JP2016222855A - Pigment composition and production method of the same, as well as pigment composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment composition which is excellent in dispersion performance of a micronized pigment, and which is produced with high production efficiency.SOLUTION: A production method of a pigment composition includes: a step (a) to micronize a pigment in the presence of at least a water-soluble inorganic salt, a water-soluble organic solvent, water, and a dispersant; a step (b) to add water thereto and obtain a suspension; a step (c) to remove the water-soluble inorganic salt, and to remove the water-soluble organic solvent such that (A) written below is satisfied; and a step (d) to remove water, in which the water-soluble organic solvent satisfies (i)-(iv) written below. (A) The water-soluble organic solvent remains in the range of 0.005-0.5 pts.mass per 100 pts.mass of the pigment contained in the pigment composition, (i) has molecular weight of 130-350, (ii) has two or more in total of functional groups constituted of a hydroxy group and/or an ester group, (iii) has viscosity of 2-140 mPa s at 60°C, and (iv) does not include an ether bond.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a pigment composition containing a micronized pigment and a method for producing the same. Moreover, it is related with the pigment composition for color filters containing the said pigment composition.

  Pigments are widely used as color materials for various industrial materials such as paints, inks, and plastic colorants. In order to use a pigment as a coloring material, a plurality of processings are performed on the crude pigment. For example, a grinding and kneading step is performed by adding a water-soluble organic solvent, a water-soluble inorganic salt and a resin to the crude pigment. Thereafter, after a purification step, a dry pulverization step is performed to obtain a powder. Although there is a use which uses a pigment with powder, it is normally used by dispersing in a dispersion medium such as a solvent or a resin. As another method, a method of obtaining a pigment composition by omitting the dry pulverization step after the purification step has also been proposed (Patent Document 1).

  In order to obtain an excellent color material, it is particularly important to maintain good dispersibility of the pigment in the dispersion medium. If the dispersibility of the pigment is poor, the composition cannot 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 a problem that the gloss of the surface of the color-extracted product is deteriorated and the leveling is poor.

  For this reason, in order to control the dispersibility of the processed pigment, research and development have been vigorously promoted so far. For example, a technique for improving the dispersibility by modifying the surface of a pigment, and development of a dispersant for maintaining a good dispersion state have been performed (for example, Patent Document 2).

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

  In the trend that demands for higher definition are becoming stricter, it is possible to refine pigments in pigment compositions such as color filter pigment compositions, color filter photosensitive pigment compositions, inkjet inks or electronic developer. It is important. However, when the pigment is refined, the pigments are likely to aggregate with each other, thereby causing problems such as a decrease in dispersibility and a deterioration in viscosity stability.

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

  In order to solve the above-mentioned problems, the present inventors have made extensive studies. Surprisingly, in the following embodiment, which is produced using a water-soluble organic solvent that satisfies all of (i) to (iv) and water, The present inventors have found that the problems of the present invention can be solved, and have completed the present invention.

[1] Step (a) in which at least a water-soluble inorganic salt, a water-soluble organic solvent, water and a dispersant are added to the pigment, and the pigment is refined by milling and kneading, and water is added after step (a) The step (b) of obtaining a suspension and the step (c) of removing the water-soluble inorganic salt so as to satisfy the following (A) after the step (b) (c) And a step (d) for removing water after step (c), wherein the water-soluble organic solvent satisfies the following (i) to (iv).
(A) The water-soluble organic solvent 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.
(I) The molecular weight is 130-350.
(Ii) It has a total of 2 or more functional groups (F) comprising 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, tripropionine, tributyrin and 2-butyl-2- The method for producing a pigment composition according to [1], which is at least one selected from ethyl-1,3-propanediol.

[3] The pigment composition according to any one of [1] and [2], wherein the pigment is at least one selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Manufacturing method.

[4] The pigment composition according to any one of [1] to [3], wherein the step (e) is performed after the step (c) and before the step (d) by adding a dispersion solvent and mixing and stirring. Manufacturing method.

[5] A pigment composition comprising a micronized 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 130-350.
(Ii) It has a total of 2 or more functional groups (F) comprising 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.

[6] A color filter pigment composition comprising the pigment composition according to [5].

  According to the present invention, there is an excellent effect that it is possible to provide a finely divided pigment composition and a method for producing the same, and a color filter pigment composition which are excellent in dispersion performance of the finely divided pigment and have high production efficiency. . Thereby, excellent fluidity, viscosity stability, haze, contrast ratio, ejection stability, etc. can be achieved.

The flowchart for demonstrating the manufacturing process of the pigment composition which concerns on embodiment. The flowchart 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 meet the spirit of the present invention. In the present specification, the description “any number A to any number B” includes the number A as a lower limit and the number B as an upper limit in the range.

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

<Process (a)>
In the step (a), at least a water-soluble inorganic salt, a water-soluble organic solvent, water and a dispersant are added to the pigment, and the pigment is refined by grinding and kneading. The method for refining the pigment by milling and kneading is not particularly limited, and any method can be applied, but a milling and kneading process by so-called salt milling is suitable. The average primary particle diameter of the pigment to be refined 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 that has undergone some processing step may be used. The pigment used may be a single type or a plurality of types.

  The milling and kneading method includes a mixture containing at least a pigment, a water-soluble inorganic salt, a water-soluble organic solvent, water, and a dispersant, a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, and a vertical sand mill. Alternatively, and / or using a kneader such as an annular bead mill. The processing conditions and the like may be adjusted as appropriate according to the type of pigment, the required degree of refinement, and the like. Heating is preferably performed when mechanically kneading. The water-soluble inorganic salt serves as a crushing aid, and crushes the pigment using the high hardness of the water-soluble inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment, a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained.

(Pigment)
The pigment is not particularly limited as long as it does not depart from the spirit of the present invention, and organic pigments and inorganic pigments can be applied. Examples of preferable pigments include at least one organic pigment selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. As the azo pigment, either a soluble azo pigment or an insoluble azo pigment may be used. Preferable specific examples of the pigment include the following pigments.

  Pigment Yellow (hereinafter abbreviated as PY) 18, PY100, PY104, 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, PBr3 etc. are mentioned.

  For 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, Examples include 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, and PY95.

  Examples of the phthalocyanine pigment include PB16, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PG7, PG36, PG58, and aluminum phthalocyanine.

  Examples of condensed polycyclic pigments include PY24, PY108, PO51, PR168, PR177, PB60, PY38, PR88, PO43, PR194, PR178, PR179, PY138, PV23, PV19, PR122, PY109, PY110, PY150, PY139, PR254 , PR255, PR272, PO71, dibromodiketopyrrolopyrrole and the like.

(Water-soluble organic solvent)
The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and needs to be dissolved (mixed) in water and does not substantially dissolve the water-soluble inorganic salt to be used. Furthermore, the water-soluble organic solvent of the present invention satisfies the following (i) to (iv). That is,
(I) the molecular weight is 130-350,
(Ii) having a total of 2 or more functional groups (F) comprising a hydroxyl group (OH group) and / or an ester group (—COO— group);
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s,
(Iv) does not contain an ether bond,
It satisfies all the conditions.

  The water-soluble organic solvent of the present invention may be used alone or in combination. A water-soluble organic solvent satisfying these (i) to (iv) (hereinafter also referred to as the water-soluble organic solvent of the present invention) is suitable as a solvent for milling and kneading. In addition, the use of a solvent other than the water-soluble organic solvent of the present invention (including a water-soluble organic solvent not satisfying any one or more of the above (i) to (iv)) is within a range not departing from the gist of the present invention. It is not excluded. However, from the viewpoint of effectively increasing the dispersibility of the fine pigment, it is preferable to substantially use the water-soluble organic solvent of the present invention. Hereinafter, the water-soluble organic solvent of the present invention will be described.

  (Ii) having a total of two or more functional groups (F) comprising hydroxyl groups and / or ester groups: a) a solvent containing two or more hydroxyl groups and no ester groups; b) two ester groups The above includes a solvent that does not include a hydroxyl group, and c) includes three modes including both a hydroxyl group and an ester group, and the sum of the two is 2 or more. The viscosity of (iii) is a viscosity when a water-soluble organic solvent is measured alone 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 plate type rotational viscometer (viscosity measuring instrument manufactured by Toki Sangyo Co., Ltd .: TVE-20L) in accordance with JIS Z 8803. Further, as specified in (iv), the water-soluble organic solvent does not contain an ether bond in its molecule.

  By using a water-soluble organic solvent that satisfies all of (i) to (iv), the dispersibility of the refined pigment can be improved. The reason is not speculative, but it is considered that the water-soluble organic solvent of the present invention gives good results in the interaction with the pigment. In addition, the water-soluble organic solvent of the present invention remains in a specific range with respect to the pigment, so that it is considered that there is an effect of suppressing the aggregation of the refined 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). As a preferred 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) ), Tripropionine (2.7 mPa · s), tributyrin (3.3 mPa · s) and 2-butyl-2-ethyl-1,3-propanediol (43.7 mPa · s). .

  The amount of the water-soluble organic solvent to be added is not particularly limited, but it is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment. The water-soluble organic solvent may be used alone or in combination.

(water)
In the present invention, a water-soluble organic solvent, a dispersing agent, and further water are included at the time of kneading, the reason is not clear, but some synergistic effect works, and a finer powdered pigment composition having a higher bulk density. Can be obtained. As water used in the step (a), it is preferable to use ion-exchanged water (deionized water). The amount of water used in step (a) is preferably 0.5 to 25 parts by mass, more preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the water-soluble organic solvent. More preferably, parts by mass are used.

(Water-soluble inorganic salt)
The water-soluble inorganic salt used in the step (a) is not limited as long as it is an inorganic salt exhibiting water-solubility as its name does not depart from the gist 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 viewpoint of price. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment, from both the treatment efficiency and the production efficiency.

(Dispersant)
Examples of the dispersant used in the step (a) include a resin or a surfactant, and it is preferable to use a resin.
The type of resin (also referred to as a resin-type dispersant) used as a 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 insoluble in water, 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 that the resin is dissolved. By using the water-soluble organic solvent of the present invention, it becomes possible to uniformly coat the resin on the pigment, and even when the pigment is dried, the coating resin suppresses aggregation of the pigments and improves dispersibility. I think it will contribute.

  Preferred examples of the resin-type dispersant used as the dispersant include polyurethane, polyester, unsaturated polyamide, phosphate ester, polycarboxylic acid and its amine salt / ammonium salt / alkylamine salt, polycarboxylic acid ester, hydroxyl group-containing polycarboxylic acid Oily dispersants such as acid esters, polysiloxanes, modified polyacrylates, (meth) acrylic acid- (meth) acrylic acid ester copolymers, (meth) acrylic acid-styrene copolymers, styrene-maleic acid copolymers, etc. These are water-soluble resins and water-soluble polymer compounds. Resin-type dispersants can be used alone or in admixture of two or more. The resin type dispersant preferably has a mass average molecular weight of 1,000 to 30,000.

  Specifically, SOLSPERSE 3000, 13240, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 41000 (above, manufactured by Nihon Lubrizol); DISPERBYK-101, 102, 106, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 161, 162, 163 , 164,166,167,168,170,171,174,180,182,183,184,185,2000,2001,2008,2009,2022,2025,2050,2070,2096,2150,2155,2163,2164 (Above Big Chemie, made in Japan); 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, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5207, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070 (or above) Manufactured by BASF Japan); Par PB821 (F), PB822, PB880, PB881, PN-411, PA-111 (above, Ajinomoto Fine Techno Co.); Hinoact (Kawaken Fine Chemical Co.); DISPARLON KS-860, KS-873N, 7004, 1831 1850, 1860, DA-7301, DA-325, DA-375, DA-234, PW-36 (above, manufactured by Enomoto Kasei Co., Ltd.).

  Suitable examples of the surfactant used as the dispersant include naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, anionic surfactant such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl ether and the like. Nonionic activators, cation activators such as alkylamine salts, quaternary ammonium salts and the like.

  Specifically, Demol N, RN, MS, SN-B; Emulgen 120, 430; Acetamine 24, 86; Cotamine 24P (above, manufactured by Kao Corporation), Prisurf AL, A208F (above, made by Daiichi Kogyo Seiyaku Co., Ltd.) ), Arcade C-50, T-28, T-50 (above, manufactured by Lion Corporation).

  In addition, a fiber derivative, a rubber derivative, and / or a protein derivative can be selected and used in accordance with the synthetic resin. In particular, epoxy resins and (meth) acrylic resins are preferably used as these synthetic resins. This is because it is versatile, has high transparency, and is excellent in various resistances when used as a color filter.

  The epoxy resin refers to an epoxide containing one or more epoxy groups in the molecule, and in the present invention, a soluble one that is not crosslinked with a curing agent is preferable. Epoxides include bisphenol-type, novolak-type, alkylphenol-type, resorcin-type, polyglycol-type, ester-type, glycidyl type such as N-glycidylamine, and cyclic aliphatic epoxides.

  The (meth) acrylic resin is a copolymer of a simple substance or a mixture selected from monomers of acrylic acid, methacrylic acid and esters thereof, and these are further radically polymerizable such as styrene, vinyl acetate, maleic anhydride and the like. It may be a copolymer with a monomer.

(Dye derivative)
In the step (a), a pigment derivative may be used in combination.
As a derivative of a dye used as a dispersant, a compound having an organic pigment as a basic skeleton and introducing a substituent imparting acidity or a substituent imparting basicity into the molecule is suitable. By adding the pigment derivative, it is considered that the pigment is adsorbed by the pigment to be dispersed and imparts polarity, thereby giving a dispersion effect from the interaction with the resin. In addition, an effect contributing to pigment crystal stabilization and dispersion stabilization can be expected.

  Specifically, in addition to synthetic products manufactured by Sanyo Dye Co., examples of commercially available products include EFKA-6745, 6750 (manufactured by EFKA Additive), BYK-Synergist 2100 (manufactured by Big Chemie Japan), Solsperse 5000, 12000, 22000 (above, manufactured by Nihon Lubrizol).

  The amount of each of the water-soluble organic solvent, water, water-soluble inorganic salt and dispersant added to the pigment is not limited as long as the pigment can be refined, but the pigment is effectively ground by the water-soluble inorganic salt. Having a viscosity and hardness to which a shearing force is applied is important for the miniaturization process.

<Step (b)>
After performing step (a), water is added thereto to obtain a suspension (FIG. 1). Preferably, after the completion of the step (a), the pigment dispersion is taken out from the grinding kneader, and water is added thereto to perform stirring to obtain a suspension. The amount of water to be added is not particularly limited as long as it is sufficient to obtain a suspension. You may heat as needed. For example, water having a mass of 10 to 10,000 times the mass of the step (a) is added and mixed and stirred. Although the mixing stirring conditions at this time are not specifically limited, For example, it can carry out at the temperature of 25-90 degreeC. As the water used in the step (b), it is preferable to use ion exchange water (deionized water).

<Step (c)>
After the treatment in step (b), the water-soluble inorganic salt is removed, and the water-soluble organic solvent is removed so as to satisfy the following (A) (FIG. 1).

(A) A water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass per 100 parts by mass of the pigment contained in the pigment composition.
The method of leaving the water-soluble organic solvent in the 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 a method of removing the filtrate by filtration is simple.

  The residual solvent per 100 parts by mass of 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 in the pigment composition, and calculated from the ratio of the pigment in the solid content. it can. Here, the ratio of the pigment in the solid content is defined as the ratio of the charged amount of the pigment to the total solid content in the finally obtained pigment composition. Actually, the pigment may be slightly lost in step (b) or the like, but the ratio of the pigment in the solid content in the present specification is as described above.

<Step (d)>
After 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 for 12 to 48 hours at 80 to 120 ° C. under normal pressure, and drying for 12 to 60 hours at 25 to 80 ° C. under reduced pressure. An example is a method of performing, and after freezing in a range of −60 to −5 ° C., a method of performing drying for about 12 to 60 hours in a range of 25 to 80 ° C. under reduced pressure. Although a drying process is not specifically limited, The method using a spray drying apparatus can be illustrated. A pulverization process may be performed simultaneously with the drying process or after the drying process.

  In the production method of the present invention, a powder pigment composition having a high bulk density can be obtained by using a water-soluble organic solvent that dissolves the dispersant and water that does not dissolve the dispersant. That is, by using the water-soluble organic solvent, water, and dispersant of the present invention, in other words, in a qualitative expression, a pigment composition containing a soft, fluffy powdery fine pigment can be obtained. The preferred bulk density may vary depending on the application, but is preferably 0.4 g / mL or less.

  In FIG. 2, an example of the preferable embodiment of the manufacturing method of the pigment composition of this invention is demonstrated. As a preferred embodiment, the steps of routes r1 to r3 shown in FIG. 2 can be exemplified.

  In addition to route r1 for obtaining powder by performing steps (a) to (d), route r2 for performing step (e) after step (d), and step (e) after step (c) Then, a route r3 for performing the step (d) is mentioned. The pigment composition obtained by the route r1 is in a powder form, and the pigment composition obtained by the routes r2 and r3 is, for example, in the form of a varnish dispersed in a dispersion 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 arbitrarily added without departing from the spirit 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, a method of directly obtaining a dispersion solvent as shown by route r3 in FIG. 2 is preferred. Moreover, as a method of taking out as a powder, the route r1 is preferable from the viewpoint of simplicity of the manufacturing process. Further, from the viewpoint of further improving the dispersibility of the obtained pigment composition, it is preferable to perform a dry pulverization treatment when removing water in the step (d) of the route r1 and the route r2.

<Process (e)>
After passing through step (d) or step (c), a dispersion solvent is added thereto and mixed and stirred (see FIG. 2). The mixing and stirring method is not particularly limited as long as it can be uniformly dispersed. Examples thereof include a stirring blade, a dissolver, a homomixer, and an ultrasonic homogenizer. Such processing may be performed in combination of two or more. In step (e), in addition to the dispersion solvent, a dispersion aid and other additives may be added. For example, a binder resin, a pigment derivative, a surfactant, other pigments, and the like can be added. These are not particularly limited as long as they do not hinder the dispersibility of the pigment, but are preferably those that are soluble in the dispersion solvent. By using a dispersion aid, the dispersibility of the pigment can be improved, and re-aggregation of the pigment after dispersion can be more effectively prevented.

(Dispersing solvent)
The dispersion solvent used in the step (e) is not particularly limited as long as it does not hinder the dispersibility of the pigment. Suitable 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 Coal 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, tripropionine, 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. Further, 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 , 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol and the like.

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

  These dispersing solvents can be used alone or in combination. The dispersion solvent can be appropriately set depending on the application to be used, but the pigment composition can be adjusted to an appropriate viscosity to form a desired filter segment with a uniform film thickness. It is preferably used in an amount of 500 to 4,000% by mass based on the standard (100% by mass). In the case of route r3, since a step of removing water is included after step (e), it is more preferable to use a water-insoluble organic solvent as the dispersion solvent.

(Dispersing aid)
[Binder resin]
As the binder resin used in the step (e), a conventionally known thermoplastic resin or thermosetting resin can be used. As a binder resin, a resin having a pigment affinity part that has the property of adsorbing to the added pigment and a part that is compatible with the pigment carrier, and acting to stabilize the dispersion to the pigment carrier by adsorbing to the added pigment Mold 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, and polyurethane series. Examples 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 the monomer which comprises 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 ethoxypolyethylene (Meth) acrylates such as lenglycol (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 acryloylmorpholine, 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, Examples include fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimide hexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, 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-succinimi Ru-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins. Especially, an epoxy resin and a melamine resin are used more suitably from a viewpoint of heat resistance improvement.

  Moreover, as a suitable example of a resin type dispersing agent, polycarboxylic acid ester, such as polyurethane and 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, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having free carboxyl groups, Oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, 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 and a high spectral transmittance is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer is preferable. Preferred are a nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a combined amino acid, a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocycle in the side chain. The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass based on the total amount of pigment (100% by mass), and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  As the commercially available resin type dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan , 171, 174, 180, 181, 182, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204 or BYK-P104 , P104S, 220S, 6919 or Lactimon, Lactimon-WS or Bykumen, etc .; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13430, 16000, 17000, 18000, 20000, 21000, 24000, 26000, manufactured by Lubrizol Japan 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc .; EFKA-46, 47, 48, 452, 4008 manufactured by BASF , 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550 , 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 4, 1101, 120, 150, 1501, 1502, 1503, etc .; Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc.

  The mass average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, 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 the separation columns of Tosoh's “TSK-GEL SUPER H5000” and “H4000” in the gel permeation chromatography “HLC-8120GPC” made by Tosoh. , “H3000” and “H2000” are connected in series, and converted to molecular weight using polystyrene as a standard substance measured at 40 ° C. using tetrahydrofuran as a mobile phase. The addition amount of the binder resin is not particularly limited, but 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 formability, weather resistance, 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 region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or isobutylene. / (Anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable 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 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 half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. The one obtained is suitable. A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also suitable as a color filter application.

[Dye derivative]
Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into an organic pigment, anthraquinone, acridone, or triazine. -305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469 and the like can be used alone. Alternatively, two or more types can be mixed and used. When using a dye derivative, 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 viewpoints of lightness and dispersibility.

  The blending amount of the pigment derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100% by mass). 3% by mass or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount (100% by mass).

[Surfactant]
Suitable examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, alkyl Anionic properties such as sodium diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Surfactant: Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polio Nonionic surfactants such as ciethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl Examples thereof include amphoteric surfactants such as alkylbetaines such as dimethylaminoacetic acid betaine and alkylimidazolines. Surfactants can be used alone or in combination.

  The amount of the resin-type dispersant or / and surfactant added is preferably 0.1 to 55% by mass, more preferably 0.1 to 45% based on the total amount of the added pigment (100% by mass). % By mass. When the blending amount of the resin type dispersant or / and the surfactant is less than 0.1% by mass, it is difficult to obtain the added effect. When the blending amount is more than 55% by mass, the dispersion is caused by an excessive dispersant. May be adversely affected.

  Through the above steps, the pigment composition according to the present invention is obtained. In many cases, the pigment composition of the present invention is used after being dispersed in a dispersion solvent. By obtaining a powdery pigment composition in the route r1, depending on the application and needs immediately before use or during product production. The type and mixing ratio of the dispersion solvent can be selected and prepared (route r2).

  In this case, long-term preservation can be ensured and transportation costs can be reduced. According to the route r1, by obtaining in powder form, it is possible to meet the needs in powder form. On the other hand, according to the route r3, the dry pulverization process is omitted, so that the manufacturing process can be simplified.

  According to the method for producing a pigment composition of the present invention, by using a water-soluble organic solvent satisfying (i) to (iv) and water, the dispersibility of the obtained pigment composition becomes excellent. This considers that by performing the step (a) using a water-soluble organic solvent and water, the resin adsorption to the pigment is promoted and a pigment composition having a high bulk density is obtained.

[Photosensitive pigment composition]
The pigment composition obtained by dispersing the finely-divided pigment obtained through the step (e) of the present invention in a dispersion solvent is used as a photosensitive pigment composition by further adding a photopolymerizable monomer. It is also possible. Photopolymerizable monomers that may be added to the photosensitive pigment composition include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether 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 Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (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, an appropriate photopolymerization initiator, sensitizer, amine compound, leveling agent, curing agent, curing accelerator, storage stability to stabilize the viscosity over time An adhesion improver such as a silane coupling agent can be added as necessary to enhance the adhesion to the agent and / or the transparent substrate. For example, it can be prepared in the form of a solvent development type or alkali development type 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, -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 methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyldimethyl 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-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -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-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound. A photoinitiator can be used 1 type or in mixture of 2 or more types.

  Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinones Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, 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 derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spiro Oxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes or Michlerketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′ or 4,4′-tetra (t-butylperoxycarbonyl) benzophen Enone, 4,4′-diethylaminobenzophenone, and the like. A sensitizer can be used 1 type or in mixture of 2 or more types.

  Further, as sensitizers, Okawara Nobu et al. “Dye Handbook” (1986, Kodansha), Okawara Nobu et al. “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Examples include 2-ethylhexyl 4-dimethylaminobenzoate and N, N-dimethylparatoluidine.

As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the 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 Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content 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, and having a hydrophilic group but low solubility in water, and when added to a photosensitive pigment composition Addition that has the feature of low surface tension lowering ability and that has good wettability to glass plate despite its low surface tension lowering ability and does not cause defects in the coating film due to foaming Those in which the chargeability can be sufficiently suppressed in the amount can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning, and examples thereof include, but are not limited to, FZ-2110, 2122, 2130, 2166, 2191, 2203, 2207. It is not a thing.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as polyethylene glycol monolaurate, alkylbetaines such as alkyldimethylaminoacetic acid betaines, and amphoteric surfactants such as alkylimidazolines, and fluorine and silicone surfactants.

  As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like are effective, but are not particularly limited to these, and are thermosetting. Any curing agent may be used as long as it can react with the resin. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents 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- Til-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 benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. 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 vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, 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-aminopropylto Ethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Examples include silane coupling agents such as 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 is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. It is preferable that the pigment composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the case where the pigment composition of this invention is applied to a color filter is demonstrated. The color filter formed using the pigment composition of the present invention can be used as, for example, a red filter segment, a green filter segment, and a blue filter segment.

  The green filter segment can be formed using a normal green pigment composition including a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used. 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. Examples of yellow pigments that can be used in combination include 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, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Mention may be made of yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue pigment composition including 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. A purple pigment can be used in combination with the blue pigment composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and lightness.

<Color filter manufacturing method>
The color filter can be produced by a printing method or a photolithography method using the pigment composition of the present invention.

  The formation of the filter segment by the printing method can be patterned simply by repeating printing and drying of the pigment composition prepared as a printing ink, and is excellent in mass production at low cost. Furthermore, a fine pattern having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by photolithography, the pigment composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, immerse in solvent or alkali developer or spray the developer with spray to remove the uncured part to form the desired pattern, then repeat the same operation for other colors to produce a color filter can do. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In the development, an aqueous solution such as sodium carbonate or sodium hydroxide can be used as an alkaline developer. Moreover, organic alkalis, such as a dimethyl benzylamine and a triethanolamine, can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, the colored resist is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, 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 for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. Moreover, an overcoat film, a transparent conductive film, or the like is formed on the color filter obtained using the pigment composition of the present invention, if necessary.

  According to the method for producing a pigment composition of the present invention, as described above, the dispersion of fine pigments is performed by performing the steps (a) to (d) using the water-soluble organic solvent of the present invention. A pigment composition having excellent performance can be provided. Furthermore, a pigment composition with high production efficiency can be provided. In addition, according to the present invention, it is possible to provide a water-soluble organic solvent for milling and kneading that is excellent in the dispersion performance of a fine pigment and has high production efficiency.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by this. In Examples and Comparative Examples, “part” means “part by mass”, and “%” means “% by weight”. First, resins, pigments, dye derivatives and solvents used in Examples and Comparative Examples will be described.

[Resin (dispersant)]
(Synthesis Example 1: Resin A)
Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer (hereinafter, a reaction vessel equipped with these is abbreviated as “reaction vessel A”), 60 parts of n-butyl methacrylate and 140 parts of benzyl methacrylate were charged. Replaced with nitrogen gas. Heat the reaction vessel to 80 ° C. and add a solution of 12 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile in 91 parts of methyl ethyl ketone. Then, the reaction was allowed to proceed for 10 hours, and it was confirmed that 95% had reacted by measuring the solid content. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 part 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 acid value measurement that 98% or more of the acid anhydride was half-esterified, and resin A was obtained after drying at 80 ° C. under reduced pressure.

(Synthesis Example 2: Resin B)
A reaction vessel A was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst, and was replaced with nitrogen gas, and then heated at 120 ° C. for 4 hours. Stirring was performed. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic dianhydride was added, and it was made to react at 120 degreeC for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and resin B was obtained after drying at 80 ° C. under reduced pressure.

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

(Synthesis Example 4: Resin D)
A reaction vessel A was charged with 20 parts of a styrene / acrylic acid resin having an acid value of 200 and a molecular weight of 5,000, 0.2 part of p-methoxyphenol, 0.2 part of dodecyltrimethylammonium chloride, and 40 parts of propylene glycol monomethyl ether acetate. Replaced with nitrogen gas. 7.7 parts of (3,4-epoxycyclohexyl) methyl methacrylate was added dropwise and reacted at a temperature of 100 ° C. for 30 hours. Resin D was obtained by reprecipitation of the reaction solution in water and drying.

(Synthesis Example 5: Resin E)
In a reaction vessel A, 15.0 parts of methyl methacrylate, 70.0 parts of terminal methacryloylated polymethyl methacrylate (“AA-6” manufactured by Toagosei Co., Ltd.), 15.0 parts of methacrylic acid and 1-methoxy-2-propanol 334 0.0 part was charged and replaced with nitrogen gas. The reaction vessel was heated to 90 ° C., 0.5 part of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 90 ° C. for 2 hours. Heating and stirring were performed. Further, 0.5 part of V-65 was added, and the mixture was heated and stirred for 3 hours, and dried at 80 ° C. under reduced pressure to obtain Resin E.

(Synthesis Example 6: Resin F)
In 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 replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were dissolved in 45.3 parts of cyclohexanone. The solution was added and allowed to react for 10 hours. After confirming that 95% had reacted by solid content measurement, 8.8 parts of 1,2,3,4-butanetetracarboxylic dianhydride (“Ricacid BT-100” manufactured by Shin Nippon Chemical Co., Ltd.), cyclohexanone 69 .2 parts, 0.28 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene was added as a catalyst, and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and resin F was obtained through drying at 80 ° C. under reduced pressure.

(Synthesis Example 7: Resin G)
In 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 was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate 45. The solution dissolved in 4 parts was added and allowed to react for 10 hours. It was confirmed that 95% had reacted by solid content measurement.
Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries), 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 reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and resin G was obtained through drying at 80 ° C. under reduced pressure.

(Synthesis Example 8: Resin H)
In reaction vessel A, 83 parts of hydroxyethyl acrylate, 821 parts of ε-caprolactone, 0.009 parts of monobutyltin oxide, and 0.93 parts of methyl hydroquinone are added, and 10% at 100 ° C. until the remaining ε-caprolactone is 1% or less. Reacted for hours. To the reaction solution at 60 ° C., 100 parts of polyethyleneimine (“SP200” manufactured by Nippon Shokubai Co., Ltd.) was added and reacted with stirring. After confirming disappearance of the acrylic group by proton NMR, resin H was obtained after drying at 80 ° C. under reduced pressure.

(Synthesis Example 9: Resin I)
In reaction vessel A, 60.3 parts of hydroxyethyl acrylate, 889 parts of ε-caprolactone, 0.042 parts of monobutyltin oxide, and 0.94 part of methyl hydroquinone are added, and 100 ° C. until the remaining ε-caprolactone is 1% or less. For 10 hours. 50 parts of polyethyleneimine (SP200: manufactured by Nippon Shokubai Co., Ltd.) was added to the reaction solution at 60 ° C. for reaction. It was confirmed by proton NMR that the acrylic group had disappeared, and resin I was obtained after drying at 80 ° C. under reduced pressure.

(Synthesis Example 10: Resin J)
A reaction vessel A was charged with 57.0 parts of a polycarbodiimide compound having an isocyanate group-containing carbodiimide equivalent of 316 and 16.0 parts of methyldiethanolamine and held at about 100 ° C. for 2 hours to react the isocyanate groups with the hydroxyl groups. Next, after 97.7 parts of propylene glycol monomethyl ether acetate was charged, 178.7 parts of a 12-hydroxystearic acid self-condensate having a carboxyl group at the terminal and having a molecular weight of 1,000 was charged and maintained at about 90 ° C. A carbodiimide group and a carboxyl group were reacted. Then, resin J was obtained through 80 degreeC vacuum drying.

(Synthesis Example 11: Resin K)
A reaction vessel A was charged with 50 parts of N, N-dimethylformamide, 50 parts of methyl methacrylate and 1.14 parts of aminoethanethiol hydrochloride, and the temperature was raised to 80 ° C. 0.082 part of 2,2-azobis (isobutyronitrile) was added, and the mixture was heated at 80 ° C. with stirring under a nitrogen stream. After reacting for 5.5 hours, 2.5 parts of dicyclohexylcarbodiimide was added, and the mixture was further heated at 80 ° C. for 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 potassium carbonate solution to obtain a white powdered resin K.

(Synthesis Example 12: Resin L)
In a four-necked flask, 150.0 parts of lauryl alcohol (“Nippon Rika Co., Ltd.“ Calcor 2098 ”) and 28% sodium methoxide methanol solution (“ SM-28 ”manufactured by Kawaken Fine Chemical Co., Ltd.) 2.63 parts are charged. The reaction was carried out at 90 ° C. for 50 minutes under reduced pressure. Next, the entire amount of the reaction mixture was charged into an autoclave, heated to 110 ° C., and then 351.9 parts of ethylene oxide was added and reacted over 3 hours so that the internal pressure of the autoclave was 0.2 to 0.4 MPa. It was. 400.0 parts of the obtained reaction product and 113.9 parts of SM-28 were charged into a four-necked flask and stirred at 80 ° C. under reduced pressure for 3.5 hours to synthesize an alkoxide.
Further, 200.0 parts of toluene and 77.27 parts of sodium monochloroacetate were charged into this four-necked flask and stirred at 110 ° C. for 14 hours. The obtained reaction mixture was cooled to 80 ° C., 244.8 parts of water and 74.93 parts of 75% aqueous sulfuric acid solution were added thereto, and the 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 sodium sulfate solution. After the toluene solution of the reaction product was concentrated, the precipitated salt was removed by filtration to obtain 416.5 parts of an ether carboxylic acid compound.
Next, 100.0 parts of a polyallylamine 15.0% aqueous solution (PAA-01: manufactured by Nitto Boseki Co., Ltd.) and 55.5 parts of the ether carboxylic acid compound were charged into the reaction vessel A and replaced with nitrogen gas. The mixture was dehydrated under reduced pressure at 100 ° C., and then the temperature was raised to 150 ° C. and reacted for 2 hours under a pressure of 1.3 kPa. Then, resin L was obtained through 80 degreeC vacuum drying.

(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 the autoclave and heated to 80 ° C. Then, nitrogen substitution was performed 3 times and it heated at 170 degreeC. 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., the mixture was stirred for 1 hour under a nitrogen stream to remove unreacted ethylene oxide outside the reaction system. Subsequently, it cooled to room temperature and obtained 540 parts of resin M.

(Synthesis Example 14: Resin N)
A reaction vessel A was charged with 50.0 parts of dimethylaminoethyl methacrylate, 50.0 parts of methyl methacrylate, and 233.3 parts of 1-methoxy-2-propanol, replaced with nitrogen gas, and then heated to 90 ° C. did. To this was added 6.0 parts of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Furthermore, 6.0 parts of V-65 was added, and the mixture was heated and stirred for 3 hours. Then, resin N was obtained through 80 degreeC vacuum drying.

(Synthesis Example 15: Resin O)
In a reaction vessel A, a mixed solution of 14.9 parts of aminobenzimidazolone, 21.2 parts of 2-isocyanatoethyl methacrylate and 150 parts of ethyl acetate is prepared, and 0.96 part of dibutyltin diacetate is added thereto and stirred. The reaction was carried out at 50 ° C. for 7.5 hours. 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 another reaction vessel A, 40.0 parts of dimethyl sulfoxide and 32.0 parts of one-end methacryloylated polymethyl methacrylate (AA-6: manufactured by Toa Gosei Co., Ltd.) were charged, replaced with nitrogen gas, and heated to 78 ° C. The temperature was raised to. The following monomer solution and initiator solution separately prepared were simultaneously added dropwise to the reaction vessel A over 2 hours.
{Monomer solution}
Benzimidazolone-containing monomer: 2.0 parts Methacrylic acid: 6.0 parts Dimethyl sulfoxide: 43.3 parts {Initiator solution}
2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.)
: 0.101 parts Dimethyl sulfoxide: 10.0 parts After the dropping, the mixture was stirred for 1 hour, 0.265 parts of V-65 was added, the internal temperature was kept at 78 ° C for 2 hours, and then heated to 90 ° C to 30 ° C. Kept for a minute. Next, 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)
A reaction vessel A was charged with 58.5 parts of 2-hydroxyethyl methacrylate, 54.0 parts of methyl methacrylate, and 4.77 parts of thioglycolic acid, and heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 0.147 parts of 2,2′-azobisisobutyronitrile was added and reacted for 2 hours, and 30 parts of tetrahydrofuran was further added and reacted 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 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 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 while 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 carboxyl group repeating unit as a white powder.
In another reaction vessel A, 40.0 parts of dimethyl sulfoxide and 14.0 parts of methacryloylated polymethyl methacrylate (AA-6: manufactured by Toa Gosei Co., Ltd.) were charged, and after replacement with nitrogen gas, heating was performed at 78 ° C. The temperature was raised to. The following monomer solution and initiator solution separately prepared were simultaneously added dropwise to the reaction vessel A over 2 hours.
{Monomer solution}
Benzimidazolone-containing monomer of Synthesis Example 15: 2.0 parts Macromonomer (MM-1): 24.0 parts Dimethyl sulfoxide: 43.3 parts {Initiator solution}
2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.)
: 0.101 part Dimethyl sulfoxide: 10.0 part After dropping, the mixture is stirred for 1 hour, 0.202 part of V-65 is added, the internal temperature is kept at 78 ° C for 2 hours, and then heated to 90 ° C to 30 ° C. Kept for a minute. Next, the reaction solution was cooled to room temperature, and the solution was reprecipitated in 3,000 parts of water and vacuum-dried to obtain a resin P.

(Synthesis Example 17: Resin Q)
A reaction vessel A was charged with 32.5 parts of 2-hydroxyethyl methacrylate, 75.1 parts of methyl methacrylate, and 2.65 parts of thioglycolic acid and heated to a temperature of 80 ° C. while stirring under a nitrogen stream. 0.082 parts of 2,2′-azobisisobutyronitrile was added and reacted for 2 hours, and further 30 parts of tetrahydrofuran was added and reacted 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 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 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. 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 monomer (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 was changed to 0 part, the addition amount of one-end methacryloylated polymethyl methacrylate was changed to 14.0 parts, and the MM-2 was changed to 24 parts. Resin Q was obtained in the same manner as in Synthesis Example 15 except that 0.0 part was added.

(Synthesis Example 18: Resin AF)
Put 800 parts of propylene glycol monomethyl ether acetate in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and drop the mixture of the following monomer and thermal polymerization initiator over 1 hour at the same temperature to react. went.
Styrene: 60.0 parts Methacrylic acid: 60.0 parts Methyl methacrylate: 65.0 parts Butyl methacrylate: 65.0 parts Azobisisobutyronitrile: 10.0 parts After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Thereafter, 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. Then, resin AF was obtained through 80 degreeC vacuum drying.

(Synthesis Example 19: Resin AG)
A biphenyltetracarboxylic dianhydride is added to a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction pipe and a thermometer (hereinafter, the four-necked flask equipped with these is abbreviated as “four-necked flask A”). 80.0 parts, 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. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added. Then, 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. Resin AG was obtained.

(Synthesis Example 20: Resin AH)
A 4-neck flask A was charged with 50.0 parts of butanetetracarboxylic dianhydride, 413.4 parts of dipentaerythritol pentaacrylate, 0.23 parts of hydroquinone, and 463.4 parts of cyclohexanone, and the temperature was raised to 85 ° C. Next, 2.32 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone were added, and then 3.73 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. 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 were charged, and the temperature was gradually raised to 90 ° C. while introducing nitrogen gas. The reaction was continued until Next, 12.2 parts of diethylaminoethanol was added, and the reaction was further carried out at 90 ° C. for 3 hours. Using 115 parts of ethyl acetate, it was transferred to a dropping tank to obtain a prepolymer. Next, 11.5 parts of isophoronediamine, 0.003 part of dibutylamine, 350.0 parts of isopropyl alcohol, and 235.0 parts of ethyl acetate were charged into the reaction tank, and the prepolymer was dropped into the reaction tank in 30 minutes from the dropping tank. . After making it react at 40 degreeC for 1 hour, resin AI was obtained through 80 degreeC pressure reduction drying.

(Synthesis Example 22: Resin AJ)
In a four-necked flask A, 263.6 parts of a polyester diol having a molecular weight of 5000 consisting of adipic acid and 3-methyl-1,5-petanetanediol, 13.3 parts of polytetramethylene glycol having a molecular weight of 1,000, isophorone diisocyanate 19. 3 parts were charged, the temperature was gradually raised to 90 ° C. while introducing nitrogen gas, and the reaction was carried out until NCO% became 0.6%. Next, 0.25 part of diethylaminoethanol was added, and the reaction was further carried out at 90 ° C. for 3 hours. Using 115.0 parts of ethyl acetate, it was transferred to a dropping tank to obtain a prepolymer. Next, 3.38 parts of isophoronediamine, 0.176 parts of dibutylamine, 350.0 parts of isopropyl alcohol, and 235.0 parts of ethyl acetate were charged into the reaction tank, and the prepolymer was dropped into the reaction tank in 30 minutes from the dropping tank. After reacting at 40 ° C. for 1 hour, resin AJ was obtained through drying at 80 ° C. under reduced pressure.

The following products were used as the resins R to Z and AA to AE.
Resin R: “DISPERBYK-110” manufactured by Big Chemie Japan
Resin S: “DISPERBYK-111” manufactured by Big Chemie Japan
Resin T: “Ajisper PA111” manufactured by Ajinomoto Fine Techno Co., Ltd.
Resin U: “Joncryl678” manufactured by BASF
Resin V: “DISPERBYK-161” manufactured by Big Chemie Japan
Resin W: “DISPERBYK-21116” manufactured by Big Chemie Japan
Resin X: “DISPERBYK-21715” manufactured by Big Chemie Japan
Resin Y: “Ajispur PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.
Resin Z: “Efka PX4300” manufactured by BASF
Resin AA: “SOLSPERSE24000” manufactured by Nihon Lubrizol
Resin AB: “SOLSPERSE17000” manufactured by Nihon Lubrizol
Resin AC: “SOLSPERSE32000” manufactured by Nippon Lubrizol
Resin AD: “Hinoact T-8000” manufactured by Kawaken Fine Chemical Co., Ltd.
Resin AE: Kyoeisha Chemical Co., Ltd. “Floren KDG-2400”
CAP resin: (Eastman Chemical "CAP-504-0.2"

[Pigment]
(Synthesis Example 23: DibromoDPP)
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring.

  After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. This cooled mixture was cooled to 75 ° C. while rotating a shear disk having a diameter of 8 cm at 4,000 rpm using a high-speed stirring disperser, and the alkali metal of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The salt solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. is adjusted while cooling so that the temperature of the mixture of methanol, acetic acid and water is always kept at −5 ° C. or lower. While being added in small portions over approximately 120 minutes.

  After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste is re-dispersed in 3,500 parts of methanol cooled to 0 ° C. to make 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. It was. Subsequently, the diketopyrrolopyrrole compound aqueous paste obtained by filtering with an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to obtain 150.8 parts of a brominated diketopyrrolopyrrole pigment. Got.

Hereinafter, pigments used in Examples or Comparative Examples are listed.
PR242: “Novoperm Scarlet 4RF” manufactured by Clariant
PR177-1: “Cinilex Red SR3C” manufactured by CINIC
PR177-2: “Cinilex Red SR4C” manufactured by CINIC
PR254-1: “Irgazin Red L 3660 HD” manufactured by BASF
PR254-2: “Irgaphor Red S 3610 CF” manufactured by BASF
PR269: “Permanent Carmine 3810” manufactured by Sanyo Dye
PR122: “FASTOGEN Super Magenta RGT” manufactured by DIC
PG36: “LIONOL GREEN 6YK” manufactured by Toyocolor Co., Ltd.
PG58: "FASTOGEN Green A110" manufactured by DIC
PY138: “Paliotol Yellow K 0961 HD” manufactured by BASF
PY150: “Yellow Pigment E4GN” manufactured by LANXESS
PY139: “Paliotol Yellow D 1819” manufactured by BASF
PB15: 6: “LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd.
PB15: 4: Toyo Color "LIONOL BLUE 7358G"
PB15: 3: “LIONOL BLUE FG-7351” manufactured by Toyocolor Co., Ltd.
PB7: “ELFTEX415 REGAL400R” manufactured by Cabot
PV23: “LIONOGEN VIOLET FG-6240” manufactured by Toyocolor Co., Ltd.
PV19: “Ink Jet Magenta E5B02 VP2984” manufactured by Clariant
PY74: “Irgalite Yellow D 1245” manufactured by BASF

[Dye derivative]
Hereinafter, the pigment derivatives used in Examples or Comparative Examples are listed in Tables 1 to 3.

[solvent]
Solvents and symbols used in Examples and Comparative Examples are listed.
PGMAc: Propylene glycol monomethyl ether acetate DEDG: Diethylene glycol diethyl ether CBAc: Diethylene glycol monoethyl ether acetate

<Preparation of pigment composition by kneading (route r1)>
[Example 1-1]
(Preparation of pigment composition 1)
120 parts of azo red pigment PR242 (“Novoperm Scarlet 4RF” manufactured by Clariant), 20 parts of pigment derivative a, 1,500 parts of sodium chloride (NaCl), 60 parts of resin A, 200 parts of monoacetin and 2 parts of water are made of 1 gallon kneader made of stainless steel. (Made by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This mixture was added to 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, washed with 10,000 parts of water at 40 ± 5 ° C., Pigment composition 1 was obtained by removing sodium chloride and monoacetin and drying at 90 ° C.

[Examples 1-2 to 46, Comparative examples 1-1 to 46]
(Preparation of pigment compositions 2-92)
Pigment compositions 2 to 92 were obtained in the same manner as in Example 1-1 except that the kneading compositions, kneading conditions, and drying conditions shown in Tables 4 to 6 were changed.

<Evaluation of pigment composition by kneading>
(Measurement of average primary particle size)
The average primary particle size of the obtained pigment composition was measured using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.) and the primary particle size of all pigment particles in the observation sample at a magnification of 100,000 times. The average value was used. In addition, when the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was defined as the particle diameter. In addition, the average primary particle diameter of subsequent Examples and Comparative Examples was also measured by the above method.

(Measurement of residual solvent)
The residual solvent is determined by gas chromatography to determine the amount of the residual solvent of the water-soluble organic solvent of the present invention relative to the solid content of the pigment composition. From the ratio of the pigment in the solid content, the amount of the water-soluble organic solvent per 100 parts by mass of the pigment is determined. It calculated | required by calculating the amount of residual solvents.
Specifically, 0.1 g of the pigment composition is precisely weighed in a 50 ml volumetric flask, and tetrahydrofuran is added to adjust to 50 ml. Thereafter, ultrasonic treatment was performed for 15 minutes, and filtration was performed with a 0.20 μm membrane filter, and the filtrate was used as a measurement sample. The residual solvents in the following examples and comparative examples were also measured by the same method.
The conditions for gas chromatography are shown below.

Separation equipment: GC2010 manufactured by Shimadzu Corporation
Column: DM-5MS (30m x 0.25mm x 0.25μm Film, Agilent Technologies)
Carrier gas: He
Pressure: 120.0kPa
Total flow rate: 50.0ml / min
Column flow rate: 1.77 ml / min
Linear velocity: 49.0cm / sec
Purge flow rate: 3.0ml / min
Column temperature: Hold at 80 ° C for 4 minutes, then heat up in 16 minutes, hold at 320 ° C for 5 minutes Injection mode: Split-less Mode
Injection volume: 1μl
The conditions of the mass spectrometer are shown below.

Measuring instrument: GCMS-GP2010, manufactured by Shimadzu Corporation
Interface temperature: 250 ℃
Ion source temperature: 200 ° C
Measurement mode: Scan Mode
Measurement range: m / z = 30-500
Measurement time: 5-20min
Event time: 0.5 sec

  Tables 4 to 6 show the average primary particle diameters and the residual solvent results of the pigment compositions 1 to 92 obtained in Examples 1-1 to 46 and Comparative Examples 1-1 to 46.

<Preparation of pigment composition by mixing (route r2)>
[Example 2-1]
(Preparation of pigment composition 93)
A compound shown below was blended, and the mixture was stirred at 80 ° C. and 7,000 rpm for 60 minutes in a dissolver equipped with a 4 cm toothed disk to prepare a pigment composition 93. The monoacetin concentration per 100 parts by mass of the pigment in the pigment composition 93 was 0.012%.
Pigment composition 1: 10.0 parts Propylene glycol monomethyl ether acetate: 40.0 parts

[Examples 2-2 to 46, Comparative examples 2-1 to 46]
(Preparation of pigment compositions 94 to 184)
Pigment compositions 94 to 184 were produced in the same manner as in Example 2-1, except that the blending compositions shown in Tables 7 to 9 were changed.

<Evaluation of pigment composition by mixing>
(Initial viscosity, viscosity stability, haze value)
In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition was measured with a B-type viscometer (25 ° C.), and the haze value was measured with a haze meter (light transmittance 20%). The performance of the object was evaluated. The initial viscosity and haze value were measured after standing at room temperature for 1 day after dispersion, and the time-lapse viscosity was allowed to stand at 40 ° C. for 1 week. Regarding the viscosity stability, the difference between the initial viscosity and the viscosity with time was less than ± 3%, ◎, ± 3% to 10% were ○, and more than ± 10% were ×. The results are shown in Tables 7-9.

  From the results of Tables 7 to 9, it can be seen that all of the examples of the present invention exhibit excellent viscosity stability as compared with the comparative examples. Moreover, also in a haze value, the Example of this invention has a small value compared with a comparative example, and it turns out that it is excellent in transparency. These results suggest that the solid component in the pigment composition does not aggregate and has good dispersibility.

  Hereinafter, although the Example according to a specific use is described, the use of the pigment composition of this invention is not limited to the following uses.

≪Color filter pigment composition≫
Next, production examples of pigment compositions suitable for color filter inks will be described. In addition, it can be suitably applied to uses other than the color filter ink.

<Preparation of CF pigment composition by kneading (route r1)>
[Example 3-1]
(Preparation of pigment composition 185)
95 parts of azo red pigment PR242 (“Novoperm Scarlet 4RF” manufactured by Clariant), 5 parts of pigment derivative a, 1,000 parts of sodium chloride, 35 parts of resin B, 65 parts of resin AF, 170 parts of triacetin and 26 parts of water, 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 10 hours. This mixture is added to 10,000 parts of water, stirred at a high speed mixer for about 1 hour while being heated to about 40 ° C. to form a slurry, and repeatedly filtered and washed with water to remove sodium chloride and water-soluble organic solvent. The resultant was dried at 40 ° C. to obtain a pigment composition 185.

[Examples 3-2 to 40, Comparative examples 3-1 to 40]
(Preparation of pigment compositions 186 to 264)
Pigment compositions 186 to 264 were obtained in the same manner as in Example 3-1, except that the kneading compositions shown in Tables 10 and 11 were changed.

  Tables 10 and 11 show the average primary particle sizes and residual solvent results of the pigment compositions 185 to 264 obtained in Examples 3-1 to 40 and Comparative Examples 3-1 to 40.

<Preparation of CF pigment composition by mixing (route r2)>
[Example 4-1]
(Preparation of pigment composition 265)
The compound shown below was mix | blended and it stirred at 70 degreeC and 5000 rpm for 60 minutes in the dissolver provided with the toothed disk of 4 cm, and the pigment composition 265 was produced. The triacetin concentration per 100 parts by mass of the pigment in the pigment composition 265 was 0.061%.
Pigment composition 185: 22.0 parts Propylene glycol monomethyl ether acetate: 78.0 parts

[Examples 4-2 to 40, Comparative examples 4-1 to 40]
(Preparation of pigment compositions 266 to 344)
Pigment compositions 266 to 344 were prepared in the same manner as in Example 4-1, except that the composition shown in Tables 12 and 13 was changed.

  The initial viscosity, viscosity stability, and haze value of the pigment compositions 265 to 344 obtained in Examples 4-1 to 40 and Comparative Examples 4-1 to 40 were evaluated in the same manner as the pigment compositions 93 to 184. The results are shown in Tables 12 and 13.

  From the results of Tables 12 and 13, it can be seen that the examples of the present invention show excellent viscosity stability as compared with the comparative examples. Moreover, also in a haze value, the Example of this invention has a small value compared with a comparative example, and it turns out that it is excellent in transparency. This suggests that the solid component in the pigment composition does not aggregate and has good dispersibility.

<Preparation of photosensitive pigment composition for CF>
[Example 5-1]
(Preparation of pigment composition 345)
A mixture having 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 345. The mixing ratio of the pigment composition was adjusted so that the colored film exhibited color characteristics of x = 0.640 and y = 0.330.
Pigment composition 265, 267: 51.0 parts Resin AF solution: 1.0 part Photopolymerizable compound: 4.0 parts (“NK Ester ATMPT” trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 3.4 parts (“Irgacure907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by BASF)
Sensitizer: 0.4 part ("EAB-F"4,4'-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-2-7, 5-13-19, Comparative Examples 5-1-7, 5-13-19]
(Preparation of pigment compositions 346-351, 369-375, 357-363, 381-387)
Except having changed the composition shown in Tables 14 and 15, red composition pigment compositions 346 to 351, 369 to 375, 357 to 363, and 381 to 387 were produced in the same manner as in Example 5-1.

[Example 5-8]
(Preparation of pigment composition 352)
A mixture having 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 352. The mixing ratio of the pigment composition was adjusted so that the colored film exhibited color characteristics of x = 0.300 and y = 0.600.
Pigment composition 274, 278: 52.0 parts Photopolymerizable compound: 4.8 parts ("NK ester ATMPT" trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 2.8 parts (“Irgacure907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by BASF)
Sensitizer: 0.2 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-9, 10, 5-20-22, Comparative Examples 5-8-10, 5-20-22]
(Preparation of pigment compositions 353, 354, 376-378, 364-366, 388-390)
Green pigment compositions 353, 354, 376 to 378, 364 to 366, and 388 to 390 were produced in the same manner as in Example 5-8 except that the blending compositions shown in Tables 14 and 15 were changed.

[Example 5-11]
(Preparation of pigment composition 355)
A mixture having 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 355. The mixing ratio of the pigment composition was adjusted so that the colored film exhibited color characteristics of x = 0.150 and y = 0.06.
Pigment compositions 281 and 284: 42.0 parts Resin AF solution: 10.0 parts Photopolymerizable compound: 5.6 parts (“NK ester ATMPT” trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator: 2.0 parts (“Irgacure907” manufactured by BASF Corporation 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
Sensitizer: 0.2 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Propylene glycol monomethyl ether acetate: 40.2 parts

[Examples 5-12, 23, 24, Comparative Examples 5-11, 12, 23, 24]
(Preparation of pigment compositions 356, 379, 380, 367, 368, 391, 392)
Blue pigment compositions 356, 379, 380, 367, 368, 391, 392 were prepared in the same manner as in Example 5-11 except that the blending compositions shown in Tables 14 and 15 were changed.

<Evaluation of photosensitive pigment composition for CF>
(Contrast ratio)
Next, a method for measuring the contrast ratio of the color filter pigment composition-coated substrate will be described.
A substrate coated with a pigment composition for a 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 and reaches the second polarizing plate. If the transmission axes of the pair of polarizing plates are parallel to each other, the light is transmitted 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 into the second polarizing plate. Cut off by the plate. However, when the light polarized by the first polarizing plate passes through the pigment composition coating substrate for the color filter, if scattering by pigment particles occurs and a part of the polarization plane shifts, 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 is reduced, and when the transmission axes of the pair of deflection plates are arranged orthogonally, the second polarizing plate is light-transmitted. A part of is transparent. This transmitted light is measured as the luminance on the polarizing plate, and the contrast ratio is defined as the ratio between the luminance with the transmission axis of the polarizing plate arranged in parallel and the luminance with the transmission axis of the polarizing plate arranged orthogonally.

Contrast ratio = (luminance of outgoing light when the transmission axes of a pair of polarizing plates are parallel) / (luminance of outgoing light when the 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 when parallel is reduced and the brightness when orthogonal is increased, the contrast ratio is lowered. For luminance measurement, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) were used. The measurement was performed under the condition of a 2 ° visual field, and a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. The thickness of the color filter pigment composition-coated substrate was constant in both Examples and Comparative Examples.

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

  It was confirmed that the color filter pigment compositions obtained in Examples 5-1 to 24 had contrast characteristics superior to those obtained in Comparative Examples 5-1 to 24, respectively.

<Production example of color filter>
The red pigment composition 370 of the present invention was applied onto a substrate by spin coating so that the dry film thickness was 1.7 μm and dried. And after performing ultraviolet exposure through a mask having a predetermined pattern provided in a non-contact state with the coating film, after spraying an alkali developer by spraying to remove the uncured portion and forming a desired pattern, Heated at 230 ° C. for 1 hour. The same operation was repeated for the green pigment composition 377 and the blue pigment composition 380 to produce a color filter and to produce an RGB three-color filter. The obtained color filter was confirmed to have high brightness and excellent heat resistance.

≪Inkjet pigment composition≫
Next, production examples of a pigment composition suitable for ink jet ink will be described. In addition, it can apply suitably also for uses other than the ink for inkjet. The thermally reactive compounds and their symbols used in the examples and comparative examples are shown below.
MX-43: “Nikarak MX-43” manufactured by Sanwa Chemical Co., Ltd.
SB-401: “Nikarak SB-401” manufactured by Sanwa Chemical Co., Ltd.

<Preparation of IJ Pigment Composition by Kneading (Route r1)>
[Example 6-1]
(Preparation of pigment composition 393)
100 parts of PY150 ("Yellow Pigment E4GN" manufactured by LANXESS), 500 parts of sodium chloride, 66.5 parts of resin E, 113.5 parts of 2-ethyl-1,3-hexanediol and 3.5 parts of water and 1 gallon made of stainless steel The mixture was charged into a kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 4 hours. This mixture is added to 10,000 parts of water, stirred at a high speed mixer for about 1 hour while being heated to about 40 ° C. to form a slurry, and repeatedly filtered and washed with water to remove sodium chloride and water-soluble organic solvent. The resultant was dried at 40 ° C. to obtain a pigment composition 393.

[Examples 6-2 to 10, Comparative examples 6-1 to 10]
(Preparation of pigment compositions 394 to 412)
Pigment compositions 394 to 412 were obtained in the same manner as in Example 6-1 except that the kneading composition and kneading conditions shown in Table 16 were changed.

  Table 16 shows the average primary particle diameters and residual solvent results of the pigment compositions 393 to 412 obtained in Examples 6-1 to 10 and Comparative Examples 6-1 to 10.

<Preparation of IJ pigment composition by mixing (route r2)>
[Example 7-1]
(Preparation of pigment composition 413)
In the dissolver equipped with the compound shown below and equipped with a 4 cm toothed disk, the mixture was stirred at 60 ° C. and 5,000 rpm for 60 minutes, and then filtered under pressure through a membrane filter to obtain a pigment composition having a pigment concentration of 13%. 413 was obtained. The concentration of 2-ethyl-1,3-hexanediol per 100 parts by mass of the pigment in the pigment composition 413 was 0.076%.
Pigment composition 393: 166.5 parts SB-401: 40.0 parts CBAc: 320.0 parts

[Examples 7-2 to 10, Comparative Examples 7-1 to 10]
(Preparation of pigment compositions 414 to 432)
Pigment compositions 414 to 432 were produced in the same manner as in Example 7-1 except that the blending composition shown in Table 17 was changed.

<Evaluation of IJ pigment composition by mixing>
The pigment compositions obtained in Examples 7-1 to 10 and Comparative Examples 7-1 to 10 were evaluated by the following methods.
(Initial viscosity)
Using a dynamic viscoelasticity measuring device, the viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured and evaluated according to the following criteria.
○: η <40
Δ: 40 ≦ η <50
×: 50 ≦ η

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

(Viscosity stability)
The viscosity after heating for 7 days in a 45 ° C. oven was measured (viscosity with time). From the values of the initial viscosity and the viscosity with time, the rate of change with time in viscosity was calculated by the following formula.
[Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100
Moreover, the viscosity stability was evaluated according to the following criteria.
○: Change rate of viscosity with time is less than 10% Δ: Change rate of viscosity with time is 10% or more and less than 30% ×: Change rate of viscosity with time is 30% or more

(Haze value)
Using a spin coater, the substrate coated on glass at 1500 rpm was dried on a hot plate at 100 ° C. for 3 minutes, and the haze of the coated surface was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.). It was evaluated with.
○: [Haze value] <3.0
Δ: 3.0 ≦ [Haze value] <4.5
×: 4.5 ≦ [Haze value]

(chemical resistance)
The glass substrate on which the coating film was formed used in the haze evaluation was immersed in N-methylpyrrolidone, and the color change ΔE of the coating film before and after immersion was measured.
○: △ E <2.0
Δ: 2.0 ≦ ΔE <4.0
×: 4.0 ≦ ΔE

(Discharge stability)
The ink was ejected with an ink jet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, the printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
○: Nozzle missing after 5 minutes intermittent is less than 5%.
Δ: Nozzle missing after 5 minutes intermittent is 5% or more and less than 10%.
X: Nozzle missing after 5 minutes intermittent is 10% or more and less than 50%.

  As is clear from Table 17, the pigment composition of the present invention is excellent in viscosity, fluidity, viscosity stability, ejection stability and haze value while maintaining high chemical resistance (2.0 or less). Recognize.

≪Flexo / Gravure ink≫
Next, production examples of a pigment composition suitable for flexographic / gravure ink will be described. In addition, it can apply suitably also for uses other than a flexo / gravure ink.

<Preparation of a flexographic / gravure pigment composition by kneading (route r1)>
[Example 8-1]
(Preparation of pigment composition 433)
PB15: 4 (Toyocolor "LIONOL BLUE 7358G") 130 parts, sodium chloride 400 parts, resin AI 120 parts, CAP resin (Eastman Chemical "CAP-504-0.2") 5 parts, 2-ethyl- 350 parts of 1,3-hexanediol and 28 parts of water were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 3 hours. The mixture was put into 10,000 parts of water, heated to about 40 ° C., stirred with a high speed mixer for about 1 hour to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and the solvent. Was dried to obtain a pigment composition 433.

[Example 8-2, Comparative Examples 8-1 and 2]
(Preparation of pigment compositions 434 to 436)
Pigment compositions 434 to 436 were obtained in the same manner as in Example 8-1, except that the kneading composition and kneading conditions shown in Table 18 were changed.

  Table 18 shows the average primary particle sizes and residual solvent results of the pigment compositions 433 to 436 obtained in Examples 8-1 and 8-1 and Comparative Examples 8-1 and 2-2.

<Preparation of flexographic and gravure pigment composition by mixing>
[Example 9-1]
(Preparation of pigment composition 437)
The following compounds were blended and stirred in a dissolver equipped with a 4 cm toothed disk at 50 ° C. and 3,000 rpm for 60 minutes, followed by pressure filtration with a membrane filter to obtain a pigment composition with a solid content concentration of 26%. Product 437 was obtained. The concentration of 2-ethyl-1,3-hexanediol per 100 parts by mass of the pigment in the pigment composition 437 was 0.082%.
Pigment composition 433: 25.5 parts Polyethylene wax: 0.5 parts Ethyl acetate: 14.0 parts
n-propyl acetate: 24.0 parts Isopropanol: 36.0 parts

[Example 9-2, Comparative examples 9-1 and 2]
(Preparation of pigment compositions 438 to 440)
Pigment compositions 438 to 440 were produced in the same manner as in Example 9-1 except that the formulation shown in Table 19 was changed.

<Evaluation of pigment composition for flexographic and gravure by dispersion>
The obtained printing ink was diluted with isopropyl alcohol alone when evaluated by flexographic printing, and diluted with ethyl acetate / isopropyl alcohol = 70/30 when evaluated by gravure printing.
As the film, a corona-treated biaxially stretched polypropylene film (P-2161 manufactured by Toyobo Co., Ltd., hereinafter referred to as OPP), a polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd., hereinafter referred to as PET), a nylon film (manufactured by Toyobo Co., Ltd.) N-1102, hereinafter referred to as Ny).
Ink flow stability, ink tape adhesion, blocking resistance, boil resistance and retort resistance were evaluated. The results are shown in Table 17.

(Ink flow stability)
A: Good fluidity and good gloss of dry ink film B: Poor fluidity and low gloss of dry ink film

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

(Blocking resistance)
The printed surface of the printed OPP film and the corona discharge treated surface of the OPP film were superposed and left to stand at a temperature of 40 ° C. for 1 day under a load of 3 kg / cm 2. Thereafter, the ink surface and the film surface were peeled off, and the transition of the ink coating to the film surface was evaluated.
Good: No transfer of the ink coating to the film surface.
Defect: Transition of the ink coating to the film surface is observed.

(Boil resistance)
An isocyanate-based anchor coating agent was applied to a printed matter of PET and Ny, and then melted polyethylene was laminated at a thickness of 30 μm by an extrusion laminating machine to obtain a laminated product. Laminated products are made into bags, sealed with a mixture of water / oil / vinegar = 1/1/1 inside, heated in hot water at 90 ° C for 30 minutes, and resists the appearance of the appearance of lambs. Boil suitability was judged.
A: There is no Lami floating.
B: Some or all of the surface is delaminated.

(Retort resistance)
After 3 g / m 2 of an isocyanate-based adhesive was applied to PET and Ny printed matter, a polyethylene film having a thickness of 60 μm was laminated by a dry laminating machine to obtain a laminated product. The laminated product was made into a bag, a water / oil mixture was put inside and sealed, and then a retort treatment was performed at 120 ° C./30 minutes, and the suitability of the retort was judged from the presence or absence of the appearance of the lami.
A: There is no Lami floating.
B: Some or all of the delamination occurred

  As is apparent from Table 19, it was revealed that the pigment composition of the present invention was excellent in each characteristic.

<Preparation of pigment composition via r3>
[Example 10-1]
(Preparation of pigment composition 441)
95 parts of azo red pigment PR242 (“Novoperm Scarlet 4RF” 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, 70 parts of triacetin and 26 parts of ion-exchanged water are made of stainless steel. A 1 gallon kneader (manufactured by Inoue Seisakusho) was charged and kneaded at 70 ° C. for 10 hours. This mixture is added to 10,000 parts of water, heated to 40 ± 5 ° C., stirred for 1 hour with a high speed mixer to form a slurry, filtered, and washed with 10,000 parts of ion-exchanged water at 40 ± 5 ° C. did. 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 441 having a solid concentration of 22%.

[Examples 10-2 to 20, Comparative Examples 10-1 to 20]
(Preparation of pigment compositions 442 to 480)
Except having changed into the kneading | mixing composition shown in Table 20, Table 21, it carried out similarly to Example 10-1, and obtained the pigment compositions 442-480.

<Evaluation of pigment composition via r3>
Tables 20 and 21 show the average primary particle sizes and residual solvent results of the pigment compositions 441 to 480 obtained in Examples 10-1 to 10 and Comparative Examples 10-1 to 20. Further, the initial viscosity, the viscosity stability, and the haze value were evaluated in the same manner as the pigment compositions 93 to 184. The results are shown in Tables 20 and 21.

  From the results of Tables 20 and 21, it can be seen that the examples of the present invention show excellent viscosity stability as compared with the comparative examples. Moreover, also in a haze value, the Example of this invention has a small value compared with a comparative example, and it turns out that it is excellent in transparency. This suggests that the solid component in the pigment composition does not aggregate and has good dispersibility.

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

Claims (6)

A step (a) of adding at least a water-soluble inorganic salt, a water-soluble organic solvent, water and a dispersant to the pigment and then refining the pigment by milling and kneading;
After step (a), water is added to obtain a suspension (b);
(C) 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 method includes a step (d) for removing water,
The water-soluble organic solvent is a method for producing a pigment composition that satisfies the following (i) to (iv).
(A) The water-soluble organic solvent 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.
(I) The molecular weight is 130-350.
(Ii) It has a total of 2 or more functional groups (F) comprising 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 water-soluble organic solvent is 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine, tributyrin and 2-butyl-2-ethyl-1 The method for producing a pigment composition according to claim 1, wherein the pigment composition is at least one selected from 1,3-propanediol.   The method for producing a pigment composition according to claim 1 or 2, wherein the pigment is at least one selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments.   The method for producing a pigment composition according to any one of claims 1 to 3, wherein a step (e) is performed after the step (c) and before the step (d) by adding a dispersion solvent and mixing and stirring. . 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 130-350.
(Ii) It has a total of 2 or more functional groups (F) comprising 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.   A pigment composition for a color filter comprising the pigment composition according to claim 5.

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