JP2009102532A - Colored composition, colored photocurable composition, color filter, liquid crystal display device, and solid state imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition leaving little residue, forming a favorable pattern after development, and having high contrast and a favorable heat resistance. <P>SOLUTION: The colored composition comprises (a) a pigment, (b) a pigment derivative having an acid group and (c) a polymer compound. In the colored composition and/or a colored curable composition, the colored composition is dissolved in an aqueous alkali solution having a KOH concentration of 0.05 mass% in 30 seconds or less when formed into a coating film with a dried thickness of 1.0 μm, and (a) the pigment is covered with (b) the pigment derivative having an acid group or (c) the polymer compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is excellent in dispersibility of pigments, excellent in coloring power and developability of colored compositions and colored 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 composition, a colored photocurable composition, and a color filter produced using the colored photocurable composition.

  The color filter contains a colored composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored photocurable composition. It is manufactured by forming a colored pattern by a photolithography method, an ink jet method or the like.

  In recent years, color filters have been used not only for monitors but also for televisions in liquid crystal display (LCD) applications, and with this expansion of applications, advanced color characteristics such as chromaticity and contrast have been required. Yes. In addition, advanced color characteristics such as reduction in color unevenness and improvement in color resolution are also demanded for solid-state imaging devices (image sensors).

  In order to meet the above requirements, the pigment particles are required to have a finer particle size and higher dispersibility. To increase the dispersibility of the pigment, for example, the surface of the phthalocyanine pigment is usually applied to the surface. Using a dispersant such as a low molecular weight resin molecule having a polar functional group that is easily adsorbed on the modified surface, the pigment surface is modified with a derivative compound, while dispersing or stabilizing the pigment, A pigment composition containing a surface modifier and a dispersant is obtained. The obtained pigment composition further contains an alkali-soluble resin, a photopolymerizable composition, a photopolymerization initiator, and other components to obtain a photocurable composition, and a color filter is obtained by using the photolithographic method. ing.

  In order to obtain high color characteristics, it is an effective means to reduce the particle diameter of the pigment. However, when the size is reduced, the surface area of the pigment particles is increased, and the dispersibility of the pigment is deteriorated. For this improvement, a larger amount of a surface modifier or a dispersant for modifying the pigment surface is required. For example, in order to improve the contrast, the amount of the surface modifier and the dispersant is 10 to 20% by mass of the pigment amount. For this reason, the surface modifier and the dispersant are colored. The influence on the color characteristics of the filter cannot be ignored. Moreover, the developability for forming the colored pattern is greatly deteriorated.

In order to improve the dispersibility of the pigment, it has been reported that various pigment derivatives are used (for example, see Patent Documents 1 and 2). However, even with these techniques, it is necessary to use a large amount of pigment derivative or dispersant in order to ensure the dispersibility of the fine pigment. For this reason, developability was extremely deteriorated, and only a colored photocurable composition having no production suitability was obtained.
In addition, in order to suppress strong secondary aggregation of the refined pigment, a rosin or rosin derivative is added during the salt milling process to treat the pigment, and a color filter having a high contrast is obtained using the pigment dispersion. A technique to obtain is proposed (see, for example, Patent Document 3).
However, even with these methods, it is impossible to meet market demands for improving color characteristics such as higher contrast, and higher dispersibility and dispersion stability in finer pigments have been desired. Development of a colored photocurable composition having a wide development latitude suitable for production is a high market need.
As mentioned above, it is possible to obtain some improvement effect by focusing only on the color characteristics such as the finer pigment particles and the contrast of the image. However, the development latitude is low if an inexpensive and highly productive color filter is to be obtained. Narrow and not usable.
JP 2006-265528 A JP 2007-79094 A Japanese Patent No. 3130217

  The present invention has been made in view of the above. That is, the problem to be solved by the present invention is to obtain a colored composition having high pigment dispersibility and dispersion stability after dispersion and good color characteristics such as contrast. Furthermore, it is to obtain a colored photocurable composition having good developability and capable of obtaining a colored pixel pattern with a wide development latitude. This provides a color filter with good productivity, provides a color filter for liquid crystal display devices with high contrast, good heat resistance, and good color characteristics, and reduces color unevenness and good color separation. An object is to provide a color filter for a solid-state imaging device.

Specific means for achieving the above object are as follows.
<1> A colored composition containing (a) a pigment, (b) a pigment derivative having an acidic group, and (c) a polymer compound, and a coating film having a dry film thickness of 1.0 μm is formed from the colored composition. When this is done, the coating composition dissolves in an alkaline aqueous solution having a KOH concentration of 0.05% by mass in 30 seconds or less.
<2> The colored composition according to <1>, wherein (a) the pigment is coated with (c) a polymer compound.
<3> The colored composition according to <1> or <2>, wherein (a) the pigment is coated with (b) a pigment derivative having an acidic group.
<4> The colored composition according to any one of <1> to <3>, wherein the pigment derivative having an acidic group (b) is a pigment derivative having a sulfonic acid group and / or a sulfonate.
<5> A colored photocurable composition, wherein the colored composition according to any one of <1> to <4> contains a photopolymerizable compound and a photopolymerization initiator.

<6> A color filter having a colored pattern using the colored photocurable composition according to <5> on a substrate.
<7> A liquid crystal display device comprising the color filter according to <6>.
<8> A solid-state imaging device comprising the color filter according to <6>.

As a more preferred embodiment, the colored photocurable composition according to <5>, comprising an acrylic resin containing <9> N-phenylmaleimide as a constituent component.
The colored photocurable composition as described in <5> containing the acrylic resin which has an alicyclic ring which has a <10> (meth) acryloyloxy group as a substituent in a side chain.
<11> The colored photocurable composition according to <5>, comprising an acrylic resin copolymerized with a hydroxyl group-containing (meth) acrylate.
<12> The colored photocurable composition according to <5>, further comprising an acrylic resin containing a polystyrene macromonomer as a constituent component.
<13> The colored composition according to <1>, wherein the polymer compound (c) is a graft polymer compound.

When the pigment is refined to improve the color characteristics, the surface area increases, and a new surface appears due to the crushing of the pigment. However, the new surface has a high surface energy, and thus the refined pigment tends to aggregate. In the present invention, aggregation is prevented by adsorbing and coating the high-energy surface of the micronized pigment with a pigment derivative having an acidic group and a polymer compound. Thus, it is presumed that the refined pigment is stabilized with primary particles. In particular, the pigment derivative having an acidic group of the present invention and the polymer compound have different molecular sizes, and the pigment derivative having a relatively low molecule enters the gap between the pigment surface coated with the polymer compound, resulting in high surface energy. It seems to cover the adsorption point and exert a high dispersion effect.
Since the pigment derivative has an acidic group, the non-exposed area exhibits high solubility during alkali development, a large development latitude, and a high color density, that is, a good pattern shape can be obtained even when the pigment density is high. It seems that was made. Further, by using a pigment derivative having an acidic group, the pigment surface is acidified and the pigment is easily developed. Therefore, the alkali developability function of the polymer compound or alkali-soluble resin can be reduced, so that the polymer compound or alkali-soluble resin can be reduced. It is thought that the heat resistant coloring of can be reduced.

  According to the present invention, a processed pigment having high pigment dispersibility and dispersion stability after dispersion, and good color characteristics such as contrast, and a pigment dispersion using the processed pigment can be obtained. In addition, it is possible to obtain a colored photocurable composition having good developability and capable of obtaining a colored pixel pattern with a wide development latitude. This provides a color filter with good productivity, a color filter for liquid crystal display devices with high contrast, good heat resistance, and good color characteristics, and a solid with reduced color unevenness and good color separation An image sensor color filter can be obtained. Further, the present invention prevents coloration due to heat in post-baking, which also contributes to the improvement of color characteristics.

Hereinafter, the best mode for carrying out the invention will be described in detail.
<Coloring composition>
The colored composition of the present invention comprises (a) a pigment, (b) a pigment derivative having an acidic group, and (c) a polymer compound as essential components.

When the colored composition of the present invention is formed into a coating film having a dry film thickness of 1.0 μm, the method used for dissolving it in an alkaline aqueous solution having a KOH concentration of 0.05 mass% in 30 seconds or less,
i) a method of increasing the affinity with an alkali developer by increasing the acid value of the polymer compound or alkali-soluble resin used in the colored composition;
ii) a method using a photopolymerizable compound having an acidic site,
iii) a method for increasing the alkali concentration of the alkali developer,
iv) A method of using a photopolymerizable initiator with low sensitivity, using a monomer having a small number of functional groups, increasing the film thickness, or reducing the exposure amount to reduce the crosslinking density of the photopolymerizable compound,
v) A method of increasing the affinity of the pigment particles with an alkaline developer by adding a resin having an acidic group during milling to cover the resin with an acidic group.
vi) In the case of using an acidic pigment derivative, methods such as increasing the acidity of the pigment derivative, increasing the number of acidic substituents of the pigment derivative, or increasing the amount of the pigment derivative added may be mentioned.

  Preferably, i) a method of increasing the acid value of a polymer compound, etc., ii) a method of using a photopolymerizable compound having an acidic site, v) a method of adding a resin having an acidic group during milling, vi) the acidity of the pigment derivative A method of increasing the number of acidic substituents of the pigment derivative, or increasing the amount of the pigment derivative added, particularly preferably i) a method of increasing the acid value of a polymer compound, etc., v) having an acidic group during milling A method of adding a resin, vi) a method of increasing the acidity of the pigment derivative, increasing the number of acidic substituents of the pigment derivative, or increasing the addition amount of the pigment derivative.

  As a method for increasing the acid value of the polymer compound or the like of i), specifically, a polymer compound having an acid value of 50 mgKOH / g to 500 mgKOH / g is used, and preferably an acid value of 80 mgKOH / g to 400 mgKOH / g. g, and particularly preferably a polymer compound having an acid value of 95 mgKOH / g to 300 mgKOH / g.

  The method of adding a resin having an acidic group during milling in v) will be specifically described in the section of (a) pigment.

  As a method for increasing the acidity of the pigment derivative of vi), specifically, a sulfonic acid group, a metal salt of sulfonic acid, an ammonium salt of sulfonic acid, a carboxylic acid group, and a phosphoric acid group are used as the acidic group. A method using a sulfonic acid group, a metal salt of sulfonic acid, or an ammonium salt of sulfonic acid as the acidic group is preferable. As a method for increasing the addition amount of the pigment derivative, specifically, the content of the pigment derivative having an acidic group with respect to the pigment is 0.1 to 50% by mass, more preferably 1.0 to 40% by mass. More preferably, it is 10-30 mass%.

Below, each component used by this invention is demonstrated.
(A) Pigment As the (a) pigment used in the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.

As the pigment, considering that the colored composition of the present invention is used for the color pattern of the color filter and preferably having a high transmittance at that time, an organic pigment is preferable, and a pigment having a particle size as small as possible. Is preferably used.
Considering the handling properties and color characteristics of the colored composition and the colored photocurable composition containing the same, the average primary particle size of the pigment used in the colored composition is preferably 60 nm or less, more preferably 30 nm or less. Preferably, 5 to 25 nm is most preferable. When the particle size 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.

  If necessary, the pigment used in the present invention can be refined by milling. Although the milling will be described later, the particle diameter of the pigment before being subjected to the milling step is about 25 to 60 nm.

  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 were changed to OH. Things, 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.
However, the present invention is not limited to these.

Among these, the pigments that can be preferably used include the following.
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 to increase color purity. Specific examples of combinations of organic pigments are shown below.
For example, as a red pigment, an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Alternatively, a perylene red pigment, an anthraquinone red pigment, and a diketopyrrolopyrrole red pigment can be mixed and 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 be lowered. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as the green pigment, a halogenated phthalocyanine pigment is used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. be able to.
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 a blue pigment, a phthalocyanine pigment can be used alone or in combination with a dioxazine purple pigment.
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.

-(B) Pigment derivative having acidic group-
The pigment derivative used in the present invention is not particularly limited as long as it is composed of a pigment dye structure, an organic linking group, and an acidic functional group. (B) The structure of the pigment derivative having an acidic group can be represented by the following general formula (1) or general formula (2).

  In the general formulas (1) and (2), [Pig] represents a pigment dye structure, and w represents a chain-like and branched organic linking group. A represents an acidic functional group. p and m represent an integer of 1 to 10.

<Pigment pigment structure>
The pigment dye structure is a portion represented by [Pig] in the general formula (1) and the general formula (2), and includes a pigment core structure or a pigment partial structure. When used as a pigment dispersion, the structure may be the same as or different from the structure of the pigment to be used, but from the viewpoint of the interaction between the pigment and the pigment derivative, it is preferably the same or similar to the pigment structure. Examples of pigment mother core structures include: Hansa yellow, disazo yellow, benzimidazolone, lake red, toluidine red, naphthol AS, isoindoline, isoindolinone, quinacridone, perylene, anthra Various pigments such as quinone, diketopyrrolopyrrole, dioxazine violet, phthalocyanine, azomethine, pteridine, naphthol, pyrazolone, indigo, thioindigo, xanthene, indazine, carbon black, etc. Can be used. As an example, if a pigment structure, (wherein which can be used a structure shown below, X is a substituent corresponding to this patent has an acidic functional group. In a molecule containing two or more X Each X may be different.) The pigment dye structure may be a pigment structure or a pigment partial structure, and is not limited to the following specific pigment structure.

<Acid functional group>
The acidic group of the pigment derivative in the present invention is A in the general formula (1) or (2), a sulfonic acid group, a sulfonate having a metal ion as a counter ion, or a monoalkylammonium having 1 to 12 carbon atoms. Examples thereof include sulfonic acid salts, carboxylic acid groups, phosphoric acid groups, hydroxyl groups, and boric acid groups having ions, dialkyl ammonium ions having 1 to 24 carbon atoms, and trialkyl ammonium ions having 1 to 36 carbon atoms as counter ions. Among these, from the viewpoint of reducing residues in development, sulfonic acid groups, sulfonates having a metal ion as a counter ion, and carboxylic acid groups are preferable, and more preferable as acidic groups in which residues on the substrate are less likely to remain. Includes sulfonates having a sulfonic acid group and a metal ion as a counter ion. As the metal ion which is a counter ion of the sulfonate, a metal ion selected from Group 1-13 of the periodic table can be used, and preferably a metal ion selected from Group 1-2 of the periodic table is used. More preferably, potassium ions and sodium ions can be used.

  The acidic group of the pigment derivative in the colored composition of the present invention can be used in combination of a plurality of types of acidic groups. For example, a sulfonate having a sulfonic acid group and a carboxylic acid group, a sulfonic acid group and a metal ion as a counter ion, and a sulfonic acid having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 36 carbon atoms as a counter ion. Examples thereof include a salt, a sulfonate group having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 72 carbon atoms as a counter ion and a hydroxyl group. The combination of acidic functional groups is not limited to these.

<Linking group>
The linking group of the pigment derivative having an acidic group in the present invention is w in the general formula (1) or the general formula (2), and is a divalent or higher valent organic linking group.

  The organic linking group is not particularly limited as long as it is a divalent or higher valent linking group, but is preferably linear or branched, which may be substituted on the chain or may have a linking group introduced into the chain. Linear alkylene group, a linear poly (alkyleneoxy) group which may be substituted on the chain, or a linking group may be introduced into the chain, which may be substituted on the chain or a linking group in the chain And a linear or branched unsaturated hydrocarbon group in which may be introduced. The substituent on the chain in the linear or branched alkylene group, linear poly (alkyleneoxy) group, linear or branched unsaturated hydrocarbon group is not particularly limited, but is a hydrogen atom, a fluorine atom, or a carbon number. An alkyl group having 1 to 24 carbon atoms, a fluoroalkyl group having 1 to 24 carbon atoms, an allyl group, an aralkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, a heteroaryl group having 1 to 24 carbon atoms, and a carbon number An amino group optionally having 1 to 24 substituents, an alkoxycarbonyl group having 1 to 24 carbon atoms, an aryloxycarbonyl group having 1 to 24 carbon atoms, and an alkylaminocarbonyl group having 1 to 24 carbon atoms An arylaminocarbonyl group having 1 to 24 carbon atoms, an alkylcarbamoyl group having 1 to 24 carbon atoms, an arylcarbamoyl group having 1 to 24 carbon atoms, or carbamoyloxy Etc. The. As a linking group in the chain of a linear or branched alkylene group, a linear poly (alkyleneoxy) group, or a linear or branched unsaturated hydrocarbon group, an oxygen atom, a sulfur atom, a nitrogen atom, an ester group, An amide group, a urea group, a carbamoyl group, etc. are mentioned. The repeating number of each of the linear poly (alkyleneoxy) groups is preferably 2 to 12, more preferably 2 to 6.

  Although the specific example of the pigment derivative in this invention is given below, it is not limited to these.

As content with respect to the pigment of the pigment derivative which has an acidic group in this invention, it is 0.1-50 mass%, More preferably, it is 1.0-40 mass%, More preferably, it is 10-30 mass%. . It is preferable for the content to be in the above-mentioned range since the dispersion stability is high and color characteristics such as contrast are not impaired.
The pigment derivative in the present invention may be used alone or in combination of two or more.

-(C) polymer compound-
As the polymer compound (c) used in the present invention, linear polymers, graft polymers, block polymers, terminal-modified polymers, etc. can be used, and acrylic, polyurethane, polyester and polyimide polymers having these structures are used. A compound can be preferably used.
Among these, a polymer compound having a graft structure and a linear polymer are preferable, and a polymer compound having a graft structure is particularly preferable. Hereinafter, preferred linear polymers and graft polymer compounds for the present invention will be described.

  The linear polymer used in the present invention is a polymer compound having a weight average molecular weight of 1,000 to 100,000 and is obtained by polymerizing a radical polymerizable monomer such as a (meth) acrylate monomer or a styrene monomer. There is no particular limitation.

The graft polymer compound used in the present invention is a graft polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less, that is, a side chain having a predetermined molecular weight (main chain). The polymer compound is not particularly limited as long as the polymer compound has a structure in which a branched polymer) is bonded.
Preferred examples of the trunk (main chain) of the graft polymer compound of the present invention include those composed of polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, polyurethane, polyamide, polyester, and the like. It is done.
Moreover, the branch part (graft chain) of the graft type polymer compound of the present invention is composed of polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylate, polycaprolactone, polyurethane, polyamide, polyester, and the like. Preferably mentioned.
In this specification, when referring to “acrylic”, “methacrylic” and “acrylate”, “methacrylate” or both, “(meth) acrylic” and “(meth) acrylate” are used respectively. There is.
Moreover, the graft type polymer compound of the present invention may be collectively referred to as a specific graft type polymer compound.

As described above, as long as the structure has a graft chain, the trunk portion and the branch portion may be formed of the same polymer species, or may be different from each other. Further, the polymer chains of the trunk part and the branch part can contain various partial structures depending on the purpose. For example, it is possible to further improve the adsorptivity of the specific graft polymer compound to the pigment surface by introducing a functional group having excellent pigment adsorptivity into the trunk.
When synthesizing a specific graft-type polymer compound that can be suitably used in the present invention, a structural unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal is used together with a structural unit derived from a monomer that forms a main chain. Copolymerization is preferable from the viewpoint of controlling the chain length and characteristics of the graft chain to be introduced, and obtaining a polymer compound that is excellent in adsorptivity to pigment and excellent in stability over time.

A polymerizable oligomer having an ethylenically unsaturated double bond at a terminal useful for forming a side chain structure in a specific graft-type polymer compound is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.
The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

The macromonomer used for the synthesis of the specific graft type polymer compound according to the present invention preferably has a polystyrene-equivalent number average molecular weight (Mn) in the range of 500 to 10,000, preferably 1,000 to 9,000. A range is particularly preferred.
From the viewpoint of the dispersibility and dispersion stability of the pigment contained in the coloring composition and the contrast of the color filter obtained by applying the coloring composition, the number average molecular weight (Mn) of the macromonomer is 500 or more. It is preferable. From the viewpoint of developability when producing a color filter with a photocurable composition containing a colored composition, the number average molecular weight (Mn) of the macromonomer is preferably 10,000 or less.

The polymer chain portion in the macromonomer includes alkyl (meth) acrylate, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N′-dialkyl (meth) acrylamide, styrene, (meth) acrylonitrile, vinyl acetate, and It may be a homopolymer or copolymer formed from at least one monomer selected from the group consisting of butadiene, or polyethylene oxide, polypropylene oxide, or polycaprolactone.
These polymer chains may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a carbamoyl group. Is mentioned.

Specific examples of the alkyl group in the alkyl (meth) acrylate, N-alkyl (meth) acrylamide, etc. that form the polymer chain include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, Octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-methoxycarbonylethyl, 2-methoxyethyl, 2-bromopropyl, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2 -Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, Tilbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3.2.1] oct-2-yl group, 1-adamantyl group, Examples thereof include dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutylaminocarbamoylmethyl group and the like.
Among such alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferable, and an unsubstituted alkyl group is particularly preferable.

Among these polymer chains, from the viewpoint of dispersion stability and developability of the resulting graft polymer compound, unsubstituted or alkyl having a hydroxyl group as a substituent and an alkoxy group having 1 to 4 carbon atoms (meta ) Acrylate, (meth) acrylamide, unsubstituted or N-alkyl (meth) acrylamide having an alkyl group having 1 to 4 carbon atoms as a substituent, unsubstituted or an alkyl group having 1 to 4 carbon atoms as a substituent N, N′-dialkyl (meth) acrylamide having a non-substituted, or styrene having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms as a substituent, and (meth) acrylonitrile Homopolymer or copolymer formed from at least one selected monomer, polycaprolactone, polyethyleneo Xoxide and polypropylene oxide are preferred, unsubstituted or substituted with a hydroxyl group and an alkyl (meth) acrylate having an alkoxy group of 1 to 4 carbon atoms, unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms. N, N′-dialkyl (meth) acrylamide having no substituent, or formed from at least one monomer selected from the group consisting of styrene having an alkoxy group having 1 to 4 carbon atoms as a substituent, and (meth) acrylonitrile. Homopolymers or copolymers and polycaprolactone are particularly preferred.
As a macromonomer useful for synthesizing a graft type polymer compound, an oligomer represented by the following general formula (5) is preferably exemplified.

R ¹¹ and R ^{13 in} the general formula (5) each independently represent a hydrogen atom or a methyl group.
R ^{12 in the} general formula (5) represents a linking group containing an alkylene group having 1 to 12 carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups The group may be linked via an ester bond, an ether bond, an amide bond or the like. The alkylene group for R ¹² is preferably an alkylene group having 2 to 4 carbon atoms. The alkylene group for R ¹² may further have a substituent such as a hydroxyl group or an alkoxy group.
Y ¹¹ represents a phenyl group which may have a substituent, -COOR ¹⁴ , a cyano group, or -CONR ¹⁵ R ¹⁶ . Here, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When R ¹⁴ , R ¹⁵ , R ¹⁶ , and Y ¹¹ represent an alkyl group or a phenyl group, these may further have a substituent. Examples of the substituent that can be introduced here include a hydroxyl group, an alkoxy group, a halogen atom, Atom.
Y ¹¹ is preferably a phenyl group, a cyano group or —COOR ¹⁴ , where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms. Y ¹¹ is most preferably —COOR ¹⁴ or a cyano group from the viewpoints of dispersion stability and developability.
q represents an integer of 10 to 200.
In the macromonomer of the general formula (5), q structural units may be connected to only one type or a copolymer including two or more types of structural units. Two or more different types of R ¹³ and Y ¹¹ may exist.

  Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene polymer, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-i-butyl (meth) acrylate, poly Acrylonitrile, polyacetoacetoxyethyl methacrylate, poly-2-methoxyethyl methacrylate, poly-2-methoxyethoxyethyl methacrylate, polyacrylamide, N, N′-dimethylacrylamide, and a copolymer thereof, A polymer having a meth) acryloyl group bonded thereto is preferable.

The polymerizable oligomer may be a commercially available product or may be appropriately synthesized. Examples of the commercially available product include a one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6). , Manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end methacryloylated poly-n-butyl Acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AA-714) Toa Gosei Chemical Co., Ltd.), one-end methacryloylated polybutyl methacrylate / -Hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated poly 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AY) -707S, AY-714S, manufactured by Toa Gosei Chemical Co., Ltd.) and the like.
The specific graft type polymer compound may contain only one type of copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, or may contain two or more types.

  As content of the said copolymerization unit in a specific graft type polymer compound, the said polymerizable oligomer is 20-80 mass%, Preferably it is 40-80 mass%. When the content of the polymerizable oligomer is within the above range, the solubility in the dispersion solvent is appropriately maintained, and it is possible to sufficiently secure an adsorption layer necessary for stabilizing the dispersion. Thus, even when a curable composition is formed, developability is not impaired.

Next, the main chain structure of the specific graft polymer compound according to the present invention will be described.
The trunk (main chain) of the specific graft polymer compound may be composed of any one of polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, polyurethane, polyamide, polyester, and the like. A polystyrene or poly (meth) acrylic acid ester skeleton is preferable.
For the purpose of enhancing the adsorption of the graft polymer and the linear polymer to the pigment, in addition to the monomer forming the main chain skeleton and the macromonomer described above for forming the graft, a functional group capable of adsorbing to the pigment It is preferred to further copolymerize a monomer having a graft polymer compound.
Specific examples of the monomer having a functional group that can be adsorbed to the pigment include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, a monomer having an ionic group, etc. Can be mentioned.
Here, the functional group capable of adsorbing to these pigments may be directly bonded to the polymerizable partial structure forming the main chain structure. You may couple | bond together through the following structural unit or the coupling group comprised combining this structural unit.

  The monomer having an organic dye structure or a heterocyclic structure is preferably a monomer represented by the following general formula (3), a maleimide, or a maleimide derivative. A monomer represented by the following general formula (4) is particularly preferable.

In general formula (3), R ¹ represents a hydrogen atom or an alkyl group. R ^{2 in the} general formula (3) represents a single bond or a divalent linking group. Y in the general formula (3) represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
The alkyl group represented by R ¹ may have a substituent, and examples of the substituent that can be introduced include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 carbon atom). -3), methoxy group, ethoxy group, cyclohexyloxy group and the like.
Specific examples of preferable alkyl group represented by R ¹ 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 ¹ is most preferably a hydrogen atom or a methyl group.

In General Formula (3), R ² represents a single bond or a divalent linking group. As the divalent linking group, an 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 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 ² 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 ² 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 ² has a substituent, examples of the substituent include a hydroxy group and an alkoxy group.
Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the above 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 be linked to Z via the heteroatom or a partial structure containing a heteroatom.

In general formula (3), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, 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.
Z 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 (4), (6) or (7) is particularly preferable.

In general formula (4), F 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 F in the general formula (4), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (7), Y ¹ and Z ¹ 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. 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 ¹ and Z ¹ in the general formula (7), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y ¹ and Z ¹ include a combination in which ^one of Y ¹ and Z ¹ is —N═ and the other is —NH—, and an imidazolyl group.

In general formulas (4), (6), and (7), ring B ¹ , ring B ² , ring C, and ring E 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 (4) 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 E 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 (4), (6) or (7), those having a benzene ring or a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion. In 4) or (7), those having a benzene ring are more preferred, and in formula (6), those having a naphthalene ring are more preferred.

  A monomer represented by the general formula (1), which is a more specific example of a monomer having an organic dye structure or a heterocyclic structure that can be suitably used for the synthesis of the specific graft-type polymer compound according to the present invention; Preferred specific examples of the maleimide and maleimide derivatives [Exemplary monomers (M-1) to (M-33)] are listed below, but the present invention is not limited thereto.

The specific graft type polymer compound according to the present invention includes a monomer represented by the general formula (3), a monomer having a functional group having a pigment adsorptivity represented by a polymer unit derived from a maleimide or a maleimide derivative. May be synthesized including only one type, or may be synthesized including two or more types.
Among the monomers represented by the general formula (3), maleimide, and maleimide derivatives, it is preferable to use the monomer represented by the general formula (3) from the viewpoint of improving the adsorptivity to the pigment.

In the specific graft type polymer compound, the content of the copolymer unit derived from the monomer represented by the general formula (3), maleimide, and maleimide derivative is not particularly limited, but the entire structure contained in the polymer When the unit is 100% by mass, it is preferable to contain 5% by mass or more of a copolymer unit derived from the monomer represented by the general formula (3), maleimide, maleimide derivative, and 10 to 50% by mass More preferably.
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 (3). The content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative is preferably 5% by mass or more. In addition, from the viewpoint of developability when producing a color filter with a photocurable composition containing a colored composition, the content of copolymer units derived from the monomer represented by the general formula (3) is: It is preferable that it is 50 mass% or less.

The specific graft-type polymer compound preferably has an acidic group as a functional group that can be adsorbed to the pigment. For this reason, it is preferable to copolymerize a monomer having an acidic group during synthesis.
Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.
Examples of the monomer having an acidic group that can be used for synthesis include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
When the specific graft-type polymer compound and the linear polymer have an acidic group, when the colored composition is applied to the photocurable composition, the development removability of the unexposed area is excellent.
The specific polymer may include only one type of copolymer unit derived from a monomer having an acidic group, or may include two or more types.

  The specific graft polymer compound and linear polymer in the present invention preferably contain an acidic group, more preferably a carboxyl group in the molecule, and the content of the carboxyl group is 50 mgKOH / g or more and 200 mgKOH / g or less. It is preferable to include in a range. That is, when applied to a colored photocurable composition and subjected to development, the formation of secondary aggregates, which are aggregates of primary particles of the pigment, are further suppressed in terms of suppressing the formation of precipitates in the developer. In order to effectively suppress or weaken the cohesive force of the secondary aggregate, it is preferable to contain a carboxyl group in the range of 50 mgKOH / g to 200 mgKOH / g.

In addition, as a functional group that can be adsorbed to the pigment, a basic nitrogen atom is also preferably exemplified. As a “group having a basic nitrogen atom” in a monomer having a basic nitrogen atom that can be used for the synthesis of a specific graft polymer compound. Is, for example, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 20 carbon atoms Preferred examples include alkyl groups, aryl groups having 6 or more carbon atoms, and aralkyl groups having 7 or more carbon atoms.), Guanidyl groups represented by the following formula (a1), amidinyl groups represented by the following formula (a2), and the like. As mentioned.

In formula (a1), R ²⁴ and R ²⁵ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ²⁴ and R ²⁵ are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ²⁴ and R ²⁵ are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ²⁶ and R ²⁷ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Specific examples of the functional group having a basic nitrogen atom include (meth) acrylic acid ester, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth ) Acrylic acid 1- (N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic N, N-diisopropylaminoethyl acid, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate , Piperidinoethyl (meth) acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyro (meth) acrylate Jill aminoethyl and (meth) acrylic acid and N, N- methylphenylamino ethyl.
Further, as (meth) acrylamides, N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylamino) Ethyl) acrylamide, N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide , Morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, etc. .

Further, in the synthesis of the specific graft type polymer compound, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, It is also possible to use a monomer having an epoxy group, an isocyanate group or a hydroxyl group.
Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number) Preferred examples include 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms. —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms). An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.

Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.
Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.
Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.
Specific examples include monomers having the following structure.

The “ionic functional group” that is a functional group that can be adsorbed to the pigment includes an anionic functional group and a cationic functional group.
As an anionic functional group, for example, an alkali metal salt of an acidic group such as a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, or a boric acid group, the acidic group and an organic amine And the like.
The alkali metal salt of an acidic group, Na salts, such as K salts can be ^{mentioned, -COO - Na +, -COO -} K +, -SO 3 - Na +, and the like.
The salt of the acidic group and an organic ^{amine, -COO - HN + R 32 R} 33 R 34, -SO 3 - HN + R 35 R 36 R 37 (R 32, R 33, R 34, R 35, R 36 , And R ³⁷ are each independently a hydrogen atom or a substituent (for example, a hydroxyl group, a sulfonamido group, an N-sulfonylamido group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms). Group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, etc.).

  Moreover, the salt represented by the following general formula is also mentioned suitably as a cationic functional group.

In the above general formula, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , and R ⁵¹ may each independently have a hydrogen atom or a substituent, and are linked to form a saturated or unsaturated cyclic structure. Represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group.
Q ⁻ represents a halogen anion (for example, Cl ⁻ , Br ⁻ , I ⁻ ), an organic acid anion such as RCOO ⁻ or RSO ₃ ^— (R may have a substituent, and is connected to be saturated or An anion such as an alkyl group having 1 to 18 carbon atoms, an aryl group or an aralkyl group which may form an unsaturated cyclic structure.
Z ² represents an atomic group that forms a heterocyclic group with nitrogen.

Examples of the ionic vinyl monomer having an ionic group that is a functional group capable of adsorbing to the pigment include an anionic vinyl monomer, an alkali metal salt of the vinyl monomer having an acidic group, and an organic amine (for example, triethylamine, dimethyl). And salts with tertiary amines such as aminoethanol).
As the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group having 1 to 18 carbon atoms: halogen atom: chlorine atom, bromine atom or iodine atom); halogenated such as benzyl chloride or benzyl bromide. Benzyl; alkyl sulfonic acid ester such as methanesulfonic acid (alkyl group having 1 to 18 carbon atoms); aryl sulfonic acid alkyl ester such as benzenesulfonic acid and toluenesulfonic acid (alkyl group having 1 to 18 carbon atoms); dialkyl sulfate ( And quaternized with an alkyl group having 1 to 4 carbon atoms) and dialkyl diallylammonium salts.
The monomer having a functional group that can be adsorbed to the pigment can be appropriately selected according to the type of pigment to be dispersed. That is, it is more preferable to select one having the same or similar skeleton as that of the organic pigment to be coated, or one that easily forms an interaction with a functional group present in the pigment. When monomers having a functional group that can be adsorbed to a pigment are used in the synthesis of the specific graft polymer, these monomers may be used alone or in combination of two or more depending on the purpose.

The specific graft type polymer compound may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect thereof is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

A preferred embodiment of the graft-type polymer compound more effective in the present invention is a copolymer obtained by copolymerizing at least the above-described macromonomer, a monomer having an organic dye structure or a heterocyclic structure, and more preferably the above-described macromonomer, The monomer represented by the general formula (1) and a monomer having an acidic group are copolymerized.
A preferred embodiment of the linear polymer of the present invention is a copolymer of monomers having an organic dye structure or a heterocyclic structure, and more preferably a monomer represented by the above general formula (1) or an acidic group. It is a copolymer of the monomers that it has.
According to this embodiment, a colored composition having excellent pigment adsorption and excellent developability can be provided.

The preferred molecular weight of the polymer compound (c) in the present invention is preferably in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30000, and the number average molecular weight (Mn) is in the range of 5000 to 15000.
That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of pigment, or effectively reducing the cohesive force of secondary aggregates, (c) polymer compound The weight average molecular weight (Mw) is preferably 1000 or more. Further, from the viewpoint of developability when applied to a colored photocurable composition and subjected to development, the weight average molecular weight (Mw) of the (c) polymer compound is preferably 30000 or less.

  The polymer compound (c) in the present invention is preferably a graft polymer compound, and preferably contains the general formula (1) of [Chemical Formula 31]. As a result, the dispersibility of the pigment is improved, and a colored composition having good dispersion stability can be obtained. Further, the heat resistance is improved, and the change in coloring before and after post-baking is small and preferable.

(Synthesis method)
The specific graft type polymer compound includes a polymerizable monomer for forming a main chain structure, a polymerizable oligomer (macromonomer) for forming a polymer branch, and preferably represented by the general formula (1). Produced by a normal radical polymerization method using a monomer having a functional group capable of adsorbing to a pigment such as a monomer to be adsorbed and, if desired, another radical polymerizable compound as a copolymerization component. be able to. 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 can be further used.
As radical polymerization initiators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate Such azo compounds, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.
Moreover, as a chain transfer agent, 2-mercaptoethanol, dodecyl mercaptan, etc. can be utilized, for example.

[Manufacture of processed pigments]
In the present invention, it is preferable to coat (a) a pigment with (b) a pigment derivative having an acidic group and (c) a polymer compound, and more preferably, simultaneously with the refinement of the pigment, (b) acidic It is effective to obtain a processed pigment coated with a pigment derivative having a group and (c) a polymer compound.

Hereinafter, the manufacturing method of a processed pigment is demonstrated.
The production of processed pigments includes i) pigments, ii) water-soluble inorganic salts, iii) a small amount of water-soluble organic solvents that do not substantially dissolve water-soluble inorganic salts, iv) pigment derivatives having acidic groups, And v) a step of mixing a polymer compound or the like and mechanically kneading with a kneader or the like (this step is called salt milling), and the mixture is put into water and stirred with a high-speed mixer or the like to form a slurry. This step is carried out through a step of further filtering, washing the slurry, and then drying.
By such a production method, the processed pigment of the present invention is obtained which is fine and has little aggregation of the pigment during drying.

The method for producing the processed pigment will be described more specifically.
First, add a small amount of a water-soluble organic solvent as a wetting agent to a mixture of an organic pigment and a water-soluble inorganic salt, and knead it strongly with a kneader. To make a slurry.
Here, as a kneading machine used for salt milling, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder, and the like can be given.
In the present invention, at the time of salt milling, a pigment derivative having an acidic group and a polymer compound are used in combination with the above-described water-soluble organic solvent, and the pigment derivative having a finer surface and having an acidic group It is possible to obtain a processed pigment which is coated with a polymer compound and has less aggregation of the pigment when dried.
In addition, the timing which adds the pigment derivative which has an acidic group, and a high molecular compound may add all at the initial stage of a salt milling process, and may divide and add each. The pigment derivative having an acidic group and the polymer compound may be added independently or in combination.

Next, the slurry is filtered, washed with water and, if necessary, dried to obtain a finer pigment, that is, the processed pigment of the present invention.
In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.
As a method for preventing dry aggregation, an alkali-soluble resin dissolved in an alkaline aqueous solution is added to the slurry, and the mixture is sufficiently stirred and then neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid to deposit the resin on the pigment, or calcium chloride. Alternatively, dry aggregation can be prevented by adding an aqueous solution of a water-soluble polyvalent metal salt such as barium chloride to precipitate the resin and deposit it on the pigment.

  Hereinafter, each component used when manufacturing the processed pigment of this invention is demonstrated.

[Ii) Water-soluble inorganic salt]
The water-soluble inorganic salt used in the present invention 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 or sodium sulfate is preferably used.
The amount of the inorganic salt used in the salt milling is preferably 1 to 30 times, particularly 5 to 25 times, that of the organic pigment from the viewpoints of processing efficiency and production efficiency.
The larger the ratio of the inorganic salt to the organic pigment is, the higher the refinement efficiency is.

[Iii) A small amount of a water-soluble organic solvent that does not substantially dissolve a water-soluble inorganic salt]
The water-soluble organic solvent used in the present invention functions to wet the above-described pigment and water-soluble inorganic salt, dissolves (mixes) in water, and substantially contains the water-soluble inorganic salt used together. It is not particularly limited as long as it does not dissolve.
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 is easily evaporated.

  Examples of the water-soluble organic solvent used in the present invention include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, and 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 Examples include monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol.

  The addition amount of the water-soluble organic solvent is preferably 5% by mass to 50% by mass with respect to the water-soluble inorganic salt. More preferably, it is 10% by mass to 40% by mass with respect to the water-soluble inorganic salt, and optimally 15% by mass to 35% by mass with respect to the water-soluble inorganic salt. When the addition amount is less than 5% by mass, uniform kneading becomes difficult, and the particle size distribution of the pigment becomes large, which is not preferable. When the addition amount is 50% by mass or more, the kneaded composition becomes too soft and the kneaded composition is less likely to be sheared, so that a sufficient refinement effect cannot be obtained.

In the present invention, all of the water-soluble organic solvent may be added at the initial stage of salt milling, or may be added in divided portions.
Moreover, a water-soluble organic solvent may be used independently and can also use 2 or more types together.

[Iv] Pigment derivative having acidic group]
In the present invention, (b) the pigment derivative having an acidic group may be added all at the time of salt milling, or a part thereof may be added. When added at the time of soft milling, it is preferably used in a mass ratio of pigment: acid group-containing pigment derivative = 100: 3 to 100: 30, more preferably in the range of 100: 5 to 100: 20. And more preferably in the range of 100: 5 to 100: 15.
By using in this range, the pigment can be made fine while maintaining the color tone of the pigment.

[V] Polymer compound]
In the present invention, the polymer compound (c) used for salt milling is preferably used in a mass ratio of pigment: polymer compound = 100: 3 to 100: 60, more preferably 100: 3 to 3. The range is 100: 40, more preferably 100: 5 to 100: 30.
By using in this range, the water-soluble inorganic salt used for salt milling can efficiently pulverize the pigment, and the polymer compound can be efficiently covered with the pigment.

Moreover, in the range which does not impair the effect of this invention, you may use another high molecular compound simultaneously with the above-mentioned specific high molecular compound as needed.
Other polymer compounds are preferably those that are solid at room temperature, insoluble in water, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. Synthetic resins, synthetic resins modified with natural resins, and the like are used.
In the present invention, when obtaining a dried processed pigment, the other polymer compound is preferably a 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 an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

  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.

  When the processed pigment of the present invention is produced, when the (c) polymer compound of the present invention is used in combination with another polymer compound, the ratio of the other polymer compound is 50 mass with respect to the total polymer compound. % Or less, and more preferably 30% by mass or less.

  In the colored composition of the present invention produced as described above, the pigment is coated with (b) a pigment derivative having an acidic group and (c) a polymer compound having excellent adsorptivity. In addition, when a colored composition or a colored photocurable composition is used, excellent dispersibility and dispersion stability can be obtained.

  Next, the coated pigment of the present invention will be described. First, the amount of liberation will be described. When the processed pigment is washed with propylene glycol monomethyl ether, the amount released (total of the pigment derivative having an acidic group and the specific polymer compound) is measured, and the pigment derivative having an acidic group used when adjusting the processed pigment The value divided by the sum total (charge amount) with the specific polymer compound is defined as% free amount. In the present invention, the coating pigment has a free amount% of preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 85 to 100% by mass. Such a high value cannot be obtained by normal adsorption.

  In a specific experimental method, the processed pigment is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the processed pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available processed pigments can be measured by the following method. That is, after dissolving the entire processed pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. Then, it is calculated as “mass of the polymer compound used in the initial treatment”. Separately, the processed pigment was washed with 1-methoxy-2-propanol, and the obtained release amount was divided by this “mass of the polymer compound used in the initial treatment” to obtain the release rate (%). Ask.
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The coloring composition of the present invention can contain a dispersant in addition to the processed pigment. By containing the dispersant, the dispersibility of the pigment can be further improved. As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

As content in the coloring composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.
As another polymer added to the coloring composition, an alkali-soluble resin described later is preferable in order to enhance alkali developability.

Dispersion methods include, for example, vertical or horizontal sand grinder mills, pin mills, slit mills, ultrasonic dispersers, etc., in which the processed pigment of the present invention is premixed with a solvent and previously dispersed with a homogenizer or the like. And a fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm to obtain a colored composition. The dispersion time is preferably about 3 to 10 hours. At this time, if necessary, the above-described dispersant and other polymer can be added and dispersed.
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.

<Colored photocurable composition>
The colored photocurable composition of the present invention comprises the above-described colored composition of the present invention, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and other components as necessary. May be included. The details of the coloring composition of the present invention are as described above. Hereinafter, each component will be described in detail.

<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.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, JP-A-2004-2004 Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer as described in each publication such as 287409 and JP-A-2006-323399 A partially esterified maleic acid copolymer, an acidic cellulose derivative having a carboxylic acid in the side chain, an acid anhydride added to a polymer having a hydroxyl group, and a (meth) acryloyl group in the side chain. The high molecular polymer is also preferable.

  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, and CH ₂ ═CR. ²⁸ R ²⁹ , CH ₂ ═C (R ²⁸ ) (COOR ³⁰ ) [wherein R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²⁹ represents an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents a ring, and R ³⁰ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

Among these, styrene, benzyl (meth) acrylate, methyl methacrylate, butyl (meth) acrylate, polymethyl methacrylate macromonomer, polymethyl methacrylate macromonomer, poly-n-butyl acrylate macromonomer, polystyrene macromonomer, and A copolymer of one or more selected from N-phenylmaleimide and (meth) acrylic acid is preferable, and a polymer compound obtained by copolymerizing 2-hydroxyethyl (meth) acrylate is more preferable.
Examples of commercially available macromonomers include one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-end methacryloylated poly- n-Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, Toa Gosei Chemical Industries ( Product)). In particular, when a polystyrene macromonomer and N-phenylmaleimide are used, the development pattern is good and there are few residues, which is convenient.

An unsaturated group-containing acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an alicyclic epoxy group and an unsaturated bond in the molecule is also preferable. Furthermore, a polymer compound obtained by further reacting a reaction product of an epoxy resin and an unsaturated group-containing carboxylic acid with a polybasic carboxylic acid or an anhydride thereof is also suitable. When an unsaturated group-containing acrylic resin is used, the sensitivity can be particularly improved, and a better pattern shape can be easily obtained.
As commercial products, cyclomer PACA200, 200M, 230AA, 250, 300, 320, 210 (all manufactured by Daicel Chemical Industries, Ltd.) can be used.

These alkali-soluble resins can be mixed and used in an arbitrary amount.
As content in the photocurable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably 3 to 10% by mass.

<Photopolymerizable compound>
As the photopolymerizable 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, and a tetrafunctional or higher functional acrylate compound 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 the above photopolymerizable compounds, those having 3 or more, more preferably 4 or more acryloyl groups in one molecule are preferable. Specifically, 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 having a very high 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 can be suitably used for adjusting the dissolution rate in an alkaline aqueous solution. Examples of commercially available products include carboxyl group-containing trifunctional acrylates manufactured by Toagosei Co., Ltd. And TO-1756 which is a carboxyl group-containing pentafunctional acrylate.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
The content of the photopolymerizable compound in the photocurable composition is preferably 3 to 60 parts, more preferably 20 to 50 parts, relative to 100 parts of the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. US Pat. No. 4,318791 and European Patent Publication EP-88050A, described in US Pat. No. 4,1994,420 Aromatic ketone compounds such as benzophenones, (thio) xanthone or acridine compounds described in Fr-2456541, coumarin or biimidazole compounds described in JP-A-10-62986, JP-A-8 Sulfonium organoboron complexes such as 015521 , Etc. can be mentioned.

  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. And oxime ester systems are preferred.

  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.

  Preferable examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. 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, the 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 oxime ester compounds described in JP-A No. 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 with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. 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).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. W represents an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is as defined in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently represent a monovalent group. Can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom or a sulfur atom or -N (R ¹ )-, and Y represents an oxygen atom or —N (R ¹ ) — R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A, R ¹ , R ² , and R ³ are Can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ¹ , R ² , and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. 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. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂₎ and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Rubonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, Methyl Phosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² , or R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of preferred substituted aryl groups as R ^{1, R 2,} or R ³ is a substituent on the ring-forming carbon atoms of the aryl group described above, (other than a hydrogen atom) a monovalent non-metallic atomic group What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. Also, as more preferred examples of R ¹ include substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A in the general formula (XVIII) will be described. A represents an aromatic ring or a hetero ring which may have a substituent, and specific examples of the aromatic ring or hetero ring which may have a substituent include R ¹ and R ² in the general formula (XVIII). , Or the same as those exemplified in the above description of R ³ .
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the formula (XVIII) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7,6,4,5-thiazoles (eg 4-methoxythianaphtheno-7,6,4,5-thiazole etc.), oxazoles (eg 4-methyl Oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxyben Zooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

  Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  In the general formula (XVIII) described above, among the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y together with the above-mentioned A and the adjacent carbon atom, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-311253 as a novel compound.

(In General Formula (XVIII-2), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form an aliphatic group. Or aromatic ring can be formed.)
In formula (XVIII-2), A and ^{R 1} are the same as in the general formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) And R ⁶ has the same meaning as R ¹ in formula (XVIII).

  Next, the compound represented by the general formula (XVIII-3), which is a preferred embodiment of the compound represented by the general formula (XVIII) used in the present invention, will be described.

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ and R ⁵ are each aliphatic or aromatic. Can be linked to form a ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In formula (XVIII-3), A and ^{R 1} have the same meanings as in formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) It is synonymous with. Ar represents an aromatic ring or heterocyclic ring having a substituent, and specific examples thereof include an aromatic ring or heterocyclic ring having a substituent among those previously described in the description of A in the general formula (XVIII). The specific example which concerns is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (XVIII-3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary compound (F1) to Illustrative compound (F56)] are shown below, but the present invention is not limited thereto. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep curability.

  The above sensitizing dye can be subjected to various chemical modifications as follows for the purpose of improving the characteristics of the photosensitive composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the colored photosensitive composition for a color filter of the present invention. More preferably, it is 0.1-5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

<Solvent>
In general, the coloring composition and the photocurable composition of the present invention can be suitably prepared using a solvent together with the above components.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

<Other ingredients>
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, a colorant, a photopolymerization initiator, and other fillers are included as necessary. Various additives such as a polymer compound other than the above alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent can be contained.

(Chain transfer agent)
Examples of the chain transfer agent which can be added to the colored curable 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 substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. 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 contain a thermal polymerization initiator in the colored 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 contain a thermal polymerization component in the coloring 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 colored composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability. In addition to the above-mentioned fluorosurfactants, nonionic, cationic and anionic Various surfactants 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.

<Other additives>
In addition to the above, various additives can be added to the photocurable composition. Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and aggregation preventing 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.

  In addition, in order to promote alkali solubility of the uncured part and further improve the developability of the colored composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added to the colored composition. Can be performed. 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 colored 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-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful. is there.

-Photocurable composition and method for producing color filter using the same-
<Preparation of photocurable composition>
The photocurable composition of the present invention is obtained by adding an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and the like to the above-described colored composition of the present invention, and further, if necessary, a surfactant. It can be prepared by adding additives such as, then mixing and stirring and filtering.

A method for producing a color filter using the photocurable composition of the present invention will be described below.
<Coating / Exposure>
The photocurable composition of the present invention is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and a photocurable coating film The film is exposed through a predetermined mask pattern, and after the exposure, the uncured portion is developed and removed with a developer to form a pattern film composed of pixels of each color (three colors or four colors), and a color filter It can be.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. For color filters for liquid crystal display devices, exposure using mainly h-line and i-line is preferable for proximity exposure machines and mirror projection exposure machines, and for color filters for solid-state imaging devices, i-line is mainly used for stepper exposure machines. It is preferable to do.

  Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, and solid-state imaging devices. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, a black matrix for isolating each pixel is usually formed, or a transparent resin layer is provided for promoting adhesion. The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  In addition, the photo-curing property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged. A color filter can be prepared by forming a patterned film made of the composition. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.

A method for applying the photocurable composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method). Is preferred. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. The discharge amount of the photocurable composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second. , Preferably 100 to 200 mm / sec. The solid content of the photocurable composition is usually 10 to 20%, preferably 13 to 18%.
When a coating film of the photocurable composition of the present invention is formed on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.4 to 4 0.0 μm, most preferably 0.5 to 3.0 μm.

<Drying / Prebaking>
Usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven, or the like, and can be performed under conditions of 10 to 300 seconds. High frequency treatment or the like may be used in combination. High frequency processing can be used alone.

<Development>
In the development process, the uncured part after exposure is eluted in the developer, and only the cured part remains. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the photo-curable photocurable composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  The coated and dried film of the photocurable composition of the present invention is particularly excellent in solubility in an alkaline developer. Since the solubility of the non-exposed part is high, a residue on the substrate is hardly generated. This is because the pigment itself and the coating solution together with the coating after the alkali-soluble resin contained in the photocurable composition is dissolved due to the affinity of the acidic group of the pigment derivative coating the pigment surface with the alkaline developer. It is considered that it dissolves emulsified.

  Next, a method for measuring the solubility of the photocurable composition in the alkaline developer of the dried coating film will be described. The photocurable composition was applied onto a glass substrate so that the dry film thickness was 1.0 μm, dried in a thermostatic bath at 90 ° C. for 60 minutes, and then the photocurable composition layer was developed with a developer CDK-1 ( 1% diluted solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) (aqueous solution containing 0.05% potassium hydroxide by mass fraction and containing nonionic surfactant, 23 ° C.). The soaking time was from 0 to 120 seconds in 1 second increments, and the time until the colored photocurable composition layer completely disappeared was taken as the dissolution time.

Examples of the organic solvent include the solvents described above that can be used in preparing the colored composition or the photocurable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.

<Rinse>
After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.

<Post bake>
After rinsing, draining and drying are performed, and then a heat treatment is usually performed at about 200 ° C to 250 ° C. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.
By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.

The use of the coloring composition and the photocurable composition of the present invention has been described mainly with respect to the use for color filters, but it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter. Can do.
The black matrix is formed by exposing and developing the colored composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and further post-baking as necessary to promote film curing. it can.

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” is based on mass.

(1) Synthesis of Pigment Derivatives (I), (II), and (III) The pigment derivative (I) and the pigment derivative (II) were synthesized by the method of JP-A-7-173406. Further, the pigment derivative (III) having no acidic group of the present invention was synthesized by the method of JP-A-2000-273346.

顔料誘導体(ＩＩＩ)

Pigment derivative (III)

(2) Synthesis of polymer compound (synthesis of polymer compound 1)
M-11 27.0 g, MMA 126.0 g, MAA 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: The mixture is stirred with a three-one motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer compound 1 was obtained.

  As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Synthesis of polymer compound 2)
M-6 27.0 g, MMA 126.0 g, MAA 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor) ) And heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer compound 2 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 with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.

(3) Adjustment of processed pigment (processed pigment 1)
C. I. Pigment Red 254 50 g, sodium chloride 500 g, polymer compound 1 (30% solution) 25 g, and diethylene glycol 100 g were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to obtain a coated processed pigment 1. .

(Processed pigment 2)
In the preparation of the processed pigment 1, the same experiment was performed without using a polymer compound, and a processed pigment 2 was obtained.

(Processed pigment 3)
In the adjustment of the processed pigment 1, the same experiment was performed using the polymer compound 2 instead of the polymer compound 1, and the processed pigment 3 was obtained.

(Processed pigment 4)
By adjusting the processed pigment 1, the same experiment was performed using the following polymer compound 3 instead of the polymer compound 1 to obtain a processed pigment 4.
(Polymer Compound 3)
Benzyl methacrylate / methacrylic acid = 85/15 (mass%), weight average molecular weight 20,000
(Processed pigment 5)
By adjusting the processed pigment 1, the same experiment was performed using 5 g of the pigment derivative (I) instead of the polymer compound 1, and the processed pigment 5 was obtained.
(Processed pigment 6)
By adjusting the processed pigment 1, a similar experiment was carried out by adding 5 g of the pigment derivative (I) in addition to the polymer compound 1 when charged, and a processed pigment 6 was obtained.

(Measurement of primary particle diameter of pigment)
The primary particle diameter of the pigment was determined by observing the obtained processed pigment with a transmission electron microscope (TEM).

(Evaluation of pigment coverage)
10 g of the obtained processed pigment was put into 100 mL of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the polymer compound released from the pigment was determined, and the release rate (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment. The results are summarized in Table 1.

  It can be seen from Table 1 that the pigment processed with the pigment derivative having an acidic group and the polymer compound of the present invention has a low liberation rate and is coated. In particular, it can be seen that processed pigments 1 and 3 using a graft polymer as the polymer compound have a low release rate and a high coverage.

(4) Preparation of coloring composition Ingredients of the following composition (1) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
-95 parts of processed pigment-5 parts of pigment derivative described in Table 2-Dispersant (Disperbyk-161, 30% solution manufactured by BYK) 150 parts-750 parts of 1-methoxy-2-propyl acetate Subsequently, obtained from above The mixed solution was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2,000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a colored composition of each processed pigment.

(5) Preparation of colored photocurable composition First, an example in which a colored photocurable composition containing a pigment is prepared for forming a color filter for a liquid crystal display device will be described.
[Example 1]
Using the colored composition obtained from the processed pigment 1, the following colored photocurable composition was prepared.
-Pigment dispersion 2000 parts-Dipentaerythritol penta-hexaacrylate 80 parts (photopolymerizable compound)
1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime (photopolymerization initiator) 30 parts benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight) 300 parts of an average molecular weight: 12,000) propylene glycol monomethyl ether acetate solution (solid content 30%) (alkali-soluble resin)
・ 390 parts of 1-methoxy-2-propyl acetate (solvent)

In Examples 2-9 and Comparative Examples 1-3, the colored photocurable composition was prepared by changing the alkali-soluble resin of Example 1 as shown in Table 2.
The resin solutions used in Table 2 are as follows.
Polymer compound 4: benzyl methacrylate / methacrylic acid / AS-6 (manufactured by Toa Gosei Chemical Co., Ltd.) copolymer in 30% propylene glycol monomethyl ether acetate solution, mass ratio: 30/15/55, Mw: 20000
Polymer compound 5: 30% propylene glycol monomethyl ether acetate solution of methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, mass ratio: 10/35/45/10, Mw: 20000
Polymer compound 6: Polymer compound obtained by adding epoxycyclohexylmethyl methacrylate to benzyl methacrylate / acrylic acid copolymer (mass ratio: 70/30, Mw: 15000)

(6) Preparation of color filter The obtained colored photocurable composition was slit-coated on a 100 mm × 100 mm glass substrate (Corning Corp. 1737) so that the film thickness after pre-baking was 2.0 μm. . It was dried (prebaked) on a hot plate at 90 ° C. for 60 seconds. Thereafter proximity exposure machine for a high-pressure mercury lamp as a light source, the exposure dose 100 mJ / cm ² (illuminance 20 mW / cm ^2), were exposed through a mask. The mask has a line width of 10 μm and a distance from the substrate of 300 μm. The exposed coating film was sprayed with a 1% aqueous solution of alkaline developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 28 ° C. Thereafter, it was washed with pure water, dried and then heat-treated (post-baked) in an oven at 220 ° C. for 1 hour to produce a colored substrate (color filter).
When evaluating color characteristics such as contrast, a solid substrate was used which was exposed without passing through a mask and was otherwise processed in the same manner.

(7) Evaluation of colored substrate The following evaluation was performed about the produced colored substrate. The results are shown in Table 2.

(I) Contrast A polarizing plate is placed on the colored layer of the colored substrate obtained above, the colored substrate is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are used using BM-5 manufactured by Topcon Corporation. The value obtained by 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.

(Ii) Viscosity After adjusting the obtained coloring composition for 3 hours, the viscosity at 25 ° C. was measured with an E-type viscometer (trade name RE-810, manufactured by Toki Sangyo Co., Ltd.), and the result was obtained. Table 2 shows the distinction as follows.
<Criteria>
◎: Less than 50 mPa · s ○: 100 mPa · s or more, less than 50 mPa · s Δ: 100 mPa · s or more, less than 200 mPa · s ×: 200 mPa · s or more

(Ii) Alkali developer dissolution rate A coated substrate on which a colored photocurable composition is applied on a glass substrate and pre-baked is applied to a developer [containing 0.05% by mass of potassium hydroxide, nonionic Development was performed by immersing in an aqueous solution containing a surfactant, 28 ° C.]. The immersion time was from 0 to 120 seconds in 1 second increments, and the time until the colored layer completely disappeared was taken as the elution time, and the dissolution rate was calculated from this elution time and the thickness of the colored photosensitive resin composition layer. .

(iii) Developability Exposure through a mask was performed, and the coated substrate after development was observed. The residue on the substrate of the non-exposed part in the vicinity of the exposed part was observed with an optical microscope to evaluate the residue. Further, the development pattern was observed by SEM for the cross section.
The evaluation of the residue was based on the following criteria.
A: No residue was observed at all in the non-exposed area.
○: A slight residue was observed only in the very vicinity of the exposed area. There is no problem in practical use.
(Triangle | delta): The residue was confirmed slightly in the non-exposed part. There was no problem in practical use.
X: Residue was remarkably confirmed in the non-exposed part.

The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred. The pattern evaluation was based on the following criteria.
A: Tapered angle in the range of 30 to less than 70 degrees (forward taper)
○: Tapered angle in the range of 70 to less than 90 degrees (forward taper)
Δ: Taper angle is 90 degrees (rectangular)
X: The taper angle exceeds 90 degrees (reverse taper)
(Iv) Heat resistance The colored solid substrate after post-baking was further heated with a hot plate at 230 ° C. for 1 hour, and before and after the heat test with a chromaticity meter (trade name: MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.). The color difference (ΔEab value) was measured. A smaller ΔEab value indicates better heat resistance.

  From Table 2, using a colored composition obtained with a pigment, a pigment derivative having an acidic group, and a polymer compound, a colored curable composition having a high alkali dissolution rate has few development residues and a pattern in order. It can be seen that the taper has good developability and has high contrast and good heat resistance. Comparative Examples 1 and 2 in which the polymer compound was not used in the coloring composition had a slow alkali dissolution rate and poor developability. Moreover, the comparative example 3 of the colored curable composition obtained with the coloring composition using the pigment derivative which does not have an acidic group had an insufficient alkali dissolution rate, and development property was also unpreferable.

Next, an example in which a colored photocurable composition containing a pigment is prepared for forming a color filter for use in a solid-state imaging device will be described.
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution for undercoat layer>
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
・ Ethyl lactate 36.67 parts ・ Resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 30.51 parts Unsaturated double bond-containing compound (dipentaerythritol hexaacrylate)
12.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0061 parts ・ Fluorosurfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts ・ Photopolymerization initiator (trihalo) Methyltriazine-based photopolymerization initiator) 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

[Production of silicon substrate with undercoat layer]
A 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 as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Got.

[Example 10]
A colored photocurable composition was prepared by stirring and mixing using the pigment dispersion that was dispersed in the same manner as in Example 1 so that the following composition ratio was obtained.
・ Colorant (pigment dispersion (P2)) 600 parts ・ Polymerization initiator (oxime photopolymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals Co., Ltd.) 30 parts · TO-1382 (manufactured by Toagosei Co., Ltd.) 15 parts (photopolymerizable compound, Toa Gosei Chemical Co., Ltd., carboxyl group-containing pentafunctional acrylate)
Dipentaerythritol hexaacrylate 20 parts Alkali-soluble resin (benzyl methacrylate / methacrylic acid / AA-6 (manufactured by Toa Gosei Chemical Co., Ltd.) copolymer 30% PGMEA solution, weight ratio: 50/15/35,
Mw: 18500) 30 parts · Solvent (PGMEA) 900 parts · Substrate adhesive (3-methacryloxypropyltrimethoxysilane) 1 part

In Examples 11 to 14 and Comparative Examples 4 and 5, the colored photocurable composition was prepared by changing the processed pigment, pigment derivative, and alkali-soluble resin of Example 10 as shown in Table 3.
The alkali dissolution rate and storage stability (viscosity) of the colored photocurable composition prepared above were evaluated in the same manner as in Example 1.
Residues, patterns, and color irregularities were evaluated by applying the obtained colored curable composition to a silicon wafer with an undercoat layer and the following method.

-Preparation of silicon wafer with undercoat layer-
Components of the following composition were mixed and dissolved to prepare a transparent resist solution.
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
-Ethyl lactate (solvent) 36.67 parts-40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18) 30.51 parts (binder polymer) )
Dipentaerythritol hexaacrylate (DPHA) 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ TAZ-107 0.586 parts (manufactured by Midori Chemical Co .; trihalomethyltriazine photopolymerization initiator)

  The 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the transparent resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A substrate was obtained.

-Formation of solid-state image sensor coloring pattern-
The colored photocurable composition was applied onto the undercoat layer of the silicon wafer with the undercoat layer obtained above so that the dry film thickness of the colored layer was 0.7 μm. Next, this colored coated substrate was heat-treated (prebaked) for 120 seconds using a hot plate at 100 ° C.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 500 mJ / cm ² through an Island pattern mask having a pattern of 1.5 μm square at a wavelength of 365 nm. Thereafter, the silicon wafer on which the colored layer 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 Co., Ltd.). After the paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd., the silicon wafer was fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer was rotated at a rotation speed of 50 r. p. m. Then, pure water was supplied as a shower from the upper part of the rotation center in a shower-like manner, followed by rinsing, and then spray-dried to obtain a wafer substrate with colored pixels.

-Evaluation of residue and pattern-
Residues were determined by SEM observation of the wafer surface in the unexposed area and the following criteria.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but there was no practical problem.
X: Residue was remarkably confirmed in the unexposed part.

The pattern was determined by observing the cross-sectional shape with an SEM and using the following criteria.
-Evaluation criteria-
○: taper angle of 75 ° or more and less than 100 ° ×: taper angle of less than 75 ° or 100 ° or more

For evaluation of color unevenness, create a substrate for evaluation in the same way as the solid-state image sensor coloring pattern formation method, except that a glass substrate is used instead of a wafer with an undercoat layer, and a solid exposure is performed without using a mask. did. The luminance distribution was analyzed by the following method, and the luminance distribution was determined based on the ratio of pixels with a deviation from the average within ± 5% to the total number of pixels.
A method for measuring the luminance distribution will be described. First, an image obtained by photographing the luminance distribution of a glass plate with a colored layer with a microscope MX-50 (manufactured by Olympus) was analyzed.
In the luminance distribution, the luminance with the largest number of pixels is defined as the average luminance.
-Evaluation criteria-
A: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels. O: 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

  From Table 3, the colored photocurable composition prepared using the colored composition of the present invention has a high alkali dissolution rate, almost no residue, and a good pattern after development. Moreover, it can be seen that the color unevenness is good and the heat resistance is good.

Claims (8)

  A colored composition comprising (a) a pigment, (b) a pigment derivative having an acidic group, and (c) a polymer compound, wherein the colored composition forms a coating film having a dry film thickness of 1.0 μm. The colored composition is characterized in that the coating film dissolves in an alkaline aqueous solution having a KOH concentration of 0.05% by mass in 30 seconds or less.   The coloring composition according to claim 1, wherein the pigment (a) is coated with a polymer compound (c).   The colored composition according to claim 1 or 2, wherein (a) the pigment is coated with (b) a pigment derivative having an acidic group.   (B) The colored composition according to any one of claims 1 to 3, wherein the pigment derivative having an acidic group is a pigment derivative having a sulfonic acid group and / or a sulfonate.   The colored photocurable composition, wherein the colored composition according to any one of claims 1 to 4 contains a photopolymerizable compound and a photopolymerization initiator.   A color filter comprising a colored pattern using the colored photocurable composition according to claim 5 on a substrate.   A liquid crystal display device comprising the color filter according to claim 6.   A solid-state imaging device comprising the color filter according to claim 6.