dark red solution. The resulting ink produces dark, intense, shiny, transparent red when printed. Example 12 0.5 g of C.I. test red 14 methyl alcohol and 0.5 g of dodecylbenzoic acid were dissolved in 4.85 g of ethyl acetate. 4.15 g of a commercially available nitrocellulose ink vehicle (residual ethanol) in 24% solids was added and then shaken to produce a completely dark red solution of 15. The resulting ink produces a dark, intense, shiny and transparent red color during printing. Example 13 0.5 g of C.I. red 14 methanol and 1.0 g of dodecaylbenzoxanthanic acid were dissolved in 4.85 g of toluene. 2.0 grams of 50% solid metal resin salt medium (more than 20 copies left) are added and shaken to produce a completely dark red solution. The resulting ink produces a dark, intense, shiny and transparent red color during printing. Example 14 0.12 g of C.I. red 14 methanol and 0.12 g of dodecylbenzene benzoic acid were dissolved in 1.2 g of toluene. 0.5 g / 50 g /. A solid metal resin salt medium (remaining 29 200530348 xylene) was added and shaken to produce a completely dark red solution. The resulting ink produces a dark, intense, shiny, transparent red color when printed. Example 15 0.12 g of CI · basic purple 16-methanol and 0.2 g of dodecylbenzenesulfonic acid 5 were co-dissolved in 1.2 g of ethyl acetate, and 1.0 g of 24% solids was added. The purchased nitrocellulose ink vehicle (residual ethanol) was shaken to produce a complete dark purple solution. The resulting ink produces a dark, intense, shiny and transparent purple color during printing. Example 16 10 g of CI · Purity Violet 16 Methanol and 0.12 g of dodecylbenzenesulfonic acid were co-dissolved in 1.2 g of toluene, and then 0.5 g of a commercially available metal resin salt ink carrier was added at 0.5 g (Remaining toluene) and shake to produce a complete dark purple solution. The resulting ink produces a dark, intense, shiny and transparent purple color during printing. 15 Example 17 2.0 g of CI · basic red 54 acid carbonate and 2.0 g of dodecylbenzenesulfonic acid and 10.0 g of 24% solid nitrocellulose varnish (residual ethanol) in 10 ml of acetic acid The ethyl acetate was mixed and mechanically shaken for 4 minutes to produce a strong dark red ink. 20 Example 18 1.5 grams of dodecylbenzenesulfonic acid and 1 > 5 grams of C. I. Basic Blue 145 carbonate in 19.8 grams of ethanol, 21.7 grams of ethyl acetate and 30 grams of diacetone alcohol and 52.5 grams of 20 % Solid cellulose cellulose varnish (residue is a 3.5: 1 blend of ethanol and ethyl acetate) are mixed together and shaken in the presence of a bead filler in a mechanical 30 • 200530348 type for 45 minutes. The resulting ink showed high color intensity, gloss, and transparency. Example 19 0.25 g of CI · Basic Blue 145 Carbonate, 0.5 g of twelve alkylbenzene 5 sulfonic acid and 1 g of toluene were mixed in a 50% solid metal resin salt ink medium (the remaining toluene) and mixed. Shake by hand. The resulting ink exhibits high color strength, gloss, and transparency. Example 20 0.25 g of CI · basic blue 145 carbonate and 0.25 g of dodecyl 10 benzoic acid and 2.1 g of 24% solid nitrocellulose varnish (residual ethanol) in 2.4 g of ethanol, 1 G of ethyl acetate and 0.3 g of dipropanol in a solvent blend were mixed and shaken by hand. The resulting ink exhibits high color strength, gloss, and transparency. Example 21 15.25 g of CI · basic blue 145 carbonate and 0.25 g of dodecayl benzylsulfonic acid and 2.1 g of 24% solid triethyl cellulose varnish (residual ethanol) in 2.4 g of acetic acid The ethyl acetate was mixed and shaken by hand. The resulting ink exhibits high color intensity, gloss, and transparency. Example 22 0.25 g of CI Basic Blue 145 Carbonate and 0.5 g of polymerized scent and 2.1 g of 24% solid nitrocellulose varnish (residual ethanol) were mixed in 24 g of ethyl acetate and mixed with Hand shake produces intense blue ink. Example 23 Salicylic acid and 0.25 g of C_I. Basic blue 145 carbonate and 0.25 g of water 31 200530348 2.1 g of 24% solid nitrocellulose varnish (residual ethanol) in 2.4 g of ethyl acetate It is mixed and shaken by hand to produce intense blue ink. Example 24 0-25 grams of CI · basic blue 145 carbonate and 0.25 grams of dodecylbenzene. Swen and 2.1 grams of 24% solid nitrocellulose varnish (residual ethanol) at 2 · 4 g of ethyl acetate was mixed in the purpose and shaken by hand to produce a strong blue ink. Example 25 0.25 g of CI · Basic Blue 145 Carbonate and 0.05 g of hydrogenated wood rosin and 2.1 g of 24% solid nitrocellulose varnish (residual ethanol) in 24 g of ethanol and 1 g of acetic acid Ethyl acetate and 03 g of a solvent blend of diacetone alcohol were mixed and shaken by hand to produce a strong blue ink. Example 26: 0.25 grams of CI · blue blue 145 carbonate and 0.25 grams of salicylic acid and 2.1 grams of 24% solid nitrocellulose varnish (residual ethanol) in 2.4 grams of acetamidine 1 g of ethyl acetate and 0.3 g of diacetone alcohol in a solvent blend were mixed and shaken by hand to produce a strong blue ink. Example 27 0.25 grams of CI · Blue Blue 145 carbonate and 0.25 grams of p-toluene 20 acid and 2.1 grams of 24% solid nitrocellulose varnish (residual ethanol) in 2.4 grams of ethanol, 1 g of ethyl acetate and 0.3 g of diacetone alcohol in a solvent blend were mixed and shaken by hand to produce a strong blue ink. Example 28 (C.I_Dodecylbenzenesulfonate of basic red 54) 0.50 g of CI · basic red 54 acid carbonate and 0.53 g of dodecane 32 200530348 based on 20 ml of benzoic acid Mix and shake in acetone until a complete solution is reached. The solvent slowly evaporates by heating, showing a dark red product. Paper chromatographic analysis (Whatman No. 42 paper and 60/40 Bake ^ Hexan * solvent system) showed a coloring point of 0.25 retention factor, which did not appear in the starting material. Beifang Dagger Example 29 (CI basic blue 145 dodecylbenzenesulfonate) 0.50 g of CI basic blue 145 carbonate and 0.54 g of dodecyl benzoic acid in 20 ml Mix and shake in acetone until a complete solution is reached. The solvent slowly evaporates by heating, showing a dark blue product. 10 The paper chromatographic analysis (Whatman No. 42 paper and 60/40 HP / Hexane solvent system) showed a coloring point of 0.40 retention factor, which did not appear in the starting material. Example 30 (CI Basic Red 54 p-toluenebenzenesulfonate) 0.50 g of CJ · basic red 54 acid carbonate and 0.50 g of p-metabenite page acid monohydrate in 20 ml Mix and shake in acetone until the solution is reached. Paper color analysis (Fisher—general purpose school grade paper and 60/40 C class / hexane solvent system) shows a coloring point of 0.35 retention factor. Appears in the starting material. Known Example 31 (CI Basic Blue 145 p-toluenesulfonate) 50 grams of C · 1 · basic blue 145 carbonate and 0.50 grams of p-toluenesulfonium monohydrate in 20 ml of acetone was mixed and shaken until the solution was reached. Paper color analysis (Fisher—general purpose school grade paper and 60M0 Ugly / Hexane solvent system) showed a coloring point of 0.21 retention factor, which did not appear. On starting materials. 33 200530348 [Schematic description] (None) [Description of main component symbols] (None)

34

Claims (1)

200530348 10. Scope of patent application: 1. An organic solvent-based printing ink composition, including: (1) cationic dyes of chemical formulas (1) to 4 (Re) m X2… (2) (3) 35 200530348 Χ2… (4) 10 Among them, RrRu is hydrogen, substituted or unsubstituted alkyl, alkoxy, cycloalkyl, aryl, heteroaryl, or allyl, and R17 and Ris can be combined with each other. Form a ring together, and then go, R p ^^ K6? K7? R95R1055Rl2? R] 4, Ri5, and R〗 6 are halogen, cyano, stone street beauty, ravenous alkalyl, alkenyl , Alkenyloxy, alkoxycarbonyl, aryloxycarbonyl, fluorenyl, fluorenyl, alkynyl, arylthio, fluorenylamino, alkynyl, sulfonyl, and aryl-R6 , R7, R9, R1 (), R12, R14, R15, or any of the 7 cyano groups, which together form an aromatic or non-aromatic soil of the same ring or heterocyclic ring, which is in the range of 0 to 4 Integers, p and k are integers from 0 to 5, t is an integer from 1 to 20, n ^ q ~ is an integer from 0 to 3, z is an integer from 0 to 4, χ "... is from an organic anion, and χ2 ... is Organic anions, 15 (2) organic solvents, (3) acidic acids or salts thereof that are soluble in the organic solvents, and (4) selective colorants. 2. If the composition of the first scope of the patent application, Among them, the component carrier (binding agent). 々 (3) series呔 3. If the composition of the scope of patent application item 1, wherein the RrRls in the dyes of HY and Y are independently hydrogen, 1 to 10 carbon atoms) to (4) 36 20 200530348 generation or substituted alkane Or alkoxy groups, cycloalkyl groups of 5 to 10 carbon atoms, aryl groups of 6 to 8 carbon atoms, heteroaromatic groups of 5 to 10 atoms containing one or more nitrogen, oxygen or sulfur as ring members Radical, or dipropyl, can be combined to form a 5 to 7-membered homocyclic or heterocyclic ring, ^ and the heart and ^ 7 and Ri8 5 can be combined to form 孓 to 6_ member The non-aromatic or aromatic N-heterocyclic shape is bad, and X], X2, D111, 11, 45 ?, \ ¥, 7 and 2 have the meanings shown. The composition of 3, wherein the substituted alkyl group includes a hydroxyalkyl group, a haloalkyl group, an aminoalkyl group, a cyanoalkyl group, or an arylalkyl group, and the substituted alkoxy group includes an arylalkoxy group And, the aryl group preferably includes phenyl or naphthyl group, and is optionally substituted by a hydroxyl group, an amino group, an amine group, a cyano group, a carboxyl group, a carbonamino group, a thio group or a thioamino group. range The composition of 3, wherein RrR18 are each independently hydrogen, a alkynyl group having 1 to 4 carbon atoms, or a cyanoalkyl group having 4 to 15 carbon atoms in the alkynyl group, and further, R6, R7, R9, Ri0, Ru, Ri < R15, and Ri6 are each independently halogen, preferably chlorine or bromine, cyano or nitro, and m, n, q, w, y, and z are each Each is an integer of 0 to 2, k and p are each an integer of 0 to 3, and t is an integer of 1 to 10. 6. The composition of item 1 in the scope of patent application, wherein the organic solvent (2) 20 is selected from the group consisting of selectively iS aliphatic hydrocarbons and selectively ii aromatic hydrocarbons, preferably benzene series, dialkyl ethers, glycol ethers, (non-polar) alcohols, esters, ketones, solubilizing inks A group of carrier components, monomers (acrylate monomers), and mixtures thereof. 7. The composition according to item 1 of the patent application scope, wherein the component (3) contains 37 200530348 resin 'which is selected from rosin acid, rosin-based resin, rosin or emerald. The composition of item 1 of the tree, wherein the component ⑺ contains non-permanent species (^ sex species'), which is selected from 6 to 36 (preferably made of organic carbon and organic residues). It is a species of fat and noodles. [If the composition of any one of items 1 to 8 in the scope of the patent application includes a component of 4.50% by weight 0), a component of 10 15 by 2095% by weight (2), 75% by weight of component (3), and 50% by weight of component (4). The composition of item 9 in the scope of the patent application, wherein the component (3) is a 哕 ink vehicle. VA 11 · If the composition of item 1 of the patent scope by the above-mentioned owner, the ink carrier (surname mixture) is also included. The sigma 12 order declares the composition of any one of items 1 to 11 of the patent scope, wherein the rich elixir is a non-polar organic solvent or a mixture thereof. The composition of any one of items 1 to 11 of the 13 ° patent application, wherein the organic cereal is a polar organic solvent or a mixture thereof. For example, the composition of any of items 1 to 13 in the scope of Shenjing's patent is a printing ink composition according to 03 printing, lithographic printing, letterpress printing, or rubber plate rotary printing. 15_ > A sulfonate of basic red 54 and CI. Basic blue 145, preferably ^-, phenylene sulfonate and p-benzenesulfonate. 38 200530348 16. A carboxylate of C.I. Basic Red 54, preferably oleate, 2-ethylhexanoate or carboxylate derived from resin acid. 17. —A method for manufacturing a printing ink composition according to item 1 of the patent application scope, comprising a dye precursor of formula (5) or (6) in which 5 (a) is dissolved or dispersed in an organic solvent Among them, Ri to R8, m and η have the meanings shown, and A is -OR, -N (R) 2, 10 -N (R) COR, -N (R) S02R? -Sr, -s (o ) r, -o2cr, -N (R) CON (R) 2, -OCON (R) 2, -S02N (R) 2 or -N (R) COOR, where R is R !, and (b) is soluble in The organic resin acid of the organic solvent and the selective colorant of (c) are mixed together. 15 18. The method according to item 17 of the patent application scope, wherein the component (b) used for the dye precursor of the chemical formula (6) is a non-resinic acid. 19. The method according to item 18 of the scope of patent application, wherein component (b) is a non-resinic acid ('acidic species of the 0th species of acid) selected from 6 39 200530348 to 36 (preferably 6 to 24) carbon groups Consisting of organic carboxylic acid and organic sulfonium) which can be aliphatic or aromatic 5 20. A method for producing printing inks containing chemical formula doors) or (4) dyes, comprising dissolving (a) or, The salt of the dye with the chemical formula of organic solvents in organic solvents, which decomposes when treated with organic acids, and) or () (b) Organic acids dissolved in organic solvents, and (c) Selective colorants, mixed together 1021 · The method such as the scope of the patent application No. 20 acid salt or bicarbonate. Among them, the salt of the dye is a carbon-based printing ink composition 22. A method for producing a dye containing chemical formula (4) 5 A precursor dye containing a chemical formula ⑷ that dissolves or disperses 溶剂 in an organic solvent Non-tree 15 fatty acids ('acidic') of 6 to 36 (preferably 24) carbon atoms dissolved in organic solvents, which are organic sulfonic acids, and (C) selective colorants are mixed together . 23. The method of claim 17 in which the components ⑻ and ⑷ together constitute a resin salt colorant. 24. A method 20 for manufacturing a printing ink composition according to item 1 of the scope of patent application, which comprises mixing a dye precursor / decomposable salt of a dye of the chemical formulae ⑴ to (4) with (b) ) 'Compound, organic (polar or non-recorded) solvent organic acid (preferably resin acid) solution, 40 200530348 Evaporate the solvent from the mixture (to reduce, and make) to dry again The color mixture is a substance that is once again soluble in an organic solvent (organic non-polar solvent) that is compatible with the desired ink medium, and (C) a remotely selectable (organic) colorant. 25. If you apply for any of the patents _ π to 24. In the organic solvent of component 选, select, use, select, halogenated aliphatic hydrocarbons, select ... aromatic cigarettes, preferably benzene. System, members of the two groups consisting of two components, diols, m-solvent ink fine components and their mixtures. ^ Day body) 10 26. The method of claim 24 in the scope of patent application, wherein the organic solvent for re-dissolving the step is selected from the group consisting of ingredients, aliphatic alcohols, and one of the constituent groups 0 27. The method of any one of claims 17 to 26, which further comprises mixing the ink vehicle with components (a), (b) and optionally (c). 15 28. The method according to item 24 of the patent application scope, further comprising mixing the ink vehicle with a component (a) and a mixture) and a selective component (c). 29. —A method for manufacturing a printing ink composition according to the scope of application for patent application item No. '1. The dye precursor of the dyes of the formulas (chemical formulas) to (4) / separate 20 salts and (b) organic acids, select The colorant of the component (c) and the optional ink vehicle are dried and mixed, and then the mixture is dissolved together in an organic solvent. 30. The method of claim 29, wherein an ink carrier (binder) is used as the component (b). 31. The method of claim 29 in the scope of patent application, wherein the component is a resin 41 200530348 acid. 32. The method of claim 29 of the patent scope, wherein the component (b) is selected from the group consisting of organic carboxylic acids and organic sulfonic acids having 6 to 36 (preferably 6 to 24) carbon atoms, and Groupless non-resinic acid ('acidic species,' which can be aliphatic or aromatic species. 33. The group knows (a), the selectivity and the selective ink vehicle.物 'is a method for applying any one of claims 23 to 25 in the scope of patent application. 10 15 20 34 · The composition of the group of wounds, (b), selective (c), and selective ink carrier is the same as that of the solution, which is based on the fourth to the% of the scope of the patent application Obtained by any one of the methods 35. The method as claimed in the appendix of the scope of the patent application, which comprises combining the components ⑷, ⑼ and selective ⑷ either individually or as a dry mixture and contained in a pre-formed ink vehicle. 36. If applied The method of any one of the items 29 to 33 of the patent scope, which comprises making the group ^ ⑷, ⑻ 杂 杂 职 mixed position or called dry age_plasticized in a dispersion, solution or paste of the water carrier body. = · An extruded product ', which is obtained according to the method of the patent application No. 36, 38 · —a printing method, which is composed of the application of τ called Xunli Qianwei any one of the 1 to 14 printing ink composition 39. A printing method that prints flat substrates with printing inks that are primarily colorants based on item Γ in item 专利 of the patent scope. 42 200530348 40. Such as The method according to any one of claims 38 and 39, wherein the printing method is a publication or Photographic apparatus of intaglio printing, flexographic printing, offset printing method or the relief printing. 43 200530348 VII. Designated Representative Map: (1) The designated representative map in this case is: (). (None) (b) Brief description of the component symbols in this representative drawing: (none) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: