JPH0579268B2 - - 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, there have been few that have a cyan color tone and have good hue, fastness, and solution stability.
In the electrostatic attraction type inkjet system, in order to obtain good ejection properties, it is necessary to maintain the specific resistance value of the recording liquid within an appropriate range. For this reason, the types of dyes and solvents used in this recording liquid are limited, and it has therefore been extremely difficult to obtain a recording liquid that provides a satisfactory cyan image. The sulfamoyl-substituted phthalocyanine dye described in Japanese Patent Publication No. 62-13998 has relatively excellent hue and light fastness, but in the specifically mentioned compounds, the carbon atom adjacent to the nitrogen atom of the sulfamoyl group is Because it is a class or secondary alkyl, it has low solubility in low polarity solvents suitable for electrostatic attraction type inkjet systems. Therefore, since a polar solvent such as ethylene glycol is used, there is a drawback that the specific resistance value is smaller than the appropriate value. "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. The object of the present invention is to obtain a recording liquid having a cyan color tone within a range. "Means for Solving the Problems" A non-aqueous inkjet recording liquid, which is composed mainly of a recording agent and a solvent, and is characterized by containing a compound represented by the following general formula (). It has been found that the above-mentioned drawbacks can be solved, and the present invention has been completed.

[Formula] In the formula, M represents a metal atom, Pc represents a phthalocyanine ring, and R ₁ and R ₂ have 1 to 4 carbon atoms.
represents a straight-chain alkyl group, and R ₃ has 2 to 12 carbon atoms.
represents a straight chain, branched or cyclic alkyl group. In this case, R ₁ and R ₃ and/or R ₂ and R ₃ may be combined to form a ring. n represents an integer from 1 to 4. Two or more kinds of compounds represented by the general formula () can be used in combination. M of the compound represented by the general formula () is Cu,
Ni, Co, Fe, Mg, Sn, and Mn are preferred, especially
Cu and Ni are preferred. Among the compounds represented by the general formula (), particularly preferred are those represented by the following structural formula.

[Formula] Specific examples of the compound represented by the general formula () used in the present invention are shown below.

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[Chemical formula] The compound used in the present invention can be synthesized by the following route.

[Chemical structure] A synthesis example is shown below. Synthesis of Compound No. 1 1.3 g of tetrachlorosulfonyl copper phthalocyanine and 1.7 g of tert-octylamine synthesized by the above route according to the method described in U.S. Pat. No. 3,482,972.
and 10 ml of dimethylacetamide at 65-70°C.
I stirred the time. The reaction mixture was poured into 100 ml of ice water containing 1.3 ml of hydrochloric acid to collect the precipitated crystals. The obtained crude product was mixed with chloroform-ethyl acetate as a developing solvent.
Purification was performed by silica gel chromatography at a ratio of 20:1 to obtain 0.5 g of the desired product. As the liquid medium of the recording liquid used in the present invention, ordinary organic solvents can be appropriately selected and used as desired, and solvents containing ester groups are particularly preferably used. Specifically, for example, ethyl acetate, amyl acetate, benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, ethyl phenyl acetate, benzyl propionate, ethyl benzoate,
Butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, diethyl phthalate, 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), diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, and 3-hexenyl cinnamate. These solvents may be used alone or in combination with
You may use a mixture of more than one species. Among these, those containing two ester groups are particularly preferred, and the boiling point of the solvent is preferably 140°C or higher. In particular, when used in an inkjet recording device that utilizes electrostatics, alcohols, glycol derivatives, ketones, polar solvents, etc. having relatively low resistivity can be contained in the recording liquid in an amount of 2 to 40%. 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. To form full color images, the cyan tone recording liquid of the present invention can be used with magenta and yellow tone recording liquids. It can also be used together with a black tone recording liquid to adjust the tone. The dyes used in these recording liquids include those described in JP-A-63-69875 (for example, monoazo, polyazo, metal complex azo, pyrazolone azo, aminopyrazole azo, stilbene azo, thiazole azo). Various azo dyes, anthrone, anthraquinone dyes consisting of anthraquinone derivatives, indigo,
Indigoid dyes consisting of thioindigo derivatives,
phthalocyanine dyes, diphenylmethane, triphenylmethane, xanthene, acridine carbonium dyes, azine, oxazine, thiazine quinone imine dyes, polymethine, azomethine methine dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, perinone dyes, etc.) Although magenta, yellow or black colors can be used, the following are particularly preferred. Magenta dye: A magenta-toned nickel chelate dye represented by the following general formula () described in JP-A No. 62-252483.

embedded image In the formula, Z represents a plurality of atoms necessary to complete at least one 5- to 7-membered aromatic ring or heterocycle. The hydrogen atoms on these rings are one or more alkyl groups, alkoxy groups, aryloxy groups, aralkyl groups, aryl groups, halogen atoms, cyano groups,
It may be substituted with a nitro group, ester group, carbamoyl group, acyl group, acylamino group, sulfonyl group, sulfamoyl group, sulfonamide group, amino group, alkylamino group, arylamino group, or hydroxyl group. Z' represents at least one 5- to 7-membered aromatic ring or heterocycle, in which case Z' binds the nitrogen atom of the nucleus, which acts as a chelating site, in a position adjacent to the point of attachment to the azo bond. Have it within the ring or
Otherwise, () has a carbon atom within the ring of the nucleus to which the nitrogen atom serving as the chelating site is directly attached. The hydrogen atom on the aromatic ring or heterocycle of Z′ may be substituted with one or more substituents,
The substituent is the same as Z. G represents a metal chelating group. Yellow dye; a dye represented by the following general formula ().

[Chemical formula] In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a carboxylic acid ester group, or a carbamoyl group, R ₂ represents a hydrogen atom, an alkyl group, or an aryl group, and R ₃ represents an aryl group. represents. However, none of R ₁ , R ₂ or R ₃ contains a sulfonic acid group. Or a yellow-toned nickel chelate dye represented by the above general formula (). Black pigment: A black color pigment represented by the following general formula ().

embedded image In the formula, Z〓 to Z〓 each represent a plurality of atoms necessary to complete at least one 5- to 7-membered aromatic ring or heterocycle. Z' represents at least one 5- to 7-membered aromatic ring or heterocycle, in which case Z' represents a nitrogen atom of the nucleus that acts as a chelating site () in a position adjacent to the point of attachment to the azo bond. Have it within the ring or
Otherwise, () has a carbon atom within the ring of the nucleus to which the nitrogen atom serving as the chelating site is directly attached. G represents a metal chelating group with one negative charge. M represents a trivalent hexadentate metal ion. The recording liquid of the present invention can be applied to various inkjet recording apparatuses by appropriately adding liquid medium components or various additives and adjusting the liquid to desired physical properties. 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. 4 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 solution. The specific resistance of this ink liquid is 3.7
×10 ⁷ Ω・cm, viscosity 7.0cp (both measured at 25℃)
It was hot. Using an electrostatic acceleration type inkjet device equipped with a head having a nozzle hole diameter of 50 μm and six nozzles, this ink liquid was sprayed into eight dots/dots.
When printed on inkjet recording paper with a coating layer containing mainly silicon oxide fine particles and polyvinyl alcohol in a weight ratio of 75:25, a clear and high-density cyan image was obtained. Ta. 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) and (2-2) having the following compositions were prepared in the same manner as in Example 1. Ink liquid (2-1) Compound No. 6 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. 7 of the present invention 5 parts by weight Maleic acid Dibutyl 65 parts by weight Diethyl phthalate 23 parts by weight N-methylpyrrolidone 7 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-
2) Both showed good ejection properties, and clear cyan images were obtained in each case. When the inkjet device was left for 3 weeks with the head filled with these inks attached and then restarted, the ink was ejected smoothly and the same clear, high-density images were obtained as before the ink 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. Example 3 Ink liquid (3-1) and Comparative liquid 1 having the following compositions were prepared in the same manner as in Example 1. Ink liquid (3-1) Compound No. 1 of the present invention 5 parts by weight Diethyl adipate 48 parts by weight Diethyl phthalate 40 parts by weight N-methylpyrrolidone 7 parts by weight Comparative liquid 1 CuPc (-SO ₂ NH-C ₈ H ₁₇ (-n) 5 parts by weight Diethyl adipate 48 parts by weight Diethyl phthalate 40 parts by weight N-methylpyrrolidone 7 parts by weight The filter that passed the ink liquid (3-1) was
Although no residue was observed, a considerable amount of undissolved matter remained on the filter through which Comparative Solution-1 had passed. When these ink solutions were placed in a sealed glass container and left indoors, no precipitation of pigment was observed in ink solution (3-1) even after 6 months, but in comparison solution 1, no precipitation of pigment was observed after 1 month. Precipitates were generated. Each of these ink solutions was printed one month after preparation on an inkjet recording paper using the same electrostatic acceleration type inkjet device as in Example 1. The results are shown in Table 1 along with the physical properties of the ink solutions.

[Table] As can be seen from Table 1, the recording liquid of the present invention did not deteriorate in ejection performance over time, and the printed images had high density and good image quality. Example 4 Ink liquids (4-1) to (4) having the following compositions
-3) was prepared in the same manner as in Example 1. Ink liquid (4-1) Oil-soluble magenta dye (shown below) 5 parts by weight Diethyl phthalate 30 parts by weight Diisopropyl adipate 45 parts by weight N,N-diethyldodecanamide 20 parts by weight Ink liquid Oil-soluble yellow dye (shown below) 5 parts by weight Diethyl phthalate 28 parts by weight Diisopropyl adipate 45 parts by weight N,N-diethyldodecanamide 22 parts by weight Ink liquid (4-3) Oil-soluble black dye (shown below) 6 parts by weight Diethyl phthalate 32 Parts by weight Diisopropyl adipate 45 parts N,N-diethyldodecanamide 17 parts by weight These ink liquids were placed together with the ink liquid of Example-1 in the same electrostatic acceleration type inkjet device used in Example-1. , printed on inkjet recording paper. The areas where ink liquids (4-1), (4-2) and the ink liquid of Example-1 were printed alone formed bright magenta, yellow and cyan images, respectively, and the two types of ink were equivalent. The overlapping areas formed a bright blue, green and red image. The color reproduction of these intermediate colors was also satisfactory. The area where the ink liquid (4-3) is printed alone forms a high-density black image, and the area where this ink liquid and the above ink liquid overlap forms a color image with good "black density". did.

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Claims (1)

[Scope of Claims] 1. A non-aqueous inkjet recording liquid characterized by containing a compound represented by the following general formula (). [Formula] In the formula, M represents a metal atom, Pc represents a phthalocyanine ring, and R ₁ and R ₂ have 1 to 4 carbon atoms.
represents a straight-chain alkyl group, and R ₃ has 2 to 12 carbon atoms.
represents a straight chain, branched or cyclic alkyl group. In this case, R ₁ and R ₃ and/or R ₂ and R ₃ may be combined to form a ring. n represents an integer from 1 to 4.