TWI303264B - - Google Patents

Description

I3Q3264 V. INSTRUCTION DESCRIPTION (1) [Technical Field] The present invention relates to an ink composition suitable for use as an oil-based ink composition for writing instruments, and having excellent pigment solubility in ink and compatibility with other materials. A writing instrument using the ink composition and a new pigment used therein. [Invention Background] In the past, oily black inks often use a low-cost aniline black considered in terms of cost or a metal complex pigment which is considered in terms of fastness. However, if aniline black is used, solubility or The problem of poor compatibility with other raw materials, if a metal complex pigment is used, has the disadvantage of low hiding power. Therefore, when the latter metal complex pigment is used, it is often used together with a pigment of a triphenylmethane-based (triarylmethane-based) which is excellent in color development. However, due to the difference in the solvent or other raw materials used and the amount thereof added, It is a cause of inconvenience in the use of inks which cause extreme ink viscosity thickening or precipitation. Further, when a pigment dispersion is used without using a metal complex pigment to impart fastness, the same problem often occurs. The object of the present invention is to provide an oil-based ink composition and a useful pigment therefor, which are used in the case of using an alcohol having a carbon number of 2 or more, a polyvalent alcohol or an alkaloid, and imparting a black or blue color to the cerium concentration. The masking pigment and the high-concentration condition contain the pigment which solves the above-mentioned disadvantages, and the compatibility of the metal complex pigment or other raw materials in the ink is excellent, and the low-temperature long-term stability is excellent. As a main pigment used in inks for writing instruments, the triaryl-based calcined pigments are used as the salt-forming pigments of the precursors, and the alkaline pigments are blended with the binders. The paper size is suitable for the national standard A4 specifications (10) 5. Introduction to the invention (2), such as C. I. Basic Violet 1, C·I. Basic Violet 3, C·I.

The amino group of the aromatic ring of Basic Blue 26 is a methylamino group and/or a dimethylamino group and/or a leather amine group. However, these widely used triphenylmethane-based pigments are used in combination with a metal-compound pigment to dissolve alcohol, ethylene glycol, and glycol ether having an inverse number of about 4 or less in a solvent used as a writing agent ink. When the stability is often poor, it will precipitate when placed at low temperatures. When using these two pigments as ink for writing instruments, in order to obtain the hiding power of the line (the necessary concentration of the twist line), a certain concentration of the pigment concentration is necessary. However, if it is a high concentration, a precipitate is generated. It is not suitable as ink for writing instruments. Such a disadvantage is particularly pronounced when a solvent having a high vapor pressure is used to obtain a fast drying property of a line, such as when #methyl-propylene glycol is used. Therefore, another object of the present invention is to provide an ink pigment suitable for a triarylmethane system, particularly a triphenylmethane-based writing device, in combination with a metal complex pigment in view of the above-mentioned problems. It is dissolved in most of the inks used as writing instruments, especially those with a carbon number of about 4 or less, ethylene glycol and ethylene glycol, especially monomethyl propylene glycol, which also has excellent fluidity and good stability. . [Disclosure of the Invention] The present invention provides the following ones for solving the above problems (1) An ink composition formula containing at least one of the following paper scales (CNS) A4 specifications ( 210X297 mm) I3Q3264 A7

(wherein Ar is an aryl group substituted or unsubstituted with _ or an alkyl group, less diethylamine or hydrogen, and at least 2 A, lanthanide is an ethylamine group, octadecyl _ oleic acid Further, A has a charge balance on the residue.) A triarylmethane pigment composed of a compound represented by the machine is used as a color material, and r contains an alcohol having a carbon number of 2 or more, a polyvalent alcohol or a glycol ether. Solvent, and 2 have a resin dissolved in the aforementioned solvent. (2) The ink composition according to the above, wherein the three aromatics of the pigment are phenyl groups. (3) The ink composition according to the above, wherein the three γ of the pigment are diethylamine groups. (4) The ink composition according to the above, wherein the aryl hydrazine of the pigment is not substituted by a halogen or an alkyl group. (5) The ink composition according to the above aspect, wherein the pigment a is a compound of an organic acid group, and is dissolved in a carbon number of 2 or more, a polyvalent alcohol or B, which is used as a solvent at a concentration of 20% by mass or more. Among the glycol ethers. (6) The ink composition according to the above, wherein the A of the pigment is a carboxyl group, a mercapto group, a thiocarboxy group, a dithiocarboxy group, a repeating acid group, a sulfonate group, a sulfenyl group, a sulfoamino group, a thiol group. An organic acid group selected from the group consisting of a phenolic hydroxyl group, a hydroxylamine group, and a hydroxyimino group. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) • 6 - 1303264 A7 -----------B7________ V. Invention description (4) (7) The ink composition as described above Wherein, the A of the aforementioned pigment is derived from hexanoic acid, acetoacetic acid, anisic acid, rosin acid, benzoic acid, succinic acid, citric acid, citric acid, oleic acid, octadecanoic acid, linoleic acid, sub-Asia Sesame oil, stupid acid, naphthoic acid, palmitic acid, hydroxybenzoic acid, cinnamic acid, hydroxycolic acid, tyrosine acid, analytic acid, phenylpropynoic acid, phenoxyacetic acid, phenylglycolic acid, cis-butan Acid, turpentine modified maleic acid, hexane carboxylic acid, hexane dithiocarboxylic acid, dodecyl sulfonic acid, hexahydropyridine sulfinic acid, benzene sulfenic acid, hexane sulfinamide Compound, phenyl sulfonium thiol, phenyldithiol, phenylhydroxylamine, hydroxylamine, cyclohexanone oxime, benzaldehyde oxime, dodecyl phthalate, dinonyl phenyl phosphate, ortho-aminobenzoic acid, An acid group of an organic acid composed of hippuric acid. (8) The ink composition according to the above, wherein the a of the pigment contains an aromatic ring having at least one sulfonic acid group. (9) The ink composition according to the above, wherein the pigment a is composed of an alkylbenzene acid and a salt thereof, an alkylnaphthalenesulfonic acid and a salt thereof, and an alkylallylsulfonate An anionic surfactant such as a salt thereof, an alkyl diphenyl ether disulfonic acid or a salt thereof, or an acid pigment selected from C. I. Acid Orange 7, CI Acid Yellow 36, C.I. Acid Red 88 or the like. (1) The ink composition as described above further contains a metal complex pigment or a colorant. (11) The ink composition according to the above, wherein the resin contains at least polyvinyl butyral. (12) The ink composition according to the above, wherein the solvent of the aliphatic solvent is the total solvent of the ink composition, wherein the solvent is composed of an alcohol having 2 or more carbon atoms, a polyvalent alcohol or a glycol ether. 40% by mass or more. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1303264 A7 B7 V. Description of invention

(13) The ink composition according to the above aspect, wherein the solvent is at least one of a solvent containing the following i) to iii) as a main solvent. 1) A solvent represented by the chemical formula CnH2n+1〇C3H6〇H (wherein n is an integer of i~3)

Ii) monomethyl ether propylene glycol iii) solvent R1 represented by the following structural formula (2): 1 I CH3 - C - " CHr 1 1 - C - R 3 1 or | 1 OH (wherein R1, R2 R3 is a separate H (2) (14) A writing instrument comprising the ink composition as described above (15), such as the writing instrument described above, which is a signature pen. (16) A writing instrument as described above, It is a ballpoint pen. (17) A writing instrument as described above is a printing pad. (18) A type of pigment, which is represented by the following general formula (3). (In the formula, 'Ar systems are independent and are Or the alkyl-substituted or unsubstituted aryl 'gamma system is each independently diethylamine or hydrogen' and at least two are diethylamino 'A-based organic acid groups, and a is a charge-balanced residue. )

L3〇3264, invention description (6) (19) The above-mentioned pigment, wherein Ar is a phenyl group. (20) The above pigment is dissolved in monomethyl ether propylene glycol or more. ^ (21) A pigment as described above, wherein all three γ are diethylamino groups. (22) A pigment according to the above, wherein the organic acid group contains an aromatic ring having at least one sulfonic acid group. [Embodiment of the Invention] The color material used in the ink composition of the present invention is a diaryl decane-based pigment represented by the formula (A). One (Please 4? Read the notes on the back and fill out this page) ν C "I A r! Υ

A, can |

(wherein Ar is independently and is aryl substituted or unsubstituted by halogen or alkyl, Y is each independently diethylamine or hydrogen, and at least 2 are ethylamino 'A-line or The organic acid group, in addition, a is a charge balance of the residue. The diarylmethane pigment is obtained by the following formula (4) r YA jt A r — Y CI A r! γ Λ

X (4 ) (wherein, Ar is an aryl group substituted or unsubstituted by _ or alkyl, Y is

9- V. INSTRUCTION DESCRIPTION (7) Diethylamino or hydrogen, and at least 2 a-7 (good) 固 1 von-ethylamine, X-based halogen, and, A, the charge balance of the residue. A triaryl carbene-based pigment or a pigment derived from an organic acid or an organic acid salt. The triarylmethacrylate pigment is a pigment in which two or three amine groups bonded to an aromatic ring are diethylamine groups. According to the present invention, the above-mentioned pigment is used to constitute the oil-based ink composition, and it is possible to solve the solvent or raw material according to the use even when the color is good and the color is used for the use of the metal complex pigment or the colorant dispersion. The difference in the amount of ink added to the extreme ink viscosity thickening or the formation of precipitates, etc., is inconvenient to make the material defective. The above pigments can be used in the carbon number X of the alcohol, the j-jitol or the ethylene glycol mystery. In the case of high degree of indifference, it is difficult to add in the middle or the blue color, and even in the case of high concentration, it is compatible with the metal complex pigment or other raw materials in the ink, especially with polyethylene. It is also good to provide an oily ink composition with excellent low temperature and long-term stability. The reason why this effect can be exerted is that the amine group introduced into the aromatic ring is a diethylamine group, and the affinity of the alkyl group of the solvent is enhanced. As a result, the solvent is easily mixed with the solvent, and the solubility stability is high. Further, metal complex pigments or colorant dispersions and the like are susceptible to acid and alkali, however, the alcoholic solution of the general formula (1) does not impair the equilibrium balance of the equilibrium ions. Because of the medium dissolution of the glutamine metal complex pigment or the colorant dispersion; the alcohol oxime or the ethylene glycol scale does not destroy the balance of the dissolution equilibrium with other materials, and therefore, even for Acetyl condensate Ding Jun's sucking ί*shengnan tree 曰 曰 ' can also inhibit the increase of viscosity or the formation of sediments and other ills 1303264

V. Description of the invention. Therefore, it is possible to provide an oily ink composition which is excellent in long-term stability under high concentration conditions or low temperature. In the triaryl arsenic-based basic pigment represented by the formula (4), the pigment which is particularly suitable for use in the present invention is, for example, CI Basic Vi〇let which is a resonance mixture represented by the following structural formula (5). 4.

Cl· Cl- (please note the λ-w·* read back _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is conducive to steric hindrance, and it is more desirable to enhance the stability of the molecule. The aryl group may be a naphthyl group or the like, but a phenyl group is preferred. The aryl group may be a halogen or a burnt group (generally having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms), i.e., a substituted phenyl group. The three papers combined with the diethylamine group are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11- 1303264 A7 ----------B7 V. Invention Description (9) ~ " ' — --^-- The base-burning pigments are conventionally known or commercially available as alkaline pigments (as well as gas), such as c, Basic Vi〇iet4. In the present invention, the triaryl methacrylate can be used as it is. However, it is preferred to use a quinone which is reacted with an organic acid or an organic acid salt to form a salt. This is because when an alcohol, a polyvalent alcohol or a member alcohol ether is used as a solvent, the triarylmethane skeleton forms an organic acid group and a strong ion pair, and is less likely to cause unnecessary interaction with other components such as the metal complex pigment. Caused by ionic interactions. Examples of the organic group of the salt-forming pigment include a carboxyl group, a mercapto group, a thiol group, a dithiocarboxy group, a sulfonic acid group, a sulfinic acid group, a sulfenyl group, a sulfoamino group, a thiol group, a phenolic hydroxyl group, and a hydroxylamine. An acidic functional group such as a hydroxyimino group or the like. In the case of the organic acid-based salt-forming salt, an organic acid or an organic acid salt is used. However, if it is a salt-forming body formed with an organic pigment, there is no particular limitation, and any one of them may be used. An organic acid or an organic acid salt which is a salt of an organic acid group can be used, specifically, for example, adipic acid, acetoacetic acid, anisic acid, rosin acid, benzoic acid, succinic acid, citric acid, citric acid. , oleic acid, octadecanoic acid, linoleic acid, linoleic acid, phenylacetic acid, naphthoic acid, palmitic acid, hydroxybenzoic acid, cinnamic acid, hydroxycolic acid, tyrosine acid, aspartic acid, phenylpropyne Acid, phenoxyacetic acid, phenylglycolic acid, maleic acid, turpentine-denatured maleic acid, hexanecarboxylic acid, hexanedithiocarboxylic acid, dodecylsulfonic acid, hexahydropyridinium sulfin Acid, benzene sulfenic acid, hexane sulfinyl chloride, phenyl sulfonium thiol, benzene dithiol, stupid hydroxylamine, hydroxy phenol, cyclohexanone oxime, benzaldehyde oxime, dodecyl phosphate, Diterpene ester phenyl phosphate, o-aminobenzoic acid, hippuric acid, etc. and salts thereof. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -12- 1303264 A7 B7 V. Invention description (10) (Please read the back note and refill this page) With these organic acid groups In the salt-forming body, a salt-forming body having an organic acid group having at least one or more sulfonic acid groups in the aromatic ring, and having higher solubility in the pigment monomer than the other having the organic acid group, even if It is particularly desirable because it is used in combination with a metal complex pigment at a high concentration and has good stability. And mono-T- an organic acid and an organic acid salt having at least one sulfonic acid group in the aromatic ring, and examples thereof include an alkylbenzenesulfonic acid and a salt thereof, an alkylnaphthalenesulfonic acid and a salt thereof, and an alkyl olefin An anionic surfactant such as a formaldehyde condensate of a sulfonate and a salt thereof, an alkyl diphenyl ether disulfonic acid and a salt thereof, c. L Acid〇range7, c·I· Acid Yellow 36, c· Ϊ AcidRed Acidic pigments such as 88. Wherein, the alkyl diphenyl ether disulfonic acid and its salt, C I. Acid 〇range 7, and I · Acnd Yell〇w 36 are preferred, and if it is a salt of an alkyl diphenyl ether disulfonic acid, It is more preferable that the carbon number of the base is 8 to 13. The method of forming the organic acid-based pigment described above may be a method of forming a salt-forming body by subjecting a basic pigment having a triaryl skeleton as described above to a general acid-base reaction with an organic acid or an organic acid salt, and is particularly limited. It can also be carried out generally by the following methods. The basic pigment is dissolved in the heated water, and an organic acid or an organic acid salt is added while stirring to form a salt. Further, an organic acid or an organic acid salt may be dissolved in the heated water, and a basic pigment may be added thereto as a k salt. The detailed conditions of the reaction temperature, the pH of the reaction, and the end of the reaction can be appropriately determined depending on the salt-forming pigment. Further, when the salt-forming body is recovered and purified from water, it can be used in combination with various methods such as filtration, salting out, solvent extraction, and addition of a poor solvent. a pigment which is not in the formula (1), particularly an organic acid group thereof, which contains a salt of -13- 30 or 1303264

DESCRIPTION OF THE INVENTION The hydrazine has excellent solubility in an alcohol having a carbon number of 2 or more, a polyvalent alcohol or a glycol ether. In particular, when the pigment is dissolved in an alcohol having a carbon number of 2 or more, a polyvalent alcohol or an ethyl alcohol ether, even if it is used in combination with a metal complex pigment or a colorant, the stability is good, particularly even if the carbon number is ό or less or 4 or less. , also has the solubility of excellent sputum, play in the ^ ^ eight. The reason is not certain, but it is generally considered to be as follows. Namely, since the amine group introduced into the aromatic ring is a diethylamine group, the affinity of the solvent of the alkane is enhanced, and as a result, the solvent is easily mixed with the infiltrant. Further, the organic acid or the organic acid salt has at least one or more sulfonic acid in the aromatic ring, and the combination is particularly good, because these compounds are easily converted into a strong ion pair with the basic pigment, and are easily present in a stable state. In the solvent.细夕.^ "", the pigment of the present invention and the metal complex pigment also have good stability when used together due to the improved solubility stability of the pigment itself, and due to the formation of strong ion pairs with the organic acid, Therefore, it is not easy to cause the action of ions with the wrong metal pigment. Further, the pigment of the present invention can exhibit no such superiority when the alcohol, polyvalent alcohol or glycol ether is a solvent component which is volatile or volatile, that is, in the case of a low carbon number. The advantage of solubility. It is, for example, soluble in 10% by mass or more of monodecyl-propylene glycol (25. The blending amount of some pigments can be 0.5 to 〜5% by mass based on the ink composition) and depending on the product to be used. For example, if I4 is a signature pen, it is 0·5~15% by mass, and if it is an oily ballpoint pen/raw stamp, it is 0·5~30% by mass. The higher the concentration of these additions, the higher the hiding power. Standard ((10) (Please read the notes on the back and fill out this page)

-14- 1303264

5. Description of the Invention The coloring agent other than the pigment represented by the formula (1) used in the oil-based ink composition of the present invention can be a pigment or a color other than the one represented by the formula (1). The pigment can be used as a direct pigment, an acid dermatology, an alkaline pigment, a mordant, an acid mordant pigment, an alcohol-soluble pigment, a water-insoluble azo pigment, a vulcanization, a sulphide-dye pigment, a smear pigment, which are used in a usual pigment ink composition. Any of inorganic and organic pigments used in smear pigments, oil-soluble pigments, food pigments, metal complex pigments, and the like, or conventional pigment ink compositions. The blending amount can be selected from the range of from 1 to 50% by mass based on the total amount of the composition. For 20 (please read the precautions on the back and fill in the page)., can be | and the color is preferably dissolved in the organic solvent used and the average particle size after dispersion is 30nm~700nm. The blending amount of the coloring material is 5% to 25% by mass based on the total amount of the ink composition, preferably 0.5 to 5% by mass, and may be blended as needed. The coloring materials to be used may be used alone or in combination of two or more. Further, it is also possible to add a dispersion or a pigment using an inorganic toner to such an extent that it does not cause adverse effects of dispersion stability. Further, the coloring material may be, for example, a resin emulsion obtained by polymerizing styrene, acrylic acid, acrylate, methacrylic acid, mercapto acrylate, acrylonitrile or olefin monomer, or swelled in the ink and becomes amorphous. A hollow resin latex or an organic multicolor toner composed of dyed resin particles obtained by dyeing these latexes themselves with a coloring agent. When the color material of the ink composition of the present invention is used as a coloring material, the dispersing agent used may be a resin, a styrene resin, a styrene-propylene resin, a terpene phenol resin, a rosin-denatured maleic acid resin, or a rosin phenol. Resin,

-15- V. INSTRUCTIONS (l3) Benzyl-based phenol, benzene-based resin, styrene maleic acid resin, rosin-based resin, propylene-based resin, amine-formaldehyde-based resin, maleic acid A resin towel represented by an acid resin, a bismuth resin, a polyethylene condensate, a polyethylene ruthenium or the like may be selected as a dispersible pigment, and an active agent or an oligomer may be used as long as it meets the purpose. For any kind of substance. Specific sub-policies can be exemplified by, for example, polyvinyl alcohol, #vinyl p, ketone, polyvinyl butyric acid, polyethylene, styrene-cis-butane dicarboxylic acid copolymer, enamel resin, warp fiber And its derivatives, styrene-acrylic acid copolymers, etc. Synthetic tree 曰 amp 乳 乳 乳 • 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧In the case of a coloring matter, various known methods can be used to produce a color-dispersed ink composition. For example, the above components are blended, and the mixture is stirred by a machine such as a dissolver or the like, and mixed with a mill, a roll mill, a ball mill, a sand mill, or a needle mill, and the like. It can be easily prepared by centrifuging or removing the coarse particles of the coloring matter, the unloved material, and the inclusion of the solid matter. The price is ▲ The solvent used in the ink composition of the present invention is preferably a solvent selected from the group consisting of alcohols and ethylene glycols. Further, in the present invention, the solvent is selected from the solvent selected from the alcohol and the polyvalent alcohol 'glycol ether. And the compound is a specific alcohol having a carbon number of 2 or more, and may be ethyl, η-propanol, isopropanol, n-butanol, pentyl alcohol, isoamyl alcohol, sec-pentyl Alcohol, 3-pentanol-hexanol, methylpentanol, 2-ethylbutanol,:: fermentation, ana alcohol, 2-heptanol, 3 1303264 V. Description of the invention (14-heptanol, octanol , 2-octyl alcohol, 2-ethylhexanol, 3,5,5-tridecylhexanol, decyl alcohol, η-sterol, undecyl alcohol, η-sterol, trimethyl sterol, fourteen Alcohol heptadecyl alcohol, cyclohexanol, 2-methylcyclohexanol, benzyl alcohol or other various higher alcohols. Further, polyvalent alcohols may be exemplified by ethylene glycol, diethylene glycol, and 3-methyl Base-1,3 butanediol, triethylene glycol, dipropylene glycol, propylene glycol, 1,3 butyl alcohol, 1,5 pentanediol, hexanediol, octanediol, etc. contain 2 molecules in the molecule. The above carbon, a polyvalent alcohol having two or more hydroxyl groups. The glycol ether may, for example, be mercapto isopropyl ether, diethyl ether, ethyl propyl ether, ethyl butyl sulphate, isopropyl _, butyl sulphate, hexacarboxylate, 2 ethylhexyl ether glycol monohexyl ether, ethylene glycol single Ether, ethylene glycol, single 2-ethyl butyric acid, ethylene glycol monomethyl amide, ethylene glycol monoacetin, ethylene glycol monobutyl sulfonate, diethylene glycol monomethylethylene glycol monoethyl ether, _ shrinkage Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 3-amino-3-methoxy-; i-butanol, 3-methoxyl^ Butanol, monomethyl propylene glycol, monoethyl propylene glycol, monopropyl propylene glycol, monobutyl propylene glycol, propylene glycol phenyl ether, propylene glycol tri butyl ether dipropylene glycol = ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monobutyltripropylene glycol monomethyl _, tripropylene glycol monobutyl bond, tetrapoly propylene monobutyl ether, etc. " The above mentioned solvents are particularly good, the effect is particularly easy to understand carbon number The glycol ether of 2 to 7. In addition, it is preferable to use an organic solvent other than an ethylene glycol derivative, etc., in consideration of safety and oral toxicity, and the present inventors provide excellent writing. Fluency, fast drying of the seven-base methyl sterols (please read the notes on the back and fill out this page)

I can use the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 1303264 A7 — ——— B7 5, is ] "" --- etc. It! The oil-based ink composition of the ballpoint pen used or used in combination, and the pigment of the present invention is also very useful for these solvents. 〇 A solvent having a chemical structural formula of CnH2n+1〇C3H6〇H (wherein n is an integer of i~3). Ii) Monomethyl propylene glycol. Iii) A solvent having the following chemical structural formula (2).

R1 1 Η 1 CH3, I ~ C — C Η〇 I I 1 ~ Q __ I : ¢ 2): I OR2 1 OH (wherein R1, R2, R3 are independent CH or CH3.) 'In addition to the solvent mentioned above, the solvent mentioned below can be added in the range which does not interfere with the solubility of an acid-filler and a miso-type active agent or polyoxyethylene alkylamine. These examples are polyvalent alcohol derivatives such as sorbitan fatty acid type, polyglycerol higher fatty acid type, sucrose fatty acid type, and propylene glycol fatty acid type derivatives. Examples of the ester solvent include propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol diethyl ether acetate, ethylene glycol ethyl ether acetate, and formic acid. Butyl ester, isobutyl formate, isoamyl formate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate , isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, this paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) ) r·- (Please read the notes on the back and fill out this page)

-18 - l3〇3264 A7

V. Description of invention (l6) Ethyl isobutyrate, propyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, methyl isovalerate, ethyl isovalerate, sodium isovalerate Ester, triethylacetate, ethyl triethylacetate, triethyl propyl acetate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, methyl decanoate, ethyl decanoate, hydrazine Acid propyl ester, methyl 10-methylate, ethyl dodecanoate, methyl oleate, ethyl oleate, triglyceride citrate, tributyl acetate, octyl octadecyl citrate, propylene glycol Various esters such as ricinoleate, methyl 2-hydroxyisoacetate, and 3-methoxybutyl acetate. Further, a solvent diether or a diester having no hydroxyl group in the molecule, specifically, for example, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethylene glycol, and a diacetate Ethylene glycol dibutyl ether, diethylene glycol dioxime ether, dilactam dimethyl ether, and the like. In the above, when the amount of the solvent component having an aromatic ring in the solvent is large, the solubility is different from that of a normal aliphatic solvent. Therefore, in order to use the C. I· Basic Violet 4 pigment of the present invention, The amount of aromatic solvent must be limited. Therefore, it is preferable that the total solvent of the ink composition is 4% by mass or more as the aliphatic solvent component. In particular, it is preferred that the aliphatic solvent component of the alcohol having 2 or more carbon atoms, the polyvalent alcohol or the glycol ether is 4% by mass or more. The resin used in the oil-based ink composition of the present invention can also be used as a colorant dispersant such as a ketone resin, a styrene resin, a styrene-propylene resin, a terpene phenol resin, a rosin-denatured maleic acid resin, Pine resin phenol resin, alkyl phenol resin, phenol resin, styrene maleic acid resin, rosin resin, propylene resin, amine guanamine resin, 匕1 11 . This paper scale applies to Chinese national standards. (CNS) A4 size (210X297 mm) " ' —--- -19- 1303264 A7 —— _____B7 V. Description of invention (17) Butylene dicarboxylic acid resin, cyclohexanone resin, polyvinyl alcohol A resin represented by an aldehyde, a polyvinyl tonolone or the like. Further, the polyvinyl butyral resin is often used as an additive resin for enhancing the film forming property of the writing twist line or the thickening action of the ink. However, since the polyvinyl butyral resin often causes the acid-base component in the solvent to be dissolved in the solvent, attention must be paid to the type of use of the raw material. In particular, when a salt-forming pigment is used, since the field of stability of the ink is highly different, in order to use polyvinyl butyral, it is preferred to use a relatively stable pigment. In short, an ink composed of C. I. Basic Violet i or C· Ϊ Basic vi〇let 3 which is used as a opaque pigment in a general color material is preferable as a pigment having a higher stability. The blending amount of these resins is preferably 1 to 3 % by mass, and more preferably 1 to 20 % by mass, based on polyvinyl butyral. When the blending amount is less than 1% by mass, the viscosity adjustment or abrasion at the tip of the pen becomes difficult. If it is more than 3% by mass, the raw material other than the resin cannot be blended, or the effect of the writing may be adversely affected. Further, in the present invention, if necessary, a rust preventive agent, a mold inhibitory property, a surfactant, a lubricant, a lubricant, and the like which do not cause adverse effects on the ink can be blended. Especially fatty acids, etc., are very suitable for use as a lubricant. Further, it is also possible to push the non-volatile solvent in which the phase of the additive for drying suppression is dissolved in the main solvent, within a range which does not adversely affect the characteristics of the mouth. The ink composition of the present invention can be used for a writing instrument such as an oil-based pen, an oil-based ball pen, or a tabletop such as an oil-based pad. In the pigment represented by the general formula (丨) used in the ink composition of the present invention, the organic acid group contains a salt dye as a new dye, and the present invention is further provided in the following formula: (3) Representation of pigment r A jr * γ Λ

c' I A rI Y

In A 3 , Ar is independently and is an aryl group substituted or unsubstituted by halogen or alkyl, Y is each independently diethylamine or hydrogen, and at least 2 are diethylamine, and A is an organic acid. Base, again, A is charge-balanced to the residue. The novel dye of the present invention can be used as a pigment constituting the oil-based ink composition as described above, and in particular, it is soluble in alcohol, ethylene glycol and glycol ether having a carbon number of about 4 or less. Monomethyl ether propylene glycol has availability in terms of 10% by weight or less (25t). By having such an intrinsic/glutinability property, when applied to an oily ballpoint pen having an ink discharge amount of 1 〇〇mg/1 〇〇m or less, excellent opacity in line drawing can be exhibited. The preferred compound among the pigments of the formula (3) has been described as being preferred in the formula (丨), and it is also desirable in terms of the above-mentioned uses. The reason why the pigment is dissolved in an alcohol having a carbon number of about 4 or less, ethylene glycol, and a glycol ether is not determined even if it is used together with a metal complex pigment, but it is generally considered to be as follows. . That is, the amine group which is introduced into the aromatic ring is a diethylamine group, so that the affinity of the solution is enhanced: the solvent is easily mixed with the solvent, and the amino group introduced into the aromatic ring is dimethyl. With an amine group and/or a monoamine group, the affinity of the portion of the grazing agent to the alkyl group is weakened to make the solvent difficult to mix. In addition, the agent of the pigment makes - 褊I (please read the note on the back and fill the nest page first) This paper scale applies to the Chinese national standard (〇iS) A4 specification (210X297 public Chu) 21- five invention description (l9) : Like a -methylamino group, a hydrogen atom is directly bonded to a nitrogen atom, and the intermolecular hydrogen is easily combined. That is, the cohesive force of the molecule itself is enhanced and the stability is reduced. If the organic acid or organic acid salt has at least one or more sulfhydryl groups in the aromatic ring, the solution is particularly good. This is because these compounds are easy to form a strong ion enthalpy with the pigment and are easy to stabilize. It is caused by the presence of a solvent. ~, the pigment of the general formula (3) and the metal complex pigment also have good stability when used together, because the solubility stability of the pigment itself is improved, and it is difficult to form a strong ion pair with the organic acid. Causes the action of ions with the metal complex pigment. χ, as the amine group of the aromatic ring is a diethylamine group, it should be because the diethylamine group is beneficial to steric hindrance and enhances the stability of the molecule itself. Further, the pigment of the formula (3) is particularly useful for developers of oil-based ink compositions, but it can be used for applications other than writing instruments. According to the present invention, a writing instrument using the above ink composition or pigment, such as a ballpoint pen, a signature pen, a pad, or the like, can also be provided. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. The following blending amounts are based on quality. Further, each of the components used in the examples and comparative examples is as follows. C· I. Acid Yellow 36 : This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -22- 1303264 A7 B7 V. Description of invention (2〇)

NaO, 1〇>~n = n —<CD^~ Brain ~ C. I. Acid Yellow 42 :

NIN /C1H3

C. I. Acid Orange 7 ^

NaO 'Sodium alkyl diphenyl ether disulfonate: h2Sc12-&lt;^H〇H^&gt; S〇3 S〇3 (Na*), VCI Basic Violet 1 · (Please read the notes on the back and fill in the form) page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) • 23- 1303264 A7 B7 V. Description of invention (21 © n(ch3):

(CH3)2N

Cr NHCH., C. I. Basic Violet 3 :

(CH,) 2N a c

Φ N(CH 3 cr C. I. Basic Green 1 : r Λ &lt;δ^

V ❿

CO 2^4 SUPIRON (7 匕. Port BLACK GMH SPECIAL: Acidic chromium-containing pigment + amine component of the salt body SUPIRON YELLOW SERIES: alkaline pigment + acidic component of the salt body BARI (, mouth) FAST BLACK: acidic chromium Pigment + Amine Fraction Printex # 3 5 : Carbon Black (Colorant) (Please read the note on the back and fill out this page)

This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -24-1303264 A7 B7 V. Invention description (22) YP90L: terpene phenolic resin LAROPAL (7 mouth A101: urea furfural condensate SABlNIRU (f匕, 二少)BLUE GLS: Salt-forming body of Saianning blue pigment + amine component (Production example containing organic acid-based pigment) The following salt-forming systems of Examples 2, 5, 8, and 21 were produced as follows. CI Acid Orange 7 was dissolved in 80 g of purified water heated to 90 ° C, and CI Basic Violet 4 was added while stirring until the pH of the reaction solution became 6.0, followed by stirring for 30 minutes. The added CI Basic Violet 4 was 25 g. After the completion of the stirring, the reaction solution was naturally cooled, and after reaching room temperature, the precipitated viscous body was separated and the water in the viscous body was removed to obtain a product of 35 g. The product was not dissolved in water. It can be confirmed that the salt formed from the cationic portion of CI Basic Violet 4 which is equivalent to the oil dissolved in alcohol or the like and the anion portion (organic acid group) of C.I. Acid Orange 7 is as follows. Comparative Example The drawn up the same as the other making the salt method for producing Using The fresh salt pigment above production of, made the following Examples and than the ink in Comparative Example of composition embodiments, and evaluated. Oily signature Hajime form (Example 1)

SUPIRON BLACK GMH SPECIAL [Carbide Valley Chemical Industry] 5.0% This paper size applies to China National Standard (CNS) A4 specification (210X297 public) (Please read the note on the back and fill out this page) Order · -25- 1303264 A7 B7 V. INSTRUCTIONS (23) Salts of CI Basic Violet 4 and CI Acid Yellow 36 4.0% polyvinyl butyral BL-1 ([J.S.) 1.5% (Please read the notes on the back and fill in the form) page)

YP90L [YASUHARA CHEMICAL] 3.0°/〇 Ethanol 30.0% Monomethyl ether propylene glycol 33.5% 3-Hydroxyl 1-butanol 20.0% (Comparative Example 1)

SUPIRON BLACK GMH SPECIAL [made by Baotu Valley Chemical Industry] 5.0% C. I· Basic Violet 1 and C. I· Acid Yellow 36 salt-forming body 4·00/〇 polyvinyl butyral BL-1 ] 1_5° / 〇 YP90L [manufactured by YASUHARA CHEMICAL] 3.0% Ethanol 30.0% Monodecyl ether propylene glycol 33.5 ° / 〇 3 - methoxy-1-butanol 20.0% (Example 2) Carbon black #25 [DEGUSSA (f ,) 3.0% C· I· Basic Violet 4 and C. I· Acid Orange 7 salt body 4.0% SUPIRON YELLOW C—GNH [made by Baotu Valley Chemical Industry] 1.5% polyvinyl butyral BL-1 [Hydrochemical Technology] 1.0°/〇ethanol 38.5% Monodecyl ether propylene glycol 40.0% Benzyl alcohol 12.0% This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -26- 1303264 A7 B7 V. Description of invention (24) (Comparative Example 2) Carbon Black #25 [DEGUSSA] 3.0% (Please read the back note and fill out this page) CI Basic Violet 1 and CI Acid Orange 7 Salt 4.0% SUPIRONYELLOWC — GNH保土谷化工工业] 1.5% polyvinyl butyral BL-1 [Shuishui Chemical System] 1.0% ethanol 38.5% monomethyl ether propylene glycol 40.0% benzofuran 12.0% (Example 3) BARI FAST BLACK # 3830 [ORIENT (Chemical Industry)] 5.0% CI Basic Violet 4 with alkyl II Salt of sodium phenyl ether disulfonate 3.0°/〇 polyvinyl butyral BL-S [made by hydrochemical science] 1·5°/〇MARUKIIDO (7 juvenile one) Νο.34 [Arakawa Chemical System] 1.5 % Ethanol 25.0% Monodecyl ether propylene glycol 49.0% Benzoyl alcohol 15.0% (Comparative Example 3) BARI FAST BLACK # 3830 [ORIENT Chemical Industry] 5.0% C· I· Basic Violet 1 and alkyl diphenyl ether disulfonic acid Sodium salt 3·0°/〇 polyvinyl butyral BL-S [made by Sekisui Chemicals] I·5% MARUKIIDO(^/V^r- K) No.34 [Arakawa Chemical] 1.5% ethanol 25.0% This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 27-

1303264 V. Description of invention (25)

Monothiol ether propylene glycol. Benzohydrin: : (Example 4) • : . · SUPIRON BLUE2BNH [Protected by Chemical Valley] 2.0% . . . .... CI Basic Violet 4 with alkyl diphenyl ether造 之 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 BL BL BL BL BL BL BL BL BL BL BL BL BL BL BL ·.. (Comparative Example 4) SUPIRON BLUE2JBNH [made by Baotu Valley Chemicals] CI Basic Violet 1 and alkyl diphenyl ether copper sulphate salt 4·0°/〇 polyethylene thin butyral BL-S 〔 Synthetic water chemical system] 2.0% ethanol 27.0% monodecyl ether propylene glycol. 55.0% .... ....... ..... :... : benzyl alcohol: 10.0% oily stamp form

(Example 5), V

Printex # 35 [DEGUSSA system] 10·00/〇C· I· Basic Violet 4 and C·I· Acid Orange 7 salt body 5.0% 3.0% 40.0°/〇42.0% !·}&gt; Polyvinyl alcohol Butyraldehyde BM — 1 [Jiangdong Chemical] Polypropylene glycol dipropylene glycol (Comparative Example 5) -28- (Please read the back note and refill 3⁄4) This paper scale applies to China National Standard (CNS).M Specifications (210X297 public poverty) 1303264 A7 B7 V. Invention description (26)

Printex #35 [DEGUSSA] 10.0% * * - (Please read the note on the back and fill out this page) CI Basic Violet 1 and C. I· Acid Orange 7 Salt 5.0% Polyvinyl butyral BM — 1 [made by Sekisui Chemicals Co., Ltd. 3.0% Polypropylene glycol 40.0% Dipropylene glycol 42.0% (Example 6) BARI FAST BLACK # 3830 [ORIENT Chemical Industry] 10·0% C. I· Basic Violet 4 with alkyl diphenyl ether Salt of disulfonate 20.0% polyvinyl butyral BL-S [made by Seki Chemical Co., Ltd.] 7.0% MARUKIIDO (7 less boast) Νο·34 [Arakawa Chemical] 5·0〇/〇 diglycerol Monostearate 1.0% Dipropylene glycol 17.0% 3-methoxy-3-methyl-1-butanol 40.0% (Comparative Example 6) BARI FAST BLACK # 3830 [ORIENT Chemical Industry] 10.0% C· I. Basic Violet 1 and sodium alkyl diphenyl ether disulfonate salt 20.0% polyvinyl butyral BL-S [made by the water chemical system] 7.0% MARUKIIDO (7 juvenile one) Νο·34 [Arakawa Chemical System] 5.0% diglycerin monostearate 1.0% dipropylene glycol 17.0% This paper scale applies to China National Standard (CNS) Α 4 specifications (210X297 public praise) - 29- 1303264 A7 ____B7 _ V. Description of the invention (27) 3-methoxy-3-methyl-1-butanol 40.0% (Example 7)

SUPIRON BLACK GMH SPECIAL [made by Hodogaya Chemical Industry Co., Ltd.] 20.0% CI Basic Violet 4 and C. I· Acid Yellow 36 salt-forming body 10.0% polyvinyl butyral BL-1 (made by Sekisui Chemical Co., Ltd.) 5.0% YP90L [YASUHARA Manufactured by CHEMICAL] 5.0% 3-methoxy-3-methyl-1-butanol 45.0% Benzoyl alcohol 15.0% (Comparative Example 7)

SUPIRON BLACK GMH SPECIAL [made by Hodogaya Chemical Industry] 20.0% C. I· Basic Violet 1 and CI Acid Yellow 36 made of salt 10.0% polyvinyl butyral BL-1 (made by Sekisui Chemical Co., Ltd.) 5.0% YP90L [YASUHARA Manufactured by CHEMICAL] 5.0% 3-methoxyl-3-methyl-1-butanol 45.0% benzyl alcohol 15.0% oily ballpoint pen (Example 8)

SUPIRON BLACK GMH SPECIAL 8.0% C. I. Basic Violet 4 and this paper size apply to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back and fill out this page)

-30- 1303264 A7 B7 V. INSTRUCTIONS (28) CI Acid Orange 7 salt-forming body 20.0% Polyethylene butyral BM-1 ([Jiyue Chemical] 5.0% LAROPAL A101 [BASF] 5.0% Dipropylene glycol 10.0 % 3 -methoxy-1-butanol 35.0% benzyl alcohol 17.0% (Comparative Example 8) SUPIRON BLACK GMH SPECIAL [Carbago Valley Chemical Industry] 8.0 ° / 〇 C. I · Basic Violet 1 and CI Acid Orange 7 Salt-forming body 20.0% polyvinyl butyral BM-1 [made by Sekisui Chemicals Co., Ltd.] 5.0% LAROPAL A101 [manufactured by BASF] 5.0% dipropylene glycol 10.0% 3-methoxy-1-butanol 35.0% benzyl alcohol 17.0% ( Example 9) SABINIRU BLUE GLS [manufactured by CLARIANT (々7 P ^ Bu)] 16.0% CI Basic Violet 4 and sodium alkyl diphenyl ether disulfonate salt 9.0% polyvinyl butyral BM-1 Synthetic water chemical system] 6.0% LAROPAL A101 [BASF system] 5.0 ° / 〇 dipropylene glycol 10.0% 3 - methoxy 1 - butanol 37.0% (Please read the back of the note before you fill in this page) This paper scale applies to China Standard (CNS) A4 size (210X297 mm) - 31 - 1303264 A7 B7 V. INSTRUCTIONS (29) Phenylnonanol 17.0% (Comparative Example 9) (Please read the notes on the back and fill out this page)

SABINIRU BLUE GLS [CLARIANT (々7 P ^ Bu)] 16.0% CI Basic Violet 1 and sodium alkyl diphenyl ether disulfonate salt 9.0% polyvinyl butyral BM-1 [Shuishui Chemical System] 6.0% LAROPAL A101 [manufactured by BASF] 5.0% dipropylene glycol 10.0% 3 - decyloxy-1-butanol 37.0% benzyl alcohol 17.0% (Example 10)

SUPIRON BLACK GMH SPECIAL [made by Hodogaya Chemical Industry] 9.0% CI Basic Violet 4 and C· I· Acid Yellow 36 salt 10.0% C· I. Basic Violet 4 and sodium alkyl sulfonate salt 8.0° /〇Vinyl butyral BM-1 (made by Sekisui Chemicals Co., Ltd.) 6.0% YP90L [manufactured by YASUHARA CHEMICAL] 5·00/〇3—decyloxy-3-methyl-1-butanol 32.0% benzoquinone 6.0 % diethylene glycol monophenyl ether 18.0% (Comparative Example 10)

SUPIRON BLACK GMH SPECIAL [Natural Valley Chemical Industry] 9.0% This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -32- 1303264 A7 B7 V. Invention description (30) C. I· Basic Violet 3 10.0% of the salt with C. I· Acid Yellow 36 (please read the note on the back and fill out this page) CI Basic Violet 1 and sodium alkyl diphenyl ether disulfonate 8.0% polyvinyl alcohol Butyral BM-1 (manufactured by Sekisui Chemicals Co., Ltd.) 6.0°/〇YP90L [manufactured by YASUHARA CHEMICAL] 5.0°/〇3—methoxy-3-methyl-1-butanol 40.0% benzyl alcohol 4.0% 1-2 Glycol monophenyl ether 12.0% (Example 11) Carbon black #25 [DEGUSSA system] 10.0°/〇CI Basic Violet 4 and alkyl diphenyl ether disulfonate salt 10.0% polyvinyl butyral BL-1 [[Jiangshui Chemical] 3.0% polyvinyl butyral BM-1 ([J. # 3830 [ORIENT CHEMICAL INDUSTRY] 10·00/〇C. I· Basic Violet 1 and C. I· Acid Yellow 42 made of salt 20.0% Vinyl butyral BM-S [manufactured by Sekisui Chemical Co., Ltd.] 8.0% MARUKIIDO (7 juvenile one) Νο·34 [Arakawa Chemical] 7·00/〇monomethyl ether propylene glycol 35.0% This paper scale applies to Chinese national standards ( CNS) Α4 size (210X297 mm) -33- 1303264 A7 B7 V. Description of invention (31) 3 -Methoxy 3-methyl-1-butanol 20.0% (Please read the notes on the back and fill in the form) Page) Note) The solubility of CI Basic Violet 1 and CI Acid Yellow 42 is less than 20%. (Reference example 1)

SUPIRON BLACK GMH SPECIAL 9.0 ° / 〇 C. I · Basic Violet 3 and CI Acid Yellow 36 made of salt 10.0% polyvinyl butyral BM - 1 [Shuishui Chemical System] 2 · 0 % YP90L [manufactured by YASUHARA CHEMICAL] 15.0% 3 - methoxyl-3 - fluorenyl-1 - butyl age 10.0% benzyl alcohol 13.0% diethylene glycol monophenyl ether 41.0% (Reference Example 2) Carbon black #25 [DEGUSSA system] 10·0〇/〇C. I· Basic Violet 1 and the alkyl salt of alkyl diphenyl ether disulfonate 10.0% polyvinyl butyral BL-1 [made by the chemical system of water] 3·0 °/〇 polyvinyl butyral BM-1 [made by Sekisui Chemicals Co., Ltd.) 2.0% phenyl decyl alcohol 20.0% diethylene glycol monophenyl ether 55.0% Using the above blending, by dispersion stirring or ball mill or The roller mill is dispersed to obtain an ink. Subsequently, an ink evaluation test as described below was carried out. Low temperature and cycle temperature stability evaluation of ink This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) -34-

1303264 V. Description of the Invention (32) 15 ml of each of the inks obtained in Examples 1 to 11 and Comparative Examples 1 to 11 and Reference Examples 1 to 2 was placed in a glass bottle of 2 mm, sealed and placed in a crucible. C strange layer for 1 month, and use the spatula to observe the bottom of the ink, in order to evaluate the low temperature stability of the ink. Also, adjust the shape of each product, and observe the deterioration of the product. Also 'circulation temperature stability The bottom of the ink was observed and evaluated by placing the same prepared glass bottle in a constant temperature bath to give a temperature change of 〇cC - 15cC - 3〇 °C - 15t - 〇〇c every 6 hours. The &gt;f stomach product was prepared as follows, and was treated in the thermostat under the same temperature conditions as the ink, and then evaluated by the following evaluation method. (In the case of the oily signature pen form) Examples and comparative examples The amount of each ink obtained in the middle is filled in a signature pen (Mitsubishi oily signature pen [pi: S [t. one])) using the refill of the hair charm, and is used as a test sample for evaluation. (Form of the oily stamp pad) In Example 5 and Comparative Example 5 Each of the obtained inks was filled in an ink pad (Mitsubishi oil-based stamping station [HSP-2G]) using wool felt and ultrafine fibers, and used as a test sample for evaluation. However, in Examples 6 and 7, and Comparative Examples 7, 7 The ink has a low viscosity, so a needle-punched drum and a plain weave are used. (In the case of an oily ballpoint pen form) The inks obtained in the examples and the comparative examples were filled in a polypropylene hose having an inner diameter of 1.60 mm and inserted. To stainless chip (the ball is the standard of the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page)

-35- 1303264

5. Description of the Invention (33) On a 1.0 mm superhard alloy, a rear portion of the ink was placed at the rear end portion to form a ballpoint pen shape, and used as a test sample for evaluation. Results 1) Evaluation of low temperature and cycle temperature stability of ink: The following conditions were evaluated by confirming the state of the bottom of the ink in the glass bottle. If there is no substance at the bottom, it is felt to cause precipitation: the object is △, and it can be confirmed that a large amount of obvious sediment is produced. 2) The deterioration degree of the product was evaluated as follows. a) In the case of the oily signature pen form, the line is drawn by hand on the PPC paper, and it is made according to the degree of ambiguity: it is not easy to produce blurred and unclear, and it is ambiguous and ambiguous. Unclear is x. b) The form of the oily pad The ink of the pad is drawn on the rubber stamp and covered on the ppC paper. According to the difference between the initial imprint and the long-term blot, the difference is 〇, the difference is △, and the difference is very obvious. c) The shape of the oily ballpoint pen is drawn on the PPC paper by hand (in a circle), and is made according to the degree of ambiguity: it is not easy to produce blurry unclearness, and it is ambiguous to be ambiguous, which is prone to blurring. It is χ. This paper size applies to the Chinese National Standard (CNS) Α 4 specification (210X297 mm) -36-

From the above results, it is understood that the ink composition of Examples 1 to ii in the scope of the present invention is superior to the ink composition of the comparative example of the present invention in terms of ink stability and performance deterioration as a product. Quite 1303264

V. INSTRUCTIONS (μ) Table 1 is excellent. (Examples 21 to 25 and Comparative Examples 21 to 25) The following salt-forming bodies were produced in the same manner as in the above-described production example of the salt-forming body. (Example 21) C. I. Basic Violet 4 and C. I. Acid Orange 7 salt. (Example 22) C. I. Basic Violet 4 and a salt of sodium alkyl sulfonate. (Example 23) C. I. Basic Violet 4 and a salt of dialkyl benzophenone sulphate. This paper scale applies to China National Standard (CNS) A4 specification U10X297 mm) -*-- — (Please read the note on the back and fill out this page)

-37- 1303264 A7 B7 V. INSTRUCTIONS (35) (EXAMPLE 24) (Please read the note on the back and then fill out this page) C. I. Basic Green 1 and the salt of dialkyl diphenyl ether sodium. (Example 25) C. I. Basic Violet 4 and C. I. Acid Yellow 36. (Comparative Example 21) C. I· Basic Violet 1 and C. I· Acid Orange 7 salt. (Comparative Example 22) C·I· Basic Violet 3 and a salt of sodium alkylsulfonate. (Comparative Example 23) C. I. Basic Violet 1 and a salt of alkyl diphenyl ether disulfonate. (Comparative Example 24) C. I. Basic Green 4 and a salt formed from sodium diphenyl ether. (Comparative Example 25) C. I· Basic Violet 3 and C. I. Acid Yellow 36. The stability of the metal complex pigment was evaluated by using SUPIRON BLACKGMH (manufactured by Hodogaya Chemical Co., Ltd.) as a metal complex pigment, and the pigment and metal complexes produced in Examples 21 to 25 and Comparative Examples 21 to 25 were tested. The dissolution stability of the pigment when used in combination was evaluated on the basis of the following criteria. (Test 1) A solution of 10% by weight of SUPIRON BLACK GMH, 10% by weight of the pigment produced in the above Examples or Comparative Examples and 80% by weight of monodecyl ether propylene glycol was blended. (Test 2) This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -38- 1303264

V. Description of the Invention (36) β Port SUPIRON BLACK GMH 25 wt%, the above examples or a solution of 25% by weight of the pigment produced in the ruthenium example and the weight % of monomethyl mycodiol. In each test, 'close the blended solution, and make 〇 ° C, 6 hr - 15 C, 6 hours ^ 3 (rc, 6 hours -, 6 hours for! Cycle ' placed in the thermostat for 7 days, And confirm whether there is a sediment in the room after being placed. (Test evaluation criteria)

Δ X XX 〇: no precipitate at all. A little precipitate. Precipitate. • High viscosity which is not suitable as a pigment for writing instruments. The results obtained in the above tests are shown in Table 3. table 3

Χτ ^ ί施两~ No. 21 22 23 24 25 21 22 23 24 7 S Test l 〇〇〇〇〇XXXX Ο 〇5 type test 2 Mountain L 〇△ 〇〇〇XX X XX XX X ~,,, 口1 π, the pigment obtained in Comparative Example 2 J to 25, and the pigment obtained in Examples 21 to 25 and the metal complex pigment were used together for good stability. Further, as an organic acid or an organic acid salt, if the aromatic ring has at least one or more sulfonic acid groups, the stability when used in combination with the metal complex pigment is higher than that of using an organic acid or an organic acid salt other than the above (implementation) Example 22) is preferred. [Industrial Applicability] -39- 1303264 A7 ~ ϋ__ V. Inventive Description (37) According to the present invention, it is possible to provide an oil-based ink composition which has a property which is not easily obtained in the oily ink composition of # When an alcohol having a carbon number of 2 or more, a polyvalent alcohol or a glycol ether is used, a pigment imparted with black or blue can be added at a high concentration, and even in a high concentration condition, for a metal complex pigment or ink The compatibility of other raw materials is also good, and it has excellent low temperature and long-term stability. Moreover, according to the present invention, it is possible to provide a good stability even when the alcohol, the ethylene glycol and the glycol ether having a carbon number of 4 or less which are used in combination with a metal complex pigment are used in a solvent for a writing instrument. The triaryl decane-based writing instrument ink pigment. When the pigment is dissolved in monomethyl ether propylene glycol, it does not cause precipitation and does not cause significant thickening. When used as an ink with a ballpoint pen or a pen with a groove or a small hole, it can maintain good fluidity. . This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) f · «« (Please read the note on the back and fill out this page)

-40-

Claims (1)

Patent application No. 91103211 Application No. 1. An ink composition for a writing instrument, which is composed of at least one compound represented by the following formula (1) Μ Μ Burning pigment as a color material, which 占 5 = mass % of the ink composition, and further contains a metal complex pigment or colorant: Υ — A r A r\〆1 A r1 • YYA (please Read the precautions on the back and then fill out this page. (wherein, the Ar series are each independently and are aryl or substituted by halogen or alkyl, Y are each independently diethylamine or hydrogen, and at least 2 Is a diethylamino group, A-line or organic acid group, and A, the charge balance of the residue, and '% of the total solvent of the ink composition is more than 4% by mass of the agent is a carbon atom An alcohol, a polyvalent alcohol or a glycol ether having a number of 2 or more and 6 or less is a fat or an aliphatic solvent, and the ink composition has a resin soluble in the solvent, and the solvent contains the following At least one of the solvents of i}~Hi) is used as the main solvent, Formula CnH2n+i〇C3H6〇H (wherein η is an integer of i~3) The solvent is represented by ii) Monomethyl propylene glycol coated paper scale is applicable to China Λ standard (CNS) Α4 specification (210 X 297 mm) - Order - • Department of Economics, Central Bureau of Standards, Bureau of Consumers, Cooperatives, Printed Intellectual Property Bureau - 41 - 1303264 Ministry of Economic Affairs D. Central Standards Consumer Cooperatives, Printing and Oxygen Intellectual Property Bureau VI, Application for Patent Parks iii) (2) The solvent R1 I Η ! 1 1 1 ' C Η, -C - w I 1 OR2 1 OH (wherein R, R, and R are independent of each other or ch3.) From ketone resin, styrene resin, styrene-acrylic resin, propylene resin, rosin-denatured butadiene dicarboxylic acid resin, rosin phenol resin, alkylphenol resin, phenolic resin, styrene Butadiene diacid resin, rosin resin, propylene resin, amine methotrexate resin, cis-butanoside resin, cyclohexene resin, polyvinyl butyral, polyvinylpyrrolidone At least one selected, and 1 to 30% by mass of the ink composition. 2. The ink composition for a writing instrument according to claim 1, wherein the three aryl groups of the pigment are all phenyl groups. 3. The ink composition for a writing instrument according to claim 1, wherein the three Ys of the pigment are diethylamine groups. 4. The ink composition for a writing instrument according to the '1 item of the patent application, wherein the aryl group of the aforementioned pigment is not substituted by a _ element or an alkyl group. 5. The ink composition for a writing instrument according to the first aspect of the invention, wherein the pigment A is a compound of an organic acid group, and is dissolved in a carbon content of 2 or more as a solvent at a concentration of 20% by mass or more. Alcohol, polyvalent alcohol or ethylene glycol scales. 6. If you are using the ink composition for writing instruments in the first paragraph of the patent scope (please read the notes on the back and fill out this page). Order — Line«; The paper size is applicable to the country of the country (CNS) M Specification (21〇&gt;&lt;297 PCT) -42- 1303264 VI. Patent application scope A of the aforementioned pigments is a carboxyl group, a mercapto group, a thiocarboxy group, a dithioindenyl group, a sulfonic acid group, a sulfinic acid group. An organic acid group selected from the group consisting of a sulfenyl group, a sulfoamino group, a thiol group, a phenolic hydroxyl group, a hydroxylamine group, and a hydroxyimino group. 7. The ink composition for a writing instrument according to claim 1, wherein the A of the pigment is adipic acid, acetoacetic acid, anisic acid, rosin acid, benzoic acid, succinic acid, citric acid, Capric acid, oleic acid, octadecanoic acid, linoleic acid, linoleic acid, phenylacetic acid, naphthoic acid, palmitic acid, hydroxybenzoic acid, cinnamic acid, hydroxycinnamic acid, tyrosine acid, ceric acid, styrene Alkynic acid, phenoxyacetic acid, phenylglycolic acid, cis-butenedioic acid, turpentine-denatured maleicene, hexanecarboxylic acid, hexanedithiocarboxylic acid, undecylated acid, 1 hexahydrop More than benzoic acid, benzene acid, sulfinyl chloride, phenyl methyl mercaptan, benzene dithiol, phenylhydroxylamine, hydroxylamine phenol, cyclohexanone oxime, benzaldehyde oxime, 12 base An acid group of an organic acid composed of a phosphate ester, a diterpene ester phenyl phosphate, an ortho-aminobenzoic acid or a hippuric acid. 8. In the case of the ink composition for writing instruments in the first application of the patent scope, the Ministry of Economic Affairs. D 夬 进 进 消费 - - - - - - - - - - - - - - - - - - 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中Fang ring. 9. The ink composition for a writing instrument according to claim 1, wherein the A of the pigment is an alkylbenzenesulfonic acid and a salt thereof, an alkylnaphthalenesulfonic acid and a salt thereof, and an alkylallylsulfonic acid. Anionic surfactant of salt formaldehyde water condensate and its salt, alkyl diphenyl ether disulfonic acid and its salts ' C · I. Acid Orange 7, C · I· Acid Yellow 36, C · I. Wood paper The scale applies to the Chinese National Standard (CNS) A4 specification (21〇X297 mm) -43- 1303264 The patent application range ^&quot; Acid Red 88 and other acidic pigments. 1〇· For example, the writing agent of the first paragraph of the patent application, and the ink composition of the product, wherein the raining resin contains at least polyethylene glycol. 11. Writing in the scope of the patent application section ^ ^ Ink composition for tools It is used for stampers. 12·If you are applying for the patent scope of the third paragraph of the writing work # &quot;,, the ink composition used for the signature of the author. 13·If you are applying for the scope of patent application ^ ^ Ink composition for tools It is used for ballpoint pens. (Please read the note on the back and fill in the book). Ordering * The Ministry of Economic Affairs is the standard for the consumption of the government. I am the Intellectual Property Bureau. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) - 44-