WO2013120273A1 - Composé de phtalocyanine de cuivre et de benzylsulfone et dérivé de celui-ci - Google Patents

Composé de phtalocyanine de cuivre et de benzylsulfone et dérivé de celui-ci Download PDF

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Publication number
WO2013120273A1
WO2013120273A1 PCT/CN2012/071283 CN2012071283W WO2013120273A1 WO 2013120273 A1 WO2013120273 A1 WO 2013120273A1 CN 2012071283 W CN2012071283 W CN 2012071283W WO 2013120273 A1 WO2013120273 A1 WO 2013120273A1
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Prior art keywords
compound
copper phthalocyanine
benzyl
reaction
benzylsulfonyl
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PCT/CN2012/071283
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English (en)
Chinese (zh)
Inventor
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
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Application filed by 大连理工大学, 珠海纳思达企业管理有限公司 filed Critical 大连理工大学
Priority to PCT/CN2012/071283 priority Critical patent/WO2013120273A1/fr
Priority to CN201280000280.5A priority patent/CN102686593B/zh
Publication of WO2013120273A1 publication Critical patent/WO2013120273A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • the molecular skeleton of the dye for color is a copper phthalocyanine sulfonic acid compound dye, such as CI Direct Blue 86, CI Direct Blue 199.
  • copper phthalocyanine sulfonate dyes are excellent in color tone and vividness, but are inferior in light resistance and ozone resistance.
  • 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.
  • bronze The reflected light that produces a metallic luster
  • 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.
  • 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 is to prevent bronze.
  • 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.
  • 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:
  • the substituent groups w 2 , w 3 , w 4 are each independently located at the ⁇ 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.
  • 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. ;
  • 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 .
  • n in the substituent group W 5 may be 1 or 2, which is more advantageous for improving the solubility of the compound.
  • n in the substituent group W 5 may be 1 or 2, which is more advantageous for improving the solubility of the compound.
  • n 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.
  • X may be selected as N (CH 2 CH 2 OH) 2 , NHCH 2 CH 2 OH, or hydrazine, ⁇ 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 substituent on the copper phthalocyanine ⁇ 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
  • 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.
  • the benzylsulfonylsulfonate (salt) group is formed.
  • a benzylsulfonylsulfonamide group the method of obtaining the compound can be specifically described as the following two.
  • the benzyl sulfide compound IV is oxidized to a benzyl sulfone compound ( V ) ;
  • 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.
  • 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).
  • the solvent is used in an amount of 4-20 times the weight of 4-nitro-phthalonitrile, generally 6-15 ⁇ ;
  • 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.
  • 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.
  • 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.
  • the reactant is added to a solvent such as decyl alcohol, ethanol, ethyl acetate or water to precipitate.
  • 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).
  • 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. .
  • a copper phthalocyanine compound for example, phenylsulfonyl copper phthalocyanine
  • a copper-containing compound is selected as a soluble copper salt
  • copper chloride is usually used to control an appropriate reaction temperature and reaction time.
  • 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).
  • 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.
  • reaction product obtained by this process should be mainly composed of a compound having the formula (particles).
  • 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.
  • t is 1-4
  • p + q + r + s + t is 4.
  • they should be integers, but for mixtures, they are averages (ie, they should also be allowed to be decimals).
  • 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 Benzen
  • an appropriate amount of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or ammonium molybdate may be used as a catalyst.
  • DBU 1,8-diazabicyclo[5.4.0]-7-undecene
  • 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;
  • H ( W ) is introduced in step 3
  • these -S0 3 H groups may also be in the process.
  • 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.
  • 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.
  • target compound (I) ie, copper phthalocyanine benzylsulfonate sulfonate compound or copper phthalocyanine benzylsulfonate sulfonamide.
  • 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.
  • HX X definition as described above
  • 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.
  • 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.
  • the target compound (I) contains two or more W 5 groups
  • W 5 in the target compound (I) is not a different group.
  • W 5 is all or part of the benzylsulfonylsulfonamide substituent of the object compound (I).
  • 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.
  • the selected reactant HX is an alkanol.
  • the preparation process of the second method can be carried out by referring to the steps of the first method as follows:
  • 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;
  • 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);
  • 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)).
  • the obtained copper phthalocyanine benzyl sulfone compound intermediate (X) is oxidized to form a copper phthalocyanine benzyl sulfone compound represented by the formula (I).
  • the substituent ⁇ VrW4 is located at the ⁇ position of the phthalocyanine ring.
  • the phthalocyanine has a total of 8 ⁇ positions, and two on each benzene ring. The ⁇ -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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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
  • 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.
  • 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, ⁇ -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, ⁇ -olefin sulfonates, polyoxyethylene alkyl ether acetates, oxime acyl amino acids and salts thereof, ⁇ -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
  • 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.
  • 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.
  • a water filter deionized water or the like
  • 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 ⁇ m, or 0.2-0.8 ⁇ m.
  • 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 most accurate molecular mass is 1191.
  • the maximum absorption wavelength of the aqueous product solution 626 nm;
  • 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
  • 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 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;
  • the product C4 (with lithium sulfonate S0 3 M) was 1391.
  • the maximum absorption wavelength of the aqueous product solution 625 nm;
  • the product C8 has the most accurate molecular mass number M of 1877.
  • 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;
  • 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.
  • 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.
  • IX copper phthalocyanine sulfonyl chloride
  • the maximum absorption wavelength of the aqueous product solution 625 nm;
  • the product C12 has the most accurate molecular mass number M of 1814.
  • Example 10
  • 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 ⁇ m 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)
  • 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.).
  • 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 ( ⁇ ) before and after the test was measured.
  • the color difference ( ⁇ ) 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.
  • ⁇ E ((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:
  • 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 ( ⁇ ) 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:
  • 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.
  • a constant temperature and humidity device manufactured by China Suray Co., Ltd.
  • the selected dyes and the phenylsulfonyl copper phthalocyanine sulfonic acid dye Dyel, the commercial dye CI Direct Blue 86, and the C ⁇ 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:
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

L'invention porte sur un composé de phtalocyanine de cuivre et de benzylsulfone, sur un dérivé de celui-ci et sur une composition d'encre pour jet d'encre contenant le composé. Le composé de phtalocyanine de cuivre et de benzylsulfone répond à la formule (I), dans laquelle les substituants W1, W2, W3 et W4 sont situés au niveau des positions β de la phtalocyanine de cuivre respectivement et indépendamment, au moins l'un des substituants est un groupe représenté par W5 et les autres substituants peuvent être indépendamment choisis parmi les substituants SO2(CH2)mSO2X. Dans les substituants, X est indépendamment choisi parmi les substituants NR1(CH2)wOH, N((CH2)wOH)2, NR1(CH2)wSO3M, NR1(CH2)wCO3M ou OM, n étant un nombre entier compris entre 0 et 2, m et w étant chacun respectivement un nombre entier compris entre 2 et 6 ; R1 représentant H, CH3 ou CH2CH3 ; et M représentant H, Li, Na, K ou Μ+R2R3R4R5, R2, R3, R4 et R5 étant identiques ou différents et choisis parmi H ou les groupes alkyle en C1-18, cyclohexyle, benzyle ou (CH2)wOH. Le composé de phtalocyanine de cuivre et de benzylsulfone permet de donner des molécules de colorant cyan. Les molécules de colorant cyan sont ajoutées dans une encre pour accroître la stabilité complète de l'encre et également pour réduire et prévenir le phénomène de bronzage, ce qui améliore de cette manière la qualité d'impression.
PCT/CN2012/071283 2012-02-17 2012-02-17 Composé de phtalocyanine de cuivre et de benzylsulfone et dérivé de celui-ci WO2013120273A1 (fr)

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CN1389464A (zh) * 2002-07-05 2003-01-08 卢忠远 一种兰色改性剂及其制备方法与应用
US20040089197A1 (en) * 2002-09-25 2004-05-13 Fuji Photo Film Co., Ltd. Inkjet recording ink
CN1705718A (zh) * 2002-12-10 2005-12-07 科莱恩有限公司 酞菁颜料制剂的生产方法
CN102686593A (zh) * 2012-02-17 2012-09-19 大连理工大学 铜酞菁苄砜基化合物及其衍生物

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JP4383007B2 (ja) * 2001-06-22 2009-12-16 富士フイルム株式会社 フタロシアニン化合物、それを含む着色画像形成組成物、インク、インクジェット用インク、インクジェット記録方法及びオゾンガス褪色耐性の改良方法
JP4190187B2 (ja) * 2002-01-22 2008-12-03 富士フイルム株式会社 水溶性フタロシアニン化合物を含むインク、インクジェット用インク、インクジェット記録方法、及び着色画像材料のオゾンガス褪色改良方法
US7255733B2 (en) * 2003-06-20 2007-08-14 Toyo Ink Mfg. Co., Ltd. Process for the production of β type copper phthalocyanine pigment and a use thereof
US7247195B2 (en) * 2005-03-09 2007-07-24 Hewlett-Packard Development Company, L.P. Dye sets for ink-jet ink imaging
GB0823267D0 (en) * 2008-12-20 2009-01-28 Fujifilm Imaging Colorants Ltd Azaphthalocyanines and their use in ink-jet printing

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Publication number Priority date Publication date Assignee Title
CN1389464A (zh) * 2002-07-05 2003-01-08 卢忠远 一种兰色改性剂及其制备方法与应用
US20040089197A1 (en) * 2002-09-25 2004-05-13 Fuji Photo Film Co., Ltd. Inkjet recording ink
CN1705718A (zh) * 2002-12-10 2005-12-07 科莱恩有限公司 酞菁颜料制剂的生产方法
CN102686593A (zh) * 2012-02-17 2012-09-19 大连理工大学 铜酞菁苄砜基化合物及其衍生物

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