JPH0579269B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a non-aqueous (or oil-based) inkjet recording liquid containing an organic solvent as a main component. ``Prior Art'' A recording liquid for an inkjet (hereinafter abbreviated as recording liquid) consists of a dye or pigment dissolved or dispersed in water or an organic solvent. When the recording liquid is a liquid medium containing water as a main component, a water-soluble dye is dissolved in water or in a medium containing water and a small amount of an organic solvent. However, in the case of an aqueous solution, the absorbency to paper having a high degree of size is poor.
Furthermore, the recorded image lacks water resistance and is difficult to handle. In addition, there are various drawbacks such as resolution may be lowered due to bleeding, and in particular, during color imaging, recording liquids of different colors tend to bleed together on the recording material, resulting in a decrease in the clarity of color tones. In order to overcome these drawbacks, it is also known to use a non-aqueous recording liquid in which an oil-soluble dye is dissolved in a liquid medium containing an organic solvent as a main component. However, among the conventionally known non-aqueous recording liquids, particularly those having a cyan color tone, satisfactory performance has not been obtained. This is due to the fact that cyan dye, which has excellent performance, is not used. As cyan dyes used in non-aqueous systems, phthalocyanine-based dyes have superior hue and fastness compared to other dyes, but have low solubility. Although the phthalocyanine dyes described in Japanese Patent Publication No. 13998/1988 are relatively good, they do not have very satisfactory solubility. "Problems to be Solved by the Present Invention" The purpose of the present invention is to solve the above-mentioned drawbacks of the conventional technology, and particularly to solve the problem of solution stability using a cyan dye that has good hue, fastness, and high solubility. The objective is to obtain a recording liquid with high "Means for Solving the Problems" It has been found that the above-mentioned drawbacks can be solved by an inkjet recording liquid characterized by containing a compound represented by the following general formula (), and the present invention has been completed. Ivy.

[Chemical formula] In the formula, M is a metal atom of Cu or Ni, Pc is a phthalocyanine ring, R ₁ is a hydrogen atom, and has 1 or more carbon atoms.
15 alkyl group or an aryl group having 6 to 21 carbon atoms, R ₂ is an alkylene group having 2 to 15 carbon atoms or an arylene group having 6 to 21 carbon atoms, and R ₃ is an arylene group having 1 to 15 carbon atoms.
represents an alkyl group having 6 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, or a heterocyclic group having 5 to 20 carbon atoms, and n represents an integer of 1 to 4. However, when M is Ni, the alkyl group of R ₃ has 2 or more carbon atoms. The above alkyl group or alkylene group may be linear, branched or cyclic. In addition, the above alkyl group, alkylene group, aryl group, and arylene group include one or more alkyl group, alkoxy group,
Aryloxy group, aralkyl group, aryl group,
It may be substituted with a halogen atom, cyano group, nitro group, ester group, carbamoyl group, acyl group, acylamino group, sulfonyl group, sulfamoyl group, sulfonamide group, amino group, alkylamino group, or arylamino group. Among the compounds represented by the general formula (), the following are preferred. M is Cu or Ni, R ₁ is a hydrogen atom, and has 1 or more carbon atoms
4 alkyl group or a substituted alkyl group having 3 to 6 carbon atoms (substituent is an ester group, acylamino group or alkoxy group), R ₂ is a straight chain or branched alkylene group having 2 to 10 carbon atoms, and R ₃ is a straight chain or branched alkylene group having 2 to 10 carbon atoms. Number of carbon atoms substituted by alkyl group or alkyl group and chlorine atom
10 to 21 phenyl groups, and n represents 4. Specific examples of the compound represented by the general formula () used in the present invention are shown below.

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embedded image The compound used in the present invention is synthesized by the following general route.

[Chemical structure] A synthesis example is shown below. Synthesis of Compound No. 1 6.0 g of tetrachlorosulfonyl copper phthalocyanine (including small amounts of tri-, di-, and mono-substituted products) synthesized according to the method of JP-A-50-44226, 3-(2,4
-di-ter-amylphenoxy)propylamine
18.0g and 30ml N,N-dimethylacetamide
The mixture was stirred at 60°C for 1 hour. Add reaction mixture to 100ml of water
and extracted with 100ml of vinegar. After washing the extract twice with water, ethyl acetate was distilled off, and the residue was purified by silica gel column chromatography using a developing solvent of chloroform-ethyl acetate in a ratio of 10:1. (including mono-substituted products) were obtained. As the liquid medium of the recording liquid used in the present invention, ordinary organic solvents are appropriately selected and used as desired. Specifically, for example, alcohols such as ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anise alcohol, ethylene glycol monoethyl ether, ethylene Glycol monophenyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, ethylene glycol diacetate, Glycol derivatives such as propylene glycol diacetate, ketones such as benzyl methyl ketone, benzyl acetone, diacetone alcohol, and citalohexanone, ethers such as butyl phenyl ether, benzyl ethyl ether, and hexyl ether, ethyl acetate, amyl acetate,
Benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, phenylethyl acetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, phthalate diethyl acid, dibutyl phthalate, diethyl malonate,
Dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, dimethyl glutarate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di(2-methoxyethyl) adipate,
Diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamic acid 3-
Esters such as hexenyl, petroleum ether, petroleum benzine, tetralin, decalin, t-amylbenzene, hydrocarbon solvents such as dimethylnaphthalene, acetonitrile, formamide, N-N-
dimethylformamide, dimethyl sulfoxide,
Examples include polar solvents such as sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N,N-diethyldodecanamide. These solvents may be used alone or in combination with
You may use a mixture of more than one species. The solvent preferably contains two ester groups, and the boiling point of the solvent is particularly preferably 140°C or higher. Particularly when used in an inkjet recording device using electrostatics, it is preferable that alcohols, glycol derivatives, ketones, or polar solvents, which have relatively low resistance, be contained in an amount of 2 to 50% of the recording liquid. Various additives may be added to the recording liquid of the present invention as desired. Examples of such additives include viscosity modifiers, surface tension modifiers, resistivity modifiers, film forming agents, ultraviolet absorbers, antioxidants, antifading agents, and the like. The recording liquid of the present invention can be applied to various inkjet recording apparatuses by appropriately adding solvent components or various additives and adjusting it to desired physical property values. When the recording liquid of the present invention is applied to an inkjet recording device that uses electrostatics, the specific resistance should be 10 ₅ to 10 5 .
It is preferable to adjust to 10 ₁₁ Ω・cm, and 10 ₆ to 10 ₈
Ω·cm is particularly preferred. Further, the concentration of the compound of the present invention is preferably 1 to 20%, particularly preferably 3 to 10%. The recording liquid of the present invention can also be used as a recording liquid other than inkjet ink, for example, for writing instruments (ballpoint pen ink, etc.). The recording support used for recording with the recording liquid of the present invention is usually paper, but cloth, plastic film, metal plates, wood plates, glass plates, etc. can also be used. Paper is mainly made of wood pulp, but synthetic fibers, synthetic pulp, inorganic fibers, etc. may be mixed as necessary. In addition, a sheet provided with a suitable ink absorbing layer on the surface of the support allows the recording liquid to permeate to an appropriate degree, giving preferable results. The ink absorbing layer is mainly composed of pigments and adhesives, and conventionally known materials can be used as appropriate. Pigments include clay, talc, calcium carbonate, calcium sulfate, calcium silicate,
Zinc oxide, kaolin, aluminum silicate, magnesium silicate, acid clay, magnesium oxide,
Examples include magnesium carbonate, aluminum oxide, silica, and organic pigments. As an adhesive, casein,
Examples include starch, gelatin, PVA, carboxymethyl cellulose, hydroxyethyl cellulose, styrene-butadiene latex, methyl methacrylate, butadiene latex, vinyl acetate latex, polyacrylic latex, and the like. The present invention will be explained in more detail in the following examples. Example 1 Compound No. 1 of the present invention 5 parts by weight Diethyl phthalate 30 parts by weight Diisopropyl adipate 45 parts by weight N,N-diethyldodecanamide 20 parts by weight After mixing and stirring the above components to form a uniform solution, the pore size was determined. The mixture was passed through a 1 μm filter to prepare an ink liquid. The specific resistance of this ink liquid is 3.8
×10 ⁷ Ω・cm, viscosity 6.9cp (both measured at 25℃)
It was hot. Using an electrostatic acceleration type inkjet device equipped with a head with a nozzle diameter of 50 μm, this ink liquid was produced at a dot count of 8 dots/mm, containing mainly silicon oxide fine particles and polyvinyl alcohol in a weight ratio of 75:25. When printed on inkjet recording paper provided with a coating layer, a clear, high-density cyan image was obtained. After this image was left exposed to room light for 3 months, the density reduction rate was less than 1%. Even when paper printed with this ink was soaked in water for 10 minutes, no bleeding or running of the image was observed. This ink liquid was placed in a sealed glass container and left indoors for 6 months, but no pigment precipitation was observed. Example 2 Ink liquids (2-1) to (2) having the following compositions
-3) was prepared in the same manner as in Example 1. Ink liquid (2-1) Compound No. 4 of the present invention 5 parts by weight Di-n-butyl adipate 75 parts by weight Benzyl alcohol 20 parts by weight Ink liquid (2-2) Compound No. 10 of the present invention 5 parts by weight Maleic acid Dibutyl 69 parts by weight Diethyl phthalate 20 parts by weight N-methylpyrrolidone 6 parts by weight Ink liquid (2-3) Compound of the present invention No. 11 5 parts by weight Diethyl adipate 43 parts by weight Diethyl phthalate 30 parts by weight Dipropylene glycol monomethyl ether
22 parts by weight Each of these ink liquids was printed on inkjet recording paper using the same electrostatic acceleration type inkjet device as in Example-1. Ink liquid (2-1) ~ (2
-3) Both exhibited good ejection properties, and clear cyan images were obtained in each case. When the inkjet device was left for three weeks with the heads filled with these ink liquids installed, and then restarted, the ink liquid was ejected smoothly and the same clear and high-density images were obtained as before the inkjet device was stopped. Even when paper printed with this ink was soaked in water for 10 minutes, no bleeding or running of the image was observed.

Claims (1)

[Scope of Claims] 1. A recording liquid for an inkjet, characterized by containing a compound represented by the following general formula (). [Formula] In the formula, M is a metal atom of Cu or Ni, Pc is a phthalocyanine ring, R ₁ is a hydrogen atom, an alkyl group or an aryl group, R ₂ is an alkylene group or an arylene group, R ₃ is an alkyl group, An aryl group or a heterocyclic group, and n represents an integer of 1 to 4. However, when M is Ni, the alkyl group of R ₃ has 2 or more carbon atoms.