JP5241283B2 - Pigment dispersion composition, photocurable composition, color filter, liquid crystal display device, and solid-state imaging device - Google Patents

Description

  The present invention is excellent in dispersibility of pigments, excellent in fluidity and coloring power of pigment dispersion compositions and photocurable compositions, and can be suitably used in a wide range of paints, printing inks, color display plates and the like. The present invention relates to a dispersion composition, a photocurable composition containing the dispersion composition, and a color filter produced using the photocurable composition.

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. With this trend of application expansion, advanced color characteristics in chromaticity, contrast, etc. Has come to be required. Similarly, in image sensor (solid-state imaging device) applications, advanced color characteristics such as reduction in color unevenness and improvement in color resolution are required.

  In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration.

  In addition, when the dispersion stability is insufficient, in the color filter manufacturing process, the film thickness uniformity particularly in the coating process of the photocurable composition is reduced, or the exposure sensitivity in the exposure process is reduced. Or the alkali solubility in the development process is likely to be reduced. In addition, when the dispersion stability of the pigment is poor, the pigment dispersion and the constituents of the photocurable composition are agglomerated with the passage of time, resulting in an increase in viscosity and a very short pot life. There is also.

In order to solve such a problem, a polymer-type pigment dispersant in which an organic dye structure and a polymer are combined has been proposed (see Patent Document 1).
However, since the surface area of the pigment particles is increased when the pigment particle size is reduced, the cohesive force between the pigment particles is increased, and it is difficult to achieve both a high level of dispersibility and dispersion stability.

  In manufacturing a color filter using a photocurable composition containing a pigment dispersion composition, the photocurable composition is applied and dried on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance. After that, the dried coating film is irradiated with radiation in a desired pattern (hereinafter referred to as “exposure”) and developed to obtain pixels of each color.

  However, the color filter manufactured in this manner is likely to cause residue and background contamination on the unexposed substrate or the light shielding layer in the development process, and the post-baked pixels after development have poor surface smoothness. There was a problem that the physical properties of the coating film were inferior. Moreover, the degree of deterioration of residues, background stains and surface smoothness on the substrate or the light-shielding layer tends to become more prominent as the concentration of the pigment contained in the photocurable composition increases. With a photocurable composition, it was difficult to achieve a sufficient color density.

  Further, for the purpose of imparting alkali developability, a pigment dispersion composition using a block type, random type, or linear polymer compound into which acrylic acid is introduced as an alkali-soluble resin is known (Patent Documents 2 and 3). The pigment dispersibility and developability when applied to a curable composition for pattern formation such as a color filter are still insufficient.

  Further, with the recent increase in size of substrates, a slit coating method has been studied as a coating method. Slit coating has the advantages of superior coating film thickness uniformity and less waste of coating liquid compared to conventional spin coating.

  However, in slit coating, since the coating liquid is exposed to the outside air at the slit opening at the head tip, the coating liquid (photocurable composition) is liable to dry and solidify at the head tip. This may cause clogging of the slit nozzles and vertical stripe unevenness of the coating film applied on the transparent substrate (vertical application stripes in the application direction).

  In addition, there is a drawback that the solidified product of the coating solution is detached from the tip of the head and the coating quality is deteriorated such as being brought into the coated film as a foreign substance. In order to avoid this, the suitability (hereinafter referred to as “dry film resolubility”) of the photocurable composition that has been dried or precipitated is rapidly required when it comes into contact with the coating solution.

  In order to improve such a problem, a method using a dispersant such as a surfactant or a resin-type dispersant is known (for example, see Patent Documents 4 and 5). However, the use of these dispersants has caused problems such as reduced coating strength, developability, adhesion to substrates such as glass, and durability, and dispersion stability of the photocurable composition. In addition, it is difficult to achieve both the excellent resolubility of the coating solution in dry film and the provision of strong adhesion between the coating film and a substrate such as glass.

In recent years, color filters have been required to have higher color densities as the thickness of the color filters has increased. In order to form a color filter with a high color density, it is necessary to increase the color material density in the colored resin composition to be used, but the components that contribute to image forming properties such as solubility in an alkaline developer are relatively As a result, there is a problem that the original image forming performance is lost. In order to solve these problems, attempts have been made to maintain the image forming property while maintaining the colorant concentration high by using a dispersant having both a dispersing function and a binder function. A pigment dispersion composition using a linear polymer compound such as a block type or a random type into which an acid is introduced is also known (see Patent Document 3). However, in particular, an extremely fine pigment has a sufficient dispersibility. Not in.
JP 2008-009426 A Japanese Patent No. 3094403 JP 2004-287409 A JP 2003-294935 A JP 2001-164142 A

The present invention provides a pigment dispersion excellent in dispersion stability, and self-solubility (dry film resolubility) when agglomerated or solidified at the tip of the coating liquid discharge port of a slit coating apparatus using the same. An object of the present invention is to provide a photocurable composition having excellent developability, excellent solubility in a developer, and suppressed development residue.
Another object of the present invention is to provide a high-quality color filter having a colored pattern using the photocurable composition, and further, the color filter provided with the color filter is excellent in color reproducibility, An object of the present invention is to provide a high-contrast liquid crystal display device and a high-resolution solid-state imaging device with small color unevenness.

As a result of intensive studies, the above-mentioned problem is obtained by using a pigment dispersion composition comprising (A) a graft polymer compound having acrylic acid in the main chain, (B) a pigment, and (C) an organic solvent. It was found that the problem can be solved, and the present invention has been achieved.
That is, the object of the present invention is achieved by the following means.

一般式（ｉ）中、Ｒ ^１ 〜Ｒ ^３ は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｘ ^１ は−Ｃ（＝Ｏ）Ｏ−を表す。Ｌ ^１ はアルキレンアミノカルボニル基を表す。ｍは５を表し、ｐは１〜１００の整数を表す。Ａ ^１ は炭素原子数１から２０までの直鎖状アルキル基、炭素原子数３から２０までの分岐状アルキル基、又は炭素原子数５から２０までの環状アルキル基を表す。
＜２＞ 前記（Ａ）グラフト型高分子重合体が、さらに、共重合体成分として下記一般式（４）で表される単量体が共重合されている＜１＞に記載の顔料分散組成物。

一般式（４）中、Ｒ ^８ は、水素原子、又はアルキル基を表す。Ｒ ^９ は、単結合、又は２価の連結基を表す。Ｐは、−ＣＯ−、−Ｃ（＝Ｏ）Ｏ−、−ＣＯＮＨ−、−ＯＣ（＝Ｏ）−、又はフェニレン基を表す。Ｑは含窒素複素環構造を有する基を表す。
＜３＞ 前記一般式（ｉ）で表される化合物が、下記式（Ａ−３）で表される化合物である＜１＞又は＜２＞に記載の顔料分散組成物。

＜４＞ 前記一般式（４）で表される化合物が、下記式Ｍ−１１で表される化合物である＜２＞又は＜３＞に記載の顔料分散組成物。

<1> (A) 40 to 90% by mass of a compound represented by the following general formula (i) and 5 to 30% by mass of acrylic acid are copolymerized in the main chain , and the weight average molecular weight is 1,000 to 100, A pigment dispersion composition comprising a graft type polymer in the range of 000 , (B) a pigment, and (C) an organic solvent.

In General Formula (i), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents —C (═O) O—. L ¹ represents an alkyleneaminocarbonyl group. m represents 5 and p represents an integer of 1 to 100. A ¹ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
<2> (A) the grayed rafts polymeric polymer further, the pigment dispersion according to <1> which monomer is copolymerized represented by the following general formula (4) as a copolymer component Composition.

In General Formula (4), R ⁸ represents a hydrogen atom or an alkyl group. R ⁹ represents a single bond or a divalent linking group. P represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Q represents a group having a nitrogen-containing heterocyclic structure.
<3> The pigment dispersion composition according to <1> or <2>, wherein the compound represented by the general formula (i) is a compound represented by the following formula (A-3).

<4> The pigment dispersion composition according to <2> or <3>, wherein the compound represented by the general formula (4) is a compound represented by the following formula M-11.

< 5 > The pigment dispersion composition according to any one of <1> to <4>, wherein an average primary particle size of the pigment (B) is in the range of 10 to 25 nm.
< 6 > The pigment dispersion composition according to any one of <1> to < 5 >, further comprising (D) a basic graft polymer compound.
< 7 > The value obtained by dividing the total mass of the polymer compound contained in the pigment dispersion composition by the total mass of the (B) pigment and the (E) pigment derivative is 0.55 or less. <1> to < 6 > The pigment dispersion composition according to any one of < 6 >.

< 8 > A photocurable composition comprising the pigment dispersion composition according to any one of <1> to < 7 >, (F) a polymerizable compound, and (G) a photopolymerization initiator.
<9> The photocurable composition according to <8>, wherein the polymerizable compound (F) is a tetrafunctional or higher functional acrylate compound.
<10> Further, an alkali-soluble resin is included, and the alkali-soluble resin is at least one selected from a copolymer obtained by copolymerizing at least an alkyl (meth) acrylate and (meth) acrylic acid <8> or <9>. The photocurable composition as described in 9>.
< 11 > The photocurable composition according to any one of <8> to <10>, wherein the pigment concentration is 35% by mass or more.
< 12 > A color filter comprising the photocurable composition according to any one of <8> to <11> .
< 13 > A liquid crystal display device using the color filter according to < 12 >.
< 14 > A solid-state imaging device using the color filter according to < 12 >.

The operation of the present invention is not clear, but is considered as follows.
When the graft type polymer compound having acrylic acid in the main chain (A) contained in the pigment dispersion composition of the present invention is used as a dispersant, the polymer compound has acrylic acid in the main chain and is a graft type. Therefore, the acrylic acid of the main chain is higher in polarity than methacrylic acid, and the main chain is flexible, so that when the acrylic acid acts on the pigment with respect to the highly polar pigment, the pigment is effectively coated, and It is considered that the re-aggregation of the pigments is suppressed because the graft chain functions as a steric repulsion chain. Therefore, it is considered that the secondary aggregate which is an aggregate of the primary particles of the pigment can be effectively loosened, and the primary particles can be effectively prevented from reaggregating into the secondary aggregate. . Therefore, it is considered that a dispersion in a state close to that of primary particles being dispersed can be obtained in the dispersion step.
Therefore, it is considered that a color filter having a high contrast and a color filter having a small color density unevenness could be obtained by providing a coloring pattern made of a photocurable composition containing such a pigment dispersion composition. .

  At the same time, the dry film resolubility is good. This is because the pigment dispersed in the primary particles is covered with the graft polymer compound, and the graft polymer on the outer wall is compatible with the solvent. It is presumed that even if it becomes a dry film, it is easily dissolved in a solvent.

  Further, the pigment dispersion composition dispersed with the polymer compound of the present invention is also effective for the problem that a part of the dispersant is precipitated when the pigment dispersion composition is stored at a low temperature. This is a problem that occurs particularly in graft-type polymer compounds having polycaprolactone as a graft chain, and since polycaprolactone is a highly crystalline polymer, dispersion stability at low temperatures is poor, but the polymer compound of the present invention In (A), since acrylic acid is copolymerized in the main chain, the flexibility of the polymer main chain is improved, and the carboxylic acid which is difficult to be solvated aggregates with respect to the organic solvent used in the pigment dispersion composition. It is estimated that polycaprolactone chains that are easily solvated are not regularly arranged but are solvated with an organic solvent, so that they easily dissolve in the solvent and can be stored stably at low temperatures. The

According to the present invention, a pigment dispersion excellent in dispersion stability, and self-solubility (dry film re-dissolution property) when aggregated or solidified at the tip of the coating liquid discharge port of the slit coating apparatus using the pigment dispersion. And a photocurable composition excellent in developability in which development residue is suppressed and generation of a development residue is suppressed.
Furthermore, the present invention provides a high-quality color filter having a colored pattern using the photocurable composition, and further, an excellent color reproducibility and high-contrast liquid crystal display device including the color filter, and A high-resolution solid-state imaging device with small color unevenness can be provided.

The present invention will be described in detail below.
In the present invention, (A) 40 to 90% by mass of the compound represented by the general formula (i) and 5 to 30% by mass of acrylic acid are copolymerized in the main chain , and the weight average molecular weight is 1,000 to 100. Is a pigment-dispersed composition comprising a graft-type polymer compound (hereinafter sometimes referred to as a specific graft polymer) in the range of 1,000,000, (B) a pigment, and (C) an organic solvent. The specific graft polymer (A) is a polymer compound further containing a heterocyclic ring in the side chain.

(A) specific graft polymer used in the particular graft polymer present invention, the main chain in the compound represented by general formula (i) 40 to 90 wt%, and 5 to 30 wt% co-acrylic acid There is no particular limitation as long as it is polymerized and is a graft polymer compound having a weight average molecular weight in the range of 1,000 to 100,000.

About the specific graft polymer, the acrylic acid group of this invention should just be included in the principal chain. Further, an acrylic acid group may be further included in the branch part.
As a method for synthesizing a specific graft polymer, as described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), etc., as a general method, (1) a method of polymerizing a branch monomer from a main chain polymer, ( 2) A method of bonding a branched polymer to a main chain polymer (3) A method of copolymerizing a main chain monomer with a branched polymer can be used.
That is, the specific graft polymer that can be used in the present invention is obtained by copolymerizing acrylic acid, a polymerizable oligomer (hereinafter referred to as a macromonomer) and another copolymerizable monomer.

The amount of acrylic acid introduced is 5 to 30% by mass from the viewpoint of dispersibility. If it exceeds 30% by mass, the amount of macromonomer to be copolymerized becomes relatively small, so that the steric repulsion chain does not contribute and sufficient dispersion stability cannot be obtained. On the other hand, if it is 5% by mass or less, sufficient flexibility cannot be obtained as a whole polymer compound, and it is difficult to obtain the effects of improving dispersion stability and developability. Furthermore, although the amount of acrylic acid introduced depends on the type and molecular weight of the macromonomer, it is preferably 10 to 30% by mass, and most preferably 10 to 25% by mass.
Structure of macromonomer, Ru der those having a repeating unit represented by the following general formula (i).

In general formulas (1) and (2), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group.
L ¹ and L ² each independently represents a single bond or an organic linking group.
A ¹ and A ² each independently represents a monovalent organic group.
m and n each independently represents an integer of 2 to 8.
p and q each independently represents an integer of 1 to 100.

R ^{1 to} R ^{6 each} represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.

Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3 -A hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group is mentioned.
R ¹ , R ² , R ⁴ and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.

X ¹ and X ² represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C (═O) O— is most preferable.

L ¹ and L ² represent a single bond or an organic linking group. As the linking group, a substituted or unsubstituted alkylene group is preferable. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
More preferably, the alkylene group is linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group. When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The organic linking group is a heteroatom selected from —C (═O) —, —OC (═O) —, —NHC (═O) —, or a partial structure containing a heteroatom, at the terminal of the above alkylene group. And those linked via a heteroatom or a partial structure containing a heteroatom are preferred from the standpoint of adsorptivity to the pigment.

A ¹ and A ² represent a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. A straight chain of 6 to 10 and a branched chain of 6 to 12 carbon atoms are more preferable.

m and n represent an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.
p and q represent an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.
From the viewpoint of dispersion stability, the repeating unit represented by the formula (1) is preferable.
Moreover, the repeating unit represented by Formula (1-2) is more preferable.

La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents —C (═O) — or —NHC (═O) —. R ^{1 to} R ³ , m, p, and A ¹ have the same meaning as in formula (1).

  The repeating units represented by the formulas (1), (2), and (1-2) are polymers or copolymers of monomers represented by the following formulas (i), (ii), and (i-2), respectively. By polymerization, it is introduced as a repeating unit of the polymer compound.

In General Formula (i), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents —C (═O) O—. L ¹ represents an alkyleneaminocarbonyl group. m represents 5 and p represents an integer of 1 to 100. A ¹ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms.
In General Formula (ii) and General Formula (i-2), R ^{1 to} R ⁶ , X ² , L ² , m, n, p, q, A ¹ , and A ² are represented by Formula ( 2), ( It is synonymous with that of 1-2). These synthesis methods can be obtained, for example, by adding a monocarboxylic acid or monoalcohol to ε-caprolactone to initiate ring-opening polymerization.
Preferred specific examples of the monomer represented by the formula (i ) are (A-1) to (A-5) and (A-11) to (A-14) in the following exemplified compounds. The invention is not limited to these.

In the general formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is a single bond or alkylene, alkenylene, cycloalkylene, phenylene, ether, thioether, ester, carbonyl, amino , An amide, a sulfonylamide, a single linking group selected from an atomic group represented by urethane, or a linking group formed by arbitrarily combining two or more thereof. A ³ represents a repeating unit composed of a radical polymerizable monomer such as (meth) acrylic acid ester, (meth) acrylonitrile, styrene derivative, (meth) acrylamides and the like.

  Specific examples of the macromonomer represented by the general formula (3) include the following.

  In the above, A is synonymous with the formula (3), and preferred compounds of A include polymethyl methacrylate, polybutyl methacrylate, polystyrene, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-styrene copolymer, and the like. It is done.

The weight average molecular weight of the specific graft polymer is not particularly limited as long as it is 1,000 to 100,000, but is preferably in the range of 3,000 to 100,000, preferably 5,000 to 50,000. The range is more preferable, and the range of 10,000 to 30,000 is more preferable. When the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.
In particular, the weight average molecular weight of the branch is preferably 300 to 10,000. Preferably it is 500-5,000, More preferably, it is 1,000-3,000. When the molecular weight of the branch portion is in the above range, the developability is particularly good and the development latitude is wide.

The specific graft polymer may contain only one type of repeating unit composed of a macromonomer, or may contain two or more types. In certain graft compound, the content of the repeating unit composed of macromonomer, when the total structural units contained in the specific graft compound is 100 mass%, is to contain 4 0-90 wt%, 50 to It is more preferable to contain 80% by mass.

  Other monomers that can be copolymerized with the specific graft polymer include (1) a monomer having an organic dye structure or a heterocyclic structure, (2) a monomer having an acidic group, (3) a monomer having a basic nitrogen atom, ( 4) A urea group, a urethane group, a hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group, a monomer having a hydroxyl group, and (5) an ionic functional group. Monomers, (6) (Meth) acrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones One or more monomers such as olefins, olefins, maleimides, (meth) acrylonitrile It can be selected. Among these, it is particularly preferable to have (1) from the viewpoint of the adsorptive power to the pigment.

  The monomer having an organic dye structure or a heterocyclic structure is preferably a monomer represented by the following general formula (4), a maleimide, or a maleimide derivative. A monomer represented by the following general formula (4) is particularly preferable.

In general formula (4), R ⁸ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁹ represents a single bond or a divalent linking group. P represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Q represents a group having a nitrogen-containing heterocyclic structure.

In General Formula (4), R ⁸ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ⁸ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.
Specifically, preferred examples of the alkyl group represented by R ⁸ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ⁸ is most preferably a hydrogen atom or a methyl group.

In General Formula (4), R ⁹ represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.

The alkylene group represented by R ⁹ may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ⁹ include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ⁹ has a substituent, examples of the substituent include a hydroxy group.
Examples of the divalent linking group represented by R ⁹ include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the end of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and may be linked to Q via the heteroatom or a partial structure containing a heteroatom.

  In general formula (4), Q represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Q is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following general formula (5), (6) or (7) is particularly preferable.

In the general formula (5), X is a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (5), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (7), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (7), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

In general formula (5), (6), or (7), ring B ¹ , ring B ² , ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring B ¹ and the ring B ² in the general formula (5) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (6) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring D in the general formula (7) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Among the structures represented by the general formula (5), (6) or (7), a benzene ring or a naphthalene ring is more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (5) or In (7), a benzene ring is more preferable, and in the general formula (6), a naphthalene ring is more preferable.

  In the specific graft polymer of the present invention, preferred specific examples of the monomer, maleimide and maleimide derivative represented by the general formula (4) are listed below, but the present invention is not limited thereto.

The specific graft polymer may contain only one type of copolymer unit derived from the monomer represented by the general formula (4), maleimide, or maleimide derivative, or may contain two or more types. .
In the specific graft polymer, the content of the copolymer unit derived from the monomer represented by the general formula (4), maleimide, and maleimide derivative is not particularly limited, but the total structural unit contained in the polymer is not limited. When the content is 100% by mass, it is preferable that the copolymer unit derived from the monomer represented by the general formula (4), the maleimide, and the maleimide derivative is contained in an amount of 5% by mass or more, and 10 to 50% by mass is contained. Is more preferable.

Among the monomers represented by the general formula (4), maleimide, and maleimide derivatives, the monomer represented by the general formula (4) is preferable because of its high adsorptivity to the pigment.
That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is represented by the general formula (4). The content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the content of copolymer units derived from the monomer represented by formula (4) Is preferably 30% by mass or less.

  The specific graft polymer uses, for example, a normal radical polymerization method using a monomer represented by the general formula (i), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. Can be manufactured by. In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.

In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.
In the pigment dispersion composition of the present invention, the content of the specific graft polymer is preferably a mass ratio of pigment: specific graft polymer = 1: 0.1 to 1: 2, more preferably 1: 0.2. To 1: 1, more preferably 1: 0.4 to 1: 0.7. The effect of the acrylic acid of the present invention appears remarkably when pigment: specific graft polymer = 1: 0.4 to 1: 0.55.
Moreover, 10-40 mass% is preferable among content of (A) specific graft polymer among all the solid content.

Further, in order to improve the high color reproducibility of the liquid crystal display device and to improve the color separation property of the solid-state imaging device, it is necessary that the pigment concentration is high. Especially effective with objects. More specifically, a value obtained by dividing the total mass of the polymer compound contained in the pigment dispersion composition by the total mass of (B) pigment and (E) pigment derivative described later is 0.2 to 0.55. Is preferable, and more preferably in the range of 0.3 to 0.4.
Even when the amount of the polymer compound is small, the dispersibility of the pigment is good, the dispersion stability is good, and when the photocurable composition is made, the re-solubility of the dry film in the solvent is good. Thus, it is possible to provide a pigment dispersion composition with little residue during development.

The pigment dispersion composition of the present invention preferably further contains (D) a basic graft polymer compound. Here, (D) is a polymer compound excluding the structure contained in the polymer (A).
(D) A basic graft polymer is a polymer having a structure in which a branch polymer is graft-bonded to a trunk polymer portion having a plurality of basic groups, and an organic pigment and an acidic derivative using the basic group of the trunk polymer portion as an anchor Because of the multi-point adsorption to the surface, the steric repulsion effect of the branched polymer part acts effectively and expresses the function of promoting fine dispersion. The basic group of the trunk polymer part is preferably an amino group from the viewpoint of excellent adsorption characteristics, and the branch polymer part is preferably organic solvent-soluble from the viewpoint of excellent steric repulsion. Further, it preferably has a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer. Such a polymer can be represented, for example, by the following formula.

  In the above formula (8), the backbone polymer represented by EE ... EE is preferably one having an amino group, and specific examples thereof include polyethyleneimine, polyethylenepolyamine, polyxylylenepoly (hydroxypropylene) polyamine, Examples include poly (aminomethylated) epoxy resins, amine-added glycidyl (meth) acrylate- (meth) acrylic acid esterified glycidyl (meth) acrylate copolymers, and the like. These synthesis methods are as follows, for example.

  Polyethyleneimine is obtained by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst. Polyethylene polyamine can be obtained by polycondensation of ethylene dichloride and ammonia in the presence of an alkali catalyst. Poly (aminomethylated) epoxy resin is aminated after chloromethylation of aromatic rings such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, etc. And is also called Mannich base. Specific examples of the amine used in the amination include monomethylamine, monoethylamine, monomethanolamine, monoethanolamine, dimethylamine, diethylamine, dimethanolamine, diethanolamine and the like. The amine-added glycidyl (meth) acrylate- (meth) acrylic esterified glycidyl (meth) acrylate copolymer is polymerized by radical polymerization of glycidyl (meth) acrylate, and then a part of the epoxy group in the polymer. An amine similar to that described above is added to obtain poly [amine-added glycidyl (meth) acrylate], and then the remaining epoxy group is obtained by esterification with a carboxylic acid of (meth) acrylic acid.

  In the formula (8), the branch polymer represented by FF... FF is preferably an organic solvent-soluble polymer. Specific examples thereof include a carboxylic acid at the polymer terminal and an amino group in the trunk polymer as described above. Examples thereof include ring-opening polymers such as poly (12-hydroxystearic acid), polyricinoleic acid, and ε-caprolactone, which are polymers capable of forming a graft bond by amidation reaction with a group. Further, when the backbone polymer has a vinyl group such as the above-mentioned amine-added glycidyl (meth) acrylate- (meth) acrylate esterified glycidyl (meth) acrylate copolymer, a polypolymer that can be graft-polymerized to the vinyl group. [Methyl (meth) acrylate], poly [(meth) ethyl acrylate] and the like can be exemplified as the branched polymer portion. These synthesis methods are as follows, for example.

  Poly (12-hydroxystearic acid) is obtained by a dehydration polycondensation polyesterification reaction of 12-hydroxystearic acid. Polyricinoleic acid is similarly obtained by a dehydration polycondensation polyesterification reaction of ricinoleic acid. A ring-opening polymer of ε-caprolactone is obtained by adding n-caproic acid, which is an aliphatic monocarboxylic acid, to ε-caprolactone to initiate ring-opening polymerization.

  (D) When adding the basic graft type polymer compound (A) The specific graft polymer and (D) the basic graft type polymer compound are mixed in a ratio of 2/1 to 1/2. It is preferable to use it, and it is particularly preferable to use it at a ratio of 1.5 / 1 to 1 / 1.5.

<(B) Pigment>
The pigment dispersion composition of the present invention contains a pigment. The pigment used here has a higher contrast as a color filter as its particle size is smaller. In particular, when a pigment having a particle size of 10 to 25 nm is dispersed with the specific graft polymer of the present invention, it can be dispersed well and the contrast is improved. In addition, since the pigment of this size is fine, there is a problem that the pigment aggregates and the viscosity is improved when the pigment dispersion is stored for a long time under high temperature and high humidity. This problem can be solved by using the introduced graft type dispersant.
When the particle diameter of the pigment is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  The pigment concentration of the photocurable composition is usually 30% by weight or less, but in recent years, a higher pigment concentration is required. When the pigment concentration is increased, components that contribute to image forming properties, such as an additive resin that imparts solubility in an alkaline developer, are relatively reduced, resulting in a problem that the image forming performance originally possessed is lost. .

When the specific graft polymer of the present invention is used as a dispersant, it can be used in a high pigment concentration region because it is sufficiently solubilized in the developer without adding another resin in order to dissolve in the alkaline developer. In addition, since the specific graft polymer has dispersion stability, it has a characteristic that a fine pigment can be used at a high pigment concentration.
The pigment concentration can be used in the range of 10 to 55% by mass, but the effect is particularly remarkable in the high pigment concentration region in the range of 35 to 55% by mass and in the range of 40 to 55% by mass.

The pigment dispersion composition of the present invention contains at least one (B) pigment in an organic solvent.
As the pigment that can be used in the pigment dispersion composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, and considering handling properties. Then, a pigment having an average primary particle diameter of 10 to 25 nm is preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, one kind of halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, when the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

(Pigment processing)
It is preferable to use the pigment of the present invention that has been subjected to a refinement treatment in advance. The finer primary particles of the pigment are well known by mechanically kneading with i) a pigment, ii) a water-soluble inorganic salt, and iii) a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader. (Salt milling method). In this step, if necessary, iv) a pigment-coated polymer compound, v) a pigment derivative, etc. may be used simultaneously.

i) Examples of the pigment include the same pigments as described above.
ii) The water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used. Sodium is preferably used. The amount of the inorganic salt used for salt milling is preferably 1 to 30 times by weight, more preferably 5 to 25 times by weight of the organic pigment, and the water content is preferably 1% or less from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the processing amount of one pigment is reduced.

  iii) A small amount of a water-soluble organic solvent that does not substantially dissolve the inorganic salt serves to wet the organic pigment and the inorganic salt, dissolves (mixes) in water, and substantially uses the inorganic salt used. If it does not melt | dissolve in this, it will not specifically limit. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

  However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  The addition amount of the water-soluble organic solvent is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic salt. More preferably, it is 10 to 40 parts by weight, and optimally 15 to 35 parts by weight. When the addition amount is less than 5 parts by weight, uniform kneading becomes difficult and the particle size may become uneven. When the addition amount is 50 parts by weight or more, the kneaded composition becomes too soft, and it becomes difficult to apply shear to the kneaded composition, so that a sufficient refinement effect may not be obtained.

All of the water-soluble organic solvent may be added at the initial stage of salt milling, or may be added in divided portions. A water-soluble organic solvent may be used independently and can also use 2 or more types together.
Although there is no particular limitation on the operating conditions of the wet pulverizing apparatus in the present invention, the operating conditions in the case where the apparatus is a kneader are as follows. 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

  iv) The pigment-coated polymer compound should preferably be solid at room temperature, water-insoluble, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. A natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or a graft polymer (A) copolymerized with acrylic acid of the present invention can be used. It is preferable to use a polymer.

When using a dried treated pigment, the compound used is preferably solid at room temperature. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and the like. Examples of the synthetic resin modified with a natural resin include rosin-modified maleic resin and rosin-modified phenol resin.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.
(A) As the specific graft polymer, the above-described polymer compounds can be used.
The timing of adding these resins may be added all at the beginning of salt milling, or may be added in divided portions.
v) Examples of the pigment derivative include those similar to the pigment derivative (E) described later.

<(E) Pigment derivative>
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is introduced into the photocurable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group to the pigment surface and using it as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective in constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1-30 weight part is preferable with respect to 100 weight part of pigments, and 3-20 weight part is more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, the dispersion stability after dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The timing of adding the pigment derivative may be added during salt milling or may be added during dispersion. It may be added to both during salt milling and dispersion.

  The dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat made by GETZMANN Co., Ltd.) that has been previously mixed with a pigment and a dispersant and previously dispersed with a homogenizer or the like. This can be done by fine dispersion. The dispersion time is preferably about 3 to 6 hours.

<Dispersant>
The pigment dispersion composition of the present invention contains at least one dispersant. With this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, it is necessary to use at least the above-mentioned (A) specific graft polymer. As a result, the dispersion state of the pigment in the organic solvent is improved, and, for example, when a color filter is configured using the pigment dispersion composition of the present invention, high developability even when the pigment is contained at a high concentration. Surface smoothness can be expressed.
(A) When the specific graft polymer is used as a dispersant, the above-described polymer compound can be used.

  If necessary, in addition to (A) a specific graft polymer and a preferred combination component (D) a basic graft polymer compound, conventionally known dispersants such as pigment dispersants and surfactants, etc. Ingredients can be added.

Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The ratio of the pigment-coated polymer compound and the dispersant is not particularly limited. However, when the dispersant is a polymer dispersant, 10/90 to 90/10 is preferable, and 20/80 to 80/20 is more preferable. preferable.

<(C) Organic solvent>
The solvent in the pigment dispersion composition of the present invention is not particularly limited as long as it is an organic solvent, and can be appropriately selected from known solvents such as 1-methoxy-2-propyl acetate and 1-methoxy-2. -(Poly) alkylene glycol monoalkyl ethers such as propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and their acetates Acetates such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl Ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, alcohols such as glycerin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers and their acetates, acetates, methyl ethyl ketone, and the like are preferable.

The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a photocurable composition to be described later, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass from the viewpoint of handleability. Can do.
(C) It is preferable to have 10% by mass or more of 1-methoxy-2-propyl acetate as the organic solvent.

  A preferred embodiment of the pigment dispersion composition of the present invention is a pigment dispersion obtained by dispersing a processed pigment coated with a polymer compound having a weight average molecular weight of 1,000 or more, a pigment derivative, and a dispersant in an organic solvent. It is a composition. (A) The specific graft polymer may be used as a pigment-coated polymer compound added at the time of pigment processing, or may be used as a dispersant, or both of the independent (A) specific graft polymers may be used. However, it is preferably used as a dispersant.

  In the case of a polymer dispersant, the addition amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% by mass with respect to the pigment. % Is particularly preferred. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, the pigment, the pigment dispersant, and the solvent are mixed using a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

  Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The pigment dispersion composition of the present invention is suitably used for a photocurable composition used for producing a color filter.

(Photocurable composition)
The photocurable composition of the present invention comprises the above-described pigment dispersion composition of the present invention, (F) a polymerizable compound, and (G) a photopolymerization initiator, and if necessary, an alkali-soluble resin. And other components may be included. Hereinafter, each component will be described in detail.

  The pigment concentration of the photocurable composition of the present invention (mass% of the pigment in the total solid content of the photocurable composition) is preferably 35% by mass or more, and more preferably 40% by mass or more. The present invention is particularly effective when the pigment concentration is high, and the dispersibility of the pigment is high, and when it is made into a photocurable composition, it exhibits dispersion stability that cannot be achieved by conventional techniques, and is a solvent for a dry film. It is possible to provide a photocurable composition having high solubility and few residues on the substrate when developed.

(F) Polymerizable compound As the polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable. Is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

(F) A polymeric compound can be used in combination of 2 or more types in addition to being used alone.
As content in the photocurable composition of a polymeric compound, 3-55 mass% is preferable in the total solid of this composition, More preferably, it is 10-50 mass%. When the content of the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.

(G) Photopolymerization initiator Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428, and the like. Active halogen compounds such as halomethyl-s-triazine as described, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers as described in US Pat. No. 4,318,871, European Patent Publication EP-88050A, etc., US patents Aromatic ketone compounds such as benzophenones described in USP-4199420, (thio) xanthone or acridine compounds described in Fr-2456541, coumarins or biimidazoles described in JP-A-10-62986 Compounds, sulfos such as JP-A-8-015521 Examples thereof include a nium organic boron complex.

  Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series) acridine series, biimidazole series An oxime ester type is preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen photopolymerization initiator (triazine, oxadiazole, coumarin) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis. (Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2, 4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxy Tyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- ( Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) ) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloro Methyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl- -Amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl A preferred example is -5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable in the total solid of this composition, More preferably, it is 0.5-5.0 mass%. It is. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

<Sensitizing dye>
In the present invention, it is preferable to add a sensitizing dye as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

<Alkali-soluble resin>
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹¹ R ¹² , CH ₂ = C (R ¹¹ ) (COOR ¹³ ) [wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ¹³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹¹ R ¹² , CH ₂ ═C (R ¹¹ ) (COOR ¹³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ = CR ¹¹ R ¹² and / or CH ₂ = C (R ¹¹ ) (COOR ¹³ ).

  As content in the photocurable composition of alkali-soluble resin, 0-15 mass% is preferable in the total solid of this composition, More preferably, it is 1-12 mass%, Most preferably, it is 1 -10 mass%.

-Other components-
In the photocurable composition of the present invention, a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and other than the above alkali-soluble resin, if necessary. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Chain transfer agent>
Examples of the chain transfer agent that can be added to the photocurable composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the object to be coated and the coating liquid is reduced to improve the wettability to the object to be coated, and the coating property to the object to be coated is improved, so a thin film of about several μm can be formed with a small amount of liquid. Even if it is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content of the fluorine-based organic compound is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass in the total solid content of the photocurable composition. is there. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 8 2 (manufactured by JEMCO (Ltd.)), and the like.

The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.
0.001-2.0 mass% is preferable with respect to the total mass of a photocurable composition, and, as for the addition amount of a fluorine-type organic compound, More preferably, it is 0.005-1.0 mass%.

<Thermal polymerization initiator>
It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Thermal polymerization component>
It is also effective to include a thermal polymerization component in the photocurable composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

<Surfactant>
The photocurable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coating properties. In addition to the above-mentioned fluorosurfactants, nonionic, cationic, and anionic Various surfactants of the system can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the photocurable composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the pigment dispersion composition is further improved, the pigment dispersion composition may be an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Thermal polymerization inhibitor>
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis of polymer 1)
M-11 (previously exemplified compound M-11) 14.0 g, polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Co., Ltd.) 105.0 g, acrylic acid 21.0 g, n-dodecyl mercaptan 5 .6 g and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C. To do. 1.1 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added thereto, and the mixture was stirred with heating at 75 ° C. for 2 hours. Thereafter, 1.1 g of V-601 was further added, and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours, and then a 30% solution of polymer 1 was obtained.
The weight average molecular weight of the obtained polymer compound was measured by a gel permeation chromatography method (GPC) using polystyrene as a standard material, and found to be 19000.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 20/65/15.

(Synthesis of polymer 2)
M-11 14.0 g, hydroxyethyl methacrylate caprolactone 5 mol addition oligomer (Placcel FM5, manufactured by Daicel Chemical Industries, Ltd.) 105.0 g, acrylic acid 21.0 g, n-dodecyl mercaptan 3.3 g and methoxypropylene glycol 327 g Then, the mixture is introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C. To this was added 1.2 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.2 g of V-601 was further added and stirred with heating for 2 hours, then heated to 90 ° C. and stirred with heating for 2 hours, and then a 30% solution of polymer 2 was obtained.
The weight average molecular weight of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and was found to be 15,000.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

(Synthesis of A-3)
Into a 500 mL three-necked flask, 160.0 g of ε-caprolactone was introduced and 18.3 g of 2-ethyl-1-hexanol was stirred and dissolved while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 100 degreeC. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 22.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, the disappearance of the raw material was confirmed by ¹ H-NMR, and then cooled to room temperature to obtain 200 g of solid (A-3). It was confirmed by ¹ H-NMR, IR, and mass spectrometry that it was (A-3).

(Synthesis of Polymer 3)
15.0 g of M-11, 105.0 g of A-3 synthesized above, 21.0 g of acrylic acid, 3.1 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 75 ° C. while flowing nitrogen into the flask. To this was added 1.2 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.2 g of V-601 was further added and stirred with heating for 2 hours, then heated to 90 ° C. and stirred with heating for 2 hours, and then a 30% solution of polymer 2 was obtained.
It was 23,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

(Synthesis of polymer 4)
28.0 g of benzyl methacrylate, 91.0 g of A-3 synthesized above, 21.0 g of acrylic acid, 4.2 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask and stirred (Shinto). The temperature is increased to 75 ° C. by stirring while flowing with nitrogen in the flask. To this, 1.0 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added, and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.0 g of V-601 was further added and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours, and then a 30% solution of polymer 4 was obtained.
It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

(Synthesis of polymer 5)
The polymer was synthesized in the same manner as the polymer 4 except that 28.0 g of benzyl methacrylate, 105.0 g of A-3 synthesized above, 7.0 g of acrylic acid, and 3.8 g of n-dodecyl mercaptan were used.
It was 23,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 39 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/5.

(Synthesis of polymer 6)
The polymer was synthesized in the same manner as the polymer 4 except that 14.0 g of benzyl methacrylate, 84.0 g of A-3 synthesized above, 42.0 g of acrylic acid, and 4.5 g of n-dodecyl mercaptan were changed.
It was 18,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 234 mg KOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 10/60/30.

(Synthesis of Comparative Polymer 1)
M-11 14.0 g, polymethyl methacrylate having a methacryloyl group at the end (AA-6: manufactured by Toagosei Co., Ltd.) 105.0 g, methacrylic acid 21.0 g, n-dodecyl mercaptan 5.6 g and methoxypropylene glycol 327 g, The mixture is introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C. To this was added 1.1 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.1 g of V-601 was further added and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours, and then a 30% solution of Comparative Polymer 1 was obtained.
It was 22,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 98 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

The resultant polymer 3-6 in the above, a (A) specific graft polymer of the present invention, any of the polymer 3-6, at least the macromonomer der Ru A - 3, co-acrylic acid A polymer obtained by polymerization.

<Preparation of pigment dispersion composition>
The components having the composition shown in Table 1 below were mixed, and the mixture was stirred for 3 hours at a rotational speed of 3,000 rpm using a homogenizer to prepare a mixed solution containing a pigment.
Subsequently, the obtained mixed solution was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.2 mmφ zirconia beads, and then further a high-pressure disperser NANO-3000 with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using -10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 1.
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer, viscosity η1 of the pigment dispersion composition immediately after dispersion, and after 10 days after dispersion (at 60 ° C.) The viscosity η2 of the pigment dispersion composition was measured, and the degree of thickening was evaluated. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. This sample was placed between two polarizing plates, and the luminance when the polarizing plate was parallel and the luminance when it was orthogonal were measured with (Topcon BM-5), and contrast = luminance when parallel / luminance when orthogonal. Asked. Here, a high contrast indicates that the pigment is uniformly dispersed in a highly refined state.

The compounds used in Table 1 are shown below.
Pigment R1: C.I. I. Pigment Red 254 Average primary particle size 30 nm
Pigment R2: C.I. I. Pigment Red 254 Average primary particle size 23 nm
Basic Graft Polymer: Polymer obtained by amidation reaction of polyester obtained by ring-opening polymerization of ε-caprolactone with dodecanoic acid and polyethyleneimine Weight average molecular weight: 20000
PGMEA: 1-methoxy-2-propyl acetate derivative A:
Derivative B: [Chemical Formula 14]

From Table 1, Examples 3, 4, 7, 8, and 11 to 14 using the specific graft polymer of the present invention have a small increase in viscosity over time and good dispersion stability as compared with Comparative Examples. It can be seen that the contrast is high and the pigment particles are finely dispersed.

<Preparation of pigment dispersion composition>
Each component of the following composition (1)-(4) was mixed, and it stirred and mixed for 3 hours at 3,000 rpm using the homogenizer, and prepared the mixed solution containing a pigment.
[Composition (1)]
・ C. I. Pigment Red 254 Average primary particle size 25 μm 110 parts Polymer 1 (30% by mass solution) as a dispersant 200 parts 1-methoxy-2-propyl acetate 750 parts

[Composition (2)]
・ C. I. Pigment Red 254 Average primary particle size 25 μm 110 parts Polymer 3 (30% by weight solution) as a dispersant 200 parts 1-methoxy-2-propyl acetate 750 parts

[Composition (3)]
・ C. I. Pigment Red 254 Average primary particle size 25 μm 110 parts. Polymer 1 (30% by weight solution) as a dispersing agent 100 parts Basic graft type dispersing agent (same as used in Example 9) 30 parts 1-methoxy 820 parts of 2-propyl acetate [composition (4)]
・ C. I. Pigment Red 254 Average primary particle size 25 μm 110 parts Polymer 3 (30% by weight solution) as dispersant 100 parts Basic graft type dispersant (same as used in Example 9) 30 parts 1-methoxy 820 parts of 2-propyl acetate

[Composition (5)]
・ C. I. Pigment Red 254 Average primary particle size 25 μm 110 parts Comparative polymer 1 (30% by mass solution) as a dispersant 200 parts 1-methoxy-2-propyl acetate 750 parts

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions (1) to (5).

<Preparation of photocurable composition>
Using the obtained pigment dispersion composition, photocurable compositions having a pigment concentration of 35 mass% and 42 mass% were prepared.

<Preparation of color filter using photocurable composition>
The obtained photocurable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Covered with and rested for a certain time. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 2 below.
(1) Contrast A polarizing plate is placed on the colored resin film of the colored filter substrate, and the colored resin film is sandwiched between them. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are obtained using BM-5 manufactured by Topcon Corporation. The value obtained by measuring and dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. Larger values indicate higher contrast.

(2) Development residue A substrate whose development time was changed to 20 seconds, 30 seconds, 50 seconds, and 70 seconds was observed with an optical microscope to see how the unexposed portions remained on the glass substrate. The higher the score, the better.
No residue at development time of 20 seconds: 5
There is no residue at a development time of 30 seconds or more, but there is a residue at a development time of 20 seconds: 4
There is no residue at a development time of 50 seconds or more, but there is a residue at a development time of 30 seconds: 3
There is no residue at development time of 70 seconds or more, but there is residue at development time of 50 seconds or less: 2
Even with a development time of 70 seconds, there are residues in the unexposed areas: 1

(3) Evaluation of re-dissolution The following re-dissolution was evaluated as an alternative method for evaluating the presence or absence of foreign matter defects in slit coating.
Each of the photocurable compositions of Examples and Comparative Examples was applied to a 50 mm square glass substrate by spin coating so that the film thickness after drying was 1 μm and air-dried for 60 minutes. Thereafter, 1 μL of a solvent 1-methoxy-2-propyl acetate (hereinafter also referred to as PGMEA) for forming the photocurable composition was dropped. A sample dissolved with 6 drops or less was marked with ◯, a sample dissolved with 7 to 8 droplets was marked with Δ, and a sample that was not re-dissolved even when dropped over 9 drops was marked with ×.
In addition, the foreign substance defect occurrence rate by slit coating was 0%, which corresponds to a film that dissolves in 6 or less drops of PGMEA in the re-solubility test.

The compounds used in Table 2 are shown below.
Polymerizable compound: dipentaerythritol pentahexaacrylate photopolymerization initiator: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine Alkali-soluble resin: 1-methoxy-2-propyl acetate solution of benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) (solid content 30%)
Solvent: 1-methoxy-2-propyl acetate

From Table 2, when Examples 16 and 18 having a pigment concentration of 35% by mass and Comparative Example 3 were compared , and Examples 20 and 22 having a pigment concentration of 42% by mass and Comparative Example 4 were compared with each other, the specification of the present invention was confirmed. It can be seen that the examples using the pigment dispersions (2) and (4) containing the graft polymer have higher contrast, less development residue, and excellent PGMEA resolubility than the comparative examples.

<Preparation of pigment dispersion composition>
Components of the following compositions (6) to (9) are mixed, and the rotational speed is 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (6)]
・ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 1 (30% by mass solution) as a dispersant 180 parts 1-methoxy-2-propyl acetate 750 parts [Composition (7)]
・ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle diameter 24 nm) 45 parts Polymer 3 (30% by weight solution) as a dispersant 180 parts 1-methoxy-2-propyl acetate 750 parts

[Composition (8)]
・ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 3 (30% by weight solution) as a dispersant 60 parts Basic graft type dispersant (same as that used in Example 9) 36 parts / 1 820 parts of methoxy-2-propyl acetate

[Composition (9)]
・ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Comparative polymer 1 (30% by mass solution) as a dispersant 180 parts 1-methoxy-2-propyl acetate 750 parts

[Composition (10)]
・ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 3 (30% by weight solution) as a dispersant 40 parts Basic graft type dispersant (same as that used in Example 9) 36 parts / 1 -750 parts of methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions (6) to (9).

<Preparation of photocurable composition>
Using the obtained pigment dispersion composition, photocurable compositions having a pigment concentration of 35 mass% and 42 mass% were prepared.
<Preparation of color filter using photocuring composition>
The obtained photocurable composition (color resist solution) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.650, It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Covered with and rested for a certain time. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated in the same manner as in Example 13. The results are shown in Table 3 below.

The compounds used in Table 3 are shown below.
Polymerizable compound: dipentaerythritol pentahexaacrylate photopolymerization initiator: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine Alkali-soluble resin: 1-methoxy-2-propyl acetate solution of benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) (solid content 30%)
Solvent: 1-methoxy-2-propyl acetate

From Table 3, when Examples 24 and 25 having a pigment concentration of 35% by mass and Comparative Example 5 were compared , Examples 27 and 28 having a pigment concentration of 42% by mass and Comparative Example 6 were compared, respectively, the identification of the present invention was confirmed. Examples using the pigment dispersions ( 7), (8), and (10) containing the graft polymer have higher contrast, less development residue, and excellent PGMEA resolubility than the comparative examples. I understand that.

<Preparation of resist solution>
Components of the following composition were mixed and dissolved to prepare a resist solution.
Composition of resist solution 1-methoxy-2-propyl acetate 19.20 parts ethyl lactate 36.67 parts benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio = 60/22/18) 40% of polymer 1-methoxy-2-propyl acetate (PGMEA) solution 30.51 parts · dipentaerythritol hexaacrylate 12.20 parts · polymerization inhibitor (p-methoxyphenol) 0.0061 parts · fluorinated surface activity Agent 0.83 parts (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Photopolymerization initiator (manufactured by Midori Chemical Co., TAZ-107) 0.586 parts

<Production of silicon wafer with undercoat layer>
The 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Got.

<Preparation of pigment dispersion composition>
Components of the following composition (11) and (12) are mixed, and the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition A]
-Pigment (pigment described in Table 4) 100 parts-Polymer 1 (30% by weight solution) 200 parts as a dispersant-1-methoxy-2-propyl acetate 750 parts

[Composition B]
-Pigment (pigment described in Table 4) 100 parts-Comparative polymer 1 (30% by mass solution) as a dispersant 200 parts-1-methoxy-2-propyl acetate 750 parts

Subsequently, each mixed solution obtained above was further subjected to a dispersion treatment for 3 hours by a bead disperser disperse mat (manufactured by GETZMANN) using 0.8 mmφ zirconia beads, and then further a high pressure disperser with a pressure reducing mechanism. Dispersion treatment was performed using NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ . This dispersion treatment was repeated 5 times to obtain the pigment dispersion compositions shown in Table 4.

<Preparation of photocurable composition (coating liquid)>
Using each of the pigment dispersions obtained above, stirring and mixing were performed to obtain the following composition to prepare a photocurable composition.
<composition>
-1000 parts of the above pigment dispersion-Photopolymerization initiator (CGI-124 manufactured by Ciba Specialty Chemicals)
20 parts Polymerizable compound Dipentaerythritol hexaacrylate 20 parts Polymerizable compound (TO-756, manufactured by Toagosei Co., Ltd.) 35 parts 1-methoxy-2-propyl acetate 20 parts

<Production and Evaluation of Color Filter with Photocurable Composition>
The photocurable composition prepared as described above was applied on the undercoat layer of the silicon wafer with the undercoat layer described above to form a colored layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), various exposure doses in the range of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.5 μm square at a wavelength of 365 nm. And exposed.

  Thereafter, the silicon wafer substrate on which the coating film after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is supplied from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. A rinsing process was performed by supplying a shower from a jet nozzle, followed by spray drying.

<Evaluation of uneven color>
In the same manner as the preparation of the silicon wafer with the undercoat layer described above, a resist solution is applied onto the glass plate to create a glass substrate with the undercoat layer, and the photocurable composition is applied onto the glass with the undercoat layer and colored. A layer (coating film) was formed. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm. The luminance distribution of the coated glass plate was analyzed from an image taken with a microscope MX-50 (Olympus).
The luminance distribution was analyzed, and the color unevenness was evaluated based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.

-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels. Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels. : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

It can be seen from Table 4 that the reference examples 30 to 32 have better color unevenness than the comparative example.

Claims (14)

(A) 40-90 mass% of the compound represented by the following general formula (i) is copolymerized in the main chain , and 5-30 mass% of acrylic acid , and the weight average molecular weight is in the range of 1,000-100,000. graft high-molecular polymer is a pigment dispersion composition characterized by containing the (B) pigment, and (C) an organic solvent.

In General Formula (i), R ^{1 to} R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents —C (═O) O—. L ¹ represents an alkyleneaminocarbonyl group. m represents 5 and p represents an integer of 1 to 100. A ¹ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. The pigment dispersion composition according to claim 1, wherein the graft polymer (A) is further copolymerized with a monomer represented by the following general formula (4) as a copolymer component.

In general formula (4), R ⁸ Represents a hydrogen atom or an alkyl group. R ⁹ Represents a single bond or a divalent linking group. P represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Q represents a group having a nitrogen-containing heterocyclic structure. The pigment dispersion composition according to claim 1 or 2, wherein the compound represented by the general formula (i) is a compound represented by the following formula (A-3).

  The pigment dispersion composition according to claim 2 or 3, wherein the compound represented by the general formula (4) is a compound represented by the following formula M-11.

5. The pigment dispersion composition according to claim 1, wherein an average primary particle diameter of the pigment (B) is in the range of 10 to 25 nm. Furthermore, (D) basic graft type polymer compound is contained, The pigment dispersion composition of any one of Claims 1-5 characterized by the above-mentioned. The value obtained by dividing the total mass of the polymer compound contained in the pigment dispersion composition by the total mass of the (B) pigment and the (E) pigment derivative is 0.55 or less. The pigment dispersion composition according to any one of claims 1 to 6 . A pigment dispersion composition according to any one of claims 1 to 7, (F) a polymerizable compound, (G) a photopolymerization initiator and a photocurable composition containing a. The photocurable composition according to claim 8, wherein the polymerizable compound (F) is a tetrafunctional or higher functional acrylate compound. Furthermore, the alkali-soluble resin is at least one selected from a copolymer obtained by copolymerizing at least an alkyl (meth) acrylate and (meth) acrylic acid. The photocurable composition as described. The photocurable composition according to any one of claims 8 to 10, wherein the pigment concentration is 35% by mass or more. The color filter which has a coloring pattern formed using the photocurable composition of any one of Claims 8-11 . A liquid crystal display device comprising the color filter according to claim 12 . A solid-state imaging device comprising the color filter according to claim 12 .