CN103649233B - The manufacture method of AZOpigments - Google Patents

Abstract

It is an object of the invention to provide can be with high efficiency (purity and productivity ratio) and the manufacture method of the AZOpigments manufacturing easy scattered AZOpigments microgranule at low cost.By the azo-compound shown in amorphous following formula (1), its salt, hydrate or solvate being carried out crystalline transformation, thus manufacture the AZOpigments shown in following formula (1).

Description

The manufacture method of AZOpigments

Technical field

The present invention relates to the manufacture method of AZOpigments.

Background technology

About the synthetic method of azo-compound, the most known various methods, have and utilize the synthesis of oxidation reaction, profit The synthesis with the synthesis of reduction reaction, utilizing substitution reaction, the synthesis utilizing additive reaction, utilize condensation reaction synthesis, its His synthetic method etc. (referring for example to non-patent literature 1).But, as the industrially preparing process institute profit of azopigment compound Method at the aspect such as acquired, cost, yield of raw material, be nearly all to make diazonium compound and aniline, phenol etc. Coupling components generation azo coupling reactions carries out the method synthesized, and additionally the method there is also diazonium compound generation blast Dangerous, different and be the shortcomings such as low yield according to the kind of diazonium compound, coupling components.Particularly, heterocycle diazonium Compound has the situation that diazonium compound is unstable, also high less than versatility synthetic method more.

It addition, the organic pigment being widely used as colorant is particularly at color filter for liquid crystal display or ink-jet oil Need to improve further distinctiveness, the transparency etc. during ink etc..In order to improve distinctiveness, the transparency, it is known that effectively Organic pigment is made to disperse imperceptibly.In order to make organic pigment fine dispersion, use is needed to be suitable to the dispersant of fine dispersion or divide Dissipate machinery, but as major premise with greater need for be organic pigment itself be fine (microgranule).When organic pigment is thick grain The period of the day from 11 p.m. to 1 a.m, is also difficult to obtain excellent fine dispersion even if improving dispersant, process for dispersing.Therefore, when making paints, except Purity, yield etc. are common to be required outside project, also requires to be manufactured into microgranule.

As the manufacture method of organic pigment microgranule, such as AZOpigments, suitable by selecting when synthesis Reaction condition, can obtain fine, through the particle of granulate sometimes.It addition, it is such just like C.I. Pigment Blue 15 viridine green, by later Operation in atomic thin, the particle generation particle growth of cohesion, the granulate that generate when making synthesis to the method making pigment；Have As copper phthalocyanine blue pigment, thick, the inconsistent particle generated during by making synthesis in operation later becomes Method fine, that its granulate is made pigment.Such as, in general diketopyrrolo-pyrrole pigment is by making succinic acid two Ester reacts in organic solvent with aromatic nitrile, (referring for example to the patent documentation 1) synthesized as rough pigment.Additionally, will be thick Diketopyrrolo-pyrrole pigment processed carries out heat treatment in water or organic solvent, then carries out powder as ground in wet type Change, thus become the form (referring for example to patent documentation 2) being adapted in use to.

Additionally, organic pigment has display pleomorphism person, it is known that although this pigment has identical chemical composition, but can be Crystal habit of more than two kinds.

Such as, the known crystal habit (referring for example to patent documentation 3) having α type and β type of C.I. paratonere 254.It addition, make Multiple crystal habit (referring for example to patent documentation 4) is had for the C.I. pigment yellow 181 of AZOpigments is known.

As it has been described above, while it is recognized that have the feature of specific crystal structure, but it is also known that have for amorphous spy The pigment levied, also by making C.I. pigment yellow 181 for noncrystalline to play the example (patent documentation 5) of dispersibility.

As the method obtaining fine organic pigment, record in patent documentation 6 and pigment dissolved will be made in amide system The method that the solution obtained in organic solvent is injected in poor solvent, obtains the microgranule of nano-scale, with good grounds poor solvent Kind is different and main record that the obtain crystal habit of pigment is different.But, in the method, the concentration of pigment solution is low to be reached About 10mM, needs to use substantial amounts of solvent to obtain pigment, the most uneconomical.

Patent documentation 7 has been recorded the method that can manufacture specific monoazo pigment with high-purity.But, as a rule It is difficult to the method is applied to more unstable heterocycle diazonium compound and obtains AZOpigments with high yield and high-purity.

Patent documentation 8 has been recorded the azo obtaining the diazonium compound employing pyrazoles with high yield and high-purity Compound.The method is effective for the manufacture of dyestuff, but the particle not having the compound about being manufactured by the method is big Little record.

Patent documentation 9 has also stated that the azo obtaining the diazonium compound employing pyrazoles with high yield and high-purity The manufacture method of compound.There is the record being obtained the microgranule being more uniformly distributed by the method, but dispersibility still has improvement further Leeway.Wherein, not about the record of crystal habit of pigment.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Laid-Open Patent Publication 58-210084 publication

Patent documentation 2: Japanese Unexamined Patent Publication 5-222314 publication

Patent documentation 3: Japanese Unexamined Patent Publication 8-48908 publication

Patent documentation 4: No. 2008/0058531 description of U.S. Patent Application Publication No.

Patent documentation 5: Japanese Unexamined Patent Publication 2003-261792 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2004-91560 publication

Patent documentation 7: Japanese Unexamined Patent Publication 2008-63524 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2007-217681 publication

Patent documentation 9: Japanese Unexamined Patent Publication 2011-74375 publication

Non-patent literature

Non-patent literature 1: new chemistry seat (Wan Shan Co., Ltd.) 14-III, 1516～1534

Summary of the invention

Invention is intended to solve the technical problem that

The present invention relates to the azo face being formed by connecting by the pyrazole ring with specified substituent via azo group and triazine ring The manufacture method of material, as it has been described above, still there is the leeway of research in terms of the performance taking into account AZOpigments and manufacturing.

It is an object of the invention to provide the AZOpigments microgranule that can manufacture favorable dispersibility in high efficiency and low cost The manufacture method of AZOpigments.

For the method solving problem

The present inventors conduct in-depth research in view of the above fact, found that: by amorphous compound is brilliant Body changes, it is possible to obtain the AZOpigments microgranule of favorable dispersibility；And then find: by making diazol send out with coupling components During raw azo coupling reactions so that it is become azo-compound will not separate out completely in reactant liquor state (azo-compound A part is dissolved in the state of reactant liquor), this reactant liquor is injected in the poor solvent of azo-compound, it is thus achieved that amorphous Compound, it is possible to realize above-mentioned problem, thus complete the present invention.

That is, the present invention is as described below.

［ 1 ］ manufacture method of the AZOpigments shown in following formula (1), it is characterised in that by amorphous following formula (1) institute The azo-compound, its salt, hydrate or the solvate that show carry out crystalline transformation.

The manufacture method of the AZOpigments described in ［ 2 ］ above-mentioned ［ 1 ］, it is characterised in that by a solvent to amorphous Azo-compound shown in described formula (1), its salt, hydrate or solvate carry out heated and stirred to carry out crystalline transformation.

［ 3 ］ above-mentioned ［ 1 ］ or ［ 2 ］ described in the manufacture method of AZOpigments, it is characterised in that by amorphous described formula Azo-compound crystalline transformation shown in (1) becomes the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction to be 4.8 °, There is at 7.2 ° and 9.7 ° the crystal formation of characteristic X-ray diffraction maximum.

［ 4 ］ above-mentioned ［ 1 ］～［ 3 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that by amorphous Azo-compound crystalline transformation shown in described formula (1) becomes the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction It it is the crystal formation at 4.8 °, 7.2 °, 9.7 °, 20.1 ° and 26.8 ° with characteristic X-ray diffraction maximum.

［ 5 ］ above-mentioned ［ 1 ］～［ 4 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that by amorphous Azo-compound crystalline transformation shown in described formula (1) becomes the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction It is, at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 °, there is characteristic X-ray diffraction maximum Crystal formation.

［ 6 ］ above-mentioned ［ 3 ］～［ 5 ］ according to any one of AZOpigments or the manufacture method of its tautomer, its feature It is, comprises following operation:

(i) the azo-compound crystalline transformation shown in amorphous described formula (1) is become in CuK α characteristic X-ray diffraction The operation that Bragg angle (2 θ ± 0.2 °) is the crystal formation at 4.8 °, 7.2 ° and 9.7 ° with characteristic X-ray diffraction maximum；And

(ii) to containing described operation (i) middle AZOpigments, water-soluble inorganic salt and the water-miscible organic solvent obtained Mixture carries out mixing, and making the BET specific surface area utilizing nitrogen adsorption method to record is 50m²The operation of the crystal of/more than g.

［ 7 ］ above-mentioned ［ 1 ］～［ 6 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that comprise following work Sequence:

The operation of the amino-compound shown in (a) mixing diazotization agent and following formula (2)；

(b) by the product obtained in described operation (a) is mixed with the coupling components shown in following formula (3) into Row reaction, it is thus achieved that be dissolved with at least one of solution of the azo-compound shown in the following formula (1) generated by this reaction Operation；And

C the solution obtained in described operation (b) is mixed by () with the poor solvent of described azo-compound, make following formula (1) operation of the amorphous azo-compound partial crystallization shown in.

The manufacture method of the AZOpigments described in ［ 8 ］ above-mentioned ［ 7 ］, it is characterised in that in described operation (b), gained Solution is acid solution.

The manufacture method of the AZOpigments described in ［ 9 ］ above-mentioned ［ 8 ］, it is characterised in that described acid solution contain acetic acid and At least one in sulphuric acid.

［ 10 ］ above-mentioned ［ 7 ］～［ 9 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that in described work In sequence (b), gained solution be the azo-compound shown in the described formula (1) generated by coupling reaction be completely dissolved molten Liquid.

［ 11 ］ above-mentioned ［ 7 ］～［ 10 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that described In (c) operation, it is below 1g/L's with the dissolubility of the azo-compound shown in the described formula (1) of acquisition in described operation (b) Poor solvent mixes.

［ 12 ］ above-mentioned ［ 7 ］～［ 11 ］ according to any one of the manufacture method of AZOpigments, it is characterised in that described bad Solvent contain selected from water and alcohol, carbon number that carbon number is 1～3 be more than a kind solvent in the glycol of 1～6.

［ 13 ］ a kind of AZOpigments, it is to be obtained by the manufacture method according to any one of above-mentioned ［ 1 ］～［ 12 ］.

［ 14 ］ a kind of pigment dispersion, it contains AZOpigments, dispersant and the water described in above-mentioned ［ 13 ］.

［ 15 ］ the aqueous pigment dispersion described in above-mentioned ［ 14 ］, it is characterised in that dispersant is water soluble polymer.

［ 16 ］ the aqueous pigment dispersion described in above-mentioned ［ 15 ］, it is characterised in that described water-soluble polymer dispersant has There is at least 1 carboxyl, there is the acid number of at least more than 50mgKOH/g.

［ 17 ］ above-mentioned ［ 15 ］ or ［ 16 ］ described in aqueous pigment dispersion, it is characterised in that described aqueous pigment dispersion Cross-linked by cross-linking agent.

Invention effect

Can high efficiency (purity and productivity ratio) and manufacture easy scattered azo at low cost by the invention it is possible to provide The manufacture method of the AZOpigments of pigment particle.

Accompanying drawing explanation

Fig. 1 is the X-ray diffractogram of the AZOpigments (1)-2 of the δ type crystal habit according to embodiment 1 synthesis.

Fig. 2 is the X-ray diffractogram of the AZOpigments (1)-4 of the δ type crystal habit according to the 2-in-1 one-tenth of embodiment.

Fig. 3 is the X-ray diffraction of the AZOpigments (1)-5 of the intermediate product i.e. ζ type crystal habit according to embodiment 3 synthesis Figure.

Fig. 4 is the X-ray diffractogram of the AZOpigments (1)-7 of the δ type crystal habit according to embodiment 3 synthesis.

Fig. 5 is the X-ray diffractogram of the AZOpigments (1)-9 of the δ type crystal habit according to embodiment 4 synthesis.

Fig. 6 is the X-ray diffractogram of the AZOpigments (1)-11 of the δ type crystal habit according to embodiment 5 synthesis.

Fig. 7 is the X-ray diffractogram of the AZOpigments (1)-13 of the δ type crystal habit according to embodiment 6 synthesis.

Fig. 8 is the X-ray diffractogram of the AZOpigments (1)-14 of the δ type crystal habit according to embodiment 7 synthesis.

Fig. 9 is the X-ray diffractogram of the AZOpigments (1)-15 of the δ type crystal habit according to embodiment 8 synthesis.

Figure 10 is the X-ray diffractogram of the AZOpigments (1)-16 of the δ type crystal habit according to embodiment 9 synthesis.

Figure 11 is the X-ray diffractogram of the AZOpigments (1)-17 of the δ type crystal habit according to embodiment 10 synthesis.

Figure 12 is the X-ray diffractogram of the AZOpigments (1)-18 of the δ type crystal habit according to embodiment 11 synthesis.

Figure 13 is the X-ray diffractogram of the AZOpigments (1)-101 of the ζ type crystal habit according to the synthesis of embodiment 11-2.

Figure 14 is the X-ray diffraction of the most amorphous AZOpigments of intermediate product (1)-19 according to embodiment 12 synthesis Figure.

Figure 15 is the X-ray diffractogram of the AZOpigments (1)-20 of the δ type crystal habit according to embodiment 12 synthesis.

Figure 16 is the X-ray diffractogram of the AZOpigments (1)-103 of the δ type crystal habit according to the synthesis of embodiment 12-2.

Figure 17 is the X-ray diffractogram of the AZOpigments (1)-21 of the δ type crystal habit according to embodiment 13 synthesis.

Figure 18 is the X-ray diffractogram of the AZOpigments (1)-22 of the δ type crystal habit according to embodiment 14 synthesis.

Figure 19 is the X-ray diffractogram of the AZOpigments (1)-23 of the δ type crystal habit according to embodiment 15 synthesis.

Figure 20 is the X-ray diffractogram of the AZOpigments (1)-24 of the δ type crystal habit according to embodiment 16 synthesis.

Figure 21 is the X-ray diffractogram of the AZOpigments (1)-25 of the δ type crystal habit according to embodiment 17 synthesis.

Figure 22 is the X-ray diffractogram of the AZOpigments (1)-27 of the δ type crystal habit according to embodiment 18 synthesis.

Figure 23 is the X-ray diffractogram of the AZOpigments (1)-104 of the δ type crystal habit according to the synthesis of embodiment 18-2.

Figure 24 is the X-ray diffractogram of the AZOpigments (1)-26 of the δ type crystal habit according to comparative example 1 synthesis.

Figure 25 is the X-ray diffractogram of AZOpigments (the 1)-2-A of the δ type crystal habit according to embodiment 20 synthesis.

Figure 26 is the X-ray diffractogram of AZOpigments (the 1)-32-A of the δ type crystal habit according to comparative example 3 synthesis.

Figure 27 is the X-ray diffractogram of AZOpigments (the 1)-29-A of the δ type crystal habit according to comparative example 4 synthesis.

Figure 28 is the X-ray diffractogram of AZOpigments (the 1)-31-A of the δ type crystal habit according to comparative example 5 synthesis.

Figure 29 is the X-ray diffractogram of AZOpigments (the 1)-30-A of the ζ type crystal habit according to comparative example 6 synthesis.

Become good reason about by the pigment-dispersing of the manufacture method manufacture of the present invention, below describe supposition. In X-ray diffraction, the molecule of the crystal of display characteristic X-ray diffraction maximum is with certain regular arrangement, intermolecular phase Interaction is securely joined with.Its result, dissolubility in a solvent reduces.It is thus possible, for instance in a solvent, when turning from this crystal When becoming another crystal formation, while dissolving on one point, crystalline transformation carried out, the crystal therefore becoming core is few, crystal raw Look bigger.On the other hand, as the present invention, in X-ray diffraction, the noncrystalline of characteristic X-ray diffraction maximum is not shown The intermolecular interaction of solid dissolubility weak, in a solvent high.During it is thus possible, for instance carry out crystalline transformation in a solvent, Owing to noncrystalline is solid, the most mostly dissolve, but owing to the dissolubility of crystal is low, be therefore immediately turned into hypersaturated state, become Crystal for core separates out in a large number, and crystal is difficult to grow up.Think that result obtains fine pigment, dispersibility becomes good.

Detailed description of the invention

The present invention explained in detail below.

In the present invention, noncrystalline refer to not as crystal long-range order but shortrange order shows certain material State, does not show characteristic X-ray diffraction maximum in X-ray diffraction.

Following Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction it is 4.8 °, 7.2 ° by this specification And the AZOpigments shown in following formula (1) at 9.7 ° with characteristic X-ray diffraction maximum is referred to as δ type crystal habit azo face Material.

It addition, be at 6.5 °, 7.1 ° and 21.8 ° by the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction The AZOpigments shown in formula (1) with characteristic X-ray diffraction maximum is referred to as alpha type crystal form AZOpigments, will be special at CuK α Bragg angle (2 θ ± 0.2 °) in property X-ray diffraction is to have characteristic X-ray diffraction maximum at 6.3 °, 6.4 ° and 22.3 ° AZOpigments shown in formula (1) is referred to as β type crystal habit AZOpigments, by the Bragg angle in CuK α characteristic X-ray diffraction (2 θ ± 0.2 °) is that the AZOpigments shown in formula (1) at 4.9 °, 8.8 ° and 13.1 ° with characteristic X-ray diffraction maximum is referred to as ε Type crystal habit AZOpigments, by the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction be 6.6 °, 9.2 ° and The AZOpigments shown in formula (1) at 21.5 ° with characteristic X-ray diffraction maximum is referred to as ζ type crystal habit AZOpigments.

In the present invention, the X-ray diffraction of the azo-compound shown in above-mentioned formula (1) and AZOpigments measures can be according to Japan Industrial standard JISK0131(X returns analysis and analyzes logical), such as use powder X-ray diffraction determinator RINT2500(strain formula Commercial firm's Rigaku system) carry out.

Fig. 2 shows X-ray diffractogram, be 4.8 ° to the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction, The AZOpigments shown in formula (1) at 7.2 ° and 9.7 ° with characteristic X-ray diffraction maximum is described in detail.

［ AZOpigments ］

By shown in the AZOpigments such as following formula (1) that the manufacture method of the AZOpigments of the present invention manufactures.

Hereinafter, the azo-compound shown in formula (1) and the AZOpigments of the present invention are explained.Wherein, this azo face Material can be its salt, hydrate or solvate.

In pigment shown in formula (1), it is also possible to be crystallization to contain the hydrate of hydrone or containing solvent (such as first The alcohols such as alcohol, ethanol, 2-propanol, the tert-butyl alcohol, the ketone such as acetone, butanone or acetonitrile, dimethyl sulfoxide, dimethylformamide, The non-protonic solvents etc. such as dimethyl acetylamide, N-Methyl pyrrolidone, toluene) solvate.

It addition, about the pigment shown in formula (1), its tautomer (tautomer of such as azo-hydrazone or formula (4) Shown geometric isomer) it is also contained in the present invention in their formula.

Formula (4):

［ manufacture method of AZOpigments ］

In detail below the manufacture method of the present invention is illustrated.The manufacture method of the AZOpigments of the present invention is to non- Azo-compound shown in following formula (1), its salt, hydrate or the solvate of crystalloid carries out the following formula (1) of crystalline transformation The manufacture method of shown AZOpigments.

Crystalline transformation in the present invention represents transformation crystal habit, refers to the azo shown in amorphous above-mentioned formula (1) Compound, its salt, hydrate or solvate are transformed into the AZOpigments with particular crystal form.Side as crystalline transformation Method, can enumerate lyonium salt mill method, salt mill method, dry milling processes, solvent mill method (solvent milling), acid pasting (acid Etc. pasting) process, solvent heat treated, preferred solvent heat treated are ground.

(solvent heat treated)

In the present invention, solvent heat treated specifically refers in a solvent to the azo compounds shown in amorphous formula (1) Thing, its salt, hydrate or solvate carry out heated and stirred.

By solvent heat treated, crystalline transformation can be carried out efficiently.Such as, by amorphous azo-compound Solvate carry out heated and stirred, the AZOpigments of δ type crystal habit can be obtained.

In the present invention, preferably the azo-compound crystalline transformation shown in formula (1) is become in CuK α characteristic X-ray diffraction Bragg angle (2 θ ± 0.2 °) is the crystal habit at 4.8 °, 7.2 ° and 9.7 ° with characteristic X-ray diffraction maximum.

By making the δ type crystal habit AZOpigments with above-mentioned characteristic X-ray diffraction maximum, dispersibility improves, I.e., it is possible to be dispersed into target grain size at short notice.

Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction is to have feature at 4.8 °, 7.2 ° and 9.7 ° The crystal habit at property X-ray diffraction peak more preferably has characteristic X-ray at 4.8 °, 7.2 °, 9.7 °, 20.1 ° and 26.8 ° and spreads out Penetrate the crystal habit at peak.Wherein, most preferably 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and There is at 26.8 ° the crystal habit of characteristic X-ray diffraction maximum.

As the solvent that can use in the crystalline transformation of the present invention, it is possible to use water, organic acid, mineral acid, You Jirong Agent, preferably water and organic solvent.It addition, suppress the angle of crystal growth in time carrying out crystalline transformation, preferably carry out crystal The solvent that the dissolubility of the AZOpigments shown in formula (1) after transformation is low.As preferred solvent, water, methanol, second can be enumerated Alcohol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, dipropylene glycol, Acetic acid, propanoic acid, sulphuric acid or their mixed solvent, more preferably ethylene glycol, water, acetic acid, sulphuric acid or their mixed solvent, optimum Select ethylene glycol.

In solvent heat treated use solvent amount relative to the AZOpigments shown in formula (1) be preferably 1～100 times, More preferably 5～50 times, more preferably 8～30 times.When being more than 1 times, owing to can ensure that stirring, the most preferably.Separately Outward, when being less than 100 times, due to productivity ratio raising, economy, the most preferably.

The temperature of heated and stirred during solvent heat treated is different with the difference of the primary particle size size of desired pigment, It is preferably 15～150 DEG C, more preferably 20～120 DEG C, more preferably 20～100 DEG C.When being more than 15 DEG C, owing to occurring Crystalline transformation need not for a long time, is efficient.On the other hand, when being less than 150 DEG C, owing to AZOpigments can be suppressed (1) a part is decomposed, the most preferably.

Mixing time for crystalline transformation is not particularly limited, preferably 5～1500 minutes, more preferably 10～600 Minute, more preferably 30～300 minutes.When being more than 5 minutes, owing to can partly suppress amorphous position residual Stay, the most preferably.On the other hand, when being less than 1500 minutes, it is efficient, the most preferably.

Detailed to the manufacture method being supplied to the azo-compound shown in amorphous following formula (1) of crystalline transformation operation below Carefully illustrate.

The manufacture method of the azo-compound shown in formula (1) used in the crystalline transformation of the present invention preferably comprises following work Sequence: the operation of the amino-compound shown in (a) mixing diazotization agent and formula (2)；B () obtains by mixing in described operation (a) Product and formula (3) shown in coupling components carry out reacting, obtain and be dissolved with the following formula (1) generated by this reaction The operation of at least one of solution of shown azo-compound；And (c) mixes the solution and institute obtained in described operation (b) State the poor solvent of azo-compound, make the operation of the amorphous azo-compound partial crystallization shown in following formula (1).

The operation (a) of the present invention is described in detail.

In operation (a), by mixing diazotization agent and amino-compound, utilize the reaction of amino-compound and diazotization agent Induction diazonium compound.This reaction is preferably carried out in the medium containing acid.In this specification, will be containing this diazo compounds The solution of thing be referred to as " diazonium compound prepare liquid ".The mixed method of amino-compound, acid and diazotization agent there is no limit especially Fixed, but in the solution of amino-compound and acid, preferably add diazotization agent.Diazotization agent in operation (a) refers to ammonia Based compound induces into the material that diazonium compound is used, as long as having this effect then indefinite.As diazotization agent Typical example, nitrous acid ester (such as amyl nitrite) can be enumerated, nitrite (such as can enumerate sodium nitrite, nitrous Acid potassium), amyl nitrite, nitrosyl sulfuric acid, more preferably sodium nitrite, potassium nitrite, nitrosyl sulfuric acid, wherein from can be steady From the viewpoint of determining and preparing diazonium compound efficiently, particularly preferred nitrosyl sulfuric acid.

Even if the acid used in operation (a) refer to make formula (2) even if shown in amino-compound be completely dissolved dissolving The acid dissolved must also be able to less, be preferably capable of the acid making amino-compound be completely dissolved.Acid can use mineral acid and organic Acid, as mineral acid, can enumerate hydrochloric acid, phosphoric acid, sulphuric acid, preferably phosphoric acid, sulphuric acid, more preferably sulphuric acid.Organic acid can be enumerated Formic acid, acetic acid, propanoic acid, methanesulfonic acid, preferably acetic acid, propanoic acid, methanesulfonic acid, more preferably acetic acid, propanoic acid.It addition, these acid can It is used alone, it is possible to be used in mixed way.As mixed acid, can enumerate phosphoric acid/acetic acid, sulphuric acid/acetic acid, methanesulfonic acid/acetic acid, acetic acid/ Propanoic acid, preferably phosphoric acid/acetic acid, sulphuric acid/acetic acid, sulphuric acid/acetic acid/propanoic acid, acetic acid/propanoic acid, the most particularly preferably sulphuric acid/second Acid, acetic acid/propanoic acid.The mass ratio of these mixed acid is preferably 1/(0.1～20), more preferably 1/(0.5～10), the most excellent Elect 1/(1～10 as).

In operation (a) addition of acid relative to amino-compound be 1～100 times by quality ratio, more preferably 2～ 50 times, more preferably 3～25 times.When mass ratio is more than 1 times, the optimization of stirring property, can more reliably induce diazonium Compound.On the other hand, when mass ratio is below 100 times, productivity ratio improves, becomes economical.

It addition, the addition of the diazotization agent relative to amino-compound in operation (a) is 1.0～20 with molar ratio computing Again, more preferably 1.0～10 times, more preferably 1.0～5 times.By making diazotization agent relative to amino-compound to rub Your ratio is calculated as more than 1 times, it is possible to more reliably induce diazonium compound, by being less than 20 times, it is possible to suppression due to Side reaction and diazonium compound is decomposed.

In the diazotization agent of operation (a) with the mixing of amino-compound, preferably implement below 50 DEG C, more preferably 40 Implement below DEG C, further preferably implement below 30 DEG C.In the preparation of the diazo liquid more than 50 DEG C, diazotization agent is had to occur to divide The misgivings solved.The mixing time of inductive formation diazonium compound be preferably 0.3～10 hour, more preferably 0.5～5 hour, More preferably 1～3 hour.By making above-mentioned mixing time be more than 0.3 hour, it is easy to fully inductive formation diazonium Compound, by being less than 10 hours, diazonium compound is difficult to decompose.It addition, use common when mixing Blender, is not particularly limited.Although also relying on manufacture equipment, but the rotating speed preferably stirred be 30～300rpm, more preferably It is 40～200rpm, more preferably 50～200rpm.By making mixing speed be calculated as more than 30rpm, diazonium with rotating speed Compound is prepared the stirring efficiency of liquid and is become good, therefore can positively implement the carrying out of desired reaction.

As long as the diazonium compound that the solvent that can mix in operation (a) is induced is not decomposed, then it is not particularly limited. As the solvent that can mix, such as, can enumerate the hydrocarbon system solvents such as hexane, benzene, toluene, the ether such as Anaesthetie Ether, oxolane system is molten Agent, the ketone series solvent such as acetone, butanone, dimethylformamide, dimethyl acetylamide, ketopyrrolidine, METHYLPYRROLIDONE Deng amide series solvent, other can enumerate dimethyl sulfoxide, sulfolane, acetonitrile, water.

Diazonium compound in operation (a) prepare the preferred pH of liquid be preferably less than 7, more preferably less than 5, further It is preferably less than 3.When the diazonium compound in operation (a) prepares the pH of liquid more than 7, the diazo compounds that can have induced The misgivings that thing is decomposed.

Then, the operation (b) of the present invention is explained.

Operation (b) is to be reacted by product and the coupling components of gained in the described operation (a) of mixing, it is thus achieved that It is dissolved with the operation of at least one of solution of the azo-compound shown in the formula (1) generated by this reaction.

In this specification, at least one of solution being dissolved with this azo-compound is referred to as " azo-compound dissolving Liquid ".

As the preparation method of azo-compound lysate, following methods can be enumerated: (i) obtain by mixed processes (a) The product and the coupling components that obtain carry out coupling reaction, and the result of reaction is to make the separated out azo face shown in formula (1) Material can be dissolved in the method for solvent；And (ii) in order to make the compound shown in the formula (1) obtained by above-mentioned coupling reaction It is dissolved in reactant liquor at least partially, implements this coupling reaction, this reactant liquor is directly prepared into the side of azo-compound lysate Method；Or make operation (c) that the azo-compound lysate so obtained is applied to be detailed below and to obtain (through partial crystallization) even Nitrogen pigment, so that the method that this AZOpigments is further able to be dissolved in solvent.

In aforesaid way (i) and (ii) any one, the diazonium compound obtained in operation (a) prepares liquid and coupling The mixed method of composition is not particularly limited, and is preferably carried out according to the mode being partly or entirely dissolved in solvent by this coupling components Add or do not use solvent to be added with solid forms, more preferably the solution of coupling components being made an addition in operation (a) The diazonium compound obtained is prepared in liquid or coupling components makes an addition to solid forms the diazonium obtained in operation (a) Compound is prepared in liquid.

It addition, about the diazonium compound obtained in described operation (a) prepare diazonium compound in liquid relative to The amount of the coupling components in operation (b), is preferably 0.8～3 equivalents relative to the coupling position of coupling components, more preferably relative to idol Connection position is 0.9～2 equivalents, is further preferably 0.95～1.5 equivalents relative to coupling position.More than for 0.8 equivalent, permissible Suppression has the coupling components residual of unreacted coupling position, below for 3 equivalents, owing to can suppress unreacted diazonium Compound remains, the most economical.

Wherein, aforesaid way (ii) in, due at least one of the azo-compound shown in formula (1) in operation (b) Dividing and dissolve, therefore coupling reaction is the most successfully carried out, it is possible to manufacture the azo-compound of higher purity.Its reason speculates such as Under.Described formula (3), therefore can be in the middle of the most only 1 reaction that coupling position reacts owing to having more than 2 coupling positions Body.When this reaction intermediate separates out in reaction system, the response speed of the 2nd later coupling reaction is slack-off.On the other hand, Owing to diazonium compound is unstable, therefore when, when long-time, having the misgivings decomposed.It is therefore important that make idol Connection reaction is carried out as soon as possible, and the result not generating the aforesaid way of precipitate manufacture method (ii) in operation (b) is to be more suitable for Manufacture highly purified pigment.

Operation (b) also can not use solvent directly add coupling components, but also can add after mixing with solvent Add, but be preferably added in the case of not using solvent.In operation (b), though when coupling components uses solvent without especially Limit, but preferably according to becoming aforesaid way (ii), i.e. preferably can obtain the described formula (1) generated after being dissolved with reaction The solvent of at least one of solution of shown azo-compound.

Aforesaid way (i) in the case of, i.e. make pigment separate out in the case of, as the example of solvent, it is possible to use Water, organic acid, mineral acid, organic solvent, particularly preferred water, organic solvent, preferably do not cause liquid segregation phenomenon when reaction And present the solvent of uniform solution with solvent.Such as can enumerate water, methanol, ethanol, propanol, isopropanol, butanol, the tert-butyl alcohol, The alcohol organic solvents such as amylalcohol, the ketone such as acetone, butanone system organic solvent, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, The glycol such as dipropylene glycol, 1,3-PD system organic solvent, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl The ether system organic solvents such as base ether, oxolane, dioxane, acetonitrile etc., these solvents can also is that mixed liquor of more than two kinds.

The preferably organic solvent that value is more than 40 of polarity parameters (ET).Wherein, preferred solvent molecule has 2 with The glycol series solvent of upper hydroxyl or alcohol series solvent that carbon number is less than 3, total carbon atom number be less than 5 ketone system molten The ketone series solvent that alcoholic solvent (such as methanol, ethylene glycol) that agent, preferably carbon number are less than 2, total carbon atom number are less than 4 (such as acetone, butanone).It addition, also comprise their mixed solvent.

It addition, aforesaid way (ii) in the case of, i.e. the most molten according to the compound shown in formula (1) Solution is in the case of the mode of reactant liquor carries out coupling reaction, as the example of solvent, can enumerate water, methanol, isopropanol, second two The alcohol series solvents such as alcohol, the ketone series solvent such as acetone, butanone, the organic acid solvent such as acetic acid, propanoic acid, methanesulfonic acid, sulphuric acid, hydrochloric acid, phosphorus The mineral acid solvents such as acid, the amide system such as dimethylformamide, dimethyl acetylamide, ketopyrrolidine, METHYLPYRROLIDONE is molten Agent, other can enumerate dimethyl sulfoxide, sulfolane, acetonitrile.Wherein, the preferably ketone such as acetone, butanone series solvent, acetic acid, propanoic acid, The organic acid solvents such as methanesulfonic acid, mineral acid solvent, more preferably organic acid or the mineral acid acid flux material such as sulphuric acid, hydrochloric acid, phosphoric acid, Preferably acetic acid, methanesulfonic acid, phosphoric acid, sulphuric acid.It is also preferable to the mixed solvent of solvent shown in above-mentioned.

Aforesaid way (ii) in the case of, particularly preferably in operation (b), will make coupling components dissolve or be suspended in acid Property solvent acid solution and operation (a) in the product that obtains mix or general in the case of not using solvent Coupling components makes an addition in the product obtained in operation (a).Acid flux material is particularly preferably containing in acetic acid and sulphuric acid The solvent of at least one.

In aforesaid way (i) and (ii) any one, relative to the addition of preferred solvent of coupling components with mass ratio Meter is preferably 0.5～200 times, more preferably 1～100 times, more preferably 1～50 times.As relative to coupling components The addition of preferred solvent amount, when by quality ratio less than 0.5 times, the stirring in manufacture machine of coupling components and solvent becomes Reaction difficult, desired will not be carried out.It addition, when more than 200 times, can become uneconomical.

The preparation method of azo-compound lysate is when for aforesaid way (i), or (ii) and makes for aforesaid way At least one of coupling reaction liquid being dissolved with compound shown in formula (1) is applied to operation (c) and obtains AZOpigments, make When this AZOpigments is further dissolved in solvent preparing azo-compound lysate, as being used for dissolving gained AZOpigments Solvent, as long as at least some of of AZOpigments can be dissolved, be then not particularly limited, can similarly enumerate at aforesaid way (ii) the solvent recorded as the example of preferred solvent in.

No matter take aforesaid way which kind of operation (i), (ii), as the azo compounds obtained final in operation (b) Thing lysate is preferably acid solution, particularly preferably containing the solution of at least one in acetic acid and sulphuric acid.

As the azo-compound lysate obtained in operation (b), it is dissolved in shown in the formula (1) of azo-compound lysate The total amount of azo-compound and the azo-compound generated by operation (b) (be dissolved in the formula in azo-compound lysate (1) azo-compound shown in and the summation of AZOpigments shown in formula (1) separated out from azo-compound lysate) ratio It is preferably more than more than more than 50 mass %, more preferably 75 mass %, more preferably 90 mass %, most preferably 100 matter Amount %(is dissolved completely in the state of reactant liquor by the azo-compound that operation (b) generates), thus have and can reduce face further The tendency of the particle diameter of material.

Diazonium compound about the operation (a) in operation (b) prepares the mixing temperature of liquid and coupling components, preferably exists Less than 50 DEG C enforcements, more preferably enforcement below 30 DEG C, further preferably enforcements below 25 DEG C.During more than 50 DEG C, have work The misgivings that in sequence (a), the diazonium compound of induction and the azo-compound shown in formula (1) of generation are decomposed.It addition, Mixing uses common blender, is not particularly limited.Although also relying on manufacture equipment, but preferably speed of agitator is preferred It is 30～300rpm, more preferably 40～200rpm, more preferably 50～200rpm.Mixing speed is less than with tachometer During 30rpm, the stirring efficiency of mixed liquor is deteriorated, and has the misgivings that desired reaction is difficult to.The mixing time of operation (b) It is preferably 0.1～10 hour, more preferably 0.3～5 hour, more preferably 0.3～3 hour.Little less than 0.1 constantly, difficult With fully inductive formation pigment, little more than 10 constantly, then have the misgivings that the azo-compound shown in formula (1) is decomposed.

Then, to operation (c) the explanation details that the present invention relates to.

Operation (c) is the dissolubility by the azo-compound lysate obtained in described operation (b) and this azo-compound Low poor solvent mixing, makes the operation of pigment partial crystallization.The azo-compound lysate obtained in operation (b) and poor solvent Mixed method is not particularly limited, and is preferably added to poor solvent by the azo-compound lysate obtained in operation (b), this Shi Youxuan poor solvent is the state stirred.

Mixing speed is preferably 100～10000rpm, more preferably 150～8000rpm, particularly preferably 200～ 6000rpm.Pump etc. is it be also possible to use during interpolation.At this point it is possible to be that to add in liquid can also be to add outside liquid, but more preferably liquid adds Add.Furthermore it is preferred that utilize pump to be continuously fed in liquid via supply pipe.

Poor solvent is not particularly limited, and the preferably dissolubility of azo-compound is below 1g/L, more preferably 0.1g/L Below.Dissolubility when this dissolubility can be to make it dissolve in the presence of acids and bases.About the azo obtained in operation (b) The good solvent of compound dissolution liquid and the compatibility of poor solvent or uniform Combination, preferably this azo-compound is not relative to The meltage of good solvent is more than more than 30 mass %, more preferably 50 mass %.In this specification, when dissolubility refers to 25 DEG C Dissolubility.

As poor solvent, such as, can enumerate the aqueous solvents such as water, hydrochloric acid, ammonia, sodium hydrate aqueous solution, methanol, second The alcohol series solvents such as alcohol, isopropanol, 1-methoxy-2-propanol, the glycol series solvent such as ethylene glycol, diethylene glycol, acetone, butanone, The ketonic compound solvent such as methylisobutylketone, Ketohexamethylene, the ether series solvent such as Anaesthetie Ether, oxolane, the hydrocarbon such as hexane, benzene, toluene Series solvent, the nitrile series solvent such as acetonitrile, the halogen series solvent such as dichloromethane, trichloro ethylene, ethyl acetate, ethyl lactate, 2-(1-first Epoxide) aqueous solvents such as ester series solvent etc., preferably water, hydrochloric acid, ammonia, sodium hydrate aqueous solution such as propyl-acetic acid ester, methanol, second The alcohol series solvents such as alcohol, isopropanol, 1-methoxy-2-propanol, the glycol series solvent such as ethylene glycol, diethylene glycol, acetone, butanone, The ketonic compound solvent such as methylisobutylketone, Ketohexamethylene, the more preferably aqueous solvent such as water, ammonia, carbon number be 1～3 alcohol molten Agent, carbon number are the glycol series solvent of 1～6.It is also preferable to the mixed solvent of solvent shown in above-mentioned.Most preferably it is selected from More than a kind solvent in the group being made up of the glycol that water and alcohol that carbon number is 1～3, carbon number are 1～6.

The azo-compound lysate obtained in operation (b) is preferably 1/50 with the mixing ratio of poor solvent with volume basis ～2/3, more preferably 1/40～1/2, particularly preferably 1/20～1/2.When being less than 2/3 with volume basis, the crystalline substance of pigment Analysis occurs fully, reaction yield improves, and when volume ratio is more than 1/50, productivity ratio improves, becomes economical.

The azo-compound lysate obtained in operation (b) is not particularly limited, preferably with the mixing temperature of poor solvent Implement at-10～50 DEG C, more preferably implement at-5～30 DEG C, most preferably implement at 10～25 DEG C.

When the azo-compound lysate obtained in operation (b) mixes with poor solvent, by regulation Reynolds number, permissible Control to separate out the particle diameter of the organic nano particle generated.Here, Reynolds number is the dimensionless group of the flow regime representing fluid, Represent with following formula.

Mathematical expression (1): Re=ρ UL/ μ

(in mathematical expression (1), Re represent Reynolds number, ρ represent the azo-compound lysate obtained in operation (b) density kg/m³, U represent that the relative velocity ［ m/s ］ when azo-compound lysate meets with poor solvent, L represent that azo-compound is molten Solve the stream of liquid and poor solvent encountering portion or the supply equivalent diameter ［ m ］ of mouth, μ represents the viscosity of azo-compound lysate Coefficient ［ Pa s ］.)

Equivalent diameter L refers to the opening footpath when the pipe arrangement relative to Arbitrary Shape Cross Section or stream, it is assumed that pipe of equal value Time, the diameter of this equivalence pipe.When the sectional area of pipe arrangement being designated as A, by outside the wet periphery (perimeter) length (girth) of pipe arrangement or stream During Zhou Jiwei p, equivalent diameter L following mathematical expression (2) represents.

Mathematical expression (2): L=4A/p

Relative velocity U when azo-compound lysate meets with the poor solvent face relative to both encountering portion is The relative velocity of vertical direction is defined.In static poor solvent, i.e., such as inject azo-compound lysate carry out During mixing, supply mouth the speed injected becomes equal with relative velocity U.The value of relative velocity U is not particularly limited, the most excellent Elect 0.5～100m/s, more preferably 1.0～50m/s as.

The density p of azo-compound lysate is the value that the kind according to selected material defines, the most actually It is 0.8～2.0kg/m³.It addition, for the viscosity μ of azo-compound lysate, be also by material therefor or environment The value that temperature etc. are defined, the most preferably 0.5～100mPa s, more preferably 1.0～50.0mPa s.

The value of Reynolds number is the least, is the most more easily formed laminar flow, the biggest, is the most more easily formed sinuous flow.Such as, by Reynolds number is adjusted Joint is to more than 60, it is also possible to the particle diameter of control pigment nanoparticle, and preferably more than 100, more preferably more than 150.Reynolds number There is no the special upper limit, such as, by being adjusted controlling in the scope below 100000, controllably obtain and have The pigment particles of desired mean diameter.Now, within the above range, generally by improving Reynolds number, controllably obtain The pigment particles that particle diameter is less.

When utilizing 1 particle that transmission-type microscope observes the pigment particles obtained by manufacture method of the present invention, major axis The length in direction is preferably 1nm～1 μm, more preferably 5～500nm, more preferably 10～200nm, is particularly preferably 10 ～100nm.

Wherein, about the particle diameter of pigment particles, have and utilize measurement method to obtain numerical value to state the side of the mean size of collective Method, but the middle position of the commonly used median having the mode particle size representing distribution maximum, being equivalent to integral distribution curve is straight Footpath, various average diameter (number is all, length is average, area is average, quality is average, volume averagely etc.) etc., if nothing in the present invention Be particularly limited to, then mean diameter refers to number average bead diameter.

As the assay method of the particle diameter of pigment particles, can enumerate microscopic method, mass method, light scattering method, light blocked method, Electric-resistivity method, sound equipment method, dynamic light scattering method, particularly preferred microscopic method, dynamic light scattering method.As what microscopic method used Microscope, such as, can enumerate scanning electron microscope, transmission electron microscope etc..As the grain utilizing dynamic light scattering method Sub-determinator, such as, can enumerate Ji Zhuan company Nano Trak UPA-EX150, big electronics corporation Dynamic light Light-scattering photometer DLS-7000 series etc..

The preferred mean diameter of above-mentioned pigment particles is by the temperature in suitably regulation (1) operation (c), (2) azo compounds Thing dissolubility in poor solvent and (3) mixing speed (or Reynolds number) realize.

When making pigment particle separate out, preparing dispersion liquid, also can in azo-compound lysate and poor solvent extremely Containing dispersant in few one.Now, in azo-compound lysate, dispersant is preferably contained.Dispersant has following work With: (1) is adsorbed in the surface of pigments of precipitation rapidly, forms fine nanoparticle, and (2) prevent these particles from again coagulating Poly-.

As dispersant, such as can use anionic property, cationic, two ionic, the low molecule of nonionic or Macromolecule dispersing agent.

As macromolecule dispersing agent, preferably its matter average molecular weight be 1000～500000, more preferably 10000～ 500000, particularly preferably 10000～100000.

Specifically can enumerate polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, Polyethylene Glycol, polypropylene glycol, Polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-part formaldehyde compound, polyvinyl alcohol-part butyraldehyde Thing, vinylpyrrolidone-vinyl acetate copolymer, polyethylene glycol oxide/oxypropylene block copolymer, polyacrylate, poly- Vinyl sulfate, P4VP salt, polyamide, polyallyl amine salt, condensation naphthalene sulfonate, cellulose derive Thing, starch derivatives etc..It addition, it be also possible to use alginate, gelatin, albumin, casein, arabic gum, Tragacanth, wooden The natural polymer subclasses such as element sulfonate.Wherein, preferably polyethylene ketopyrrolidine.These macromolecular compounds can be used alone a kind Or it is applied in combination two or more, the dispersant that use low-molecular-weight additionally be can also be combined.About dividing of using in the dispersion of pigment Powder, " material dispersion stabilization と surface reason skill " (chemistry feelings meeting, calendar year 2001 December row) 29 ～page 46 are documented.

As anionic property dispersant (anionic surfactant), N-acyl-N-alkyltaurate, fat can be enumerated Fat hydrochlorate, alkyl sulfate salt, alkylbenzenesulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinates, alkyl phosphate Salt, naphthalene sulfonic acid-formaldehyde condensation product, polyoxyethylene alkyl sulfate salt etc..Wherein, preferably N-acyl-N-alkyltaurate.Make For N-acyl-N-alkyltaurate, the preferably material described in Japanese Unexamined Patent Publication 3-273067 description.These aniones Property dispersant can be used alone or be applied in combination two or more.

Cationic dispersant (cationic surfactant) comprises quaternary ammonium salt, alkoxylated polyamines, aliphatic amine Polyglycol ether, aliphatic amine, by the derivative diamidogen of aliphatic amine and aliphatic alcohol and polyamine, by fatty acid derived imidazoline and The salt of these cationic substance.These cationic dispersants can be used alone or be applied in combination two or more.

Two ionic dispersants be intramolecular have simultaneously the moon that described anionic property dispersant has in intramolecular from The dispersant of the cation base section that subbase part and cationic dispersant have in intramolecular.

As nonionic dispersant (nonionic surfactant), polyoxyethylene alkyl ether, polyoxyethylene can be enumerated Alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly- Oxygen vinyl alkyl amine, fatty acid glyceride etc..Wherein, preferred polyoxyethylene alkylaryl ether.These nonionic dispersants can It is used singly or in combination two or more.

The content of dispersant is preferably the scope of 0.1～1000 mass parts relative to pigment 100 mass parts, is more preferably 1 ～500 scopes of mass parts, the scope of more preferably 5～200 mass parts.It addition, dispersant can be used alone, it is possible to group Close use multiple.

In the manufacture method of the pigment of the present invention, the product obtained by above-mentioned operation (a)～(c) is according to usual organic conjunction After the post-processing approach becoming reaction processes, it is supplied to below in the case of or can not carrying out refining after carrying out refining Crystalline transformation operation.

I.e., such as can material free from reaction system is not carried out refined in the case of or individually or group Close after carrying out utilizing recrystallization, one-tenth salt etc. to carry out the operation refined, supply.

Furthermore it is also possible to after the completion of reaction, reaction dissolvent is distilled off or is not carrying out situation about being distilled off Under be directly injected in water or ice, be neutralized or be not neutralized ground, to free material or use organic solvent/water The material that solution extracting obtains does not carries out refined or carries out alone or in combination utilizing recrystallization, partial crystallization, one-tenth salt etc. to refine Operation, then supply.

The noncrystalline azo-compound obtained in operation (c) can also be by azo-compound not hanging from azo-compound Crystalline transformation is directly carried out, it is possible to after taking-up, carry out crystalline transformation in the case of supernatant liquid takes out.

When the solid obtained in operation (c) is not noncrystalline, can by azo-compound is dissolved in good solvent, with The poor solvent that can obtain amorphous solid mixes, thus obtains amorphous azo-compound.

Then, to the pigment particles obtained by the manufacture method of the present invention, i.e. above method is passed through from amorphous idol The AZOpigments shown in formula (1) that nitrogen compound carries out crystalline transformation and obtains is illustrated.

The volume average particle size of the pigment particles obtained by the manufacture method of the present invention is preferably 1nm～10 μm, more excellent Elect 5nm～5 μm, more preferably 10nm～1 μm, particularly preferably 10～500nm as.

Wherein, the volume average particle size of pigment particles refers to itself particle diameter of pigment, or at additives such as dispersants In the case of being attached on colorant, refer to be attached with the particle diameter of additive.In the present invention, the volume average particle size of pigment particles Determinator can use Nano Trak UPA grain size analysis meter (UPA-EX150；Ji Zhuan company system).Its mensuration can be as follows Carry out: pigment dispersion 3ml is encased in cell, carry out according to the assay method of regulation.Wherein, as input when measuring Parameter, viscosity use ink viscosity, dispersed particle density use pigment density.

The preferred volume mean diameter of above-mentioned pigment particles can be by shown in the formula (1) after using already described crystalline transformation The dissolubility of AZOpigments low solvent suppression crystal growth or suitably adjust the temperature of crystalline transformation when carrying out crystalline transformation Degree, time, quantity of solvent realize.

From the viewpoint of becoming more preferably from the dispersibility making pigment, further improving tinting strength, tinting power, preferably following formula (1) institute The BET specific surface area utilizing nitrogen adsorption method to record of the δ type crystal habit AZOpigments shown is 50m²/ more than g, particularly preferably 60m²/ more than g.

Here, the BET specific surface area utilizing nitrogen adsorption method to record be instigate nitrogen adsorption in powder particle, to try to achieve absorption flat Adsorption equilibrium pressure under weighing apparatus state, the specific surface area tried to achieve by the relational expression calculating monolayer adsorption amount of BET.Utilize nitrogen The BET specific surface area that absorption method records can be according to " 1 method of regulation in the adnexa 2 of such as Japanese Industrial Standards JIS Z8830 To I Ru body sorption amount determines method " it is measured.Specifically, can be by using specific area measuring device " MONOSORBMS-17 " (Yuasa Ionics Co., Ltd. system) etc. is measured.

By making the BET specific surface area utilizing nitrogen adsorption method to record be above-mentioned scope, the primary particle of pigment is by fully Miniaturization, even under the state of miniaturization, the δ type crystal habit AZOpigments shown in formula (1) also can not reduce resistance to In the case of photosensitiveness, dispersibility and tinting strength, tinting power improve further.

The BET specific surface area utilizing nitrogen adsorption method to record is 50m²During/more than g, the δ type crystal shape shown in following formula (1) State AZOpigments preferably can be manufactured by the operation comprising lyonium salt described later mill method.

Post processing also can be carried out as required by the AZOpigments shown in the formula (1) that the method for the present invention manufactures.As The method of this post processing, such as, can enumerate and utilize lyonium salt mill method, salt mill method, dry milling processes, solvent mill method, acid is molten etc. grinds place The pigment particles of reason, solvent heat treated etc. controls operation, utilizes the surface science and engineering of resin, surfactant and dispersant etc. Sequence.

It addition, the compound shown in the formula of the present invention (1) preferably carries out lyonium salt mill method as post processing.

(lyonium salt mill method)

As lyonium salt grind method, such as can enumerate by containing AZOpigments (the most sometimes by the azo face before mixing grinding Material is referred to as " thick AZOpigments "), inorganic salt and its mixture of organic solvent insoluble load in muller, carry out wherein Mixing grind.As above-mentioned inorganic salt, preferably use water-soluble inorganic salt, such as, sodium chloride, potassium chloride, sulphuric acid are preferably used The inorganic salt such as sodium, potassium sulfate.It addition, the particle diameter as described water-soluble inorganic salt is not particularly limited, from controlling AZOpigments 2 agglomerates particle diameter from the viewpoint of, the particle diameter of water-soluble inorganic salt in terms of the median diameter of volume reference be preferably 0.5 ～50 μm, more preferably 1～20 μm, more preferably 1～10 μm.The consumption of this inorganic salt is permissible relative to thick AZOpigments It is 1～30 mass times, from the viewpoint of productivity ratio, preferably 3～20 mass times, more preferably 5～15 mass times.As having Machine solvent, preferably uses water-miscible organic solvent, owing to temperature rising time mixing, solvent are in the state being prone to evaporate, Therefore from the preferred high boiling solvent of the angle of safety.As this organic solvent, such as, can enumerate diethylene glycol, sweet Oil, ethylene glycol, propylene glycol, liquid macrogol, liquid polypropylene glycol, 2-(methoxymethoxy) ethanol, butoxy ethanol, 2 (isoamoxy) ethanol, 2-(hexyloxy) ethanol, diethylene glycol monomethyl ether, TC, diethylene glycol list Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethyoxyl-2-propanol, dipropylene glycol, two Propylene glycol monomethyl ether, DPGME, dipropylene glycol or their mixture.It addition, as other water solublity Organic solvent, will also be preferred 1 yuan of alcohol series solvent such as propanol, 2-butanol, the tert-butyl alcohol.The consumption phase of this water-miscible organic solvent 0.1～5 mass times, more preferably 2～3 mass times are preferably for thick AZOpigments.Melting temperature be preferably 20～130 DEG C, Particularly preferably 40～110 DEG C.As mixing roll, such as, can use kneader or mixer-mill etc., specifically can use and pinch Batch-type mixing roll, super mixer (Co., Ltd.'s KAWATA system) or Trimix(Inoue MFG. Inc. systems such as conjunction machine) Etc. batch-type mixing roll, continuous way list extruders KCK mill(Asada Iron Works Co., Ltd. system) etc. continuous way mixing roll.

As described continuous way mixing roll, such as preferably its grind that part has can be using required for mixing dispersion The compression of key element, shear, (displacement) these 3 effects that mix are given to fixing blade and the rotating blade of thick pigment.It addition, it is described Fixing blade forms gap (gap) with the projection of rotating blade with projection, and shear action occurs in this gap, the most described rotation Material between the depression of blade and fixing blade is preferably mutually cut (cavity slice) by die cavity.

The shape of described fixing blade and rotating blade is not particularly limited, and is preferably respectively selected from chrysanthemum type, fan and mortar shape These 3 kinds of type.Preferably by the most multistage to fixing blade and rotating blade overlap, thus can be on the two sides of each blade with radiation Shape forms die cavity.Additionally, it is preferred that rotating blade and middle bolt are alternately assembled on the rotary shaft, fixing blade and fluid shear chamber Cylinder alternately passes through pull bar and is fixed on feed cylinder, from there through fixing blade and rotating blade and the combination of bolt, and can So that mixing thing is extruded.

Additionally, continuous way mixing roll preferably at the throw-in part of mixture, grind portion and extrusion portion have the temperature at least 6 places Degree regulation portion.Thus, it is possible to set the temperature range grinding operation of thick AZOpigments in a wide range.

It is not particularly limited as the described treatment temperature grinding operation, such as, can be 5～200 DEG C, from AZOpigments From the viewpoint of the variable color of particle, particle size distribution, preferably 5～50 DEG C, more preferably 10～35 DEG C.

It addition, described continuous mixer preferably can pass through thick AZOpigments, water-soluble inorganic salt and water-miscible organic solvent Mixed proportion or screw speed change discharge-amount.By changing discharge-amount, can by AZOpigments to grind particle diameter easy Ground controls as desired particle diameter.

The manufacture method of the AZOpigments triturate of the present invention except described grind operation in addition to, also can possess as required Other operation.As other operation, such as, can enumerate the described mixture after grinding operation and put in water etc. and carry out After stirring, by filtration etc., AZOpigments triturate is separated, thus water-soluble inorganic salt and water-miscible organic solvent are removed Washing procedure, the drying process etc. that the AZOpigments triturate obtained by described washing procedure is dried.

These washing procedures and drying process can be applied in the present invention without particular limitation at so-called lyonium salt Commonly used approach in mill method.

As the particle diameter of 1 particle of AZOpigments triturate of the present invention, preferably below 80nm, more preferably 30～ 50nm.It addition, the particle diameter of 2 particles as 1 particle coacervation, preferably below 120nm, more preferably 60～ 100nm。

1 particle of described AZOpigments triturate and the particle diameter of 2 particles use transmission electron microscope (TEM) to survey Fixed.

The invention still further relates to the manufacture method of AZOpigments or its tautomer, it is the azo shown in following formula (1) The manufacture method of pigment, it is characterised in that by the azo-compound shown in amorphous following formula (1), its salt, hydrate or molten Agent solvate crystal be transformed into the Bragg angle (2 θ ± 0.2 °) at CuK α characteristic X-ray diffraction be (a) 4.8 °, 7.2 ° and 9.7 °, (b) 4.8 °, 7.2 °, 9.7 °, 20.1 ° and 26.8 ° or (c) 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, Having the crystal formation of characteristic X-ray diffraction maximum at 20.1 ° and 26.8 °, it comprises following operation: (i) by amorphous described formula Azo-compound crystalline transformation shown in (1) becomes the Bragg angle (2 θ ± 0.2 °) at CuK α characteristic X-ray diffraction to be 4.8 °, There is at 7.2 ° and 9.7 ° the operation of the crystal formation of characteristic X-ray diffraction maximum；And (ii) to containing the (i) middle acquisition of described operation The mixture of AZOpigments, water-soluble inorganic salt and water-miscible organic solvent carries out mixing, and making specific surface area is 50m²/ g with On the operation of crystal.

It is used as material same as described above, preferably scope as above-mentioned water-soluble inorganic salt and water-miscible organic solvent Too.The mixing roll of mixing middle use is used as muller same as described above.

(water system) pigment dispersion of the present invention at least contains AZOpigments, the dispersant obtained by described manufacture method And water.Described dispersant at random can select, from printed article from low molecule and macromolecule and then water solublity and water-insoluble Image quality from the viewpoint of, preferably macromolecule.Additionally, due to disperse in water system, therefore stable from dispersibility, dispersion From the viewpoint of property, preferably water solublity.In the present invention, dispersant is particularly preferably water soluble polymer.

It addition, " dispersant " also means that the state utilizing cross-linking agent to be cross-linked in the present invention.The pigment of the present invention In dispersion, preferably make this dispersant adsorption on pigment.

Dispersant is owing to having the effect that electrical charge rejection is brought in the molecule, therefore from the storage stability of dispersion Viewpoint is set out, and preferably has more than 1, the carboxyl of more preferably more than 10.When cross-linking agent has 2 epoxy radicals, owing to passing through Cross-linking reaction, epoxy radicals crosslink with carboxyl, and carboxyl reduces, and therefore polymer preferably has the carboxyl of more than 10.

Carboxyl in polymer can be the form of acid (-COOH), can also be the form of salt.As salt, such as, can lift Go out metal ion, ammonium, replacement ammonium, quaternary ammonium or pyridiniujm etc..Metal ion, ammonium, more preferably potassium ion, sodium ion.

The macromolecule dispersing agent of the present invention contains polyurethane, polyester, polyvinyl compound, more preferably polyurethane, poly- Ester, polyvinyl compound, most preferably polyvinyl compound (polyvinyl).The present invention can also combine 2 kinds with On polymer.

Carboxyl importing in polymer can be obtained by the copolymerization of the monomer containing at least 1 carboxyl.The most poly- In vinyl compound, use itaconic acid, maleic acid, fumaric acid .beta.-methylacrylic acid, methacrylic acid, acrylic acid, β-carboxylic as monomer Base ethyl propylene acid esters, is preferably used methacrylic acid, acrylic acid, β-carboxyethyl acrylate.

First carboxyl in polymer has and carries out, with the crosslinkable groups in cross-linking agent, the effect that cross-links.As bridging property Group, can enumerate anhydride, epoxy radicals, particularly preferred epoxy radicals.Its reason is, due to reactive high, and therefore can be in gentleness Under conditions of cross-link.Additionally, unreacted carboxyl groups for final microgranule dispersion to sedimentation and cohesion stability be effective 's.Carboxyl is effective as stability group in polar solvent, particularly aqueous solvent.When carboxyl is in pigment dispersion When contributing to unique group of stability, if all of carboxyl and cross-linking agent there occurs crosslinking, then the stability of dispersion is bright Aobvious reduction.Therefore, in order to after cross-linking reaction terminates, remain unreacted carboxyl groups, preferably with respect to epoxy radicals, carboxyl mole Number excess, makes carboxyl as 30:1 relative to epoxy radicals with molar ratio computing～1.1:1, more preferably 25:1～1.1:1, particularly preferably For 20:1～2:1.

Polymer also can have other stability group.Selection and the amount thereof of stability group are heavily dependent on solvent Character.Stability group substantially rely on solvent be hydrophilic (such as polar solvent) or hydrophobicity (the most nonpolarity Solvent).

Preferably polymeric dispersant can be obtained by hydrophilic monomer, both hydrophobic monomers.

Hydrophilic monomer is containing the hydrophilic monomer as ionic group or nonionic group.Ionic group Can be cation, but preferably anion.It is stable that cationic groups, anionic property group all can give both sexes to dispersant Property (amphoteric stabilisation).Preferably anionic property group is phenoxy group, sulfonic acid, sulphuric acid, phosphonic acids, poly-phosphorus Acid, the group (can also be salt) of phosphoric acid.Preferably cationic groups is quaternary ammonium, benzalkonium, guanidine, biguanide and pyridine.It Can be with the form being the salt such as hydroxide, sulfate, nitrate, chloride, bromide, iodide and fluoride.Preferably Nonionic group is glycoside, saccharide, ketopyrrolidine, acrylamide and particularly hydroxyl and poly-(oxyalkylene) base, more excellent Select poly-(ethylene oxide) base or poly-(propylene oxide) base, particularly-(CH₂CH₂O)_nH or-(CH₂CH₂O)_nC_1-4-Alkyl.Here, n Represent that 3～200(are preferably 4～20).Hereinafter, such as C_1-4-Statement represent " carbon number is 1～4 ".Polymer can To contain only nonionic group, in terms of polymer entirety containing multiple nonionic groups or containing containing nonionic base The polymer chain of more than 1 of group.Hydroxyl uses polyvinyl alcohol, the acrylic resin of poly-hydroxyl functional and cellulose to insert Enter.Ethyleneoxy uses the polymer chains such as polyethylene glycol oxide to insert.

Hydrophobic monomer is the monomer containing hydrophobic group.Have the typical example of hydrophobic group be have less than 3, The preferably hydro carbons of 0 hydrophilic radical, fluorocarbon class, poly-C_3-4Oxidation alkenes and alkylsiloxane class.Hydrophobic group is excellent Elect C as_3-50Chain or can have propylene oxide in hydrophobic monomer as side chain or straight chain.

Polymer can also is that homopolymer, preferably copolymer.Polymer includes atactic polymer, and (the shortest is embedding Section or segment), but preferably include graft polymers (long block or segment).It addition, polymer can also is that alternately (alternating) polymer.Polymer can also is that side chain, but preferably straight chain.Polymer can also have 2 with On segment (such as block and grafting, copolymer), but the most random.

In mode when polymer has more than 2 segments, preferably at least 1 segment is hydrophobicity, at least 1 segment For mutual related hydrophilic.Make the method for optimizing of hydrophobicity and hydrophilic segment respectively by hydrophobicity and hydrophilic list The copolymerization of body is carried out.When polymer is for having at least 1 hydrophobic chain segment and at least 1 hydrophilic segment, carboxyl can position In hydrophobic chain segment, hydrophilic segment can also be positioned at, may be located on both segments.

Polyvinyl (polyvinyl compound) can be by any suitable means manufacture.Polyvinyl Preferable production process is to use the trip of the vinyl monomer such as (methyl) acrylate and vinyl naphthalene (particularly styrene monomer) From radical polymerization.It is poly-that suitable free radical polymerization is not limited to suspension polymerisation, solution coincidences, dispersin polymerization, emulsifying Close, preferably polymerisation in solution.

Polyvinyl is preferably used the situation of (methyl) acrylate monomer.

Polyvinyl is preferably copolymer (copolymer).

The copolymerizable vinyl groups dispersant derived by hydrophobic monomer and hydrophilic monomer is preferably essentially without segment.Such as Copolymerization of ethylene based polyalcohol is the shortest by chain segment length or non-existent free radical polymerization manufacture forms.Now, usually It is referred to as " randomly " polymerization.There is the copolymerization of ethylene based polyalcohol of segment by living polymerization, particularly group transfer (group Transfer) polymerization, atom transfer (atom transfer) polymerization, macromonomer (macromonomer) are polymerized, are grafted and gather The polymerizations such as conjunction, anion or cationic polymerization are fabricated by.Preferably hydrophilic vinylic monomer be nonionic and from Sub-property monomer.Preferably non-ionic monomer is saccharide, glucose, amide, ketopyrrolidine, particularly preferably has hydroxyl and ethoxy Base person.The preferably example of non-ionic monomer can enumerate Hydroxyethyl Acrylate, hydroxyethyl methacrylate, vinylpyridine Pyrrolidone, through (methyl) acrylate of ethoxylation and (methyl) acrylamide.Preferably ionomeric ethylene base monomer is permissible It is cationic, preferably anionic property.

Preferably anionic property vinyl monomer contains carboxyl and/or phosphate and/or sulfonic group (these acid can be trip From can also be salt).As preference, (methyl) acrylic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, ethylene can be enumerated Base sulfonic acid, (methyl) acryloyloxyalkyl sulfonic acid (such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulphonic acid, third Alkene propyl sulfonic acid, acryloxy butyl sulfonic acid, methacryloxymethyl sulfonic acid, methacryloxyethyl Sulfonic acid, methacryloxypropyl sulfonic acid, methacryloxy butyl sulfonic acid), 2-acrylamide-2-alkyl alkane sulfonic acid (such as 2-acrylamide-2-methyl ethyl sulfonic acid, 2-acrylamide-2-methyl propane sulfonic, 2-acrylamide-2-methyl fourth sulphur Acid), 2-Methacrylamide-2-alkyl alkane sulfonic acid (such as 2-Methacrylamide-2-methyl ethyl sulfonic acid, 2-metering system Amide-2-methyl propane sulfonic acid, 2-Methacrylamide-2-methyl fourth sulfonic acid), single (acryloxyalkyl) phosphate (such as Single (acryloyl-oxyethyl) phosphate, list (3-acryloxypropyl) phosphate), single (methacryloxyalkyl) phosphorus Hydrochlorate (such as single (methacryloxyethyl) phosphate, list (3-methacryloxypropyl) phosphate).

Preferably cationic vinyl monomer includes quaternary amine, pyridine, guanidine and biguanide.

Preferably hydrophobic vinyl monomers does not has hydrophilic radical.As preferred hydrophobic vinyl monomers, can lift Go out C_1-20-Alkyl (methyl) acrylate, butadiene, styrene and vinyl naphthalene, preferably C_1-20-Alkyl (methyl) acrylate (such as (methyl) acrylic acid methyl ester., (methyl) butyl acrylate, (methyl) 1-Octyl acrylate, (methyl) acrylic acid 2-ethyl hexyl Ester, isobornyl acrylate, lauryl acrylate, stearyl acrylate ester, (methyl) benzyl acrylate, (methyl) acrylic acid benzene oxygen Base ethyl ester), particularly preferred methyl methacrylate, benzyl methacrylate, 2-Ethylhexyl Methacrylate, methacrylic acid Phenoxy ethyl.Their alkyl can be side chain, but preferably straight chain.

The polyester with at least 1 carboxyl is generated by the reaction of diol monomer with the dicarboxylic acid monomer of excess.Carboxyl can Import with the copolymerization of glycol with dicarboxylic acid monomer by having carboxyl.

Polyester is fabricated by typically via the esterification of dicarboxylic acids with glycol.

There is the polyester of carboxyl such as by remaining according to carboxyl, utilize the known method such as fusion method, solvent method to containing The compound of carboxyl and the compound of hydroxyl carry out dehydration condensation and manufacture.

Polyester can be enumerated and suitably select monoacid, polyprotic acid etc. to have the compound of carboxyl and glycol, polyhydric alcohol etc. have The compound of hydroxyl so that it is the polyester etc. that dehydrating condensation is obtained, the polyester employing oils or fatty acid in addition becomes Alkyd resin.

The carboxyl that the polyester used in the present invention is had is mainly from the polyprotic acid constituting more than the binary acid of polyester Unreacted carboxyl groups.

As polyprotic acid, such as, can enumerate adipic acid, succinic acid (acid anhydride), decanedioic acid, dimeric dibasic acid, maleic acid (acid anhydride), adjacent benzene Dioctyl phthalate (acid anhydride), M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid (acid anhydride), hexahydrophthalic acid (acid anhydride), hexahydro pair Phthalic acid, 2,6-naphthalene diacid, trimellitic acid (acid anhydride), PMA (acid anhydride) etc..

As the compound with carboxyl that can use in addition to polyprotic acid, such as, can enumerate p-phthalic acid diformazan The low alkyl group esters of the acid such as ester；The unitary acids such as benzoic acid, p-tert-butyl benzoic acid, Colophonium, hydrogenated rosin；Fatty acid and oil Lipid；Molecular end has the macromonomer class of 1 or 2 carboxyl；5-sodium sulfo isophthalate and dimethyl esters thereof Deng.

As having the compound of hydroxyl, such as, can enumerate ethylene glycol, neopentyl glycol, propylene glycol, diethylene glycol, dipropyl two Alcohol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propylene glycol, 1,4-butanediol, 1,3-propylene glycol, 1,6-HD, 1,4 cyclohexane dimethanol, 1,5-pentanediol, the alkylen oxide adducts of bisphenol-A, hydrogenated bisphenol A, the oxyalkylene of hydrogenated bisphenol A add Become the glycolss such as thing, Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol；Glycerol, trimethylolpropane, trimethylolethane, two sweet The polyalcohols such as oil, tetramethylolmethane, trihydroxy ethyl isocyanate；" カ ジ ュ ラ E-10 " (Shell chemical industry strain formula meeting The ethylene oxidic ester of the synthetic fatty acid of society) etc. single glycidyl compound class, molecule list end there is the big of 2 hydroxyls Molecule monomer class etc..

It addition, during synthesizing polyester, it be also possible to use hydroxyl fatty acid or the oils such as Semen Ricini oil, 12-hydroxy stearic acid； Dihydromethyl propionic acid, P-hydroxybenzoic acid, 6-caprolactone etc. have the compound etc. of carboxyl and hydroxyl.

Additionally, also a part for binary acid can be replaced to diisocyanate cpd.

It addition, have the polyester of carboxyl also by by maleic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, The method that the anhydride such as hexahydrophthalic anhydride, trimellitic anhydride carries out additive reaction with the polyester with hydroxyl manufactures.

Have the polyester of hydroxyl and carboxyl such as also by the dehydration condensation of polyester resin according to known Method, the mode remained according to hydroxyl and carboxyl make it react to be easily manufactured.

The polyester with tertiary amino and carboxyl such as can be by by triethanolamine, N methyldiethanol amine, N, N-dimethyl Ethanolamine etc. have the compound of tertiary amino and hydroxyl and are easily manufactured as alcohol composition when manufacturing polyester resin.

The polyester with free-radical polymerised unsaturated group and carboxyl such as can be easily manufactured by the following method: 1 ］ make 2-methacryloxyethyl isocyanates etc. have NCO containing free-radical polymerised unsaturated group Monomer class or maleic anhydride etc. there is the anhydride of free-radical polymerised unsaturated group and the polyester with hydroxyl and carboxyl The method carrying out additive reaction；［ 2 ］ the polymerizable monomer class with epoxy radicals and the polyester resin with carboxyl is made to carry out addition The method of reaction；［ 3 ］ monomer containing free-radical polymerised unsaturated group such as maleic anhydride is used to synthesize as acid composition The method etc. of polyester resin.

Polyurethane is preferably by the condensation of polyol component (such as diisocyanate) with polyol component (such as glycol) Reaction manufactures.

The polyurethane with carboxyl such as can be by making containing tools such as the dihydromethyl propionic acids as the composition importing carboxyl The polyol component having the compound of carboxyl and hydroxyl reacts with polisocyanate component and is easily manufactured.

As polyol component, in addition to the diol component enumerated in the manufacture method of polyester, also can be as required Use 3 officials can above polyol compound.

As polisocyanate component, such as except 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), 4, 4 '-methyl diphenylene diisocyanate, hexamethylene diisocyanate, phenylene vulcabond, 1,5-naphthalene diisocyanate, M xylene diisocyanate, isophorone diisocyanate, hydrogenation toluene di-isocyanate(TDI), hydrogenation 4,4 '-diphenyl methane Diisocyanate, the hydrogenation diisocyanate such as m xylene diisocyanate, rough 4,4 '-methyl diphenylene diisocyanate Outside compound, it be also possible to use the polyisocyanate compounds such as polymethylene polyphenyl isocyanate.

The manufacture of polyurethane can be carried out according to conventional methods.Such as inert organic do not react with NCO In solvent solution, preferably at a temperature of room temperature or about 40～100 DEG C, carry out additive reaction.Now, it be also possible to use two Laurels The known catalyst such as acid dibutyl tin.

Reaction system when manufacturing polyurethane it be also possible to use the N-alkyl two such as diamidogen, polyamine, N methyldiethanol amine Alkanolamine；The known chain elongation agent such as dihydrazide compound.

The polyurethane with hydroxyl and carboxyl such as can be by being more than NCO when manufacturing polyurethane with hydroxyl Ratio makes it react to be easily manufactured.Or, there is the compound of more than 2 hydroxyls also by making 1 molecule and there is carboxylic The polyisocyanate of base and terminal isocyanate group carries out additive reaction and is easily manufactured.

The polyurethane with tertiary amino and carboxyl such as can use N-methyl by the part as polyol component The N-alkyl dialkanol amine such as diethanolamine are easily manufactured.

The polyurethane with blocked isocyanates base and carboxyl such as by making known block agent and can have carboxyl Carry out additive reaction with the polyisocyanate of terminal isocyanate group to be easily manufactured.

The polyurethane with epoxy radicals and carboxyl such as can be by making the compound with hydroxyl and epoxy radicals and having carboxylic The polyisocyanate of base and terminal isocyanate group carries out additive reaction and is easily manufactured.

As having the compound of hydroxyl and epoxy radicals, such as, can enumerate (+)-2,3-Epoxy-1-propanol, glycerin diglycidyl ether, three hydroxyls Methylpropane diglycidyl ether, the diglycidyl ether etc. of bisphenol-A.

Have free-radical polymerised unsaturated group and as acidic-group carboxyl polyurethane such as can by make as The aforesaid polymerizable monomer class with hydroxyl and glycerol list (methyl) acrylate, trimethylolpropane two (methyl) acrylic acid Ester, pentaerythritol triacrylate etc. have the compound of hydroxyl and free-radical polymerised unsaturated group and have terminal isocyanate The polyisocyanate of perester radical carries out additive reaction and is easily manufactured.

There is water-disintegrable alkoxysilane group and the polyurethane as the carboxyl of acidic-group such as can be by making γ-sulfydryl Propyl trimethoxy silicane, γ-mercaptopropyi methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, gamma-amino Propyl-triethoxysilicanes etc. have the silane coupler of the reactive hydrogen that can react with NCO and have terminal isocyanate The polyisocyanate of perester radical carries out additive reaction and is easily manufactured.

Polymer adapts according to the liquid medium used during manufacturing microgranule dispersion or divides with microgranule The mode that the liquid color spreading agent (excipient) dissipated in thing in the final composition (such as ink) of use adapts selects.Example As, when using microgranule dispersion in the ink for ink-jet recording of aqueous, preferred polymers is hydrophilic.

［ molecular weight ］

The weight average molecular weight of dispersant is preferably 10000～200000, more preferably 15000～150000, the most excellent Elect 20000～100000 as.When being more than 10000, the image quality of printed article is excellent, very preferred, and when being less than 200000, permissible Suppression viscosity increases and then can prevent the reduction of storage stability, the most preferably.

［ D/P value ］

The content of dispersant relative to pigment 100 mass parts be preferably the scope of 20～100 mass parts, more preferably 25～ The scope of 90 mass parts, more preferably 30～the scope of 70 mass parts.It addition, dispersant can be used alone, it is possible to combination Use multiple.

When the content of dispersant is less than 20 mass parts, the amount of dispersant becomes insufficient relative to pigment, storage stability Become insufficient.On the other hand, during more than 100 mass, viscosity increases and then storage stability reduces, and is therefore not suitable for.

When the content of the coloring agent in described pigment dispersion is designated as P, the content of dispersant is designated as D, by content D with When the ratio of content P is designated as D/P value, D/P value is preferably 0.15～1.0, more preferably 0.16～0.8, more preferably 0.17 ～0.7.

［ acid number ］

Dispersant in order to cross-linking agent carry out cross-link needs there is sufficient acid number, preferably at least have 50mgKOH/g with On acid number.

In all of mode, above-mentioned acid number is preferably 70～200mgKOH/g, more preferably 70～160mgKOH/g.Tool The dispersant having described acid number can give the storage stability of improvement.

During it addition, be less than 50mgKOH/g, owing to the dissolubility in water solvent is low, be therefore not suitable for.

［ dissolubility ］

Dispersant can be any one in water-insoluble, water solublity, is preferably 1g/ as the dissolubility in water More than 100mL, more preferably more than 3g/100mL, particularly preferably more than 5g/100mL.

Less than 1g/(100m) L time, owing to the dissolubility in water is low, therefore have be difficult to absorption on pigment particles, dispersion Property reduce situation.

［ crosslinking ］

Described water system (pigment) dispersion is preferably cross-linked by cross-linking agent.

The more preferably mode of the present invention is that dispersant adsorbed on the surface of the pigment before crosslinking, forms metastable point Dissipate thing, and then implement to use cross-linking agent to carry out the operation cross-linked after this dispersion step, thus obtain the guarantor with higher degree Deposit the dispersion of the image quality excellence of stability, printed article.

Use time there is the dispersant of at least more than 50mg/KOH acid number, cross-linking agent can have oligomer dispersing group, Also can be without oligomer dispersing group.The term of so-called " oligomer " does not has the upper limit, repetitive not to have the upper limit with molecular weight yet Implication use.The cross-linking agent with more than 1 oligomer dispersing group can increase the stability of generated microgranule dispersion. In the liquid color spreading agent (excipient) that the stability of this increase uses in ink mist recording particularly useful.This is owing to utilization has During less than the dispersant of the acid number of 50mg/KOH, difficulties in dispersion.

Oligomer dispersing group is preferably polyoxyalkylene, the most poly-C_2-4-Oxyalkylene, particularly preferably polyoxyethylene Alkene.Polyoxyalkylene can improve the stability of generated microgranule dispersion.Polyoxyalkylene have preferably 3～200, more preferably 5～ 50, the oxyalkylene repeat units of particularly preferred 5～20.

Cross-linking agent preferably has more than 2 epoxy radicals.The preferred cross-linking agent with at least 2 epoxy radicals is epoxychloropropane Derivant.The cross-linking agent have more than 2 epoxy radicals, not having an oligomer dispersing group is Ethylene glycol diglycidyl ether, isophthalic Diphenol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, through halogenated bisphenol-A Diglycidyl ether, trimethylolpropane polyglycidyl ether, polyglycereol polyglycidyl ether, glycerol polyglycidyl ether, season Penta tetrol polyglycidyl ether, two glycerol polyglycidyl ethers, Sorbitol polyglycidyl ether and polybutadiene two shrink sweet Oil ether.There are 2 epoxy radicals and to have the preferred cross-linking agent of more than 1 oligomer dispersing group be that diethylene glycol diglycidyl is sweet Oil ether, polyethyleneglycol diglycidylether or dipropylene glycol diglycidyl ether.

It addition, it be also possible to use the anhydride such as phthalic anhydride, succinic anhydrides as cross-linking agent.

［ temperature, pH ］

In the present invention cross-linking reaction preferably below 100 DEG C, pH be 6 carried out above.Preferred cross-linking reaction is 30 DEG C ～90 DEG C, more preferably 40 DEG C～85 DEG C.

The preferred pH of cross-linking reaction is 7～10, more preferably 8～9.5.

Preferably cross-linking agent possibly together with the cross-linking reaction between carboxyl, carboxyl and epoxy radicals below 100 DEG C, pH be more than 6 Carry out.

Cross-linking reaction owing to carrying out in water system, the most preferably less than 100 DEG C.On the contrary, at low temperatures due to cross-linking reaction Make slow progress, the most preferred, preferably more than 30 DEG C, be more preferably more than 40 DEG C.

When pH is more than 10, when applying heat in cross-linking reaction, there is polymer that the probability of hydrolysis occurs.And pH is less than When 6, owing to pigment dispersion is prone to cause cohesion, become unstable, the most preferred.

［ film refines ］

Film is refined can be used and counter be impregnated with film (NF film), ultrafilter membrane (UF film), can pressurize and also can be not pressurized, the essence when pressurization Time required for system shortens, very effective percentage.It is 10000～150000 as UF film, preferably molecular cut off, is more preferably 20000～100000.During less than 10000, elongated for the refined time, the most inefficent.And during more than 150000, due to There is the probability that dispersant flows out, the most preferred.

As the purposes of the AZOpigments of the present invention, the image note for forming image, particularly coloured image can be enumerated Record material, specifically, with the ink-jetting style recording materials that are detailed below as representative, has heat-sensitive recording material, pressure-sensitive record material Material, the use recording materials of electronic photo mode, transfer-type photosensitive silve halide material, printing-ink, pen etc., be preferably spray Ink mode recording materials, heat-sensitive recording material, the recording materials of use electronic photo mode, more preferably ink-jetting style record material Material.

It addition, also can apply for the coloured image used in the display such as solid-state imager or LCD, PDP such as CCD In the color filter carry out recording, reappearing, in the dyeing liquor of the dyeing of various fibers.

By the manufacture method of present invention mentioned above, by being carried out crystalline transformation by amorphous azo-compound, Crystal growth can be controlled, manufacture easy scattered AZOpigments.

In operation (b), the azo-compound shown in formula (1) is due to dissolving at least partially in reactant liquor, therefore When the preparation method of azo-compound lysate be aforesaid way (ii) time, coupling reaction is the most successfully carried out, and can obtain more Highly purified azo-compound.This contributes to the high efficient production of the AZOpigments finally obtained.

But, as mentioned above, it is difficult to make in the reactant liquor after coupling reaction separate out patent documentation 6 pigment (once Property as particle obtain pigment) dissolve in organic solvent.That is, in order to make the particle diameter of pigment become the finest, when be intended to by The pigment dissolved of patent documentation 6 in organic solvent time, need to use substantial amounts of organic solvent, not only manufacturing cost increases, and Even and if often have the situation using substantial amounts of organic solvent also will not dissolve, not to mention being very difficult to make it fully dissolve.

On the other hand, according to the present invention, after operation (b) terminates, do not use substantial amounts of organic solvent (high concentration), can obtain Obtaining at least some of lysate dissolved of target azo-compound, this contributes to the high efficiency system of the AZOpigments finally obtained Make.It addition, by the azo-compound lysate obtained in operation (b) is mixed with the poor solvent of this azo-compound, can So that AZOpigments separates out as microgranule.

As it has been described above, by the manufacture method of the AZOpigments of the present invention, can manufacture with high efficiency and low cost and easily divide The AZOpigments microgranule dissipated.

［ coloured composition ］

The coloured composition of the present invention contains the AZOpigments of at least one the invention described above, its salt, hydrate or solvent and closes Thing.The coloured composition of the present invention can contain medium, but when using solvent as medium, special as ink for ink-jet recording Preferably.The coloured composition of the present invention can be by using lipophile medium or aqueous medium as medium, by disperseing wherein The pigment of the present invention makes.The situation of aqueous medium is preferably used.Possibly together with removing in the coloured composition of the present invention The ink compositions of medium.The coloured composition of the present invention can not damage in the range of effect of the present invention as required Additive containing other.As other additive, such as, can enumerate dry preventing agent (wetting agent), anti-fading agent, emulsifying Stabilizer, impregnation-accelerator, UV absorbent, preservative, antifungus agent, pH adjusting agent, surface tension modifier, defoamer, The known additive such as viscosity modifier, dispersant, dispersion stabilizer, antirust agent, chelating agen (is recorded in Japanese Unexamined Patent Publication 2003- In No. 306623 publications).These various additives, when for water-based ink, directly make an addition in ink.For oil-soluble ink Time, generally make an addition in dispersion after the preparation of AZOpigments dispersion, but also can make an addition to oil phase or aqueous phase in the preparation In.

Embodiment

The present invention is described in more detail below based on embodiment, but the present invention is not limited to these embodiments.Wherein, In embodiment, " part " represents mass parts.

＜ azo-compound, the manufacture ＞ of AZOpigments

1 particle diameter of the azo-compound obtained in following example is used transmission-type microscope (NEC strain formula Commercial firm's system: JEM-1010 ultramicroscope) by visually observing.

Azo-compound, the mensuration of X-ray diffraction of AZOpigments return analysis according to Japanese Industrial Standards JISK0131(X Analyze logical), utilize powder X-ray diffraction determinator RINT2500(Co., Ltd. Rigaku system), use CuK alpha ray, Carry out under conditions of below.

Use determinator: Rigaku company system automatic X-ray diffraction device RINT2500

X-ray tube: Cu

Tube voltage: 55KV

Tube current: 280mA

Scan method: 2 θ/θ scanning

Scanning speed: 6deg./min

Sampling interval: 0.100deg.

Start angle (2 θ): 5deg.

Stop angle (2 θ): 55deg.

Divergent slit: 2deg.

Scatter slit: 2deg.

Receive slit: 0.6mm

Use vertical goniometer

［ embodiment 1 ］

Sodium nitrite 2.2g is dissolved in water 50mL.It addition, make the amino-compound 5.8g shown in formula (2) be dissolved in dense After in hydrochloric acid 50mL, it is cooled to interior temperature and reaches-10 DEG C.Wherein, reach the mode of less than 0 DEG C according to interior temperature and drip described Asia Sodium nitrate aqueous solution.After stirring 1 hour at Nei Wen is-10 DEG C～0 DEG C, add carbamide 1.8g interior temperature less than 0 DEG C.Interpolation terminates After synthermal lower stirring 15 minutes, it is thus achieved that diazonium salt solution.It addition, the compound 5g of formula (3) is made an addition to methanol 175mL Heat up after in, make it dissolve under reflux.This solution is cooled to interior temperature and reaches 0 DEG C, reach less than 10 DEG C according to interior temperature Mode add described diazonium salt solution.After stirring 1 hour at interior temperature 10 DEG C, the solid separated out is filtered.Utilize methanol, After water is sufficiently washed so that it is be suspended in water 300mL, add 28% ammonia spirit, by pH regulator to 6.0.The solid that will separate out Filter, be sufficiently carried out washing with water, after being dried at 60 DEG C, it is thus achieved that the amorphous azo-compound of 9.8g (1)-1.

The length of the long axis direction of 1 particle of described amorphous azo-compound (1)-1 is about 0.5 μm.

Carried out the mensuration of the X-ray diffraction of amorphous azo-compound (1)-1 by above-mentioned condition, result has no feature The X-ray diffraction peak of property.

Amorphous for 5g gained azo-compound (1)-1 is suspended in ethylene glycol 50mL.It is warming up to interior temperature and reaches 100 DEG C After, synthermal lower stirring 2 hours.Being cooled to after interior temperature reaches 30 DEG C, the solid that will separate out filters, it is thus achieved that the δ type of 4.5g is brilliant The AZOpigments (1)-2 of volume morphing.

The length of the long axis direction of 1 particle of the AZOpigments (1)-2 of gained δ type crystal habit is about 0.6 μm.

The X-ray diffraction of the AZOpigments (1)-2 carrying out gained δ type crystal habit under these conditions measures, and result exists Bragg angle (2 θ ± 0.2 °) is to show at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Distinctive X-ray diffraction peak.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 1.

［ embodiment 2 ］

Sodium nitrite 2.2g is dissolved in water 50mL.It addition, make the amino-compound 5.8g shown in formula (2) be dissolved in dense After in hydrochloric acid 50mL, it is cooled to interior temperature and reaches-10 DEG C.Wherein, reach the mode of less than 0 DEG C according to interior temperature and drip described Sodium nitrite in aqueous solution.After stirring 1 hour at Nei Wen is-10 DEG C～0 DEG C, add carbamide 1.8g interior temperature less than 0 DEG C.Add Synthermal lower stirring 15 minutes after end, it is thus achieved that diazonium salt solution.The mode of less than 5 DEG C is reached by formula (3) according to interior temperature Compound 5g little by little add to this diazonium salt solution.Add after terminating, be warming up to interior temperature 10 DEG C, under synthermal After stirring 3 hours, the solid separated out is filtered.After being sufficiently washed with water so that it is be suspended in water 200mL, add 28% ammonia Solution, by pH regulator to 6.0.Solid is filtered, is sufficiently carried out washing with water, after being dried at 60 DEG C, it is thus achieved that 9.9g Amorphous azo-compound (1)-3.

The length of the long axis direction of 1 particle of described azo-compound (1)-3 is about 0.3 μm.

Carried out the mensuration of the X-ray diffraction of azo-compound (1)-3 by above-mentioned condition, result has no that distinctive X penetrates Line diffraction maximum.

Amorphous for 5g gained azo-compound (1)-3 is suspended in ethylene glycol 50mL.It is warming up to interior temperature and reaches 120 DEG C After, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type crystal habit of 4.5g AZOpigments (1)-4.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-4 is about 0.5 μm.

Carry out under these conditions gained AZOpigments (1)-4 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray diffraction peak of display at 4.8 °, 7.2 ° and 9.7 °.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 2.

［ embodiment 3 ］

Being suspended in acetic acid 150g by the compound 34.6g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips Sulphuric acid 24g.And then reach the mode of 20 DEG C～30 DEG C according to interior temperature and drip the sulfuric acid solution 48.6g of 43% nitrosyl sulfuric acid, including After stirring 1 hour at temperature 20 DEG C, add carbamide 0.28g, it is thus achieved that diazonium salt solution.20 DEG C～the side of 30 DEG C is reached according to interior temperature The compound 30g of formula (3) is added batch-wise to this diazonium salt solution by formula, stirs 1 hour, it is thus achieved that azo at interior temperature 25 DEG C The homogeneous reaction liquid of compound.At interior temperature 25 DEG C, additionally prepare the methanol of 360g, reach the mode of less than 30 DEG C according to interior temperature Add the homogeneous reaction liquid of above-mentioned azo-compound, after stirring 10 minutes, filter the solid separated out.Wash with the methanol of 300mL After washing so that it is be suspended in water 900mL, add 28% ammonia spirit, by pH regulator to 6.0.Solid is filtered, it is thus achieved that ζ type crystal The AZOpigments (1)-5 of form.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-5 is about 2 μm.

Carry out under these conditions gained AZOpigments (1)-5 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray diffraction peak of display at 6.5 °, 6.7 °, 9.1 ° and 21.3 °.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 3.

Being suspended in sulphuric acid 50mL by 5g gained azo-compound (1)-5, the mode reaching less than 15 DEG C according to interior temperature adds Add to water 300mL.Filter the solid separated out, after being sufficiently washed with water so that it is be suspended in water 300mL, add 28% ammonia Solution, by pH regulator to 6.1.Solid is filtered, is sufficiently washed with water, dried at 60 DEG C, it is thus achieved that the noncrystalline of 3.9g AZOpigments (1)-6.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-6 is about 0.2 μm.

The X-ray diffraction carrying out gained AZOpigments (1)-6 under these conditions measures, and result has no that distinctive X penetrates Line diffraction maximum.

Amorphous azo-compound (1)-6 of 3g gained is suspended in ethylene glycol 30mL.It is warming up to interior temperature and reaches 120 After DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type crystal shape of 2.4g The AZOpigments (1)-7 of state.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-7 is about 0.3 μm.

Carry out under these conditions gained AZOpigments (1)-7 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 4.

［ embodiment 4 ］

The AZOpigments (1)-5 obtained in 5g embodiment 3 is dissolved in phosphoric acid 50mL, reaches less than 15 DEG C according to interior temperature Mode add to water 300mL.The solid separated out is filtered, after being sufficiently washed with water, is suspended in water 300mL, Add 28% ammonia spirit by pH regulator to 7.2.Solid is filtered, is sufficiently carried out washing with water, dried at 60 DEG C, obtain Obtain amorphous azo-compound (1)-8 of 4.2g.

The length of the long axis direction of 1 particle of gained azo-compound (1)-8 is about 0.2 μm.

The X-ray diffraction carrying out gained AZOpigments (1)-8 under these conditions measures, and result has no that distinctive X penetrates Line diffraction maximum.

Amorphous azo-compound (1)-8 of 3g gained is suspended in ethylene glycol 30mL.It is warming up to interior temperature and reaches 120 After DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type crystal shape of 2.4g The AZOpigments (1)-9 of state.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-9 is about 0.2 μm.

Carry out under these conditions gained AZOpigments (1)-9 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 5.

［ embodiment 5 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.Additionally, after stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain weight Nitrogen salt solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), reach 20 DEG C～25 DEG C according to interior temperature Mode drops in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that azo-compound (1) uniformly anti- Answer liquid.Additionally prepare water 150g, at interior temperature 20 DEG C～25 DEG C, drip the homogeneous reaction liquid of above-mentioned azo-compound (1).Filter The solid separated out.It is sufficiently carried out washing so that it is be suspended in water 200mL, add 28% ammonia spirit, by pH regulator with water To 6.2.Solid is filtered, is sufficiently washed with water, it is thus achieved that amorphous AZOpigments (1)-10.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-10 is about 0.2 μm.

Carrying out determination of water, the containing ratio of result water is 68%.

A part for azo-compound (1)-10 is dried, carries out the mensuration of X-ray diffraction under these conditions, knot Fruit has no distinctive X-ray diffraction peak.

The amorphous aqueous azo-compound (1)-10 of 10g gained is suspended in ethylene glycol 30mL.It is warming up to interior temperature After reaching 95 DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type of 2.9g The AZOpigments (1)-11 of crystal habit.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-11 is about 0.15 μm.

Carry out under these conditions gained AZOpigments (1)-11 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, show that distinctive X-ray is spread out at 20.1 ° and 26.8 Penetrate peak.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 6.

［ embodiment 6 ］

It is dried in embodiment 5 the amorphous aqueous azo-compound (1)-10 obtained, it is thus achieved that azo-compound (1)-12. 10g azo-compound (1)-12 is suspended in ethylene glycol 100mL, is warming up to after interior temperature reaches 120 DEG C, in synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the AZOpigments (1)-13 of the δ type crystal habit of 9.1g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-13 is about 0.2 μm.

Carry out under these conditions gained AZOpigments (1)-13 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 7.

［ embodiment 7 ］

10g azo-compound (1)-12 is suspended in the mixed solvent of ethylene glycol 50mL, water 50mL, is warming up to Nei Wenda After 95 DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type of 9.3g is brilliant The AZOpigments (1)-14 of volume morphing.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-14 is about 0.2 μm.

Carry out under these conditions gained AZOpigments (1)-14 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 8.

［ embodiment 8 ］

10g azo-compound (1)-12 is suspended in the mixed solvent of ethylene glycol 5mL, water 95mL, is warming up to Nei Wenda After 85 DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type of 9.5g is brilliant The AZOpigments (1)-15 of volume morphing.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-15 is about 0.15 μm.

Carry out under these conditions gained AZOpigments (1)-15 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Fig. 9.

［ embodiment 9 ］

10g azo-compound (1)-12 is suspended in the mixed solvent of isopropanol 40mL, water 60mL, is warming up to Nei Wenda After 80 DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type of 8.2g is brilliant The AZOpigments (1)-16 of volume morphing.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-16 is about 5 μm.

Carry out under these conditions gained AZOpigments (1)-16 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 10.

［ embodiment 10 ］

10g azo-compound (1)-12 is suspended in the mixed solvent of isopropanol 100mL, water 10mL, is warming up to interior temperature After reaching 80 DEG C, synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the δ type of 7.9g The AZOpigments (1)-17 of crystal habit.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-17 is about 15 μm.

Carry out under these conditions gained AZOpigments (1)-17 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 11.

［ embodiment 11 ］

10g azo-compound (1)-12 is suspended in butyl acetate 100mL, is warming up to after interior temperature reaches 90 DEG C, with At a temperature of stir 2 hours.It is cooled to after interior temperature reaches 30 DEG C, be filtered by solid, it is thus achieved that the azo face of the δ type crystal habit of 8.5g Material (1)-18.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-18 is about 20 μm.

Carry out under these conditions gained AZOpigments (1)-18 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 12.

［ embodiment 11-2 ］

10g azo-compound (1)-12 is suspended in methanol 100mL.After being stirred at room temperature 2 hours, by solid mistake Filter, it is thus achieved that the AZOpigments (1)-101 of the δ type crystal habit of 9.4g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-101 is about 10 μm.

The X-ray diffraction carrying out gained AZOpigments (1)-101 under these conditions measures, and result is at Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray diffraction peak of display at 6.5 °, 6.7 °, 9.1 ° and 21.3 °.

CuK α characteristic X-ray diffraction pattern is shown in Figure 13.

［ embodiment 12 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.After stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain diazol Solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), the mode reaching 20 DEG C～25 DEG C according to interior temperature is dripped Add in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that the homogeneous reaction liquid of azo-compound (1).Separately Outer preparation water 150g, drips the homogeneous reaction liquid of above-mentioned azo-compound (1) at interior temperature 20 DEG C～25 DEG C.Filtration is separated out After solid, it is sufficiently carried out washing with water, it is thus achieved that amorphous AZOpigments (1)-19.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-19 is about 0.2 μm.

CuK α characteristic X-ray diffraction pattern is shown in Figure 14.

The X-ray diffraction carrying out azo-compound (1)-19 under these conditions measures, and result has no distinctive X-ray Diffraction maximum.

Amorphous azo-compound (1)-19 of gained is suspended in water 120mL, the mixed solvent of ethylene glycol 180mL In.Use 28% ammonia by after pH regulator to 6.28, be warming up to after interior temperature reaches 85 DEG C, synthermal lower stirring 2 hours.Cooling After reaching 30 DEG C to interior temperature, crystallization is filtered, be sufficiently carried out washing with water, it is thus achieved that the azo face of the δ type crystal habit of 19.5g Material (1)-20.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-20 is about 0.3 μm.

Carry out under these conditions gained AZOpigments (1)-20 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 15.

［ embodiment 12-2 ］

The homogeneous reaction drop of the azo-compound (1) in embodiment 12 is entered in ethylene glycol 150g, in addition with reality Execute example 12 similarly to operate, it is thus achieved that amorphous azo-compound (1)-102.

The length of the long axis direction of 1 particle of gained azo-compound (1)-102 is about 0.7 μm.

The X-ray diffraction carrying out azo-compound (1)-102 under these conditions measures, and result has no that distinctive X penetrates Line diffraction maximum.

Then, the operation identical with embodiment 12 is utilized to carry out crystalline transformation, it is thus achieved that the idol of the δ type crystal habit of 19.1g Nitrogen pigment (1)-103.

The length of the long axis direction of 1 particle of gained azo-compound (1)-103 is about 0.7 μm.

Carry out under these conditions azo-compound (1)-103 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 16.

［ embodiment 13 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.After stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain diazol Solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), the mode reaching 20 DEG C～25 DEG C according to interior temperature is dripped Add in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that the homogeneous reaction liquid of azo-compound (1).Separately Outer preparation water 150g, drips the homogeneous reaction liquid of above-mentioned azo-compound (1) at interior temperature 20 DEG C～25 DEG C.Stir under synthermal After mixing the suspension after solid (amorphous azo-compound) separates out, add ethylene glycol 20mL, be warming up to interior temperature and reach 85 DEG C, Synthermal lower stirring 2 hours.It is cooled to after interior temperature reaches 30 DEG C, after filtering the solid separated out, be sufficiently carried out washing with water Wash, it is thus achieved that the AZOpigments (1)-21 of the δ type crystal habit of 19.9g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-21 is about 0.2 μm.

Carry out under these conditions gained AZOpigments (1)-21 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 17.

［ embodiment 14 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.After stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain diazol Solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), the mode reaching 20 DEG C～25 DEG C according to interior temperature is dripped Add in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that the homogeneous reaction liquid of azo-compound (1).Separately Outer preparation water 150g, drips the homogeneous reaction liquid of above-mentioned azo-compound (1) at interior temperature 20 DEG C～25 DEG C.Stir under synthermal Mix the suspension after 30 minutes after solid (amorphous azo-compound) separates out, add ethylene glycol 20mL.Reach according to interior temperature The mode of less than 30 DEG C adds 28% ammonia spirit, after pH regulator to 4.01, is warming up to interior temperature and reaches 85 DEG C, under synthermal Stir 2 hours.It is cooled to after interior temperature reaches 30 DEG C, after filtering the solid separated out, be sufficiently carried out washing with water, it is thus achieved that The AZOpigments (1)-22 of the δ type crystal habit of 19.9g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-22 is about 0.5 μm.

Carry out under these conditions gained AZOpigments (1)-22 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 18.

［ embodiment 15 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.After stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain diazol Solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), the mode reaching 20 DEG C～25 DEG C according to interior temperature is dripped Add in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that the homogeneous reaction liquid of azo-compound (1).Separately Outer preparation water 150g, drips the homogeneous reaction liquid of above-mentioned azo-compound (1) at interior temperature 20 DEG C～25 DEG C.Stir under synthermal Mix the suspension after 30 minutes after solid (amorphous azo-compound) separates out, add ethylene glycol 20mL, be warming up to Nei Wenda To 85 DEG C, synthermal lower stirring 2 hours.Being cooled to after interior temperature reaches 30 DEG C, the mode reaching less than 30 DEG C according to interior temperature adds Add 28% ammonia spirit, by pH regulator to 6.50.Filter the crystal separated out, be sufficiently carried out washing with water, it is thus achieved that the δ of 19.9g The AZOpigments (1)-23 of type crystal habit.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-23 is about 0.4 μm.

Carry out under these conditions gained AZOpigments (1)-23 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 19.

［ embodiment 16 ］

Being suspended in acetic acid 50g by the compound 11.5g of formula (2), the mode reaching 20 DEG C～30 DEG C according to interior temperature drips 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.After stirring 1 hour at interior temperature 20 DEG C, add carbamide 0.1g and obtain diazol Solution.It addition, be dissolved in acetic acid 100mL by the compound 10g of formula (3), the mode reaching 20 DEG C～25 DEG C according to interior temperature is dripped Add in above-mentioned diazonium salt solution.Stir 1 hour at interior temperature 20 DEG C, it is thus achieved that the homogeneous reaction liquid of azo-compound (1).Separately Outer preparation water 150g, drips the homogeneous reaction liquid of above-mentioned azo-compound (1) at interior temperature 20 DEG C～25 DEG C.Stir under synthermal Mix the suspension after 30 minutes after solid (amorphous azo-compound) separates out, add ethylene glycol 20mL, be warming up to Nei Wenda To 85 DEG C, synthermal lower stirring 2 hours.Being cooled to after interior temperature reaches 30 DEG C, the crystal that will separate out filters, and enters fully with water Row washing, washs with 1% sodium bicarbonate aqueous solution 100mL.And then it is sufficiently carried out washing with water, it is thus achieved that the δ type of 19.8g The AZOpigments (1)-24 of crystal habit.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-24 is about 0.15 μm.

Carry out under these conditions gained AZOpigments (1)-24 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 20.

［ embodiment 17 ］

The azo-compound (1)-12 obtained in the embodiment 6 of 10g is suspended in ethylene glycol 100mL, at room temperature stirs Mix 24 hours.Solid is filtered, it is thus achieved that the AZOpigments (1)-25 of the δ type crystal habit of 9.5g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-25 is about 0.2 μm.

Carry out under these conditions gained AZOpigments (1)-25 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, show that distinctive X-ray is spread out at 20.1 ° and 26.8 Penetrate peak.

CuK α characteristic X-ray diffraction pattern is shown in Figure 21.

［ embodiment 18 ］

The compound 11.4g of formula (2) is suspended in 90% acetic acid 50g, is cooled to interior temperature and reaches 10 DEG C～20 DEG C.At this Dropping sulphuric acid 4g in temperature range, then drip 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.Stir at interior temperature 10～20 DEG C After mixing 1 hour, add carbamide 0.1g and obtain diazonium salt solution.It addition, reach the mode general in batches of 10～20 DEG C according to interior temperature The compound 10g of formula (3) adds to this diazonium salt solution.Stir 1 hour at interior temperature 10～20 DEG C, it is thus achieved that azo compounds The homogeneous reaction liquid of thing (1).Suspension after synthermal lower stirring solid (amorphous azo-compound) separates out 15 minutes After, add ethylene glycol 20g.Then, it is warming up to interior temperature and reaches 70 DEG C, within 1 hour, carry out crystalline transformation in synthermal lower stirring.Cooling After reaching 30 DEG C to interior temperature, the crystal separated out is filtered, is sufficiently carried out washing with water and methanol, it is thus achieved that the δ type crystal of 19.9g The AZOpigments (1)-27 of form.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-27 is about 0.5 μm.

Carry out under these conditions gained AZOpigments (1)-27 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) it is the distinctive X-ray of display at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 22.

［ embodiment 18-2 ］

The compound 11.4g of formula (2) is suspended in 90% acetic acid 50g, is cooled to interior temperature and reaches 10 DEG C～20 DEG C.At this Dropping sulphuric acid 4g in temperature range, then drip 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid.Stir at interior temperature 10～20 DEG C After mixing 1 hour, add carbamide 0.1g and obtain diazonium salt solution.It addition, reach the mode general in batches of 10～20 DEG C according to interior temperature The compound 10g of formula (3) adds to this diazonium salt solution.Stir 1 hour at interior temperature 10～20 DEG C, it is thus achieved that azo compounds The homogeneous reaction liquid of thing (1).It addition, prepare water 150g, at interior temperature 40 DEG C～45 DEG C, drip the equal of above-mentioned azo-compound (1) Even reactant liquor.Suspension after synthermal lower stirring solid (amorphous azo-compound) separates out, after 15 minutes, adds second Glycol 20g.Within 16 hours, crystalline transformation is carried out in synthermal lower stirring.It is cooled to after interior temperature reaches 30 DEG C, the crystal mistake that will separate out Filter, is sufficiently carried out washing with water and methanol, it is thus achieved that the AZOpigments (1)-104 of the δ type crystal habit of 19.9g.

The length of the long axis direction of 1 particle of gained AZOpigments (1)-104 is about 0.4 μm.

The X-ray diffraction carrying out gained AZOpigments (1)-104 under these conditions measures, and result is at Bragg angle (2 θ ± 0.2 °) it is at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 °, to show that distinctive X penetrates Line diffraction maximum.

CuK α characteristic X-ray diffraction pattern is shown in Figure 23.

［ comparative example 1 ］

The AZOpigments (1)-5 embodiment 3 of 5g obtained is suspended in ethylene glycol 50mL, is warming up to interior temperature and reaches 120 After DEG C, synthermal lower stirring 2 hours.Being cooled to after interior temperature reaches 30 DEG C, the solid that will separate out filters, it is thus achieved that the δ type of 3.9g The AZOpigments (1)-26 of crystal habit.

Utilize optical microscope (Nikon Co., Ltd. system: ECLIPSE LV150) by visualization gained AZOpigments (1)-26, the length of the long axis direction of 1 particle is about 80 μm as a result.

Carry out under these conditions gained AZOpigments (1)-26 X-ray diffraction measure, result Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, show that distinctive X-ray is spread out at 20.1 ° and 26.8 Penetrate peak.

CuK α characteristic X-ray diffraction pattern is shown in Figure 24.

The making ＞ of ＜ pigment dispersion

By the δ type crystal habit AZOpigments (1)-2 of synthesis, enuatrol 0.5 part, glycerol 5 in 2.5 parts of above-described embodiments 1 Part, the mixing of 42 parts of water, use planetary ball mill to carry out per minute 300 together with the zirconium oxide beadlet 100 parts of a diameter of 0.1mm Turn, the dispersion of 3 hours.After dispersion terminates, separate zirconium oxide beadlet, it is thus achieved that the pigment dispersion 1 of yellow.

Same operation is carried out respectively for the δ type crystal habit AZOpigments of synthesis in above-described embodiment 2～17, it is thus achieved that The pigment dispersion 2～17 of yellow.

In order to compare, by the δ type crystal habit AZOpigments (1)-26 of synthesis, oleic acid in 2.5 parts of above-described embodiments 1 0.5 part of sodium, glycerol 5 parts, the mixing of 42 parts of water, use planetary ball mill together with the zirconium oxide beadlet 100 parts of a diameter of 0.1mm Carry out 300 turns per minute, the dispersion of 8 hours.After dispersion terminates, separate zirconium oxide beadlet, it is thus achieved that the comparison pigment dispersion of yellow Thing 1.

Additionally, by amorphous AZOpigments (1)-1 of synthesis, enuatrol 0.5 part, glycerol in 2.5 parts of above-described embodiments 1 5 parts, the mixing of 42 parts of water, use planetary ball mill to carry out per minute together with the zirconium oxide beadlet 100 parts of a diameter of 0.1mm 300 turns, the dispersion of 7 hours.After dispersion terminates, separate zirconium oxide beadlet, it is thus achieved that the comparison pigment dispersion 2 of yellow.

Use Nikkiso Company Limited Nanotrac150(UPA-EX150) body of pigment in mensuration pigment dispersion Long-pending mean diameter.Measurement result is shown in table 1.

Table 1

As can be known from the above results, the AZOpigments with specific crystalline texture obtained by the manufacture method of the present invention The dispersion that volume average particle size (nm) is little can be prepared in shorter time.

［ it is 50m containing specific surface area²The manufacture method of the pigment dispersion of the pigment of/more than g and performance evaluation ］

＜ does not comprise the manufacture ＞ of the AZOpigments (1) of the crystalline transformation operation of amorphous AZOpigments

The manufacture of ［ synthesis example 1 ］ alpha type crystal form AZOpigments (1)-29

Compound 67.5g shown in described formula (2) is dissolved in phosphoric acid 530mL, carries out ice-cold making interior temperature be cooled to 3 ℃.The mode reaching less than 4 DEG C according to interior temperature is added batch-wise sodium nitrite 26.9g with the time of 15 minutes.Add after terminating, Synthermal lower stirring 50 minutes, is added batch-wise carbamide 18.6g, it is thus achieved that diazonium salt solution.It addition, by shown in described formula (3) Compound 47.9g is added in methanol 1680mL, makes it be completely dissolved under reflux.Carry out ice-cold interior temperature being cooled to 0 DEG C, Here the mode reaching less than 10 DEG C according to interior temperature adds above-mentioned diazonium salt solution with the time of 30 minutes.At interior temperature 5 DEG C After stirring 1 hour 30 minutes, add to water 1.6L, stir 30 minutes.The crystal separated out is filtered, washs with water 1L. By the crystal suspension of gained in water 2.5L, adding 28% ammonia, the mode of 6.1 of reaching according to pH is prepared.To crystallize Filter, is sufficiently carried out washing with water, it is thus achieved that γ type crystal habit AZOpigments.Gained crystallization is suspended in acetone 1.5L, enters Row heats up, stirs 2 hours under reflux.While hot crystallization is filtered, be sufficiently carried out washing with acetone, it is thus achieved that the β type of 103.5g Crystal habit AZOpigments (1)-28.

At 60 DEG C, gained β type crystal habit AZOpigments (1)-28 is dried 24 hours, it is thus achieved that the alpha type crystal of 92.8g Form AZOpigments (1)-29(yield is 88.8%).

The manufacture of ［ synthesis example 2 ］ ε type crystal habit AZOpigments (1)-31

With the times of 20 minutes, 43% sulfuric acid solution 16.2g of nitrosyl sulfuric acid is added to by the acetic acid of 50g, the sulfur of 8g In the mixed solvent that acid is constituted.This solution is cooled to 3 DEG C, adds the compound 11.55g shown in described formula (2) with powder, enter Row diazo-reaction.After synthermal lower stirring 1 hour, unnecessary nitrosyl sulfuric acid is made to inactivate with carbamide 0.094g, it is thus achieved that weight Nitrogen compound prepares liquid.

With powder body, the compound 10g shown in described formula (3) is added batch-wise to this above-mentioned diazo compounds below 5 DEG C Thing is prepared in liquid.Add after terminating, be warming up to 20 DEG C and make it react 2 hours, it is thus achieved that azo-compound lysate.Wherein, coupling Reaction having no, the precipitation of pigment, azo-compound lysate are the states being completely dissolved by gained azo-compound.

Prepare the poor solvent that is made up of methanol 150mL, 5 DEG C, be stirred under 200rpm.By above-mentioned azo-compound Lysate drops in this poor solvent.

After stirring 15 minutes in this case, the crystal that will generate filters, it is thus achieved that the ζ type crystal shape shown in described formula (1) The AZOpigments (1)-30 of state.

By the crystal suspension of the AZOpigments (1)-30 of gained ζ type crystal habit in water 200mL, adding 28% ammonia will PH regulator is to 6.0.The crystal (ζ type) separated out is filtered, is sufficiently carried out washing with water, be dried 24 hours at 60 DEG C.By institute (ζ type) must be crystallized be suspended in acetone 200mL, carry out heating up, stirring 2 hours under reflux.It is cooled to room temperature, will crystallize Filter, it is thus achieved that the AZOpigments of the η type crystal habit shown in described formula (1).Fully gained crystallization is washed with acetone, It is dried 24 hours at 60 DEG C, it is thus achieved that the ε type crystal habit AZOpigments (1)-31 shown in described formula (1) of 18.9g.

The synthesis of the AZOpigments (1)-32 of ［ synthesis example 3 ］ δ type crystal habit

Compound 34.6g shown in described formula (2) is suspended in acetic acid 150g, reaches 20 DEG C～30 DEG C according to interior temperature Mode drips sulphuric acid 24g.And then reach the mode of 20 DEG C～30 DEG C according to interior temperature and drip the sulfuric acid solution of 43% nitrosyl sulfuric acid 48.6g, after stirring 1 hour, adds carbamide 0.28g, it is thus achieved that diazonium salt solution at interior temperature 20 DEG C.20 DEG C are reached according to interior temperature ～the compound 30g of described formula (3) is added batch-wise to this diazonium salt solution by the mode of 30 DEG C, stir at interior temperature 25 DEG C 1 hour, it is thus achieved that the homogeneous reaction liquid of azo-compound.It addition, prepare the methanol of 360g at interior temperature 25 DEG C, reach according to interior temperature The mode of less than 30 DEG C adds the homogeneous reaction liquid of above-mentioned azo-compound, after stirring 10 minutes, is filtered by the solid separated out.With After the methanol of 300mL washs, it is suspended in water 900mL, is added 28% ammonia spirit by pH regulator to 6.0.To separate out Solid filter, it is thus achieved that the AZOpigments shown in described formula (1).

The length of the long axis direction of 1 particle of gained AZOpigments is about 2 μm.

The X-ray diffraction carrying out gained AZOpigments under these conditions measures, and result is in Bragg angle (2 θ ± 0.2 °) It is the distinctive X-ray diffraction peak of display at 6.5 °, 6.7 °, 9.1 ° and 21.3 °, there is ζ type crystal habit.

The ζ type crystal habit AZOpigments 5g of above-mentioned acquisition is suspended in ethylene glycol 50mL, is warming up to interior temperature and reaches 120 After DEG C, synthermal lower stirring 2 hours.Being cooled to after interior temperature reaches 30 DEG C, the solid that will separate out filters, it is thus achieved that 3.9g's is described The AZOpigments (1)-32 of the δ type crystal habit shown in formula (1).

Utilize optical microscope (Nikon Co., Ltd. system: ECLIPSE LV150) by visualization gained δ type crystal The AZOpigments (1)-32 of form, the length of the long axis direction of 1 particle is about 80 μm as a result.

The X-ray diffraction of the AZOpigments (1)-32 carrying out gained δ type crystal habit under these conditions measures, and result exists Bragg angle (2 θ ± 0.2 °) is to show at 4.8 °, 7.2 °, 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° Distinctive X-ray diffraction peak.

＜ mills ＞

［ embodiment 19 and comparative example 2 ］

The AZOpigments of embodiment 19 uses the pigment do not milled embodiment 1 gained AZOpigments (1)-2.With Sample, the AZOpigments of comparative example 2 directly uses the face do not milled the AZOpigments (1)-30 generated during synthesis example 2 Material.

The AZOpigments pigment through milling used as described below of other embodiments 20 and comparative example 3～6.

［ embodiment 20 ］

According to reaching the mode of consisting of, super mixer puts into thick AZOpigments and Sal mixes.One Limit rotates super mixer and little by little adds diethylene glycol on one side, prepares mixture (hereinafter sometimes referred to as " ready-mixed Thing ").

AZOpigments (1)-2 150g obtained in embodiment 1

Sal (NaiKai salt industry Co., Ltd. Nakuru UM-05) 1500g

Diethylene glycol 300g

Then, by the portion that grinds of continuous way list extruders (Asada Iron Works Co., Ltd.'s system, MIRACLE KCK-L) and At the 5 of extrusion portion, temperature is set as 15～20 DEG C, screw speed is set as 50rpm, puts into the ready-mixed of above-mentioned middle acquisition Thing, it is thus achieved that mixing thing.Now, current value (load) be about 4A, discharge-amount be 50g/ minute, the temperature of shooing out thing be 16 DEG C.

The mixing thing so obtained is put in 1% dilute hydrochloric acid 5000g and is stirred, then filter and fill The washing divided, removes Sal and diethylene glycol, is dried.Carry out gained δ type crystal habit azo face under these conditions The X-ray diffraction of material (1)-2-A measures, result Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.6 °, 10.7 °, Distinctive X-ray diffraction peak is shown at 17.3 °, 18.9 °, 20.0 ° and 26.7 °.

CuK α characteristic X-ray diffraction pattern is shown in Figure 25.

［ comparative example 3～6 ］

Comparative example 3: the AZOpigments (1)-32 of synthesis example 3

Obtain Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.1 °, 9.6 °, 10.7 °, 17.3 °, 18.9 °, 20.0 ° and δ type AZOpigments (the 1)-32-A at distinctive X-ray diffraction peak is shown at 26.7 °.

CuK α characteristic X-ray diffraction pattern is shown in Figure 26.

Comparative example 4: the AZOpigments (1)-29 of synthesis example 1

Obtain Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and δ type AZOpigments (the 1)-29-A at distinctive X-ray diffraction peak is shown at 26.8 °.

CuK α characteristic X-ray diffraction pattern is shown in Figure 27.

Comparative example 5: the AZOpigments (1)-31 of synthesis example 2

Obtain Bragg angle (2 θ ± 0.2 °) be 4.8 °, 7.2 °, 9.5 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and δ type AZOpigments (the 1)-31-A at distinctive X-ray diffraction peak is shown at 26.8 °.

CuK α characteristic X-ray diffraction pattern is shown in Figure 28.

Comparative example 6: the AZOpigments (1)-30 generated during synthesis example 2

Obtaining at Bragg angle (2 θ ± 0.2 °) is to show at 6.6 °, 9.2 °, 10.3 ° and 21.4 ° that distinctive X-ray is spread out Penetrate δ type AZOpigments (the 1)-30-A at peak.

CuK α characteristic X-ray diffraction pattern is shown in Figure 29.

［ embodiment 21 ］

In addition to the consumption of the Sal in embodiment 20 is changed into 750g, obtain the crystallization of δ type similarly to Example 6 AZOpigments (1)-2-B.The X-ray diffraction carrying out gained δ type crystal habit AZOpigments (1)-2-B under these conditions is surveyed Fixed, result is at 4.8 °, 7.1 °, 9.5 °, 10.7 °, 17.3 °, 18.9 °, 20.0 ° and 26.7 ° at Bragg angle (2 θ ± 0.2 °) Show distinctive X-ray diffraction peak.

［ embodiment 22 ］

In addition to the consumption of the diethylene glycol in embodiment 20 is changed into 400g, obtain δ type similarly to Example 6 Crystallization AZOpigments (1)-2-C.Carry out the X-ray diffraction of gained δ type crystal habit AZOpigments (1)-2-C under these conditions Measuring, result is 4.8 °, 7.1 °, 9.5 °, 10.7 °, 17.3 °, 18.9 °, 20.0 ° and 26.7 ° at Bragg angle (2 θ ± 0.2 °) Place shows distinctive X-ray diffraction peak.

Mensuration ＞ of ＜ BET specific surface area

Vacuum drying pigment 0.1g will be carried out at 80 DEG C in advance and make an addition in sample cell, use specific area measuring Device " MONOSORB MS-17 " (Yuasa Ionics Co., Ltd. system) is measured.Wherein, use He:N is measured₂=7:3 Mixed gas.

The manufacture ＞ of ＜ pigment dispersion

By in 10g above-described embodiment 20 synthesis δ type crystal habit AZOpigments (1)-2-A, enuatrol 5g, glycerol 10g, Water 75g mixes, and uses sand mill TSG1(IMEX company system) enter lines per minute together with the zirconium oxide beadlet 375g of a diameter of 0.1mm 1500 turns of clock, dispersion at 45 DEG C.Reach after the mode of below 100nm disperses, to separate oxygen according to volume average particle size Mv Change zirconium beadlet, it is thus achieved that pigment dispersion.

For embodiment 19 and comparative example 2 without each azo face of synthesis in the AZOpigments milled and comparative example 3～6 Material, utilizes same method to obtain pigment dispersion.

The following evaluation of the pigment dispersion of embodiment 20 and comparative example 2～6 is by the pigment dispersion with embodiment 19 Relative evaluation carry out.

＜ dispersibility evaluates ＞

The time that dispersibility reaches below 100nm by volume average particle size Mv in the manufacture of above-mentioned pigment dispersion is carried out Evaluate (using Nikkiso Company Limited Nanotrac150(UPA-EX150) to be measured).To crystallize than the δ type before milling Be AZOpigments excellent be evaluated as A, by with mill before δ type system of crystallization AZOpigments be being evaluated as B, comparing of equal extent What the δ type system of crystallization AZOpigments before milling was poor is evaluated as C.Show the result in table 2.

＜ tinting strength, tinting power evaluates ＞

With water, the pigment dispersion obtained in above-described embodiment and comparative example is diluted to 10 mass times, then uses No.3 Bar coater be coated on EPSON company photo mat paper.Use reflection of the concentration (X-Rite company X-Rite938) Measure the image color of gained coating material, in order to lower standard evaluation " tinting strength, tinting power (OD:Optical Density) ".By OD than grinding What δ type system of crystallization AZOpigments before mill was excellent be evaluated as A, by with mill before δ type system of crystallization AZOpigments be equal extent Be evaluated as B, poorer than the δ type system of crystallization AZOpigments before milling be evaluated as C.Show the result in table 2.

Table 2

［ synthesis example 4 ］

In a nitrogen environment dipropylene glycol 58.7g is warming up to interior temperature and reaches 70 DEG C, drip with the time of 3 hours wherein It is mixed with methacrylic acid 10.8g, the V-601 of benzyl methacrylate 39.4g, 1.2g, the solution of dipropylene glycol 58.7g.? After synthermal lower further stirring 1 hour, add V-601(polymerization initiator: and Guang Chun medicine company system) 0.6g, under synthermal Stirring 2 hours further.After synthermal lower dropping 50% potassium hydroxide aqueous solution 11.3g, synthermal lower stirring 1 hour.Cold But to room temperature, it is thus achieved that benzyl methacrylate (66.7 moles of %), methacrylic acid (33.3 moles of %) copolymer (Mw=83, 000, acid number is 140mgKOH) dipropylene glycol solution.

［ synthesis example 5 ］

Measuring from 1.2g increment the V-601 of synthesis example 4 to 2.5g, making temperature is 86 DEG C, carries out identical operation, it is thus achieved that first Base benzyl acrylate (66.7 moles of %), (Mw=25,000, acid number are the copolymer of methacrylic acid (33.3 moles of %) Dipropylene glycol solution 128mgKOH).

［ synthesis example 6 ］

In a nitrogen environment dipropylene glycol 41.1g is warming up to interior temperature and reaches 70 DEG C, drip with the time of 3 hours wherein It is mixed with methacrylic acid 9.6g, methyl methacrylate 16.8g, the V-of 2-Ethylhexyl Methacrylate 8.9g, 2.5g 601, the solution of dipropylene glycol 41.1g.Other operations are carried out in the same manner as synthesis example 4, it is thus achieved that (47.8 rub methyl methacrylate Your %), methacrylic acid (31.8 moles of %), 2-Ethylhexyl Methacrylate (20.4 moles of %) copolymer (Mw=83, 000, acid number is 154mgKOH) dipropylene glycol solution.

［ embodiment 23 ］

20g above-described embodiment 20 mixes in synthesis example 4 in δ type crystal habit AZOpigments (the 1)-2-A of synthesis and obtains Dispersant (benzyl methacrylate (66.7 moles of %), the dipropylene glycol of copolymer of methacrylic acid (33.3 moles of %) Solution, Mw=83,000, acid number are 140mgKOH) 32.2g(solid constituent containing ratio is 30.8%, solid constituent is 9.9g), water 58g, uses sand mill TSG1(IMEX company system) carry out per minute 1500 together with the zirconium oxide beadlet 375g of a diameter of 0.1mm Turn, after dispersion at 45 DEG C 3 hours, zirconium oxide beadlet separated, washs with water, it is thus achieved that pigment concentration is 15.4 weight % Thick dispersible pigment dispersion (1) 99g(average volume particle diameter Mv=91.7nm).

Interpolation DENACOL EX-321(Nagase ChemiteX Co., Ltd. in gained thick dispersible pigment dispersion (1) 99g System) 0.43g, the boric acid aqueous solution 3.02g of 6.18%, water 40g, at 70 DEG C stir 5 hours.After reaction terminates, it is cooled to room Temperature, after oversize grain being removed by filter that aperture is 1.0 μm, utilize centrifuge make oversize grain sedimentation (7000rpm, 10 minutes).After being removed by the solid of sedimentation, the filter water using molecular cut off to be 50,000 is sufficiently washed, it is thus achieved that Pigment concentration is dispersible pigment dispersion (1) 121g of 10.8%.

［ embodiment 24 ］

20g above-described embodiment 6 mixes in synthesis example 5 in δ type crystal habit AZOpigments (the 1)-3-A of synthesis and obtains Dispersant (benzyl methacrylate (66.7 moles of %), methacrylic acid (33.3 moles of %) the dipropylene glycol of copolymer molten Liquid, Mw=25,000, acid number are 128mgKOH) 28.6g(solid constituent containing ratio is 35%, solid constituent is 10.0g), water 58g, uses sand mill TSG1(IMEX company system) carry out per minute 1500 together with the zirconium oxide beadlet 375g of a diameter of 0.1mm Turn, after dispersion at 45 DEG C 2 hours, zirconium oxide beadlet separated, washs with water, it is thus achieved that pigment concentration is 14.6 weight % Thick dispersible pigment dispersion (2) 109g(average volume particle diameter Mv=89.6nm).

Interpolation DENACOL EX-321(Nagase ChemiteX Co., Ltd. in gained thick dispersible pigment dispersion (2) 109g System) 0.17g, the boric acid aqueous solution 1.19g of 6.18%, water 50g, at 70 DEG C stir 5 hours.After reaction terminates, it is cooled to room Temperature, after oversize grain being removed by filter that aperture is 1.0 μm, utilize centrifuge make oversize grain sedimentation (7000rpm, 10 minutes).After being removed by the solid of sedimentation, the filter water using molecular cut off to be 50,000 is sufficiently washed, it is thus achieved that Pigment concentration is dispersible pigment dispersion (2) 149g of 9.7%.

［ embodiment 25 ］

20g above-described embodiment 6 mixes in synthesis example 6 in δ type crystal habit AZOpigments (the 1)-3-A of synthesis and obtains Dispersant (methyl methacrylate (47.8 moles of %), methacrylic acid (31.8 moles of %), 2-Ethylhexyl Methacrylate The dipropylene glycol solution of copolymer of (20.4 moles of %), Mw=83,000, acid number are 154mgKOH) 28.4g(solid constituent contains To have rate be 35.2%, solid constituent is 10.0g), water 62g, use sand mill TSG1(IMEX company system) with a diameter of 0.1mm's Zirconium oxide beadlet 375g carries out 1500 turns per minute together, after dispersion at 45 DEG C 3 hours, is separated by zirconium oxide beadlet, use water Wash, it is thus achieved that pigment concentration is thick dispersible pigment dispersion (3) the 112g(average volume particle diameter Mv=of 13.9 weight % 96.7nm).

Interpolation DENACOL EX-321(Nagase ChemiteX Co., Ltd. in gained thick dispersible pigment dispersion (3) 112g System) 0.77g, the boric acid aqueous solution 5.4g of 6.18%, water 30g, at 70 DEG C stir 5 hours.After reaction terminates, it is cooled to room temperature, After oversize grain being removed by filter that aperture is 1.0 μm, utilize centrifuge make oversize grain sedimentation (7000rpm, 10 points Clock).After being removed by the solid of sedimentation, the filter water using molecular cut off to be 50,000 is sufficiently washed, it is thus achieved that pigment Concentration is dispersible pigment dispersion (3) 127g of 10.4%.

［ embodiment 26 ］

The δ type crystal habit AZOpigments (1)-2 of synthesis mixes in the above-mentioned synthesis example of 20g 2 acquisition in synthesis example 4 Dispersant (benzyl methacrylate (66.7 moles of %), methacrylic acid (33.3 moles of %) copolymer dipropylene glycol solution, Mw=83,000, acid number be 140mgKOH) 32.4g(solid constituent containing ratio is 30.8%, solid constituent is 10.0g), water 46g, Use sand mill TSG1(IMEX company system) carry out together with the zirconium oxide beadlet 375g of a diameter of 0.1mm 1500 turns per minute, After dispersion at 45 DEG C 9 hours, zirconium oxide beadlet is separated, washs with water, it is thus achieved that pigment concentration is the thick of 15.3 weight % Dispersible pigment dispersion (4) 98g(average volume particle diameter Mv=98.2nm).

Interpolation DENACOL EX-321(Nagase ChemiteX Co., Ltd. in gained thick dispersible pigment dispersion (4) 98g System) 0.75g, the boric acid aqueous solution 5.3g of 6.18%, water 50g, at 70 DEG C stir 5 hours.After reaction terminates, it is cooled to room temperature, After being removed by oversize grain by the filter that aperture is 1.0 μm, centrifuge is utilized to make oversize grain settle further (7000rpm, 10 minutes).After being removed by the solid of sedimentation, the filter use water using molecular cut off to be 50,000 is fully Washing, it is thus achieved that pigment concentration is dispersible pigment dispersion (4) 145g of 9.4%.

［ comparative example 7 ］

In 20g P.Y.128(Cromophtal Yellow8GN, Ciba company system) in mixing synthesis example 5 obtains point Powder (benzyl methacrylate (66.7 moles of %), the dipropylene glycol solution of copolymer of methacrylic acid (33.3 moles of %), Mw =83,000, acid number is 140mgKOH) 32.4g(solid constituent containing ratio is 30.8%, solid constituent is 10.0g), water 46g, make By sand mill TSG1(IMEX company system) carry out together with the zirconium oxide beadlet 375g of a diameter of 0.1mm 1500 turns per minute, 45 After dispersion at DEG C 6 hours, zirconium oxide beadlet is separated, washs with water, it is thus achieved that pigment concentration is the comparison of 16.3 weight % With thick dispersible pigment dispersion (1) 81g(average volume particle diameter Mv=93.4nm).

Compare with thick dispersible pigment dispersion (1) 81g adds DENACOL EX-321(Nagase ChemiteX strain at gained Formula commercial firm system) 0.66g, the boric acid aqueous solution 4.7g of 6.18%, water 45g, at 70 DEG C stir 5 hours.After reaction terminates, cooling To room temperature, after being removed by oversize grain by the filter that aperture is 1.0 μm, centrifuge is utilized to make oversize grain settle further (7000rpm, 10 minutes).After being removed by the solid of sedimentation, the filter use water using molecular cut off to be 50,000 is fully Washing, it is thus achieved that pigment concentration is comparison dispersible pigment dispersion (4) 115g of 10.2%.

＜ tinting strength, tinting power evaluates ＞

With water, the pigment dispersion obtained in above-described embodiment 23～26 is diluted to 10 mass times, then uses No.3's Bar coater is coated on EPSON company photo mat paper.Reflection of the concentration (X-Rite company X-Rite938) is used to survey Determine the image color of gained coating material, in order to lower standard evaluation " tinting strength, tinting power (OD:Optical Density) ".By OD than implementing Example 20 excellence be evaluated as A, by with embodiment 20 equal extent be evaluated as B, will be poorer than embodiment 20 but more excellent than embodiment 19 Different be evaluated as C, by with being evaluated as D, E will be evaluated as than embodiment 19 difference of embodiment 19 equal extent.Show the result in Table 3.

Table 3

	Tinting strength, tinting power
		Embodiment 20	B
Embodiment 19	D
		Embodiment 23	A
Embodiment 24	A
		Embodiment 25	A
Embodiment 26	C
		Comparative example 7	E

［ embodiment 27 ］

Reach 5 mass % according to the dispersible pigment dispersion (1) obtained in embodiment 23 with solid component meter, glycerol reaches 10 matter Amount %, 2-Pyrrolidone reaches 5 mass %, 1,2-hexanediol reaches 2 mass %, triethylene glycol monobutyl base ether reaches 2 mass %, the third two Alcohol reaches 0.5 mass %, Surfynol465 reaches 1 mass %, ion exchange water reaches the mode of 74.5 mass % and adds each composition, Utilization is provided with the capacity of 1.2 μm filters (cellulose acetate membrane, external diameter: 25mm, society of Fuji Photo Film Co., Ltd. system) The mixed liquor of the syringe filtering gained of 20mL, removes oversize grain, it is thus achieved that pigment ink (1).

［ embodiment 28,29 ］

Dispersible pigment dispersion (1) in above-described embodiment 27 is replaced in embodiment 24 obtain dispersible pigment dispersion (2) and The dispersible pigment dispersion (3) obtained in embodiment 25, obtains pigment ink (2) and pigment ink (3) respectively.

［ comparative example 8 ］

Society of SEIKO EPSON Co., Ltd. ICY-42 is used to carry out following evaluation.

＜ evaluates ＞

Ink liquid is seated in the Yellow ink liquid of society of SEIKO EPSON Co., Ltd. ink-jet printer PX-V630 In print cartridge, by photo material be make on society of SEIKO EPSON Co., Ltd. photo paper using ChrisPia ＜ high glaze ＞ by Take color to set: without complementary color, press quality: picture, the O.D. of yellow reach the mode of 1.0 and print the product obtained and carry out The product of field printing, evaluates light resistance and concentration.

＜ tinting strength, tinting power evaluates ＞

Reflection of the concentration (X-Rite company X-Rite938) is used to measure the image color of the product through field printing, In order to lower standard evaluation " tinting strength, tinting power (OD:Optical Density ".OD is evaluated as than comparative example 8 excellence A, will with compare Example 8 equal extent be evaluated as B, by than comparative example 8 difference be evaluated as C.Show the result in table 4.

＜ Investigation on Photodegradation ＞

The photo using fadometer to print the mode reaching 1.0 according to O.D. irradiates xenon light (99000lux；TAC filters In the presence of device) 28 days, the image color after using reflection of the concentration to measure xenon pre-irradiation is ［ (after irradiation dense by pigment residue rate Degree/pre-irradiation concentration) × 100% it is more than 90% be evaluated as A, be evaluated as B less than 90%.Show the result in table 4.

Table 4

Industrial applicability

The manufacture method of the AZOpigments of the present invention can high efficiency and manufacture the azo face of favorable dispersibility at low cost Material microgranule.

Although illustrating the present invention with reference to specific embodiment the most in detail, but those skilled in the art obviously can be The most various changes or correction.

The application be based on Japanese patent application (Japanese Patent Application 2011-167831) filed in 29 days July in 2011 and The application of Japanese patent application (Japanese Patent Application 2012-33394) filed in 17 days February in 2012, its content is as with reference to including in The application.

Claims (14)

1. the manufacture method of the AZOpigments shown in following formula (1), it is characterised in that shown in amorphous following formula (1) Azo-compound or its salt crystalline transformation at a temperature of 15 DEG C～150 DEG C becomes the Prague in CuK α characteristic X-ray diffraction Angle (2 θ ± 0.2 °) is the crystal formation at 4.8 °, 7.2 ° and 9.7 ° with characteristic X-ray diffraction maximum；

The solvent used in described crystalline transformation is water, methanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, diethylene glycol Anaesthetie Ether, diethylene glycol monomethyl ether, dipropylene glycol, acetic acid, propanoic acid, sulphuric acid or their mixed solvent.

The manufacture method of AZOpigments the most according to claim 1, it is characterised in that by a solvent to amorphous Azo-compound shown in described formula (1) or its salt carry out heated and stirred to carry out crystalline transformation.

The manufacture method of AZOpigments the most according to claim 1, it is characterised in that by amorphous described formula (1) institute The azo-compound crystalline transformation shown becomes the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction to be 4.8 °, 7.2 °, There is at 9.7 °, 20.1 ° and 26.8 ° the crystal formation of characteristic X-ray diffraction maximum.

The manufacture method of AZOpigments the most according to claim 1, it is characterised in that by amorphous described formula (1) institute The azo-compound crystalline transformation shown becomes the Bragg angle (2 θ ± 0.2 °) in CuK α characteristic X-ray diffraction to be 4.8 °, 7.2 °, There is at 9.5 °, 9.7 °, 10.7 °, 17.4 °, 19.0 °, 20.1 ° and 26.8 ° the crystal formation of characteristic X-ray diffraction maximum.

The manufacture method of AZOpigments the most according to claim 1, it is characterised in that comprise following operation:

I cloth that azo-compound crystalline transformation shown in amorphous described formula (1) is become in CuK α characteristic X-ray diffraction by () Glug angle (2 θ ± 0.2 °) is the operation of the crystal formation at 4.8 °, 7.2 ° and 9.7 ° with characteristic X-ray diffraction maximum；And

(ii) to the mixing containing AZOpigments, water-soluble inorganic salt and the water-miscible organic solvent obtained in described operation (i) Thing carries out mixing, and making the BET specific surface area utilizing nitrogen adsorption method to record is 50m²The operation of the crystal of/more than g.

The manufacture method of AZOpigments the most according to claim 1, it is characterised in that comprise following operation:

The operation of the amino-compound shown in (a) mixing diazotization agent and following formula (2)；

B () is by carrying out anti-by the coupling components mixing shown in the product obtained in described operation (a) and following formula (3) Should, it is thus achieved that be dissolved with the work of at least one of solution of the azo-compound shown in the following formula (1) generated by this reaction Sequence；And

C the solution obtained in described operation (b) is mixed by () with described solvent, make the amorphous azo shown in following formula (1) The operation of compound partial crystallization；

The manufacture method of AZOpigments the most according to claim 6, it is characterised in that in described operation (b), gained Solution is acid solution.

The manufacture method of AZOpigments the most according to claim 7, it is characterised in that described acid solution contain acetic acid and At least one in sulphuric acid.

The manufacture method of AZOpigments the most according to claim 6, it is characterised in that in described operation (b), gained is molten Liquid is the solution that the azo-compound shown in the described formula (1) generated by coupling reaction is completely dissolved.

10. an AZOpigments, it is to be obtained by the manufacture method according to any one of claim 1～9.

11. 1 kinds of pigment dispersions, it contains the AZOpigments described in claim 10, dispersant and water.

12. pigment dispersions according to claim 11, it is characterised in that dispersant is water soluble polymer.

13. pigment dispersions according to claim 12, it is characterised in that described water-soluble polymer dispersant have to Few 1 carboxyl, there is the acid number of at least more than 50mgKOH/g.

14. according to the pigment dispersion described in claim 12 or 13, it is characterised in that described aqueous pigment dispersion is by handing over Join agent and cross-link.