WO2013120273A1

WO2013120273A1 - Copper phthalocyanine benzyl sulfone compound and derivative thereof

Info

Publication number: WO2013120273A1
Application number: PCT/CN2012/071283
Authority: WO
Inventors: 彭孝军; 戴正亮; 秦学孔; 樊江莉; 王风; 李少磊
Original assignee: 大连理工大学; 珠海纳思达企业管理有限公司
Priority date: 2012-02-17
Filing date: 2012-02-17
Publication date: 2013-08-22
Also published as: CN102686593B; CN102686593A

Abstract

A copper phthalocyanine benzyl sulfone compound and a derivative thereof and an ink-jet ink composition containing the compound. The copper phthalocyanine benzyl sulfone compound has a formula (I), wherein substituents W₁, W₂, W₃, W₄ are located at β positions of copper phthalocyanine respectively and independently, at least one of the substituents is a W₅-represented group, and the other substituents can be independently selected from SO₂(CH₂)_mSO₂X. In the substituents, X is independently selected from NR₁(CH₂)_wOH, N((CH₂)_wOH)₂, NR₁(CH₂)_wSO₃M, NR₁(CH₂)_wCO₃M or OM, wherein n is an integer between 0 and 2, m and w are respectively an integer between 2 and 6; R₁ is H, CH₃ or CH₂CH₃; and M is H, Li, Na, K or Μ⁺R₂R₃R₄R₅, where R₂, R₃, R₄, R₅ are selected from the same or different H, C_1-18alkyl, cyclohexyl, benzyl or (CH₂)_wOH. The copper phthalocyanine benzyl sulfone compound can provide cyan dye molecules. The cyan dye molecules are added in ink to enhance comprehensive stability of the ink, and also reduce and prevent the bronze phenomenon, thereby improving print quality.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper phthalocyanine benzyl sulfone compound and a derivative thereof, and further provides an ink jet ink composition containing the same. Background technique

Currently, inkjet printing is one of the more commonly used printing methods. Since the head does not come into contact with the material to be recorded, it is quiet in the printing operation because no sound is produced. In addition, it is also characterized by being easy to miniaturize, high speed, and color. Therefore, it has been rapidly developed and widely used in recent years.

With the development of inkjet printers and their print quality, there is a higher standard for the fastness of printing inks and print contents such as water resistance, moisture resistance, light resistance, and gas resistance. For water resistance: Usually, the surface of the substrate is adsorbed with porous silica, cationic polymer, alumina sol or special ceramic, and the dye is coated on the surface of the printing material (paper) together with these organic or inorganic particles and PVA resin. Therefore, it provides a guarantee for greatly improving the water resistance; for moisture resistance: when the printed image is stored in a high humidity environment, it is required to have a strong penetration of the dye in the recorded material, and if there is penetration of the dye, Especially in the case where the photo coloring requirement is high, the image quality is remarkably lowered. For gas resistance: Due to the popularity of digital printing, when the obtained printed matter is stored, there is an oxidizing gas in the indoor air. The resulting image discoloration has also become a concern. The oxidizing gas reacts with the dye on the recording paper or in the recording paper, which causes the printed image to discolor and fade, and ozone is the main substance that promotes the oxidative fading of the inkjet printed image; in addition, the printed image is discolored under the illumination environment. , fading, etc., also have an important relationship with the light fastness of the dye in the printing ink.

Dissolving the water-soluble dye in an aqueous medium, adding a water-soluble organic solvent that prevents the nib and the nozzle from clogging, making the printing ink is a process of conventionally manufacturing the ink. From the above analysis, it can be known that the prepared ink is formed in addition to the performance of a high-density printed image, no clogging of the tip or nozzle, good drying property on the recorded material, less penetration, and excellent storage stability. The image should also have good water resistance, light resistance, moisture resistance and other characteristics. Therefore, for the four primary colors providing color characteristics, not only are better tones and vividness, but also their printability and comprehensive resistance to ink are put forward higher. Blue used in inkjet ink The molecular skeleton of the dye for color, the representative is a copper phthalocyanine sulfonic acid compound dye, such as CI Direct Blue 86, CI Direct Blue 199. However, these copper phthalocyanine sulfonate dyes are excellent in color tone and vividness, but are inferior in light resistance and ozone resistance.

Recent studies and practices have shown that cyan dyes containing sulfone-based groups of copper phthalocyanines, especially some phthalocyanine-containing copper phthalocyanine sulfonate dyes, have been shown to have bright, light and odor resistant properties. Patent publications such as: USP 7247195B2 and USP 7264662B2 have related publications. Application practice shows that these copper phthalocyanine dyes have an improved effect on light resistance and ozone resistance, but their effects on water resistance, stability and bronze are reduced.

In summary, among the cyan dyes currently available, dyes which satisfy both hue, vividness, light resistance, water resistance, ozone resistance, and solution stability have not yet been obtained. For example, the long-term stability of the dye in the ink is related to the solubility of the dye, especially the solubility of the dye in water. The cyan dye currently used is not ideal in many cases; at high density, the dye precipitates on the printed image to form crystals. The reflected light that produces a metallic luster is called bronze. As a result of the study, it is considered that when the water solubility of the dye is lowered, the phenomenon of bronze is liable to occur because the ability to associate (aggregate) the dye is improved. In the print job, the occurrence of the bronze phenomenon not only causes a decrease in the optical density of the recorded image, but also causes a large difference between the obtained recorded image and the desired (color) hue. Therefore, one of the important properties that inkjet inks need to satisfy is to prevent bronze. Specifically, the copper phthalocyanine sulfonic acid dye with a phenylsulfone group has a strong structural rigidity, insufficient flexibility, low solubility of the dye, and difficulty in infiltrating the photographic paper coating, which should result in bronze phenomenon and light resistance and resistance. One of the important reasons for low ozone performance. SUMMARY OF THE INVENTION The main technical problem to be solved by the present invention is to provide a copper phthalocyanine benzyl sulfonate compound, by introducing a benzylsulfonyl group-containing group by selecting a substituent in the compound, thereby increasing the flexibility of the compound molecule. At the same time, the solubility can be improved. The compound is used as a dye for the formulation of inks, which is advantageous for improving the overall stability and application of the ink.

The present invention also provides a printing ink composition containing the copper phthalocyanine benzyl sulfonate compound, which provides a cyan dye molecule to be added to the ink, which not only improves the overall stability of the ink, but also Reduce and avoid bronze and improve print quality. The invention also provides a preparation method of the copper phthalocyanine benzyl sulfone compound.

In the conventional inkjet ink of the present invention, a copper phthalocyanine phenylsulfonylsulfonic acid compound is often selected as a cyan dye from the viewpoint of comprehensive properties. The present invention first provides a copper phthalocyanine benzyl sulfone group compound having the following general formula (I) for the problem that its solubility is low, resulting in unsatisfactory stability and print quality:

In the formula (I), the substituent groups w ₂ , w ₃ , w ₄ are each independently located at the β position of the copper ruthenium, and at least one of them is a group represented by w ₅ , and the other substituents may be independently selected from the group consisting of S0 ₂ (CH ₂ ) _m S0 ₂ X; in the substituents S0 ₂ (CH ₂ ) _m S0 ₂ X and W ₅ ,

X is independently selected from

N((CH ₂ ) _w OH) ₂ , NR !(CH ₂ ) _W S0 ₃ M , NRi CH wCOzM or OM, n is an integer of 0-2, m, w are independently an integer of 2-6;

Ri is H, CH ₃ or CH ₂ CH ₃ ;

M is independently selected from H, Li, Na, K or N ⁺ R ₂ R ₃ R ₄ R ₅ , wherein R ₂ , R ₃ , R ₄ , R _{5 are} selected from the same or different H, C _{1 - 18} Alkyl, cyclohexyl, benzyl or (CH ₂ ) _w OH. The copper phthalocyanine benzyl sulfone compound (I ) provided by the present invention may be a copper phthalocyanine benzylsulfonate sulfonic acid or a salt thereof or a copper phthalocyanine by introducing a benzylsulfonyl group-containing group into the copper phthalocyanine molecular structure. A benzylsulfonylsulfonamide compound becomes a new copper phthalocyanine dye. The dye is used for the formulation of inkjet ink, has good solubility and stability, and is beneficial to improve the printing quality of the ink.

The copper phthalocyanine benzyl sulfone compound represented by the above formula (I) can be obtained by a process of synthesizing a copper phthalocyanine having a benzylsulfone group by using a compound having a benzyl sulfone group as a raw material.

The present invention also provides an inkjet ink composition, the composition of which is a copper phthalocyanine benzyl sulfone compound as a coloring agent, and has a weight content of 0.1-20%, and comprises 0.1-30% of a water-soluble organic solvent, 0.1-5. % ink additive and balance water.

a dye containing a copper phthalocyanine benzyl sulfone compound represented by the general formula (I), compared with the prior art, Has the following advantages:

1. The molecular structure contains a benzylsulfone group, and the fluorenyl (CH ₂ ) single bond attached to the benzene ring can be freely rotated, which greatly increases the flexibility of the dye molecule, improves the solubility of the dye and the stability of the inkjet ink. ;

2. The improvement of the flexibility of the dye molecules makes the dye more easily penetrate into the interior of the photographic paper coating, improving the water resistance, light resistance and ozone stability of the image;

3. The internal permeability of the dye to the photographic paper coating is improved, the bronze phenomenon is eliminated, and the color density and image quality are improved. BEST MODE FOR CARRYING OUT THE INVENTION The present invention first provides a copper phthalocyanine benzyl sulfone compound having the following formula (I):

The substituents on the copper tibia are selected as described above, that is, at least one of w ₂ , w ₃ , and w ₄ is a benzylsulfonyl group-containing substituent represented by w ₅ .

In the copper phthalocyanine benzyl sulfone compound provided by the present invention, n in the substituent group W ₅ may be 1 or 2, which is more advantageous for improving the solubility of the compound. In a specific embodiment, when n is 1, -S0 ₂ X may be in the meta or para position of the benzylsulfonyl group; when n is 2, the two -S0 ₂ X may be in the ortho position of the benzamidine group, respectively. Counterpoint.

It should be understood that the compound substituents W ₂ , W ₃ , W ₄ (wherein at least one of W ₅ ) may be the same or different, and when W ₅ has two -S0 ₂ X, the choice of X may be the same or different. That is, the substituents on the benzene ring providing the benzylsulfonyl group may be the same or different; of course, the phenylsulfone group may have no other substituent (n=0) on the benzene ring.

The copper phthalocyanine benzyl sulfone based compound provided by the present invention, in the substituents Wi, W ₂ , W ₃ , W ₄ (wherein at least one is W ₅ ), X may be selected as N (CH ₂ CH ₂ OH) ₂ , NHCH ₂ CH ₂ OH, or hydrazine, Μ is Li, Na, K, N ⁺ H ₂ (CH ₂ CH ₂ OH) ₂ , N ⁺ H ₃ CH ₂ CH ₂ OH or N ⁺ H (CH ₂ CH ₂ OH) ₃ . In some embodiments of the present invention, the substituent on the copper phthalocyanine β position of the copper phthalocyanine sulfonate compound may include one or more substituents having a W ₅ structure, or all have a W ₅ structure. Substituents, of course, the substituents of these W ₅ structures may be the same or different (depending on the choice of X and n).

The copper phthalocyanine benzyl sulfone compound (I) of the present invention can be used as a cyan dye for the formulation of an inkjet ink, and the inorganic compound content of the dye compound of 1% or less is more advantageous for controlling the electrical conductivity of the entire formulated ink system.

The compound of the formula (I) of the present invention is produced by a process comprising the steps of: benzylsulfonyl compound (V) or benzylsulfonate compound V) and phthalic acid which provides a substituent represented by W _r W ₄ a process in which a mixture of a phthalonitrile compound and/or a phthalimide compound is reacted with a copper-containing compound to form a benzylsulfonyl copper phthalocyanine; or

Mixing a benzyl sulfide compound (IV) or a benzyl sulfide compound IV with a phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by the reaction with a copper-containing compound Benzyl sulfide-based copper phthalocyanine, and a process in which benzyl sulfide-based copper phthalocyanine is further oxidized to form benzylsulfonyl copper phthalocyanine.

IV V

DESCRIPTION OF THE INVENTION The description of the "substituent represented by a substituent which may be provided" is understood to mean that W ₅ is not included and is treated according to the method, in order to obtain a target product having a W ₅ substituent. It also has at least one substituent of W _r W ₄ .

In a specific embodiment of the present invention, when a benzene ring of the substituent W ₅ introduced by the target compound of the formula (I) has one or two groups attached thereto, the benzylsulfonylsulfonate (salt) group is formed. Or a benzylsulfonylsulfonamide group, the method of obtaining the compound can be specifically described as the following two.

method one :

The benzyl sulfide compound IV ) is oxidized to a benzyl sulfone compound ( V ) ;

a mixture of a benzylsulfonyl compound (V) or a benzylsulfonyl compound V) with an phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by w _r w ₄ , and a copper-containing compound The reaction produces benzylsulfonyl copper phthalocyanine and further chlorosulfonation to form benzylsulfonyl copper phthalocyanine sulfonyl Chlorine compound

The benzylsulfonyl copper phthalocyanine sulfonyl chloride compound is subjected to a hydrolysis reaction or a sulfonymidation reaction to form a copper phthalocyanine benzyl sulfone compound represented by the formula (I), wherein n in the substituent W ₅ is 1 or 2. A mixture of a benzyl sulfide compound (IV) or a benzyl sulfide compound (IV) and an phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by H is reacted with a copper-containing compound Forming a benzyl sulfide-based copper phthalocyanine, and further forming a benzyl sulfide-based copper phthalocyanine sulfonyl chloride compound by chlorosulfonation;

The benzyl sulfide-based copper phthalocyanine sulfonyl chloride compound is subjected to a hydrolysis reaction or a sulfoamidation reaction to form a copper phthalocyanine benzyl sulfide-based compound intermediate;

The obtained copper phthalocyanine benzyl sulfone compound intermediate is oxidized to form a copper phthalocyanine benzyl sulfone compound represented by the formula (I), and n in the substituent W ₅ is 1 or 2.

It can be understood that in the preparation method, it is necessary to introduce a benzyl group in the reaction product for synthesizing copper phthalocyanine, and further to synthesize a copper phthalocyanine having a benzyl group. The benzyl sulfide compound (IV) for synthesizing benzyl copper phthalocyanine can be prepared by any known method, and a specific embodiment can be: using benzyl mercaptan or its salt (III) as a raw material, The benzyl sulfide compound (IV) is obtained by reacting with 4-nitro-phthalonitrile (II) in the presence of an inorganic base in the presence of an inorganic base, and the benzyl thiol or its salt (III) is M, can, K) or ammonium, etc.:

Therefore, the main preparation process according to method one can be:

Step 1: 4-Nitro-phthalonitrile (II) is reacted with a benzyl mercaptan or a salt thereof (III) to form a benzyl sulfide compound (IV).

Ν, Ν-dimercaptoamide, hydrazine, hydrazine-dimercaptoacetamide, dimethyl sulfoxide, etc., the solvent is used in an amount of 4-20 times the weight of 4-nitro-phthalonitrile, generally 6-15倍; The inorganic base may be, for example, sodium carbonate, potassium carbonate or sodium hydrogencarbonate, and the amount of the inorganic base is 0.3-1.2 mol relative to 1 mol of 4-nitro-phthalonitrile; 0.5-1.0 mol.

In the above reaction process, the benzyl mercaptan or its salt may be in an appropriate excess, for example, relative to 1 mol. 4-Nitrophthalonitrile, benzyl mercaptan or a salt thereof is used in an amount of about 1-1.5 mol, which may be 1.05-1.1 mol.

During the reaction, the controlled temperature of 40-100 ° C is more favorable for the complete conversion of the reactants in a shorter period of time, generally controlled at 60-90 ° C. The reaction time is generally l-8h, which can be adjusted appropriately according to the reaction temperature, generally 2-4h.

After completion of the reaction by thin layer analysis, HPLC or the like (the basic reaction of 4-nitro-phthalonitrile is completed), the reactant is added to a solvent such as decyl alcohol, ethanol, ethyl acetate or water to precipitate. The product can be obtained by filtration, and the amount of the solvent is 1.5 to 10 times the weight of the reaction mixture (the reaction mixture includes the raw materials to be reacted, the solvent for the reaction, the product after the reaction, and by-products, etc.), and may be 2 to 5 times.

Step 2: The benzyl sulfide compound (IV) is oxidized to form a benzylsulfonyl compound (V). The use of a suitable oxidizing agent, in terms of facilitating the control operation and obtaining the target product, uses hydrogen peroxide in the embodiment of the present invention, for example, a concentration of 25-50% hydrogen peroxide, usually 30-40% hydrogen peroxide, relative to 1 mol. The benzyl sulfide compound (IV) and the hydrogen peroxide are used in an amount of from 2.0 to 10 mol, and may be from 3 to 7 mol.

The above oxidation reaction can be carried out in a conventional organic acid, and the organic acid is generally selected to have good solubility in the reactants and the oxidizing agent (e.g., hydrogen peroxide), and may be, for example, acetic acid, citric acid, chloroacetic acid, trifluoroacetic acid or the like. The organic acid is used in an amount of 5-20 times the weight of the benzyl sulfide, which may be 6-15 times; the temperature of the oxidation reaction can be determined according to the characteristics of the oxidizing agent, generally at 50-100 ° C, which is advantageous for controlling the reaction rate and completing the oxidation. .

The reaction is completed by thin layer analysis, HPLC, etc. (the benzyl sulfide compound is basically reacted), and after cooling and filtration, the product benzylsulfonyl phthalonitrile compound (V) can be obtained.

Step 3: A benzylsulfonyl copper phthalocyanine as shown in the structural formula (particles) is produced.

The reaction process can be controlled according to a method for preparing a copper phthalocyanine compound (for example, phenylsulfonyl copper phthalocyanine), for example, a copper-containing compound is selected as a soluble copper salt, and copper chloride is usually used to control an appropriate reaction temperature and reaction time. . In order to obtain a copper phthalocyanine group-containing copper phthalocyanine, the reactant of the present invention is required to include a benzylsulfonyl group-containing compound, that is, to obtain a benzylsulfonyl group-containing copper phthalocyanine compound in addition to a copper-containing compound, depending on the design of the target product. The reactants may all be the above benzylsulfonyl phthalonitrile compound (V) (the substituents of the final product are all w ₅ groups), or may be the benzylsulfonyl phthalonitrile compound (V) and A mixture of an orthophthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented (the final product obtainable at this time contains both \¥ ₅ and a substituent group). In the latter case, the material ratio of the benzylsulfonyl phthalonitrile compound (V) to the phthalonitrile compound and/or the phthalimide compound which can provide the represented substituent can be determined according to design requirements.

It is apparent that the reaction product obtained by this process should be mainly composed of a compound having the formula (particles).

It should be noted that the equation (ring) is only a schematic structure, and p, q, r, s can be independently 0 or 1 , t is 1-4, and p + q + r + s + t is 4. For a single molecule, they should be integers, but for mixtures, they are averages (ie, they should also be allowed to be decimals). The same applies to the following formulas (VI), (VII), (IX) and (x).

The orthophthalonitrile compound capable of providing a substituent represented by n can be expressed as

VJ, V _3, for example, or other compounds satisfying the above definition, can provide a phthalimide compound represented by the substituent e.g. V _2:

W represents any group defined above (excluding W ₅ ).

The reaction temperature of the synthetic benzylsulfonyl copper phthalocyanine process can be controlled at 80-300 ° C, generally can be controlled at 100-250 ° C, especially 130-230 ° C; the reaction is generally at a boiling point of 80 ° C or In a higher organic solvent, the choice of an organic solvent having a boiling point higher than 130 ° C is more favorable for the reaction, for example: n-pentanol, n-hexanol, cyclohexanol, 2-mercapto-1-pentanol, 1-g Alcohol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, hexanediol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimercaptoaminoethanol, two Ethylaminoethanol, trichlorobenzene, chloronaphthalene, sulfolane, nitro Benzene, quinoline, urea, etc. The amount of the organic solvent is basically controlled to be 1 - 100 times the total weight of the reactants of the process, and may be 5 to 20 times.

In the above reaction, an appropriate amount of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or ammonium molybdate may be used as a catalyst. With respect to 1 mol of the benzylsulfonyl phthalonitrile compound or the benzylsulfonyl phthalonitrile compound (V) and the phthalonitrile compound capable of providing a substituent represented by \¥ ₁ -\¥ ₄ / or a mixture of phthalimide compounds, the amount of the catalyst is from 0.01 to 10 mol, and may be from 0.01 to 2 mol.

The end point of the reaction is the benzylsulfonyl phthalonitrile, or benzylsulfonyl phthalonitrile, and an phthalonitrile compound and/or a phthalimide capable of providing a substituent represented by w _r w ₄ . The mixture of the compounds is completely reacted (to form copper phthalocyanine) as a mark, and the reaction time is generally controlled for 2-20 h, that is, the reaction can be substantially completed and the obtained benzylsulfonyl copper phthalocyanine can be prevented from decomposing, and the actual operation can be controlled at 5- 15h, can be 5-10h.

The obtained benzylsulfonyl copper phthalocyanine is subjected to a refining treatment for the subsequent reaction, but refining is not essential. Conventional purification means such as recrystallization, column chromatography purification, etc. may be employed, and several purification means may be used as needed.

Step 4: The above benzylsulfonyl copper phthalocyanine (particle) is chlorosulfonated with chlorosulfonic acid to form a benzylsulfonyl copper phthalocyanine sulfonyl chloride compound (for example, represented by the formula (IX)), and the chlorosulfonate introduced by the process The acyl group is mostly located in the meta or para position of the benzyl sulfone group;

IX

For the case where H ( W ) is introduced in step 3, if some or all of \VrW4 has a -S0 ₃ H group (X=OH), these -S0 ₃ H groups may also be in the process. It is also sulfonyl chloride, that is, -S0 ₃ H at these positions is simultaneously converted to -S0 ₂ C1, which participates in subsequent hydrolysis or sulfonymidation, and is converted into a sulfonic acid group, a sulfonate group or a sulfonamide group. group.

Usually, the chlorosulfonation reaction uses chlorosulfonic acid as a sulfonating agent in an amount of 4-20 times the weight of the benzylsulfonyl copper phthalocyanine, which may be 5-10 times; the thionyl chloride may also be added in the reaction. , three An acylating agent such as oxyphosphorus promotes the reaction in an amount to provide the desired degree of acylation (i.e., at least the sulfonyl chloride on the benzylsulfone group, and as the end point of the reaction) and at the end of the reaction at which the degree of acylation is reached. The reasonable response time required is the principle. The larger the dosage, the faster the end point is reached. The chlorosulfonation reaction process is familiar to those having a basic knowledge of chemistry, and the purpose is to introduce a chlorosulfonyl group. Therefore, the amount of the sulfonating agent and the control of the reaction temperature and the reaction end point are not Special restrictions are required.

The reaction temperature may be from 50 to 100 ° C, and the reaction rate is appropriate and the decomposition and discoloration of the product are prevented as a control standard, for example, the control is 70-90 ° C.

After the completion of the reaction, a conventional treatment method such as adding the reactant to ice water and filtering to obtain a benzylsulfonyl copper phthalocyaninesulfonyl chloride compound having the formula (IX) can be obtained.

Step 5: The benzylsulfonyl copper phthalocyanine sulfonyl chloride compound is subjected to hydrolysis and/or sulfonymidation to give the target compound (I), ie, copper phthalocyanine benzylsulfonate sulfonate compound or copper phthalocyanine benzylsulfonate sulfonamide. Class of compounds.

The reaction temperature can be controlled at 0 to 100 ° C, usually at 20 to 80 ° C.

This step can be carried out according to the conventional hydrolysis and / or sulfonylation reaction conditions, the appropriate HX (X definition as described above) is added to the reaction system to hydrolyze or sulfoamidate the sulfonyl chloride group which has been formed. , forming a sulfonate group or a sulfonamide derivative group. According to the specific choice of HX, the previously introduced sulfonyl chloride group will undergo hydrolysis or sulfonylation, or both reactions will occur simultaneously, and the target compound (I) obtained is copper phthalocyanine sulfonate with benzylsulfonate group. A compound and/or a copper phthalocyanine sulfonamide derivative having a benzylsulfonyl group.

In a specific operation, when the target compound is a copper phthalocyanine sulfonate compound having a benzylsulfonyl group (whose W ₅ is a sulfonate group having a benzylsulfonyl group), the step is to add an appropriate base (HX=MOH). The hydrolysis may be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, or an aqueous solution or a salt solution of an alkanolamine such as ethanolamine or diethanolamine. Triethanolamine or the like; when a mixture thereof is used, the target compound has a different sulfonate group.

It is understood that when the target compound (I) contains two or more W ₅ groups, if the selected HX is a mixture, W ₅ in the target compound (I) is not a different group. According to a particular embodiment of the invention, W _{5 is} all or part of the benzylsulfonylsulfonamide substituent of the object compound (I). Compared with the amount of the sulfonyl chloride group, the HX added in this step includes at least an appropriate amount or even an excess of an aqueous solution of an alkanolamine or a salt solution thereof to make the sulfonyl chloride group in the reactants all. Or partially sulfonylated to the corresponding sulfonamide group. Depending on the target compound, for example, more than two W ₅ groups need to include a partial sulfonate (for example, at least one sulfonate group bearing a benzylsulfonate group), then the selected reactant HX is an alkanol. a solution of an amine or a salt thereof, or a mixture thereof with an alkali solution, to control or adjust the tendency of the sulfonyl chloride group to hydrolyze in the reaction system to obtain a product which is all a benzylsulfonylsulfonamide substituent (referred to as W ₅ ), or It also contains the target product of a sulfonate substituent and a sulfonamide substituent (further hydrolyzed by the sulfonamide product).

In summary, the mechanism and control of the hydrolysis and sulfonamide reaction of sulfonyl chloride are the basic knowledge of the related art, and the target product can be easily prepared by those having basic knowledge of chemistry and theory according to the above description or with reference to the following specific examples.

Similarly, the preparation process of the second method can be carried out by referring to the steps of the first method as follows: According to the first step of the first method, the benzyl sulfide compound (IV) or the benzyl sulfide compound (IV) can be provided and the \VrW4 can be provided. a mixture of a substituted phthalic nitrile compound and/or a phthalimide compound, and reacting directly with the copper-containing compound according to the procedure described in Step 3 of Method 1, to form a benzyl sulfide-based copper phthalocyanine ( For example, the structural formula (VI) shows;

VI

Chlorosulfonation according to the method of Step 4 in Method 1, to form a benzyl sulfide-based copper phthalocyanine sulfonyl chloride compound (which can be represented by the formula (VII)), introduction of a chlorosulfonyl group and selection of reaction conditions as described above The chlorosulfonyl group introduced at this time may be ortho, meta, para, or o/pair of the benzylsulfonyl group (eg, ultimately forming a 2,4-disulfonyl compound or a purine thereof);

For the product containing \VrW4 at the same time, the treatment process can be referred to the relevant description in the first method, and the obtained benzyl sulfide-based copper phthalocyanine sulfonyl chloride compound (VII) is reacted with HX according to the method in the first step of the first method to form copper. A phthalocyanine benzyl sulfide intermediate (as shown for structural formula (X)).

X

Finally, according to the step 2 in the first method, the obtained copper phthalocyanine benzyl sulfone compound intermediate (X) is oxidized to form a copper phthalocyanine benzyl sulfone compound represented by the formula (I).

It can be understood that when n is 0 in the W ₅ of the designed target product, neither the first method nor the second method requires the sulfonyl chloride reaction and the subsequent introduction of the hydrolysis or sulfonamidation reaction of HX.

In the compound of the present invention, in the formula (I), the substituent \VrW4 is located at the β position of the phthalocyanine ring. From the general formula (I), the phthalocyanine has a total of 8 β positions, and two on each benzene ring. The β-position will be attached to the substituent, so the product synthesized by any process including the above method should be a mixture of substituents at these positions.

In the specific implementation process of the present invention, the method (I) of the finally obtained compound is refined to have a content of the inorganic salt of 1% or less in order to control the conductance of the entire formulated ink system. rate. For example, the product can be desalted using a general method such as a high pressure reverse osmosis membrane.

The compound of the formula (I) provided by the present invention can be used as a dye for the formulation of an inkjet ink, and the specific molecular structure of the compound of the formula (I), but not limited to these structures, is shown in Table 1 below. As before As indicated, each dye will have an isomer with a different substituent at the beta position.

The copper phthalocyanine benzyl sulfone compound represented by the formula (I) of the present invention can be used as a cyan dye in an inkjet ink, and can exhibit a sharp color, a high purity and a high brightness on an ink jet recording paper, and is excellent in water solubility. , in the manufacturing process of the ink composition, can show good filtration of the filter Sex. Further, the ink composition using the copper phthalocyanine benzyl sulfone-based compound of the present invention has no crystal precipitation, color change, and the like after long-term storage, and has good storage stability; no special recording material is required for inkjet printing ( Paper, film, etc., all provide ideal cyan tones, good color reproduction when printing color images, no bronze defects, good image light resistance, ozone resistance, moisture resistance, etc.

The present invention also provides an inkjet ink composition comprising the above copper phthalocyanine benzyl sulfone compound (I) as a colorant, in an amount of 0.1-20% by weight, and comprising 0.1-30% of a water-soluble organic solvent, 0.1-5% ink additive and balance water.

The water-soluble organic solvent used in the present invention may have, for example, decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, etc. (^ to C ₄ An alcohol; an amide of a carboxylic acid such as hydrazine, hydrazine-dimercaptoamide, hydrazine, hydrazine-dimercaptoacetamide; a lactam such as 2-pyrrolidone or fluorenyl-mercapto-2-pyrrolidone; Nitrogen-containing heterocyclic cyclic nitrogen-containing solvent such as imidate-2-one, 1,3-dimercaptohexahydropyrimidin-2-one; acetone, mercaptoethyl ketone, 2-mercapto-2-hydroxyl a ketone or keto alcohol such as pent-4-ketone; a cyclic ether such as tetrahydrofuran or dioxane; ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,4-butanediol, 1 , 6-hexanediol; diethylene glycol (diethylene glycol), triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiol, polyethylene glycol, polypropylene glycol, etc. having (C ₂ to C ₆ ) a monomer, oligomer or polyalkylene glycol or thioglycol of an alkylene unit; glycerin, 1,2,6-trihexanol; ethylene glycol monoterpene ether or ethylene glycol monoethyl ether, diethylene glycol Alcohol monoterpene ether, diethylene glycol monobutyl ether; diethylene glycol monoethyl ether, triethylene glycol monoterpene , ((^ _1-4) alkyl triethylene glycol monoethyl ether and other ethers of polyhydric alcohols; [gamma] -butyrolactone or dimethyl sulfoxide Yue, inkjet inks are commonly used in production of these water-soluble organic solvent may be the solvent. Used alone or in combination.

In the embodiment of the ink composition of the present invention, the water-soluble organic solvent may be glycerin, diethylene glycol monobutyl ether, 2-pyrrolidone, fluorenyl-mercapto-2-pyrrolidone, monoethylene glycol, diethylene glycol, triethyl ethane. Glycol, dipropylene glycol, etc.; more use of glycerin, diethylene glycol monobutyl ether, 2-pyrrolidone, indole-yl-2-pyrrolidone, diethylene glycol and the like.

The additive in the ink composition of the present invention may be: an antiseptic and antifungal fungicide, a ruthenium adjuster, a chelating agent, a rust preventive, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolver, and a surfactant. a plurality of, which may be selectively added as needed, and their respective addition amounts are determined according to a conventional means, that is, the total amount of the additives is 0.1 to 5%, specifically,

Antiseptic and mildew fungicides, for example: organic sulfur, organic nitrogen sulfur, organic halogens, halogenated allylsulfones, iodopropynes, sulfonium-alkylthios, nitriles, pyridines, 8-hydroxyl quinoline, Benzothiazoles, isothiazolines, dithiols, pyridine oxides, nitropropanes, organotins, phenols, quaternary ammonium salts, triazines, thiadiazines, anilides , adamantanes, dithiocarbamates, indanones, benzoylbromoacetates, inorganic salts, etc.; for example: sodium pentachlorophenol, 2-pyridinethiol-1-oxide , sodium acetate, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-indolyl-4-isothiazoline-3 -ketone, 5-chloro-2-indolyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-indolyl-4-isothiazolin-3-one calcium chloride, 2-indenyl- 4-isothiazolin-3-one calcium chloride, sodium sorbate, sodium benzoate, and the like.

The pH adjuster is not particularly limited as long as the pH of the ink can be controlled within the range of 8.0-11.0. For example: alkanolamine such as diethanolamine or triethanolamine; alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; ammonium hydroxide or ammonia; alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate .

The chelating agent is, for example, sodium edetate, sodium nitrotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium urethane diacetate or the like.

The rust inhibitor is, for example, an acid sartite, a sodium sulphate, an ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite or the like.

The water-soluble ultraviolet absorber is, for example, a sulfonated dibenzophenone or a sulfonated benzotriazole or the like. The water-soluble polymer compound is, for example, polyvinyl alcohol, sodium hydroxydecyl cellulose (CMC), polyetherimide (PEI) or the like.

The dye solubilizing agent is, for example, urea, ε-caprolactam, diethyl carbonate or the like.

Surfactants are commonly used anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Anionic surfactants such as: alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, oxime acyl amino acids and salts thereof, Ν-acyl hydrazino taurine Salt, castor oil sulfate, lauryl sulfate, alkylphenol phosphate, alkyl phosphate, alkyl allyl sulfonate, diethyl sulfosuccinate, diethylhexyl Sulfosuccinic acid, dioctyl sulfosuccinate, etc.; cationic surfactants such as 2-vinylpyridine derivatives, poly-4-vinylpyridine derivatives, etc.; amphoteric surfactants, for example: lauryl Dimercaptoacetic acid betaine, 2-alkyl-indole-carboxymethyl-indole-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amide propyl dimercapto glycine betaine, polyoctyl polyaminoethyl Other imidazoline derivatives such as glycine; nonionic surfactants such as: polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl phenyl ether, Polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxygen Vinyl lauryl ether, polyoxyethylene Ethers such as alkenyl alkyl ethers; polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate Ester, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and other esters; 2,4,7,9- Tetradecyl-5-decyne-4,7-diol, 3,6-dimercapto-4-octyne-3,6-diol, 3,5-dimercapto-1-hexyne-di Alkynediols such as alcohols (for example, Surfynol 104, 82, 465, Olfine STG, etc., manufactured by Nisshin Chemical Co., Ltd.) and the like.

The ink composition of the present invention is prepared by dissolving the dye compound represented by the formula (I) in water or the above water-soluble solvent (water containing a water-soluble organic solvent), and if necessary, by dissolving it together with the above-mentioned ink additive or the like.

In the above ink preparation method, the order of addition of the components is not particularly limited, and all operations can be carried out according to a conventional method, for example, using a water filter (deionized water or the like) having as little impurity as possible, and a filter filter for ink prepared. The infiltration of the insoluble matter by precise filtration, for example, the pore size of the filter for precision filtration is usually 0.1-1 μm, or 0.2-0.8 μm.

The cyan ink composition containing the copper phthalocyanine benzyl sulfone compound in the present invention is suitable for use in copying, marking, writing, drawing, stamping or printing, and is particularly suitable for inkjet printing, and has the advantage that the formed image imprint pair Water, daylight, ozone, and friction have excellent resistance, and the cyan ink can also be used for color matching, for example, it can be made into black.

The compound of the present invention represented by the formula (I) is a coloring agent which can be used for coloring a plurality of substrates, such as: paper, fiber or cloth (containing cellulose, nylon, wool, etc.), leather, color filter base. Materials, etc., but are not limited to this. The coloring method may, for example, be a dip dyeing method, a printing method (printing method such as screen printing), inkjet printing or the like, and among them, it is preferably used for inkjet printing.

The substrate to be recorded which can be applied to the ink jet printing method of the present invention may be a sheet for information transfer such as paper, various types of films, fibers, leather, etc., which is commonly referred to as an ink jet special paper (film) or glossy paper ( Film), for example: professional glossy paper, top gloss paper, mat gloss paper, photo paper gloss, light pad paper, ultra-fine special gloss film, high-quality gloss paper, high-quality gloss film, light paper, etc. Of course, it can also be plain paper.

The ink composition of the present invention does not precipitate or separate during storage, and the use of the ink of the present invention in ink jet printing does not block the head. The ink of the present invention does not undergo physical changes even if it is used by a continuous ink jet printer for a long period of time or intermittent use.

The invention will be described in detail below in conjunction with the specific embodiments, so that the reader can understand the essence of the invention and the beneficial technical effects produced by the reader, but is not to be construed as being Any limitation of the scope. Further, [parts] and [%] in the present invention are understood to be parts by weight and % by weight unless otherwise specified. Example 1

Synthesis of dye compounds CO:

(1) Synthesis of benzyl sulfide compound ( IV ): 70 parts of 4-nitrophthalic acid nitrile ( II ) is added to 1000 parts of hydrazine, hydrazine-dihydrazinamide, stirred and dissolved, and then added After 54 parts of potassium carbonate, 48 parts of benzyl mercaptan was added dropwise, and after the completion of the dropwise addition, the temperature was raised to 80 ° C, the total reaction time was about 5 h, and finally lowered to room temperature. The reaction solution was poured into 10,000 parts of water with stirring, filtered, washed, and dried to obtain 100 parts of a benzyl sulfide compound (IV).

Melting point: 142.3-144.5 ° C;

Mass spectrum m/z (-): 250.05;

Ifi-NMR (CDC1 ₃ ) δ values based on TMS: 4.3 (s, 2H), 7.26-7.36 (m, 5H), 7.48-7.51 (dd, 1H), 7.57 (d, 1H), 7.6-7.62 (d, 1H).

(2) Synthesis of benzylsulfonyl compound (V): Take 275 parts of benzyl sulfide compound (IV), add it to 4000 parts of glacial acetic acid, heat it to about 90 ° C to dissolve it, and slowly drop at this temperature. Add 6000 parts of 30% hydrogen peroxide, the dropping time is controlled at 4h, after the addition is completed, it is cooled to room temperature and stirred overnight until a white solid in the solution slowly precipitates. After filtering the reaction product, it was washed with water and washed with ethanol to obtain 250 parts of a benzylsulfonyl compound (V).

Melting point: 162.5-165.3 °C;

Ifi-NMR (CDC1 ₃ ) δ value based on TMS: 4.42 (s, 2H), 7.0-7.5 (m, 5H), 7.87-7.9 (t, 2H), 7.97 (s, lH).

(3) Synthesis of benzylsulfonyl copper phthalocyanine (particles): Adding 800 parts of ethylene glycol to 53.4 parts of benzyl 3⁄4 compound (V), heating to 90 ° C with stirring, and adding 7.7 parts of copper chloride dihydrate and 0.5 parts of ammonium molybdate catalyst, continue to raise the temperature to 125-130 ° C, react for 6h, then reduce to about 60 °C, then add 600 parts of sterol to stir for 1h, then reduce to room temperature, filter, wash with decyl alcohol to the filtrate It is colorless and dried to obtain 50 parts of benzylsulfonyl copper phthalocyanine CO (wherein the substituent at the β position of the phthalocyanine ring is benzylsulfonyl).

Mass spectrometry (ESI-MS) m/z peaks were: 1192 [M+H] ⁺ ;

The most accurate molecular mass is 1191.

Example 2

Synthesis of dye compound C1

Taking the CO compound of the step (3) of the first embodiment as a raw material, the following operations are continued:

(4) Synthesis of copper phthalocyanine benzylsulfonylsulfonyl chloride (IX): Weigh 100 parts of chlorosulfonic acid in a flask, and slowly add 10 parts of the above-mentioned benzylsulfonyl copper phthalocyanine CO to the flask under constant stirring. The condenser is connected to the dryer, heated to about 90 ° C, and the reaction is about 5 h. After the reaction is completed, the temperature is lowered to room temperature. The reaction solution is slowly poured into ice and continuously stirred to control the temperature below 5 ° C. The solid was filtered, and the filter cake was washed with ice water several times, washed until the pH of the filtrate was about 3, then washed three times with acetonitrile, and dried to obtain 12 parts of copper phthalocyanine benzylsulfonylsulfonyl chloride (IX).

(5) Synthesis of dye compound C1: 12 parts of copper phthalocyanine benzylsulfonylsulfonyl chloride (IX) is beaten in 200 parts of water, heated to 50 ° C, and maintained with stirring to adjust the pH to about 10 with stirring. , continue to heat lh. The insoluble matter was removed by filtration, and the filtrate was subjected to a desalting (NaCl) process to obtain an aqueous solution of the dye C1, which was concentrated and dried to obtain 12 parts of the dye compound Cl.

The maximum absorption wavelength of the aqueous product solution: 626 nm;

Mass spectrometry (ESI-MS) m/z peaks: 376.7 [M-4Na] ⁴ 74, 510.1 [M-3Na] ³ 73 , 776.5 [M-2Na] ² 72;

The product C1 (calculated as sodium sulfonate S0 ₃ Na) has the most accurate molecular mass of 1599. Example 3

Synthesis of dye compound C2:

According to the synthesis methods of Examples 1 and 2, in the step (5), the aqueous sodium hydroxide solution was replaced with an aqueous lithium hydroxide solution, and the pH of the reaction system was maintained at about 10 to obtain 12 parts of the dye compound C2.

The maximum absorption wavelength of the aqueous product solution: 626 nm;

Mass spectrometry (ESI-MS) m/z peaks are: 376.7 [M-4Li] ⁴ 74, 504.7 [M-3Li] ³ 73 760.5[M-2Li] 72;

The product C2 (calculated as lithium sulfonate S0 ₃ Li) has the most accurate molecular mass number M of 1535. Example 4

Synthesis of dye compound C3:

According to the synthesis methods of Examples 1 and 2, in the step (5), the aqueous sodium hydroxide solution was replaced with an aqueous solution of triethanolamine, and the pH of the reaction system was maintained at about 10 to obtain 13 parts of the dye compound C3.

The maximum absorption wavelength of the aqueous product solution: 626 nm;

The mass spectrum (ESI-MS) m/z peaks are: 376.8 [M-4NH(CH ₂ CH ₂ OH) ₃ ] ⁴ 74 , 502.7 [M-4NH(CH ₂ CH ₂ OH) ₃ +H] ³ 73, 7547.5 [ M-4NH(CH ₂ CH ₂ OH) ₃ +2H] ² 72; Product C3 (calculated as S0 ₃ NH(CH ₂ CH ₂ OH) ₃ ) The most accurate molecular mass number M is 2,107. Example 5

Synthesis of dye compound C4:

20.4 parts of the compound (XI) (synthesis method is described in WO2011042735A1), 7.05 parts of the compound (V) (prepared according to the example 1), ²⁰⁰ parts of ethylene glycol is added, the temperature is raised to 80 ° C, and then 3.4 parts are added. Chlorinated copper chloride, heated to 125-130 ° C, reacted for 6 h, cooled to about 60 ° C, added 300 parts of sterol, stirred for 1 h, cooled to room temperature, filtered, washed with decyl alcohol until the filtrate was colorless. The obtained product was subjected to chlorosulfonation reaction according to the step (4) in Example 1, to obtain a compound containing a sulfonyl chloride, followed by the step (5) in Example 2, but replacing the sodium hydroxide therein with lithium hydroxide for the reaction. Finally, 24 parts of the dye compound C4 were obtained.

The maximum absorption wavelength of the aqueous product solution: 625 nm;

Mass spectrometry (ESI-MS) m/z peaks: 340.8 [M-4Li] ⁴ 74, 456.7 [M-3Li] ³ 73, 694.5 [M-2 Li] ² 72;

The product C4 (with lithium sulfonate S0 ₃ M) was 1391.

Example 6

Synthesis of dye compound C8: Copper phthalocyanine sulfonyl chloride (IX) was synthesized by the steps (1) to (4) in the same manner as in Examples 1 and 2. Take 8 parts of the copper phthalocyanine sulfonyl chloride (IX), control the temperature at 5 ° C, add to 100 parts of chloroform solution containing 10 parts of diethanolamine while stirring, then stir at room temperature for 30 min, then raise the temperature to 55 ° C And reacting at this temperature for another hour, finally cooling to 20 ° C, adding 100 parts of petroleum ether extraction to recover unreacted diethanolamine, and further removing unreacted diethanolamine by high pressure reverse osmosis membrane, filtering and drying to obtain 8.5 parts of dye Compound C8.

The maximum absorption wavelength of the aqueous product solution: 625 nm;

Mass spectrometry (ESI-MS) m/z: [M+H] ⁺ =1878;

The product C8 has the most accurate molecular mass number M of 1877. Example 7

Synthesis of dye compound C10:

Copper phthalocyanine sulfonyl chloride (IX) was synthesized by the steps (1) to (4) in the same manner as in Examples 1 and 2. Take 8 parts of copper phthalocyanine sulfonyl chloride (IX), control the temperature at 5 ° C, add to a solution of 4.5 parts of diethanolamine in 100 parts of water with stirring, then stir at room temperature for 30 min, then warm to 55 ° C, and The reaction was further carried out at this temperature for 1 hour, and finally cooled to 20 ° C, and the residue was removed by filtration, and the unreacted excess diethanolamine was removed by a high pressure reverse osmosis membrane, and vacuum-dried to obtain 9.2 parts of the dye compound C10.

The maximum absorption wavelength of the aqueous product solution: 625 nm;

Mass-spectrum product (ESI-MS) m/z: [M-NH ₂ (CH ₂ CH ₂ OH) ₂ ] ⁺ =1771 ;

The CIO's most accurate molecular mass number M is 1877. Example 8

Synthesis of dye compound C11:

Copper phthalocyanine sulfonyl chloride (IX) was synthesized by the steps (1) to (4) in the same manner as in Examples 1 and 2. Take 8 parts of the copper phthalocyanine sulfonyl chloride (IX), and control the temperature at 5 ° C, add copper phthalocyanine sulfonyl chloride (IX ) to 100 parts of aqueous solution containing 1.7 parts of diethanolamine while stirring, then at room temperature After stirring for 30 min, the temperature was raised to 45-50 ° C, and further reacted at 45-50 ° C for 2 h. During the reaction, aqueous sodium hydroxide solution was added dropwise, and the pH of the reaction system was maintained at 9-11, and finally cooled to room temperature, filtered. The residue was removed, and the unreacted excess diethanolamine was removed by a conventional high pressure reverse osmosis membrane and vacuum dried to obtain 9.5 parts of the dye compound Cl1.

The maximum absorption wavelength of the aqueous product solution: 625 nm; Mass spectrometry (ESI-MS) m/z: 850.5 [M-Na-NH ₂ (CH ₂ CH ₂ OH) ₂ ] ² 72; The product Cl l has the most accurate molecular mass number M of 1830. Example 9

Synthesis of dye compound C12:

According to the methods of Examples 1 and 2, the steps (1) to (4) were synthesized to obtain copper phthalocyanine sulfonyl chloride (IX). Take 8 parts of the copper phthalocyanine sulfonyl chloride (IX), and control the temperature at 5 ° C, add copper phthalocyanine sulfonyl chloride ( IX ) to 100 parts of aqueous solution containing 1.7 parts of diethanolamine while stirring, then at room temperature After stirring for 3 Omin, the temperature was raised to 45-50 ° C, and further reacted at 45-50 ° C for 2 h. During the reaction, an aqueous solution of lithium hydroxide was added dropwise, and the pH of the reaction system was maintained at 9-11, and finally cooled to room temperature, and filtered. The residue was removed, and the unreacted excess diethanolamine was removed by a conventional high pressure reverse osmosis membrane, and vacuum-dried to obtain 9.5 parts of the dye compound C12.

The maximum absorption wavelength of the aqueous product solution: 625 nm;

Mass Spectrometry (ESI-MS) m/z: 850.5 [M - Li-NH ₂ (CH ₂ CH ₂ OH) ₂ ] ² 72;

The product C12 has the most accurate molecular mass number M of 1814. Example 10

( A ) Modulation of ink

The dye compound C1 in the above Example 2 was used as a cyan dye, and the ink composition shown in the following Table 2 was prepared by first mixing a raw material other than water and triethanolamine, filtering through a 0.45 μm membrane filter, and adding deionized water. The pH of the ink composition was adjusted to 8-10 with triethanolamine, and finally made up to 100 parts by weight with deionized water to obtain an aqueous cyan ink composition of the present invention.

Composition of ink solution (parts by weight)

(The composition of the ink solution may also contain 0.1 part of preservative Proxel GXL) (B) Inkjet printer:

High-gloss photographic paper (manufactured by Epson Co., Ltd.) was subjected to inkjet printing using an ink jet printer (Epson Model 270 manufactured by Epson Co., Ltd.).

(C) Evaluation of printed images:

(1) Xenon lamp light resistance test for printed images

The test piece of the printed glossy photo paper was irradiated with a illuminance of 0.36 W/m 2 at a humidity of 60% RH and a temperature of 24 ° C using a Xenon lamp weatherproofer ZG-P (manufactured by China Surui Co., Ltd.). 50h, the color difference (ΔΕ) before and after the test was measured. The color difference (ΔΕ) is the value of each L*, a*, and b* before and after the measurement test by the above-described color measurement system (manufactured by Unterlab Co., Ltd.), and the values of L*, a*, and b* are obtained by the following formula. The difference before and after the test.

ΔE=((the difference of L*) ² + (the difference of _a *) ² + (the difference of b*) ² ) ^1/2 .

The evaluation is based on the following criteria in three levels:

ΔΕ < 10 o

ΔΕ < 20 Δ

ΔΕ > 20

(2) Recording image ozone resistance test

The printed glossy photo paper was placed in an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C for 6 hours using an ozone weatherproofer ZG-P (manufactured by China Surrey Co., Ltd.). The color difference (ΔΕ) before and after the test was obtained in the same manner as in the above test (1), and evaluated in three levels according to the following criteria:

ΔΕ < 10 o

ΔΕ < 20 Δ

ΔΕ > 20

(3) Recording image moisture resistance test

The printed high-gloss photographic paper test piece was placed at a temperature of 50 ° C and 90% RH for 168 hours using a constant temperature and humidity device (manufactured by China Suray Co., Ltd.) to visually determine the exudation property before and after the test. Three levels of evaluation:

(D) Solution stability evaluation: A mixture of 20 parts of dye, 70 parts of water and 10 parts of ethylene glycol was heated and dissolved, and after cooling, stored under a closed condition at a constant temperature of 50 ° C for 7 days, cooled to room temperature and then filtered, and divided into three according to the following criteria. Level evaluation:

No precipitation o

a little precipitation △

Many precipitates

( E ) Evaluation of bronze phenomenon:

After the above-described image-formed glossy photo paper was dried for 24 hours, it was observed with the eyes whether or not the bronze phenomenon occurred and was evaluated. Samples confirming that there was no bronze at all were rated as o, samples with a slight bronze were confirmed as A, and samples confirmed to have bronze were rated as χ. When it was confirmed that bronze was produced, the printing density was lower than that without the occurrence of bronze. Therefore, the occurrence of bronze phenomenon can also be confirmed by a decrease in print density.

The selected dyes and the phenylsulfonyl copper phthalocyanine sulfonic acid dye Dyel, the commercial dye CI Direct Blue 86, and the C丄 Direct Blue 199 used for the control were respectively prepared into comparative ink compositions (all the control dyes were from commercial use). Product). These ink compositions were used for ink jet printing, and evaluation of printed images was performed. All results are shown in Table 3:

Dye1 Table 3 Comparison of dye properties

Dye, ultraviolet resistance, ozone resistance, water resistance, stability, bronze phenomenon

C1 o 〇〇〇〇

C2 o 〇〇〇〇

C3 o 〇〇〇〇

C4 o 〇〇〇〇

C8 o 〇〇〇〇 CIO o 〇〇〇〇

Cl l o 〇〇〇〇

C12 o 〇〇〇〇

Dyel △ △ △ △ △

C丄Direct Blue 86 X X 〇〇〇

C丄Direct Blue 199 XX 〇〇〇 By comparison of the above Table 3, it is found that the copper phthalocyanine benzyl sulfone compound of the present invention is extremely useful as an inkjet dye as compared with the copper phthalocyanine phenylsulfonate dye (Dyel). Excellent stability, light resistance, ozone resistance, moisture resistance, and at the same time overcome the phenomenon of bronze. Industrial applicability

The copper phthalocyanine benzyl sulfone compound represented by the formula (I) of the present invention has not only high water solubility but also color and vividness suitable for ink jet printing. Since the cyan ink composition containing the compound is excellent in storage stability, and the printed image using the ink is excellent in light resistance, moisture resistance, ozone resistance, and overcoming the bronze phenomenon, the compound is suitable for inkjet printing. Cyan dye.

Claims

Claim

1. A copper phthalocyanine benzyl sulfone compound represented by the following formula (I):

In the formula (I), the substituent groups w ₂ , w ₃ , w ₄ are each independently located in the β position of the copper phthalocyanine, and at least one is a group represented by w ₅ , and the other substituents may be independently selected from the group S0. ₂ (CH ₂ ) _m S0 ₂ X; in the substituent W ₅ ,

X is independently selected from NR CH wOH N((CH ₂ ) _w OH) ₂ , NR!(CH ₂ ) _W S0 ₃ M , NRi CH wCOzM or OM, n is an integer from 0 to 2, m, w are independently An integer of 2-6; and,

Ri is H, CH ₃ or CH ₂ CH ₃ ;

M is independently selected from H, Li, Na, K:, N ⁺ R ₂ R ₃ R ₄ R ₅ , wherein R ₂ , R ₃ , R ₄ , R _{5 are} selected from the same or different H, C _{1 - 18} alkyl, cyclohexyl, benzyl or (CH ₂ ) _w OH.

2, copper phthalocyanine benzyl sulfone compound according to claim 1, substituent group \ _{¥. 5,} n is 1 or 2.

The copper phthalocyanine benzyl sulfone-based compound according to claim 2, wherein, in the substituent group W ₅ , when n is 1, the meta- or para-position of -S0 ₂ X on the benzylsulfone group; n is 2 When -S0 ₂ X is in the ortho and para positions on the benzylsulfone group.

The copper phthalocyanine benzyl sulfone compound according to any one of claims 1 to 3, wherein, in the substituents W ₂ , W ₃ , W ₄ , X is independently selected from N (CH ₂ CH ₂ OH) ₂ , NHCH ₂ CH ₂ OH or OM , M is Li, Na, K:, N ⁺ H ₂ (CH ₂ CH ₂ OH) ₂ , N ⁺ H ₃ CH ₂ CH ₂ OH or N ⁺ H (CH ₂ CH ₂ OH) ₃ .

The copper phthalocyanine benzyl sulfone compound according to any one of claims 1 to 4, wherein the copper ruthenium The substituents at the β position of the cyanine are all substituents having a w ₅ structure.

Use of a copper phthalocyanine benzyl sulfone compound according to any one of claims 1 to 5 for formulating an ink composition.

7. The use according to claim 6, wherein the ink is cyan ink.

The method for preparing a copper phthalocyanine benzyl sulfone compound according to any one of claims 1 to 5, wherein the method comprises at least the following steps:

Mixing a benzylsulfonyl compound (V) or a benzylsulfonyl compound (V) with a phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by the reaction with a copper-containing compound to form a benzyl group a sulfone-based copper phthalocyanine process; or

a mixture of a benzyl sulfide compound (IV) or a benzyl sulfide compound (IV) and an phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by W _r W ₄ The copper-containing compound is reacted to form a benzyl sulfide-based copper phthalocyanine, and a process in which the benzyl sulfide-based copper phthalocyanine is further oxidized to form a benzylsulfonyl copper phthalocyanine;

IV v

9. The preparation method according to claim 8, wherein the method comprises at least the following steps:

The benzyl sulfide compound (IV) is oxidized to a benzyl sulfone compound (V).

10. The preparation method according to claim 8, comprising the steps of: oxidizing a benzyl sulfide compound (IV) to a benzylsulfonate compound (V);

Mixing a benzylsulfonyl compound (V) or a benzylsulfonyl compound (V) with a phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by the reaction with a copper-containing compound to form a benzyl group Sulfone-based copper phthalocyanine, and further chlorosulfonation to form a benzylsulfonyl copper phthalocyanine sulfonyl chloride compound;

The benzylsulfonyl copper phthalocyanine sulfonyl chloride compound is subjected to a hydrolysis reaction or a sulfonymidation reaction to form a copper phthalocyanine benzyl sulfone compound represented by the formula (I), and 1 in the substituent W ₅ is 1 or 2.

1 1. The preparation method according to claim 8, the method comprising the following steps: a mixture of a benzyl sulfide compound (IV) or a benzyl sulfide compound (IV) with an phthalonitrile compound and/or a phthalimide compound capable of providing a substituent represented by n, and a copper-containing compound Reacting to form benzyl sulfide-based copper phthalocyanine, and further by chlorosulfonation reaction to form a benzyl sulfide-based copper phthalocyanine sulfonyl chloride compound;

12. The method according to claim 8, 10 or 11, further comprising:

Using benzyl mercaptan or its salt ( III ) as a raw material, in a polar solvent and in the presence of an inorganic base,

4-nitro-phthalonitrile (II) is reacted to obtain a benzyl sulfide compound (IV). In the structure of the benzyl thiol or its salt (ΠΙ), M' is an alkali metal or ammonium.

The preparation method according to claim 12, wherein in the reaction, benzyl mercaptan or a salt thereof ( ΠΙ ) is excessive with respect to 4-nitro-phthalonitrile (II), and the reaction is controlled. The temperature is 40-100 ° C.

The preparation method according to claim 12 or 13, wherein the polar solvent is selected from the group consisting of hydrazine, hydrazine-dimercaptoamide, hydrazine, hydrazine-dimercaptoacetamide or dimethyl sulfoxide, a solvent The amount is 4-20 times the weight of 4-nitro-phthalonitrile (II).

The process according to claim 13, wherein the molar ratio of benzyl mercaptan or its salt (III) to ⁴ -nitro-phthalonitrile (II) is from 1 to 1.5:1.

The production method according to any one of claims 8 to 11, wherein the oxidation is carried out using hydrogen peroxide, and the reaction temperature is controlled to be 50 to 100 °C.

The preparation method according to claim 16, wherein a hydrogen peroxide having a concentration of 25 to 50% is used, and a molar ratio to the oxide to be used is 2.0 to 10:1.

The production method according to claim 8 or 10, wherein the benzylsulfonyl compound (V) or the benzylsulfonyl compound (V) and the phthalonitrile compound capable of providing the represented substituent are provided. And/or a mixture of phthalimide compounds, reacting with a copper-containing compound to form a benzylsulfonyl copper phthalocyanine is carried out in an organic solvent having a boiling point of 80 ° C or higher, and using 1,8-diaza Ring [5.4.0]-7-undecene (DBU) or ammonium molybdate is used as a catalyst, the reaction temperature is 80-300 ° C, and the reaction time is 2-20 hours.

The production method according to claim 8 or 11, wherein the benzyl sulfide compound (IV) or the benzyl sulfide compound (IV) and the phthalic acid capable of providing the represented substituent are used. The reaction of a mixture of a phthalonitrile compound and/or a phthalimide compound with a copper-containing compound to form a benzyl sulfide-based copper phthalocyanine is carried out in an organic solvent having a boiling point of 80 ° C or higher, and 1,8- is used. Diazabicyclo[5.4.0]-7-undecene (DBU) or ammonium molybdate is used as a catalyst, the reaction temperature is 80-300 ° C, and the reaction time is 2-20 hours.

The production method according to claim 18 or 19, wherein the organic solvent has a boiling point higher than 130 °C.

The production method according to claim 10 or 11, wherein the chlorosulfonation reaction uses chlorosulfonic acid as a sulfonating agent, and the reaction temperature is 50 to 100 °C.

An inkjet ink composition comprising the copper phthalocyanine benzylsulfonate compound according to any one of claims 1 to 5 as a colorant, in an amount of 0.1 to 20% by weight, and including 0.1 to 30% by weight. Water soluble organic solvent, 0.1-5% ink additive and balance water.

The inkjet ink composition according to claim 22, wherein the colorant has a weight content of from 1 to 15%.

The inkjet ink composition according to claim 22 or 23, wherein the ink additive comprises an antiseptic and antifungal bactericide, a pH adjuster, a chelating agent, a rust preventive, a water-soluble ultraviolet absorber, and a water-soluble agent. One or more of a polymeric compound, a dye solubilizing agent, and a surfactant.