JP6520063B2 - Pigment composition, method for producing the same, and pigment composition for color filter - Google Patents

Description

  The present invention relates to a pigment composition containing a finely divided pigment and a method of producing the same. The present invention also relates to a water-soluble organic solvent for grinding and kneading suitable for the production of the pigment composition. Furthermore, the present invention relates to a pigment composition for color filter comprising the pigment composition.

  Pigments are widely used as coloring materials for various industrial materials such as paints, inks, coloring materials for plastics and the like. In order to use a pigment as a colorant, a plurality of processes are performed on the crude pigment. For example, a water-soluble organic solvent, a water-soluble inorganic salt and a resin are added to the crude pigment to carry out a grinding and kneading step. Thereafter, through a purification process, a dry pulverization process is performed to obtain a powder. Although the pigment may be used in the form of powder, it is usually dispersed in a dispersion medium such as a solvent or a resin. As another method, a method of obtaining a pigment composition by omitting the drying and grinding step after the purification step has also been proposed (Patent Document 1).

  In order to obtain an excellent colorant, it is particularly important to keep the pigment well dispersed in the dispersing medium. If the dispersibility of the pigment is poor, there is a problem that the composition can not be taken out from the disperser during the production process, the viscosity stability of the product is poor, or gelation occurs during storage. In addition, there is also a problem that the glossiness of the surface of the spread product is lowered, the leveling failure and the like occur.

  For this reason, research and development have been energetically promoted to control the dispersibility of processed pigments. For example, a technique for modifying the surface of the pigment to improve the dispersibility, and a dispersant for maintaining the dispersed state well have been developed (for example, Patent Document 2).

JP, 2010-106260, A International Publication No. 2008/007776

  To make the pigment in a pigment composition such as a pigment composition for a color filter, a photosensitive pigment composition for a color filter, an inkjet ink or an electronic developer in a stream where the demand for high definition becomes severe It is important. However, when the pigment is subjected to the refining treatment, the pigments are easily aggregated to cause problems such as deterioration of dispersibility and deterioration of viscosity stability.

  The present invention has been made in view of the above background, and the object of the present invention is to provide a finely divided pigment composition excellent in the dispersion performance of the finely divided pigment and having high production efficiency, and a method of producing the same It is an object of the present invention to provide a water-soluble organic solvent for grinding and kneading, and a pigment composition for a color filter.

The inventors of the present invention diligently studied to solve the above problems, and it is surprising that the following aspects of the present invention are produced using a water-soluble organic solvent satisfying all of (i) to (iv). It has been found that the problems can be solved, and the present invention has been completed.
[1] A step of adding at least a water-soluble inorganic salt and a water-soluble organic solvent to a pigment and refining the pigment by grinding and kneading (a) and, after the step (a), adding water to a suspension And (c) removing the water-soluble inorganic salt after the step (b), and removing the water-soluble organic solvent so as to satisfy the following (A); The method for producing a pigment composition, comprising the step (d) of removing water after c), wherein the water-soluble organic solvent satisfies the following (i) to (iv).
(A) The water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the pigment contained in the pigment composition.
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of two or more functional groups (F) consisting of a hydroxyl group and / or an ester group.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) does not contain an ether bond.
[2] The water-soluble organic solvent is 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-methylpentane-2 At least one selected from 2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,2,6-hexanetriol The manufacturing method of the pigment composition as described in [1].
[3] The method for producing a pigment composition according to [1] or [2], further including a resin in the step (a).
[4] The pigment composition according to any one of [1] to [3], wherein the pigment is at least one selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Manufacturing method.
[5] The pigment composition according to any one of [1] to [4], which is subjected to a step (e) of adding a dispersion solvent and mixing and stirring it after the step (c) and before the step (d) Manufacturing method.
[6] A pigment composition comprising a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm,
A pigment in which a water-soluble organic solvent satisfying the following (i) to (iv) remains in a range of 0.005 to 0.5 parts by mass per 100 parts by mass of the pigment contained in the pigment composition Composition.
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of two or more functional groups (F) consisting of a hydroxyl group and / or an ester group.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) does not contain an ether bond.
[7] A water-soluble organic solvent for milling and kneading, which is used for producing a pigment composition containing a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm, which comprises the following (i) Water-soluble organic solvent for grinding and kneading which satisfies (iv).
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of two or more functional groups consisting of hydroxyl groups and / or ester groups.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) does not contain an ether bond.
[8] The water-soluble organic solvent is 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-methylpentane-2 At least one selected from 2,4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol and 1,6-hexanediol [13] Water-soluble organic solvent for water.
[9] A pigment composition for color filter comprising the pigment composition according to [6].

  According to the present invention, a finely divided pigment composition excellent in the dispersion performance of the finely divided pigment and having high production efficiency, a method for producing the same, a water-soluble organic solvent for grinding and kneading, and a pigment composition for color filter It has the excellent effect of being able to provide goods.

The flowchart figure for demonstrating the manufacturing process of the pigment composition which concerns on embodiment. The flowchart figure for demonstrating the manufacturing process of the pigment composition which concerns on embodiment.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. Needless to say, other embodiments are also included in the scope of the present invention as long as they conform to the spirit of the present invention. Further, in the present specification, the description “arbitrary number A to arbitrary number B” includes the number A as the lower limit and the number B as the upper limit in the range.

  The pigment composition of the present invention is obtained by at least performing the following steps (a) to (d) shown in FIG.

<Step (a)> In the step (a), at least a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment, and the pigment is refined by grinding and kneading. The method of pulverizing the pigment by grinding and kneading is not particularly limited, and any method can be applied, but a grinding and kneading step or the like by so-called salt milling is suitable. The average primary particle size of the finely divided pigment may vary depending on the application, but is usually 5 to 1,000 nm. As the pigment used here, an untreated crude pigment is usually used, but a pigment which has undergone some processing steps may be used. Moreover, the pigment to be used may be a single kind or plural kinds.

  The grinding and kneading method is a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, horizontal sand mill, vertical sand mill or / and an anula type, a mixture containing at least a pigment, a water soluble inorganic salt and a water soluble organic solvent. It can carry out using kneaders, such as a bead mill. The processing conditions and the like may be appropriately adjusted in accordance with the type of pigment, the degree of miniaturization required, and the like. It is preferable to carry out heating when mechanically kneading. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed using the high hardness of the water-soluble inorganic salt. By optimizing the conditions for salt milling, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

The pigment is not particularly limited as long as it does not deviate from the spirit of the present invention, and organic pigments and inorganic pigments can be applied. Examples of preferred pigments include at least one organic pigment selected from dyed lake pigments, azo pigments, phthalocyanine pigments and condensed polycyclic pigments. The azo pigment may be either a soluble azo pigment or an insoluble azo pigment. The following pigments are mentioned as a preferable specific example of the said pigment.
As dyed lake pigments, pigment yellow (hereinafter abbreviated as PY) 18, PY 100, PY 104, pigment orange (hereinafter abbreviated as PO) 39, pigment red (hereinafter abbreviated as PR) PR81, PR83, PR90, PR169, PR172, PR173, PR174, PR193, pigment violet (hereinafter abbreviated as PV) 1, PV2, PV3, PV4, PV12, PV27, PV39, pigment blue (hereinafter abbreviated as PB) 1, PB2, PB14, PB62, pigment green (hereinafter abbreviated as PG) PG1, PG2, PG3, PG4, PG45 and the like can be mentioned.
In the case of azo pigments, soluble azo pigments such as PR53, PR50, PR49, PR57: 1, PR48: 1, PR52: 1, PR1, PR3, PO5, PR21, PR114, PR5, PR146, PR170, PO38, PR187, PY1, Insoluble azo pigments such as PY3, PY167, PY154, PO36, PY12, PY13 and PY14, and condensed azo pigments such as PR144, PR166, PR214, PR242, PY93, PY94, PY95 and the like can be mentioned.
Examples of phthalocyanine pigments include PB16, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PG7, PG36, PG58, aluminum phthalocyanine and the like.
As condensed polycyclic pigments, PY24, PY108, PO51, PR168, PR177, PB60 etc., PY38, PR88, PO43, PR194, PR178, PR179, PY138, PV23, PV19, PR122, PY109, PY110, PY139, PY139, PR254 , PR255, PR272, PO71, dibromodiketopyrrolopyrrole and the like.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and it needs to be soluble (miscible) in water and substantially insoluble in the water-soluble inorganic salt used. Furthermore, the water-soluble organic solvent of the present invention satisfies the following (i) to (iv). That is,
(I) The molecular weight is 100 to 350, more preferably 130 to 350,
(Ii) having a total of two or more functional groups (F) consisting of hydroxyl group (OH group) and / or ester group (-COO- group), and (iii) viscosity at 60 ° C. of 2 to 140 mPa · s Yes,
(Iv) does not contain an ether bond,
It meets all the conditions. The water-soluble organic solvent of the present invention may be used alone or in combination of two or more. A water-soluble organic solvent satisfying these (i) to (iv) (hereinafter also referred to as a water-soluble organic solvent of the present invention) is suitable as a solvent for grinding and kneading. In addition, use of solvents other than the water-soluble organic solvent of this invention (The water-soluble organic solvent which does not satisfy any one or more of said (i)-(iv) is included) is a range which does not deviate from the meaning of this invention. It is not something to exclude. However, from the viewpoint of effectively enhancing the dispersibility of the finely divided pigment, it is preferable to use the water-soluble organic solvent of the present invention substantially. Hereinafter, the water-soluble organic solvent of the present invention will be described.

  (Ii) having a total of two or more functional groups (F) consisting of a hydroxyl group and / or an ester group is a) a solvent having two or more hydroxyl groups and no ester group, b) two ester groups The solvent containing the above and containing no hydroxyl group, and c) the case where both the hydroxyl group and the ester group are contained and the total of the both is 2 or more are included. The viscosity of (iii) is a viscosity when the water-soluble organic solvent alone is measured at a temperature of 60 ° C. The viscosity of the water-soluble organic solvent in the present specification is a value measured using a conical and flat plate-type rotational viscometer (viscometer made by Toki Sangyo Co., Ltd .: TVE-20L) according to the definition of JIS Z 8803. Also, as specified in (iv), the water-soluble organic solvent is one that does not contain an ether bond in its molecule.

  By using a water-soluble organic solvent satisfying all of (i) to (iv), the dispersibility of the finely divided pigment can be improved. The reason is not speculative, but it is believed that the water-soluble organic solvent of the present invention has produced good results in the interaction with the pigment. In addition, it is considered that when the water-soluble organic solvent of the present invention remains in a specific range with respect to the pigment, it is possible to suppress aggregation of the finely divided pigment.

  The water-soluble organic solvent used in the step (a) is not particularly limited as long as it satisfies all of the above (i) to (iv), but as a preferable example, 2-ethyl-1,3-hexanediol (16. 6 mPa · s), 2,4-diethyl-1,5-pentanediol (67.2 mPa · s), monoacetin (13.7 mPa · s), diacetin (8.2 mPa · s), triacetin (4.1 mPa · s) ), Tripropionin (2.7 mPa · s), tributyrin (3.3 mPa · s), 2-methylpentane-2,4-diol (5.8 mPa · s), 2-butyl-2-ethyl-1,3- Propanediol (43.7 mPa · s), 1,5-pentanediol (20.9 mPa · s), 1,6-hexanediol (25.2 mPa · s) and 1,2,6-hexene At least one selected from Ntorioru (137.6mPa · s) and the like.

  Although the addition amount of the water-soluble organic solvent of this invention is not specifically limited, It is preferable to use 5-1,000 mass parts with respect to 100 mass parts of pigments, and it is more preferable to use 50-500 mass parts. The water-soluble organic solvent may be used alone or in combination of two or more.

  The water-soluble inorganic salt used in the step (a) may be an inorganic salt exhibiting water solubility as the name indicates, and is not limited in the scope of the present invention. Preferred examples include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. It is preferable to use sodium chloride (salt) from the point of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, with respect to 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

  In the step (a), additives such as dispersants and dye derivatives may be further included. As a dispersing agent, resin and / or surfactant of low molecular weight etc. are mentioned.

  The type of resin used as the dispersant is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. This resin is solid at room temperature, preferably water-insoluble, and more preferably soluble in the water-soluble organic solvent of the present invention. It is preferable that the usage-amount of resin is the range of 5-100 mass parts with respect to 100 mass parts of pigments. One of the advantages of using the water-soluble organic solvent of the present invention in carrying out the resin treatment is to dissolve the resin. By using the water-soluble organic solvent of the present invention, it becomes possible to coat the resin uniformly on the pigment, and even when the pigment is dried, the coating resin suppresses the aggregation of the pigments to improve the dispersibility. I believe it will contribute.

Polyurethane, polyester, unsaturated polyamide, phosphoric acid ester, polycarboxylic acid and its amine salt, ammonium salt, alkylamine salt, polycarboxylic acid ester, hydroxyl group-containing polycarboxylic acid ester as preferable examples of the resin used as the dispersing agent Oil-based dispersants such as polysiloxane and modified polyacrylate, (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid-styrene copolymer, water-soluble such as styrene-maleic acid copolymer Examples thereof include resins and water-soluble polymer compounds. The resin type dispersant may be used alone or in combination of two or more. The mass average molecular weight of the resin type dispersant is preferably about 1,000 to 30,000.
Specifically, SOLSPERSE 3000, 13240, 13940, 16000, 17000, 18000, 20000, 21000, 24000 SC, 24000 GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 34550, 35100, 35200, 36000, 36600, 36600 37500, 38500, 39000, 41000 (above, manufactured by Nippon Lubrizol Corporation); DISPERBYK-101, 102, 106, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 161, 162, 163 164, 166, 167, 168, 170, 171, 174, 180, 182, 184, 185, 2000, 2001, 2008, 2009, 2022, 2025, 2050, 2070, 2096, 2150, 2155, 2163, 2164 BYK-P104, P104S, P105, 9076, 9077, 220S (above, made by Big Chemie Japan), EFKA 4008, 4009, 4010, 4015, 4046, 4047, 4010, 4015 , 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4401, 4402, 4406, 4800, 5010, 5044, 5207, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070 (more , BASF Japan Ltd.); Par PB821 (F), PB822, PB880, PB881, PN-411, PA-111 (all manufactured by Ajinomoto Fine Techno Co., Ltd.); Hinoacto (manufactured by Kawaken Fine Chemicals Co., Ltd.); DISPARLON KS-860, KS-873N, 7004, 1831 1850, 1860, DA-7301, DA-325, DA-375, DA-234, PW-36 (manufactured by Kushimoto Chemical Co., Ltd.) and the like.

Preferable examples of the surfactant used as the dispersant include naphthalene sulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, anionic surfactant such as polyoxyethylene alkyl phosphate, polyoxyethylene alkyl ether and the like. Examples of the surfactant include cationic surfactants such as nonionic surfactants, alkylamine salts and quaternary ammonium salts.
Specifically, Demol N, RN, MS, SN-B; Emulgen 120, 430; Acetamine 24, 86; Cortamine 24 P (above, manufactured by Kao Corporation), Plysurf AL, A 208 F (above, Dai-ichi Kogyo Seiyaku Co., Ltd.) Arcard C-50, T-28, T-50 (all manufactured by Lion Corporation) and the like.

As a derivative of an organic pigment used as a dispersant, a compound having an organic pigment as a basic skeleton and having introduced therein a substituent imparting acidity in a molecule or a substituent imparting basicity is preferable. By adding a derivative of an organic pigment, the pigment to be dispersed is adsorbed to give polarity, and it is considered that the dispersing effect is given from the interaction with the dispersant and the resin. Further, the effect of contributing to crystal stabilization and dispersion stabilization of the pigment can be expected.
Specifically, in addition to synthetic products manufactured by Sanyo Dye Co., Ltd., as examples of commercial products, EFKA-6745, 6750 (manufactured by EFKA Additive), BYK-Synergist 2100 (manufactured by Bick Chemie Japan), Solspers 5000, 12000, 22000 (above, manufactured by Nippon Lubrizol Corporation) and the like.
In addition, fibrous derivatives, rubber derivatives and / or protein derivatives can also be selected and used according to the synthetic resin and having similar performance. Among these synthetic resins, epoxy resins and (meth) acrylic resins are preferably used. This is because the versatility is wide, the transparency is high, and the resistance to color filters is excellent.
The epoxy resin is an epoxide having one or more epoxy groups in the molecule, and in the present invention, an epoxy resin which is not crosslinked by a curing agent and is soluble is preferable. Examples of epoxides include bisphenols, novolaks, alkylphenols, resorcins, polyglycols, esters, glycidyls such as N-glycidylamine, and cyclic aliphatic epoxides.
The (meth) acrylic resin is a copolymer of a single substance or a mixture selected from monomers of acrylic acid, methacrylic acid and esters thereof, which further have a radical polymerizable property such as styrene, vinyl acetate and maleic anhydride It may be a copolymer with a monomer.

  The amount of each of the water-soluble organic solvent, water-soluble inorganic salt, dispersant, etc. to be added to the pigment is not limited as long as the pigment can be finely processed, but the shear force effectively grinds the pigment with the water-soluble inorganic salt. It is important for the refining process to have a viscosity and hardness given by

<Step (b)> After step (a), water is added thereto to obtain a suspension (FIG. 1). Preferably, after completion of step (a), the pigment dispersion is removed from the grinding and kneading machine, water is added and stirring is performed to obtain a suspension. The amount of water to be added may be an amount sufficient to obtain a suspension, and is not particularly limited. You may heat as needed. For example, water having a mass of 10 to 10,000 times the mass of step (a) is added and mixed and stirred. The mixing and stirring conditions at this time are not particularly limited, and for example, the mixing and stirring can be performed at a temperature of 25 to 90 ° C.

<Step (c)> After the treatment of step (b), the water-soluble inorganic salt is removed, and the water-soluble organic solvent satisfying the following (A) is removed (FIG. 1).
(A) The water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the pigment contained in the pigment composition.
The method of making the water-soluble organic solvent remain in the above specific range can be easily adjusted by controlling the removal conditions (for example, washing conditions, drying conditions, filtration conditions). The treatment process is not limited as long as the above object can be achieved, but the method of removing the filtrate by filtration is simple.
The residual solvent per 100 parts by mass of the pigment contained in the pigment composition is obtained by measuring the residual solvent of the water-soluble organic solvent of the present invention in the total solid content of the pigment composition, and calculated from the ratio of the pigment in the solid content it can. Here, the ratio of the pigment to the solid content is the ratio of the charged amount of the pigment to the total solid content in the finally obtained pigment composition. In addition, although the pigment may be slightly lost in the step (b) and the like in practice, the proportion of the pigment in the solid content in the present specification is as described above.

<Step (d)> After the step (c), water is removed (FIG. 1). Although it will not be limited if it is the method of removing water, the method of performing a drying process can be mentioned as a suitable method. The drying conditions in the step (d) are, for example, a method of drying at about 80 to 120 ° C. for about 12 to 48 hours under normal pressure, and drying for about 12 to 60 hours at about 25 to 80 ° C. under reduced pressure. The method to perform, after freezing in the range of −60 to −5 ° C., can be exemplified a method of drying in the range of 25 to 80 ° C. for about 12 to 60 hours under reduced pressure. Although a drying process is not specifically limited, The method of utilizing a spray-drying apparatus can be illustrated. The grinding treatment may be performed simultaneously with or after the drying treatment.

  By using the water-soluble organic solvent of the present invention, a powdery pigment composition having a high bulk density can be obtained. That is, by using the water-soluble organic solvent of the present invention, it is possible to obtain a pigment composition containing a soft, fluffy powder-like finely divided pigment in qualitative expression. The preferred bulk density may vary depending on the application, but is preferably 0.4 g / mL or less.

An example of the preferable embodiment of the manufacturing method of the pigment composition of this invention is demonstrated in FIG. As a preferred embodiment, the process of routes r1 to r3 shown in FIG. 2 can be exemplified.
Step (a) to step (d), route r1 for obtaining powder, route r2 for performing step (e) after step (d), and step (e) after step (c) , And the route r3 for performing the step (d) after that. The pigment composition obtained by route r1 is in powder form, and the pigment composition obtained by route r2, r3 is, for example, in the form of varnish dispersed in a dispersing solvent. In addition, the pigment composition of this invention should just contain process (a)-process (d), and process (e) can be added arbitrarily. In addition, other steps can be optionally added without departing from the scope of the present invention.

  The preferred production method may vary depending on the type of product or needs, but from the viewpoint of the simplicity of the production process, the method of directly obtaining the dispersion solvent as in route r3 of FIG. 2 is preferred. Moreover, as a method of taking out as powder, route r1 is preferable from the viewpoint of simplicity of the production process. Further, from the viewpoint of further enhancing the dispersibility of the pigment composition to be obtained, it is preferable to carry out a dry pulverization treatment when removing water in the step (d) of the route r1 and the route r2.

<Step (e)> After the step (d), a dispersion solvent is added to the mixture and mixed and stirred (see FIG. 2). The mixing and stirring method is not particularly limited as long as it can be uniformly dispersed. For example, a stirring blade, a dissolver, a homomixer, an ultrasonic homogenizer and the like can be mentioned. Such processing may be performed in combination of two or more. In step (e), in addition to the dispersing solvent, dispersing aids and other additives may be added. For example, binder resins, dye derivatives, surfactants, other dyes and the like can be added. These are not particularly limited as long as they do not interfere with the dispersibility of the pigment, but are preferably those which are soluble in the dispersion solvent. By using a dispersing aid, the dispersibility of the pigment can be enhanced, and reaggregation of the pigment after dispersion can be prevented more effectively.

(Dispersion Solvent) The dispersion solvent used in the step (e) is not particularly limited as long as it does not disturb the dispersibility of the pigment. Preferred examples include 1,2,3-trichloropropane, 2-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, n-butylbenzene, n-propyl acetate, o-xylene, o- Chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Cole monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol Monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol Cole monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monomethyl ether, diacetone alcohol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-methylpentane-2 , 4-diol, 2-butyl-2-ethyl-1,3-propanediol 1,5-pentanediol, 1,6-hexanediol, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Isoamyl acetate, isobutyl acetate, vinegar Propyl, dibasic acid esters and the like. Also, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-methyl-1,3-propanediol, 3-methyl-1 And 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol and the like.

  Among these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. because the solubility and coating properties of each component of the pigment composition are good. It is preferable to use glycol acetates of the above, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone.

  These dispersion solvents can be used alone or in combination. The dispersion solvent can be appropriately set according to the application to be used, but since the pigment composition can be adjusted to an appropriate viscosity and a filter segment having an intended uniform film thickness can be formed, the total mass of the pigment can be determined. It is preferable to use it in the amount of 500 to 4,000% by mass (100% by mass). In the case of the route r3, it is more preferable to use a non-water-soluble organic solvent as the dispersion solvent, since the step of removing water is included after the step (d).

(Binder resin) As binder resin used at a process (e), a conventionally well-known thermoplastic resin or thermosetting resin etc. can be used. A resin which has as a binder resin a pigment affinity site having a property of adsorbing to an additive pigment and a site compatible with the pigment carrier, and adsorbs to the additive pigment to stabilize the dispersion in the pigment carrier Type dispersants are preferred. Binder resin can be used individually or in mixture of 2 or more types.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane type Examples thereof include resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene and polyimide resins.
The following are mentioned as a suitable example of a monomer which constitutes a thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate or ethoxypolyether (Meth) acrylates such as glycol (meth) acrylate or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloyl morpholine, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate or vinyl propionate.
Also, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bis maleimide ethane 1,6-bis maleimide hexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimidodiphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4 Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimide -3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzoimidazolyl) phenyl N-substituted maleimides such as maleimide, 9-maleimidacridine and the like.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, and phenol resin. Among them, epoxy resin and melamine resin are more preferably used from the viewpoint of heat resistance improvement.

  Further, as preferable examples of the resin type dispersant, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkyl Amine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups Oil-based dispersants such as salts, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyesters, Polyacrylate, ethylene oxide / propylene oxide adduct, phosphoric acid ester and the like.

  The resin type dispersant is preferably a polymer dispersant having a basic functional group because the viscosity of the pigment composition becomes low with a small amount of addition and high spectral transmittance is exhibited, and the nitrogen atom-containing graft copolymer is used. A nitrogen atom-containing acrylic block copolymer, a urethane polymer dispersant and the like having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring and the like in the side chain are preferable. The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass based on the total amount of the pigment (100% by mass), and more preferably about 10 to 100% by mass from the viewpoint of film formation.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204 or BYK-P104. , P104 S, 220 S, 6919 or Lactimon, Lactimon-WS or Bykumen et al. 27000, 28000, 31845, 32000, 32500, 32500, 33600, 34500, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc .; BASF EFKA-46, 47, 48, 452, 4008 , 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4550 , 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 4, 1101, 120, 150, 1501, 1502, 1503 and the like; Azispar PA111, PB711, PB821, PB822, PB824 and the like manufactured by Ajinomoto Fine Techno Co., Ltd.

  The mass average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, and more preferably in the range of 7,000 to 50,000, in order to disperse the pigment preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are “TSK-GEL SUPER H5000” and “H4000” manufactured by Tosoh Corp. as separation columns in gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corp. It is the conversion molecular weight which used "H3000" and "H2000" in series, and measured polystyrene at 40 ° C using tetrahydrofuran as a mobile phase as a standard substance. Although the addition amount of the binder resin is not particularly limited, it is preferably used in an amount of 20 to 500% by mass based on the total mass of the pigment (100% by mass) in consideration of film forming property, weatherability and color characteristics.

  When used as a color filter application, the binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light range. When used in the form of an alkali-developable colored resist, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Moreover, in order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  As alkali-soluble resin which copolymerized the acidic group containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer or isobutylene / (Anhydride) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, in particular an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency.

  As an energy ray curable resin having an ethylenically unsaturated active double bond, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group is subjected to a reactive substitution such as an isocyanate group, an aldehyde group or an epoxy group A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or a cinnamic acid is used. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is a half ester by a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Are preferred. For color filter applications, thermoplastic resins having both alkali-soluble performance and energy ray curing performance are also suitable.

(Dye derivative) As the dye derivative, a compound obtained by introducing a phthalimidomethyl group which may have a basic substituent, an acidic substituent or a substituent into an organic pigment, anthraquinone, acridone or triazine may be mentioned, for example, Those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. And these can be used individually or in mixture of 2 or more types. When a dye derivative is used, those having an azo skeleton, a naphthol azo skeleton, a diketopyrrolopyrrole skeleton, an anthraquinone skeleton, a quinophthalone skeleton, and a perylene skeleton are preferable from the viewpoint of lightness and dispersibility.

  The compounding amount of the dye derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably, based on the total amount (100% by mass) of the additive pigment from the viewpoint of improving the dispersibility of the additive pigment. It is 3% by mass or more. In addition, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 100% by mass or less, and more preferably 35% by mass or less.

(Surfactant) Preferred examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, alkyl naphthalene Sodium sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Anionic surfactants such as esters; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether Nonionic surfactants such as teryl, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof Agents; alkyl betaines such as alkyl dimethylamino acetic acid betaines; and amphoteric surfactants such as alkyl imidazolines. Surfactants can be used alone or in combination.

  The compounding amount in the case of adding the resin type dispersant and / or the surfactant is preferably 0.1 to 55% by mass, more preferably 0.1 to 45% based on the total amount (100% by mass) of the additive pigment. It is mass%. When the blending amount of the resin type dispersant and / or the surfactant is less than 0.1% by mass, the added effect is hardly obtained, and when the blending amount is more than 55% by mass, the dispersing agent is dispersed by an excessive dispersing agent Can have an adverse effect on

Through the above steps, the pigment composition according to the present invention is obtained. The pigment composition of the present invention is often used by being dispersed in a dispersion solvent, but by obtaining a powdered pigment composition at route r1, it is possible to use it immediately before use or at the time of product manufacture depending on the application and needs. The type and blending ratio of the dispersion solvent can be selected and formulated (route r2).
In this case, long-term storability can be secured, and transportation costs and the like can be reduced. According to the route r1, by obtaining in powder form, it is possible to meet the needs of the powder. On the other hand, according to the route r3, the drying and pulverizing process step is omitted, so the manufacturing process can be simplified.

  According to the method for producing a pigment composition of the present invention, the dispersibility of the obtained pigment composition becomes excellent by using the water-soluble organic solvent satisfying (i) to (iv). It is considered that by performing steps (a) to (d) using a water-soluble organic solvent, a pigment composition having a higher bulk density can be obtained as compared to the case of using a conventionally used solvent. There is.

  The pigment composition in which the finely divided pigment obtained through the step (e) of the present invention is dispersed in a dispersing solvent is further used as a photosensitive pigment composition by adding a photopolymerizable monomer. It is also possible. The photopolymerizable monomer which may be added to the photosensitive pigment composition includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. A photopolymerizable compound can be used individually or in mixture of 2 or more types.

  When a polymerizable monomer is used as the photosensitive pigment composition, a suitable photopolymerization initiator, a sensitizer, an amine compound, a leveling agent, a curing agent, a curing accelerator, storage stability in order to stabilize viscosity over time An adhesion improver such as a silane coupling agent may be added as needed to enhance the adhesion to the agent and / or the transparent substrate. For example, it can be prepared in the form of a solvent-developable or alkali-developable photosensitive pigment composition in order to cure the pigment composition by ultraviolet irradiation and form a filter segment by photolithography.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, also Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxy] Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) Phosphine compounds such as -trimethyl benzoyl) phenyl phosphine oxide or 2,4, 6 -trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9, 10- phenanthrene quinone, camphor quinone, ethyl anthraquinone; borate compounds; Carbazole compounds; imidazole compounds; or titanocene compounds are used. A photoinitiator can be used 1 type or in mixture of 2 or more types.

  As the sensitizer, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives , Tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spiro Oxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes or Michler's ketone derivatives, α-acyloxy esters, acyl phosphine oxides, methylphenyl glyoxylates, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′ or 4,4′-tetra (t-butylperoxycarbonyl) ben Zophenone, 4,4'-diethylamino benzophenone and the like can be mentioned. The sensitizers can be used alone or in combination of two or more.

  Furthermore, as sensitizers, there is a compilation by Nobu Ogawara et al., “Dye Handbook” (1986, Kodansha), “Okahara Nobuyuki et al.”, “Chemicals of functional dyes” (1981, CMC), Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate and N, N-dimethyl paratoluidine.

  As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total mass of the photosensitive pigment composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and is added to the photosensitive pigment composition In addition, it has a feature that its surface tension reducing ability is low, and it is useful that the wettability to the glass plate is good despite the low surface tension reducing ability, and a defect of the coating film due to foaming does not appear. It is preferable to use one that can sufficiently suppress the chargeability in the amount. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning and include, but are not limited to, for example, FZ-2110, 2122, 2130, 2166, 2191, 2203, 2207. It is not a thing.

  The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.

  Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetic acid betaine; amphoteric surfactants such as alkyl imidazoline; and fluorine-based and silicone-based surfactants.

  As the above-mentioned curing agent, although a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound etc. are effective, they are not particularly limited to these, and they are thermosetting. Any curing agent may be used as long as it can react with the resin. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg, dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Tyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct etc. can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

  Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine and the like. Organic phosphines, phosphites and the like. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

  Examples of the adhesion improver include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropylt Ethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples of the silane coupling agent include aminosilanes such as phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the photosensitive pigment composition.

  The pigment composition of the present invention can be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. The pigment composition preferably contains substantially no particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

(Color Filter) Next, application of the pigment composition of the present invention to a color filter will be described. The color filter formed using the pigment composition of this invention can be utilized as a red filter segment, a green filter segment, and a blue filter segment, for example.

  The green filter segment can be formed using a conventional green pigment composition comprising green pigment and a pigment carrier. As a green pigment, for example, C.I. I. Pigment green 7, 10, 36, 37, 58, etc. are used. In addition, blue pigments such as aluminum phthalocyanine can also be used.

  In addition, a yellow pigment can be used in combination with the green pigment composition. As a yellow pigment which can be used in combination, C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221 may be mentioned. In addition, it is also possible to use a salt-forming compound of a basic dye or an acid dye exhibiting a yellow color in combination.

  The blue filter segment can be formed using a conventional blue pigment composition comprising a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. In addition, a violet pigment can be used in combination with the blue pigment composition. As a purple pigment which can be used in combination, C.I. I. And violet pigments such as CI pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like. In addition, it is also possible to use a salt forming compound of a basic dye or an acid dye exhibiting a blue or purple color. When a dye is used, xanthene dyes are preferred in terms of heat resistance and lightness.

(Method of Producing Color Filter) The color filter can be produced by the printing method or the photolithography method using the pigment composition of the present invention.

  Since formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the pigment composition prepared as printing ink, it is excellent in mass productivity at low cost. Furthermore, with the development of printing technology, printing of fine patterns having high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or an extender pigment.

  In the case of forming a filter segment by photolithography, the pigment composition prepared as the above-mentioned solvent development type or alkali development type colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, etc. The dry film is applied to a thickness of 0.2 to 5 μm by a method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the developer is dipped in a solvent or an alkaline developer, or the developer is sprayed to remove an uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. can do. Furthermore, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

  At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like can be used as an alkali developer. In addition, organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the ultraviolet exposure sensitivity, after applying and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

  The color filter can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the pigment composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. . In the transfer method, filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate.

  Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, although a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed is used, it is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the above-described transparent substrate or reflective substrate, and then the color filter segments may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter obtained by using the pigment composition of this invention as needed.

  According to the method for producing the pigment composition of the present invention, as described above, the dispersion of the finely divided pigment is carried out by performing the steps (a) to (d) using the water-soluble organic solvent of the present invention. It is possible to provide a pigment composition excellent in performance. Furthermore, a pigment composition with high production efficiency can be provided. Further, according to the present invention, it is possible to provide a water-soluble organic solvent for milling and kneading which is excellent in the dispersion performance of the finely divided pigment and which is high in production efficiency.

<< Example >>
Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In Examples and Comparative Examples, "part" means "part by mass". First, resins, pigments, dye derivatives and solvents used in Examples and Comparative Examples will be described.

[resin]
Synthesis Example 1: Resin A 60 parts of n-butyl methacrylate in a reaction vessel equipped with a gas introduction pipe, a thermometer, a condenser and a stirrer (hereinafter, the reaction vessel equipped with these is abbreviated as “reaction vessel A”) And 140 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The reaction vessel is heated to 80 ° C., and a solution of 12 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile is added thereto, The reaction was carried out for a time, and solid content measurement confirmed that 95% had reacted. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours . It was confirmed by measurement of acid value that acid anhydride of 98% or more was half-esterified, to obtain resin A.

Synthesis Example 2 Resin B 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged in a reaction vessel A, and replaced with nitrogen gas. Then, heating and stirring were performed at 120 ° C. for 4 hours. After solid content measurement confirmed that 98% had reacted, 73.3 parts of pyromellitic dianhydride were added, and reaction was carried out at 120 ° C. for 2 hours. It was confirmed by measurement of acid value that acid anhydrides of 98% or more were half-esterified, to obtain resin B.

Synthesis Example 3: Resin C 160 parts of n-butyl acrylate and 40 parts of 2-([1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (manufactured by Showa Denko KK) were charged in a reaction vessel A, and nitrogen was added. It was replaced by gas. The inside of the reaction vessel was heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol was added, and the reaction was allowed to proceed for 12 hours. Solid content measurement confirmed that 95% had reacted. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst are added and reacted at 100 ° C. for 7 hours The It was confirmed by measurement of the acid value that acid anhydrides of 98% or more were half-esterified, to obtain Resin C.

Synthesis Example 4 Resin D In a reaction vessel A, 20 parts of styrene-acrylic acid resin having an acid value of 200 and a molecular weight of 5,000, 0.2 parts of p-methoxyphenol, 0.2 parts of dodecyltrimethylammonium chloride, propylene glycol 40 parts of monomethyl ether acetate was charged and replaced with nitrogen gas. 7.7 parts of (3,4-epoxycyclohexyl) methyl methacrylate was dropped and reacted at a temperature of 100 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain Resin D.

Synthesis Example 5 Resin E 15.0 parts of methyl methacrylate, 70.0 parts of terminal methacryloylated polymethyl methacrylate [Resin Toagosei Co., Ltd. “AA-6”], 15.0 parts of methacrylic acid 334.0 parts of 1-methoxy-2-propanol were charged and replaced with nitrogen gas. The inside of the reaction vessel is heated to 90 ° C., 0.5 part of 2,2-azobis (2,4-dimethyl valeronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.) is added, and 2 hours at 90 ° C. Heating and stirring were performed. Furthermore, 0.5 part of V-65 was added, and it heat-stirred for 3 hours, and obtained resin E.

Synthesis Example 6 Resin F Into a reaction vessel A, 45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate were charged and purged with nitrogen gas. The reaction vessel is heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2′-azobisisobutyronitrile are dissolved in 45.3 parts of cyclohexanone. The solution was added and allowed to react for 10 hours. After confirming that 95% has been reacted by solid content measurement, 8.8 parts of 1,2,3,4-butanetetracarboxylic acid dianhydride ("Rikasid BT-100" manufactured by Shin Nippon Rika Co., Ltd.) and cyclohexanone 69 .2 parts and 0.2 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C for 7 hours. It was confirmed by measurement of acid value that acid anhydride of 98% or more was half-esterified, to obtain resin F.

Synthesis Example 7: Resin G Into a reaction vessel A, 5.0 parts of methacrylic acid, 15.0 parts of methyl methacrylate, and 60.0 parts of 2-methoxyethyl acrylate were charged, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2′-azobisisobutyronitrile are dissolved in propylene glycol monomethyl ether acetate 45. The solution dissolved in 4 parts was added and allowed to react for 10 hours. Solid content measurement confirmed that 95% had reacted. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of propylene glycol monomethyl ether acetate, 1,8-diazabicyclo- [5.4.0] -7 as a catalyst 0.2 parts of undecene was added and allowed to react at 120 ° C. for 7 hours. It was confirmed by measurement of acid value that acid anhydride of 98% or more was half-esterified, to obtain resin G.

Synthesis Example 8 Resin H 83 parts of hydroxyethyl acrylate, 821 parts of ε-caprolactone, 0.009 parts of monobutyl tin oxide and 0.93 parts of methyl hydroquinone are added to reaction vessel A, and the remaining ε-caprolactone is 1%. The reaction was allowed to proceed at 100 ° C. for 10 hours until the temperature reached below. 100 parts of polyethylenimine ("SP200" manufactured by Nippon Shokuhin Co., Ltd.) was added to the reaction liquid which had been heated to 60 ° C with stirring to cause reaction. It was confirmed by proton NMR that the acryl group had disappeared, and a resin H was obtained.

Synthesis Example 9 Resin I 60.3 parts of hydroxyethyl acrylate, 889 parts of ε-caprolactone, 0.042 parts of monobutyl tin oxide and 0.94 parts of methylhydroquinone are added to a reaction vessel A, and the remaining ε-caprolactone is The reaction was allowed to proceed at 100 ° C. for 10 hours until it became 1% or less. 50 parts of polyethyleneimine (SP200: manufactured by Nippon Shokubai Co., Ltd.) was added to the reaction solution which was heated to 60 ° C. to cause a reaction. It was confirmed by proton NMR that the acryl group had disappeared, and a resin I was obtained.

Synthesis Example 10: Resin J 57.0 parts of a polycarbodiimide compound of carbodiimide equivalent 316 having an isocyanate group and 16.0 parts of methyldiethanolamine are charged in a reaction vessel A, and maintained at about 100 ° C. for 2 hours to obtain an isocyanate group. Was reacted with hydroxyl group. Then, after charging 97.7 parts of propylene glycol monomethyl ether acetate, 178.7 parts of a 12-hydroxystearic acid self-condensing product having a molecular weight of 1,000 having a carboxyl group at the end are charged and maintained at about 90 ° C. The carbodiimide group was reacted with the carboxyl group. Thereafter, 97.7 parts of propylene glycol monomethyl ether acetate was charged to obtain a resin J.

Synthesis Example 11 Resin K Into a reaction vessel A, 50 parts of N, N-dimethylformamide, 50 parts of methyl methacrylate and 1.14 parts of aminoethanethiol hydrochloride were charged, and the temperature was raised to 80 ° C. 0.082 parts of 2, 2- azobis (isobutyronitrile) was added, and it heated at 80 degreeC, stirring under nitrogen stream. After reacting for 5.5 hours, 2.5 parts of dicyclohexylcarbodiimide was added, and the mixture was heated at 80 ° C. for further 4 hours. After completion of the reaction, the solution in the flask was cooled to room temperature and reprecipitated in 1,000 parts of a 0.5% aqueous solution of potassium carbonate to obtain Resin K as a white powder.

Synthesis Example 12: Resin L In a four-necked flask, 150.0 parts of lauryl alcohol ("CALCOL 2098" manufactured by Shin Nippon Rika Co., Ltd.), 28% sodium methoxide methanol solution ("SM-28" manufactured by Kawaken Fine Chemical Co., Ltd.) 2.63 parts were charged, and reacted under reduced pressure at 90 ° C. for 50 minutes. Next, the entire amount of the reaction mixture is charged into an autoclave, and after raising the temperature to 110 ° C., 351.9 parts of ethylene oxide are added and reacted over 3 hours so that the internal pressure of the autoclave becomes 0.2 to 0.4 MPa. The 400.0 parts of the obtained reaction product and 113.9 parts of SM-28 were charged in a four-necked flask, and stirred at 80 ° C. under reduced pressure for 3.5 hours to synthesize an alkoxide. Into this four-necked flask, 200.0 parts of toluene and 77.27 parts of sodium monochloroacetate were further charged, and stirred at 110 ° C. for 14 hours. The resulting reaction mixture was cooled to 80 ° C., to which 244.8 parts of water and 74.93 parts of 75% aqueous sulfuric acid solution were added, and this mixture was stirred at 80 ° C. for 30 minutes and allowed to stand for 30 minutes. Thereafter, liquid separation was performed to collect a toluene solution of the reaction product. Thereafter, the toluene solution of the collected reaction product was further washed twice with 244.8 parts of a 10% aqueous solution of sodium sulfate. After concentration of the toluene solution of the reaction product, the precipitated salt was removed by filtration to obtain 416.5 parts of an ether carboxylic acid compound.
Subsequently, 100.0 parts of polyallylamine 15.0% aqueous solution (PAA-01: made by Nitto Boseki Co., Ltd.) and 55.5 parts of the above-mentioned ether carboxylic acid compounds were charged into a reaction vessel A, and replaced with nitrogen gas. The mixture was dehydrated at 100 ° C. under reduced pressure, the temperature was raised to 150 ° C., and reaction was performed for 2 hours under a pressure of 1.3 kPa to obtain Resin L.

Synthesis Example 13 Resin M 50 parts of polyethyleneimine (number average molecular weight 600) and 1.0 part of powdered sodium hydroxide were added to an autoclave and heated to 80.degree. Thereafter, nitrogen substitution was performed three times and heated to 170 ° C. Next, a total of 500 parts of ethylene oxide was added over 5 hours so as not to exceed 0.5 MPa and then heated for 2 hours. After cooling to 80 ° C., stirring was carried out under a nitrogen stream for 1 hour to remove unreacted ethylene oxide out of the reaction system. Subsequently, it cooled to room temperature and obtained resin M540 part.

Synthesis Example 14: Resin N After charging 50.0 parts of dimethylaminoethyl methacrylate, 50.0 parts of methyl methacrylate and 233.3 parts of 1-methoxy-2-propanol in a reaction vessel A, and substituting with nitrogen gas, The temperature was raised to 90 ° C. 6.0 parts of 2, 2- azobis (2, 4- dimethyl valeronitrile) ("V-65" by Wako Pure Chemical Industries, Ltd.) was added to this, and heat stirring was performed at 90 degreeC for 2 hours. Further, 6.0 parts of V-65 was added, and heating and stirring were performed for 3 hours to obtain a resin N.

Synthesis Example 15: Resin O A mixed solution of 14.9 parts of aminobenzimidazolone, 21.2 parts of 2-isocyanatoethyl methacrylate and 150 parts of ethyl acetate was prepared in a reaction vessel A, and dibutyltin diacetate 0 was added thereto. .96 parts were added and allowed to react at 50 ° C. for 7.5 hours while stirring. The reaction solution was cooled to room temperature, and dropped into 1,000 parts of hexane to precipitate a solid. The precipitated solid was filtered and air-dried to obtain 26.0 parts of a benzimidazolone-containing monomer.
In a separate reaction vessel A, 40.0 parts of dimethyl sulfoxide and 32.0 parts of one-end methacryloylated polymethyl methacrylate (AA-6: manufactured by Toagosei Co., Ltd.) are charged, and after replacing with nitrogen gas, the mixture is heated to 78 ° C. The temperature rose to the end. The following monomer solution and initiator solution separately prepared were dropped to the reaction vessel A simultaneously over 2 hours.
(Monomer solution)
The above-mentioned benzimidazolone-containing monomer: 2.00 parts Methacrylic acid: 6.00 parts Dimethyl sulfoxide: 43.3 parts (initiator solution)
2, 2-Azobis (2,4-dimethyl valeronitrile) ("V-65" manufactured by Wako Pure Chemical Industries, Ltd.): 0.101 parts Dimethyl sulfoxide: 10.0 parts After addition, the mixture is stirred for 1 hour, V-650. 202 parts were added and the internal temperature was kept at 78 ° C for 2 hours, and then heated and kept at 90 ° C for 30 minutes. Then, the reaction solution was cooled to room temperature, and the solution was reprecipitated in 3,000 parts of water and vacuum dried to obtain resin O.

Synthesis Example 16 Resin P 58.5 parts of 2-hydroxyethyl methacrylate, 54.0 parts of methyl methacrylate, and 4.77 parts of thioglycolic acid are charged in a reaction vessel A, and the temperature is 80 ° C. while stirring under a nitrogen stream. It warmed up. 0.147 parts of 2,2'-azobisisobutyronitrile was added and allowed to react for 2 hours, and then 30 parts of tetrahydrofuran was added and allowed to react for 3 hours. After cooling, the reaction solution was diluted with 200 parts of ethyl acetate and reprecipitated with 3,000 parts of hexane to obtain 105.5 parts of a white powder. Next, 200 parts of xylene, 13.5 parts of glycidyl methacrylate, 0.142 parts of N, N-dimethyldodecylamine and 0.1 part of hydroquinone were added to 90 parts of this white powder, and the mixture was stirred at 150 ° C. for 3 hours . After cooling, the reaction solution was reprecipitated with 3,000 parts of hexane to obtain 88 parts of white powder. Further, a mixed solution of 80 parts of the obtained white powder, 31.0 parts of succinic anhydride and 160 parts of 1-methoxy-2-propyl acetate was reacted at 90 ° C. for 6 hours with stirring. The reaction solution was diluted with 200 parts of ethyl acetate and reprecipitated with 3,000 parts of hexane to obtain 70 parts of a macromonomer (MM-1) having a repeating unit of carboxyl group of white powder.
In the subsequent steps, for the composition of Synthesis Example 15, the addition amount of methacrylic acid is changed to 0 part, the addition amount of methacryloylated polymethyl methacrylate at one end is changed to 14.0 parts, and the above MM-1 is 24 Resin P was obtained in the same manner as in Synthesis Example 15 except that 0 part was added.

Synthesis Example 17 Resin Q 32.5 parts of 2-hydroxyethyl methacrylate, 75.1 parts of methyl methacrylate, and 2.65 parts of thioglycolic acid are charged in a reaction vessel A, and the temperature is 80 ° C. while stirring under a nitrogen stream. It warmed up. 0.082 parts of 2,2'-azobisisobutyronitrile was added and allowed to react for 2 hours, and then 30 parts of tetrahydrofuran was added and allowed to react for 3 hours. After cooling, the reaction solution was diluted with 200 parts of ethyl acetate and reprecipitated with 3,000 parts of hexane to obtain 99.2 parts of a white powder. Next, 200 parts of xylene, 13.5 parts of glycidyl methacrylate, 0.142 parts of N, N-dimethyldodecylamine and 0.1 part of hydroquinone were added to 90 parts of this white powder, and the mixture was stirred at 150 ° C. for 3 hours . After cooling, the reaction solution was reprecipitated with 3,000 parts of hexane to obtain 87.5 parts of white powder. Further, a mixed solution of 80 parts of the obtained white powder, 17.8 parts of succinic anhydride and 160 parts of 1-methoxy-2-propyl acetate was reacted at 90 ° C. for 6 hours with stirring. The reaction solution was diluted with 200 parts of ethyl acetate and reprecipitated with 3000 parts of hexane to obtain 73.6 parts of a white powder (a macromonomer (MM-2) having a repeating unit having a carboxyl group).
In the subsequent steps, with respect to the composition of Synthesis Example 15, the addition amount of methacrylic acid is 0 part, the addition amount of one end methacryloylated polymethyl methacrylate is 14.0 parts, further, the above MM-2 is 24 Resin Q was obtained in the same manner as in Synthesis Example 15 except that 0 part was added.

(Synthesis example 18: Resin AF) 800 parts of propylene glycol monomethyl ether acetate is put into a reaction vessel, heated at 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is heated at the same temperature. The reaction was carried out dropwise over time.
-Styrene: 60.0 parts-Methacrylic acid: 60.0 parts-Methyl methacrylate: 65.0 parts-Butyl methacrylate: 65.0 parts-Azobis isobutyro nitrile: 10.0 parts After dropping, further at 100 ° C After reacting for 3 hours, a solution of 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. After cooling to room temperature, approximately 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content in the previously synthesized resin solution becomes 20% by mass propylene glycol monomethyl ether Acetate was added to obtain resin AF.

Synthesis Example 19: Resin AG In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet, and a thermometer (hereinafter, a four-necked flask equipped with these will be abbreviated as “four-necked flask A”) Then, 80.0 parts of biphenyltetracarboxylic acid dianhydride, 250.0 parts of pentaerythritol triacrylate, 0.16 parts of hydroquinone and 141.2 parts of cyclohexanone were charged, and the temperature was raised to 85 ° C. Then, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst and stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone are added, and then 2.65 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours and cooled to room temperature to complete the reaction. A yellow transparent resin AG was obtained.

Synthesis Example 20: Resin AH 50.0 parts of butanetetracarboxylic acid dianhydride, 413.4 parts of dipentaerythritol pentaacrylate, 0.23 parts of hydroquinone, and 463.4 parts of cyclohexanone are charged in a 4-neck flask A, and the temperature is 85 ° C. The temperature rose to the end. Then, 2.32 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst and stirred at 85 ° C. for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone are added, and then 3.73 parts of dimethylbenzylamine is added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature to complete the reaction, Yellow transparent resin AH was obtained.

Synthesis Example 21: Resin AI In a four-necked flask A, 218.9 parts of polytetramethylene glycol having a molecular weight of 2,000 and 57.4 parts of isophorone diisocyanate are charged, and the temperature is gradually raised to 90 ° C. while introducing nitrogen gas. The reaction was carried out until the isocyanate group reached 4.5%. Next, 12.2 parts of diethylaminoethanol was added, and the reaction was further carried out at 90 ° C. for 3 hours. The mixture was transferred to a dropping tank using 115 parts of ethyl acetate to obtain a prepolymer. Next, 11.5 parts of isophorone diamine, 0.003 parts of dibutylamine, 350.0 parts of isopropyl alcohol and 235.0 parts of ethyl acetate were charged in the reaction tank, and the prepolymer was dropped from the dropping tank into the reaction tank in 30 minutes. . Thereafter, the reaction was carried out at 40 ° C. for 1 hour to obtain a resin AI having a solid content of 30%.

Synthesis Example 22: Resin AJ In a four-necked flask A, 263.6 parts of polyester diol having a molecular weight of 5,000 consisting of adipic acid and 3-methyl-1,5-petantandiol, and polytetramethylene glycol 13 having a molecular weight of 1,000 .3 parts and 19.3 parts of isophorone diisocyanate were charged, the temperature was gradually raised to 90 ° C while introducing nitrogen gas, and the reaction was carried out until the NCO% became 0.6%. Next, 0.25 part of diethylaminoethanol was added and reaction was further performed at 90 ° C. for 3 hours. 115.0 parts of ethyl acetate were used and transferred to the dropping tank to obtain a prepolymer. Next, 3.38 parts of isophorone diamine, 0.176 parts of dibutylamine, 350.0 parts of isopropyl alcohol and 235.0 parts of ethyl acetate were charged in the reaction tank, and the prepolymer was dropped from the dropping tank into the reaction tank in 30 minutes. Then, the reaction was carried out at 40 ° C. for 1 hour to obtain a resin AJ with a solid content of 30%.

The following products were used for Resins R to Z and AA to AE.
Resin R: Big Chemie Japan "DISPERBYK-110"
Resin S: "DISPERBYK-111" manufactured by Big Chemie Japan Ltd.
Resin T: Ajinomoto Fine Techno Co., Ltd. "Addisper PA 111"
Resin U: "Joncryl 678" manufactured by BASF.
Resin V: "DISPERBYK-161" manufactured by Big Chemie Japan Ltd.
Resin W: "DISPERBYK-21116" manufactured by Big Chemie Japan Ltd.
Resin X: Big Chemie Japan "DISPERBYK-21715"
Resin Y: "Addisper PB 821" manufactured by Ajinomoto Fine Techno Co., Ltd.
Resin Z: BASF "Efka PX4300"
Resin AA: "SOLSPERSE 24000" manufactured by Nippon Lubrizol
Resin AB: "SOLSPERSE 17000" manufactured by Nippon Lubrizol
Resin AC: "SOLSPERSE 32000" manufactured by Nippon Lubrizol
Resin AD: "Hinoact T-8000" manufactured by Kawaken Fine Chemicals Co., Ltd.
Resin AE: "Floren KDG-2400" manufactured by Kyoeisha Chemical Co., Ltd.

[Pigment]
Synthesis Example 23 DibromoDPP To a stainless steel reaction vessel equipped with a reflux condenser, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added under nitrogen atmosphere and stirred at 100 ° C. The solution was heated to prepare an alcoholate solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated at 90 ° C. with stirring to dissolve, and a solution of these mixtures was prepared. The heated solution of this mixture was slowly dropped into the above alcoholate solution heated to 100 ° C. at a constant speed over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a glass jacketed reaction vessel, and cooled to -10 ° C. The cooled mixture was cooled to 75 ° C. while rotating an 8 cm diameter shear disk at 4,000 rpm using a high-speed stirring disperser, and the alkali metal of the diketopyrrolopyrrole compound previously obtained. The salt solution was added in small portions. At this time, while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water always keeps the temperature below -5 ° C, adjust the addition rate of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. While adding little by little over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and filtered off to obtain a red paste. This paste is re-dispersed in 3,500 parts of methanol cooled to 0 ° C., made into a suspension with a methanol concentration of about 90%, stirred at 5 ° C. for 3 hours, and subjected to particle sizing and washing with crystal transition. The Subsequently, the water paste of the diketopyrrolopyrrole compound obtained is separated by filtration using an ultrafiltration apparatus, dried at 80 ° C. for 24 hours, and pulverized to 150.8 parts of a brominated diketopyrrolopyrrole pigment. I got

Hereinafter, pigments used in Examples or Comparative Examples will be listed.
PR 242: Clariant "Novoperm Scarlet 4 RF"
-PR177-1: "Cinilex Red SR4C" manufactured by CINIC
-PR177-2: "Cinilex Red SR4C" manufactured by CINIC
-PR254-1: BASF "Irgazin Red L 3660 HD"
-PR254-2: "Irgaphor Red S 3610 CF" manufactured by BASF.
・ PR 269: Sanyo Dye Co., Ltd. "Permanent Carmine 3810"
・ PG36: "LIONOL GREEN 6YK" made by Toyo Color
・ PG 58: DIC "FASTOGEN Green A110"
・ PY138: "Paliotol Yellow K 0961 HD" manufactured by BASF.
・ PY150: "Yellow Pigment E4GN" manufactured by LANXESS
・ PY139: BASF "Paliotol Yellow D 1819"
・ PB 15: 6: "LIONOL BLUE ES" manufactured by Toyo Color Corporation
· PV23: "LIONOGEN VIOLET FG-6240" manufactured by Toyo Color Corporation
・ PB 15: 3: "LIONOL BLUE FG-7351" manufactured by Toyo Color Corp.
・ PR 122: DIC's "FASTOGEN Super Magenta RGT"
・ PV19: Clariant "Ink Jet Magenta E5B02 VP2984"
・ PY 74: BASF "Irgalite Yellow D 1245"
・ PB7: "ELFTEX 415 REGAL400R" manufactured by Cabot

[Dye derivative]
Hereinafter, dye derivatives used in the examples or comparative examples are listed in Tables 1A and 1B.

[solvent]
The solvents used in Examples and Comparative Examples and their symbols are listed.
· PGMAc: propylene glycol monomethyl ether acetate · DEDG: diethylene glycol diethyl ether · CBAc: diethylene glycol monoethyl ether acetate

<Preparation of a pigment composition (hereinafter simply referred to as “pigment composition”) by kneading>
Example 1-1
(Preparation of pigment composition 1) 120 parts of azo red pigment PR 242 ("Novoperm Scarlet 4 RF" manufactured by Clariant), 10 parts of pigment derivative a, 1,500 parts of sodium chloride and 250 parts of monoacetin The mixture was charged into a product manufactured by Mfg. Co., and kneaded at 70 ° C. for 6 hours. The mixture is poured into 10,000 parts of water, stirred for 1 hour with a high speed mixer while heating to 40 ± 5 ° C. to form a slurry, filtered, and washed with 10,000 parts of water at 40 ± 5 ° C. The pigment composition 1 was obtained by drying at 90 ° C. except sodium chloride and monoacetin.

[Examples 1-2 to 66, Comparative Examples 1-1 to 66]
(Preparation of pigment compositions 2 to 132) Pigment compositions 2 to 132 were obtained in the same manner as in Example 1-1 except that the mixing compositions, mixing conditions and drying conditions shown in Tables 2 to 5 were changed. However, with regard to the resin solution containing a solvent, it was appropriately substituted with a kneading solvent or used, or a solid resin dried at 80 ° C. under reduced pressure was used so as to have the compositions in Tables 2 to 5.

(Measurement of Average Primary Particle Size) The average primary particle size of the obtained pigment composition is determined by using a transmission electron microscope ("JEM-1200EX" manufactured by Nippon Denshi Co., Ltd.) to measure all the pigments in the sample observed at 100,000 times. The primary particle diameter of the particles was measured and the average value was used. When the particle shape is not spherical, the major axis and minor axis were measured, and the value determined by (major axis + minor axis) / 2 was defined as the particle size. In addition, the average primary particle diameter of a subsequent example and a comparative example was also measured by the said method.

(Measurement of residual solvent)
The residual solvent is obtained by gas chromatography determining the amount of residual solvent of the water-soluble organic solvent of the present invention with respect to the solid content of the pigment composition, and based on the proportion of the pigment in the solid content, It calculated | required by computing the amount of residual solvents.
The conditions of gas chromatography are shown below.
Separation equipment: Shimadzu Corporation GC 2010
Column: DM-5MS (30m x 0.25mm x 0.25μm Film, Agilent Technologies)
Carrier gas: He
Pressure: 120.0 kPa
Total flow rate: 50.0 ml / min
Column flow rate: 1.77 ml / min
Linear velocity: 49.0 cm / sec
Purge flow rate: 3.0 ml / min
Column temperature: After holding at 80 ° C. for 4 minutes, heat up in 16 minutes, hold at 320 ° C. for 5 minutes Injection mode: Split-less Mode
Injection volume: 1 μl

The conditions of the mass spectrometer are shown below.
Measuring instrument: Shimadzu GCMS-GP2010
Interface temperature: 250 ° C
Ion source temperature: 200 ° C
Measurement mode: Scan Mode
Measurement range: m / z = 30-500
Measurement time: 5 to 20 min
Event time: 0.5 sec

(Sample Preparation Method) 0.1 g of a sample is precisely weighed in a 50 ml volumetric flask, and tetrahydrofuran is added to adjust to 50 ml. Then, ultrasonication was performed for 15 minutes, and it filtered with a 0.20 micrometer membrane filter, and made the filtrate the sample for measurement. In addition, the measurement of the residual solvent of a subsequent Example and a comparative example was also measured by the said method.

  The results of the average primary particle diameter and the residual solvent of pigment compositions 1 to 132 obtained in Examples 1-1 to 66 and Comparative Examples 1-1 to 66 are shown in Tables 2 to 5.

<Preparation of a pigment composition by dispersion>
Example 2-1
Preparation of Pigment Composition 133 The following compounds were added, 100 parts of zirconia beads having a diameter of 1.2 mm were added, and the mixture was dispersed with a paint conditioner for 3 hours to prepare a pigment composition 133. The monoacetin concentration per 100 parts by mass of pigment in pigment composition 133 was 0.05%.
Pigment composition 1: 6.5 parts Dye derivative a: 0.5 parts Resin C: 3.0 parts Propylene glycol monomethyl ether acetate: 40.0 parts

[Examples 2-2 to 17 and Comparative Examples 2-1 to 17]
(Preparation of pigment compositions 134 to 166) Pigment compositions 134 to 166 were prepared in the same manner as in Example 2-1 except that the composition shown in Table 6 was changed.

[Example 2-18]
(Preparation of Pigment Composition 167) The following compounds were blended and stirred at 7,000 rpm for 60 minutes at 80 ° C. in a dissolver equipped with a 4 cm toothed disk to prepare a pigment composition 167. The monoacetin concentration per 100 parts by mass of the pigment in the pigment composition 167 was 0.06%.
Pigment composition 35: 10.0 parts Propylene glycol monomethyl ether acetate: 40.0 parts

[Examples 2-19 to 66, Comparative Examples 2-18 to 66]
Preparation of pigment compositions 168 to 264: Pigment compositions 168 to 264 were prepared in the same manner as in Example 2-18, except that the composition shown in Tables 7 to 9 was changed. Examples 2-18 to 2-49 and Comparative Examples 2-18 to 2-49, as shown in the table, are pigment compositions to which a dye derivative and a resin-type dispersant are not added. Moreover, Examples 2-5 to 2-66 and Comparative Examples 2-50 to 2-66 are pigment compositions to which no dye derivative is added, as shown in the table.

(Evaluation of pigment composition)
In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition is measured with a B-type viscometer (25 ° C.), and the haze value is measured with a haze meter (light transmittance 20%). The performance of the object was evaluated. The initial viscosity and the haze value were measured after being left at room temperature for one day after dispersion, and the temporal viscosity was often measured after leaving at 40 ° C. for one week. For viscosity stability, the difference between the initial viscosity and the temporal viscosity was ± 10% or less, and ± 10% over. The results are shown in Tables 6-9.

  From the results of Tables 6 to 9, it can be seen that Examples of the present invention show superior viscosity stability as compared with Comparative Examples. Moreover, also in the haze value, it is understood that the example of the present invention has a smaller value than the comparative example and is excellent in transparency. These results suggest that the solid components in the pigment composition do not aggregate and have good dispersibility.

  Examples of specific applications will be described below, but the application of the pigment composition of the present invention is not limited to the following applications.

«Ink for color filter»
Next, production examples of pigment compositions suitable for color filter inks will be described. In addition, it can apply suitably also for uses other than the ink for color filters.

<Preparation of a pigment composition by kneading>
Example 3-1
(Preparation of pigment composition 265) 90 parts of azo red pigment PR 242 ("Novoperm Scarlet 4 RF" manufactured by Clariant), 10 parts of pigment derivative a, 1,000 parts of sodium chloride, and 170 parts of triacetin are stainless steel 1 gallon kneader (Ihoue The mixture was charged into a product manufactured by Mfg. Co., and kneaded at 70 ° C. for 10 hours. The mixture is poured into 10,000 parts of water and stirred for about 1 hour with a high speed mixer while heating to about 40 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and water-soluble organic solvent, and reduced pressure The resultant was dried at 40 ° C. to obtain a pigment composition 265.

[Examples 3-2 to 60, Comparative Examples 3-1 to 60]
(Preparation of Pigment Compositions 266 to 384) Pigment compositions 266 to 384 were obtained in the same manner as in Example 3-1 except that the kneading compositions shown in Tables 10 to 12 were changed. However, with regard to the resin solution containing a solvent, it is suitably substituted with a water-soluble organic solvent which is a kneading solvent, or a solid resin dried at 80 ° C. under reduced pressure is used to make the compositions in Tables 10 to 12 .

  The results of the average primary particle diameter and the residual solvent of the pigment compositions 265 to 384 obtained in Examples 3-1 to 66 and Comparative Examples 3-1 to 60 are shown in Tables 10 to 12.

<Preparation of a pigment composition by dispersion>
Example 4-1
Preparation of Pigment Composition 385 The following compounds were added, 100 parts of zirconia beads having a diameter of 1.2 mm were added, and the mixture was dispersed for 3 hours with a paint conditioner to prepare a pigment composition 385. The triacetin concentration per 100 parts by weight of pigment in pigment composition 385 was 0.25%.
Pigment composition 265: 11.0 parts Resin C: 3.85 parts Resin AF: 7.15 parts Propylene glycol monomethyl ether acetate: 78.0 parts

[Examples 4-2 to 20, comparative examples 4-1 to 20]
(Preparation of pigment compositions 386 to 424) Pigment compositions 386 to 424 were prepared in the same manner as in Example 4-1 except that the composition shown in Table 13 was changed.

[Example 4-21]
Preparation of pigment composition 425 The following compounds were blended and stirred at 5000 rpm for 60 minutes at 70 ° C. in a dissolver equipped with a 4 cm toothed disk to prepare a pigment composition 425. The triacetin concentration per 100 parts by weight of pigment in pigment composition 425 was 0.28%.
Pigment composition 305: 22.0 parts Propylene glycol monomethyl ether acetate: 78.0 parts

[Examples 4-22 to 60, comparative examples 4-21 to 60]
(Preparation of pigment compositions 426 to 504) Pigment compositions 426 to 504 were prepared in the same manner as in Example 4-21 except that the composition shown in Tables 14 to 15 was changed.

(Evaluation of pigment composition) In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the composition obtained is measured with a B-type viscometer (25 ° C.), and the haze is measured by a haze meter (20% light transmittance) The performance of the pigment composition was evaluated by the initial viscosity and the haze. The initial viscosity and the haze were measured after being left at room temperature for 1 day after dispersion, and the temporal viscosity was measured after being left at 40 ° C. for 1 week. For viscosity stability, the difference between the initial viscosity and the temporal viscosity was ± 10% or less, and ± 10% over. The results are shown in Tables 13-15.

  From the results of Tables 13 to 15, it can be seen that the examples of the present invention show superior viscosity stability as compared with the comparative examples. Moreover, also in the haze value, it is understood that the example of the present invention has a smaller value than the comparative example and is excellent in transparency. This suggests that solid components in the pigment composition do not aggregate and have good dispersibility.

<Method of producing photosensitive pigment composition>
Example 5-1
Preparation of Pigment Composition 505 The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red pigment composition 505.
-Pigment composition 385, 387: 51.0 parts-Resin AF solution: 1.0 parts-Active energy ray-curable monomer: 4.0 parts ("NNK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) Acrylate)
Active energy ray polymerizable initiator: 3.4 parts ("Irgacure 907" manufactured by BASF Corp. 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one)
-Sensitizer: 0.4 parts ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd. 4, 4 '-bis (diethylamino) benzophenone)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-2-7, 5-13-19, 5-25-31, Comparative Examples 5-1-7, 5-13-19, 5-25-31]
(Preparation of pigment compositions 506 to 511, 529 to 535, 553 to 559, 517 to 523, 541 to 547, 565 to 571) Example 5-1 was used except that the composition shown in Table 16 to 18 was changed. Similarly, red composition pigment compositions 506 to 511, 529 to 535, 553 to 559, 517 to 523, 541 to 547, and 565 to 571 were produced.

[Example 5-8]
Preparation of Pigment Composition 512 The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green pigment composition 512.
Pigment composition 394, 399: 52.0 parts Active energy ray-curable monomer: 4.8 parts ("NNK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd. Trimethylolpropane triacrylate)
-Active energy ray polymerizable initiator: 2.8 parts ("Irgacure 907" made by BASF Corp. 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one)
Sensitizer: 0.2 parts ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd. 4,4'-bis (diethylamino) benzophenone)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-9, 10, 5-20 to 22, 5-32 to 34, Comparative Examples 5-8 to 10, 5-20 to 22, 5-32 to 34]
(Preparation of Pigment Composition 513, 514, 536 to 538, 560 to 562, 524 to 526, 548 to 550, 572 to 574) Example 5-8 was used except that the composition shown in Table 16 to 18 was changed. Similarly, green pigment compositions 513, 514, 536 to 538, 560 to 562, 524 to 526, 548 to 550, and 572 to 574 were prepared.

[Example 5-11]
Preparation of Pigment Composition 515 The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue pigment composition 515.
-Pigment composition 401, 404: 42.0 parts-Resin AF solution: 10.0 parts-Active energy ray-curable monomer: 5.6 parts ("NK Ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) Acrylate)
Active energy ray polymerizable initiator: 2.0 parts ("Irgacure 907" manufactured by BASF Corp.) 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
Sensitizer: 0.2 parts ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd. 4,4'-bis (diethylamino) benzophenone)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-12, 23, 24, 35, 36, Comparative Examples 5-11, 12, 23, 24, 35, 36]
(Preparation of Pigment Composition 516, 539, 540, 563, 564, 527, 528, 551, 552, 575, 576) The same as Example 5-11 was carried out except that the composition shown in Tables 16 to 18 was changed. Pigment blue pigments 516, 539, 540, 563, 564, 527, 528, 551, 552, 575, 576 were prepared.

Next, a method of measuring the contrast ratio of the color filter pigment composition coated substrate will be described.
The substrate coated with the pigment composition for color filter is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate and is polarized, and then passes through the color filter pigment composition-coated substrate to reach the second polarizing plate. If the transmission axes of the pair of polarizing plates are parallel to each other, light passes through the second polarizing plate, but if the transmission axes of the pair of polarizing plates are orthogonal to each other, the light is polarized to the second sheet It is intercepted by the board. However, when light polarized by the first polarizing plate passes through the pigment composition-coated substrate for a color filter, scattering by the pigment particles or the like occurs and a part of the polarization plane is deviated, a pair of polarized light When the transmission axes of the plates are arranged in parallel, the amount of light transmitted through the second polarizing plate decreases, and when the transmission axes of the pair of polarizing plates are arranged orthogonally, the second polarizing plate A part of is transparent. The transmitted light is measured as the brightness on the polarizing plate, and the ratio of the brightness of the transmission axis of the polarizing plate in parallel arrangement to the brightness of the transmission axis of the polarizing plate in orthogonal arrangement is the contrast ratio.

Contrast ratio = (brightness of outgoing light when transmission axes of a pair of polarizing plates are parallel) / (brightness of outgoing light when transmission axes of a pair of polarizing plates are orthogonal)
When scattering occurs due to the pigment in the color filter pigment composition coating film, the brightness in parallel decreases and the brightness in orthogonal increases, so the contrast ratio decreases.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) were used for luminance measurement. The measurement was performed under the condition of 2 ° field of view and in order to block unnecessary light, a black mask in which a 1 cm square hole was opened was put on the measurement portion. The thickness of the pigment composition-coated substrate for a color filter was constant in all of the examples and the comparative examples.

(Measurement Sample of Contrast Ratio) The pigment composition for color filter obtained in Examples and Comparative Examples was rotated on a glass substrate of 100 mm × 100 mm and 0.7 mm thickness using a spin coater at 500 rpm, 1000 rpm and 1500 rpm. By coating with a number, three kinds of coated substrates having different film thicknesses were obtained. The pigment composition coated substrate for color filter is dried at 70 ° C. for 20 minutes, exposed to ultraviolet light at 150 mJ of integrated light quantity using an ultra-high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and contrast ratio Was measured. Next, the chromaticity (Y, x, y) at the C light source of the coating film was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, y = 0.14 for the blue coating, y = 0.60 for the green coating, and x = for the red coating for the color filter pigment composition coated substrate. The contrast ratio at 0.64 was determined using the approximation method.

  The pigment compositions for color filters obtained in Examples 5-1 to 36 were confirmed to have superior contrast characteristics as compared with those obtained in Comparative Examples 5-1 to 36, respectively.

Production Example of Color Filter Using the red pigment composition 530 of the present invention, the green pigment composition 537 and the blue pigment composition 540, the dry film thickness becomes 1.7 μm by spin coating on a substrate. Applied and dried. Then, UV exposure is performed through a mask having a predetermined pattern provided in a noncontact state with the coating film, and then an alkaline developer is sprayed by spraying to remove an uncured portion to form a desired pattern. Heated at 230 ° C. for 1 hour. The same operation was repeated for green and blue to produce color filters, and RGB three-color filters were produced. It was confirmed that the obtained color filter had high lightness and was excellent in heat resistance.

«Ink jet ink»
Next, production examples of pigment compositions suitable for inkjet inks will be described. In addition, it can apply suitably also for uses other than the ink for inkjets.
The thermally reactive compounds used in Examples and Comparative Examples and their symbols are shown below.
-MX-43: "Nikalac MX-43" manufactured by Sanwa Chemical Co., Ltd.
SB-401: "Nikalac SB-401" manufactured by Sanwa Chemical Co., Ltd.

<Preparation of a pigment composition by kneading>
Example 6-1
(Preparation of pigment composition 577) 100 parts of PY150 ("Yellow Pigment E4GN" manufactured by LANXESS), 500 parts of sodium chloride, 66.5 parts of resin E and 113.5 parts of 2-ethyl-1,3-hexanediol are made of stainless steel The mixture was charged in a 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120 ° C. for 4 hours. The mixture is poured into 10,000 parts of water and stirred for about 1 hour with a high speed mixer while heating to about 40 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and water-soluble organic solvent, and reduced pressure The resultant was dried at 40 ° C. to obtain a pigment composition 577.

[Examples 6-2 to 10, Comparative Examples 6-1 to 10]
Preparation of pigment compositions 578 to 596 Pigment compositions 578 to 596 were obtained in the same manner as in Example 6-1 except that the mixing compositions and mixing conditions shown in Table 19 were changed. However, with regard to the resin solution containing the solvent, it was suitably replaced with a kneading solvent or used, or a solid resin dried at 80 ° C. under reduced pressure was used to obtain the composition of Table 19.

  The results of the average primary particle diameter and the residual solvent of the pigment compositions 577 to 596 obtained in Examples 6 to 10 and Comparative Examples 6 to 10 are shown in Table 19.

<Preparation of a pigment composition by kneading>
[Example 7-1]
(Preparation of Pigment Composition 597) The compounds shown below were compounded and stirred at 5,000 rpm for 60 minutes at 60 ° C. in a dissolver equipped with a 4 cm toothed disk, and then pressure filtered with a membrane filter, A pigment composition 597 having a pigment concentration of 13% was obtained. The 2-ethyl-1,3-hexanediol concentration per 100 parts by mass of the pigment in the pigment composition 597 was 0.24%.
Pigment composition 577: 166.5 parts SB-401: 40 parts CBAc: 320 parts

[Examples 7-2 to 10, Comparative Examples 7-1 to 10]
Preparation of Pigment Compositions 598 to 616 Pigment compositions 598 to 616 were prepared in the same manner as in Example 7-1 except that the composition shown in Table 20 was changed.

  The viscosity, fluidity, storage stability, and haze of the pigment compositions obtained in Examples 7-1 to 10 and Comparative Examples 7-1 to 10 were evaluated by the following methods. Further, the pigment compositions obtained in Examples 7-1 to 10 and Comparative Examples 7-1 to 10 are discharged by an ink jet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, and the discharge is performed by the following method. Stability was assessed.

(Viscosity) The viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured by a dynamic viscoelasticity measuring apparatus, and evaluated based on the following criteria.
○: η <40
Δ: 40 ≦ η <50
×: 50 ≦ η

(Flowability) The viscosity (粘度 a: mPa · s) at a shear rate of 10 (1 / s) was measured by a dynamic viscoelasticity measuring apparatus, and the viscosity (η :: at a shear rate of 100 (1 / s) previously measured. The ratio ηa / η to the mPa · s) was determined, and the fluidity was evaluated based on the following criteria.
○: 0.9 ≦≦ a / η <1.5
Δ: 1.5 ≦ ηa / η <2.0
×: 2.0 ≦ ηa / η

(Storage stability) The viscosity was measured after heating for 7 days in an oven at 45 ° C. The rate of change in viscosity over time was calculated from the values of the initial viscosity and the viscosity over time according to the following equation.
[Temporal viscosity change rate] = | ([initial viscosity]-[temporal viscosity]) / [initial viscosity] | × 100
Moreover, the time-dependent viscosity change rate was evaluated on the basis of the following references | standards.
:: Viscosity change rate over time is 10% or less Δ: Viscosity change rate over time 10% or more and 30% or less ×: Viscosity change rate over time 30% or more

(Haze value) A substrate coated on glass at 1500 rpm using a spin coater is dried at 100 ° C. for 3 minutes on a hot plate, and the haze of the coated surface is measured with a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd.) The following criteria were evaluated.
○: [Haze value] <3
Δ: 3 ≦ [haze value] <4.5
×: [haze value] 4.5 4.5

(Chemical resistance) The glass substrate on which the coating film was formed was immersed in N-methylpyrrolidone, and the color change ΔE of the coating film before and after the immersion was measured.
○: E E <2
Δ: ΔE <4
×: ΔE ≧ 4

(Ejection stability) The printing condition was visually observed, and the ejection stability was evaluated according to the following criteria.
:: The nozzle missing is 5% or less after intermittent 5 minutes.
Δ: Intermittent nozzle missing 10% or less after intermittent 5 minutes.
X: The nozzle loss is 50% or more after intermittent 5 minutes.

  As apparent from Table 20, the pigment composition of the present invention is excellent in viscosity, flowability, storage stability, ejection stability and haze value while maintaining high chemical resistance (2.0 or less). Recognize.

«Magnetic recording paint»
Next, production examples of pigment compositions suitable for magnetic recording paints will be described. In addition, it can apply suitably also for uses other than a magnetic recording paint.

<Preparation of a pigment composition by kneading>
[Example 8-1]
(Preparation of pigment composition 617) 100 parts of carbon black A (average primary particle diameter 17 nm), 5 parts of a pigment derivative, 38 parts of Byron UR 8300, 1,000 parts of sodium chloride and 180 parts of monoacetin The mixture was charged in Inoue Seisakusho Co., Ltd. and kneaded at 65 ° C. for 1 hour. The mixture is poured into 100,000 parts of water and stirred for about 1 hour with a high speed mixer while heating to about 40 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and water-soluble solvent, and under reduced pressure Drying at 40 ° C. gave a pigment composition 617.

[Examples 8-2 to 9 and comparative examples 8-1 to 9]
Preparation of Pigment Compositions 618 to 634 Pigment compositions 618 to 634 were obtained in the same manner as in Example 8-1, except that the mixing compositions and mixing conditions shown in Table 21 were changed. However, with regard to the resin solution containing a solvent, it was appropriately replaced with a kneading solvent and used to obtain the composition of Table 21.

  The results of the average primary particle diameter and the residual solvent of pigment compositions 617 to 634 obtained in Examples 8 to 10 and Comparative Examples 8 to 10 are shown in Table 21.

<Preparation of a pigment composition for back layer formation>
[Example 9-1]
(Preparation of pigment composition 635) The compounds shown below were compounded, stirred at 5,000 rpm for 60 minutes at 40 ° C. in a dissolver equipped with a 4 cm toothed disk, and filtered through a 5 μm filter for pigment composition An object 635 was produced. The monoacetin concentration per 100 parts by weight of pigment in pigment composition 635 was 0.25%.
Pigment composition 617: 138 parts 70% wet nitrification cotton ("HIG-1" manufactured by SNPE Japan): 81 parts cyclohexanone: 68 parts Toluene: 250 parts Methyl ethyl ketone: 250 parts

[Examples 9-2 to 6 and comparative examples 9-1 to 6]
(Pigment compositions 618 to 622, 626 to 631) Pigment compositions 618 to 622, 626 to 631 were produced in the same manner as in Example 9-1 except that the composition shown in Table 22 was changed.

<Preparation of pigment composition for nonmagnetic layer>
[Example 9-7]
Preparation of pigment composition 641 The compounds shown below were compounded, stirred at 5,000 rpm for 60 minutes at 40 ° C. in a dissolver equipped with a 4 cm toothed disk, and filtered through a 5 μm filter to give a pigment composition An object 635 was produced.
Pigment composition 623: 128 parts Cyclohexanone: 60 parts Toluene: 60 parts Methyl ethyl ketone: 60 parts

[Examples 9-8 and 9, Comparative Examples 9-7 to 9]
(Pigment compositions 642, 643, 650-652) Pigment compositions 642, 643, 650-652 were produced in the same manner as in Example 9-7 except that the composition shown in Table 22 was changed.

(Evaluation of pigment composition) In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the composition obtained is measured with a B-type viscometer (25 ° C.), and the haze is measured by a haze meter (20% light transmittance) The performance of the pigment composition was evaluated by the initial viscosity and the haze. The initial viscosity and the haze value were measured after being left at room temperature for one day after dispersion, and the temporal viscosity was measured after being left at 40 ° C. for one week. For viscosity stability, the difference between the initial viscosity and the temporal viscosity was ± 10% or less, and ± 10% over. The results are shown in Table 22.

<Formation of magnetic layer>
Metal magnetic powder (specific surface area 50 m ² / g, coercivity 1,500 Oe): 100 parts Vinyl chloride resin ("MR-110" manufactured by Nippon Zeon Co., Ltd.): 10 parts Polyurethane resin ("UR-" manufactured by Toyobo Co., Ltd.) 8300 ′ ′): 20 parts α-alumina (particle diameter: 0.2 μ): 3 parts Carbon black (“Conductex SC” manufactured by Colombian Carbon Ltd.): 5 parts Stearic acid: 1 part butyl stearate: 1 part · Cyclohexanone: 60 parts · Toluene: 120 parts · Methyl ethyl ketone: 120 parts The above composition is dispersed by a sand mill filled with glass beads of 1 mm diameter, and then 5 parts of polyisocyanate ("Colonate L" manufactured by Nippon Polyurethane Industry Co., Ltd.) In addition, the resultant was filtered through a 5μ filter to obtain a coating composition for forming a magnetic layer. The coating composition for forming a magnetic layer was coated on a polyethylene terephthalate support having a thickness of 9 μm, oriented, and dried, and then mirror-finished by calendering to form a magnetic layer having a thickness of 1.5 μm.

<Formation of back layer>
Example 10-1 Three parts of pigment composition 638 were mixed with 100 parts by mass of pigment composition 635 to prepare a back layer-forming coating composition (1). Two parts of polyisocyanate ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd.) is mixed with 100 parts by mass of the obtained coating composition for forming a back layer (1), and the mixture is filtered with a 5 μm filter to form a coating composition for forming the back layer I got the thing (2). This was applied to the surface of the support after the formation of the magnetic layer opposite to the magnetic layer, and dried to form a back layer 1 μm thick. Thereafter, curing was promoted at 60 ° C. for 24 hours, and cut to 1/2 inch width to produce a magnetic tape.

Example 10-2 A magnetic tape was produced in the same manner as in Example 10-1, except that the pigment composition 635 was changed to the pigment composition 636, and the pigment composition 638 was changed to the pigment composition 639.

Example 10-3 A magnetic tape was produced in the same manner as in Example 10-1, except that the pigment composition 635 was changed to the pigment composition 637, and the pigment composition 638 was changed to the pigment composition 640.

Comparative Example 10-1 A magnetic tape was produced in the same manner as in Example 10-1, except that the pigment composition 635 was changed to the pigment composition 644, and the pigment composition 638 was changed to the pigment composition 647.

Comparative Example 10-2 A magnetic tape was produced in the same manner as in Example 10-1 except that the pigment composition 635 was changed to the pigment composition 645, and the pigment composition 638 was changed to the pigment composition 648.

Comparative Example 10-3 A magnetic tape was produced in the same manner as in Example 10-1, except that the pigment composition 635 was changed to the pigment composition 646, and the pigment composition 638 was changed to the pigment composition 649.

<Formation of nonmagnetic layer>
[Coating composition for forming nonmagnetic layer (1)]
Α-iron oxide (average major axis diameter 0.10 μm, BET value: 55 m ² / g): 100 parts Vinyl chloride resin (“MR 110” manufactured by Nippon Zeon Co., Ltd.): 19 parts Polyurethane resin (manufactured by Toyobo Co., Ltd.) Byron UR 8300 ′ ′): 8 parts Myristic acid: 1 part Butyl stearate: 1 part • Cyclohexanone: 60 parts • Toluene: 60 parts • Methyl ethyl ketone: 14 parts The above composition is dispersed with a 3-roll mill and filtered with a 20 μm filter. The mixture was filtered to obtain a nonmagnetic layer-forming coating composition (1).

Example 10-4
70 parts of the pigment composition 641 was mixed with 100 parts by mass of the nonmagnetic layer forming coating composition (1) to prepare a nonmagnetic layer forming coating composition (2). 2 parts of polyisocyanate ("Coronate L" manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to 100 parts by mass of the obtained coating composition for forming a nonmagnetic layer (2), and the nonmagnetic material is obtained by filtering with a 5 μm filter The layer coating composition (3) was applied onto a 9 μm thick polyethylene terephthalate support, dried, and mirror-finished by calendering to form a 1.5 μm thick nonmagnetic layer.

[Example 10-5] A nonmagnetic layer was formed in the same manner as in Example 10-4 except that the pigment composition 641 was changed to the pigment composition 642.

Example 10-6 A nonmagnetic layer was formed in the same manner as in Example 10-4 except that the pigment composition 641 was changed to the pigment composition 643.

Comparative Example 10-4 A nonmagnetic layer was formed in the same manner as in Example 10-4 except that the pigment composition 641 was changed to the pigment composition 650.

Comparative Example 10-5 A nonmagnetic layer was formed in the same manner as in Example 10-4 except that the pigment composition 641 was changed to the pigment composition 651.

Comparative Example 10-6 A nonmagnetic layer was formed in the same manner as in Example 10-4 except that the pigment composition 641 was changed to the pigment composition 652.

  The media produced in the above Examples 10-1 to 6 and Comparative Examples 10-1 to 6 were evaluated by the methods shown below.

(Center line average roughness) The surface of the back layer and nonmagnetic layer was measured with a stylus value surface roughness meter (diameter of stylus 1 μm) at a cutoff value of 0.08 based on JIS-B-0601-1982, and the center was measured. The line average roughness Ra was determined. The smaller Ra is, the smoother it is. Moreover, about Ra, it measured about each of the coating film which produced the coating medium immediately after preparation of coating composition, and the coating film which produced the coating medium, after preserve | saving a coating composition at 40 degreeC for 1 month.

(Number of coarse particles) Using an image analyzer (“SV-250” manufactured by SEIKO), measure the number of particles of 1 μm or more in the coating film in a 1 mm square field of view, and find the integrated value of 10 fields of view It was the number of particles. The smaller the coarse particles, the better the dispersion state. In addition, the number of coarse particles was measured for each of the coating film prepared as a coating medium immediately after preparation of the coating composition and the coating film prepared as a coating medium after storing the coating composition at 40 ° C. for 1 month.
The above evaluation results are summarized in Table 23. As apparent from Table 23, according to the present invention, the dispersibility and the fluidity of the composition for a magnetic recording medium are greatly improved, and the paint fluidity and the smoothness of the coated film are similar to those immediately after preparation even after storage for 1 month at 40 ° C. The properties were obtained and showed excellent storage stability.

«Laminated body»
The materials used in Examples and Comparative Examples are shown below.
(Pigment)
Sb ₂ O ₅ : “San epoch EFR-6N” manufactured by Nissan Chemical Industries, Ltd. (average primary particle diameter: 20 nm)
· ZrO ₂ : "PCS-60" manufactured by Nippon Denko Corporation (average primary particle diameter: 20 nm)
-TiO ₂ : "TTO-51 (A)" manufactured by Ishihara Sangyo Co., Ltd. (average primary particle diameter: 20 nm)
・ ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle diameter: 20 nm)
· SiO ₂ : "AEROSIL 50" manufactured by Nippon Aerosil (average primary particle diameter: 50 nm)
· Al ₂ O ₅ : "Aluminium Oxide C" (average primary particle size: 13 nm) manufactured by Nippon Aerosil Co., Ltd.
(solvent)
-MIBK: methyl isobutyl ketone-metho pig: 3-methoxy-1-butanol-PGMAc: propylene glycol monomethyl ether (photocurable compound)
Photocurable compound 1: "UA-306T" manufactured by Kyoeisha Chemical Co., Ltd.
Photocurable compound 2: "KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.
(Photopolymerizable initiator)
Photopolymerization initiator: "Irgacure 184" manufactured by BASF

<Preparation of a pigment composition by kneading>
[Example 11-1]
(Preparation of pigment composition 653) 150 parts of ZrO ₂ ("PCS-60" manufactured by Nippon Denko Co., Ltd.), 500 parts of sodium chloride, 50.0 parts of resin AG and 300 parts of 2 monoacetin are stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) ) And kneaded at 120 ° C. for 4 hours. This mixture is poured into 10,000 parts of water and stirred for about 1 hour with a high speed mixer while heating to about 40 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and solvent, and under reduced pressure 40 ° C. And dried to obtain a pigment composition 653.

[Examples 11-2 to 6 and comparative examples 11-1 to 6]
(Preparation of pigment compositions 654 to 664) Pigment compositions 654 to 664 were obtained in the same manner as in Example 11-1 except that the kneading compositions shown in Table 24 were changed. However, regarding resin, it implemented so that it might become a composition of Table 24, using solid resin suitably substituted by using a kneading | mixing solvent, or was dried at 80 degreeC under pressure reduction.

  The results of the average primary particle diameter and the residual solvent of the pigment compositions 653 to 664 obtained in Examples 11-1 to 6 and Comparative Examples 11-1 to 6 are shown in Table 24.

<Preparation of a pigment composition by dispersion>
[Example 12-1]
Preparation of Pigment Composition 665 The following compounds were blended and stirred at 5,000 rpm for 60 minutes at 50 ° C. in a dissolver equipped with a 4 cm toothed disc to prepare a pigment composition 665.
Pigment composition 653: 100 parts Methyl isobutyl ketone (MIBK): 75 parts 3-methoxybutanol (Metopig): 75 parts

[Examples 12-2 to 6 and comparative examples 12-1 to 6]
(Pigment compositions 666 to 676) Pigment compositions 666 to 676 were produced in the same manner as in Example 12-1 except that the composition shown in Table 25 was changed.

<Method of producing photosensitive pigment composition>

Examples 13-1 to 6 and Comparative Examples 13-1 to 6
(Preparation of pigment compositions 677 to 698) Using the pigment composition prepared above, a metal oxide composition having the composition shown in Table 26 was prepared (the compounding amount represents the solid content). The obtained metal oxide composition was coated on a 100 μm thick easy-adhesion treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) with a bar coater so that the film thickness after drying would be 5 μm. Thereafter, ultraviolet light of 400 mJ / cm ² was irradiated with a metal halide lamp to form a cured film (hard coat layer). About the obtained cured film, refractive index, abrasion resistance, pencil hardness, transparency (haze value), light resistance, and surface resistance were evaluated by the following method. The results are shown in Table 26.

<Production of laminate>

(Preparation of low refractive coating liquid) 50 parts by mass of 1,2,9,10-tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane, 30% dispersion of silica sol (Nissan 120 parts by mass of MEKST manufactured by Chemical Industry Co., Ltd., 2 ', 2'-bis ((meth) acryloyloxymethyl) propionic acid (2-hydroxy) -4,4,5,5,6,6,7,7,8 , 8, 9, 9, 10, 10, 11, 11, 11-10 parts by mass of nonadecafluoroundecyl, 900 parts by mass of butyl alcohol, and 5 parts by mass of a photopolymerization initiator (KAYACURE BMS manufactured by Nippon Kayaku Co., Ltd.) And prepared a low refractive coating solution.

[Examples 14-1 to 6]
(Preparation of pigment compositions 699 to 704) Using the pigment compositions of Examples 12 to 6, the pigment compositions having the compositions according to the formulations shown in Table 27 were adjusted (the amount of the compound indicates the solid content). This pigment composition was coated on the easy adhesion treated surface of a 100 μm thick easy adhesion treated PET film (refractive index of easy adhesion treated layer = 1.60) to a dry film thickness of 6 μm using a bar coater. . The obtained coated layer was dried at 100 ° C. for 1 minute and then irradiated with ultraviolet light of 400 mJ / cm ² with a metal halide lamp. Further, the low refractive coating solution was applied onto the obtained cured film by a spin coater by adjusting the thickness of the layer so that the wavelength of light showing λ / 4 in dry thickness would be about 550 nm. The obtained coated layer was dried at 100 ° C. for 1 minute and then irradiated with ultraviolet light of 400 mJ / cm ² with a metal halide lamp to obtain a laminate.
About the obtained laminated body, while measuring the refractive index of a cured film by the following method, the abrasion resistance of a cured film, pencil hardness, transparency (haze), refractive index, and a reflective interference fringe were evaluated. The results are shown in Table 27.

・基材：１００μｍ厚の易接着処理ＰＥＴフィルム（東洋紡社製「コスモシャインＡ−４１００」、易接着処理面（屈折率１．６０）に塗工）

Base material: 100 μm thick easy-adhesion treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd., coated on easy-adhesion treated surface (refractive index 1.60)

(Evaluation method)
(1) Refractive Index The refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd.
(2) Scratch resistance The coated material was set on a Gakushin tester, and using No. 0000 of steel wool, it was subjected to 10 shakings with a load of 250 g. The degree of scratching of the removed coated material was judged according to the following five-step visual evaluation. The larger the value, the better the scratch resistance of the cured film.
5: no scratch 4: slightly scratched 3: scratched, but substrate not visible 2: scratched, partially cured film is peeled 1: cured film is peeled (3) Pencil hardness According to JIS-K5600, using a pencil hardness tester ("Scratching Tester HEIDON-14" manufactured by HEIDON), variously changing the hardness of the pencil core , With a load of 500g five times. Among the five times, the hardness of the core when it was not scratched once or scratched once was taken as the pencil hardness of the cured film. In consideration of practical required physical properties, the pencil hardness of the cured film was determined as follows.
A: 2 H or more B: 1 H or more C: 1 H or less (4) Transparency (Haze value)
The turbidity (Haze value) in the obtained coated material was measured using a Haze meter.
(5) Reflection interference fringes The reflection interference fringes of the obtained cured film were evaluated visually according to the following criteria.
A: Reflection interference fringes can not be observed D: Reflection interference fringes can be observed

«Flexo / gravure ink»
Next, production examples of pigment compositions suitable for flexo / gravure inks will be described. In addition, it can apply suitably also for uses other than a flexo / gravure ink.

<Preparation of a pigment composition by kneading>
[Example 15-1]
(Preparation of Pigment Composition 705) 130 parts of PB 15: 4 ("LIONOL BLUE 7358G" manufactured by Toyo Color Corp.), 400 parts of sodium chloride, 120 parts of resin AI, CAP resin ("CAP-504-0.2" manufactured by Eastman Chemical Co., Ltd.) 5 parts and 350 parts of 2-ethyl-1,3-hexanediol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120 ° C. for 3 hours. This mixture is poured into 10,000 parts of water and stirred for about 1 hour with a high speed mixer while heating to about 40 ° C. to form a slurry, repeated filtration and washing with water to remove sodium chloride and solvent, and under reduced pressure 40 ° C. And dried to obtain a pigment composition 705.

[Example 15-2, Comparative Examples 15-1, 2]
Preparation of pigment compositions 706 to 808 Pigment compositions 706 to 708 were obtained in the same manner as in Example 15-1 except that the mixing compositions and mixing conditions shown in Table 28 were changed. However, with regard to the resin solution containing a solvent, the composition was changed to a kneading solvent as appropriate, or used as a solid resin dried at 80 ° C. under reduced pressure to obtain the composition of Table 28.

  The results of the average primary particle size and residual solvent of the pigment compositions 705 to 708 obtained in Examples 15-1 and 2 and Comparative Examples 15-1 and 2 are shown in Table 28.

<Preparation of a pigment composition by dispersion>
[Example 16-1]
(Preparation of pigment composition 709) The compounds shown below were compounded, stirred at 3,000 rpm for 30 minutes at 50 ° C. in a dissolver equipped with a 4 cm toothed disk, and then pressure filtered with a membrane filter, A pigment composition 709 having a solid concentration of 26% was obtained. The 2-ethyl-1,3-hexanediol concentration per 100 parts by mass of the pigment in the pigment composition 709 was 0.32%.
Pigment composition 705: 25.5 parts Polyethylene wax: 0.5 parts Ethyl acetate: 14.0 parts n-Propyl acetate: 24.0 parts Isopropanol: 36.0 parts

[Example 16-2, Comparative Example 16-1, 2]
Preparation of Pigment Compositions 710 to 712: Pigment compositions 710 to 712 were prepared in the same manner as in Example 16-1 except that the composition shown in Table 29 was changed.

  The obtained printing ink was diluted with isopropyl alcohol alone when evaluating by flexographic printing, and was diluted with ethyl acetate / isopropyl alcohol = 70/30 when evaluating by gravure printing.

  The film is a corona-treated biaxially oriented polypropylene film (using P-2161 manufactured by Toyobo Co., Ltd., hereinafter referred to as OPP), a polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd. hereinafter, described as PET), a nylon film (manufactured by Toyobo Co., Ltd.) N-1 102 (hereinafter referred to as Ny) was used.

  The evaluation evaluated the flow stability of the ink, the tape adhesion of the ink, the blocking resistance, the boiling resistance and the retort resistance. The results are shown in Table 29.

(Flow stability of ink)
A: Good fluidity, good gloss of dry ink film B: Poor flowability, low gloss of dry ink film

(Adhesive tape) Ink is applied to OPP, PET, Ny film, dried, pressure-bonded cellophane tape, and then the tape is peeled off. The peeling state of the ink surface was observed.

(Blocking resistance) The printed surface of the OPP film printed matter and the corona discharge treated surface of the OPP film were superposed, applied a load of 3 kg / cm ² , and left at a temperature of 40 ° C. for 1 day. Thereafter, the ink surface and the film surface were peeled off, and the transfer of the ink film to the film surface was evaluated.

(Boiling resistance) After applying an isocyanate-based anchor coating agent to PET and Ny printed matter, molten polyethylene was laminated with a thickness of 30 μm by an extrusion laminating machine to obtain a laminated product. The laminated product is made into a bag, a mixture of water / oil / vinegar = 1/1/1 is put in the inside and sealed, and then heated in hot water at 90 ° C./30 minutes, and appearance resistance to peeling off I judged the boil aptitude.
A: There is no lift-off.
B: Some or all of the film had delamination.

(Retort resistance) 3 g / m ² of an isocyanate-based adhesive was applied to PET and Ny printed matter, and then a 60 μm thick polyethylene film was laminated by a dry laminating machine to obtain a laminate. The laminated product was formed into a bag, a water / oil mixture was put therein, and sealed. Retort treatment was carried out at 120 ° C. for 30 minutes, and the retort resistance was judged from the presence or absence of appearance delamination.
A: There is no lift-off.
B: Partial or whole surface delamination occurred

  As apparent from Table 29, it became clear that the pigment composition of the present invention is excellent in each characteristic.

<Preparation of pigment composition via r3>
[Example 17-1]
(Preparation of pigment composition 713) 95 parts of azo red pigment PR 242 ("Novoperm Scarlet 4 RF" manufactured by Clariant), 5 parts of pigment derivative a, 35 parts of resin B, 65 parts of resin AF, 1,000 parts of sodium chloride, and 70 parts of triacetin The resultant was charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 10 hours. The mixture was poured into 10,000 parts of water, stirred at a high speed mixer for 1 hour while heating to 40 ± 5 ° C. to form a slurry, filtered, and washed with 10,000 parts of 40 ± 5 ° C. water. The wet cake was put into 709 parts of propylene glycol monomethyl ether acetate, and mixed and stirred at 25 ° C. for 1 hour. Water in the solution was distilled off under reduced pressure at 40 ° C. to obtain a pigment composition 713 having a solid concentration of 22%.

[Examples 17-2 to 20, Comparative Examples 17-1 to 20]
Preparation of Pigment Compositions 714 to 752 Pigment compositions 714 to 752 were obtained in the same manner as in Example 17-1 except that the kneading compositions shown in Tables 30A and 30B were changed. However, with regard to the resin solution containing a solvent, it is suitably substituted with a water-soluble organic solvent which is a kneading solvent, or a solid resin dried at 80 ° C. under reduced pressure is used, and the compositions in Tables 30A and 30B and did.

  From the results of Tables 30A and 30B, it can be seen that the examples of the present invention show superior viscosity stability as compared with the comparative examples. Moreover, also in the haze value, it is understood that the example of the present invention has a smaller value than the comparative example and is excellent in transparency. This suggests that solid components in the pigment composition do not aggregate and have good dispersibility.

  The pigment composition of the present invention includes various inks including paints, inkjet inks, gravure and flexo inks etc., colorants for plastics, electronic developers, prints, color toners, pigment compositions for color filters, photosensitive pigments It is used in various applications including compositions, magnetic recording media, hard coat applications of laminates.

Claims (6)

Adding at least a water-soluble inorganic salt and a water-soluble organic solvent to the pigment and finely grinding the pigment by milling and kneading (a);
After step (a), a step (b) of pouring water to obtain a suspension;
After the step (b), removing the water-soluble inorganic salt and removing the water-soluble organic solvent so as to satisfy the following (A):
After the step (c), the step of removing water (d),
The water-soluble organic solvent includes 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-butyl-2-ethyl-1 The manufacturing method of the pigment composition which is 3, 3- propanediol and 1, 2, 6- hexane triol, and satisfies following (i)-(iv).
(A) The water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass with respect to 100 parts by mass of the pigment contained in the pigment composition.
(I) The molecular weight is 130 to 350.
(Ii) It has a total of two or more functional groups (F) consisting of a hydroxyl group and / or an ester group.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) does not contain an ether bond. The method for producing a pigment composition according to claim 1, further comprising a resin in step (a). The method for producing a pigment composition according to claim 1 or 2 , wherein the pigment is at least one selected from a dyed lake pigment, an azo pigment, a phthalocyanine pigment, and a condensed polycyclic pigment. The method for producing a pigment composition according to any one of claims 1 to 3 , wherein the step (e) of adding a dispersion solvent and mixing and stirring it after the step (c) and before the step (d) is carried out. . A pigment composition comprising a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm,
The following (i) to (iv) are satisfied per 100 parts by mass of the pigment contained in the pigment composition , and 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5- The water-soluble organic solvent which is any of pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, 2-butyl-2-ethyl-1,3-propanediol and 1,2,6-hexanetriol is 0.005 to The pigment composition which remains in the range of 0.5 mass part.
(I) The molecular weight is 130 to 350.
(Ii) It has a total of two or more functional groups (F) consisting of a hydroxyl group and / or an ester group.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) does not contain an ether bond.   The pigment composition for color filters containing the pigment composition of Claim 5.

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