WO2014010687A1 - Pigment dispersion for colour filter - Google Patents

Abstract

The present invention provides a pigment dispersion for a colour filter having excellent storage stability and low viscosity, which can form a cured film with excellent contrast, a method for manufacturing same, a colouring composition comprising said pigment dispersion for a colour filter, and a colour filter. Disclosed are: (1) A pigment dispersion for a colour filter comprising a pigment dispersant having a structural unit derived from a dialkylaminoalkyl (meth)acrylamide (A) and a structural unit derived from an alkoxypolyalkylene glycol (meth)acrylate (B), with a rate of quaternarization of 10 to 80 mol%, an organic pigment and an ether-based organic solvent; (2) a colouring composition for a colour filter comprising said pigment dispersion; (3) a method for manufacturing the pigment dispersion of (1); and (4) a colour filter manufactured using the pigment dispersion described in (1).

Description

Pigment dispersion for color filters

The present invention relates to a pigment dispersion for a color filter, a production method thereof, a coloring composition for a color filter containing the pigment dispersion for a color filter, and a color filter.

A color filter used in a liquid crystal display device is manufactured by a photolithography method in which a coloring composition obtained by blending a pigment dispersion with a resin or the like is applied to a transparent substrate such as glass, and then exposed, cured, developed, and thermally cured. Yes. The pigment dispersion used here is a non-aqueous pigment dispersion in which a pigment is dispersed in an organic solvent. As a method for producing a non-aqueous pigment dispersion, a production method using a polymer dispersant such as a graft polymer is known. ing.

For example, Patent Document 1 discloses that a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal, a nitrogen atom and an ethylenic group are used for the purpose of preventing aggregation of pigments and realizing good dispersion of the pigment. Pigment dispersion characterized by containing a graft copolymer having a nitrogen atom and an ether group, comprising a nitrogen-containing monomer having an unsaturated double bond and a polymerizable monomer having an ether group as a copolymer unit Agents are disclosed.
Patent Document 2 discloses a monofunctional macromonomer having a specific molecular weight and structure, a monomer having a specific structure, and a monomer having a specific structure as a coloring composition capable of dispersing fine particles of pigment and having excellent dispersion stability over time and pattern reproducibility. A radiation-sensitive coloring composition containing a copolymer comprising a quaternary ammonium salt monomer, a radiation-sensitive compound and a pigment is disclosed.
Patent Document 3 contains a colorant, a vinyl polymer, and an organic solvent for the purpose of reducing the viscosity and improving the stability, and the vinyl polymer is a structural unit such as benzyl (meth) acrylate and poly (ethylene glycol). An oil-based ink composition that is a polymer having a structural unit such as propylene glycol) mono (meth) acrylate is disclosed.
Patent Document 4 discloses a pigment dispersion containing a specific aliphatic saturated alcohol for the purpose of improving the contrast and the coating stability of a dried coating film.
Patent Document 5 discloses a radiation-sensitive composition for forming a colored layer containing an alkali-soluble resin composed of a macromer having a specific structure for the purpose of preventing undissolved substances from remaining during development.
Patent Document 6 discloses a pigment dispersion containing a pigment dispersant having an amino group, a quaternary salt, and a polyethylene oxide chain for the purpose of improving dispersibility.
In Patent Document 7, for the purpose of improving dispersibility and dispersion stability, a main chain portion having a nitrogen atom, a group having a functional group having a pKa of 14 or less, and an oligomer chain or a polymer chain in the side chain, Dispersion resins for pigments are disclosed.

JP 2001-31885 A Japanese Patent Laid-Open No. 10-14296 JP 2007-45903 A JP 2008-248109 A JP 2007-241247 A International Publication No. 2010/050650 JP 2009-203462 A

The present invention relates to the following [1] to [4].
[1] It has a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and the quaternization rate is 10 to 80 mol%. A pigment dispersion for a color filter containing a pigment dispersant, an organic pigment, and an ether organic solvent.
[2] It has a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and the quaternization rate is 10 to 80 mol%. A method for producing a pigment dispersion for a color filter, comprising a step of dispersing a mixture of a pigment dispersant, an organic pigment, and an ether organic solvent.
[3] A coloring composition for a color filter comprising the pigment dispersion of [1] and an alkali-soluble resin which is a copolymer of (meth) acrylic acid ester and (meth) acrylic acid.
[4] A color filter produced using the pigment dispersion according to [1].

The color filter is required to have a high contrast as the display image becomes higher in definition. As a method for improving the contrast, the pigment is further refined. For example, when the dispersion force is increased to make the pigment finer, the cohesive force between the pigments increases, so that the obtained pigment dispersion and coloring composition are obtained. The viscosity of the product increases, storage stability decreases, and it is difficult to improve contrast. On the other hand, when the amount of the dispersing agent is increased and refined, the refinement progresses, but the viscosity also increases, the handling property of the colored composition deteriorates, and the uniform thickness when applied to a transparent substrate such as glass. There was a problem that it was difficult to form a coating film and the contrast could not be improved.
Therefore, a pigment dispersion having a low viscosity, excellent storage stability, and high contrast is desired.
The present invention is capable of forming a cured film excellent in contrast, having a low viscosity and excellent in storage stability, a color filter pigment dispersion, a production method thereof, and a color containing the color filter pigment dispersion. It is an object to provide a coloring composition for a filter and a color filter.

In the pigment dispersion for a color filter, the present inventors have a pigment dispersion having a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B). By using a pigment dispersant having a quaternization ratio within a predetermined range, the aggregation of the pigment can be suppressed, the viscosity is low, the storage stability is high, and a high contrast is obtained when used for a color filter. It has been found that a pigment dispersion for a color filter can be obtained.
That is, the present invention provides the following [1] to [4].
[1] It has a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and the quaternization rate is 10 to 80 mol%. A pigment dispersion for a color filter containing a pigment dispersant, an organic pigment, and an ether organic solvent.
[2] It has a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and the quaternization rate is 10 to 80 mol%. A method for producing a pigment dispersion for a color filter, comprising a step of dispersing a mixture of a pigment dispersant, an organic pigment, and an ether organic solvent.
[3] A coloring composition for a color filter comprising the pigment dispersion of [1] and an alkali-soluble resin which is a copolymer of (meth) acrylic acid ester and (meth) acrylic acid.
[4] A color filter produced using the pigment dispersion according to [1].

According to the present invention, it is possible to form a cured film excellent in contrast, has a low viscosity, and has excellent storage stability, a color filter pigment dispersion, a production method thereof, and a color filter pigment dispersion. A coloring composition for a color filter and a color filter can be provided.

The pigment dispersion for a color filter of the present invention has a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and is quaternized. It contains a pigment dispersant, an organic pigment, and an ether organic solvent having a ratio of 10 to 80 mol%.

The coloring composition for a color filter containing the pigment dispersion for a color filter of the present invention can form a cured film having excellent contrast, has a low viscosity, and is excellent in storage stability. It is considered as follows.
The pigment dispersion for a color filter of the present invention comprises a dialkylaminoalkyl (meth) acrylamide moiety having a dialkylaminoalkyl group and an amide group having a strong adsorptivity to the pigment surface, and an alkoxy poly having affinity for an ether organic solvent. It includes a pigment dispersant having an alkylene glycol (meth) acrylate portion and a quaternary ammonium group having a predetermined quaternization rate and capable of maintaining strong adsorptivity on the pigment surface for a long period of time.
Since the alkoxypolyalkylene glycol group of the pigment dispersant spreads in the solvent, a strong repulsive force is generated between the pigment particles, it is possible to effectively suppress the aggregation of the pigments, and the viscosity of the dispersion can be kept low. It is thought that. On the other hand, since the dialkylaminoalkyl group, the amide group and the quaternary ammonium group have good compatibility with organic pigments and excellent adsorptivity, this pigment dispersant has a high affinity for solvents. It is considered that it is difficult to detach from the pigment surface. For this reason, it is considered that the dispersion stability is maintained even during long-term storage at high temperatures and in the coating (pigment concentration) step, and the storage stability of the dispersion and the contrast of the resulting cured film are excellent.
Hereafter, each component, process, etc. used for this invention are demonstrated.

[Pigment dispersant]
The pigment dispersant used in the present invention is a dialkylaminoalkyl (meth) from the viewpoints of improving the dispersibility of the pigment, keeping the viscosity of the dispersion low, improving the storage stability, and improving the contrast of the resulting cured film. It has a structural unit derived from acrylamide (hereinafter also referred to as “component (A)”) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (hereinafter also referred to as “component (B)”), and is quaternary. It consists of a polymer having a conversion rate of 10 to 80 mol%.

The quaternization rate of the pigment dispersant of the present invention is 10 to 80 mol%. When the quaternization rate of the pigment dispersant is lower than 10 mol%, it is difficult to obtain the effects of lowering viscosity and improving storage stability obtained by quaternization. When it exceeds 80 mol%, the tertiary amino group derived from dialkylaminoalkyl (meth) acrylamide (A) is lost, and the viscosity and storage stability of the pigment dispersion are lowered. The quaternization rate is preferably 15 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 20 to 50 mol%, and more preferably 25 to 40 mol% from the viewpoint of keeping the dispersion low and improving the storage stability. Even more preferred.
Further, the quaternization rate is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more, from the viewpoint of keeping the dispersion viscosity low and enhancing the storage stability. From the viewpoint, it is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, and even more preferably 40 mol% or less.
“Quaternization ratio” means the ratio (mol%) of the number of molar equivalents of quaternary ammonium groups to the total number of molar equivalents of tertiary amino groups and quaternary ammonium groups contained in the pigment dispersant. The quaternization rate can be measured by the method described in the examples.
The pigment dispersant having the quaternization rate can be obtained, for example, by quaternizing the component (A) and introducing a quaternary ammonium group. The component (A), the component (B), and the quaternary ammonium can be obtained. It can also be obtained by copolymerizing a monomer component having a group (hereinafter also referred to as “component (C)”).
When the amine value of the pigment dispersant before quaternization of the pigment dispersant is unknown or when a dispersant copolymerized with a monomer having a quaternized ammonium group is used, nuclear magnetic resonance (NMR) The value calculated from the contents of the tertiary amino group and the quaternary ammonium group identified by (1) is regarded as the quaternization rate.

Weight ratio excluding the component derived from the quaternizing agent of the structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) to the structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B) in the pigment dispersant [( A) / (B)] is preferably 5/95 to 49/51, more preferably 10/90 to 40/60, and more preferably 15/85 to 51/51 to improve the dispersibility of the pigment and enhance the storage stability. 30/65 is more preferable, and 20/80 to 22.5 / 77.5 is still more preferable.
The content of the structural unit derived from (A) in the total of the structural unit derived from (A) and the structural unit derived from (B) [(A) / (A + B) × 100] (quaternary agent-derived component Is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 13% by weight or more, and still more preferably 15% from the viewpoint of atomization of the pigment and improvement of storage stability. From the same viewpoint, it is preferably 49% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 25% by weight or less, and even more preferably 22% by weight. .5% by weight or less.
The “weight ratio excluding the component derived from the quaternizing agent” means a component derived from the quaternizing agent that forms a quaternary ammonium group, that is, an alkyl group derived from the quaternizing agent and a pair of anionic components The converted weight of the structural unit excluding the weight. The alkyl group derived from the quaternizing agent was introduced by quaternization by comparing the alkyl group of the tertiary amino group derived from (A) remaining in the dispersant with the quaternary ammonium group. Alkyl groups can be deduced.
The pigment dispersant used in the present invention may contain a structural unit derived from a monomer other than the component (A) and the component (B) as long as the effects of the present invention are not impaired. And the content of the structural unit derived from the component (B) is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more in the pigment dispersant. More preferably, it is preferably composed only of structural units derived from the component (A) and the component (B).

The weight average molecular weight in terms of polyethylene glycol of the pigment dispersant is preferably 5,000 to 50,000, more preferably 10,000 to 40,000 from the viewpoint of improving the dispersibility of the pigment and enhancing the storage stability. 000, more preferably 10,000 to 20,000, and still more preferably 11,000 to 15,000.
The weight average molecular weight can be measured by the method described in the examples, and the weight average molecular weight before quaternization is regarded as the molecular weight of the present dispersant.

<Dialkylaminoalkyl (meth) acrylamide (A)>
The dialkylaminoalkyl (meth) acrylamide (A) is preferably dimethylaminoalkyl (meth) acrylamide or diethylaminoalkyl (meth) acrylamide, and more preferably dimethylaminoalkyl (meth) acrylamide, from the viewpoint of improving the dispersibility of the pigment. In this specification, (meth) acrylamide means at least one selected from acrylamide and methacrylamide.
As the dimethylaminoalkyl (meth) acrylamide, dimethylaminoalkylacrylamide is preferable from the above viewpoint, and N, N-dimethylaminopropylacrylamide or N, N-dimethylaminoethylacrylamide is preferable. From the viewpoint of adsorptivity, N, N-dimethylaminopropylacrylamide is preferred.

In the present invention, the tertiary amino group of the component (A) is preferably quaternized. When the component (A) is treated with a quaternizing agent to introduce a quaternary ammonium group, the alkyl group introduced into the tertiary amino group is preferably an ethyl group or a methyl group, and more preferably a methyl group. The counter ion of the quaternary ammonium group is preferably one or more selected from alkyl sulfate ions, halogen ions and p-toluenesulfonate ions, more preferably alkyl sulfate ions, and still more preferably methyl sulfate ions.
Specifically, the component (A) is presumed to exist in the polymer in the form of a unit such as a (meth) acryloylaminoalkyltrimethylammonium salt or a (meth) acryloylaminoalkyltriethylammonium salt by quaternization. In this specification, (meth) acryloyl means at least one selected from acryloyl and methacryloyl.
Moreover, the pigment dispersant of this invention may be obtained by copolymerizing the said ammonium salt as a monomer component as (C) component.

The content of the structural unit derived from (A) in all the structural units of the pigment dispersant is preferably 3 to 46% by weight, more preferably 10 to 40% by weight from the viewpoint of improving the dispersibility of the pigment. More preferably 20 to 30% by weight, and still more preferably 20 to 22.5% by weight. In addition, let content in this paragraph be content in the conversion weight which excluded the weight of the component derived from a quaternizing agent.
Further, the content of the structural unit derived from (A) in all the structural units of the pigment dispersant is preferably 3% by weight or more, more preferably 10% by weight from the viewpoint of atomization of the pigment and improvement of storage stability. Or more, more preferably 13% by weight or more, still more preferably 15% by weight or more, and from the same viewpoint, preferably 46% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, Even more preferably, it is at most 25% by weight, even more preferably at most 22.5% by weight.
The content of the constituent unit derived from (A) and not quaternized among all constituent units of the pigment dispersant is preferably 1 to 41% by weight from the viewpoint of improving the dispersibility of the pigment. More preferably, it is 5 to 30% by weight, still more preferably 10 to 20% by weight, and still more preferably 10 to 17% by weight.
The content of the structural unit derived from (A) and not quaternized among all structural units of the pigment dispersant is preferably 1 from the viewpoint of atomization of the pigment and improvement of storage stability. % By weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and from the same viewpoint, preferably 41% by weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less. Even more preferably, it is 17% by weight or less, and still more preferably 13% by weight or less.
The content of the quaternized constituent unit derived from (A) in the total constituent units of the pigment dispersant is preferably 0.3 to 36% by weight from the viewpoint of improving the dispersibility of the pigment. More preferably, it is 3 to 20% by weight, still more preferably 4 to 14% by weight, still more preferably 5 to 8% by weight.
The content of the constituent unit derived from (A) and quaternized among all constituent units of the pigment dispersant is preferably 0 from the viewpoint of atomization of the pigment and improvement of storage stability. 3% by weight or more, more preferably 3% by weight or more, still more preferably 4% by weight or more, still more preferably 5% by weight or more, and from the same viewpoint, preferably 36% by weight or less, more preferably 20% by weight. % By weight or less, more preferably 14% by weight or less, even more preferably 10% by weight or less, and even more preferably 8% by weight or less.

<Alkoxy polyalkylene glycol (meth) acrylate (B)>
In the alkoxypolyalkylene glycol (meth) acrylate (B), the polyalkylene glycol moiety preferably contains a constituent unit derived from propylene oxide, more preferably a constituent unit derived from propylene oxide and a constituent unit derived from ethylene oxide.
The polyalkylene glycol moiety is preferably an adduct of ethylene oxide, propylene oxide, or a mixed adduct of propylene oxide and ethylene oxide, and the polyalkylene glycol moiety has an average alkylene oxide addition mole number of 20 to 200. preferable.
The alkoxy polyalkylene glycol (meth) acrylate may be either an alkoxy polyalkylene glycol methacrylate or an alkoxy polyalkylene glycol acrylate, but an alkoxy polyalkylene glycol methacrylate is preferred. In this specification, (meth) acrylate means at least one selected from acrylate and methacrylate.

When the polyalkylene glycol moiety is a mixed adduct of propylene oxide and ethylene oxide, the weight ratio of the structural unit derived from ethylene oxide to the structural unit derived from propylene oxide of the polyalkylene glycol moiety [(structural unit derived from ethylene oxide) / (propylene The structural unit derived from oxide)] is preferably from 90/10 to 10/90, more preferably from 50/50 to 10/90, and more preferably from 50/50 to 20 from the viewpoint of enhancing the dispersibility of the pigment in the ether organic solvent. / 80 is more preferable, and 40/60 to 25/75 is still more preferable.
Further, the content of the structural unit derived from propylene oxide in the polyalkylene glycol moiety [(structural unit derived from propylene oxide) / (structural unit derived from ethylene oxide + structural unit derived from propylene oxide) × 100] is dispersibility and dispersion stability. From the viewpoint of improving the property and solvent redispersibility, it is preferably at least 10% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight, even more preferably at least 60% by weight. From the viewpoint of ease, it is preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 75% by weight or less.
The polyalkylene glycol moiety may be either a block adduct or a random adduct, but is preferably a block adduct from the viewpoint of enhancing the dispersibility of the pigment in an organic solvent, and the methacrylate side is a structural unit derived from ethylene oxide. More preferably, it is a block adduct whose terminal side is a structural unit derived from propylene oxide.
Such a block adduct can be obtained, for example, by the following method. By using aliphatic alcohol, alkoxypropylene glycol or alkoxydipropylene glycol as a starting material, ring-opening polymerization of propylene oxide in the presence of a base catalyst, followed by further ring-opening polymerization of ethylene oxide in the presence of a base catalyst Polypropylene glycol polyethylene glycol is obtained. Furthermore, the alkoxy polyalkylene glycol (meth) acrylate (B) is obtained by dehydrating the alkoxy polypropylene glycol polyethylene glycol and (meth) acrylic acid.

The alkoxypolyalkylene glycol (meth) acrylate (B) preferably has an average number of moles of alkylene oxide added to the polyalkylene glycol moiety of 20 to 200 from the viewpoint of enhancing the dispersibility of the pigment in an organic solvent. 20 to 150 is more preferable, 20 to 50 is still more preferable, and 30 to 43 is still more preferable.
The alkoxy group of the alkoxypolyalkylene glycol (meth) acrylate (B) preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, from the viewpoint of improving dispersibility and availability of raw materials. Numbers 1 to 6 are more preferable. Examples of the alkoxy group include a methoxy group and an ethoxy group, and a methoxy group is preferable.

By the way, the color filter is manufactured by applying a colored composition prepared using the pigment dispersion to a glass substrate. When the color filter is continuously applied, the colored composition is dried to form a nozzle. Therefore, it is necessary to disperse it again in a solvent and remove it. In addition, with a demand for further miniaturization of pigments, a method of imparting a strong shearing force to the pigment and a method of using a large amount of a dispersant have been performed. However, there are problems such as promotion of fixation of the coloring composition due to aggregation of the pigments due to finer pigments, and deterioration of the dispersibility of the fixed matter in the solvent due to the use of a large amount of dispersant. Accordingly, there is a need for a coloring composition that is excellent in dispersibility and dispersion stability of a pigment dispersion and that is excellent in the solvent redispersibility described above.

The pigment dispersant used in the pigment dispersion of the present invention is excellent in dispersibility, redispersibility and contrast by setting the number of carbon atoms of the alkoxy group of the component (B) of the dispersant to preferably 6 or more and 22 or less. Demonstrate the effect.
The mechanism by which the dispersant having an alkoxy group having the above carbon number further improves the solvent redispersibility is not clear, but is estimated as follows. As described above, the dispersant having polyalkylene glycol is excellent in dispersibility. On the other hand, since the polyalkylene glycol part absorbs moisture by moisture in the air, it also has the property of being easily hydrated and aggregated. However, since the dispersant has the alkoxy group, hydration aggregation due to moisture absorption can also be suppressed. Further, in the coloring composition coating step, the pigment adsorbed by the dispersant having an alkoxy group suppresses aggregation of the pigment because the dispersant is difficult to hydrate and aggregate. Furthermore, generation | occurrence | production of the fixed substance by drying of a coloring composition is suppressed, and the solvent redispersibility of a fixed substance improves. However, these are estimations, and the effect of solvent redispersibility is not limited to these mechanisms.

From the viewpoint of improving the dispersibility and the viewpoint of improving the solvent redispersibility, the number of carbon atoms of the alkoxy group of the component (B) is preferably 6 or more, more preferably 8 or more, and still more preferably 10 or more. From the same viewpoint, it is preferably 22 or less, more preferably 18 or less, and still more preferably 16 or less.
The alkoxy group of the component (B) is preferably an alkyloxy group or an alkenyloxy group from the viewpoint of improving dispersibility and improving the solvent redispersibility, and is a linear or branched alkyloxy group or alkenyloxy group. Is more preferable.
From the same viewpoint, examples of the alkoxy group preferably include an octoxy group, a lauroxy group, a myristoxy group, a stearoxy group, an oleyloxy group, and the like, and a lauroxy group is more preferable.

The content of the structural unit derived from the component (B) in all the structural units of the pigment dispersant is preferably 51 to 95% by weight, more preferably 60 to 90% by weight from the viewpoint of improving dispersibility. More preferably, it is 70 to 80% by weight, and further preferably 75 to 80% by weight.
In addition, the content of the structural unit derived from the component (B) in all the structural units of the pigment dispersant is preferably 51% by weight or more, more preferably 60% by weight, from the viewpoint of atomization of the pigment and improvement of storage stability. % Or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, and from the same viewpoint, preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less. It is. In addition, let the said content be the conversion weight which excluded the weight of the component derived from a quaternizing agent.

<Manufacture of pigment dispersant>
Examples of the pigment dispersant include (Method 1) a method in which a mixture of the components (A), (B) and (C) is copolymerized by a known polymerization method, and (Method 2) a dialkylamino. A method comprising a step of polymerizing alkyl (meth) acrylamide and alkoxy polyalkylene glycol (meth) acrylate to obtain a copolymer, and a step of treating the copolymer with a quaternizing agent to obtain a pigment dispersant. Can be obtained at Among these production methods, (Method 2) is preferable from the viewpoint of obtaining a homogeneous polymer and improving the storage stability and contrast, which are the effects of the present invention.

The component (C) in (Method 1) is preferably a structure obtained by quaternizing the tertiary amino group of the dialkylaminoalkyl (meth) acrylamide unit (A), and the structure before quaternization is It is preferable that they have the same structure.
More specifically, as the component (C), a (meth) acryloylaminoalkyltrialkylammonium salt can be used, but it improves the adsorptivity to the pigment, and thus maintains the viscosity of the resulting dispersion at a low level for storage. From the viewpoint of improving the stability and improving the contrast of the cured film, (meth) acryloylaminoalkyltrimethylammonium salt is preferable, and from the above viewpoint, acryloylaminoalkyltrimethylammonium salt is preferable, acryloylaminopropyltrimethylammonium salt or acryloylamino. Ethyltrimethylammonium salt is more preferable, and acryloylaminopropyltrimethylammonium salt is particularly preferable from the viewpoint of strong adsorptivity to the pigment surface.
The counter ion of the quaternary ammonium group of the ammonium salt is preferably one or more selected from alkyl sulfate ions, halide ions, and p-toluenesulfonate ions, and more preferably alkyl sulfate ions.
The quaternization rate can be adjusted by adjusting the ratio of the component (C) to the component (A) and the component (B).

Hereinafter, (Method 2) will be described in detail.
A solution polymerization method is preferable as a polymerization method when copolymerizing dialkylaminoalkyl (meth) acrylamide and alkoxy polyalkylene glycol (meth) acrylate.
The solvent used in the solution polymerization method is preferably an ether organic solvent used in the present invention described later or an organic solvent having a boiling point of 100 ° C. or lower, and an ether organic solvent is preferable from the viewpoint of enhancing the dispersion stability of the pigment.
As the ether organic solvent, (poly) alkylene glycol monoalkyl ether acetate is preferable, propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol monobutyl ether acetate (BCA) are more preferable, and propylene glycol monomethyl ether acetate (PGMEA) is still more preferable. .
An organic solvent having a boiling point of 100 ° C. or lower is preferably used because it can be easily removed after polymerization. Examples thereof include acetone, methyl ethyl ketone, and ethanol.

In the polymerization, a polymerization initiator or a polymerization chain transfer agent can be used. As the polymerization initiator, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable, and the polymerization chain transfer agent is used. Is preferably 2-mercaptoethanol.
Although preferable polymerization conditions vary depending on the type of polymerization initiator and the like, the polymerization temperature is preferably 50 to 80 ° C., and the polymerization time is preferably 1 to 20 hours. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.

The step of obtaining a pigment dispersant by treating with a quaternizing agent comprises adding a quaternizing agent to the copolymer of dialkylaminoalkyl (meth) acrylamide and alkoxypolyalkylene glycol (meth) acrylate obtained in the above step. Perform by reacting.
The content of the structural unit derived from (A) in all the structural units of the pigment dispersant before quaternization is preferably 5 to 49% by weight, more preferably 10%, from the viewpoint of improving the dispersibility of the pigment. -40% by weight, more preferably 20-30% by weight, and still more preferably 20-22.5% by weight.
The content of the structural unit derived from (A) in all the structural units of the pigment dispersant before quaternization is preferably 5% by weight or more from the viewpoint of atomization of the pigment and improvement of storage stability. Preferably, it is at least 10% by weight, more preferably at least 13% by weight, even more preferably at least 15% by weight. From the same viewpoint, it is preferably at most 49% by weight, more preferably at most 40% by weight, still more preferably. 30 wt% or less, even more preferably 25 wt% or less, and even more preferably 22.5 wt% or less.
As the quaternizing agent, a substance that reacts with a tertiary amino group to convert the amino group to quaternary ammonium is used, and examples thereof include dialkyl sulfate, alkyl halide, and alkyl p-toluenesulfonate. Examples of the dialkyl sulfate include dimethyl sulfate and diethyl sulfate. Examples of the alkyl halide include methyl chloride, methyl iodide, and benzyl chloride. Examples of the p-toluenesulfonate include methyl p-toluenesulfonate, p. -Ethyl toluenesulfonate and the like. Dialkyl sulfate is preferable, dimethyl sulfate and diethyl sulfate are more preferable, and dimethyl sulfate is more preferable.
The step of obtaining the quaternized pigment dispersant is preferably carried out in a solvent, and the solvent preferably used is preferably an ether organic solvent. As the ether organic solvent, (poly) alkylene glycol monoalkyl ether acetate is preferable, propylene glycol monomethyl ether acetate (PGMEA) and diethylene glycol monobutyl ether acetate (BCA) are more preferable, and propylene glycol monomethyl ether acetate (PGMEA) is still more preferable. .
Moreover, it is preferable that the reaction atmosphere in the said process is inert gas atmosphere, such as nitrogen gas atmosphere and argon.
The temperature of the reaction in this step depends on the type of quaternizing agent, but is preferably 50 to 100 ° C., and preferably 80 to 100 ° C. from the viewpoint of promoting the reaction.
The quaternization rate can be adjusted by adjusting the addition molar ratio of the quaternizing agent to the copolymer.

[Organic pigments]
The organic pigment used in the present invention (hereinafter also simply referred to as “pigment”) may be any pigment that can be suitably used for a color filter, and examples thereof include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, lake pigments, and the like. .
As the azo pigment, C.I. I. Insoluble azo pigments such as CI Pigment Red 3; I. Soluble red azo pigments such as CI Pigment Red 48: 1; I. And condensed azo pigments such as CI Pigment Red 144. Examples of the phthalocyanine pigment include C.I. I. And copper phthalocyanine pigments such as CI Pigment Blue 15: 6.
Examples of the condensed polycyclic pigment include C.I. I. Anthraquinone pigments such as CI Pigment Red 177; I. Perylene pigments such as CI Pigment Red 123; I. Perinone pigments such as C.I. Pigment Orange 43; I. Quinacridone pigments such as C.I. Pigment Red 122; I. Dioxazine pigments such as CI Pigment Violet 23, C.I. I. Pigment Yellow 109 and other isoindolinone pigments, C.I. I. Pigment Orange 66 and other isoindoline pigments, C.I. I. Quinophthalone pigments such as CI Pigment Yellow 138; I. Pigment azo complex pigments such as CI Pigment Yellow 150, C.I. I. Indigo pigments such as CI Pigment Red 88; I. Metal complex pigments such as C.I. Pigment Green 8; I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. And diketopyrrolopyrrole pigments such as CI Pigment Orange 71.
Among these, a diketopyrrolopyrrole pigment represented by the following general formula (1) is preferable from the viewpoint of more effectively expressing the effects of the present invention.

In formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Y ¹ and Y ² each independently represent a hydrogen atom or a —SO ₃ H group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom.
Suitable examples of commercially available diketopyrrolopyrrole pigments include BASF Corporation C.I. I. Pigment Red 254, trade names "Irgaphor Red B-CF", "Irgaphor Red BK-CF", "Irgaphor Red BT-CF", "Irgazin DPP Red BO", "Irgazin DPP Red BL", "Cromophtal DPP Red BP" , “Cromophtal DPP Red BOC” and the like.
For the organic pigment, from the viewpoint of improving the brightness Y value, it is desirable to use an atomized product having an average primary particle size of preferably 100 nm or less, more preferably 20 to 60 nm. The average primary particle diameter of the organic pigment can be determined by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the short axis diameter and the long axis diameter of each primary particle are measured, and the average value thereof is defined as the particle diameter of the particle. For 100 or more particles, the volume of each particle is expressed as one side of the particle diameter. The volume average particle diameter is obtained by approximating to the cube as described above, and this is used as the average primary particle diameter.
Said organic pigment can be used individually or in combination of 2 or more types.
In addition, from the viewpoint of increasing the affinity between the organic pigment and the ether organic solvent and enhancing the dispersion stability, a pigment that has been previously surface-treated with a resin, polymer, pigment derivative, or the like is used on the surface of the organic pigment. You can also.

[Ether-based organic solvent]
In the present invention, from the viewpoint of improving the dispersibility of the pigment and the compatibility with the binder component used in the color filter, and achieving both substrate adhesion and developability of the cured film obtained, an ether organic solvent is used. Used.
The viscosity of the ether organic solvent at 25 ° C. is preferably 0.8 to 5.0 mPa · s, and preferably 0.9 to 4.0 mPa · s from the viewpoint of improving the contrast of the cured film using the pigment dispersion. More preferred is 1.0 to 3.5 mPa · s.
From the viewpoint of improving the contrast of the cured film obtained by increasing the SP value of the ether-based organic solvent, the moderate affinity with the pigment surface, low surface tension, compatibility with the binder component used in the color filter, and the like are improved. 0.5 to 10.5 is preferable, 8.0 to 9.5 is more preferable, and 8.5 to 9.0 is still more preferable. The SP value is obtained by the Fedor method.
The boiling point of the ether-based organic solvent is preferably 50 to 300 ° C., more preferably 100 to 260 ° C., and still more preferably 120 to 200 ° C., from the viewpoint of easy removal by coating film drying and work safety.

As ether-based organic solvents, moderate affinity with the pigment surface, ease of removal by drying the coating, low surface tension, increased compatibility with binder components used in color filters, and the resulting cured film From the viewpoint of improving contrast, (poly) alkylene glycol monoalkyl ether acetate, (poly) alkylene glycol monoalkyl ether propionate and (poly) alkylene glycol dialkyl ether are preferred, and (poly) alkylene glycol monoalkyl ether acetate is more preferred. preferable. In this specification, (poly) alkylene glycol means at least one selected from alkylene glycol and polyalkylene glycol.
Examples of (poly) alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate and the like. Among them, from the viewpoint of dispersibility of the organic pigment, propylene glycol monomethyl ether acetate (PGMEA, boiling point: 146 ° C., 25 ° C. Viscosity: 1.1 mPa · s, SP value: 8 73), 3-methoxybutyl acetate (boiling point: 171 ° C., viscosity at 25 ° C .: 1.2 mPa · s, SP value: 8.71), diethylene glycol monobutyl ether acetate (BCA, boiling point: 247 ° C., at 25 ° C.) Viscosity: 3.1 mPa · s, SP value: 8.94) is preferable, and propylene glycol monomethyl ether acetate (PGMEA) is more preferable.
Examples of (poly) alkylene glycol monoalkyl ether propionate include ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, etc. Is mentioned.
Examples of (poly) alkylene glycol dialkyl ethers include dipropylene glycol dimethyl ether and dipropylene glycol methyl propyl ether.

[Copolymer of alkyl (meth) acrylate and (meth) acrylic acid (D)]
The pigment dispersion of the present invention preferably further contains a copolymer (D) of alkyl (meth) acrylate and (meth) acrylic acid from the viewpoint of enhancing the redispersibility of the dried colored composition. The copolymer (D) used in the present invention is preferably a copolymer of alkyl (meth) acrylate and (meth) acrylic acid having an alkyl group having 1 to 3 carbon atoms from the viewpoint of redispersibility. Examples of the alkyl group of the component (D) include a methyl group, an ethyl group, an isopropyl group, and a normal propyl group. Among these, a methyl group is preferable from the viewpoint of improving redispersibility. As the alkyl (meth) acrylate, methyl (meth) acrylate is preferable, and methyl methacrylate is more preferable. As (meth) acrylic acid, methacrylic acid is preferred.

From the viewpoint of improving the redispersibility of the resulting colored composition in the solvent and improving the storage stability of the pigment dispersion, the copolymer (D) is composed of structural units derived from alkyl (meth) acrylate and (meta ) The weight ratio of the structural units derived from acrylic acid [alkyl (meth) acrylate / (meth) acrylic acid] is preferably 95/5 to 70/30, from the viewpoint of improving the redispersibility in the solvent. 95/5 to 80/20, and more preferably 95/5 to 90/10. From the viewpoint of reducing the viscosity, the weight ratio is preferably 95/5 to 80/20, and more preferably 95/5 to 90/10. From the viewpoint of improving the contrast of the resulting cured film, the weight ratio is preferably 95/5 to 70/30.
Further, the weight average molecular weight in terms of polyethylene glycol of the copolymer (D) is preferably 3,000 or more, and preferably 7,000 or more, and preferably 20,000 or less, from the viewpoint of reducing the viscosity. More preferably, it is 17,000 or less from the viewpoint of reducing the viscosity, and more preferably 15,000 or less from the viewpoint of improving the contrast of the resulting cured film.
The molecular weight can be measured by the method described in the examples.

From the viewpoint of enhancing redispersibility, the acid value of the copolymer (D) is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 55 mgKOH / g or more, and preferably 170 mgKOH / g. g or less, more preferably 140 mgKOH / g or less, still more preferably 120 mgKOH / g or less, still more preferably 90 mgKOH / g or less.
An acid value is based on the measuring method based on JISK0070.

[Method for producing pigment dispersion]
The method for producing a pigment dispersion for a color filter of the present invention comprises the following steps from the viewpoint of producing a pigment dispersion for a color filter that forms a cured film with excellent contrast, has a low viscosity, and is excellent in storage stability. It is preferable to contain.
A pigment dispersant having a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B) and having a quaternization rate of 10 to 80 mol% , A step of dispersing a mixture of an organic pigment and an ether organic solvent.
In addition, the said mixture may contain the copolymer (D) of (meth) acrylic acid ester and (meth) acrylic acid.

Further, the method for producing a pigment dispersion for a color filter of the present invention may have a step of producing a pigment dispersant used in the dispersing step. That is, it is preferable to have the process which consists of the method 1 or the method 2 in manufacture of a pigment dispersant, and it is more preferable that the process which consists of the said method 2 is included.

The dispersion method in the dispersion step of the present production method may obtain the desired pigment dispersion by one dispersion of the mixture, but it is finer to further disperse the mixture after preliminary dispersion. And preferable from the viewpoint of obtaining a uniform pigment dispersion.

(Preliminary dispersion)
In the preliminary dispersion, all components of the pigment dispersant, the organic pigment, and the ether organic solvent may be mixed and dispersed at one time, but the pigment dispersant and the ether organic solvent are mixed in advance to prepare a preliminary mixture. Then, it is preferable to mix the pigment into the resulting premix and disperse to obtain the final mixture.
In the preliminary dispersion step, the ratio of the pigment in the pigment dispersion is preferably 3% by weight or more from the viewpoint of obtaining good colorability, and preferably 3 to 30% by weight from the viewpoint of obtaining good colorability and viscosity. 5 to 20% by weight is more preferable.
In the preliminary dispersion step, the content of the pigment dispersant in the pigment dispersion is preferably 2 to 15% by weight, more preferably 3 to 9% by weight from the viewpoint of obtaining a cured film excellent in substrate adhesion and developability. .
In the preliminary dispersion step, the weight ratio of the pigment dispersant to the pigment [pigment dispersant / pigment] causes the pigment dispersant to adhere to the pigment in the required amount, and thus improves the contrast of the resulting cured film, thereby improving the substrate adhesion and development. From the viewpoint of improving the property, it is 0.1 to 1.6, preferably 0.2 to 1.2, and more preferably 0.3 to 0.8.
In the preliminary dispersion step, the content of the ether organic solvent is preferably 20 to 95% by weight and more preferably 40 to 90% by weight from the viewpoint of uniform dispersion.
The dispersion time in the preliminary dispersion step is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, and further preferably 1 to 4 hours.

Various known dispersers can be used as the mixing disperser used in the preliminary dispersion. Examples thereof include high-speed stirring and mixing devices such as homomixers, kneaders such as roll mills, kneaders and extruders, high-pressure dispersers such as high-pressure homogenizers, media-type dispersers such as paint shakers and bead mills. These devices can be used in combination.
Among these, from the viewpoint of uniformly mixing the organic pigment in the ether organic solvent, a high-speed stirring and mixing apparatus such as a homomixer, and a media type dispersing machine such as a paint shaker or a bead mill are more preferable.
In the case of using a media type disperser, the material of the media used in the preliminary dispersion step is preferably a ceramic material such as zirconia or titania, a polymer material such as polyethylene or nylon, a metal, or the like, and zirconia is preferable from the viewpoint of wear. The diameter of the media is preferably 0.1 to 0.5 mm, more preferably 0.1 to 0.4 mm, from the viewpoint of crushing the aggregated particles in the organic pigment.

(Distributed)
This dispersion is a step of dispersing the preliminary dispersion obtained in the preliminary dispersion, and is performed to further refine the mixture obtained in the preliminary dispersion step. From the viewpoint of miniaturizing the organic pigment, It is preferable to use a media-type disperser, and the above-described high-pressure disperser may be used in combination.
As the material of the media used in this dispersion step, ceramics such as zirconia and titania, polymer materials such as polyethylene and nylon, metals and the like are preferable, and zirconia is preferable from the viewpoint of wear. Further, the diameter of the medium is preferably 0.15 mm or less, more preferably 0.1 mm or less, further preferably 0.07 mm or less from the viewpoint of making the organic pigment finer, and from the viewpoint of separating the media from the pigment, 0. 0.003 mm or more is more preferable, and 0.01 mm or more is even more preferable.
From the above viewpoint, the media diameter used in this dispersion step is preferably 0.003 to 0.1 mm, and more preferably 0.01 to 0.07 mm.
As described above, it is preferable that the present dispersion step is dispersed using a medium smaller than the preliminary dispersion step.
That is, in the present invention, the step of dispersing the mixture preferably includes a preliminary dispersion step of dispersing using a medium and a main dispersion step of dispersing using a medium smaller than the preliminary dispersion step.
As the media type disperser used in this dispersion step, a paint shaker, a bead mill or the like is preferable. As a commercially available media type disperser, Ultra Apex Mill (trade name, manufactured by Kotobuki Industries Co., Ltd.), Pico Mill (Asada Tekko Co., Ltd.) Company name, product name) and the like.
From the viewpoint of the storage stability of the resulting pigment dispersion, the temperature during dispersion is preferably maintained at 10 to 35 ° C, more preferably 15 to 30 ° C, and even more preferably 18 to 27 ° C.
The dispersion time of this dispersion is preferably 2 to 200 hours, more preferably 3 to 50 hours, from the viewpoint of sufficiently miniaturizing the organic pigment.

In this dispersion step, the ratio of the organic pigment in the pigment dispersion, the content of the pigment dispersant in the pigment dispersion, the weight ratio of the pigment dispersant to the pigment [pigment dispersant / pigment], the content of the ether organic solvent Is the same as in the preliminary dispersion step.

[Pigment dispersion for color filter]
The pigment dispersion for a color filter obtained by the production method of the present invention contains the pigment dispersant, an organic pigment, and an ether organic solvent.
The content of the organic pigment in the pigment dispersion is preferably 3% by weight or more from the viewpoint of obtaining good colorability, and preferably 3 to 30% by weight from the viewpoint of obtaining good colorability and viscosity. Weight percent is more preferred.
The weight ratio of the pigment dispersant to the pigment in the pigment dispersion [pigment dispersant / pigment] is preferably 0.2 to 1.5, more preferably 0.3 to 1.2, from the viewpoint of improving contrast. 0.4 to 1.0 is more preferable, and 0.5 to 1.0 is even more preferable from the viewpoint of storage stability.
The content of the ether-based organic solvent in the pigment dispersion is preferably 20 to 95% by weight, more preferably 40 to 90% by weight, from the viewpoint of good colorability and low viscosity of the dispersion.

The average particle diameter of the organic pigment in the pigment dispersion is preferably 200 nm or less, more preferably 20 to 100 nm, still more preferably 20 to 90 nm, and further preferably 20 to 70 nm in order to obtain good contrast as a color material for a color filter. Even more preferred is 20-60 nm.
The average particle size is measured using a particle size measuring device (trade name: SZ-100, manufactured by Horiba, Ltd.). For example, in the case of a diketopyrrolopyrrole pigment, the pigment particle refractive index is 1. 51, Pigment density: 1.45 g / cm ³ , PGMEA refractive index: 1.400, PGMEA viscosity: 1.136 mPa · s, Measurement temperature: 25 ° C.
The viscosity (20 ° C.) at a pigment concentration of 10% by weight of the pigment dispersion obtained by the production method of the present invention is preferably 1 to 200 mPa · s in order to obtain a favorable viscosity as a color material for a color filter. · S is more preferable, and 2 to 10 mPa · s is more preferable. Among these, from the viewpoint of improving the substrate adhesion of the cured film, 3 to 5.7 mPa · s is preferable. The viscosity is measured by the method described in the examples.

[Coloring composition for color filter]
The coloring composition for a color filter of the present invention contains a pigment dispersion for a color filter obtained by the above production method, but contains a binder component in addition to the polymer, the organic pigment and the ether organic solvent that are the pigment dispersant. can do.
Examples of the binder component include a binder component containing an ionizing radiation curable component.
The binder component containing an ionizing radiation curable component contains an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator activated by ionizing radiation, and further a polyfunctional oligomer, a monofunctional monomer, a sensitizer, etc. Can be blended.
The content of the binder component in the colored composition comprising the ionizing radiation curable component is preferably 20 to 80% by weight, more preferably 30 to 70% by weight in the effective component excluding the solvent, and the photopolymerization initiator The content is preferably 0.2 to 20% by weight in the effective component excluding the solvent.

As the alkali-soluble resin, those generally used for negative resists can be used. Resins having solubility in an alkaline aqueous solution, that is, 1 wt.% At 20 ° C. in a 0.05 wt% tetramethylammonium hydroxide aqueous solution. % Or more of the resin is preferred.
Examples of the alkali-soluble resin preferably include a copolymer of (meth) acrylic acid ester and (meth) acrylic acid from the viewpoint of maintaining the dispersion of the pigment in the cured film and improving the contrast. A copolymer of alkyl acrylate or benzyl (meth) acrylate and (meth) acrylic acid is more preferred, and a copolymer of benzyl (meth) acrylate and (meth) acrylic acid is more preferred. The copolymerization ratio (molar ratio) of (meth) acrylic acid ester and (meth) acrylic acid is preferably 97/3 to 50/50, and more preferably 95/5 to 70/30.
The weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 50,000.
The content of the alkali-soluble resin is preferably 20 to 80% by weight and more preferably 15 to 50% by weight in the effective amount excluding the solvent in the color filter coloring composition.

As polyfunctional monomer, (meth) acrylic acid ester (for example, dipentaerythritol hexaacrylate) having two or more ethylenically unsaturated double bonds, urethane (meth) acrylate, (meth) acrylic acid amide, allyl compound And vinyl esters. The content of the polyfunctional monomer is preferably 1 to 60% by weight in the effective component excluding the solvent in the color filter coloring composition. Further, the content of the polyfunctional monomer is preferably 1% by weight or more, more preferably 2% by weight or more, and further preferably 5% by weight or more, in an effective amount excluding the solvent in the color filter coloring composition. Moreover, 60 weight% or less is preferable and 30 weight% or less is more preferable.
Examples of the photopolymerization initiator include aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens and the like. For example, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 4- [pN, N-di (ethoxycarbonylmethyl) -2, 6-di (trichloromethyl) -s-triazine], 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone is preferred.
The above-mentioned alkali-soluble resins, polyfunctional monomers, photopolymerization initiators, polyfunctional oligomers, monofunctional monomers, additives such as sensitizers, and the like can be used alone or in combination of two or more. .

The coloring composition of the present invention is used for producing a color filter.
A method for producing a color filter includes a step (a) of applying the colored composition of the present invention on a substrate, drying, photocuring, and developing to obtain a coating film, and a coating film obtained in the step (a) 200. And a step (b) of obtaining a cured film by heating to ~ 300 ° C.
After the application, it is preferable to dry the organic solvent and to heat or reduce the pressure from the viewpoint of the smoothness and productivity of the coating film.
In the photocuring, for example, the coating film is irradiated with ultraviolet rays, and the polyfunctional monomer in the colored composition undergoes a crosslinking reaction to cure the coating film. Photocuring is performed to leave a pattern on the glass substrate in the subsequent development, and it is preferable not to cure the portion removed by development by placing a photomask for preventing ultraviolet rays.
In the above development, for example, the photocured cured coating film is immersed in an alkaline aqueous solution and further rinsed with water to remove uncured portions.
Step (b) is a post-baking step, and by performing this step, a cured film having excellent hardness can be formed.

As described above, in this specification, the following color dispersion for a color filter, a method for producing the same, a coloring composition for a color filter containing the pigment dispersion for a color filter, and a color filter are disclosed.
<1> A structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and a quaternization rate of 10 to 80 mol%. A pigment dispersion for a color filter containing a pigment dispersant, an organic pigment, and an ether organic solvent.

<2> The quaternization rate is preferably 15 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 20 to 50 mol%, still more preferably 25 to 40 mol%, and preferably 15 mol% or more. Preferably it is 20 mol% or more, more preferably 25 mol% or more, preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 40 mol% or less, <1> The pigment dispersion for color filters described in 1.
<3> Weight ratio [(A) / (B)] excluding the component derived from the quaternizing agent of the component (A) of the structural unit derived from (A) to the structural unit derived from (B) in the pigment dispersant. Is preferably 5/95 to 49/51, more preferably 10/90 to 40/60, still more preferably 15/85 to 30/65, and still more preferably 20/80 to 22.5 / 77.5. The pigment dispersion for color filters according to <1> or <2>.
<4> The content of the structural unit derived from the component (A) and the component (B) of the pigment dispersant is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably in the pigment dispersant. The pigment dispersion for a color filter according to any one of <1> to <3>, which is 90% by weight or more.
<5> The pigment dispersion for a color filter according to any one of <1> to <4>, wherein the pigment dispersant preferably comprises only structural units derived from the components (A) and (B).
<6> The weight average molecular weight in terms of polyethylene glycol of the pigment dispersant is preferably 5,000 to 50,000, more preferably 10,000 to 40,000, still more preferably 10,000 to 20,000, and still more. The pigment dispersion for a color filter according to any one of <1> to <5>, preferably 11,000 to 15,000.

<7> The pigment dispersion for a color filter according to any one of <1> to <6>, wherein (A) is preferably N, N-dimethylaminoalkylacrylamide.
<8> The pigment dispersion for a color filter according to any one of <1> to <7>, wherein the pigment dispersant preferably has a quaternary ammonium group, and a counter ion thereof is an alkyl sulfate ion.
<9> The content of the structural unit derived from (A) in all the structural units of the pigment dispersant is a converted weight excluding the weight of the component derived from the quaternizing agent, preferably 3 to 46% by weight, more preferably The pigment dispersion for color filters according to any one of <1> to <8>, wherein is 10 to 40% by weight, more preferably 20 to 30% by weight, and still more preferably 20 to 22.5% by weight.
<10> Of all the structural units of the pigment dispersant, the content of the structural unit derived from (A) and not quaternized is a converted weight excluding the weight of the component derived from the quaternizing agent, Preferably, it is 1 to 41% by weight, more preferably 5 to 30% by weight, still more preferably 10 to 20% by weight, still more preferably 10 to 17% by weight, and any one of <1> to <9> Pigment dispersion for color filters.
<11> Of all the structural units of the pigment dispersant, the content of the quaternized constituent unit derived from (A) is a converted weight excluding the weight of the component derived from the quaternizing agent, Preferably it is 0.3 to 36% by weight, more preferably 3 to 20% by weight, still more preferably 4 to 14% by weight, still more preferably 5 to 8% by weight, and any one of <1> to <10> The pigment dispersion for a color filter as described.

<12> The polyalkylene glycol moiety of (B) preferably includes a structural unit derived from propylene oxide, more preferably includes a structural unit derived from propylene oxide and a structural unit derived from ethylene oxide. The pigment dispersion for a color filter according to any one of the above.
<13> The polyalkylene glycol part of (B) preferably contains a structural unit derived from ethylene oxide and a structural unit derived from propylene oxide, and the weight ratio of the structural unit derived from ethylene oxide and the structural unit derived from propylene oxide [(ethylene oxide The structural unit derived from) / (the structural unit derived from propylene oxide)] is preferably 90/10 to 10/90, more preferably 50/50 to 10/90, still more preferably 50/50 to 20/80, and more. The pigment dispersion for color filters according to any one of <1> to <12>, more preferably 40/60 to 25/75.
<14> The pigment dispersion for a color filter according to any one of <1> to <13>, wherein the polyalkylene glycol moiety of (B) is preferably a block adduct.
<15> The polyalkylene glycol moiety of (B) is preferably a block adduct in which the (meth) acrylate side is a structural unit derived from ethylene oxide, and preferably the terminal side is a structural unit derived from propylene oxide. <14> The pigment dispersion for a color filter according to any one of the above.
<16> The average alkylene oxide addition mole number of the polyalkylene glycol moiety of (B) is preferably 20 to 200, more preferably 20 to 150, still more preferably 20 to 50, and still more preferably 30 to 43. <1> to <15> The color filter pigment dispersion according to any one of <15>.
<17> The alkoxy group in (B) is preferably any one of <1> to <16>, preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms. The pigment dispersion for a color filter as described.
<18> The pigment dispersion for a color filter according to any one of <1> to <17>, wherein the alkoxy group of (B) is preferably one or more selected from a methoxy group and an ethoxy group.
<19> The content of the structural unit derived from the component (B) in all the structural units of the pigment dispersant is a converted weight excluding the weight of the component derived from the quaternizing agent, preferably 51 to 95% by weight, The colorant pigment dispersion according to any one of <1> to <18>, preferably 60 to 90% by weight, more preferably 70 to 80% by weight, and still more preferably 75 to 80% by weight.

<20> (B) is preferably a step of polymerizing dialkylaminoalkyl (meth) acrylamide and alkoxypolyalkylene glycol (meth) acrylate to obtain a copolymer, and treating the copolymer with a quaternizing agent. The pigment dispersion for a color filter according to any one of <1> to <19>, which is obtained by a method comprising a step of obtaining a pigment dispersant.
<21> The content of the structural unit derived from (A) in the total structural units of the pigment dispersant before quaternization is preferably 5 to 49% by weight, more preferably 10 to 40% by weight, and still more preferably 20%. The pigment dispersion for a color filter according to <20>, which is ˜30% by weight, more preferably 20 to 22.5% by weight.
<22> The pigment for a color filter according to <20> or <21>, wherein the quaternizing agent is preferably one or more selected from dialkyl sulfate, alkyl halide, and alkyl p-toluenesulfonate. Dispersion.

〔式（１）中、Ｘ¹及びＸ²は、それぞれ独立して、水素原子又はハロゲン原子を示し、Ｙ¹及びＹ²は、それぞれ独立して、水素原子又は－ＳＯ₃Ｈ基を示す。なお、ハロゲン原子はフッ素原子、塩素原子が好ましい。〕
＜２５＞　エーテル系有機溶媒が、好ましくはプロピレングリコールモノメチルエーテルアセテートである、＜１＞～＜２４＞のいずれかに記載のカラーフィルター用顔料分散体。 <23> The pigment dispersion for a color filter according to any one of <1> to <22>, wherein the organic pigment is preferably a diketopyrrolopyrrole pigment.
<24> The pigment dispersion for a color filter according to any one of <1> to <23>, wherein the organic pigment is preferably a diketopyrrolopyrrole pigment represented by the following general formula (1).

[In Formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Y ¹ and Y ² each independently represent a hydrogen atom or a —SO ₃ H group. The halogen atom is preferably a fluorine atom or a chlorine atom. ]
<25> The pigment dispersion for a color filter according to any one of <1> to <24>, wherein the ether organic solvent is preferably propylene glycol monomethyl ether acetate.

<26> The content of the organic pigment in the pigment dispersion for a color filter is preferably 3% by weight or more, more preferably 3 to 30% by weight, still more preferably 5 to 20% by weight, <1> to <25> The pigment dispersion for a color filter according to any one of 25>.
<27> The weight ratio of the pigment dispersant to the pigment [pigment dispersant / pigment] is preferably 0.2 to 1.5, more preferably 0.3 to 1.2, and still more preferably 0.4 to 1. The pigment dispersion for color filters according to any one of <1> to <26>, which is 0, still more preferably 0.5 to 1.0.
<28> The content of the ether organic solvent in the pigment dispersion for a color filter is preferably 20 to 95% by weight, more preferably 40 to 90% by weight, and any one of <1> to <27> The pigment dispersion for a color filter as described.
<29> The average particle size of the organic pigment in the pigment dispersion for the color filter is preferably 200 nm or less, more preferably 20 to 100 nm, still more preferably 20 to 90 nm, still more preferably 20 to 70 nm, and still more preferably. The pigment dispersion for a color filter according to any one of <1> to <28>, which is 20 to 60 nm.
<30> The viscosity (20 ° C.) of the pigment dispersion for a color filter at a pigment concentration of 10% by weight is preferably 1 to 200 mPa · s, more preferably 1 to 50 mPa · s, still more preferably 2 to 10 mPa · s, preferably The pigment dispersion for color filters according to any one of <1> to <29>, wherein is 3 to 5.7 mPa · s.

<31> The number of carbon atoms of the alkoxy group of (B) is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 22 or less, more preferably 18 or less, still more preferably 16 The pigment dispersion for a color filter according to any one of <1> to <30>, wherein:
<32> The alkoxy group in (B) is preferably an alkyloxy group or alkenyloxy group, more preferably a linear or branched alkyloxy group or alkenyloxy group, and any one of <1> to <31> The pigment dispersion for a color filter as described.
<33> The content of the structural unit derived from the component (B) in all the structural units of the pigment dispersant is a converted weight excluding the weight of the component derived from the quaternizing agent, preferably 51% by weight or more. Preferably it is 60% by weight or more, more preferably 70% by weight or more, still more preferably 75% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less. The pigment dispersion for a color filter according to any one of <1> to <32>, wherein
<34> Content of the structural unit derived from (A) in the total of the structural unit derived from (A) and the structural unit derived from (B) in the pigment dispersant [(A) / (A + B) × 100] (Weight ratio excluding quaternizing agent-derived component) is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 13% by weight or more, and even more preferably 15% by weight or more. , Preferably 49% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight or less, even more preferably 25% by weight or less, and even more preferably 22.5% by weight or less, <1> The pigment dispersion for a color filter according to any one of to <33>.
<35> The content of the structural unit derived from (A) in all structural units of the pigment dispersant is preferably 3% by weight or more, more preferably 10% by weight or more, still more preferably 13% by weight or more, and even more preferably. Is not less than 15% by weight, preferably not more than 46% by weight, more preferably not more than 40% by weight, still more preferably not more than 30% by weight, still more preferably not more than 25% by weight, still more preferably 22.5%. The pigment dispersion for a color filter according to any one of <1> to <34>, which is not more than% by weight.
<36> The content of the constituent unit derived from (A) and not quaternized among all the constituent units of the pigment dispersant is preferably 1% by weight or more, more preferably 5% by weight or more, and further Preferably, it is 10% by weight or more, preferably 41% by weight or less, more preferably 30% by weight or less, still more preferably 20% by weight or less, still more preferably 17% by weight or less, and even more preferably 13% by weight. % Or less of the pigment dispersion for color filters according to any one of <1> to <35>.
<37> The content of the constituent unit derived from (A) and quaternized among all the constituent units of the pigment dispersant is preferably 0.3% by weight or more, more preferably 3% by weight or more. More preferably 4% by weight or more, still more preferably 5% by weight or more, and preferably 36% by weight or less, more preferably 20% by weight or less, still more preferably 14% by weight or less, and even more preferably 10% by weight. The pigment dispersion for a color filter according to any one of <1> to <36>, which is not more than% by weight, more preferably not more than 8% by weight.
<38> The content of the structural unit derived from propylene oxide in the polyalkylene glycol part of (B) [(the structural unit derived from propylene oxide) / (the structural unit derived from ethylene oxide + the structural unit derived from propylene oxide) × 100] Preferably it is 10% by weight or more, more preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, and preferably 90% by weight or less, more preferably 80% by weight or less. More preferably, the pigment dispersion for a color filter according to any one of <1> to <37>, which is 75% by weight or less.

<39> Preferably an alkyl (meth) acrylate and a copolymer (D) of (meth) acrylic acid, more preferably an alkyl (meth) acrylate and (meth) acryl having an alkyl group having 1 to 3 carbon atoms. The pigment dispersion for a color filter according to any one of <1> to <38>, further comprising an acid copolymer (D).
<40> The weight ratio of the structural unit derived from alkyl (meth) acrylate and the structural unit derived from (meth) acrylic acid in the copolymer (D) [(meth) alkyl acrylate / (meth) acrylic acid] is preferable. The pigment dispersion for color filters according to <39>, wherein is 95/5 to 70/30, more preferably 95/5 to 80/20, and more preferably 95/5 to 90/10.
<41> The weight average molecular weight of the copolymer (D) in terms of polyethylene glycol is preferably 3,000 or more, preferably 7,000 or more, and preferably 20,000 or less, more preferably 17,000. Hereinafter, the pigment dispersion for a color filter according to <39> or <40>, which is more preferably 15,000 or less.
<42> The acid value of the copolymer (D) is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 55 mgKOH / g or more, and preferably 170 mgKOH / g or less, more preferably. The pigment dispersion for color filters according to any one of <39> to <41>, wherein is 140 mgKOH / g or less, more preferably 120 mgKOH / g or less, and still more preferably 90 mgKOH / g or less.

<43> A structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B), and a quaternization rate of 10 to 80 mol%. A method for producing a pigment dispersion for a color filter, comprising a step of dispersing a mixture of a pigment dispersant, an organic pigment, and an ether organic solvent.
<44> Preferably, a step of obtaining a copolymer by polymerizing dialkylaminoalkyl (meth) acrylamide and alkoxypolyalkylene glycol (meth) acrylate, and treating the copolymer with a quaternizing agent to disperse the copolymer. A method for producing a pigment dispersion for a color filter according to <43>, further comprising a step of obtaining a pigment dispersant used in the step.
<45> The step of dispersing the mixture preferably includes a preliminary dispersion step of dispersing using a medium and a main dispersion step of dispersing using a medium smaller than the preliminary dispersion step, in <43> or <44> The manufacturing method of the pigment dispersion for color filters of description.
<46> The method for producing a pigment dispersion for a color filter according to <45>, wherein the diameter of the medium in the preliminary dispersion step is preferably 0.1 to 0.5 mm, more preferably 0.1 to 0.4 mm. .
<47> The diameter of the medium in the dispersion step is preferably 0.15 mm or less, more preferably 0.003 to 0.1 mm, and still more preferably 0.01 to 0.07 mm, <45> or <46> The manufacturing method of the pigment dispersion for color filters as described in any one of.

<48> A color comprising the pigment dispersion according to any one of <1> to <42> and an alkali-soluble resin which is preferably a copolymer of (meth) acrylic acid ester and (meth) acrylic acid Coloring composition for filters.
<49> The colored composition for a color filter according to <48>, wherein the alkali-soluble resin is preferably other than the copolymer (D).
<50> The colored composition for a color filter according to <48> or <49>, preferably further comprising a polyfunctional monomer and a photopolymerization initiator activated by ionizing radiation.
<51> The content of the alkali-soluble resin is preferably 20 to 80% by weight, preferably 15 to 50% by weight, in the effective amount excluding the solvent in the color filter coloring composition, <48> to <50> The coloring composition for a color filter according to any one of 50>.
<52> The content of the polyfunctional monomer is preferably 1 to 60% by weight, preferably 1% by weight or more, more preferably 2% by weight, in an effective amount excluding the solvent in the color filter coloring composition. The color filter coloring according to any one of <48> to <51>, more preferably 5% by weight or more, preferably 60% by weight or less, more preferably 30% by weight or less. Composition.
<53> Any one of <48> to <52>, wherein the content of the photopolymerization initiator is preferably 0.2 to 20% by weight in an effective amount excluding the solvent in the color filter coloring composition. The coloring composition for color filters as described in 2.
<54> Use of the pigment dispersion according to any one of <1> to <42> for the production of a color filter.
<55> Use of the colored composition according to any one of <48> to <53> for the production of a color filter.
<56> A color filter produced using the pigment dispersion according to any one of <1> to <42>.
<57> A step (a) in which the colored composition according to any one of <48> to <53> is applied on a substrate, dried, photocured, and developed to obtain a coating film, and the step (a). A method for producing a color filter, comprising the step (b) of obtaining a cured film by heating the obtained coating film to 200 to 300 ° C.

In the following production examples, examples and comparative examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified. X in the notation “alkylene glycol (X)” means the average number of moles of alkylene oxide added to the alkylene glycol. The molecular weight, solid content, quaternization rate, pigment dispersion viscosity, storage stability, average particle size, and contrast ratio of the pigment dispersant were evaluated by the following methods.

(1) Measurement of weight average molecular weight of pigment dispersant The weight average molecular weight of the pigment dispersant was measured under any of the following conditions. In addition, all the weight average molecular weights of a pigment dispersant show the value measured in the state before quaternization.
<Condition 1>
Using a solution obtained by dissolving lithium bromide and acetic acid in ethanol / water (weight ratio 3/7) so as to have a concentration of 50 mmol / L and 1% by weight, respectively, gel chromatography [GPC apparatus manufactured by Tosoh Corporation] (HLC-8320GPC), detector: differential refractometer (attached to the device), Tosoh Corporation column (TSK-GEL, α-M × 2), flow rate: 0.6 mL / min], polyethylene glycol as standard substance It measured using.
<Condition 2>
Using a solution obtained by dissolving lithium bromide and acetic acid in ethanol / water (weight ratio 8/2) so as to have a concentration of 50 mmol / L and 1% by weight, respectively, gel chromatography [GPC apparatus manufactured by Tosoh Corporation] (HLC-8320GPC), detector: differential refractometer (attached to the device), Tosoh Corporation column (TSK-GEL, α-M × 2), flow rate: 0.6 mL / min], polyethylene glycol as standard substance It measured using.

(2) Measurement of Solid Content of Pigment Dispersant Weigh 10 parts of glass rod and dry anhydrous sodium sulfate in a petri dish, add 2 parts (sample amount) of pigment dispersant solution and mix with glass rod, It dried for 2 hours with the vacuum dryer (pressure 8kPa). The weight after drying was measured, and the solid content was calculated from the following formula.
Solid content = [(weight after drying) − (weight of petri dish + glass rod + anhydrous sodium sulfate)] / (sample amount) × 100

(3) Calculation method of quaternization rate The quaternization rate was calculated from the following formula using the amine value obtained from potentiometric titration with an alcoholic hydrochloric acid standard solution according to ASTM D 2073 measurement method.
Quaternization ratio [mol%] = {(Amine value of pigment dispersant before quaternization−Amine value of pigment dispersant after quaternization) / Amine value of pigment dispersant before quaternization} × 100

(4) Measurement of viscosity of pigment dispersion After holding 1 mL of pigment dispersion adjusted to a pigment concentration of 10% for 5 minutes at 20 ° C., an E-type viscometer (TV-25 typeL, manufactured by Toki Sangyo Co., Ltd.) The viscosity of the pigment dispersion was measured at 20 ° C. using a rotor 1 ° 34 ′ × R24). The rotation speed of the rotor was measured at 20 rpm, and when it exceeded 150 mPa · s, it was changed to 10 rpm and measured.

(5) Evaluation of Storage Stability of Pigment Dispersion The pigment dispersion adjusted to 10% as in (4) was filled in a glass sealed container and allowed to stand at 40 ° C. for 7 days. After 1 mL of this dispersion was held at 20 ° C. for 5 minutes, a pigment dispersion was used at 20 ° C. using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-25 type L, rotor 1 ° 34 ′ × R24). The viscosity of was measured. The rotation speed of the rotor was measured at 20 rpm, and when it exceeded 150 mPa · s, it was changed to 10 rpm and measured.

(6) Measurement of Average Particle Diameter of Pigment Dispersion Pigment dispersions obtained in Examples and Comparative Examples were placed in a 20 ml screw tube containing 15 g of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”). 01 g was added, and the mixture was stirred at 2500 rpm for 1 minute using a test tube mixer (manufactured by IKA, trade name: Minishaker MS1). Using a particle size measuring device (trade name: SZ-100, manufactured by HORIBA, Ltd.), the measurement conditions are as follows: particle refractive index of diketopyrrolopyrrole pigment: 1.51, refractive index of PGMEA: 1.400 Viscosity: 1.136 mPa · s, measurement temperature: 25 ° C. was input, and measurement was performed at 25 ° C. The average particle size of cumulant obtained by cumulant analysis based on particle size analysis-photon correlation method (JIS Z 8826) was defined as the average particle size of the pigment dispersion.

(7) Evaluation of contrast (measurement of contrast ratio of cured film)
After applying the coloring composition on the glass substrate with a spin coater, it was allowed to stand for 6 minutes on a horizontal table and dried on a hot plate at 80 ° C. for 3 minutes. Next, the obtained coating film was irradiated with ultraviolet rays up to 60 mJ / cm ² using an ultraviolet fiber spot irradiation device (MUV-202U, manufactured by Moritex Co., Ltd.) and then heated for 90 minutes in a 230 ° C. clean oven. Baking (baking) was performed to prepare a cured film. The contrast ratio of the cured film was measured with a contrast ratio measuring device (CT-1 manufactured by Aisaka Electric Co., Ltd.).
The larger the contrast ratio value, the better the contrast.

(8) Evaluation of solvent redispersibility A glass plate (thickness 0.7 mm, width 5 mm, length 100 mm) was immersed in the colored composition for 1 second to a length of 40 mm, then pulled up, and both sides were traced with a glass rod to remove excess liquid. And then dried in an environment of 23 ° C. and 80% RH for 30 minutes to obtain a dried coating film. The coating film part of this glass plate was immersed in 5 g of PGMEA and rocked for 15 seconds, and then the glass plate was pulled up. Within 5 minutes after pulling up the glass plate, the average particle size of cumulant was measured by the method described in “(6) Measurement of average particle size of pigment dispersion” using PGMEA containing the exfoliated material and dissolved material as a sample solution. Was measured.

Synthesis Example 1 [Synthesis of methoxypolypropylene glycol (10)]
In a 6.0 L autoclave equipped with a stirrer and a temperature controller, 965 g (6.5 mol) of methylpropylene diglycol (manufactured by Nippon Emulsifier Co., Ltd., trade name: MFDG), 38.7 g of 48% potassium hydroxide aqueous solution After charging and replacing the inside of the autoclave with nitrogen, water was removed at 100 ° C. and 4.7 kPa for 1.0 hour. After returning to atmospheric pressure with nitrogen and raising the temperature to 110 ° C., 8920 hours while introducing 2920 g (50.3 mol) of propylene oxide (hereinafter also referred to as “PO”) to a pressure of 0.1 to 0.45 MPa The addition reaction was performed. Thereafter, the mixture was cooled to 60 ° C. to obtain 3901 g of methoxypolypropylene glycol (10).

Synthesis Example 2 [Synthesis of methoxypolypropylene glycol (19)]
The autoclave having a volume of 6.0 L equipped with a stirrer and a temperature controller was charged with 974 g (1.6 mol) of methoxypolypropylene glycol (10) obtained in the same manner as in Synthesis Example 1, and the inside of the autoclave was purged with nitrogen. After raising the temperature to 0 ° C., an addition reaction was carried out for 10 hours while introducing 882 g (15.2 mol) of PO at a pressure of 0.1 to 0.45 MPa. Then, it cooled to 60 degreeC and obtained 1855g of methoxy polypropylene glycol (19).

Synthesis Example 3 [Synthesis of methoxypolypropylene glycol (27)]
16.0 g (1.0 mol) of methoxypolypropylene glycol (19) obtained in the same manner as in Synthesis Example 2 was charged into a 6.0 L volume autoclave equipped with a stirrer and a temperature controller, and the inside of the autoclave was purged with nitrogen. After the temperature was raised to 0 ° C., an addition reaction was carried out for 18 hours while introducing 576 g (9.9 mol) of PO at a pressure of 0.1 to 0.45 MPa. Thereafter, the mixture was cooled to 60 ° C. to obtain 1692 g of methoxypolypropylene glycol (27).

Synthesis Example 4 [Synthesis of Methoxypolypropylene Glycol (10) Polyethylene Glycol (15)]
529 g (0.9 mol) of methoxypolypropylene glycol (10) obtained in the same manner as in Synthesis Example 1 was charged in a 1.5 L autoclave equipped with a stirrer and a temperature controller, and the inside of the autoclave was purged with nitrogen. After the temperature was raised to 0 ° C., an addition reaction was carried out for 2 hours while introducing 570 g (12.9 mol) of ethylene oxide (hereinafter also referred to as “EO”) at a pressure of 0.1 to 0.4 MPa. Thereafter, the mixture was cooled to 60 ° C. to obtain 1095 g of methoxypolypropylene glycol (10) polyethylene glycol (15).

Synthesis Example 5 [Synthesis of methoxypolypropylene glycol (10) polyethylene glycol (29)]
To a 6.0 L autoclave equipped with a stirrer and a temperature controller, 919 g (1.5 mol) of methoxypolypropylene glycol (10) obtained in the same manner as in Synthesis Example 1 was charged. In the same manner as in Synthesis Example 4, except that 570 g of EO of Synthesis Example 4 was changed to 1980 g (45.0 mol) and the reaction time was changed to 3 hours, 2896 g of methoxypolypropylene glycol (10) polyethylene glycol (29) was obtained. .

Synthesis Example 6 [Synthesis of Methoxypolypropylene Glycol (19) Polyethylene Glycol (21)]
650 g (0.6 mol) of methoxypolypropylene glycol (19) obtained in the same manner as in Synthesis Example 2 was charged into a 1.5 L autoclave equipped with a stirrer and a temperature controller. In the same manner as in Synthesis Example 4 except that 570 g of EO of Synthesis Example 4 was changed to 542 g (12.3 mol) and the reaction time was changed to 3 hours, 1188 g of methoxypolypropylene glycol (19) polyethylene glycol (21) was obtained. .

Synthesis Example 7 [Synthesis of Methoxypolypropylene Glycol (27) Polyethylene Glycol (15)]
In a 6.0 L autoclave equipped with a stirrer and a temperature controller, 1510 g (0.9 mol) of methoxypolypropylene glycol (27) obtained in the same manner as in Synthesis Example 3 was charged. 2074 g of methoxypolypropylene glycol (27) polyethylene glycol (15) was obtained in the same manner as in Synthesis Example 4 except that the reaction time in Synthesis Example 4 was changed to 2.5 hours.

Synthesis Example 8 [Synthesis of methoxypolypropylene glycol (10) polyethylene glycol (15) methacrylate]
500 g (0.39) of the methoxypolypropylene glycol (10) polyethylene glycol (15) obtained in Synthesis Example 4 was added to a 1 liter four-necked flask equipped with a stirrer, a thermometer, an air blowing tube, a Dean-Stark tube and a Dimroth tube. Mol), toluene (376 g), p-toluenesulfonic acid monohydrate (22.4 g) and hydroquinone (1.1 g) were charged, the temperature was raised to 50 ° C., and the mixture was stirred at 50 to 60 ° C. for 30 minutes. Thereafter, 40.6 g (0.47 mol) of methacrylic acid was added, and the mixture was reacted at 110 to 120 ° C. for 9 hours while blowing air through a blowing tube. After cooling to 50-60 ° C., the mixture was transferred to a separatory funnel, 5N aqueous sodium hydroxide solution was added, and the mixture was shaken well, and the lower layer produced after standing was separated. Further, 20% by weight sodium chloride aqueous solution was added and shaken well, and the lower layer produced after standing was separated. Further, the operation of adding a 20% by weight aqueous sodium chloride solution and shaking well and separating the lower layer produced after standing was repeated until the pH of the lower layer reached 7-8. To the upper layer, 0.05 g of p-methoxyphenol was added, and toluene was removed at 60 ° C. under reduced pressure to obtain methoxypolypropylene glycol (10) polyethylene glycol (15) methacrylate.

Synthesis Example 9 [Synthesis of methoxypolypropylene glycol (10) polyethylene glycol (29) methacrylate]
In Synthesis Example 8, methoxypolypropylene glycol (10) polyethylene glycol (15) was added to 500 g (0.26 mol) of methoxypolypropylene glycol (10) polyethylene glycol (29) obtained in Synthesis Example 5, and 376 g of toluene was changed to 362 g. p-Toluenesulfonic acid monohydrate was synthesized except that 22.4 g was changed to 15.1 g, hydroquinone 1.1 g to 0.7 g, and methacrylic acid 40.6 g to 27.3 g (0.32 mol). In the same manner as in Example 8, methoxypolypropylene glycol (10) polyethylene glycol (29) methacrylate was obtained.

Synthesis Example 10 [Synthesis of methoxypolypropylene glycol (19) polyethylene glycol (21) methacrylate]
In Synthesis Example 8, methoxypolypropylene glycol (10) polyethylene glycol (15) was added to 500 g (0.24 mol) of methoxypolypropylene glycol (19) polyethylene glycol (21) obtained in Synthesis Example 6, and 376 g of toluene was added to 360 g. -Toluenesulfonic acid monohydrate Synthesis example, except that 22.4 g was changed to 13.8 g, hydroquinone 1.1 g was changed to 0.7 g, and methacrylic acid 40.6 g was changed to 25.1 g (0.29 mol). In the same manner as in No. 8, methoxypolypropylene glycol (19) polyethylene glycol (21) methacrylate was obtained.

Synthesis Example 11 [Synthesis of methoxypolypropylene glycol (27) polyethylene glycol (15) methacrylate]
In Synthesis Example 8, methoxypolypropylene glycol (10) polyethylene glycol (15) was added to 500 g (0.22 mol) of methoxypolypropylene glycol (27) polyethylene glycol (15) obtained in Synthesis Example 7, and 376 g of toluene was added to 357 g. -Toluenesulfonic acid monohydrate Synthesis example, except that 22.4 g was changed to 12.6 g, hydroquinone 1.1 g was changed to 0.6 g, and methacrylic acid 40.6 g was changed to 22.8 g (0.29 mol). In the same manner as in No. 8, methoxypolypropylene glycol (27) polyethylene glycol (15) methacrylate was obtained.

The number of moles of PO / EO added in alkoxypolypropylene glycol polyethylene glycol methacrylate was determined by proton nuclear magnetic resonance ( ¹ H -NMR) spectrum (measurement conditions: non-decoupling method, relaxation time 10 seconds, number of integrations 32 times). The PO addition mole number and the EO addition mole number were calculated by the following equations, respectively.
PO addition mole number = (integral value of signal derived from methyl group of polyoxypropylene) / {(integral value of signal derived from vinylidene group) × 1.5}
EO addition mole number = (integral value of signal derived from methylene group of polyoxyethylene) / {(integral value of signal derived from vinylidene group) × 2}

Production Example 1 [Pigment dispersant (1) (quaternized product of 3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol (45) methacrylate copolymer (23/77 wt%); quaternization rate 27 mol%)
To a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 3- (N, N-dimethylamino) propylacrylamide (trade name: DMAPAA-MHQ, manufactured by Kojin Co., Ltd., hereinafter “DMAPAA” 28 g, methoxypolyethylene glycol (45) methacrylate (trade name: NK ester M-450G, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as “M-450G”) 92 g, 2-mercaptoethanol (Toyobo Co., Ltd.) Manufactured, hereinafter referred to as “ME”) 0.36 g and PGMEA 180 g were added, and the inside of the reaction vessel was stirred and purged with nitrogen. After the temperature in the reaction vessel was increased to 78 ° C. with stirring, a separately prepared monomer solution [DMAPAA 65 g, M-450G 220 g, ME 0.84 g, PGMEA 420 g, 2,2-azobis- (2,4-dimethylvalero) Nitrile) (trade name: V-65B, manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “V-65”) 8.0 g] was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 1.0 g of V-65 in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pre-quaternization pigment dispersant (1). The solid content of the solution was 40.3%, and the weight average molecular weight of the pre-quaternized pigment dispersant (1) was 18400 (measured value under <Condition 1>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 14 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of pigment dispersant (1) (quaternized product of DMAPAA / M-450G copolymer). The solid content of the solution was 38.6%, and the quaternization rate was 27 mol% of DMAPAA before quaternization.

Production Example 2 [Quaternized product of pigment dispersant (2) (3- (N, N-dimethylamino) propylacrylamide / methoxypolypropylene glycol (10) polyethylene glycol (15) methacrylate copolymer (33/67 wt%) Synthesis of quaternization rate of 27 mol%)
In the same reaction vessel as in Production Example 1, DMAPAA 15 g, methoxypolypropylene glycol (10) polyethylene glycol (15) methacrylate (hereinafter referred to as “M-PO (10) EO (15)”) 30 g, ME 0.14 g, PGMEA 68 g was added, and nitrogen substitution was performed while stirring the inside of the reaction vessel.
After the temperature in the reaction vessel was raised to 78 ° C. with stirring, a separately prepared monomer solution [DMAPAA 35 g, M-PO (10) EO (15) 70 g, ME 0.32 g, PGMEA 160 g, V-65 3.0 g ] Was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 4.5 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 4.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (2) before quaternization. The solid content of the solution was 39.3%, and the weight average molecular weight of the pre-quaternized pigment dispersant (2) was 39000 (measured value under <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 18 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (2) (a quaternized product of DMAPAA / M-PO (10) EO (15) copolymer). The solid content of the solution was 37.4%, and the quaternization rate was 27 mol% of DMAPAA before quaternization.

Production Example 3 Quaternized product of pigment dispersant (3) (3- (N, N-dimethylamino) propylacrylamide / methoxypolypropylene glycol (10) polyethylene glycol (29) methacrylate copolymer (11/89 wt%) A quaternization rate of 54 mol%)
In a reaction vessel similar to Production Example 1, 4.8 g of DMAPAA, 40 g of methoxypolypropylene glycol (10) polyethylene glycol (29) methacrylate (hereinafter referred to as “M-PO (10) EO (29)”), and 0.14 g of ME Then, 68 g of PGMEA was added, and nitrogen substitution was performed while stirring the inside of the reaction vessel. After the temperature in the reaction vessel was raised to 78 ° C. with stirring, a separately prepared monomer solution [DMAPAA 11 g, M-PO (10) EO (29) 94 g, ME 0.32 g, PGMEA 160 g, V-65 3.0 g ] Was added dropwise over 3.5 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 4.5 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 4.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (3) before quaternization. The solid content of the solution was 39.3%, and the weight average molecular weight of the pre-quaternization pigment dispersant (3) was 20000 (measured value under <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 13 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped while stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (3) (a quaternized product of DMAPAA / M-PO (10) EO (29) copolymer). The solid content of the solution was 38.3%, and the quaternization rate was 54 mol% of DMAPAA before quaternization.

Production Example 4 [Quaternized product of pigment dispersant (4) (3- (N, N-dimethylamino) propylacrylamide / methoxypolypropylene glycol (10) polyethylene glycol (29) methacrylate copolymer (24/76 wt%) Synthesis of quaternization rate of 26 mol%)
In a reaction vessel similar to Production Example 1, 11 g of DMAPAA, 34 g of M-PO (10) EO (29), 0.41 g of ME, and 68 g of PGMEA were placed, and the atmosphere in the reaction vessel was replaced with nitrogen. After the temperature in the reaction vessel was raised to 78 ° C. with stirring, a separately prepared monomer solution [DMAPAA 25 g, M-PO (10) EO (29) 80 g, ME 0.95 g, PGMEA 160 g, V-65 3.0 g ] Was added dropwise over 3.5 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 4.5 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 4.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pre-quaternization pigment dispersant (4). The solid content of the solution was 39.7%, and the weight average molecular weight of the pre-quaternized pigment dispersant (4) was 19000 (measured value under <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 14 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of pigment dispersant (4) (quaternized product of DMAPAA / M-PO (10) EO (29) copolymer). The solid content of the solution was 38.2%, and the quaternization rate was 26 mol% of DMAPAA before quaternization.

Production Example 5 [Quaternized product of pigment dispersant (5) (3- (N, N-dimethylamino) propylacrylamide / methoxypolypropylene glycol (19) polyethylene glycol (21) methacrylate copolymer (23/77 wt%) Synthesis of quaternization rate of 26 mol%)
In a reaction vessel similar to Production Example 1, DMAPAA 10 g, methoxypolypropylene glycol (19) polyethylene glycol (21) methacrylate (hereinafter referred to as “M-PO (19) EO (21)”) 35 g, ME 0.41 g, PGMEA 68 g was added, and nitrogen substitution was performed while stirring the inside of the reaction vessel.
The temperature inside the reaction vessel was raised to 78 ° C. with stirring, and then separately prepared monomer solution [DMAPAA 24 g, M-PO (19) EO (21) 81 g, ME 0.95 g, PGMEA 160 g, V-65 3.0 g ] Was added dropwise over 3.5 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 4.5 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 4.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (5) before quaternization. The solid content of the solution was 39.7%, and the weight average molecular weight of the pre-quaternization pigment dispersant (5) was 13000 (measured value under <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 14 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (5) (DMAPAA / M-PO (19) EO (21) copolymer quaternized product). The solid content of the solution was 38.6%, and the quaternization rate was 26 mol% of DMAPAA before quaternization.

Production Example 6 [Quaternized product of pigment dispersant (6) (3- (N, N-dimethylamino) propylacrylamide / methoxypolypropylene glycol (27) polyethylene glycol (15) methacrylate copolymer (22/78 wt%) Synthesis of quaternization rate of 26 mol%)
In the same reaction vessel as in Production Example 1, DMAPAA 13 g, methoxypolypropylene glycol (27) polyethylene glycol (15) methacrylate (hereinafter referred to as “M-PO (27) EO (15)”) 47 g, ME 0.54 g, PGMEA 88 g was added and nitrogen substitution was performed while stirring the inside of the reaction vessel. The temperature inside the reaction vessel was raised to 78 ° C. with stirring, and then separately prepared monomer solution [DMAPAA 30 g, M-PO (27) EO (15) 111 g, ME 1.3 g, PGMEA 205 g, V-65 4.0 g ] Was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 4.5 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, another solution of 1.0 g of V-65 dissolved in 4.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (6) before quaternization. The solid content of the solution was 40.8%, and the weight average molecular weight of the pre-quaternization pigment dispersant (6) was 14000 (measured value under <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 14 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (6) (DMAPAA / M-PO (27) EO (15) copolymer quaternized product). The solid content of the solution was 39.3%, and the quaternization rate was 26 mol% of DMAPAA before quaternization.

Production Example 7 [Pigment dispersant (7) (3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol (45) methacrylate copolymer (15/85 wt%); quaternization rate 0 mol%)] Synthesis)
In the same reaction vessel as in Production Example 1, 18 g of DMAPAA, 102 g of M-450G, 0.36 g of ME and 184 g of PGMEA were charged, and nitrogen substitution was performed. While stirring at 80 ° C., a solution in which 42 g of DMAPAA, 238 g of M-450G and 0.84 g of ME were dissolved in 358 g of PGMEA and a solution in which 8.0 g of V-65 was dissolved in 72 g of PGMEA were added dropwise over 3 hours. . After completion of the dropwise addition, a solution obtained by dissolving 1.0 g of V-65 in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution in which 1.0 g of V-65 was dissolved in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, the mixture was cooled and 300.0 g of PGMEA was added to obtain a PGMEA solution of the pigment dispersant (1) (DMAPAA / M-450G copolymer). The solid content of the solution was 29.8%, and the weight average molecular weight of the pigment dispersant (7) was 14200 (measured value according to <Condition 1>).

Production Example 8 [pigment dispersant (8) (quaternized product of 3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol (45) methacrylate copolymer (23/77 wt%); quaternization rate 99 mol%)]
150 g of the pre-quaternized pigment dispersant (1) solution of Production Example 1 was added, and nitrogen substitution was performed. To this, 56 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (8) (DMAPAA / M-450G copolymer quaternized product). The solid content of the solution was 34.8%, and the quaternization rate was 99 mol% of DMAPAA before quaternization.

Production Example 9 [Synthesis of Pigment Dispersant (9) (Dimethylaminoethyl Methacrylate / Methoxypolyethylene Glycol (45) Methacrylate Copolymer (15/85 wt%) Quaternized Product; Quaternization Rate 25 mol%))
A reaction vessel similar to Production Example 1 was charged with 18 g of dimethylaminoethyl methacrylate (hereinafter referred to as “DMAEMA”), 102 g of M-450G, 0.36 g of ME, and 184 g of PGMEA, and was purged with nitrogen. While stirring at 80 ° C., a solution obtained by dissolving DMAEMA 42 g, M-450G 238 g, and ME 0.84 g in PGMEA 358 g and a solution obtained by dissolving V-65 8.0 g in PGMEA 72 g were added dropwise over 3 hours. . After completion of the dropwise addition, a solution prepared by dissolving 1.0 g of V-65 in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution in which 1.0 g of V-65 was dissolved in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, the mixture was cooled to obtain a PGMEA solution of the pre-quaternization pigment dispersant (9). The solid content of the solution was 41.0%, and the weight average molecular weight of the pre-quaternization pigment dispersant (9) was 11000 (measured value according to <Condition 1>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 9 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (9) (a quaternized product of DMAEMA / M-450G copolymer). The solid content of the solution was 39.9%, and the quaternization rate was 25 mol% of DMAEMA before quaternization.

Production Example 10 [Pigment dispersant (10) (3- (N, N-dimethylamino) propylacrylamide / polymethyl methacrylate macromonomer copolymer (15/85 wt%) quaternized product; quaternization rate 99 mol%] )
In the same reaction vessel as in Production Example 1, DMAPAA 18 g, polymethyl methacrylate macromonomer (manufactured by Toagosei Co., Ltd., trade name: Macromonomer AA-6, number average molecular weight 6000 (catalog value). Hereinafter, “AA-6” 102g, ME 0.36g, and PGMEA 184g were charged, and nitrogen substitution was performed. While stirring at 80 ° C., a solution in which 42 g of AA-6, 238 g of M-450G and 0.84 g of ME were dissolved in 358 g of PGMEA, and a solution in which 8.0 g of V-65 was dissolved in 72 g of PGMEA were taken over 3 hours. It was dripped. After completion of the dropwise addition, a solution prepared by dissolving 1.0 g of V-65 in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution in which 1.0 g of V-65 was dissolved in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, the mixture was cooled to obtain a PGMEA solution of the quaternized pigment dispersant (10). The solid content of the solution was 40.0%, and the weight average molecular weight of the pigment dispersant (10) before quaternization was 25700 (measured value according to <Condition 2>). 150 g of the solution was placed in a glass container, and nitrogen substitution was performed. To this, 36 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of pigment dispersant (10) (quaternized product of DMAPAA / AA-6 copolymer). The solid content of the solution was 36.3%, and the quaternization rate was 99 mol% of DMAPAA before quaternization.

Production Example 11 [Pigment dispersant (11) (3- (N, N-dimethylamino) propylacrylamide / methoxypolyethylene glycol (45) methacrylate / polymethyl methacrylate macromonomer copolymer (15/20/65 wt%); Synthesis of quaternization rate 0 mol%)
In the same reaction vessel as in Production Example 1, DMAPAA 18 g, M-450G 24 g, AA-6 78 g, ME 0.36 g, and PGMEA 184 g were charged and purged with nitrogen. While stirring at 80 ° C., a solution prepared by dissolving 42 g of DMAPAA, 56 g of M-450G, 182 g of AA-6, and 0.84 g of ME in 358 g of PGMEA, and a solution obtained by dissolving 8.0 g of V-65 in 72 g of PGMEA, respectively. It was added dropwise over time. After completion of the dropwise addition, a solution prepared by dissolving 1.0 g of V-65 in 10 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution in which 1.0 g of V-65 was dissolved in 10 g of PGMEA was added, and stirring was continued for 1 hour. Then, it cooled and obtained the PGMEA solution of the pigment dispersant (11). The solid content of the solution was 40.0%, and the weight average molecular weight of the pigment dispersant (11) (DMAPAA / M-450G / AA-6 copolymer) was 45000 (measured value under <Condition 2>). .

Example 1 (Preparation of pigment dispersion (1))
119.5 g of PGMEA, 15.5 g of the pigment dispersant (1) solution obtained in Production Example 1 (effective amount 6.0 g), diketopyrrolopyrrole pigment (Clariant Japan Co., Ltd., CI Pigment Red 254) , 15.0 g of the product name “Hostaperm Red D2B-COF LV3781” and 300 g of zirconia beads having a diameter of 0.3 mm are put into a 500 ml plastic container, and stirred for 3 hours in a paint shaker. Obtained.
Next, 100 g of this preliminary dispersion and 200 g of φ0.05 mm zirconia beads were placed in a 250 ml plastic container, stirred for 24 hours with a paint shaker to remove the zirconia beads, and pigment dispersion (1) was obtained.

Examples 2 to 6 and Comparative Examples 1 to 5 (Preparation of pigment dispersions (2) to (6) and comparative pigment dispersions (7) to (11))
In Example 1, the pigment dispersant (1) was replaced with the pigment dispersants (2) to (11), respectively, so that the effective amount was 6.0 g, and the amount of PGMEA in the pigment dispersion was changed to Example 1. Pigment dispersions (2) to (6) and comparative pigment dispersions (7) to (11) were obtained in the same manner as in Example 1 except that the amount was adjusted to be the same as in Example 1.
Table 1 shows the evaluation results of the obtained pigment dispersions (1) to (6) and comparative pigment dispersions (7) to (11).

Example 7 (Preparation of colored composition (1))
1.00 part of pigment dispersion (1) adjusted to a pigment concentration of 10%, benzyl methacrylate / methacrylic acid copolymer (binder, molar ratio: 80/20, weight average molecular weight: 14000, PGMEA having a solid content of 40% by weight Solution) 0.298 parts, dipentaerythritol hexaacrylate (polyfunctional monomer: Nippon Kayaku Co., Ltd., DPHA) 0.036 parts, 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone (light Polymerization initiator: Wako Pure Chemical Industries, Ltd.) 0.027 parts and PGMEA 0.250 parts were mixed with a test tube mixer until uniform to obtain a colored composition (1). Table 1 shows the evaluation results of the obtained colored composition (1).

Examples 8 to 12 and Comparative Examples 6 to 10 (Preparation of colored compositions (2) to (6) and comparative colored compositions (7) to (11))
In Example 7, the colored compositions (2) to (6) and the comparison were made in the same manner as in Example 7, except that the pigment dispersion (1) was changed to the pigment dispersions (2) to (11), respectively. Coloring compositions (7) to (11) were obtained.
Table 1 shows the evaluation results of the obtained colored compositions (2) to (6) and comparative colored compositions (7) to (11).

From Table 1, since the pigment dispersions of Examples 1 to 6 have a smaller average particle size than the pigment dispersions of Comparative Examples 1 to 5, the pigment dispersion is good and the viscosity is low. The coloring compositions of Examples 7 to 12 which are excellent in storage stability and contain the pigment dispersions of Examples 1 to 6 are the coloring compositions of Comparative Examples 6 to 10 containing the pigment dispersions of Comparative Examples 1 to 5. It can be seen that a cured film excellent in contrast can be formed.

Synthesis Example 12 [Synthesis of octyloxypolyethylene glycol (30)]
An autoclave having a volume of 6.0 L equipped with a stirrer and a temperature controller was charged with 350 g (2.69 mol) of 1-octanol (product name: Calcoal 0898) and 6.0 g of 48% potassium hydroxide aqueous solution. After the inside was replaced with nitrogen, water was removed at 100 ° C. and 4.7 kPa for 1.0 hour. After returning to atmospheric pressure with nitrogen and raising the temperature to 140 ° C., an addition reaction was carried out for 6 hours while introducing 3554 g (80.8 mol) of EO at a pressure of 0.1 to 0.45 MPa. Then, it cooled to 60 degreeC and obtained 3900g of octyl oxypolyethylene glycol (30).

Synthesis Example 13 [Synthesis of lauryloxypolypropylene glycol (28) polyethylene glycol (15)]
A 6.0 L autoclave equipped with a stirrer and a temperature controller was charged with 400 g of lauryl alcohol (2.15 mol) and 12.6 g of a 48% aqueous potassium hydroxide solution, and the inside of the autoclave was purged with nitrogen. Water was removed at 7 kPa for 1.0 hour. After returning to atmospheric pressure with nitrogen and raising the temperature to 110 ° C., an addition reaction was carried out for 12 hours while introducing 3490 g (60.2 mol) of PO to a pressure of 0.1 to 0.45 MPa. Thereafter, the mixture was cooled to 60 ° C. to obtain 3850 g of lauryloxypolypropylene glycol (28).
Next, 2800 g of lauryloxypolypropylene glycol (1.67 mol) was charged into a 6.0 L autoclave equipped with a stirrer and a temperature controller, and the autoclave was purged with nitrogen. After the temperature was raised to 140 ° C., EO 1100 g ( The addition reaction was carried out for 4 hours while introducing 25.0 mol) at a pressure of 0.1 to 0.45 MPa. Thereafter, the mixture was cooled to 60 ° C. to obtain 3900 g of lauryloxypolypropylene glycol (28) polyethylene glycol (15).

Synthesis Example 14 [Synthesis of octyloxypolyethylene glycol (30) methacrylate]
500 g (0.34 mol) of octyloxypolyethylene glycol (30) obtained in Synthesis Example 12 was added to a 1 liter four-necked flask equipped with a stirrer, a thermometer, an air blowing tube, a Dean-Stark tube and a Dimroth tube. 360 g, p-toluenesulfonic acid monohydrate 20.0 g, and hydroquinone 1.0 g were charged, the temperature was raised to 50 ° C., and the mixture was stirred at 50 to 60 ° C. for 30 minutes. Thereafter, 36.0 g (0.46 mol) of methacrylic acid was added, and the mixture was reacted at 110 to 120 ° C. for 9 hours while blowing air through a blowing tube. After cooling to 50-60 ° C., the mixture was transferred to a separatory funnel, 5N aqueous sodium hydroxide solution was added, and the mixture was shaken well, and the lower layer produced after standing was separated. Further, 20% by weight sodium chloride aqueous solution was added and shaken well, and the lower layer produced after standing was separated. Further, the operation of adding a 20% by weight aqueous sodium chloride solution and shaking well and separating the lower layer produced after standing was repeated until the pH of the lower layer reached 7-8. 0.05 g of p-methoxyphenol was added to the upper layer, and toluene was removed at 60 ° C. under reduced pressure to obtain octyloxypolyethylene glycol (30) methacrylate.

Synthesis Example 15 [Synthesis of lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate]
In Synthesis Example 14, octyloxypolyethylene glycol (30) was added to 500 g (0.21 mol) of lauryloxypolypropylene glycol (28) polyethylene glycol (15) obtained in Synthesis Example 13 with p-toluenesulfonic acid monohydrate. In the same manner as in Synthesis Example 14, except that 20.0 g of the product was changed to 12.3 g, 1.0 g of hydroquinone to 0.6 g, and 36.0 g of methacrylic acid to 22.5 g (0.29 mol), lauryl was obtained. Oxypolypropylene glycol (28) polyethylene glycol (15) methacrylate was obtained.

Synthesis Example 16 [Synthesis of oleyloxypolyethylene glycol (30) methacrylate]
In Synthesis Example 14, octyloxypolyethylene glycol (30) was added to oleyloxypolyethylene glycol (30) (trade name: Emulgen 430, manufactured by Kao Corporation) with 500 g (0.32 mol) of p-toluenesulfonic acid monohydrate. In the same manner as in Synthesis Example 14, except that 20.0 g of the product was changed to 18.0 g, 1.0 g of hydroquinone was changed to 0.9 g, and 36.0 g (0.42 mol) of methacrylic acid was changed to oleyl. Oxypolyethylene glycol (30) methacrylate was obtained.

Production Example 12 [Quaternized product of pigment dispersant (12) (3- (N, N-dimethylamino) propylacrylamide / octyloxypolyethylene glycol (30) methacrylate copolymer (16/84% by weight); Synthesis of 32 mol%)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 5.1 g of DMAPAA, 24.8 g of octyloxypolyethylene glycol (30) methacrylate obtained in Synthesis Example 14, 20.1 g of ME, 0.18 g of ME, PGMEA 45 g was added, and nitrogen substitution was performed while stirring the inside of the reaction vessel. The temperature inside the reaction vessel was raised to 78 ° C. with stirring, and then a separately prepared monomer solution [12.3 g of DMAPAA, 57.8 g of octyloxypolyethylene glycol (30) methacrylate, 0.42 g of ME, 105 g of PGMEA, V-65 2 0.0 g] was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pre-quaternization pigment dispersant (12). The solid content of the solution was 40.6%, and the weight average molecular weight of the pre-quaternized pigment dispersant (12) was 11700 (measured value under <Condition 1>). 100 g of the solution was put into a glass container, and nitrogen substitution was performed. To this, 9.2 g of 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (12) (DMAPAA / octyloxypolyethylene glycol (30) methacrylate copolymer quaternized product). The solid content of the solution was 38.9%, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 13 Quaternized product of pigment dispersant (13) (3- (N, N-dimethylamino) propylacrylamide / lauryloxypolyethylene glycol (30) methacrylate copolymer (17.5 / 82.5 wt%) ; Synthesis of quaternization rate 32 mol%)
In a container similar to Production Example 12, DMAPAA 5.3 g, lauryloxypolyethylene glycol (30) methacrylate (trade name: Blenmer PLE-1300, manufactured by NOF Corporation, hereinafter referred to as “PLE-1300”) 24.8 g, ME 0.18g and PGMEA 45g were put, and nitrogen substitution was performed, stirring the inside of reaction container. The temperature inside the reaction vessel was raised to 78 ° C. with stirring, and then separately prepared monomer solution [12.3 g DMAPAA, 57.8 g PLE-1300, 0.42 g ME, 105 g PGMEA, 2.0 g V-65] 3 It was added dropwise over time. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (13) before quaternization. The solid content of the solution was 40.3%, and the weight average molecular weight of the pre-quaternization pigment dispersant (13) was 12400 (measured value according to <Condition 1>). 100 g of the solution was put into a glass container, and nitrogen substitution was performed. To this, 9.2 g of 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (13) (a quaternized product of DMAPAA / PLE-1300 copolymer). The solid content of the solution was 38.9%, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 14 Quaternized product of pigment dispersant (14) (3- (N, N-dimethylamino) propylacrylamide / stearyloxypolyethylene glycol (30) methacrylate copolymer (17.0 / 83.0 wt%) ; Synthesis of quaternization rate 32 mol%)
In the same container as in Production Example 12, DMAPAA 5.1 g, stearyloxypolyethylene glycol (30) methacrylate (trade name: Blenmer PSE-1300, manufactured by NOF Corporation, hereinafter referred to as “PSE-1300”) 24.9 g, ME 0.18g and PGMEA 45g were put, and nitrogen substitution was performed, stirring the inside of reaction container. The temperature inside the reaction vessel was increased to 78 ° C. while stirring, and then a separately prepared monomer solution [DMAPAA 11.9 g, PSE-1300 58.1 g, ME 0.42 g, PGMEA 105 g, V-65 2.0 g] 3 It was added dropwise over time. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pre-quaternization pigment dispersant (14). The solid content of the solution was 40.3%, and the weight average molecular weight of the pre-quaternized pigment dispersant (14) was 17200 (measured value according to <Condition 1>). 100 g of the solution was put into a glass container, and nitrogen substitution was performed. To this was added dropwise 8.9 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature with stirring. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of pigment dispersant (14) (quaternized product of DMAPAA / PSE-1300 copolymer). The solid content of the solution was 38.9%, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 15 [Pigment dispersant (15) (3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82.5 wt% And quaternized product thereof; quaternization rate: 32 mol%)
In a container similar to Production Example 12, 10.6 g of DMAPAA, 49.6 g of lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate obtained in Synthesis Example 15, 0.36 g of ME, and 90 g of PGMEA were placed, and a reaction container Nitrogen substitution was performed while stirring the inside. The temperature inside the reaction vessel was raised to 78 ° C. while stirring, and then a separately prepared monomer solution [DMAPAA 24.6 g, lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate 115.6 g, ME 0.84 g, PGMEA 210 g , V-65 4.0 g] was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (15) before quaternization. The solid content of the solution was 40.3%, and the weight average molecular weight of the pre-quaternization pigment dispersant (15) was 14300 (measured value according to <Condition 2>).
In addition, (3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82.5% by weight) before quaternization was pigment-dispersed. Agent (18) was obtained.
Next, 100 g of the solution was put in a glass container, and nitrogen substitution was performed. To this, 9.2 g of 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring at room temperature. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (15) (DMAPAA / lauryloxypolypropylene glycol (28) polyethylene glycol (15) quaternized product of methacrylate copolymer). The solid content of the solution was 38.9%, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 16 [Pigment dispersant (16) (3- (N, N-dimethylamino) propylacrylamide / oleyloxypolyethylene glycol (30) methacrylate copolymer (17/83 wt%) and quaternized product thereof; quaternary Synthesis of 32 mol%)
In a container similar to Production Example 12, 5.1 g of DMAPAA, 24.9 g of oleyloxypolyethylene glycol (30) methacrylate obtained in Synthesis Example 16, 20.1 g of ME, 0.18 g of ME, and 45 g of PGMEA are added, and the inside of the reaction vessel is stirred. Nitrogen replacement was performed. The temperature inside the reaction vessel was raised to 78 ° C. while stirring, and then a separately prepared monomer solution [DMAPAA 11.9 g, oleyloxypolyethylene glycol (30) methacrylate 58.1 g, ME 0.42 g, PGMEA 105 g, V-65 2 0.0 g] was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by dissolving 0.5 g of V-65 in 2.0 g of PGMEA was added, and stirring was continued for 1 hour. This was cooled to obtain a PGMEA solution of the pigment dispersant (16) before quaternization. The solid content of the solution was 40.3%, and the weight average molecular weight of the pre-quaternization pigment dispersant (16) was 15600 (measured value under <Condition 1>). Next, 100 g of the solution was put in a glass container, and nitrogen substitution was performed. To this was added dropwise 8.9 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature with stirring. After further stirring for 5 minutes, the mixture was stirred at 85 ° C. for 3 hours under a nitrogen atmosphere to react. This was cooled to obtain a PGMEA solution of the pigment dispersant (16) (DMAPAA / oleyloxypolyethylene glycol (30) methacrylate copolymer quaternized product). The solid content of the solution was 38.9%, and the quaternization rate was 32 mol% of DMAPAA before quaternization.

Production Example 17 [Pigment dispersant (17) (3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82.5 wt% ) Quaternized product; quaternized rate 70 mol%)]
(3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82) before quaternization prepared in Production Example 15 in a glass container. 0.5 wt.) 100 g of the solution was added, and nitrogen substitution was performed, and 20.1 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at room temperature with stirring for 5 minutes. Thereafter, the mixture was stirred and reacted at 85 ° C. for 3 hours under a nitrogen atmosphere, and this was cooled to obtain a pigment dispersant (17) (DMAPAA / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer). The solid content of the solution was 37.2%, and the quaternization rate was 4. It was 70mol% of the previous DMAPAA of.

Production Example 18 [Pigment dispersant (19) (3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82.5 wt% ) Quaternized product; quaternized rate of 99 mol%)]
(3- (N, N-dimethylamino) propylacrylamide / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer (17.5 / 82) before quaternization prepared in Production Example 15 in a glass container. 0.5 wt.%) 100 g of the solution was added, and nitrogen substitution was performed, and 28.7 g of a 20% PGMEA solution of dimethyl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at room temperature with stirring for 5 minutes. Thereafter, the mixture was stirred and reacted at 85 ° C. for 3 hours under a nitrogen atmosphere, and this was cooled, and the pigment dispersant (15) (DMAPAA / lauryloxypolypropylene glycol (28) polyethylene glycol (15) methacrylate copolymer A PGMEA solution of quaternized product was obtained, the solid content of which was 36%, and the quaternization rate was quaternized. It was 99mol% of the DMAPAA.

Production Example 19 [Synthesis of methyl methacrylate / methacrylic acid copolymer (copolymer (D))]
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, 3.6 g of methacrylic acid (hereinafter referred to as “MAA”), 36.4 g of methyl methacrylate (hereinafter referred to as “MMA”), 3- Mercaptopropionic acid 0.56g and PGMEA 40g were put, and nitrogen substitution was performed, stirring the inside of reaction container.
The temperature inside the reaction vessel was raised to 78 ° C. with stirring, and then separately prepared monomer solution [14.4 g of methacrylic acid, 145.6 g of methyl methacrylate, 2.2 g of 3-mercaptopropionic acid, 160 g of PGMEA, 2 g of V-65 ] Was added dropwise over 3 hours. After completion of the dropwise addition, a solution prepared by dissolving 1.0 g of V-65 in 10.0 g of PGMEA was added, and stirring was continued for 1 hour. Thereafter, a solution obtained by further dissolving 1.0 g of V-65 in 10.0 g of PGMEA was added, and stirring was continued for 1 hour, and then 100 g of PGMEA was added. This was cooled to obtain a PGMEA solution of MMA / MAA copolymer (D). The solid content of the solution was 40.3%, and the weight average molecular weight of the MMA / MAA copolymer (D) was 12400 (measured value according to <Condition 2>). The acid value was 65 mgKOH / g.

Example 13 (Preparation of pigment dispersion (12))
97.1 g of PGMEA, 19.3 g of the pigment dispersant (12) solution obtained in Production Example 12 (effective content 7.5 g), 18.6 g of the MMA / MAA copolymer (D) obtained in Production Example 19 ( Effective amount 7.5 g), diketopyrrolopyrrole pigment (Clariant Japan Co., Ltd., CI Pigment Red 254, product name “Hostaperm Red D2B-COF LV3781) 15.0 g, and φ0.3 mm zirconia beads 300 g Was placed in a 500 ml plastic container and stirred with a paint shaker for 3 hours, and then the zirconia beads were removed to obtain a preliminary dispersion.
Next, 100 g of this preliminary dispersion and 200 g of φ0.05 mm zirconia beads were placed in a 250 ml plastic container, stirred for 12 hours with a paint shaker to remove the zirconia beads, and a pigment dispersion (12) was obtained.
Table 2 shows the average particle size, viscosity, and viscosity after storage of this dispersion.

Examples 14 to 18 and Comparative Examples 11 to 12 (Preparation of pigment dispersions (13) to (17) and comparative pigment dispersions (18) to (19))
In Example 13, the pigment dispersant (12) is replaced with the pigment dispersants (13) to (19), respectively, so that the effective amount is 6.0 g, and the amount of PGMEA in the pigment dispersion is determined in Example 13. Pigment dispersions (13) to (17) and comparative pigment dispersions (18) to (19) were obtained in the same manner as in Example 13, except that the amount was adjusted to be the same as in Example 13.
Table 2 shows the evaluation results of the obtained pigment dispersions (13) to (17) and comparative pigment dispersions (18) to (19).

Example 19 (Preparation of colored composition (12))
1.00 part of pigment dispersion (12) adjusted to a pigment concentration of 10%, benzyl methacrylate / methacrylic acid copolymer (binder, molar ratio: 80/20, weight average molecular weight: 14000, PGMEA having a solid content of 40% by weight Solution) 0.298 parts, dipentaerythritol hexaacrylate (polyfunctional monomer: Nippon Kayaku Co., Ltd., DPHA) 0.036 parts, 2-methyl-4 ′-(methylthio) -2-morpholinopropiophenone (light Polymerization initiator: Wako Pure Chemical Industries, Ltd.) 0.027 parts and PGMEA 0.250 parts were mixed with a test tube mixer until uniform to obtain a colored composition (12). Table 2 shows the evaluation results of the obtained colored composition (12).

Examples 20 to 24 and Comparative Examples 13 to 14 (Preparation of Colored Compositions (13) to (17) and Comparative Colored Compositions (18) to (19))
In Example 19, the colored compositions (13) to (17) and the comparison were made in the same manner as in Example 19 except that the pigment dispersion (12) was replaced with the pigment dispersions (13) to (19), respectively. Coloring compositions (18) to (19) were obtained.
Table 2 shows the evaluation results of the obtained colored compositions (13) to (17) and comparative colored compositions (18) to (19).

Example 25 (Preparation of pigment dispersion (20))
115.7 g of PGMEA, 19.3 g of the pigment dispersant (15) solution obtained in Production Example 15 (effective amount: 7.5 g), diketopyrrolopyrrole pigment (CI pigment red 254, manufactured by Clariant Japan KK) , 15.0 g of the product name “Hostaperm Red D2B-COF LV3781” and 300 g of zirconia beads having a diameter of 0.3 mm are put in a 500 ml plastic container, and stirred for 3 hours in a paint shaker. Obtained.
Next, 100 g of this preliminary dispersion and 200 g of φ0.05 mm zirconia beads were placed in a 250 ml plastic container, stirred for 12 hours with a paint shaker to remove the zirconia beads, and then a pigment dispersion (20) was obtained.
Table 3 shows the average particle size, viscosity, and viscosity after storage of this dispersion.

Example 26 (Preparation of Pigment Dispersion (21))
In Example 25, the pigment dispersant (15) is replaced with the pigment dispersant (6) so that the effective amount is 7.5 g, and the amount of PGMEA in the pigment dispersion is the same as in Example 25. A pigment dispersion (21) was obtained in the same manner as in Example 25 except for adjusting to
Table 3 shows the average particle size, viscosity, and viscosity after storage of this dispersion.

Example 27 (Preparation of colored composition (20))
1.00 parts of pigment dispersion (20) adjusted to a pigment concentration of 10%, benzyl methacrylate / methacrylic acid copolymer (binder, molar ratio: 80/20, weight average molecular weight: 14000, PGMEA having a solid content of 40% by weight Solution) 0.417 parts, dipentaerythritol hexaacrylate (polyfunctional monomer: Nippon Kayaku Co., Ltd., DPHA) 0.050 part, 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone (light Polymerization initiator: Wako Pure Chemical Industries, Ltd.) 0.038 parts and PGMEA 0.350 parts were mixed with a test tube mixer until uniform to obtain a colored composition (20). Table 3 shows the evaluation results of the obtained colored composition (20).

Example 28 (Preparation of colored composition (21))
In Example 27, a colored composition (21) was obtained in the same manner as in Example 27 except that the pigment dispersion (20) was replaced with the pigment dispersion (21).
Table 3 shows the evaluation results of the obtained colored composition (21).

From Table 2 and Table 3, the pigment dispersions of Examples 13 to 18, 25 and 26 have low viscosity and excellent storage stability, and Example 19 containing the pigment dispersions of Examples 13 to 18, 25 and 26. In the evaluation of the colored compositions of -24, 27 and 28, it can be seen that a cured film having better contrast than the colored compositions of Comparative Examples 13 and 14 containing the dispersions of Comparative Examples 11 and 12 can be formed. Further, it can be seen that the coloring compositions of Examples 19 to 24 and 27 containing the pigment dispersions of Examples 13 to 18 and 25 have excellent solvent redispersibility.

Examples 29 and 30 (Preparation of pigment dispersions 22 and 23)
The same as in Examples 25 and 26, except that the pigment was changed from a diketopyrrolopyrrole pigment to an anthraquinone pigment (Pigment made by Daiichi Seika Kogyo Co., Ltd., CI Pigment Red 177, trade name “Chromofine Red 6128EC”). In the same manner as in Examples 25 and 26, pigment dispersions (22) and (23) were obtained.

Examples 31 and 32 (Preparation of colored compositions 22 and 23)
Colored compositions (22) and (23) were obtained in the same manner as in Example 27 except that the pigment dispersion (20) was replaced with the pigment dispersions (22) and (23) in Example 27.
Table 4 shows the evaluation results of the obtained colored compositions (22) and (23).

Example 33 (Preparation of Pigment Dispersion 24)
A pigment dispersion (24) was obtained in the same manner as in Example 25 except that the solvent was changed from PGMEA to 3-methoxybutyl acetate in Example 25.

Example 34 (Preparation of colored composition 24)
A colored composition (24) was obtained in the same manner as in Example 27, except that the pigment dispersion (20) was replaced with the pigment dispersion (24) in Example 27.
Table 4 shows the evaluation results of the obtained colored composition (24).

From Table 4, the pigment dispersions of Examples 29, 30 and 33 have low viscosity and excellent storage stability, and the coloring compositions of Examples 31, 32 and 34 containing the pigment dispersions of Examples 29, 30 and 33 It can be seen that a cured film having excellent contrast can be formed by evaluating the product. Furthermore, it turns out that the coloring composition of Examples 31 and 34 containing the pigment dispersion of Examples 29 and 33 shows the outstanding solvent resolubility.

Claims (18)

A pigment dispersant having a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B) and having a quaternization rate of 10 to 80 mol% A pigment dispersion for a color filter containing an organic pigment and an ether organic solvent. The weight ratio [(A) / (B)] excluding the quaternizing agent-derived component of the component (A) of the structural unit derived from (A) to the structural unit derived from (B) in the pigment dispersant is 5 / The pigment dispersion for color filter according to claim 1, which is 95 to 49/51. The pigment dispersion for a color filter according to claim 1 or 2, wherein the polyalkylene glycol moiety of (B) contains a structural unit derived from propylene oxide. The polyalkylene glycol part of (B) contains a structural unit derived from ethylene oxide, and the weight ratio of the structural unit derived from ethylene oxide to the structural unit derived from propylene oxide [(structural unit derived from ethylene oxide) / (structural unit derived from propylene oxide). The pigment dispersion for a color filter according to claim 3, wherein)] is 50/50 to 10/90. The polyalkylene glycol part of (B) is a block adduct in which the (meth) acrylate side is a structural unit derived from ethylene oxide and the terminal side is a structural unit derived from propylene oxide. Pigment dispersion for color filters. The pigment dispersion for a color filter according to any one of claims 1 to 5, wherein (A) is N, N-dimethylaminoalkylacrylamide. The pigment dispersion for a color filter according to any one of claims 1 to 6, wherein the pigment dispersant has a quaternary ammonium group and the counter ion is an alkyl sulfate ion. The pigment dispersion for color filter according to any one of claims 1 to 7, wherein the organic pigment is a diketopyrrolopyrrole pigment. The pigment dispersion for a color filter according to any one of claims 1 to 8, wherein the alkoxy group in (B) has 6 to 22 carbon atoms. The pigment dispersion for a color filter according to any one of claims 1 to 9, wherein the alkoxy group in (B) is an alkyloxy group or an alkenyloxy group. The pigment dispersion for a color filter according to any one of claims 1 to 10, further comprising an alkyl (meth) acrylate and a copolymer (D) of (meth) acrylic acid. A pigment dispersant having a structural unit derived from dialkylaminoalkyl (meth) acrylamide (A) and a structural unit derived from alkoxypolyalkylene glycol (meth) acrylate (B) and having a quaternization rate of 10 to 80 mol% A method for producing a pigment dispersion for a color filter, comprising a step of dispersing a mixture of an organic pigment and an ether organic solvent. Pigment used in the step of polymerizing dialkylaminoalkyl (meth) acrylamide and alkoxypolyalkylene glycol (meth) acrylate to obtain a copolymer, and the step of dispersing the copolymer by treating the copolymer with a quaternizing agent A method for producing a pigment dispersion for a color filter according to claim 12, comprising a step of obtaining a dispersant. The pigment dispersion for a color filter according to claim 12 or 13, wherein the step of dispersing the mixture has a preliminary dispersion step of dispersing using a medium and a main dispersion step of dispersing using a medium smaller than the preliminary dispersion step. Body manufacturing method. A coloring composition for a color filter comprising the pigment dispersion according to any one of claims 1 to 11 and an alkali-soluble resin which is a copolymer of (meth) acrylic acid ester and (meth) acrylic acid. Use of the pigment dispersion according to any one of claims 1 to 11 for producing a color filter. Use of the colored composition according to claim 15 for producing a color filter. A color filter produced using the pigment dispersion according to any one of claims 1 to 11.