WO2015083352A1 - Pigment composition and method for producing same, water-soluble organic solvent for milling and kneading, and pigment composition for color filter - Google Patents

Abstract

　This method for producing a pigment composition is furnished with a step (a) for micronizing a pigment by kneading in a milling manner by adding at least a water-soluble inorganic salt and a water-soluble organic solvent that satisfies (i)-(iv) below, a step (b) for adding water and obtaining a suspension, a step (c) for removing the water-soluble inorganic salt and removing the water-soluble organic solvent so as to satisfy (A) below, and a step (d) for removing water. (A) The residual water-soluble organic solvent is within a range of 0.005-0.5 parts by mass per 100 parts by mass of pigment contained in the pigment composition. (i) The molecular weight is 100-350, and preferably 130-350. (ii) There is a total of two or more functional groups (F) comprising hydroxyl groups and/or ester groups. (iii) The viscosity at 60°C is 2-140 mPa∙s. (iv) No ether bonds are contained.

Description

Pigment composition and method for producing the same, water-soluble organic solvent for milling and kneading, and pigment composition for color filter

The present invention relates to a pigment composition containing a refined pigment and a method for producing the same. The present invention also relates to a water-soluble organic solvent for milling and kneading suitable for producing the pigment composition. Furthermore, it is related with the pigment composition for color filters containing the said pigment composition.

Pigments are widely used as coloring materials for various industrial materials, including paints, inks, and coloring materials for plastics. 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 colorant, 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.

Therefore, research and development has been energetically promoted so far to control the dispersibility of the processed pigment. 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.

As a result of extensive studies by the present inventors in order to solve the above-mentioned problems, surprisingly, in the following embodiment, which is produced using a water-soluble organic solvent satisfying all of (i) to (iv), The present inventors have found that the problem can be solved and have completed the present invention.
[1] Step (a) in which at least a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment and the pigment is refined by milling and kneading, and after step (a), water is added to the suspension. After the step (b), the step (b), the step (c) of removing the water-soluble inorganic salt so as to satisfy the following (A), and the step (b) (c) is followed by a step (d) of removing water, wherein the water-soluble organic solvent satisfies the following (i) to (iv).
(A) The water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass per 100 parts by mass of the pigment contained in the pigment composition.
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of 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, 2-methylpentane-2 , 4-diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,2,6-hexanetriol The manufacturing method of the pigment composition as described in [1].
[3] The method for producing a pigment composition according to [1] or [2], further including a resin in the step (a).
[4] The pigment composition according to any one of [1] to [3], wherein the pigment is at least one selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Manufacturing method.
[5] The pigment composition according to any one of [1] to [4], wherein the step (e) is performed after adding the dispersion solvent and mixing and stirring after the step (c) and before the step (d). Manufacturing method.
[6] A pigment composition comprising a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm,
A pigment in which a water-soluble organic solvent satisfying the following (i) to (iv) remains in a range of 0.005 to 0.5 parts by mass per 100 parts by mass of the pigment contained in the pigment composition Composition.
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of 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.
[7] A water-soluble organic solvent for milling and kneading used in the production of a pigment composition containing a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm, comprising the following (i) A water-soluble organic solvent for grinding and kneading satisfying (iv).
(I) The molecular weight is 100 to 350, more preferably 130 to 350.
(Ii) It has a total of 2 or more functional groups composed of a hydroxyl group and / or an ester group.
(Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
(Iv) Does not contain an ether bond.
[8] The water-soluble organic solvent is 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, and 1,6-hexanediol. Water-soluble organic solvent for use.
[9] A color filter pigment composition comprising the pigment composition according to [6].

ADVANTAGE OF THE INVENTION According to this invention, the refined pigment composition excellent in the dispersibility of the refined pigment, and high production efficiency, its manufacturing method, the water-soluble organic solvent for grinding kneading | mixing, and the pigment composition for color filters There is an excellent effect of providing goods.

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 this 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.

<Step (a)> In step (a), at least a water-soluble inorganic salt and a water-soluble organic solvent are added to the pigment, and the pigment is refined by grinding and kneading. The method 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 size 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 mixing a mixture containing at least a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent into a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, and / or an annula type. It can be performed using a kneader such as a 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.

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.

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 100 to 350, more preferably 130 to 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), and (iii) a viscosity at 60 ° C. of 2 to 140 mPa · s. Yes,
(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. 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 device manufactured by Toki Sangyo Co., Ltd .: TVE-20L) in accordance with the provisions of 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 satisfying 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), but preferred examples include 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), 2-methylpentane-2,4-diol (5.8 mPa · s), 2-butyl-2-ethyl-1,3- Propanediol (43.7 mPa · s), 1,5-pentanediol (20.9 mPa · s), 1,6-hexanediol (25.2 mPa · s) and 1,2,6-f At least one selected from Suntory ol (137.6mPa · s) and the like.

The amount added of the water-soluble organic solvent of the present invention 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.

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 the viewpoint of both processing efficiency and production efficiency.

In step (a), additives such as a dispersant and a pigment derivative may be further included. Examples of the dispersant include a resin and / or a low molecular weight surfactant.

The type of resin used as the dispersant is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. This resin is solid at room temperature, preferably insoluble in water, and more preferably soluble in the water-soluble organic solvent of the present invention. The amount of the resin used is preferably in the range of 5 to 100 parts by mass with respect to 100 parts by mass of the pigment. 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 with the pigment. Even when the pigment is dried, the coating resin suppresses aggregation of the pigments and improves dispersibility. I think it will contribute.

As preferable examples of the resin used as the dispersant, polyurethane, polyester, unsaturated polyamide, phosphate ester, polycarboxylic acid and its amine salt / ammonium salt / alkylamine salt, polycarboxylic acid ester, hydroxyl group-containing polycarboxylic acid ester, Oil-soluble dispersants such as polysiloxane and modified polyacrylate, water-soluble such as (meth) acrylic acid- (meth) acrylic acid ester copolymer, (meth) acrylic acid-styrene copolymer, styrene-maleic acid copolymer Examples include 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 about 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).

As a derivative of an organic pigment 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 in the molecule is suitable. By adding an organic 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 dispersant and 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).
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. Examples of 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.

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

<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 step (a) is added and mixed and stirred. The mixing and stirring conditions at this time are not particularly limited, but can be carried out at a temperature of 25 to 90 ° C., for example.

<Step (c)> After the treatment in step (b), the water-soluble inorganic salt is removed, and the water-soluble organic solvent satisfying the following (A) is removed (FIG. 1).
(A) The water-soluble organic solvent remains in the range of 0.005 to 0.5 parts by mass 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, or drying for 12 to 60 hours at 25 to 80 ° C. under reduced pressure. Examples thereof include a method of performing freezing in the range of −60 to −5 ° C. and then drying in a range of 25 to 80 ° C. for about 12 to 60 hours under reduced pressure. Although a drying process is not specifically limited, The method using a spray drying apparatus can be illustrated. A pulverization process may be performed simultaneously with the drying process or after the drying process.

By using the water-soluble organic solvent of the present invention, a powdery pigment composition having a high bulk density can be obtained. That is, by using the water-soluble organic solvent of the present invention, in other words, in a qualitative expression, a pigment composition containing a soft and fluffy powdered finely divided 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 the route r1 for obtaining the powder by performing the steps (a) to (d), the route r2 for performing the step (e) after the step (d), and the step (e) after the 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. The pigment composition of the present invention only needs to include the steps (a) to (d), and the step (e) can be arbitrarily added. 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 according to needs, but from the viewpoint of the simplicity of the production process, a method of directly obtaining a dispersion solvent as shown in 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.

<Step (e)> After passing through step (d), 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.

(Dispersion solvent) The dispersion solvent used in the step (e) is not particularly limited as long as it does not interfere with the dispersibility of the pigment. Preferred examples include 1,2,3-trichloropropane, 2-heptanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, n-butylbenzene, n-propyl acetate, o-xylene, o- Chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol 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 dispersion 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 (d), it is more preferable to use a water-insoluble organic solvent as the dispersion solvent.

(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, 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-bismaleimidehexane, 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- Phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimi 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 dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer, polyester, Sex 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, 7554, 1101, 120, 150, 1501, 1502, 1503, etc .; Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno Co.

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 “TSK-GEL SUPER H5000” and “H4000” manufactured by Tosoh Corporation as separation columns in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. , “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, 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 copolymerized with 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. Further, 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 obtained by introducing a basic substituent, an acidic substituent or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone or triazine. Those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in admixture of two or more. 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) As a suitable example of surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, alkylnaphthalene Sodium sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as esters; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether Nonionic surfactants such as tellurium, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts Agents: amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic 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), the dispersibility of the obtained pigment composition becomes excellent. This is because it is considered that a pigment composition having a higher bulk density can be obtained by performing the steps (a) to (d) using a water-soluble organic solvent as compared with the case where a conventionally used solvent is used. Yes.

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.

Monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyme Diether ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca 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-hydroxy Examples include, but are not necessarily limited to, methyl (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, -Hydroxycyclohexylphenyl 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, Is a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as — (4′-methoxystyryl) -6-triazine; 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxy) Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as -trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; A carbazole compound; an imidazole compound; or a titanocene compound is used. A photoinitiator can be used 1 type or in mixture of 2 or more types.

Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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 Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, Spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes or Michler ketone 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) Nzophenone, 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 BYK 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.

¡Anionic, cationic, nonionic or amphoteric surfactants 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 chaotic surfactants that are 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- And methacryloyloxyethyl-S-triazine / isocyanuric acid adduct). These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

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-aminopropyl Riethoxysilane, 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 the present invention is applied to a color filter will be described. 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.

(Manufacturing method of color filter) The color filter can be manufactured 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 the method, it is applied so that the dry film thickness is 0.2 to 5 μm. 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 of sodium carbonate, sodium hydroxide or the like 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, etc. 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.

Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, 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 the pigment composition of the present invention, as described above, the dispersion of the finely divided pigment is performed by performing the processes (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.

<< Example >>
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”. First, resins, pigments, dye derivatives and solvents used in Examples and Comparative Examples will be described.

[resin]
(Synthesis Example 1: Resin A) In a reaction vessel equipped with a gas introduction pipe, a thermometer, a condenser, and a stirrer (hereinafter, the reaction vessel equipped with these is abbreviated as “reaction vessel A”), 60 parts of n-butyl methacrylate And 140 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 12 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were dissolved was added. It was made to react for time and 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 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.

(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 replaced with nitrogen gas. Thereafter, the mixture was heated and stirred at 120 ° C. for 4 hours. 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. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and Resin B was obtained.

(Synthesis Example 3: Resin C) A reaction vessel A was charged with 160 parts of n-butyl acrylate and 40 parts of 2-([1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (manufactured by Showa Denko KK). Replaced with 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. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and Resin C was obtained.

Synthesis Example 4: Resin D In a reaction vessel A, 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, propylene glycol 40 parts of monomethyl ether acetate was charged and replaced with nitrogen gas. 7.7 parts of (3,4-epoxycyclohexyl) methyl methacrylate was 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 Resin Toa Gosei Co., Ltd.), 15.0 parts of methacrylic acid and First, 334.0 parts of 1-methoxy-2-propanol 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 to obtain Resin E.

(Synthesis Example 6: Resin F) A reaction vessel A was charged with 45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, and 40.0 parts of ethyl acrylate, and replaced with nitrogen gas. Heat the reaction vessel to 80 ° C. and dissolve 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile 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 (“Rikacid BT-100” manufactured by Shin Nippon Chemical Co., Ltd.), cyclohexanone 69 .2 parts and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and Resin F was obtained.

(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. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and Resin G was obtained.

(Synthesis Example 8: Resin H) 83 parts of hydroxyethyl acrylate, 821 parts of ε-caprolactone, 0.009 parts of monobutyltin oxide, and 0.93 parts of methylhydroquinone were added to the reaction vessel A, and the remaining ε-caprolactone was 1%. The reaction was carried out at 100 ° C. for 10 hours until the following. To the reaction solution at 60 ° C., 100 parts of polyethyleneimine (“SP200” manufactured by Nippon Shokubai Co., Ltd.) was added and reacted with stirring. Proton NMR confirmed that the acrylic group had disappeared, and Resin H was obtained.

(Synthesis Example 9: Resin I) 60.3 parts of hydroxyethyl acrylate, 889 parts of ε-caprolactone, 0.042 part of monobutyltin oxide, and 0.94 part of methylhydroquinone were added to the reaction vessel A, and the remaining ε-caprolactone was added. The reaction was carried out at 100 ° C. for 10 hours until 1% or less. 50 parts of polyethyleneimine (SP200: manufactured by Nippon Shokubai Co., Ltd.) was added to the reaction solution at 60 ° C. for reaction. Proton NMR confirmed that the acrylic group had disappeared, and Resin I was obtained.

(Synthesis Example 10: Resin J) A reaction vessel A was charged with 57.0 parts of a polycarbodiimide compound having an carbodiimide equivalent of 316 having an isocyanate group and 16.0 parts of methyldiethanolamine, and held at about 100 ° C. for 2 hours to obtain an isocyanate group. And a hydroxyl group were reacted. 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. Thereafter, 97.7 parts of propylene glycol monomethyl ether acetate was added to obtain Resin J.

(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 (“CALCOL 2098” manufactured by Shin Nippon Chemical Co., Ltd.), 28% sodium methoxide methanol solution (“SM-28” manufactured by Kawaken Fine Chemical Co., Ltd.) ) 2.63 parts were charged and reacted at 90 ° C. under reduced pressure for 50 minutes. 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 the gas was replaced with nitrogen gas. The mixture was dehydrated at 100 ° C. under reduced pressure, and then the temperature was raised to 150 ° C. and reacted at a pressure of 1.3 kPa for 2 hours to obtain Resin L.

(Synthesis Example 13: Resin M) 50 parts of polyethyleneimine (number average molecular weight 600) and 1.0 part of powdered sodium hydroxide were added to an autoclave and heated to 80 ° 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 resin M540 part.

(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, and replaced with nitrogen gas. It heated and heated up to 90 degreeC. 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 stirred with heating at 90 ° C. for 2 hours. Further, 6.0 parts of V-65 was added, and the mixture was heated and stirred for 3 hours to obtain Resin N.

(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 was prepared, and dibutyltin diacetate 0 was added thereto. 96 parts were added and reacted at 50 ° C. for 7.5 hours with stirring. The reaction solution was cooled to room temperature and dropped into 1,000 parts of hexane to precipitate a solid. The precipitated solid was filtered and air-dried to obtain 26.0 parts of a benzimidazolone-containing monomer.
In 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: 2.00 parts Methacrylic acid: 6.00 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 202 parts were added, and the internal temperature was maintained at 78 ° C. for 2 hours, and then heated to 90 ° C. for 30 minutes. 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 stirred at a temperature of 80 ° C. under a nitrogen stream. Warmed to. 0.147 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 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 the subsequent steps, with respect to the composition of Synthesis Example 15, the addition amount of methacrylic acid was changed to 0 part and the addition amount of one-end methacryloylated polymethyl methacrylate was changed to 14.0 parts. Resin P was obtained in the same manner as in Synthesis Example 15 except that 0.0 part was added.

(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 stirred at a temperature of 80 ° C. in a nitrogen stream. Warmed to. 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 while stirring. The reaction solution was diluted with 200 parts of ethyl acetate and reprecipitated with 3000 parts of hexane to obtain 73.6 parts of 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 0 part, the addition amount of one-end methacryloylated polymethyl methacrylate was 14.0 parts, a polarizer, and the MM-2 was 24 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) 800 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator at the same temperature was 1 The reaction was performed dropwise over time.
-Styrene: 60.0 parts-Methacrylic acid: 60.0 parts-Methyl methacrylate: 65.0 parts-Butyl methacrylate: 65.0 parts-Azobisisobutyronitrile: 10.0 parts After addition, at 100 ° C After reacting for 3 hours, 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate was added, and the reaction was further continued at 100 ° C. for 1 hour. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether so that the nonvolatile content was 20% by mass in the previously synthesized resin solution. Acetate was added to obtain Resin AF.

(Synthesis Example 19: Resin AG) 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 was abbreviated as “four-necked flask A”). , 80.0 parts of biphenyltetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate, 0.16 parts of hydroquinone, and 141.2 parts of cyclohexanone were added, 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, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. A yellow transparent 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 at 85 ° C. The temperature was raised to. 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, stirred at 85 ° C. for 6 hours, cooled to room temperature, and the reaction was terminated. A yellow transparent resin AH was obtained.

(Synthesis Example 21: Resin AI) In a four-necked flask A, 218.9 parts of polytetramethylene glycol having a molecular weight of 2,000 and 57.4 parts of isophorone diisocyanate were charged. The reaction was continued until the isocyanate group was 4.5%. 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. . Then, it was made to react at 40 degreeC for 1 hour, and resin AI with a solid content of 30% was obtained.

(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-pentanetanediol, and a polytetramethylene glycol 13 having a molecular weight of 1,000. .3 parts and 19.3 parts of isophorone diisocyanate were charged, the temperature was gradually raised to 90 ° C. while introducing nitrogen gas, and the reaction was carried out until the NCO% became 0.6%. Next, 0.25 part of diethylaminoethanol was added, and 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. Then, it was made to react at 40 degreeC for 1 hour, and resin AJ with a solid content of 30% was obtained.

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: "Ajisper 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 Nippon Lubrizol
Resin AC: “SOLSPERSE32000” manufactured by Nihon Lubrizol
Resin AD: “Hinoact T-8000” manufactured by Kawaken Fine Chemical Co., Ltd.
Resin AE: Kyoeisha Chemical Co., Ltd. “Floren KDG-2400”

[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 were added in a nitrogen atmosphere and stirred at 100 ° C. To prepare an alcoholate solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and 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. Further, 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 SR4C” 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
・ 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.
・ PV23: “LIONOGEN VIOLET FG-6240” manufactured by Toyocolor Co., Ltd.
・ PB15: 3: “LIONOL BLUE FG-7351” manufactured by Toyocolor Co., Ltd.
・ PR122: “FASTOGEN Super Magenta RGT” manufactured by DIC
-PV19: "Ink Jet Magenta E5B02 VP2984" manufactured by Clariant
・ PY74: “Irgalite Yellow D 1245” manufactured by BASF
・ PB7: Cabot "ELFTEX415 REGAL400R"

[Dye derivative]
Hereinafter, the pigment derivatives used in Examples or Comparative Examples are listed in Tables 1A and 1B.

[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 (hereinafter simply referred to as “pigment composition”)>
[Example 1-1]
(Preparation of Pigment Composition 1) 120 parts of azo red pigment PR242 (“Novoperm Scarlet 4RF” manufactured by Clariant), 10 parts of pigment derivative a, 1,500 parts of sodium chloride, and 250 parts of monoacetin were added to a 1 gallon kneader made of stainless steel (Inoue 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 66, Comparative Examples 1-1 to 66]
(Preparation of pigment compositions 2 to 132) Pigment compositions 2 to 132 were obtained in the same manner as in Example 1-1 except that the kneading compositions, kneading conditions, and drying conditions shown in Tables 2A to 5B were changed. However, the resin solution containing the solvent was appropriately replaced with a kneading solvent, or a solid resin dried at 80 ° C. under reduced pressure was used to achieve the compositions shown in Tables 2A to 5B.

(Measurement of average primary particle diameter) The average primary particle diameter of the obtained pigment composition was measured using a transmission electron microscope ("JEM-1200EX" manufactured by JEOL Ltd.) and all the pigments in the observation sample at a magnification of 100,000. The primary particle diameter of the particles was measured and 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 It calculated | required by calculating the amount of residual solvents.
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: held at 80 ° C for 4 minutes, then heated up in 16 minutes, held 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

(Sample preparation method) 0.1 g of a sample is precisely weighed into 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. In addition, the measurement of the residual solvent of a following example and a comparative example was also measured by the said method.

Tables 2A to 5B show the average primary particle diameters and the residual solvent results of pigment compositions 1-132 obtained in Examples 1-1 to 66 and Comparative Examples 1-1 to 66.

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

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

[Example 2-18]
(Preparation of Pigment Composition 167) A compound shown below was blended and 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 167. The monoacetin concentration per 100 parts by mass of the pigment in the pigment composition 167 was 0.06%.
Pigment composition 35: 10.0 parts Propylene glycol monomethyl ether acetate: 40.0 parts

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

(Evaluation of pigment composition)
In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition 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 within ± 10%, and the difference between ± 10% and over was ± 10%. The results are shown in Tables 6-9.

From the results of Tables 6 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, examples according to specific applications will be described, but the application of the pigment composition of the present invention is not limited to the following applications.

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

<Preparation of pigment composition by kneading>
[Example 3-1]
(Preparation of pigment composition 265) 90 parts of azo red pigment PR242 (“Novoperm Scarlet 4RF” manufactured by Clariant), 10 parts of pigment derivative a, 1,000 parts of sodium chloride, and 170 parts of triacetin were added to a 1 gallon kneader made of stainless steel (Inoue 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 265.

[Examples 3-2 to 60, Comparative Examples 3-1 to 60]
(Preparation of pigment compositions 266 to 384) Pigment compositions 266 to 384 were obtained in the same manner as in Example 3-1, except that the kneading compositions shown in Tables 10A to 12B were changed. However, regarding the resin solution containing the solvent, it was used by appropriately replacing with a water-soluble organic solvent as a kneading solvent, or a solid resin dried at 80 ° C. under reduced pressure was used, and the compositions shown in Tables 10A to 12B were obtained. .

Tables 10A to 12B show the average primary particle sizes and residual solvent results of the pigment compositions 265 to 384 obtained in Examples 3-1 to 66 and Comparative Examples 3-1 to 60.

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

[Examples 4-2 to 20, Comparative Examples 4-1 to 20]
(Preparation of pigment compositions 386 to 424) Pigment compositions 386 to 424 were prepared in the same manner as in Example 4-1, except that the blending compositions shown in Tables 13A and 13B were changed.

[Example 4-21]
(Preparation of Pigment Composition 425) A pigment composition 425 was prepared by blending the compounds shown below and stirring at 70 ° C. and 5000 rpm for 60 minutes in a dissolver equipped with a 4 cm toothed disk. The triacetin concentration per 100 parts by mass of the pigment in the pigment composition 425 was 0.28%.
Pigment composition 305: 22.0 parts Propylene glycol monomethyl ether acetate: 78.0 parts

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

(Evaluation of Pigment Composition) 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 was measured with a haze meter (light transmittance 20%). The performance of the pigment composition was evaluated based on the initial viscosity and haze. The initial viscosity and haze were measured after standing at room temperature for 1 day after dispersion, and the time-lapse viscosity was measured after standing at 40 ° C. for 1 week. Viscosity stability was evaluated as ○ when the difference between the initial viscosity and the viscosity with time was within ± 10%, and x when exceeding ± 10%. The results are shown in Tables 13A-15.

From the results of Tables 13A to 15, 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. This suggests that the solid component in the pigment composition does not aggregate and has good dispersibility.

<Method for producing photosensitive pigment composition>
[Example 5-1]
(Preparation of Pigment Composition 505) 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 505.
Pigment compositions 385 and 387: 51.0 parts Resin AF solution: 1.0 parts Active energy ray-curable monomer: 4.0 parts (“NK Ester ATMPT” made by Shin-Nakamura Chemical Co., Ltd. Trimethylolpropane tri Acrylate)
Active energy ray polymerizable initiator: 3.4 parts (“Irgacure907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by BASF)
・ Sensitizer: 0.4 parts (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
Propylene glycol monomethyl ether acetate: 40.2 parts

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

[Example 5-8]
(Preparation of Pigment Composition 512) 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 512.
Pigment composition 394, 399: 52.0 parts Active energy ray-curable monomer: 4.8 parts (“NK ester ATMPT” trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)
Active energy ray polymerizable initiator: 2.8 parts (“Irgacure907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by BASF)
・ Sensitizer: 0.2 parts (“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 to 22, 5-32 to 34, Comparative Examples 5-8 to 10, 5-20 to 22, 5-32 to 34]
(Preparation of pigment compositions 513, 514, 536-538, 560-562, 524-526, 548-550, 572-574) Except for changing the composition shown in Tables 16-18, Examples 5-8 and Similarly, green pigment compositions 513, 514, 536 to 538, 560 to 562, 524 to 526, 548 to 550, and 572 to 574 were prepared.

[Example 5-11]
(Preparation of Pigment Composition 515) 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 515.
-Pigment composition 401, 404: 42.0 parts-Resin AF solution: 10.0 parts-Active energy ray-curable monomer: 5.6 parts ("NK ester ATMPT" made by Shin-Nakamura Chemical Co., Ltd. Trimethylolpropane tri Acrylate)
Active energy ray polymerizable initiator: 2.0 parts (“Irgacure907” manufactured by BASF Corporation 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
・ Sensitizer: 0.2 parts (“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, 35, 36, Comparative Examples 5-11, 12, 23, 24, 35, 36]
(Preparation of pigment compositions 516, 539, 540, 563, 564, 527, 528, 551, 552, 575, and 576) The same as in Example 5-11 except that the blending compositions shown in Tables 16 to 18 were changed. And blue pigment compositions 516, 539, 540, 563, 564, 527, 528, 551, 552, 575, and 576 were produced.

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.

(Contrast Ratio Measurement Sample) The color filter pigment compositions obtained in the examples and comparative examples were rotated at 500 rpm, 1000 rpm, and 1500 rpm on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater. Three types of coated substrates having different film thicknesses were obtained by coating with a number. 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 36 have excellent contrast characteristics as compared with those obtained in Comparative Examples 5-1 to 36, respectively.

(Production Example of Color Filter) Using the red pigment composition 530 of the present invention, the green pigment composition 537, and the blue pigment composition 540, a dry film thickness is 1.7 μm by spin coating on a substrate. And then 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 green and blue to produce a color filter and an RGB three-color filter. The obtained color filter was confirmed to have high brightness and excellent heat resistance.

<Preparation of pigment composition via r3>
[Example 17-1]
(Preparation of pigment composition 713) 95 parts of azo red pigment PR242 ("Novoperm Scarlet 4RF" manufactured by Clariant), 5 parts of dye derivative a, 35 parts of resin B, 65 parts of resin AF, 1,000 parts of sodium chloride, and 70 parts of triacetin Was charged in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 10 hours. The 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, and washed with 10,000 parts of water at 40 ± 5 ° C. The wet cake was put into 709 parts of propylene glycol monomethyl ether acetate, and mixed and stirred at 25 ° C. for 1 hour. Water in the solution was distilled off under reduced pressure at 40 ° C. to obtain a pigment composition 713 having a solid content concentration of 22%.

[Examples 17-2 to 20, Comparative Examples 17-1 to 20]
(Preparation of pigment compositions 714 to 752) Pigment compositions 714 to 752 were obtained in the same manner as in Example 17-1, except that the kneading compositions shown in Tables 19A and 19B were changed. However, for the resin solution containing a solvent, it is used by appropriately replacing with a water-soluble organic solvent that is a kneading solvent, or a solid resin dried at 80 ° C. under reduced pressure is used, and the compositions shown in Tables 19A and 19B are used. did.

From the results of Table 19A and Table 19B, it can be seen that the Examples of the present invention show superior 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.

This application claims priority based on Japanese Patent Application No. 2013-251962 filed on December 5, 2013, and Japanese Patent Application No. 2014-232911 filed on November 17, 2014, The entire disclosure is incorporated herein.

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 (9)

1. A step (a) of adding at least a water-soluble inorganic salt and a water-soluble organic solvent to the pigment and then refining the pigment by grinding 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 the 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 100 to 350, more preferably 130 to 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, 2-methylpentane-2,4- 2. At least one selected from diol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,2,6-hexanetriol The manufacturing method of the pigment composition as described in 1 ..
3. The process for producing a pigment composition according to claim 1 or 2, further comprising a resin in step (a).
4. The method for producing a pigment composition according to any one of claims 1 to 3, wherein the pigment is at least one selected from dyed lake pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. .
5. The method for producing a pigment composition according to any one of claims 1 to 4, wherein a step (e) is performed after the step (c) and before the step (d) by adding a dispersion solvent and mixing and stirring. .
6. A pigment composition comprising a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm,
   A pigment in which a water-soluble organic solvent satisfying the following (i) to (iv) remains in a range of 0.005 to 0.5 parts by mass per 100 parts by mass of the pigment contained in the pigment composition Composition.
   (I) The molecular weight is 100 to 350, more preferably 130 to 350.
   (Ii) It has a total of 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.
7. A water-soluble organic solvent for milling and kneading used for producing a pigment composition containing a finely divided pigment having an average primary particle size in the range of 5 to 1,000 nm,
   A water-soluble organic solvent for milling and kneading that satisfies the following (i) to (iv):
   (I) The molecular weight is 100 to 350, more preferably 130 to 350.
   (Ii) It has a total of 2 or more functional groups composed of a hydroxyl group and / or an ester group.
   (Iii) The viscosity at 60 ° C. is 2 to 140 mPa · s.
   (Iv) Does not contain an ether bond.
8. 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionine, tributyrin, 2-methylpentane-2,4-diol, 2-butyl-2 8. The material for milling and kneading according to claim 7, which is at least one selected from ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol and 1,2,6-hexanetriol. Water-soluble organic solvent.
9. A pigment composition for a color filter comprising the pigment composition according to claim 6.

Images