JP6186702B2 - Pigment dispersion for color filter and photosensitive coloring composition using the same - Google Patents

Description

  The present invention relates to a pigment dispersion for a color filter, and more particularly to a photosensitive coloring composition for a color filter.

  Generally, when manufacturing ink etc., it is known that it is difficult to disperse | distribute a pigment stably at high concentration, and it is known that it will cause various problems with respect to a manufacturing process or the product itself. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from the disperser, and if bad, cause gelation during storage and use It can even be difficult. Furthermore, regarding the surface of the color-exposed product, a state defect such as a decrease in gloss and a leveling defect occurs. In addition, when different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause color unevenness or a significant reduction in coloring power.

  Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites. Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but an acidic dispersant is generally used for pigments having a surface that is biased toward basicity. In this case, the acidic functional group becomes the adsorption site of the pigment. Dispersants having a carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

  However, these have some dispersibility, but it was necessary to increase the amount of use in order to produce a low viscosity and stable dispersion. However, increasing the amount used is not preferable in view of development in inks, paints, etc., because the resistance of the coating film may be reduced.

Then, the dispersing agent for obtaining the pigment dispersion which is excellent in the dispersibility, fluidity | liquidity, and storage stability by the low usage-amount is developed (patent documents 5-8).
However, the recent demand for color filter pigment dispersions is severe, and a higher solid content concentration and a higher pigment concentration are required. In such a case, in order to obtain a stable dispersion having a low viscosity, it is necessary to use a large amount of a dispersant, which causes a problem that the resistance of the coating film decreases. Therefore, it is difficult to obtain a desired dispersion only by using an amount of the dispersant within a range that does not reduce the resistance of the coating film.

  On the other hand, it is known that an acrylic resin is used as a binder component in a pigment dispersion for a color filter or a photosensitive coloring composition for a color filter (hereinafter sometimes abbreviated as a resist). In addition to forming a coating film, these acrylic resins are not only required to have physical properties such as alkali developability and solvent resistance, but are considered to contribute to some extent to pigment dispersibility. For example, there is a document (Patent Document 9) that further improves pigment dispersibility for a binder. A component having an affinity for the pigment is introduced into the binder component. However, the dispersion stabilization at a high solid content concentration and a higher pigment concentration is not achieved by using only the binder resin described in Reference 9. It was enough. In addition, it is difficult to achieve both pigment dispersibility and developability and solvent resistance.

JP-A-61-61623 JP-A-1-141968 Japanese Patent Laid-Open No. 2-219866 JP 11-349842 A Patent 4020150 Japanese Patent No. 4396777 JP 2009-185277 A Japanese Patent No. 2009-255063 JP 2004-101728 A

  An object of the present invention is to provide a dispersion having a low viscosity and high stability even at a high solid content concentration and a high pigment concentration, and a photosensitive coloring composition for a color filter which is excellent in developability and solvent resistance.

By making the glass transition temperature of the acrylic resin used in combination with the dispersant 10 ° C. or less, even a pigment dispersion having a high solid content concentration and / or a high pigment concentration, a stable dispersion having a low viscosity can be obtained. A photosensitive coloring composition for color filters having excellent developability and solvent resistance can be obtained.
That is, the present invention is a pigment dispersion for a color filter comprising a pigment (A), a solvent (B), a dispersant (C), and an acrylic resin (D),
The acrylic resin (D) is an ethylenically unsaturated monomer having a carboxyl group (d1), an ethylenically unsaturated monomer having a hydroxyl group (d2), an ethylenically unsaturated monomer having an aromatic group (d3) ) (Excluding (d1) or (d2)) and other ethylenically unsaturated monomers (d4), and having a glass transition temperature of 10 ° C. or less. The present invention relates to a pigment dispersion for a color filter.

  Moreover, this invention relates to said pigment dispersion for color filters characterized by the weight average molecular weights of acrylic resin (D) being 5000-50000.

  The present invention also relates to the pigment dispersion for a color filter, wherein the acrylic resin (D) has an acid value of 10 to 150 mgKOH / g.

  Moreover, this invention relates to said pigment dispersion for color filters characterized by the hydroxyl value of acrylic resin (D) being 10-200 mgKOH / g.

  The present invention also provides an ethylenically unsaturated monomer having an aromatic group when the total of the monomers (d1) to (d4) is 100% by weight in the copolymer composition of the acrylic resin (D). (D3) is 20 to 60 weight%, It is related with said pigment dispersion for color filters characterized by the above-mentioned.

  The present invention also relates to the above-described pigment dispersion for a color filter, wherein the pigment (A) is Pigment Yellow 138 and / or Pigment Green 58.

  Furthermore, this invention relates to the photosensitive coloring composition for color filters characterized by including said pigment dispersion for color filters, and an active energy ray hardening monomer.

  The pigment dispersion for a color filter of the present invention is excellent in dispersibility, fluidity and storage stability. This makes it possible to obtain a low-viscosity and stable dispersion even at high solids concentration and high pigment concentration required for recent color filters, and to obtain a photosensitive coloring composition for color filters which is excellent in developability and solvent resistance. be able to.

  The color filter dispersion of the present invention contains a pigment (A), a solvent (B), a dispersant (C), and an acrylic resin (D). First, the dispersant (C) and the acrylic resin (D) will be described.

<Dispersant (C)>
It is essential that the dispersant (C) used in the present invention has a controlled structure, and this is the difference from the acrylic resin (D) described later.
A dispersant with a controlled structure is a resin that has both a part that has a high affinity for the pigment and a part that has a high affinity for the solvent as the dispersion medium in a single molecule or in multiple molecules that function together. I mean. A site having a high affinity for the pigment functions as a pigment adsorption site, and a site having a high affinity for the solvent functions as a steric repulsion site. Since the performance of the dispersant is determined by the balance between the two parts, both are very important.

In order to control the structure within one molecule, a site that adsorbs to the pigment is introduced into one end region, and the other part is a site that has a high affinity for the solvent, or the main chain of the resin adsorbs to the pigment. When a site is provided and the side chain bonded to the main chain is a site having a high affinity for the solvent, the resin has a block structure, and a site that adsorbs to the pigment is introduced into one block. There is a case where one block is a site having a high affinity for the solvent. In the case of using a pigment having an acidic surface such as G58, a basic dispersant is preferable.
Examples of commercially available products include BYK series manufactured by Big Chemie, EFKA series manufactured by Ciba Japan, and specific examples include BYK6919, BYK21715, BYK21116, and EFKA4300.

In addition, as a dispersant other than a commercially available product, a resin-type dispersant disclosed in JP2009-255063 and JP4930494 can be used particularly for G58.
In the case of using a plurality of molecules, a resin having an unstructured structure having a pigment adsorbing ability and a structure-controlling resin having a portion having a high affinity for the resin having an adsorbing ability of the pigment are used in combination. There are cases where various types of resins function as a pigment dispersing agent. In any case, it is important that the structure of the pigment dispersant is controlled within one molecule or within a plurality of molecules that function as a unit.

The content of the dispersing agent (C) is preferably 2 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the pigment, although it depends on the size and difficulty of dispersion of the pigment. . If the amount is less than 2 parts by weight, the effect is not so much. If the amount is more than 50 parts by weight, the binder component imparting developability and coating film performance becomes too small, and the coating film performance may deteriorate.
The molecular weight is preferably 1000 to 50000 in terms of weight average molecular weight. If the weight average molecular weight is lower than 1000, the steric repulsion effect may not be sufficiently exhibited and the dispersibility may be deteriorated. If the weight average molecular weight is greater than 50000, the number of molecules of the dispersant is relatively reduced, and thus the dispersibility may be deteriorated. is there.

<Acrylic resin (D)>
Next, the acrylic resin (D) will be described. The color filter dispersion generally contains an acrylic resin, which is a random copolymer of ethylenically unsaturated monomers, as a binder component, in addition to the pigment, solvent, and dispersant. The acrylic resin (D) of the present invention is a random copolymer of an ethylenically unsaturated monomer or a modified product thereof, and is different from the dispersant (C) whose structure is controlled in that respect.

In general, the above-mentioned acrylic resin is included for the purpose of forming a coating film of a pigment dispersion or for imparting alkali developability. Furthermore, dispersion not only with pigments, solvents, and dispersants, but also with the above acrylic resins may result in higher quality dispersions. The above acrylic resins are also important in creating dispersions. Play an important role.
In the present invention, a higher-quality dispersion can be obtained by improving the pigment dispersibility of the acrylic resin (D).

It is important that the acrylic resin (D) used in the present invention has a glass transition temperature of 10 ° C. or lower. In the process of producing a color filter dispersion, an acrylic resin is added together with a pigment, a solvent, and a dispersant to perform dispersion. At that time, when trying to obtain a dispersion having a high solid content concentration and a high pigment concentration, a dispersion having a high viscosity and insufficient stability may be obtained. At that time, it was found that when an acrylic resin having a glass transition temperature of 10 ° C. or lower is used, a good dispersion may be obtained.
The reason is not clear, but by using an acrylic resin with a low glass transition temperature in the dispersion step, the fluidity of the acrylic resin has been greatly improved, and the efficiency of adsorption to the pigment and fragmentation of the pigment has improved. It is thought that there is not.

The glass transition temperature referred to in the present invention means an ethylenically unsaturated monomer (d1) having a carboxyl group to be copolymerized, an ethylenically unsaturated monomer (d2) having a hydroxyl group, and an ethylenically unsaturated monomer having an aromatic group. The values calculated by the following Fox equation from the Tg of the saturated monomer (d3), the other ethylenically unsaturated monomer (d4), and the respective homopolymers are shown.
Formula of Fox 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).
Tg (glass transition temperature) of the homopolymer of the main monomer used for calculation is illustrated below.

Methacrylic acid (MAA): 130 ° C
Methyl methacrylate (MMA): 105 ° C
Butyl acrylate (BA): -54 ° C
Butyl methacrylate (BMA): 20 ° C
2-hydroxyethyl methacrylate (HEMA): 55 ° C.
4-hydroxybutyl acrylate (4HBA): -80 ° C
Benzyl acrylate (BzA): 0 ° C
Benzyl methacrylate (BzMA): 55 ° C
Biscote # 315 (manufactured by Osaka Organic Chemical Industry): 35 ° C

  From the viewpoint of dispersion stability, the glass transition temperature is preferably −40 to 10 ° C., more preferably −30 to 10 ° C., and further preferably −20 to 10 ° C.

First, the ethylenically unsaturated monomer (d1) having a carboxyl group will be described. First, developability which is one of the purposes for which the acrylic resin (D) is used will be described.
When creating a color filter, add an active energy ray-curable monomer or photoinitiator to the dispersion for the color filter, coat the glass substrate as a color filter coloring composition, volatilize the solvent, Necessary portions are irradiated with light, and unirradiated portions are further removed by flowing an alkaline solution. The step of flowing the alkaline solution is called a development step. Here, the property removed when the alkaline solution is passed is called developability.
If the time required for development is too long, that is, developability is poor, it is not preferable from the viewpoint of simplifying the production process. On the other hand, a certain permissible width in which development takes a certain time is called a development margin, and even when the development margin is narrow, management of the manufacturing process becomes difficult, which is not preferable.

  In addition, when the compatibility of the coloring composition is poor, the characteristics contributing to image forming properties are relatively lowered. That is, the development state of the colored composition in the non-exposed area in the development process is not due to dissolution and remains undissolved, or remains undissolved on the substrate as a peeled piece. It may cause As a result, the quality of the color filter is deteriorated and the yield during production is reduced. Therefore, the development state is preferably a dissolved state.

  In the development step, it is important to have an acid value in order to be removed by an alkaline solution. Accordingly, it is important that the acrylic resin (D) contains an ethylenically unsaturated monomer (d1) having a carboxyl group in the copolymer composition.

  The content of the ethylenically unsaturated monomer (d1) having a carboxyl group is preferably 5% to 20% by weight, more preferably 5% to 15%, with the total of (d1) to (d4) being 100% by weight. %. When it is more than 20%, the development margin may be narrowed, and when it is less than 5%, developability may be deteriorated.

The carboxyl group-containing ethylenically unsaturated monomer (d1) is not particularly limited as long as it is a monomer having a carboxyl group and an ethylenically unsaturated group. For example, (meth) acrylic acid, (meth) acrylic acid Dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2 -(Meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone (meth) acrylate and the like.
(Meth) acrylic acid is preferred.

Next, the ethylenically unsaturated monomer (d2) having a hydroxyl group will be described. First, the formation of a coating film, which is one of the purposes for which the acrylic resin (D) is used, will be described.
When creating a color filter, there is a step of baking the color filter coating film on glass after the development step, and there is a step of heat curing at 230 ° C. for about 20 minutes to 1 hour. This is called post-baking.
Here, the color filter coating film is thermally cross-linked, and the solvent resistance and the like are changed to a sufficient coating film. It is very important that the resin is cross-linked in this step, and it is very important that the acrylic resin has heat cross-linkability because only the dispersant may not have heat cross-linkability.
In general, it is the hydroxyl group of the acrylic resin that plays this role. When heated at 230 ° C., the hydroxyl group reacts with the carboxyl group of the acrylic resin to form an ester bond or transesterify with the ester group of the acrylic resin to crosslink the resins.
Accordingly, it is important that the acrylic resin (D) contains an ethylenically unsaturated monomer (d2) having a hydroxyl group as a copolymer composition.

  The content of the ethylenically unsaturated monomer (d2) having a hydroxyl group is preferably 5% to 50% by weight, more preferably 10% to 30%, with the total of (d1) to (d4) being 100% by weight. It is. If it is more than 50%, the hydrophilicity is too strong and the solubility in a solvent and compatibility with other components may be deteriorated. If it is less than 5%, the resistance may be insufficient.

The ethylenically unsaturated monomer (d2) having a hydroxyl group is not particularly limited as long as it is a monomer having a hydroxyl group and an ethylenically unsaturated group. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxy Hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, and 2-hydroxy-3-phenoxypropyl acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl Ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate,
(Poly) alkylene glycol monoalkyl ether (meth) acrylates, such as polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate;
And preferably,
2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether ( (Meth) acrylate is preferably used.
In order to adjust the glass transition temperature to 10 ° C. or lower, it is particularly preferable to use 4-hydroxybutyl acrylate.

  Next, the ethylenically unsaturated monomer (d3) having an aromatic group will be described. In the step of dispersing the pigment, it is important that the acrylic resin (D) has a portion having an affinity for the pigment. In the case of an organic pigment, since it contains many aromatic rings, the aromatic ring becomes a site having an affinity for the pigment. Accordingly, it is important that the acrylic resin (D) contains an ethylenically unsaturated monomer (d3) having an aromatic group in the copolymer composition.

  The content of the ethylenically unsaturated monomer (d3) having an aromatic group is preferably 20% by weight to 80% by weight, more preferably 30% by weight, with the total of (d1) to (d4) being 100% by weight. 60%. If it is more than 80%, there are too many aromatic rings and the compatibility with other components may be deteriorated. If it is less than 20%, the affinity with the pigment is lowered and the stability as a dispersion is obtained. It may not be possible.

  The ethylenically unsaturated monomer (d3) having an aromatic group is not particularly limited as long as it is a monomer having an aromatic group and an ethylenically unsaturated group, and examples thereof include benzyl (meth) acrylate and phenoxyethyl. (Meth) acrylate, styrene, α-methylstyrene and the like can be mentioned. Preferably, it is benzyl (meth) acrylate.

Next, other ethylenically unsaturated monomers (d4) will be described. The other ethylenically unsaturated monomer (d4) is not particularly limited as long as it has an ethylenically unsaturated group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate And isostearyl (meth) linear or branched alkyl acrylates such as (meth) acrylates;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
Tertiary amino such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, etc. (Meth) acrylates having a group;
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine; In addition, nitriles such as (meth) acrylonitrile are exemplified.
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
In addition, vinyl acetate and fatty acid vinyls such as vinyl propionate can also be used.

One or two or more types can be selected from the ethylenically unsaturated monomers listed above, and at least methyl (meth) acrylate, ethyl (meta) from the viewpoint of solubility in solvents and resistance. ) Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate Is preferably used in part. More preferred are methyl methacrylate and n-butyl (meth) acrylate.
The content of the other ethylenically unsaturated monomer (d4) is preferably 10% by weight to 70% by weight, more preferably 30% to 50%, with the total of (d1) to (d4) as 100% by weight. However, it can be appropriately adjusted according to the contents of (d1) to (d3).

  Content of an acrylic resin (D) is 5 weight part-100 weight part with respect to 100 weight part of pigments. When the amount is less than 5 parts by weight, the amount in the pigment dispersion is too small, so that the compatibility with the acrylic resin added at the time of preparing the photosensitive coloring composition is deteriorated. When the amount is more than 100 parts by weight, the pigment concentration is too low, and there is no room for adding a monomer or an initiator when preparing the photosensitive coloring composition.

  The acrylic resin (D) preferably has a weight average molecular weight of 5000 to 50000. More preferably, the weight average molecular weight is 10,000 to 40,000. When the weight average molecular weight is less than 5,000, the film forming property of the coating film of the pigment dispersion is poor, and there is a possibility that the development margin is narrow. On the other hand, if the weight average molecular weight is larger than 50000, the fluidity of the pigment dispersion may be deteriorated.

  Here, the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene in gel permeation chromatography (GPC) measurement.

  The acrylic resin (D) preferably has an acid value of 10 to 150 mgKOH / g. Since the acrylic resin (D) is also a resin for imparting developability, if the acid value is less than 10 mgKOH / g, the developability tends to deteriorate, and if the acid value is greater than 150 mgKOH / g, the pigment dispersion Fluidity may be worse.

  Here, the acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

  The acrylic resin (D) preferably has a hydroxyl value of 10 to 200 mgKOH / g. In the case of a color filter dispersion, it is necessary to thermally crosslink in the post-baking step described above. If the hydroxyl value is less than 10 mgKOH / g, the thermal crosslinkability may be poor and the solvent resistance may be poor. If the hydroxyl value is 200 mgKOH / g or more, the hydrophilicity is too strong and the solubility in the solvent and other components There is a possibility that the compatibility with.

  Here, the hydroxyl value refers to a pyridine solution containing acetic anhydride, acetylate the hydroxyl group, hydrolyze the excess acetylating reagent with water, and titrate the produced acetic acid with potassium hydroxide. , In terms of solid content. Titration is based on the potentiometric titration method of JIS K 0070.

<Pigment (A)>
Examples of the pigment (A) contained in the color filter dispersion of the present invention include various pigments used in inks and the like. Such pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments. , Anthanthrone pigment, Indanthrone pigment, Flavanthrone pigment, Pyranthrone pigment, Diketopyrrolopyrrole pigment, etc. More specific examples are shown by the generic names of Color Index: Pigment Black 7, Pigment Blue 6, 15 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 58, 97, 122, 144, 146, 149 , 166, 168, 177, 17 , 179, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment yellow 12, 13, 14, 17, 20 , 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180 , 185, pigment orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, and the like. However, it is not limited to illustration.

  In particular, when Pigment Yellow 138 and / or Pigment Green 58 is used, there is a remarkable effect, which is preferable.

<Solvent (B)>
The following are mentioned as a solvent (B) contained in the dispersion for color filters of this invention. However, it is not limited to illustration.
As a solvent, for example,
1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3- Propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy- 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N- Dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chloro Ruene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene Glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol Monomethyl ether, ethylene glycol Monoethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, di Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Acetic acid Propyl, or dibasic acid esters and the like. These may be used singly or in combination.

  Among these, since the dispersibility of the pigment and the coating property of the coloring composition are good, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono It is preferable to use glycol acetates such as ethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  The organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the pigment because the colored composition can be adjusted to an appropriate viscosity to form a filter segment with a desired uniform film thickness. preferable.

<Solid concentration and pigment concentration>
Here, the solid content concentration and the pigment concentration of the pigment dispersion of the present invention will be described. The solid content concentration is the content of the total solid content in the dispersion, and the pigment concentration is the content of the pigment in the total solid content. Moreover, a pigment shows what also contains the below-mentioned pigment derivative.
Conventionally, yellow pigments such as P.I. Y. In the case of No. 138, the solid content concentration was 20% by weight or less, the pigment concentration was 50% by weight or less, and in this range, the viscosity was 50 cps or less.
However, a dispersion having a higher solid content concentration and pigment concentration has been required, and one of the reasons is cost reduction in the production process. Further, resists having higher performance have been demanded, and higher solid content concentration and pigment concentration are required in order to further increase the degree of freedom of materials added at the time of resist formation.
At present, for example, P.I. Y. In the case of a yellow pigment such as 138, the solid concentration needs to be 25% by weight or more, the pigment concentration needs to be 55% by weight or more, and the viscosity needs to be 50 cps or less. P.P. B. Blue pigments such as 15: 6; R. Red pigments such as 254; G. Green pigments such as 58 require a solid content concentration of 25% by weight or more and a pigment concentration of 60% by weight or more, both of which have a viscosity of 50 cps or less.

<Active energy ray-curable monomer>
The active energy ray-curable monomer contained in the color filter coloring composition of the present invention means a compound having an ethylenically unsaturated double bond that is cured by irradiation with active energy rays to form a resin. The monomer includes a low polymer having an average molecular weight of less than 1000, generally called an oligomer, and having an ethylenically unsaturated double bond.

As an active energy ray-curable monomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalates,
Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, Poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, or glycerol (meth) acrylate (Meth) acrylates having a hydroxyl group such as;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate;
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate Di (meth) acrylate and the like;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether, Alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) acrylic acid adduct, bisphenol A di Glycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, epichlorohydride -Modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl ether- (meta ) Acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid adduct,
Epoxy (meth) acrylates such as cresol novolac type epoxy resin- (meth) acrylic acid adduct or other epoxy resin- (meth) acrylic acid adduct;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile. These can be used alone or in admixture of two or more.

<Active energy ray polymerization initiator>
In the coloring composition for color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, an active energy ray polymerization initiator or the like is added to the solvent developing type or alkali developing. It can be prepared in the form of a type photosensitive coloring composition.

Examples of the active energy ray polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Acetophenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like.
These active energy ray polymerization initiators can be used singly or as a mixture of two or more at any ratio as required.

  The content of the active energy ray polymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 10 to 150 parts by weight from the viewpoint of active energy ray curability and developability. preferable.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Dye derivative>
In the coloring composition for a color filter of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the pigment. The dye derivative is represented by the following general formula (1) in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine. Compounds.
P-Lm General formula (1)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group m: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The compounding amount of the pigment derivative is preferably 0.1 to 40% by weight based on the total weight of the pigment (100% by weight), and most preferably 0 based on the total weight of the pigment (100% by weight). .5 to 35% by weight. When the blending amount of the pigment derivative is less than 0.1% by weight, dispersibility may be deteriorated, and when it exceeds 40% by weight, heat resistance and light resistance may be deteriorated. By including a pigment derivative, the initial contrast ratio and viscosity are excellent, and the storage stability is also good, which is preferable.

  Examples of the dispersion step of the color filter pigment dispersion of the present invention include a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using a kneader mixer such as a kneader, 3-roll mill, etc., solid dispersion with 2-roll mill, etc. Also good. In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used for producing the pigment dispersion.

<Method for producing pigment dispersion>
Next, the manufacturing method of the pigment dispersion of this invention is demonstrated.
In order to obtain a pigment dispersion for a color filter having a high contrast ratio and a low viscosity, it is preferably dispersed by a media type wet disperser such as a bead mill.

(Media type wet disperser)
Types of media type wet dispersers include horizontal and vertical types of cylindrical dispersers, and also annular types (annular types), such as paint conditioners, attritors, sand mills, dyno mills, ball mills, super apex mills, There are bead mills such as Coball Mill, Diamond Fine Mill, DCP Mill, OB Mill, Eiger Mill, Spike Mill, and Pico Glen Mill. Among them, Super Apex Mill, Eiger Mill, DCP Mill, Pico Glen Mill, etc. which are annular type (annular type) dispersers. preferable.

  The material of the medium is not particularly limited as long as it is a rigid body, and generally used glass, steel, stainless steel, ceramics, zircon, zirconia and the like can be mentioned. The media particle size is preferably 1.0 mmφ or less in order to achieve fine dispersion and a high contrast ratio. Further, when a media in the range of 0.5 to 0.05 mmφ is used, a higher contrast ratio effect is exhibited. It is preferable because it is easy. It is also preferable in terms of dispersion efficiency to disperse in a wet disperser using a medium having a large particle diameter in advance and then perform multistage wet dispersion using a medium having a smaller particle diameter. As a dispersion method, either circulation or path dispersion can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example.
The weight average molecular weight (Mw) is a polystyrene equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with RI detector and using DMF as a developing solvent.

<Manufacture of acrylic resin>
(Synthesis of acrylic resin (D-1))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 94.5 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. Heat the reaction vessel to 110 ° C,
15.0 parts of methacrylic acid as a monomer, 20.0 parts of butyl acrylate, 15.0 parts of 4-hydroxybutyl acrylate, 50.0 parts of benzyl methacrylate, V-601 (manufactured by Wako Pure Chemical Industries) as an initiator A mixture of 1.5 parts and 3.5 parts of methoxypropyl acetate was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 110 ° C. for 3 hours, and then V-601 (manufactured by Wako Pure Chemical Industries) was mixed with 0.15 part of 0.35 part of methoxypropyl acetate, and further at 110 ° C. for 1 hour. The reaction was continued to obtain a methoxypropyl acetate solution of acrylic resin (D-1). This was diluted with methoxypropyl acetate to obtain a 30.0% solid solution of acrylic resin (D-1). When the acid value and the hydroxyl value were measured, the acid value was 98.0 mgKOH / g, and the hydroxyl value was 58.2 mgKOH / g. Moreover, the glass transition temperature was 5.8 degreeC and the weight average molecular weight (Mw) was 29000.

(Synthesis of acrylic resins (D-2 to D-16))
The synthesis was performed in the same manner as the acrylic resin (D-1) except that the raw materials and preparation amounts (parts by weight) described in Table 1 were used, and the acrylic resin (solid content of D-2 to D-16 was 30%). A methoxypropyl acetate solution was obtained.

The raw materials used in Table 1 are listed below.
MAA: methacrylic acid 4HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate BzA: benzyl acrylate BzMA: benzyl methacrylate BA: butyl acrylate BMA: butyl methacrylate MMA: methyl methacrylate biscoat # 315 (manufactured by Osaka Organic Chemical Industry): Paracumylphenol ethylene oxide modified acrylate

<Manufacture of dispersant>
(Synthesis of Dispersant (C-1))
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 80 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of thioglycerol, and 105 parts of methoxypropyl acetate and replaced with nitrogen gas. . The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN [2,2′-azobis (isobutyronitrile)] was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature to obtain a 50% solid content solution of a vinyl polymer having a weight average molecular weight of 4,500 and having two free hydroxyl groups in one end region. It was.
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of a 50% solid solution of this vinyl polymer, 10.9 parts of isophorone diisocyanate, 10.9 parts of methoxypropyl acetate, As a catalyst, 0.03 part of dibutyltin dilaurate was charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 3 hours, and then cooled to 40 ° C. to obtain a colorless transparent solution.
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with a mixed solution of 3.54 parts of methyliminobispropylamine and 104.5 parts of methoxypropyl acetate and heated to 100 ° C. After adding 100 parts of a colorless transparent solution dropwise over 30 minutes and reacting for 1 hour, the reaction was terminated by cooling to room temperature. The solid content was adjusted to 40%, and a colorless transparent solution of Dispersant C-1 having a main chain amino group as a pigment adsorption site and a solvent affinity site in the side chain was obtained. Dispersant C-1 had a weight average molecular weight of 12,000 and an amine value of 47.0 mgKOH / g.

(Synthesis of dispersant (C-2))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was stirred with heating at 120 ° C. for 4 hours. The solid content measurement confirmed that 98% had reacted, and the first step was completed. The number average molecular weight of this reaction product was 1350, and the weight average molecular weight was 1890.
To the reaction product, 36.6 parts of pyromellitic dianhydride was added and reacted at 100 ° C. for 5 hours. The acid value was measured to confirm that 97% or more of the acid anhydride was half-esterified, and the second step was completed to obtain a dispersant C-2 having a carboxyl group as a pigment adsorption site at one end. . This was a waxy solid at 25 ° C. and had a weight average molecular weight of 3,500 and an acid value of 49.0 mgKOH / g. Here, the waxy solid means a solid that is opaque at room temperature but changes to a transparent liquid upon heating, and the dispersant obtained in Synthesis Example 11 becomes a transparent liquid at about 50 ° C. It was a thing.

(Synthesis of dispersant (C-3))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 200 parts of n-butyl methacrylate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of thioglycerol was added to react for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 12 parts of pyromellitic anhydride, 230 parts of methoxypropyl acetate and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. I let you. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, diluted with methoxypropyl acetate, the main chain had a carboxyl group as a pigment adsorption site, and the side chain A 40% solution of Dispersant C-3 having a solvent affinity site was obtained. The weight average molecular weight was 9000.

(Synthesis of dispersant (C-4))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and heated to 100 ° C. while purging with nitrogen. In a dropping tank, 200 parts of N, N-dimethylaminoethyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged and stirred until uniform, followed by reaction. The solution was dropped into the tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours, and finally diluted with methoxypropyl acetate. In this way, a 40% methoxypropyl acetate solution of a non-structure-controlled dispersant C-4 having a tertiary amino group having an amine value per solid content of 345 mg KOH / g and a weight average molecular weight of 5000 was obtained.

[Example 1]
After the mixture having the following composition was stirred and mixed uniformly, the mixture was dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then with a 5 μm filter. Filtration was performed to prepare a yellow pigment dispersion (P-1).
The amount of solid content is shown below.
Pigment: P.I. Y. 138 50.0 parts Derivative: Dye derivative A 10.0 parts Dispersant: C-1 15.0 parts Acrylic resin: D-1 25.0 parts These were diluted with methoxypropyl acetate to give a solid content of 28% Solution.

[Examples 2 to 14]
Except having used the raw material and preparation amount which were described in Table 2, it mix | blended like Example 1 and the pigment dispersion (P-2 to P-14) was obtained.

[Example 15]
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed for 2 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and filtered through a 5 μm filter. A green pigment dispersion was prepared.
The amount of solid content is shown below.
Pigment: P.I. Y. 138 50.0 parts Derivative: Dye derivative A 10.0 parts Dispersant: C-3 10.0 parts Dispersant: C-4 5.0 parts Acrylic resin: D-1 25.0 parts Dilution with methoxypropyl acetate gave a solution with a solids content of 28%.
Subsequently, after stirring and mixing using the raw material and preparation amount described in Table 2, it filtered with a 1 micrometer filter, and obtained the yellow photosensitive coloring composition.

[Examples 16 to 34]
A pigment dispersion was obtained by blending in the same manner as in Example 15 except that the raw materials and preparation amounts shown in Table 2 were used.
However, Examples 16 to 34 do not use a derivative.

[Example 35]
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a yellow photosensitive coloring composition (R-1).
The amount of solid content is shown below.
-Pigment dispersion: 8.33 parts of yellow pigment dispersion (P-1)-Acrylic resin: 5.67 parts of D-14-Active energy ray-curable monomer: 4.00 parts (manufactured by Shin-Nakamura Chemical Co., Ltd. NK ester ATMPT "trimethylolpropane triacrylate)
Active energy ray polymerizable initiator: 1.80 parts (“Irgacure 907” 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one manufactured by Ciba Geigy))
Sensitizer: 0.20 part (“EAB-F” 4,4′-bis (diethylamino) benzophenone manufactured by Hodogaya Chemical Co., Ltd.)
These were diluted with methoxypropyl acetate to obtain a solution having a solid content of 15%.

[Examples 36 to 71]
Except having used the raw material and preparation amount which were described in Table 3, it mix | blended like Example 35 and obtained the photosensitive coloring composition (R-2 to R-37).

The raw materials used in Table 2 are listed below.
BYK111: Acidic dispersant manufactured by Big Chemie EFKA4300: Basic dispersant manufactured by BASF BYK6919: Basic dispersant manufactured by BYK Chemie BYK21715: Basic dispersant manufactured by BYK Chemie BYK21116: Basic dispersant manufactured by BYK Chemie

(Dye derivative A)

(Dye derivative B)

(Dye derivative C)

<Evaluation>
Next, the following measurements were performed. The evaluation results are shown in Tables 2 and 3.
(Measurement of initial viscosity and viscosity increase with time)
The viscosity of the pigment dispersion for the color filter is the viscosity (initial viscosity) at a rotational speed of 20 rpm using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. on the day of adjusting the color filter pigment dispersion. ) Was measured.
And about what was left to stand at 40 degreeC for 7 days from the day of color dispersion pigment dispersion adjustment, after returning sample temperature to 25 degreeC, according to the said viscosity measuring method, a time-dependent viscosity was measured, and time-dependent expression was obtained from the following formula. The thickening rate was determined.
Thickening ratio with time = (viscosity with time) / (initial viscosity) x 100 (%)

(Development time evaluation)
A substrate in which the obtained photosensitive coloring composition for a color filter was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater at a rotation speed of 2 μm after drying was obtained. A coating film was formed by drying at 20 ° C. for 20 minutes. This coating film is exposed to ultraviolet light with an integrated light amount of 150 mJ using a super high pressure mercury lamp through a test mask, and then developed with a spray using an alkaline developer composed of a 0.2% aqueous sodium carbonate solution. It was evaluated with.

Green color filter coated substrate for color composition ○: Can be completely removed within 40 seconds Δ: Can be completely removed within 40 to 60 seconds ×: Cannot be completely removed even after 60 seconds

Red color filter coated substrate for color composition ○: Can be completely removed within 60 seconds Δ: Can be completely removed within 60 to 80 seconds ×: Cannot be completely removed even after 80 seconds

Blue color filter coated substrate for color composition ○: Those that can be completely removed within 20 seconds Δ: Those that can be completely removed within 20 to 40 seconds ×: Those that cannot be completely removed even after 40 seconds

(Development margin evaluation)
The coating film prepared in the same manner as above was exposed to ultraviolet light with an integrated light amount of 150 mJ using a super high pressure mercury lamp through a test mask, and then sprayed with an alkaline developer composed of a 0.2% sodium carbonate aqueous solution to uncured parts. The time (development margin) during which the desired pattern can be maintained by spraying an alkali developer was evaluated in three stages from the state where the desired pattern was obtained by removing the film.

Green color filter coloring composition coated substrate ○: Time required for maintaining a desired pattern is 10 seconds or longer Δ: Time required for maintaining a desired pattern 5 seconds or longer and 10 seconds or shorter ×: Maintaining a desired pattern Within 5 seconds

Red color filter coloring composition coated substrate ○: Time required for maintaining a desired pattern is 10 seconds or longer Δ: Time required for maintaining a desired pattern 5 seconds or longer and 10 seconds or shorter ×: Maintaining a desired pattern Within 5 seconds

Blue color filter coated substrate for color composition ○: Time required for maintaining a desired pattern 10 seconds or longer Δ: Time required for maintaining a desired pattern 5 seconds or longer 10 seconds or shorter ×: Maintaining a desired pattern Within 5 seconds

(Development state evaluation)
The coating film prepared in the same manner as above was exposed to ultraviolet light with an integrated light amount of 150 mJ using a super high pressure mercury lamp through a test mask, and then sprayed with an alkaline developer composed of a 0.2% sodium carbonate aqueous solution to uncured parts. Was removed. In that case, it confirmed about the development state of the coloring composition of an unexposed part.
Dissolution: It is dissolved and developed by a developer. Peeling without precipitate: Peeled and developed by developer. With deposit

(Coating film heat resistance evaluation)
A coating film was prepared in the same manner as above, and alkali development was performed to prepare a cured coating film substrate. The cured coated film substrate was cut into a size of 10 mm × 20 mm, immersed in a 20 cc NMP solution for 0.5 hour, rinsed with pure water and dried. The brightness (L *) and chromaticity coordinates (a *, b *) of the coating film before and after this test were measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.), and the color difference (ΔEab *) Was calculated.

Using the measured color difference value, the color difference change rate ΔEab * was calculated by the following formula, and the heat resistance of the coating film was evaluated in the following four stages.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

[Comparative Examples 1-12, 13-24]
Except having used the raw material and preparation amount which were described in Table 2, Table 3, it mix | blended like Example 1 and Example 35, and obtained the pigment dispersion. However, as shown in Table 2, since the viscosity was high, a photosensitive coloring composition could not be obtained. Further, since the viscosity is high, the viscosity increase rate with time is not measured.

From the above, the viscosity of the pigment dispersion for color filters was greatly reduced by using a copolymer having a glass transition temperature of 10 ° C. or lower as an acrylic resin, and the stability over time was good. In particular, when Pigment Yellow 138 or Pigment Green 58 was used as a pigment component, the viscosity was low, the stability over time was good, and the effect was remarkable.

Claims (6)

A pigment dispersion for a color filter comprising a pigment (A), a solvent (B), a dispersant (C), and an acrylic resin (D),
The acrylic resin (D) is an ethylenically unsaturated monomer having a carboxyl group (d1), an ethylenically unsaturated monomer having a hydroxyl group (d2), an ethylenically unsaturated monomer having an aromatic group (d3) ) (Excluding (d1) or (d2)), and other ethylenically unsaturated monomers (d4), and having a glass transition temperature of 10 ° C. or lower,
The ethylenically unsaturated monomer (d2) having a hydroxyl group is 4-hydroxybutyl acrylate,
A pigment dispersion for a color filter, wherein the acrylic resin (D) has an acid value of 10 to 150 mgKOH / g .   The pigment dispersion for a color filter according to claim 1, wherein the acrylic resin (D) has a weight average molecular weight of 5,000 to 50,000. The pigment dispersion for a color filter according to claim 1 or 2 , wherein the acrylic resin (D) has a hydroxyl value of 10 to 200 mgKOH / g. When the total of the monomers (d1) to (d4) is 100% by weight in the copolymer composition of the acrylic resin (D), the ethylenically unsaturated monomer (d3) having an aromatic group is 20 to 20%. It is 80 weight%, The pigment dispersion for color filters in any one of Claims 1-3 characterized by the above-mentioned. The pigment dispersion for a color filter according to any one of claims 1 to 4 , wherein the pigment (A) is Pigment Yellow 138 and / or Pigment Green 58. A photosensitive coloring composition for a color filter, comprising the pigment dispersion for a color filter according to any one of claims 1 to 5 and an active energy ray-curable monomer.