JP5543210B2 - Pigment dispersion aid, pigment dispersion containing the same, and use thereof - Google Patents

Description

The present invention relates to a pigment dispersion aid and its use. More specifically, even when an organic pigment is finely dispersed, the resulting pigment dispersion can be maintained by maintaining good fluidity and dispersion stability. Is used in a wide range of fields such as printing inks, paints, pigment dispersion resist compositions for color filters, ink jet inks, etc., especially when used in pigment dispersion resist compositions for color filters. The present invention relates to a pigment dispersion aid that can be increased to a level and its use.

Organic pigments have long been known as colorants and have begun to be used not only in various inks and paints but also in fields requiring high transparency and high contrast ratios such as color filters and inkjet inks.

These organic pigment dispersion techniques have made remarkable progress in recent years, and a method of dispersing with a pigment concentration as high as possible is also being studied in order to rationalize the production. However, basically, when the pigment concentration is increased, there is a problem that fluidity and dispersion stability are lowered.

In addition, high fastness and clear hue are required in the field of color filters and ink jet recording. Therefore, it is necessary to disperse a robust high-grade organic pigment until it has a finer particle size. Originally, a high-grade organic pigment has poor dispersion stability compared to other pigments and should be finer. As a result, aggregation easily occurs, and it is difficult to obtain a stable dispersion.

Therefore, in order to solve such problems, the pigment has been treated (surface treatment / modification), pigment dispersants having good wettability (adsorption), and surfactants have been developed. The dispersion stability of organic pigments has been studied, and many researches are still underway.

For example, a method is disclosed in which a pigment dispersant having a basic group is used for dispersing an acidic pigment, and the pigment dispersant is adsorbed on the pigment surface by acid-base affinity to obtain good dispersion stability ( For example, see Patent Document 1 and Patent Document 2). However, such improvement in pigment dispersibility by acid-base affinity has not yet been sufficient to achieve the higher transmittance and contrast required in the field of color filters and inkjet printing.

Therefore, a pigment dispersion aid that improves pigment dispersibility in combination with a pigment dispersant has also been studied. For example, a method for improving pigment dispersibility using a pigment dispersant and a pigment dispersion aid containing a specific condensed azo compound having a sulfonic acid group is disclosed (for example, see Patent Document 3). Since the pigment dispersibility can be improved by using such a pigment dispersion aid, it is considered as one means for realizing the high transmittance and contrast required in the color filter field.

Here, in order to be applied to a color liquid crystal display device for television and a color liquid crystal display device for personal computers in recent years, high transmittance and high contrast of visible light are required. In the case of a red filter using a red organic pigment, the transmittance and contrast performance of visible light largely depend on the performance of the red pigment dispersed in the color filter. It is difficult to realize, and it has been proposed to use other toning pigments together.

For example, a system in which another red toning pigment is used in combination with Pigment Red 177, which is a red main pigment (see, for example, Patent Document 4), specifically, a toning pigment of 535 to 555 nm is proposed. Pigment Red 5, 9, 10, 17, 48, 48: 1, 48: 2, 48: 3, 48: 4, 52: 2, 119, 166, characterized by having a maximum absorption peak in the wavelength region 216, 224, 226. However, the combination system of these red pigments has limitations in improving the transmittance and contrast performance.

Further, for example, a system using another yellow toning pigment (Pigment Yellow 139) with respect to Pigment Red 254, which is a red main pigment, is proposed (for example, see Patent Document 5 and Patent Document 6). However, in the combined system of these red main pigment and yellow toning pigment, the transmittance and contrast performance are not sufficient, and in order to improve the transmittance and contrast performance, further micronization can be considered. However, when Pigment Yellow 139 is further finely divided, there is a problem in fluidity and dispersibility, and there is a limit to improvement in transmittance and contrast performance.

Currently, a system using Pigment Red 177 or 254 as a toning pigment in combination with Pigment Red 242 as a main pigment (see, for example, Patent Document 7), or a system using 254 as a toning pigment in Pigment Red 242 as a main pigment. Then, since the color tone is biased to yellow, a system in which Pigment Red 242 is used as a toning pigment in combination with Pigment Red 254, which is an improved main pigment (see, for example, Patent Document 8) has been proposed. In addition, a system in which Pigment Orange 38 is used in combination with Pigment Red 254 as a toning pigment has been proposed (for example, see Patent Document 9). Furthermore, for example, a photosensitive coloring composition for color filters (for example, see Patent Document 10) containing at least one red pigment other than pigment red 254 and pigment red 254 (for example, pigment red 177) has been proposed. .

In these systems, the transmittance and contrast performance are improved to some extent. However, these systems all have room for improvement in fluidity and dispersion stability. In recent years, further improvements in transmittance and contrast have been demanded.
JP 54-037082 A JP 2001-272524 A JP 2006-321979 A Japanese Patent Laid-Open No. 10-148712 Japanese Patent Laid-Open No. 11-209632 Japanese Patent Laid-Open No. 10-115709 Japanese Patent Laid-Open No. 11-014824 JP 2002-372628 A JP 2003-183511 A JP 2006-321979 A

Thus, the problem of the present invention has been difficult until now by developing a novel pigment dispersion aid that can maintain good fluidity and dispersion stability even in a finely dispersed state of an organic pigment. High transparency and contrast ratio in the field of color filters and inkjets.
Specifically, a pigment dispersion having good fluidity and dispersion stability, which can be applied to fields where organic pigments need to be finely dispersed, such as pigment dispersion resist compositions for color filters and inkjet inks, The object is to provide a pigment dispersion aid capable of obtaining a pigment-dispersed resist composition for a color filter capable of obtaining a color filter having high transmittance and excellent contrast and the like. Another object of the present invention is to provide a pigment dispersion having good fluidity and dispersion stability. Furthermore, it is providing the pigment dispersion resist composition which can obtain the color filter which is excellent in contrast etc. with high transmittance | permeability.

As a result of diligent research to solve the above-mentioned problems, the present inventors have used a pigment dispersion aid in which a sulfonic acid group is introduced into a specific monoazo pigment, or an amine salt or a metal salt thereof. It has been found that all the above problems can be solved, and the present invention has been completed.

That is, the present invention provides (1) relates to the following general formula (33) and / or (34) to contain Pigment dispersing aid is a compound represented by the color filter pigment dispersion resist composition comprising .

[Wherein, M is H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ (R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with other substituents; A saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with another substituent). Represent. m represents an integer of 1 or more. ]

Also, the present invention provides (2) an organic pigment, a color filter pigment dispersion resist composition further contains a pigment dispersant 及 beauty organic solvent.
In the present invention, (3) the organic pigment is C.I. I. Pigment Red 166, and the toning pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. At least one red coloring pigment (1) selected from the group consisting of CI Pigment Red 254, C.I. I. Pigment red 242, C.I. I. Pigment red 254 and C.I. I. Red coloring pigment (2) containing at least two selected from the group consisting of CI Pigment Red 177, C.I. I. Pigment orange 38, C.I. I. Pigment red 254 and / or C.I. I. A red coloring pigment (3) comprising CI Pigment Red 166, or C.I. I. Pigment red 177, C.I. I. Pigment red 166 and / or C.I. I. It is related with the pigment dispersion resist composition for color filters of the said (2) description which is a red coloring pigment (4) which consists of pigment orange 38.
The present invention also relates to (4) the pigment-dispersed resist composition for color filters described in (2) or (3) above, wherein the pigment dispersant is a pigment dispersant having a basic group.
The present invention also relates to (5) a pigment-dispersed resist composition for a color filter according to any one of (2) to (4) above, wherein the organic pigment is an organic pigment that has been finely divided.
The present invention also relates to (6) a color-dispersed resist composition for color filters as described in (5) above, wherein the finely divided color pigment is a color pigment that has been subjected to salt milling.
The present invention also provides (7) kneading wherein a mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble dispersion medium that does not substantially dissolve the inorganic salt revolves while rotating three stirring blades. after kneading the apparatus, pigments for color filter according to any of the inorganic salts and the use of salt milling-treated pigment obtained by removing the aqueous dispersion medium (2) to (6) section The present invention relates to a dispersed resist composition .
Below, the color filter pigment dispersion resist composition of the present invention will be described in detail.

<Pigment dispersion aid>
First, the pigment dispersion aid of the present invention will be specifically described.
The pigment dispersion aid of the present invention is a compound represented by the above general formula (1) and / or (2).
In the general formulas (1) and (2), X and Y are the same or different and represent a phenyl group which may be substituted with F, Cl, Br, NO ₂ , CH ₃ or OCH ₃ . M represents H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ .

With respect to “NR ¹ R ² R ³ R ⁴ ” (M) in the above general formulas (1) and (2), R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with other substituents. Represents a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with another substituent. Here, as the saturated or unsaturated aliphatic hydrocarbon group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group Alkyl groups such as octyl group and decyl group; alkenyl groups such as vinyl group, allyl group and 1-butenyl group; alkynyl groups such as ethynyl group and propynyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Moreover, as said other substituent, a hydroxyl group, a halogen, a carboxyl group, an amino group, a lower alkyl group (C1-C5) etc. are mentioned.
In the above R ¹ , R ² , R ³ and R ⁴ , one may be substituted with other substituents, or two or more may be substituted with other substituents.
Furthermore, “m” in the general formulas (1) and (2) is an integer of 1 or more.

In the compound (pigment dispersion aid) of the present invention, the compound represented by the general formula (1) is an enol type, and the compound represented by the general formula (2) is a keto type tautomer. The invention includes both compounds. That is, the pigment dispersion aid of the present invention is a compound represented by the formula (1) or (2) and a case where both of the compounds represented by the formulas (1) and (2) are included. included.

Such a pigment dispersion aid is a novel compound and can be produced, for example, by subjecting a monoazo compound of the following formulas (3) to (30) to a conventionally known sulfonation treatment. For example, a monoazo compound powder of the following formulas (3) to (30) is dissolved in concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof, heated to room temperature to 80 to 90 ° C., and then with a large amount of water. The suspension obtained after dilution is filtered, washed with water, and the obtained filter cake is dried and pulverized to obtain the desired pigment dispersion aid. The sulfonated product obtained by the reaction is neutralized with, for example, an inorganic basic compound such as sodium hydroxide or an aqueous ammonia solution, or an organic basic compound such as an organic amine, so that sodium salt, potassium salt, ammonium salt or Needless to say, the organic ammonium salt may be used.

Therefore, a product obtained by sulfonating the compound represented by the above formula (31) and / or (32) can also be used as the pigment dispersion aid in the present invention. Also in this case, the effect of the present invention can be obtained satisfactorily. The “product obtained by the sulfonation treatment” is obtained by neutralizing the sulfonated product obtained by the sulfonation treatment with the inorganic basic compound or the organic basic compound to obtain the sodium salt or the like. Needless to say, is also included.
There are no commercially available pigment dispersion aids.

Among these pigment dispersion aids, a coloring composition for a color filter that has good fluidity and dispersion stability even when the organic pigment is finely dispersed, and has a higher level of transparency and contrast ratio. From the point that can be obtained, a compound represented by the following general formula (33) wherein X in the general formula (1) and / or (2) is a 2,5-dichlorophenyl group and Y is a phenyl group (the above formula) Using the monoazo compound of (3), the compound obtained by the above production method: enol type and / or the compound represented by the following general formula (34) (using the monoazo compound of the above formula (4), the above production method, etc. The resulting compound: keto type) is preferred. From the same viewpoint, the monoazo compound of the above formula (3) and / or (4) wherein X in the general formula (31) and / or (32) is a 2,5-dichlorophenyl group and Y is a phenyl group is a sulfone. A product obtained by the chemical conversion treatment is also suitable.

<Pigment dispersion>
Next, a pigment dispersion containing an organic pigment, a pigment dispersant, the pigment dispersion aid and an organic solvent will be described.
The usage-amount of the pigment dispersion adjuvant which comprises the pigment dispersion of this invention is 30 mass parts or less normally with respect to 100 mass parts of all the organic pigments, Preferably it is 0.1-20 mass parts. Even if the amount of the pigment dispersion aid exceeds the above range, the pigment dispersion effect tends not to be further improved.

Examples of organic pigments constituting the pigment dispersion of the present invention include dianthraquinonyl pigments, diketopyrrolopyrrole pigments, and condensed azo pigments conventionally used for printing inks, paints, color filters, and inkjet printing. , An isoindoline pigment, a perinone pigment, a perylene pigment, an azo pigment having a heterocycle, a benzimidazolone pigment, an anthraquinone pigment, a quinacridone pigment, and a dibromoanthanthrone pigment. Various red pigments, yellow pigments, orange pigments, purple pigments and the like can be used. Further, as a specific example, the generic name of the color index, the red pigments include pigment red 9, 19, 38, 43, 48, 49, 52, 53, 57, 88, 97, 122, 123, 144, 146. , 149, 155, 166, 168, 177, 178, 179, 180, 185, 188, 190, 202, 206, 207, 208, 209, 216, 217, 220, 221, 224, 226, 238, 242, 254 255, 264, etc .; Pigment Yellow 138, 139, 150, etc. as yellow pigments; Pigment Orange 38, 43, 71, etc. as orange pigments; Pigment Violet 23, etc. as purple pigments.

When the pigment dispersion of the present invention is used as a red pigment dispersion for a color filter for television, the main pigment is C.I. I. Pigment Red 166, and the toning pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. At least one red coloring pigment (1) selected from the group consisting of CI Pigment Red 254 is preferably used. In the present invention, the “main pigment” means a pigment having the highest blending ratio among the organic pigments used. That is, in the red coloring composition, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. Among pigment red 254, C.I. I. Pigment Red 166 is the most compounded amount.

The red coloring pigment (1) is C.I. I. Pigment red 166 and C.I. I. Pigment red 177 and C.I. I. The total amount of pigment red 242 used is preferably 70% by mass or more based on the total organic pigment used.

In the pigment dispersion containing the red color pigment (1), other organic pigments can be added and mixed in addition to the red color pigment (1) as long as the effects of the present invention are not impaired. Examples of other organic pigments include red pigments other than the red colored pigment (1), yellow pigments, and orange pigments. The addition of other organic pigments is C.I. I. Pigment red 166 and C.I. I. Pigment red 177 and C.I. I. Pigment Red 242 and C.I. I. It is usually 30 parts by mass or less with respect to 100 parts by mass in total with Pigment Red 254.

When the pigment dispersion of the present invention is used as a red pigment dispersion for a color filter, the organic pigment includes C.I. I. Pigment red 242, C.I. I. Pigment red 254 and C.I. I. A red coloring pigment (2) containing at least two selected from the group consisting of CI Pigment Red 177 is preferably used.
For example, in a pigment dispersion for notebook computers, C.I. I. Pigment Red 242 and C.I. I. A combination of Pigment Red 254 is preferable, and the mixing ratio (mass ratio) is preferably in the range of 99: 1 to 1:99, more preferably in the range of 95: 5 to 51:49.
In the case of a coloring composition for television use, C.I. I. Pigment Red 242 and C.I. I. Pigment Red 177 combination or C.I. I. Pigment red 254 and C.I. I. A combination of CI Pigment Red 177 is preferable. I. Pigment Red 242 and C.I. I. The mixing ratio (mass ratio) of Pigment Red 177 is preferably in the range of 99: 1 to 1:99, more preferably in the range of 70:30 to 30:70, C.I. I. Pigment red 254 and C.I. I. The mixing ratio (mass ratio) of Pigment Red 177 is preferably in the range of 99: 1 to 1:99, more preferably in the range of 95:50 to 51:49.

C. in the red coloring pigment (2). I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. It is preferable that the pigment red 177 has a particle diameter of 0.05 to 0.3 μm and 0.05 to 0.2 μm, respectively.

The red coloring pigment (2) is C.I. I. Pigment Red 242 and C.I. I. Pigment red 254 and C.I. I. It is preferable that the total use amount of Pigment Red 177 is 70% by mass or more based on the total organic pigment.

In the pigment composition containing the red color pigment (2), other pigments can be added and mixed in addition to the red color pigment (2) as long as the effects of the present invention are not impaired. Examples of other pigments include red pigments other than the red color pigment (2), yellow pigments, and orange pigments. The amount of other pigments used is usually 30 parts by mass or less in the total organic pigment.

When the pigment dispersion of the present invention is used as a red pigment dispersion for a color filter, the organic pigment includes C.I. I. Pigment orange 38, C.I. I. Pigment red 254 and / or C.I. I. A red coloring pigment (3) consisting of CI Pigment Red 166 is preferably used.
For example, in a pigment dispersion for flat display applications, C.I. I. Pigment orange 38 and C.I. I. Pigment Red 254 combination, C.I. I. Pigment orange 38 and C.I. I. Pigment red 254 and C.I. I. A combination of Pigment Red 166 is preferred. The mixing ratio (mass ratio) is C.I. I. Pigment orange 38 and C.I. I. In the case of a combination of CI Pigment Red 254, C.I. I. Pigment orange 38: C.I. I. Pigment Red 254 = 90: 10 to 2:98, more preferably 80:20 to 20:80. C. I. Pigment orange 38 and C.I. I. Pigment red 254 and C.I. I. In the case of a combination of Pigment Red 166, it is preferable to contain at least 5% by mass of each component, and more preferably 15% by mass or more.

The red coloring pigment (3) is C.I. I. Pigment orange 38 and C.I. I. Pigment red 254 and C.I. I. The total amount of pigment red 166 used is preferably 70% by mass or more based on the total organic pigment used.

In the pigment composition containing the red color pigment (3), other organic pigments can be added and mixed in addition to the red color pigment (3) as long as the effects of the present invention are not impaired. Examples of other organic pigments include red pigments other than the red color pigment (3), yellow pigments, and orange pigments. The amount of other organic pigment added is C.I. I. Pigment orange 38 and C.I. I. Pigment red 254 and C.I. I. It is usually 30 parts by mass or less with respect to 100 parts by mass as a total with Pigment Red 166.

When the pigment dispersion of the present invention is used as a red pigment dispersion for a color filter, the organic pigment includes C.I. I. Pigment red 177, C.I. I. Pigment red 166 and / or C.I. I. A red coloring pigment (4) comprising Pigment Orange 38 is preferably used.
When these specific red colored pigments are used in combination, and the pigment is dispersed using a pigment dispersant having a basic group described below and a specific pigment dispersion aid, excellent transmittance and contrast performance can be obtained. In addition, good fluidity and dispersibility can be obtained at the same time.

For example, C.I. I. Pigment red 177 and C.I. I. Pigment red 166 and / or C.I. I. A combination of CI Pigment Orange 38 is preferred. The mixing ratio (mass ratio) is C.I. I. Pigment red 177 and C.I. I. Pigment red 166 and / or C.I. I. In the case of the combination of pigment orange 38, C.I. I. Pigment Red 177: (CI Pigment Red 166 + CI Pigment Orange 38) = 30: 70 to 80:20. In this range, C.I. I. Pigment red 166 and C.I. I. The use ratio (mass ratio) with Pigment Orange 38 is C.I. I. Pigment Red 166: Pigment Orange 38 is preferably in the range of 40:60 to 1:99.

The red coloring pigment (4) is C.I. I. Pigment red 177 and C.I. I. Pigment red 166 and C.I. I. The total amount of pigment orange 38 used is preferably 70% by mass or more based on the total organic pigment used.

In the pigment dispersion containing the red color pigment (4), other organic pigments can be added and mixed in addition to the red color pigment (4) as long as the effects of the present invention are not impaired. Examples of other organic pigments include red pigments other than the red color pigment (4), yellow pigments, and orange pigments. The amount of other organic pigment added is C.I. I. Pigment red 177 and C.I. I. Pigment red 166 and C.I. I. It is usually 30 parts by mass or less per 100 parts by mass of the total amount with Pigment Orange 38.

In the present invention, the amount of the organic pigment is a mass fraction with respect to the total solid content of the pigment dispersion, and is preferably 5 to 80% by mass, more preferably 20 to 50% by total amount of the organic pigment used. % Range.

In order to increase the transmittance and contrast ratio of color filters and ink jet printing, the organic pigment is preferably finely divided. In addition, using a kneader or a kneading device that revolves while rotating each of the three stirring blades, the organic pigment is ground with an inorganic salt and salted so that the primary particle size of the organic pigment becomes even finer. More preferably milled. Among them, it is preferable to use an organic pigment obtained by a salt milling process using a kneader that revolves while rotating each of the three stirring blades. In this case, salt milling can be performed so that the primary particle diameter of the pigment becomes finer and uniform. The salt milling process using a kneading device that revolves while rotating each of the three stirring blades is also called a trimix process.

The above-mentioned trimix process is a process described in International Publication WO 06/098261.
Specifically, the above trimix treatment includes an organic pigment, a water-soluble inorganic salt (such as sodium chloride), and a water-soluble dispersion medium that does not substantially dissolve the inorganic salt (such as alkoxy alcohols, glycols, and ethers). Is carried out by removing the inorganic salt and the water-soluble dispersion medium after the mixture is kneaded in a kneading apparatus that revolves while rotating the three stirring blades.

The pigment dispersant constituting the pigment dispersion of the present invention will be described.
As said pigment dispersant, what has a basic group can be used conveniently, for example.
Examples of the pigment dispersant having a basic group include basic polymer pigment dispersants conventionally used in printing inks, paints, pigment dispersion resist compositions for color filters, inks for ink jet printing, and the like. The following can be mentioned. The pigment dispersant is appropriately selected depending on the type of organic pigment used, the type of organic solvent described later, and the like.

(1) From polyesters, polyamides, and polyesteramides having an amino group and / or imino group of a polyamine compound (for example, poly (lower alkylene amine) such as polyallylamine, polyvinylamine, and polyethylenepolyimine) and a free carboxyl group A reaction product with at least one selected from the group consisting of (JP-A-2001-59906),
(2) A carbodiimide compound having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain and a polyacryl side chain, and a basic nitrogen-containing group in the molecule ( International Publication WO 04/000950)
(3) Reaction products of low molecular amino compounds such as poly (lower) alkyleneimine and methyliminobispropylamine and polyesters having a free carboxyl group (Japanese Patent Laid-Open Nos. 54-37082 and 01-311177) Issue gazette),
(4) Polyesters having one hydroxyl group such as alcohols such as methoxypolyethylene glycol and caprolactone polyester in the isocyanate group of the polyisocyanate compound, compounds having 2 to 3 isocyanate group-reactive functional groups, isocyanate group reactivity A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amino group (Japanese Patent Laid-Open No. 02-612),
(5) a reaction product obtained by reacting a polyisocyanate compound and a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group,
(6) a reaction product obtained by adding a polyether chain to a low molecular amino compound,
(7) a reaction product obtained by reacting an isocyanate group-containing compound with an amino group-containing compound (Japanese Patent Application Laid-Open No. 04-210220),
(8) a reaction product obtained by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having one secondary amino group (Japanese Patent Laid-Open No. 09-87537),
(9) a reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound (Japanese Patent Laid-Open No. 09-194585),
(10) selected from methacrylic acid esters and acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate At least one of acrylamide, methacrylamide, N-methylolamide, vinylimidazole, vinylpyridine, amino group-containing polymerizable monomers such as monomers having a polycaprolactone skeleton, styrene, styrene derivatives , A copolymer with at least one other polymerizable monomer (JP-A-01-164429),
(11) Acrylic block copolymer composed of a block having a basic group such as a tertiary amino group or quaternary ammonium base and a block having no basic functional group (Japanese Patent Application Laid-Open No. 2005-55814) Description column of acrylic block copolymer described in the book),
(12) A pigment dispersant obtained by Michael addition reaction of a polycarbonate compound to polyallylamine (Japanese Patent Laid-Open No. 09-194585),
(13) A carbodiimide compound having at least one polybutadiene chain and a basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243),
(14) a carbodiimide compound having at least one side chain having an amide group in the molecule and at least one basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-176657),
(15) Polyurethane compounds having structural units having an ethylene oxide chain and a propylene oxide chain and having an amino group quaternized with a quaternizing agent (Japanese Patent Application Laid-Open No. 10-246812, Japanese Patent Application No. 2008-16404) issue).

The usage-amount of the pigment dispersant in this invention is 1-200 mass parts normally with respect to 100 mass parts of all the organic pigments to be used, Preferably it is 1-60 mass parts. If the amount of the pigment dispersant used is less than 1 part by mass, the pigment dispersibility may decrease. On the other hand, when it exceeds 200 mass parts, there exists a possibility that developability may fall.

Examples of the organic solvent constituting the pigment dispersion of the present invention include organic solvents suitably used in the fields of ink, paint, color filter, and inkjet. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Ether organic solvents such as butyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene group Ether ester organic solvents such as coal monomethyl ether acetate and propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone and δ-butyrolactone; methyl 2-hydroxypropionate and 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Esters organic solvents such as ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate; alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol; N- Examples thereof include nitrogen-containing organic solvents such as methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These can be used alone or in admixture of two or more.
The organic solvent is appropriately selected depending on the use of the pigment dispersion and desired physical properties.

The pigment dispersion of the present invention may contain a binder resin in advance.
Examples of the binder resin include thermosetting resins, thermoplastic resins, alkali-soluble resins, photopolymerizable compounds (photopolymerizable resins, monomers having one or more photopolymerizable unsaturated bonds in the molecule, oligomers, etc.), and the like. Can be mentioned. These can be used alone or in admixture of two or more. Among them, a binder resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region is preferable.

Such a binder resin is a mass fraction with respect to the total solid content of the pigment dispersion of the present invention, and is preferably 5 to 94% by mass, more preferably 20 to 50% by mass, based on the total amount of the binder resin used. It is a range.

Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyurethane resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, celluloses, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin Etc.

As the photopolymerizable resin as the photopolymerizable compound, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group is bonded to a (meta) group via an isocyanate group, an aldehyde group, an epoxy group, or the like. ) A resin into which a photocrosslinkable group such as an acrylic compound or cinnamic acid is introduced is used. A linear 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. A polymerized product is also used.

Examples of the monomer having one photopolymerizable unsaturated bond in the molecule as the photopolymerizable compound include alkyl methacrylate such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, Acrylate; aralkyl methacrylate or acrylate such as benzyl methacrylate or benzyl acrylate; alkoxyalkyl methacrylate or acrylate such as butoxyethyl methacrylate or butoxyethyl acrylate; aminoalkyl such as N, N-dimethylaminoethyl methacrylate or N, N-dimethylaminoethyl acrylate Methacrylate or acrylate; diethylene glycol ethyl ether, triethylene glycol Methacrylic acid ester or acrylic acid ester of polyalkylene glycol alkyl ether such as tilether, dipropylene glycol methyl ether; Methacrylic acid ester or acrylic acid ester of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Isobornyl methacrylate or acrylate; Examples include glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate.

Monomers having two or more photopolymerizable unsaturated bonds in the molecule as the photopolymerizable compound include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate. Methacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, Dipentaerythritol hexamethacrylate, dipentaerythritol Rupentamethacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate , Tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
The alkali-soluble resin will be described in detail for the pigment dispersion used as a pigment dispersion resist composition for a color filter in the photolithography method described later.

The pigment dispersion of the present invention is mainly composed of an organic pigment, a pigment dispersant, a pigment dispersion aid, a binder resin, and an organic solvent, and these components usually occupy 90 to 100% by mass in the pigment dispersion.

In addition, various additives such as a photopolymerization initiator, a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be appropriately used depending on the method for producing the pigment dispersion of the present invention described later. Examples of the photopolymerization initiator include those described later.

In order to produce the pigment dispersion of the present invention from the above constituent materials, a conventionally known production method can be used. For example, it can be produced by the following production method.
First, a mixture comprising an organic pigment, the above-described pigment dispersion aid, pigment dispersant, and organic solvent is obtained. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirrer bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine to obtain a pigment dispersion.

<Method for Producing Pigment Dispersion Containing Two or More Organic Pigments>
Moreover, the example in the case of containing the red coloring pigment (4) mentioned above is demonstrated as a method of manufacturing the pigment dispersion in the case of containing 2 or more types of organic pigments using the above-mentioned material. In addition, also when it contains other red coloring pigments (1)-(3), it is the same as the case where it contains a red coloring pigment (4) except the organic pigment to be used differing.
〔Production method〕
(After individual dispersion, blended so as to have a predetermined pigment ratio)
C. obtained by salt milling an organic pigment. I. Pigment Red 177 pigment is mixed with a pigment dispersant, a pigment dispersion aid, an organic solvent, a binder resin if necessary, and a complementary pigment if necessary, and other additives. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine. I. A pigment dispersion composition of CI Pigment Red 177 is obtained. Similarly, C.I. I. Pigment Red 166 pigment dispersion composition, C.I. I. A pigment dispersion composition of CI Pigment Orange 38 is obtained.
The resulting C.I. I. Pigment Red 177 pigment dispersion composition, C.I. I. Pigment Red 166 pigment dispersion composition and / or C.I. I. The pigment dispersion composition of Pigment Orange 38 is blended so as to have a predetermined pigment content, and if necessary, a binder resin, an organic solvent and other additives are added, and a stirrer such as a high-speed stirrer is used. After uniformly mixing, the mixture is filtered with a filter to obtain the pigment dispersion of the present invention containing the red colored pigment (4). In the said manufacturing method, binder resin can be added at the time of preparation of a pigment dispersion composition. Further, after preparing the pigment dispersion composition, it can be added at the time of preparing the pigment dispersion.

(Covariance)
C. obtained by salt milling treatment I. Pigment Red 177, C.I. obtained by salt milling treatment. I. Pigment red 166 and / or C.I. I. A mixture comprising Pigment Orange 38, a pigment dispersant, a pigment dispersion aid, an organic solvent, a binder resin if necessary, and a complementary color pigment if necessary, and other additives is obtained. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine to obtain a pigment dispersion composition. .
Next, to the obtained pigment dispersion composition, a binder resin, an organic solvent, and other additives are added as necessary, and uniformly mixed using a stirrer such as a high-speed stirrer, and then filtered through a filter. A pigment dispersion of the invention containing a red colored pigment (4) is obtained. In the said manufacturing method, binder resin can be added at the time of preparation of a pigment dispersion composition. Further, after preparing the pigment dispersion composition, it can be added at the time of preparing the pigment dispersion.

As a method for producing a pigment dispersion containing two or more organic pigments as described above, as described in the above methods (“individually dispersed and then blended so as to have a predetermined pigment ratio” and “co-dispersion”) An organic pigment (CI Pigment Red 177, CI Pigment Red 166, CI Pigment Orange 38) is subjected to a dispersion treatment using a pigment dispersant and a pigment dispersion aid together to obtain a pigment dispersion composition. Next, a method of producing the pigment dispersion composition by mixing other components is preferable. In this case, for example, it is superior in dispersion stability and fluidity compared to the case where the dispersion treatment is performed with a pigment dispersant (without using a pigment dispersion aid), and performance such as high contrast can be obtained.

The pigment dispersion obtained in this manner contains various binder resins, organic solvents, surfactants, and other various additives as necessary, and is used for printing inks, paints, and pigment dispersion resist compositions for color filters. Ink jet ink, writing instrument ink, ribbon ink, liquid developer and the like are preferably used.

<Pigment-dispersed resist composition for color filter>
As an example of a preferred application of the pigment dispersion of the present invention, a pigment dispersion resist composition for color filters will be described in more detail.
The pigment-dispersed resist composition for color filters is an active energy ray-curable resist composition that can be developed with an alkali. In addition to the pigment dispersion, an alkali-soluble resin, a photopolymerizable compound, and photopolymerization initiation Contains various additives such as organic solvents, thermal polymerization inhibitors, and silane coupling agents, titanate coupling agents, UV absorbers, antioxidants, etc. to improve adhesion to the substrate, if necessary. It has been made.

The use amount of the organic pigment constituting the pigment dispersion resist composition for color filters of the present invention is preferably a mass fraction relative to the total solid content of the pigment dispersion resist composition for color filters, and is preferably the total amount of organic pigments used. Is in the range of 5 to 80 mass%, more preferably 20 to 50 mass%.

The alkali-soluble resin constituting the pigment-dispersed resist composition for a color filter of the present invention has solubility in a developer used in the development processing step, particularly preferably an alkali developer, when producing a color filter. If it is a thing, it will not specifically limit. Among them, an alkali-soluble resin having a carboxyl group is preferable, and in particular, a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is used. preferable.

Specifically, an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid or methacrylic acid, styrene, 2-hydroxyethyl acrylate, 2 copolymerizable with an ethylenically unsaturated monomer having a carboxyl group, 2 -Selected from the group consisting of hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycerol monoacrylate, glycerol methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer And a copolymer with at least one ethylenically unsaturated monomer.

The acid value of the copolymer is preferably 50 to 300 mgKOH / g. In this case, if the acid value is less than 50 mgKOH / g, the solubility of the resist composition in an alkaline developer tends to decrease. On the other hand, if it exceeds 300 mgKOH / g, the solubility in an alkali developer becomes excessive, and when developing with an alkali developer, the colored layer tends to fall off from the substrate or the surface of the colored layer tends to be rough.

In addition, in this specification, an acid value is a theoretical acid value and means the value calculated | required arithmetically based on the ethylenically unsaturated monomer which has a carboxyl group, and its usage-amount.

The weight average molecular weight of the alkali-soluble resin in the present invention is usually preferably from 1,000 to 100,000. When the weight average molecular weight of the alkali-soluble resin is less than 1,000, the solubility in an alkali developer may increase and the development characteristics may deteriorate. On the other hand, when it exceeds 100,000, the solubility in an organic solvent may decrease, and the viscosity of the resist composition may increase.

In addition, in this invention, the weight average molecular weight of the said alkali-soluble resin is a weight average molecular weight of polystyrene conversion obtained based on GPC. In the present invention, Water 2690 (manufactured by Waters) is used as the apparatus, and PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) is used as the column.

The usage-amount of the alkali-soluble resin in this invention is 10-1,000 mass parts normally with respect to 100 mass parts of all the organic pigments to be used, Preferably it is 20-500 mass parts. When the amount of the alkali-soluble resin used is less than 10 parts by mass, for example, the alkali developability may be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. On the other hand, when the amount exceeds 1,000 parts by mass, the concentration of the organic pigment is relatively lowered, so that it may be difficult to achieve the target color density as a thin film.

As the photopolymerizable compound constituting the pigment dispersion resist composition for a color filter of the present invention, the same compounds as those described for the pigment dispersion can be used.
In this invention, the usage-amount of the said photopolymerizable compound is a mass fraction with respect to the total solid in the pigment dispersion resist composition for color filters of this invention, Preferably it is the range of 3-50 mass%.

The photopolymerization initiator constituting the pigment-dispersed resist composition for color filters of the present invention is not particularly limited, and examples thereof include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4 ′. -Dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t -Butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-ben Anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl-anthraquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triazine photopolymerization initiators, and the like. These photoinitiators are used individually or in combination of 2 or more types.

In this invention, the usage-amount of the said photoinitiator is a mass fraction with respect to the total solid in the pigment dispersion resist composition for color filters of this invention, Preferably it is the range of 1-20 mass%.

The organic solvent constituting the pigment dispersion composition for a color filter of the present invention is the same as the above-mentioned water-soluble dispersion medium, and preferably has a boiling point of 100 at normal pressure (1.013 × 10 ² kPa). Examples of the organic solvent include an ester organic solvent, an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an aromatic hydrocarbon solvent, and a nitrogen-containing organic solvent. Specific examples of the preferable organic solvent include the same organic solvents as those described in the pigment dispersion of the present invention.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone due to solubility, dispersibility, coatability, etc. , Ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, and more preferably propylene glycol monomethyl ether acetate It is.

Further, these organic solvents are used in an amount of 50% by mass or more based on the solubility of the alkali-soluble resin, pigment dispersibility, coatability, etc. in the total organic solvent used in the pigment dispersion resist composition for color filters of the present invention. Is preferably contained in an amount of 70% by mass or more.

If a large amount of an organic solvent having a boiling point exceeding 220 ° C. is contained, the organic solvent does not sufficiently evaporate when pre-baked on the coated film, and remains in the dried film. There is a risk that the heat resistance of the will decrease. In addition, when a large amount of an organic solvent having a boiling point of less than 100 ° C. is contained, it is difficult to uniformly apply the organic solvent uniformly, and a coating film having excellent surface smoothness may not be obtained.

The pigment dispersion resist composition for a color filter of the present invention is mainly composed of an organic pigment, a pigment dispersant, a pigment dispersion aid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent, and these components. Occupies 90-100 mass% normally in the pigment dispersion resist composition for color filters of this invention.

Various additives such as other photopolymerizable compounds, thermal polymerization inhibitors, ultraviolet absorbers, antioxidants and the like can be appropriately used in the pigment-dispersed resist composition for color filters of the present invention as necessary. .

A method for producing the pigment-dispersed resist composition for a color filter of the present invention using the above constituent materials will be described.
The method for producing the pigment-dispersed resist composition for a color filter of the present invention is an example of a preferred embodiment of the present invention, and the present invention is not limited thereto.
In order to produce the pigment dispersion resist composition for a color filter of the present invention from the constituent materials described above, the above-mentioned photopolymerizable compound, photopolymerization initiator, alkali are added to the pigment dispersion obtained by the above method. A method of adding a soluble resin, an organic solvent and other additives as required, and stirring and mixing using a stirring device or the like can be used.

<The manufacturing method of the pigment dispersion resist composition for color filters containing 2 or more types of organic pigments>
Moreover, the example in the case of containing the red coloring pigment (4) mentioned above is demonstrated as a method of manufacturing the pigment dispersion resist composition for color filters in the case of containing 2 or more types of organic pigments using the above-mentioned material. . In addition, also when it contains other red coloring pigments (1)-(3), it is the same as the case where it contains a red coloring pigment (4) except the organic pigment to be used differing.
〔Production method〕
(After individual dispersion, blended so as to have a predetermined pigment ratio)
C. obtained by salt milling an organic pigment. I. Pigment Red 177 pigment is obtained in the form of a pigment dispersant, a pigment dispersion aid, an organic solvent, and, if necessary, an alkali-soluble resin and other additives. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine. I. A pigment dispersion composition of CI Pigment Red 177 is obtained. Similarly, C.I. I. Pigment Red 166 pigment dispersion composition, C.I. I. A pigment dispersion composition of CI Pigment Orange 38 and, if necessary, a pigment dispersion coloring composition of a complementary color pigment are obtained.
The resulting C.I. I. Pigment Red 177 pigment dispersion color composition, C.I. I. Pigment Red 166 pigment dispersion composition and / or C.I. I. Pigment Orange 38 pigment dispersion composition and, if necessary, a pigment dispersion coloring composition of a complementary color pigment are blended so as to have a predetermined pigment content, a photopolymerizable compound, a photopolymerization initiator, and if necessary. An alkali-soluble resin, an organic solvent, and other additives are added and mixed uniformly using a stirrer such as a high-speed stirrer, followed by filtration with a filter to obtain a pigment-dispersed resist composition for a color filter. In the said manufacturing method, alkali-soluble resin can be added at the time of preparation of a pigment dispersion composition. Moreover, it can also be added at the time of preparation of the pigment dispersion resist composition for color filters after preparing the pigment dispersion composition.

(Covariance)
C. obtained by salt milling treatment I. Pigment Red 177, C.I. obtained by salt milling treatment. I. Pigment red 166 and / or C.I. I. A mixture comprising CI Pigment Orange 38, a pigment dispersant, a pigment dispersion aid, an organic solvent, an alkali-soluble resin as necessary, and a complementary color pigment as needed, and other additives is obtained. The obtained mixture is kneaded and dispersed using various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic dispersing machine, and a high-pressure dispersing machine to obtain a colored composition.
Next, to the obtained colored composition, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, an organic solvent, and other additives are added as necessary, and uniform using a stirrer such as a high-speed stirrer. Then, the mixture is filtered with a filter to obtain a pigment-dispersed resist composition for color filters. In the said manufacturing method, alkali-soluble resin can be added at the time of preparation of a coloring composition. Moreover, after producing a coloring composition, it can also be added at the time of preparation of the pigment dispersion resist composition for color filters.

As the method for producing the pigment dispersion resist composition for a color filter, an organic pigment (C) described in the above methods (“individually dispersed and then blended so as to have a predetermined pigment ratio” and “co-dispersion”). Pigment Red 177, CI Pigment Red 166, and CI Pigment Orange 38) are used in combination with a pigment dispersant and a pigment dispersion aid to disperse the pigment dispersion composition (coloring composition). Then, the method of producing the pigment dispersion composition (coloring composition) obtained by mixing other components is preferred. In this case, for example, it is superior in dispersion stability and fluidity compared to the case where the dispersion treatment is performed with a pigment dispersant (without using a pigment dispersion aid), and performance such as high contrast can be obtained.

Since the pigment dispersion aid of the present invention is a compound having the above-described configuration, it can maintain good fluidity and dispersion stability even when the organic pigment is finely dispersed. When applied to the inkjet field, it is possible to achieve high transparency and contrast ratio.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.

<Pigment dispersion aid>
(Pigment dispersion aid 1)
30 ml of concentrated sulfuric acid was charged into a 100 ml Erlenmeyer flask, and 10 g of Pigment Red 2 (compound represented by the above formula (3) and / or (4)) was added while stirring with a magnetic stirrer, and stirred at room temperature for 30 minutes. A mixture of 50 g of water and 50 g of ice was placed in a 1 L beaker, and the reaction product was poured into this ice water and stirred for 30 minutes with a magnetic stirrer. This was filtered and washed under reduced pressure, and the resulting solid was dried to obtain the desired product (compound represented by the above general formula (33) and / or (34): M = H, m = 1 or 2). 12 g was obtained.

<Organic pigment>
Preparation Example 1 (Trimix-treated Pigment Red 254)
In the tank of Trimix TX-15 (trade name, manufactured by Inoue Seisakusho Co., Ltd.) I. 750 parts by mass of Pigment Red 254, 7500 parts by mass of sodium chloride having a particle diameter of 20 μm, and 1800 parts by mass of diethylene glycol were added. The mixture was kneaded for 3 hours at 45 ° C. within a range of 70% of the rated current value of 9.3 A and subjected to salt milling. Next, 1300 parts by mass of the obtained kneaded material was put into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 40 ° C. to obtain 95 parts by mass of trimix-treated pigment red 254 (PR254).

Preparation Example 2 (Trimix-treated Pigment Red 177)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment red 177 (PR177) was obtained in the same manner as in Preparation Example 1, except that the pigment red 177 was used.

Preparation Example 3 (Trimix-treated Pigment Red 242)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment red 242 (PR242) was obtained in the same manner as in Preparation Example 1, except that the pigment red 242 was used.

Preparation Example 4 (Trimix-treated Pigment Red 166)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment red 166 (PR166) was obtained in the same manner as in Preparation Example 1 except that the pigment red 166 was used.

Preparation Example 5 (Trimix-treated Pigment Red 224)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment red 224 (PR224) was obtained in the same manner as in Preparation Example 1 except that the pigment red 224 was used.

Preparation Example 6 (Trimix-treated Pigment Red 264)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment red 264 (PR264) was obtained in the same manner as in Preparation Example 1 except that the pigment red 264 was used.

Preparation Example 7 (Trimix-treated Pigment Orange 38)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment orange 38 (PO38) was obtained in the same manner as in Preparation Example 1, except that the pigment orange 38 was used.

Preparation Example 8 (Trimix-treated Pigment Orange 71)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment orange 71 (PO71) was obtained in the same manner as in Preparation Example 1, except that the pigment orange 71 was used.

Preparation Example 9 (Trimix-treated Pigment Yellow 139)
C. I. Pigment Red 254 instead of C.I. I. A trimix-treated pigment yellow 139 (PY139) was obtained in the same manner as in Preparation Example 1, except that Pigment Yellow 139 was used.

Preparation Example 10 (Trimix-treated Pigment Yellow 150)
C. I. Pigment Red 254 instead of C.I. I. Trimix-treated pigment yellow 150 (PY150) was obtained in the same manner as in Preparation Example 1, except that Pigment Yellow 150 was used.

Preparation Example 11 (Trimix-treated Pigment Violet 23)
C. I. Pigment Red 254 instead of C.I. I. Trimix-treated Pigment Violet 23 (PV23) was obtained in the same manner as Preparation Example 1, except that Pigment Violet 23 was used.

Preparation Example 12 (Salt Milling Pigment Red 254 Using Kneader)
In a tank of a kneader (trade name: KHD-2, manufactured by Inoue Seisakusho), C.I. I. 100 parts by mass of Pigment Red 254, 1000 parts by mass of sodium chloride having a particle size of 20 μm, and 240 parts by mass of diethylene glycol were added, and kneaded at 75 ° C. for 10 hours to perform salt milling. Next, 1300 parts by mass of the obtained kneaded material was put into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing were repeated until sodium chloride and diethylene glycol were removed, followed by drying at 40 ° C. to obtain 95 parts by mass of salt milling treatment pigment red 254 (kneader treatment PR254).

Preparation Example 13 (Salt Milling Pigment Red 177 using a kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment red 177 (kneader treatment PR177) was obtained in the same manner as in Preparation Example 12 except that the pigment red 177 was used.

Preparation Example 14 (Salt Milling Pigment Red 242 Using Kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment red 242 (kneader treatment PR242) was obtained in the same manner as in Preparation Example 12 except that the pigment red 242 was used.

Preparation Example 15 (Salt Milling Pigment Red 166 Using Kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment red 166 (kneader treatment PR166) was obtained in the same manner as in Preparation Example 12 except that the pigment red 166 was used.

Preparation Example 16 (Salt Milling Pigment Red 224 using a kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment red 224 (kneader treatment PR224) was obtained in the same manner as in Preparation Example 12 except that the pigment red 224 was used.

Preparation Example 17 (Salt milling treatment Pigment Red 264 using a kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment red 264 (kneader treatment PR264) was obtained in the same manner as in Preparation Example 12 except that the pigment red 264 was used.

Preparation Example 18 (Salt Milling Pigment Orange 38 Using Kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling-treated pigment orange 38 (kneader-treated PO38) was obtained in the same manner as in Preparation Example 12 except that Pigment Orange 38 was used.

Preparation Example 19 (Salt milling treatment Pigment Orange 71 using a kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling treatment pigment orange 71 (kneader treatment PO71) was obtained in the same manner as in Preparation Example 12, except that the pigment orange 71 was used.

Preparation Example 20 (Salt Milling Pigment Yellow 139 Using Kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling-treated pigment yellow 139 (kneader-treated PY139) was obtained in the same manner as in Preparation Example 12 except that Pigment Yellow 139 was used.

Preparation Example 21 (Salt milling treatment Pigment Yellow 150 using a kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling-treated pigment yellow 150 (kneader-treated PY150) was obtained in the same manner as in Preparation Example 12 except that Pigment Yellow 150 was used.

Preparation Example 22 (Salt Milling Pigment Violet 23 Using Kneader)
C. I. Pigment Red 254 instead of C.I. I. A salt milling-treated pigment violet 23 (kneader-treated PV23) was obtained in the same manner as in Preparation Example 12 except that the pigment violet 23 was used.

In addition, commercially available fine C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150 (commercial fine PR254, commercial fine PR177, commercial fine PY139, commercial fine PY150) was also used as a pigment.

<Pigment dispersant having basic group>
Disperbyk-2001 (DB-2001, manufactured by Big Chemie Co., Ltd., acrylic block copolymer having a basic group)
<Alkali-soluble resin>
BMM / MAA copolymer (benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mgKOH / g, weight average molecular weight: 25,000)
<Photopolymerizable compound>
DPEHA (dipentaerythritol hexaacrylate)
<Photopolymerization initiator>
Irgacure 907 (Ciba Specialty Chemicals, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
<Organic solvent>
PGMEA (propylene glycol monomethyl ether acetate)

Examples 1-18 and Comparative Examples 1-15
<Pigment dispersion composition>
With the compositions shown in Tables 1 and 2, the mixture was kneaded for 3 hours at a temperature of 40 to 50 ° C. with a bead mill to obtain a pigment dispersion. In addition, the unit of the numerical value showing a composition is a mass part.

<Pigment-dispersed resist composition for color filter>
The pigment dispersion and other materials were uniformly mixed using a high-speed stirrer so as to have the compositions shown in Tables 1 and 2, and then filtered with a filter having a pore size of 3 μm to obtain a pigment dispersion resist composition for a color filter. . In addition, the unit of the numerical value showing a composition is a mass part.

(Evaluation method)
The following evaluation was performed and the results are shown in Tables 3-4.
<Fluidity>
About the pigment dispersion resist compositions for color filters of Examples and Comparative Examples, each was taken in a glass bottle, sealed and stored at room temperature for 1 day, and then the viscosity at 25 ° C. was measured using a B-type viscometer (manufactured by Tokimec). The fluidity was evaluated.

<Dispersion stability>
The pigment dispersion resist compositions for color filters of Examples and Comparative Examples were respectively taken in glass bottles, sealed and stored at room temperature for 1 day, and then viscosity at 25 ° C. and viscosity after storage at 40 ° C. for 7 days were B-type viscosities. It measured using the meter (made by Tokimec). The dispersion stability was evaluated by calculating (viscosity after 7 days storage at 40 ° C.) / (Viscosity after 1 day storage at room temperature).

<Contrast of pigment dispersed resist composition for color filter>
The pigment dispersion resist compositions for color filters of Examples and Comparative Examples were applied on a glass substrate using a spin coater so that the film thickness was 1.0 μm, prebaked at 100 ° C. for 3 minutes, and then exposed with a high-pressure mercury lamp. And post-baked at 230 ° C. for 30 minutes.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
The color characteristics (x, y, Y) of the resists of Examples and Comparative Examples having a film thickness of 1.0 μm were measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° visual field). In Examples 1 to 3 and Comparative Examples 1 and 2, brightness Y at chromaticity (x, y) = (0.578, 0.312), and in Examples 4 to 5 and Comparative Example 3, chromaticity (x, y ) = (0.476, 0.263) brightness Y, Example 6 and Comparative Example 4 have chromaticity (x, y) = (0.455, 0.267), Examples 7-8 and Comparative Examples 5, the brightness Y at chromaticity (x, y) = (0.564, 0.357) was obtained.

From the table, in Examples using the pigment dispersion aid, excellent fluidity and dispersion stability were obtained, and the contrast and color characteristics were also excellent. On the other hand, in the comparative example in which the pigment dispersion aid was not added, a product excellent in all these characteristics could not be obtained.

Examples 19 to 26, Comparative Examples 16 to 19
<Pigment dispersion according to red colored pigment (1)>
The composition of Table 5 was kneaded with a bead mill at a temperature of 40 to 50 ° C. for 3 hours to obtain pigment dispersions 1 to 20. In addition, the unit of the numerical value showing a composition is a mass part.

<Pigment-dispersed resist composition for color filter>
The pigment dispersions 1 to 20 and other materials were uniformly mixed using a high-speed stirrer so as to have the composition shown in Table 6, and then filtered with a filter having a pore diameter of 3 μm. Examples 19 to 26 and Comparative Examples 16 to 19 pigment dispersed resist compositions for color filters were obtained. In addition, the unit of the numerical value showing a composition is a mass part.

(Evaluation method)
The following evaluation was performed and the results are shown in Tables 6-7.
<Fluidity>
About the pigment dispersion resist compositions for color filters of Examples and Comparative Examples, each was taken in a glass bottle, sealed and stored at room temperature for 1 day, and then the viscosity at 25 ° C. was measured using a B-type viscometer (manufactured by Tokimec). The fluidity was evaluated.

<Dispersion stability>
The pigment dispersion resist compositions for color filters of Examples and Comparative Examples were respectively taken in glass bottles, sealed and stored at room temperature for 1 day, and then viscosity at 25 ° C. and viscosity after storage at 40 ° C. for 7 days were B-type viscosities. It measured using the meter (made by Tokimec). The dispersion stability was evaluated by calculating (viscosity after 7 days storage at 40 ° C.) / (Viscosity after 1 day storage at room temperature).

<Contrast of pigment dispersed resist composition for color filter>
The pigment-dispersed resist compositions for color filters of Examples and Comparative Examples are formed on a glass substrate so that the film thickness is 1.0 to 1.1 μm (the film thickness is adjusted to have the same chromaticity) using a spin coater. And then pre-baked at 100 ° C. for 3 minutes, exposed with a high-pressure mercury lamp, and further post-baked at 230 ° C. for 30 minutes.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
Spectrophotometer (Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view) color characteristics (x, y, Y) of each resist of Examples and Comparative Examples having a film thickness of 1.0 to 1.1 μm Measured with In Examples and Comparative Examples, the lightness Y at the red chromaticity (x, y) = (0.585, 0.350) required by the notebook computer was obtained.

<Coloring power>
The pigment-dispersed resist compositions for color filters of Examples and Comparative Examples were applied on a glass substrate using a spin coater so as to have a film thickness of 1 μm, pre-baked at 100 ° C. for 3 minutes, and then exposed with a high-pressure mercury lamp, Further, post-baking was performed at 230 ° C. for 30 minutes.
The absorbance at 550 to 600 nm of Examples and Comparative Examples was measured, and Comparative Example 16 was used as a reference (100), and the coloring power of Examples and Comparative Examples was relatively evaluated.

From the table, the main pigment is C.I. I. Pigment Red 166, and the toning pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. In Examples using a pigment dispersion aid containing at least one red coloring pigment (1) selected from the group consisting of CI Pigment Red 254, excellent fluidity and dispersion stability are obtained, brightness, contrast, Excellent coloring power. On the other hand, in the comparative example in which the pigment dispersion aid was not added, none of the properties as excellent as those of the examples were obtained.

Examples 27-43, Comparative Examples 20-30
<Pigment dispersion according to red colored pigment (2)>
The composition shown in Table 8 was kneaded for 3 hours at a temperature of 40 to 50 ° C. with a bead mill to obtain pigment dispersions 21 to 37. In addition, the unit of the numerical value showing a composition is a mass part.

<Pigment-dispersed resist composition for color filter>
The pigment dispersions 21 to 37 and other materials were uniformly mixed using a high-speed stirrer so as to have the compositions shown in Tables 9 to 12, and then filtered with a filter having a pore diameter of 3 μm. 34 and pigment dispersion resist compositions for color filters of Comparative Examples 20 to 24, Examples 35 to 43 for TV and pigment dispersion resist compositions for color filters of Comparative Examples 25 to 30 were obtained. In addition, the unit of the numerical value showing a composition is a mass part.

Evaluation method The following evaluation was performed, and the results are shown in Tables 9-12.
<Fluidity>
About the pigment dispersion resist composition for color filters of Examples 27 to 34 and Comparative Examples 20 to 24 for notebook computers, and Examples 35 to 43 for TV and Comparative Examples 25 to 30 for color filters, Each sample was taken in a glass bottle, sealed, and stored at room temperature for 1 day, and then the viscosity at 25 ° C. was measured using a B-type viscometer (manufactured by Tokimec) to evaluate the fluidity.

<Dispersion stability>
About the pigment dispersion resist composition for color filters of Examples 27 to 34 and Comparative Examples 20 to 24 for notebook computers, and Examples 35 to 43 for TV and Comparative Examples 25 to 30 for color filters, Each was taken in a glass bottle, sealed, and the viscosity at 25 ° C. after storing at room temperature for 1 day and the viscosity after storing at 40 ° C. for 7 days were measured using a B-type viscometer (manufactured by Tokimec). The dispersion stability was evaluated by calculating (viscosity after 7 days storage at 40 ° C.) / (Viscosity after 1 day storage at room temperature).

<Contrast of pigment dispersed resist composition for color filter>
Spinning the pigment dispersion resist compositions for color filters of Examples 27 to 34 and Comparative Examples 20 to 24 for notebook computers, and Examples 35 to 43 for TV and Comparative Examples 25 to 30 for TVs Using a coater, Examples 27-34 and Comparative Examples 20-24 for laptop computers have a film thickness of 1.1-1.2 μm, and Examples 35-43 and Comparative Examples 25-30 for TV have a film thickness. It was coated on a glass substrate so as to have a thickness of 1.8 to 2.0 μm (the film thickness was adjusted to have the same chromaticity), pre-baked at 100 ° C. for 3 minutes, then exposed to a high-pressure mercury lamp, and further at 230 ° C. Post-baked for 30 minutes.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
Examples 27 to 34 and Comparative Examples 20 to 24 for notebook computers with a film thickness of 1.1 to 1.2 μm, Examples 35 to 43 for TVs with a film thickness of 1.8 to 2.0 μm, and Comparative Examples The color characteristics (x, y, Y) of each resist of 25 to 30 were measured with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° visual field). In Examples 27 to 34 and Comparative Examples 20 to 24 for laptop computers, the x value of the required red chromaticity is set to 0.600, and the lightness Y is adjusted to the optimum y value, and Examples 35 to 35 for TVs are used. In 43 and Comparative Examples 25 to 30, the required value of red chromaticity x was 0.650, and the brightness Y was determined according to the optimum y value.

From the table, C.I. I. Pigment red 242, C.I. I. Pigment red 254 and C.I. I. In the Example using the red coloring pigment (2) containing at least two selected from the group consisting of CI Pigment Red 177 and using the pigment dispersing aid, excellent fluidity and dispersion stability are obtained, and the lightness The contrast was excellent. On the other hand, in the comparative example in which the pigment dispersion aid was not added, none of the properties as excellent as those of the examples were obtained.

Examples 44-55, Comparative Examples 31-33, Reference Examples 1-10
<Pigment dispersion composition according to red colored pigment (3)>
The composition of Table 13 was kneaded with a bead mill at a temperature of 40 to 50 ° C. for 3 hours to obtain pigment dispersions 38 to 44.
All the organic pigments have been subjected to a salt milling process using a kneader. “Process PY139 (1)” is the kneader process PY139 obtained in Preparation Example 20, and “Process PY139 (2) ) "Is a pigment refined from the treated PY139 (1) with the amount of sodium chloride at the time of the salt milling treatment being" 1500 parts by mass ", and the" commercial dispersion aid "is a commercially available azo dispersion aid (above Dispersion aids other than the compounds represented by formulas (1) and (2). The unit of numerical values representing the composition is parts by mass.

<Pigment-dispersed resist composition for color filter>
The pigment dispersions 38 to 44 and other materials were uniformly mixed using a high speed stirrer so as to have the compositions shown in Tables 14 to 15, and then filtered with a filter having a pore size of 3 μm. Examples 44 to 55, Comparative Examples Pigment-dispersed resist compositions for color filters of 31 to 33 and Reference Examples 1 to 10 were obtained. In addition, the unit of the numerical value showing a composition is a mass part.

Evaluation method The following evaluation was performed and the results are shown in Tables 13-15.
<Fluidity>
The pigment dispersions 38 to 44 were each taken in a glass bottle, sealed and stored at room temperature for 1 day, and then the viscosity at 25 ° C. was measured using a B-type viscometer (manufactured by Tokimec) to evaluate the fluidity.

<Dispersion stability>
For each of the pigment dispersions 38 to 44, use a B-type viscometer (manufactured by Tokimec Co., Ltd.) for the viscosity at 25 ° C. after being sealed in a glass bottle and stored at room temperature for 1 day, and the viscosity after 7 days at 40 ° C. Measured. The dispersion stability was evaluated by calculating (viscosity after 7 days storage at 40 ° C.) / (Viscosity after 1 day storage at room temperature).

<Contrast of pigment dispersed resist composition for color filter>
After applying the pigment-dispersed resist compositions for color filters of Examples 44 to 55, Comparative Examples 31 to 33 and Reference Examples 1 to 10 onto a glass substrate using a spin coater and prebaking at 100 ° C. for 3 minutes, a high pressure mercury lamp And post-baked at 230 ° C. for 30 minutes.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
The color characteristics (x, y, Y) of the resists of Examples 44 to 55, Comparative Examples 31 to 33 and Reference Examples 1 to 10 were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view). ). In Examples 44 to 55, Comparative Examples 31 to 33, and Reference Examples 1 to 10, x is set to 0.580 for red chromaticity required for the flat display, and y is adjusted so that the same density is obtained. Asked.

From the table, red pigment (3) (treated PO38 and treated PR254 and / or 166) is used as a colored pigment, and these pigments are used in combination with a pigment dispersant having a basic group and a specific pigment dispersion aid. In the dispersed examples, excellent fluidity and dispersion stability were obtained, and the brightness and contrast were also excellent. On the other hand, in the comparative example and the reference example using the processing PY139 (1) and (2) instead of the processing PO38, none of these properties were as excellent as those of the examples. Further, when dispersed using a pigment dispersant having a basic group without using a pigment dispersion aid, the fluidity and dispersion stability were low, and the contrast was poor.

Examples 56-62, Comparative Examples 34-44, Reference Example 11
<Pigment dispersion composition according to red coloring pigment (4)>
The composition of Table 16 was kneaded with a bead mill at a temperature of 40 to 50 ° C. for 3 hours to obtain pigment dispersions 45 to 53. All organic pigments have been subjected to salt milling using a kneader, and “commercial dispersion aids” are commercially available azo dispersion aids (represented by the above formulas (1) and (2)). Dispersion aids other than these compounds). The unit of numerical values representing the composition is parts by mass.

<Pigment-dispersed resist composition for color filter>
The pigment dispersions 45 to 53 and other materials were uniformly mixed using a high-speed stirrer so as to have the compositions shown in Tables 17 to 18, and then filtered with a filter having a pore diameter of 3 μm. Examples 56 to 62 and Comparative Example 34 To 44 and Reference Example 11 were obtained. In addition, the unit of the numerical value showing a composition is a mass part.

Evaluation method The following evaluation was performed and the results are shown in Tables 16-18.
<Flowability and dispersion stability of pigment dispersion>
(Liquidity)
The pigment dispersions 45 to 53 were each taken in a glass bottle, sealed and stored at room temperature for 1 day, and then the viscosity at 25 ° C. was measured using a B-type viscometer (manufactured by Tokimec) to evaluate the fluidity.

(Dispersion stability)
For each of the pigment dispersions 45 to 53, use a B-type viscometer (manufactured by Tokimec Co., Ltd.) after taking them in glass bottles, sealing them and storing them at room temperature for 1 day at a temperature of 25 ° C. Measured. The dispersion stability was evaluated by calculating (viscosity after 7 days storage at 40 ° C.) / (Viscosity after 1 day storage at room temperature).

<Dispersion stability of pigment dispersed resist composition for color filter>
The red pigment-dispersed resist compositions for color filters of Examples 56 to 62, Comparative Examples 34 to 44 and Reference Example 11 were each taken in glass bottles, sealed and stored at room temperature for 7 days, and the states were evaluated according to the following evaluation criteria. .
A: Neither thickening nor sediment is observed.
B: Thickening and sediment that return to the original when lightly shaken are observed.
C: Thickening or sediment that does not return to the original value even when shaken strongly is observed.

<Contrast of pigment dispersed resist composition for color filter>
The pigment-dispersed resist compositions for color filters of Examples 56 to 62, Comparative Examples 34 to 44 and Reference Example 11 were coated on a glass substrate using a spin coater, prebaked at 100 ° C. for 3 minutes, and then exposed with a high pressure mercury lamp. And post-baked at 230 ° C. for 30 minutes.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
The color characteristics (x, y, Y) of the resist compositions of Examples 56 to 62, Comparative Examples 34 to 44 and Reference Example 11 were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view). Measured with In Examples 56 to 62, Comparative Examples 34 to 44, and Reference Example 11, the brightness Y was obtained with (x, y) = (0.650, 0.321) for the red chromaticity required for the flat display.

From the table, Examples in which a red colored pigment (4) (treated PR177 and treated PR166 and / or treated PO38) is used as an organic pigment, and these pigments are dispersed using a pigment dispersant and a specific pigment dispersing aid in combination. , Excellent fluidity and dispersion stability were obtained, and the brightness and contrast were also excellent. On the other hand, in Comparative Examples and Reference Examples, none of these properties were as excellent as those in Examples. For example, when the red coloring pigment (4) is not used in combination (Reference Example 11: combined use of treatment PR177 and treatment PR254), the basic pigment dispersant and the specific pigment dispersion aid may be used in combination. -Although the optical characteristic was superior to the comparative example which did not use a specific pigment dispersion aid, it was inferior to the examples. Moreover, when a specific pigment dispersion aid was not used (Comparative Examples 34 to 44), the dispersion stability and spectral / optical properties were inferior.

The pigment dispersion aid of the present invention can be applied to applications in the color filter and ink jet fields.

Claims (7)

Following general formula (33) and / or (34) to contain Pigment dispersing aid is a compound represented by the color filter pigment dispersion resist composition characterized.

[Wherein, M is H, Na, K, NH ₄ or NR ¹ R ² R ³ R ⁴ (R ¹ , R ² , R ³ and R ⁴ are the same or different and are substituted with other substituents; A saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with another substituent). Represent. m represents an integer of 1 or more. ] Organic pigments, pigment dispersing agents 及 beauty organic solvent further claim 1 color filter pigment dispersion resist composition according containing. Organic pigments
The main pigment is C.I. I. Pigment Red 166, and the toning pigment is C.I. I. Pigment red 177, C.I. I. Pigment red 242 and C.I. I. At least one red color pigment (1) selected from the group consisting of CI Pigment Red 254,
C. I. Pigment red 242, C.I. I. Pigment red 254 and C.I. I. A red coloring pigment (2) containing at least two selected from the group consisting of CI Pigment Red 177,
C. I. Pigment orange 38, C.I. I. Pigment red 254 and / or C.I. I. A red coloring pigment (3) consisting of CI Pigment Red 166, or
C. I. Pigment red 177, C.I. I. Pigment red 166 and / or C.I. I. Pigment Orange 38 and red coloring pigment (4)
The pigment-dispersed resist composition for color filters according to claim 2 . The pigment dispersion resist composition for a color filter according to claim 2 or 3 , wherein the pigment dispersant is a pigment dispersant having a basic group. The pigment-dispersed resist composition for a color filter according to claim 2, 3 or 4, wherein the organic pigment is an organic pigment that has been finely divided. The pigment-dispersed resist composition for a color filter according to claim 5 , wherein the finely divided organic pigment is a salt milled organic pigment. A mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble dispersion medium that does not substantially dissolve the inorganic salt is kneaded in a kneading device that revolves while rotating three stirring blades, and then the inorganic salt. And a pigment-dispersed resist composition for a color filter according to claim 2, 3, 4, 5, or 6, wherein a pigment subjected to salt milling treatment obtained by removing the water-soluble dispersion medium is used.