JP2009109750A - Colored polymerizable composition, color filter, and solid-state imaging device - Google Patents

Abstract

Disclosed is a colored polymerizable composition capable of forming a thin-layer colored region with high definition, which can be cured with high sensitivity and has excellent developability even when the pigment content is high. . The colored polymerizable composition of the present invention is useful for forming a color filter having a high-definition colored region having excellent color characteristics and a solid-state imaging device.
SOLUTION: (A) (a-1) a pigment, (a-2) a compound having a pigment nucleus structure and an amino group in the molecule, and (a-3) an acid value of 2.9 mmol / g to A colored polymerizable composition comprising a pigment dispersion containing 7 mmol / g polymer, (B) a polymerization initiator, and (C) a polymerizable compound. (A-2) The compound having a pigment mother nucleus structure and an amino group in the molecule preferably has at least one of an amide structure and a urea structure and a heterocyclic structure in the molecule.
[Selection figure] None

Description

  The present invention relates to a colored polymerizable composition suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state image sensor (CCD, CMOS, etc.), a color filter using the same, and a solid filter The present invention relates to an image sensor.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

  In color filter applications for liquid crystal displays (LCDs), the substrate size is increasing for large TV production, and low energy curing is desired to improve productivity when large substrates are used. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity. In order to improve the contrast, the curable composition used for the production of the color filter is required to have a finer particle size of the colorant (organic pigment or the like) used. (For example, refer to Patent Document 1.) Along with this, the amount of dispersant added for dispersing the pigment tends to increase. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of a curable composition for color purity improvement. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content in the curable composition tends to decrease.

  On the other hand, curing with low energy is also desired in color filter applications for solid-state imaging devices. Moreover, the pattern thinning is progressing and the pigment density | concentration in a composition is improving with this. Furthermore, in the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment becomes finer. In addition, in order to cope with problems such as color unevenness that occurs because the pigment is relatively coarse particles, a technique using an organic solvent-soluble dye instead of the pigment as a colorant has been proposed (for example, Patent Documents). 2). However, in dye-based color filters, with the increase in dye concentration, the problem of the polymerization inhibition effect derived from dyes has become prominent. Due to such factors, the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition, is limited in both cases for liquid crystal displays and solid-state imaging devices. In addition, the concentration of the colorant is high, it is difficult to make a thin layer, it is difficult to achieve a desired sensitivity with a low polymerization component ratio, and there is no room for adding a development regulator, etc. It is difficult to ensure developability.

That is, as the colored region, particularly the colored pattern becomes thinner, the ratio of the pigment and the pigment dispersant in the curable composition increases, the content ratio of the curable component (polymerization material) decreases relatively, It becomes difficult to maintain the sensitivity, and other components not related to coloring or curing, for example, a high acid value polymer added for the purpose of ensuring developability, an addition amount of a development accelerator, etc. are inevitably added. Therefore, there is a problem that development failure occurs.
In order to ensure sensitivity without degrading colorability, attempts have been made to reduce the amount of pigment dispersant added while maintaining the pigment content. This raises the viscosity and causes a new problem that it is difficult to form a uniform coating film.
As described above, when the colored polymerizable composition is used for forming a colored region in a color filter, particularly a color filter for a solid-state imaging device, it is necessary to satisfy both the thinning and the color value, and the pigment concentration is high. In addition, a colored polymerizable composition that can achieve both sensitivity and developability is eagerly desired.
JP 2006-30541 A JP-A-2-127602

The present invention has been made in consideration of the above-mentioned problems associated with the thinning of the colored region in the color filter, and the object of the present invention is high sensitivity even when the pigment content is high. Provided is a colored polymerizable composition which can be cured and has excellent developability and can form a thin layer colored region having a good hue with high definition, particularly a colored polymerizable composition useful for forming a colored region of a color filter. There is.
A further object of the present invention is to provide a color filter having a high-definition colored region having excellent color characteristics in a thin layer formed from the colored polymerizable composition, and a solid-state imaging device having a color filter having excellent color characteristics. It is to provide.

As a result of earnest research, the present inventor can secure high dispersion stability of pigments by combining a compound having a specific structure and a high acid value resin, and achieves both sensitivity and developability in a film having a high pigment concentration. The present invention has been completed.
That is, the configuration of the present invention is as follows.

<1> (A) at least (a-1) pigment, (a-2) a compound having a pigment nucleus structure and an amino group in the molecule, and (a-3) an acid value of 2.9 mmol / g to A colored polymerizable composition comprising a pigment dispersion containing 7 mmol / g of polymer, (B) a polymerization initiator, and (C) a polymerizable compound.
<2> The compound according to <1>, wherein the compound (a-2) having a pigment mother nucleus structure and an amino group in the molecule is a compound having at least one of an amide structure and a urea structure. Colored polymerizable composition.
<3> The colored polymerization according to <1> or <2>, wherein the compound (a-2) having a pigment mother nucleus structure and an amino group in the molecule is a compound having a heterocyclic structure. Sex composition.
<4> A color filter comprising a colored region using the colored polymerizable composition according to any one of <1> to <3>.
<5> A solid-state imaging device comprising the color filter according to <4>.

Conventionally, in the preparation of commonly used pigment dispersions, in order to develop high dispersion stability, an amino group is used to develop an interaction between the acid group of the dispersion resin and / or the pigment nucleus. It is difficult to increase the concentration of the pigment as the coloring component in the pigment dispersion because it requires a large amount of a dispersant having an acid group and a predetermined amount of an acid group-containing resin to ensure alkali developability. In the present invention, it was difficult to achieve a thin layer. In the present invention, a pigment dispersion prepared using a pigment derivative having an amino group in the molecule and a polymer having a specific acid value is used. An acid-base interaction is formed with an acid group-containing polymer having a specific acid value that is used to ensure the stability, and dispersion stability is easily exhibited. Therefore, the content of the compound that contributes to dispersion can be reduced as compared with the case where a conventional pigment derivative having a general acid group is used, and since a high acid value polymer is used in combination, Even if the component ratio of the pigment dispersion is increased, it is considered that both the decrease in sensitivity and the decrease in developability, which are usually a concern, can be effectively suppressed.
In the present invention, the “pigment mother nucleus structure” is a structure containing at least a part of the chromophoric group in the organic pigment, usually a heterocyclic structure or amide containing a nitrogen atom, an oxygen atom, a sulfur atom or the like. The main skeleton structure of a pigment composed of a group, a urea structure, and the like. Furthermore, the “pigment mother core structure” in the present invention has a structure similar to the main pigment skeleton, or a partial structure of the main pigment skeleton, thereby allowing interaction with the pigment skeleton of the organic pigment. The “similar structure of pigment skeleton” and “partial structure of pigment skeleton” that can be formed are also included.

According to the present invention, even when the pigment content is high, coloring of a color filter that can be cured with high sensitivity, developability, and can form a thin layer colored region with good hue with high definition. A colored polymerizable composition useful for region formation can be provided.
Also provided are a color filter having a high-definition colored region having excellent color characteristics with a thin layer formed from the colored polymerizable composition of the present invention, and a solid-state imaging device having a color filter having excellent color characteristics. Can do.

  The present invention is described in detail below. The colored polymerizable composition of the present invention comprises (A) (a-1) a pigment, (a-2) a compound having a pigment nucleus structure and an amino group in the molecule, and (a-3) an acid value of 2. A pigment dispersion containing a polymer of .9 mmol / g to 7 mmol / g, (B) a polymerization initiator, and (C) a polymerizable compound. That is, by preparing a (A) pigment dispersion excellent in pigment dispersion stability, and further adding (B) a polymerization initiator and (C) a polymerizable compound to the colored polymerizable composition. Even if it is a thin layer, a colored region having excellent color characteristics can be formed. Hereinafter, each component contained in the colored polymerizable composition will be described.

[(A) Pigment dispersion]
The colored polymerizable composition of the present invention comprises at least (a-1) a pigment, (a-2) a compound having a pigment nucleus structure and an amino group in the molecule, and (a-3) an acid value of 2.9 mmol. / G to 7 mmol / g of polymer (hereinafter referred to as a specific acid value polymer as appropriate), and (a-4) a solvent.

<(A-2) Compound having pigment mother nucleus structure and amino group in molecule (specific pigment derivative)>
In the present invention, by using the specific pigment derivative (a-2), an interaction is formed between the pigment mother nucleus structure in the specific pigment derivative and the (a-1) pigment, and the adsorptivity of both is increased. As well as ensuring the interaction with the acid group in the specific acid value polymer (a-3) due to the amino group in the specific pigment derivative, the dispersion stability of the pigment in the pigment dispersion is ensured. .

  The specific pigment derivative (a-2) used in the present invention is preferably a compound represented by the following general formula (A).

In the general formula ^{(A), R 1, R} 2 each independently represent a hydrogen atom, or a monovalent organic group, preferably a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms A saturated or unsaturated cycloalkyl group or an aryl group. These organic groups may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. , Aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, amide Groups, carbonyl groups, nitro groups or substituents having these groups.
R ¹ and R ² may be bonded to each other to form a ring.

In particular, the compound represented by the general formula (A) is preferably a compound having at least one of an amide structure and a urea structure in the molecule.
Moreover, it is preferable that the compound represented by general formula (A) is a compound which has a heterocyclic structure.

X is an m-valent group containing a pigment mother nucleus structure.
Here, examples of the pigment mother nucleus structure include a chromogenic atomic group in an organic pigment, a similar structure, or a partial structure thereof. Specifically, a skeleton having an azo group, a skeleton having a urea structure, and an amide structure. A structure containing one or more partial structures selected from a skeleton having a skeleton, a skeleton having a cyclic amide structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring X is a substituent containing these pigment mother nucleus structures.
X in the present invention preferably has a pigment mother nucleus structure, or a pigment mother nucleus structure and an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and the amino group is a pigment mother structure. It is bonded directly or through a linking group to any one of the core structure, aromatic ring, nitrogen-containing aromatic ring, oxygen-containing aromatic ring and sulfur-containing aromatic ring.
Most preferably, it has a pigment mother nucleus structure and an aromatic ring or a nitrogen-containing aromatic ring, and is preferably bonded with an amino group and a divalent linking group.
m is an integer of 1 to 8, preferably 1 to 6, and more preferably 1 or 2 from the viewpoint of dispersibility and storage stability of the dispersion.

  Although the preferable specific example of the (a-2) pigment derivative used for this invention below is shown, it is not limited to these.

  These (a-2) specific pigment derivatives are appropriately selected in consideration of the type of pigment to be used, and those having the same or similar structure as the pigment core structure of the organic pigment that requires dispersion are selected. Is preferred. The amino group present in the molecule together with the pigment nucleus structure is preferably one having a tertiary amino structure such as a dialkylamino group from the viewpoint of the interaction with the polymer.

In preparing the (A) pigment dispersion in the present invention, (a-2) the content of the specific pigment derivative in the pigment dispersion is 0.5% by mass or more and 40% by mass or less as a solid content. Is preferable, and it is more preferable that they are 1 mass% or more and 15 mass% or less.
Moreover, it is preferable that they are 0.5 mass part or more and 50 mass parts or less with respect to 100 mass parts of (a-1) pigment mentioned later, and it is more preferable that they are 1 mass part or more and 25 mass parts or less.

<(A-1) Pigment>
As the pigment that can be used in the (A) pigment dispersion according to the present invention, various conventionally known inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, and considering handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. 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.

  Examples of inorganic pigments 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, etc. And metal oxides of the above metals.

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

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

-Finer pigments-
In the present invention, a fine and sized organic pigment can be used as necessary. Finer pigments are prepared by preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and water-soluble inorganic salts, and applying a stress using a wet pulverizer and grinding. Achieved.

Water-soluble organic solvents used in the pigment refinement process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include monobutyl ether, propylene glycol, propylene glycolic monomethyl ether acetate and the like.
Further, as long as it is adsorbed to the pigment by being used in a small amount and is not washed away in the waste water, the water solubility is low or other solvents that are not water soluble, such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, Nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like may be used.
Only one type of solvent may be used in the pigment refinement step, or two or more types may be mixed and used as necessary.

Examples of the water-soluble inorganic salt used in the pigment refinement step in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the miniaturization step is 1 to 50 times by mass of the pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times by mass in terms of productivity. Moreover, it is preferable to use inorganic salts having a moisture content of 1% or less.
The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is the range of 50 mass parts to 300 mass parts with respect to 100 mass parts of pigments, Preferably it is the range of 100 mass parts to 200 mass parts.

  There are no particular restrictions on the operating conditions of the wet pulverizer in the pigment refinement process. However, in order to effectively carry out the grinding with the pulverizing media, the operating condition when the apparatus is a kneader is the rotational speed of the blade in the apparatus. Is preferably 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because of its great grinding effect. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

-Preparation of pigment-(Color matching)
These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. In this range, the light transmittance from 400 nm to 500 nm can be suppressed, the color purity can be improved, and a sufficient coloring power can be achieved. 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.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. In the above mass ratio range, the light transmittance of 400 to 450 nm can be suppressed, the color purity can be improved, the main wavelength does not become a long wavelength, and the hue in the vicinity of the NTSC target hue according to the home position. Can be obtained. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

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

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

-Dye-
In the present invention, it is possible to use a dye together with a pigment as a colorant in order to adjust the color tone.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

  In the present invention, the content of the (a-1) pigment in the (A) pigment dispersion is preferably 5 to 80% by mass with respect to the total solid content (mass) in the (A) pigment dispersion. -70 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

<(A-3) Polymer having an acid value of 2.9 mmol / g to 7 mmol / g>
In the curable composition of the present invention, (A) In the pigment dispersion, an acid value of 2.9 mmol / g to 7 mmol / g is used as a binder for the purpose of improving film properties, ensuring developability, ensuring dispersibility, and the like. It is necessary to use the following polymer.
As the specific acid value polymer, a linear organic polymer is preferably used. As such a “linear organic polymer”, a known one can be appropriately selected and used as long as the acid value is within the specific range. When the colored polymerizable composition of the present invention is used to form a colored film having excellent color characteristics, particularly in a thin film, with high resolution, the pigment dispersibility and the alkali of the non-image area are ensured while ensuring a desired pigment concentration. It is necessary to maintain developability at a high level.
In the present invention, the pigment mother nucleus structure in the above-mentioned (a-2) specific pigment derivative expresses the interaction with (a-1) the pigment, and (a-2) the amino group in the specific pigment derivative has (A-3) In order to form an interaction with a polymer having an acid value of 2.9 mmol / g to 7 mmol / g, by combining (a-3) a specific acid value polymer and (a-2) a specific pigment derivative In addition, it is possible to maintain dispersion stability while ensuring developability. As described above, in the present invention, the dispersion stability in the (A) pigment dispersion containing the components (a-1) to (a-3) is excellent. From the viewpoint of improvement, it is possible to ensure the excellent dispersibility and dispersion stability of the pigment by adding no other dispersant used in combination or by adding a very small amount, particularly for the formation of a thin colored film. It is valid.
Here, that the film formed from the colored polymerizable composition is “thin layer” means that the film thickness is 1.0 μm or less, and in particular, a thin film of 0.8 μm or less, and further 0.55 μm or less. In forming, it can be said that the effect of the present invention is remarkable.

In the present invention, (a-3) the acid group that the specific acid value polymer can have in the molecule includes a carboxyl group, a sulfo group, a phosphonic acid group, a phenol group, a sulfinic acid group, a sulfonamide group, and an α-carbonyl ester group. And carboxylic anhydride groups.
From the viewpoints of dispersion stability, developability, and suppression of radical polymerization, a carboxyl group, a sulfo group, a phosphonic acid group, a sulfonamide group, an α carbonyl ester group, and a carboxylic anhydride group are preferable, and further, synthesis suitability, etc. In view of production and cost, a carboxyl group is most preferable.

In the present invention, the polymer structure and the like can be used in any shape as long as the acid group is introduced into the polymer in a range where the acid value is 2.9 mmol / g to 7 mmol / g in the solid content of the polymer. is there. The acid value is more preferably in the range of 3.1 mmol / g to 6.0 mmol / g.
Examples of the method for measuring the acid value of a polymer include a method in which a polymer is dissolved in an organic solvent, a water mixed solution, etc., an alkali solution is added, and an acid value is obtained from the amount of the alkali solution required for neutralization. The value measured by this method is used.

As for the structure and skeleton of the polymer, for example, a (meth) acrylic structure, a styryl structure, a radical polymerization polymer obtained by curing an ethylenic double bond with a radical, and the like can be used. JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A 63-287944, JP-A 63-287947, JP-A 1-271741, JP-A 10-116232 Also suitable are urethane-based binder polymers containing acid groups as described in No. etc., and urethane-based binder polymers having an acid group and a double bond in the side chain as described in JP-A No. 2002-107918.
Polysaccharide polymers such as polyimide, novolak resin, cresol resin, cellulose, and glucose can also be used in the present invention as long as the acid value is in the above range.

As the structure of the specific acid value polymer, a urethane polymer or a radical polymerization polymer is preferable from the viewpoint of easy introduction of an acid group, development property, and improvement of dispersion stability. From the viewpoints of molecular weight control and stability, a radical polymerization polymer is most preferable.
Examples of the method for introducing an acid group into the polymer obtained by radical polymerization in the present invention include a method of copolymerizing the above-mentioned acid group structure and a monomer having an ethylenic double bond. The acid value of the polymer obtained can be controlled by the amount of monomer charged.
As another method for introducing an acid group, there is a method in which a nucleophilic monomer such as a hydroxyl group or an amino group is polymerized and then reacted with a cyclic acid anhydride such as succinic anhydride to form an acid group. It is also possible to introduce an acid group by such a method.

  Preferred monomers having an acid group or acid anhydride used for the synthesis of a polymer having an acid value of 2.9 mmol / g to 7 mmol / g obtained by radical polymerization include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid. Acid, fumaric acid, 4-carboxylstyrene, α-hydroxymethacrylic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxy Ethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, β-carboxyethyl acrylate, ω-carboxypolycaprolactone monoacrylate, maleic anhydride, 2-acryloyloxyethyl acid phosphate, 2-acrylamido-2-methyl- 1- Etc. Ropansuruhon acid, and the like.

  It is possible to copolymerize the monomer having the acid group as necessary in order to develop a desired performance. Preferable copolymer components having such acid groups and ethylenic double bonds that can be used for the synthesis of (a-3) specific acid value polymer are shown below.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.
(13) Macromonomer having a polymerizable group at the terminal, for example, AA-6 having methyl methacrylate as a segment, manufactured by Toa Gosei Co., Ltd., AS-6 having styrene as a segment, AB-6 having butyl methacrylate as a segment, styrene AN-6 etc. which make acrylonitrile a segment are mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 are preferable because they have an excellent balance of film-forming property, sensitivity, and developability.

  In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups as described in JP 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in sensitivity and can be preferably used.

In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 2,500 or more, more preferably 3,000 to 200,000, and the number average molecular weight is preferably 1,000 or more. Yes, more preferably in the range of 2,000-150,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers, and the like. In particular, from the viewpoint of dispersion stability in the present invention, a graft polymer obtained by copolymerizing a macromonomer can be preferably used.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  (A-3) The specific acid value polymer has a function as a binder polymer, and (A) when preparing a pigment dispersion, (a-1) is added and dispersed together with the pigment. A) It is 2 to 70% by weight, more preferably 4 to 50% by weight, and most preferably 5 to 40% by weight in the solid content of the pigment dispersion.

In preparing the (A) pigment dispersion in the present invention, various compounds can be added in addition to the essential components (a-1) to (a-3). Hereinafter, (A) Optional components useful for preparing the pigment dispersion will be described.
Examples of such components include (a-3) binder polymers other than the specific acid value polymer, known dispersants, and the like.
The binder polymer as an optional component can be added in the range of 0 wt% to 50 wt%, more preferably 2 wt% to 30 wt% in the total solid content during preparation of the polymerizable composition.

-Dispersant-
The (A) pigment dispersion in the present invention may contain a known dispersant in addition to the (a-3) specific acid value polymer. By adding a 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 types 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. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Nippon Lubrizol Corporation); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, 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). 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 pigment dispersion liquid of the well-known dispersing agent as an arbitrary component, it is 0-100 mass parts with respect to 100 mass parts of above-mentioned (a-1) pigments, Preferably it is 3-70 mass parts. .

-Pigment derivative-
Other pigment derivatives other than the (a-2) specific pigment derivative according to the present invention can be added to the (A) pigment dispersion in the present invention, if necessary.
By using other pigment derivatives, the pigment derivative can be used as the adsorption point of the dispersant by adsorbing the pigment derivative with a portion having affinity with the dispersant or a polar group to the pigment surface. It can be dispersed in a curable composition to prevent re-aggregation, and is effective in constituting a color filter having high contrast and excellent transparency.

  As other pigment derivatives, known compounds having an organic pigment as a base skeleton can be appropriately used. Specific examples of the organic pigment include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, Indoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoimidazolone pigments and the like can be mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion liquid of the other pigment derivative in this invention, 0-30 mass parts is preferable with respect to 100 mass parts of pigments, and 3-20 mass parts is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

<Preparation of (A) Pigment Dispersion>
As a method for preparing a pigment dispersion containing the above (a-1) to (a-3) and an optional component, for example, (a-1) a pigment and (a-3) a specific acid value polymer are mixed in advance. In addition, the particles dispersed with a homogenizer or the like can be finely dispersed using a bead disperser using zirconia beads or the like (for example, a disperse mat manufactured by GETZMANN). The dispersion time is preferably about 3 to 6 hours. (A-2) The specific pigment derivative can be added at any step for forming a pigment dispersion, but is preferably added at the time of the finer step and / or fine dispersion.

The colored polymerizable composition of the present invention is prepared by blending (B) a polymerization initiator, (C) a polymerizable compound, and other components, which will be described later, using the thus prepared (A) pigment dispersion. Get things.
The amount of the (A) pigment dispersion contained in the colored polymerizable composition of the present invention is preferably in the range of 5 to 90% by mass, and more preferably in the range of 25 to 85% by mass.
Moreover, the amount of the (a-1) pigment contained in the colored polymerizable composition of the present invention is preferably in the range of 25 to 65% by mass in the solid content by including (A) the pigment dispersion in the above-mentioned blending amount. Therefore, even a thin layer can form a colored region having a sufficient hue.

<(B) Polymerization initiator>
The polymerization initiator used in the colored polymerizable composition of the present invention is not particularly limited as long as it can be decomposed by application of energy such as radiation, light irradiation, and heating to generate an initial species, but is not limited. Preferable examples include a 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 US Pat. No. 4,318,791 and European Patent Application No. 88050, described in US Pat. No. 4,199,420 Aromatic ketone compounds such as benzophenones, (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, and coumarin-based or lophine dimers described in JP-A-10-62986 Biimidazole compounds, such as JP-A-8-015521 Sulfonium organic boron complex, etc., etc. can be mentioned.

  Photopolymerization initiators include (1) acetophenone series, (2) ketal series, (3) benzophenone series, (4) benzoin series / benzoyl series, (5) xanthone series, (6) active halogen compounds [(6- 1) polymerization of triazine series, (6-2) halomethyloxadiazole series, (6-3) coumarin series], (7) acridine series, (8) biimidazole series, (9) oxime ester series, etc. Initiators are preferred.

  (1) As the acetophenone photopolymerization initiator, for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino Acetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. are preferred Can be listed.

  (2) Preferred examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  (3) Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy. -Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  (4) 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.

  (5) Preferred examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  (6) Examples of (6-1) triazine photopolymerization initiators that are active halogen compounds 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-dimethoxystyryl-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- A triazine etc. can be mentioned suitably.

(6-2) Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl). -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl- Preferable examples include 1,3,4-oxodiazole.
Examples of (6-3) coumarin-based photopolymerization initiators include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin and 3-chloro-5-diethylamino. Preferred examples include-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. be able to.

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

  (8) Examples of biimidazole photopolymerization initiators known as lophine dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5. Preferred examples include -diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like. be able to.

  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 JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

(10) Oxime ester-based initiator In the colored polymerizable composition of the present invention, particularly when forming a thin film, it is necessary to increase the pigment concentration as described above, so that a large amount of initiator that generates radicals cannot be added. . Further, since the pigment concentration is high, the concentration of the sensitizer and the initiator cannot be sufficiently obtained, and the effect of improving the curability by the initiation mechanism by the electron transfer and energy transfer using the sensitizer cannot be sufficiently obtained.
In particular, when the curable composition of the present invention is used to form a high-definition and finely colored region such as a solid-state image sensor, the start of a triazine system that generates a halogen by exposure even if it is highly sensitive. The agent cannot be used because it may contaminate a light source such as a stepper exposure apparatus. Therefore, an oxime compound that can be widely applied to a light source of 300 nm or more under these conditions and that is directly decomposed by light is used as an initiator, that is, an oxime ester-based initiator (hereinafter referred to as an oxime initiator as appropriate). Is preferably used. In particular, the use of the oxime type initiator is more effective in a composition containing a pigment in a solid content of 30% or more, further 40% or more and having a low ratio of the polymerizable component.

  The oxime compound that can be used as an initiator in the present invention can be used without limitation as long as it is a compound having a [—C═N—O—] bond in the molecule, but preferably the following general formula (I) , (II).

In the general formulas (I) and (II), R ¹ is a monovalent organic group, preferably an organic group having a carbonyl group or a sulfo group in the structure. From the viewpoint of sensitivity and stability, R 1 ¹ is preferably a monovalent organic group represented by the following general formula (III) or general formula (IV).

In the general formulas (III) and (IV), R ⁴ represents a monovalent organic group, specifically, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, A cycloalkynyl group, an aryl group, a heterocyclic group, and an alkoxy group are preferable. These organic groups may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. Group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, Examples thereof include an amide group, a carbonyl group, a nitro group, and a substituent having these groups.
Among these, from the viewpoint of stability over time, sensitivity, and productivity, the substituent represented by the general formula (III) is most preferable, and R ⁴ is an alkyl group or an aryl group.

In the general formulas (I) and (II), R ² represents a hydrogen atom or a monovalent organic group, and the organic group in the case where R ² represents a monovalent organic group includes, for example, 1 to 20 alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heterocyclic groups, alkoxy groups and the like can be mentioned. These organic groups may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. Group, cyano group, aryl group, heterocyclic group, alkoxy group, aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, Examples thereof include an amide group, a carbonyl group, a nitro group, and a substituent having these groups.

R ³ represents a monovalent organic group, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heterocyclic group, or an alkoxy group. Can be mentioned. These organic groups may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. Group, aryl group, cyano group, heterocyclic group, alkoxy group, aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, Examples thereof include an amide group, a carbonyl group, a nitro group, and a substituent having these groups.

Among the above, from the viewpoint of sensitivity, R ³ is preferably an aryl group or a heterocyclic group. When R ³ is an aryl group, it is preferably substituted with a substituent having a nitrogen atom or a sulfur atom, and when it is a heterocycle, it preferably contains a nitrogen atom, an oxygen atom or a sulfur atom. .

  Specific examples of (10) oxime type initiators that are particularly preferably used among (B) polymerization initiators that can be used in the present invention are shown below, but the present invention is not limited thereto.

Among these compounds, R ³ in the general formula (I) or general formula (II) is preferably an aryl group containing a sulfur atom or a nitrogen-containing aromatic ring, and R ¹ is an aryl group or It is a compound that is an alkyl group. Most preferred is a compound in which R ³ is a nitrogen-containing aromatic ring and R ¹ is an alkyl group having 1 to 3 carbon atoms in general formula (II).
As (B) polymerization initiator content in the coloring polymeric composition of this invention, 0.1-15.0 mass% is preferable with respect to the total solid of this composition, More preferably, 0.5- It is 8.0 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.

<(C) Polymerizable compound>
As a general polymerizable compound that can be used in the present invention, a compound widely known as a compound having an ethylenically unsaturated double bond in the industrial field can be used without any particular limitation. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. . Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (E) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (E)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in 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 curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In this invention, when adding a radically polymerizable compound, it is preferable to contain 2 or more ethylenically unsaturated bond from a viewpoint of hardening sensitivity, and it is more preferable to contain 3 or more. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

(C) Only 1 type may be used for a polymeric compound and it may use 2 or more types together.
The content of the polymerizable compound (C) in the colored polymerizable composition of the present invention is preferably in the range of 4 to 80% by mass, more preferably in the range of 7 to 50% by mass in terms of solid content. preferable.
In particular, when a cured film having a film thickness of 0.8 μm or less is to be formed, the content of the polymerizable compound (C) is preferably 5 to 40% by mass, particularly 6 to 25% by mass in the total solid content. It is effective in the range.

In the colored polymerizable composition of the present invention, in addition to the components (A) to (C), various additives can be used depending on the purpose within a range not impairing the effects of the present invention.
Hereinafter, optional components that can be contained in the colored polymerizable composition of the present invention will be described.

<(D) Resin>
Moreover, in this invention, it is possible to add (D) resin in a curable composition as needed. (D) By adding a resin, it is possible to improve the film properties of the polymerizable composition or to adjust the developability.
The (D) resin usable in the present invention includes polyester, polyimide, polyurethane, for the purpose of coating properties, film-forming properties, composition stabilization, exposure area color loss suppression during development, and adjustment of developability. Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, polymer having hydroxyl group, acid anhydride added, alcohol-soluble nylon, bisphenol And phenoxy resin formed from A and epichlorohydrin.

In many cases, the dispersion is phase-separated in the polymerizable composition, and is formed when the resin is added to the dispersion and when the resin is added later to the polymerizable composition containing the dispersion. Different coatings may exhibit different developability and stability.
In the present application, a resin having the same structure and / or the same physical property as the resin used in the dispersion liquid for the purpose of coating property, film forming property, composition stabilization, development property adjustment and the like is used in the polymerizable composition. However, different resins can be used depending on the purpose.
The alkali-soluble resin that can be used as the (D) resin in the present invention is a linear organic high molecular polymer, and a molecule (preferably an acrylic copolymer or a styrene copolymer is used as the main chain. The molecule can be appropriately selected from alkali-soluble resins having at least one group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.) in the molecule. Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. As this (D) resin (resin having an alkali-soluble group), (a-3) a polymer having an acid value of 2.9 mmol / g to 7 mmol / g used in the preparation of the (A) pigment dispersion may be used. Is possible.

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

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

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

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

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a generic name indicating either or both of acrylic acid and methacrylic acid, and similarly (meth) acrylate is a generic name indicating either or both of acrylate and methacrylate.

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

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).
Further, in the present application, a (meth) acrylic resin having an allyl group, a vinyl ester group and a carboxyl group in the side chain, and a double bond in the side chain described in JP-A Nos. 2000-187322 and 2002-62698 are disclosed. Or an alkali-soluble resin having an amide group in the side chain described in JP-A-2001-242612 can be used.
From the viewpoint of the balance of film formability, sensitivity, and developability, the (D) resin used in the present invention is preferably an alkali-soluble resin having an acid group, more preferably an alkali-soluble resin having a polymerizable group in the side chain. Can be mentioned.

  (D) As content in resin photocurable composition, 1-30 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-20 mass%, Most preferably Is 3-10 mass%.

<Compound having an adhesive group>
In the colored polymerizable composition of the present invention, a compound having an adhesive group can be used for the purpose of improving the adhesiveness of the cured film to the support or the substrate. In particular, when the colored polymerizable composition of the present invention is used for forming a colored region of a color filter, it is preferable to use such a compound from the viewpoint of improving the adhesion between the colored region and the substrate.
The adhesive group possessed by such a compound may be any substituent having adhesiveness to the substrate used in the color filter, but is particularly preferably a compound having adsorptivity to a glass substrate or a silicon substrate.
Preferred adhesive groups include acid groups such as sulfonic acid groups, phosphonic acid groups and carboxyl groups; ester groups of these acids; metal salts of these acids; onium salts of these metals; onium groups such as ammonium groups and pyridinium groups; alkoxy It is preferably a group selected from a substituent that generates a silanol group by hydrolysis such as a silyl group; a zwitterionic group such as a phenolic hydroxyl group and an N-oxide group; and a chelating group such as iminodiacetic acid.
From the viewpoint of adhesion, an alkoxysilyl group and / or a hydrolyzed group thereof is preferable.

In addition, the compound having an adhesive group in the present invention is a compound having a group for improving sensitivity, such as a group for improving developability, a carbon-carbon double bond group, or a cyclic alkoxy group, if necessary. It is possible to use.
As the group for improving developability, a functional group having a hetero atom is preferable, and examples thereof include an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, an amino group, a urethane group, an amide group, a thiol group, a sulfo group, and a urea group. It is preferable to use a compound further having such a functional group.
As the group for improving the sensitivity, a methacryl group, an acrylic group, a styryl group, a vinyl ether group, an allyl group, a cyclic alkenyl group, a furyl group, an oxetane group, an epoxy group, and a tetrahydrofuran group are preferably mentioned. From the viewpoint of sensitivity, a methacryl group, It is preferable to use a compound further having an acrylic group and a styryl group.

<Sensitizer>
The curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
In addition, European Patent No. 568,993, U.S. Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And compounds described in Japanese Patent No. 271969.

  More preferable examples of the sensitizer include compounds represented by the following general formulas (i) to (v).

(In formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with the adjacent A ² and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic 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.)

(In Formula (ii), 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 synonymous with that shown in the general formula (i).)

(In the formula (iii), 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 an adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² —, R ⁶² represents a substituted or unsubstituted alkyl group, or 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 cooperation with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group. Can be bonded to each other to form an aliphatic or aromatic ring.)

(In the formula (v), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ may be bonded together to form an aliphatic or aromatic ring, respectively. it can.)

  Preferable specific examples of the compounds represented by the general formulas (i) to (v) include those shown below.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is 0. More preferably, the content is 5 to 15% by mass.

<Co-sensitizer>
The curable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Thermal polymerization component>
It is also effective to contain a thermal polymerization component in the colored polymerizable 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 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) and their similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UCB) can 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 Toto 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 polymerizable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coating properties, and includes various fluorine-based, nonionic-based, cationic-based, and anionic-based surfactants. Can be used. Of these, fluorine-based surfactants and nonionic surfactants are preferable.

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, 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 Co., Ltd.) Asahi Guard AG 7105, 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, 802 (manufactured by JEMCO Corporation).

  In particular, the fluorosurfactant is effective in preventing coating unevenness and thickness unevenness when forming a thin coating film using the colored polymerizable composition of the present invention. Furthermore, it is also effective when the colored polymerizable composition of the present invention is applied to slit coating that easily causes liquid breakage.

  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., etc. 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 used in the colored polymerizable composition of the present invention. Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and aggregation inhibitors such as sodium polyacrylate. There are fillers such as glass and alumina.

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

Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

  The colored polymerizable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

<Method for Producing Color Filter Using Colored Polymerizable Composition>
The colored polymerizable composition of the present invention comprises (B) a polymerization initiator, (C) a polymerizable compound, and an alkali-soluble resin used in combination as desired (preferably together with a solvent). It can be prepared by mixing and dispersing additives such as surfactants if necessary, and mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

An example of the manufacturing method of the coloring polymeric composition of this invention is shown below.
(1. Preparation of fine pigment)
A mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed with a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. Is used to grind the pigment while applying a strong shearing force, and the mixture is put into water and made into a slurry with a stirrer or the like. Subsequently, this slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a refined pigment.

(2. (A) Preparation of pigment dispersion)
(A-1) A pigment, (a-2) a specific pigment derivative, (a-3) a polymer having an acid value of 2.9 mmol / g to 7 mmol / g and a solvent are blended to perform bead dispersion. Using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., and finely dispersing with beads made of 0.01 to 1 mm particle size glass, zirconia, etc. (A) Pigment A dispersion is obtained. Here, it is possible to omit the process of making the pigment fine.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
The (A) pigment dispersion obtained as described above is added with (C) a polymerizable compound, (B) a polymerization initiator, and other (D) resin used in combination as desired. The colored polymerizable composition of the present invention is obtained.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

A step of applying the curable composition of the present invention on a support to form a curable composition layer (hereinafter abbreviated as “curable composition layer forming step” as appropriate), and the curable composition. A step of exposing the layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter referred to as “development step” as appropriate). Abbreviated as “.”).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Curable composition layer forming step>
The color filter of the present invention is formed on a substrate such as glass by using the above-described photocurable composition of the present invention, and the photocurable composition of the present invention is directly or via other layers. Then, after forming a coating film on the substrate by, for example, slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display element and a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

The colored polymerizable composition of the present invention can be 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 or the like.
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, usually, a black matrix for isolating each pixel is 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 color polymerization 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 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 colored polymerizable composition of the present invention to the 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 0.5 to 4 0.0 μm, most preferably 0.8 to 3.0 μm.
In addition, when applying the colored polymerizable composition of the present invention to the formation of a color filter for a high-resolution solid-state imaging device, the film thickness is most preferably in the range of 0.35 μm to 2.0 μm.
The present invention is particularly effective for forming a colored region having a film thickness of 0.38 μm to 1.0 μm, and further 0.45 μm to 0.8 μm.

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.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.

When using the color filter of the present invention for a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Also, when using the color filter of the present invention for the solid-state imaging device, it is more preferably preferably 50~1000mJ / cm ² 30~1500mJ / cm ² within the above range, and most preferably 80~500mJ / cm ² . When producing a color filter for a solid-state imaging device, it is preferable to mainly use i-line in a stepper exposure machine because high-definition pattern formation is required.

<Development process>
In the development process, the uncured portion after the exposure is eluted in the developer, and only the cured portion 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.

Examples of the organic solvent include the solvents described above that can be used when preparing a pigment dispersion or a colored polymerizable composition.
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, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. 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.
Paddle development may be used when producing a color filter for a solid-state imaging device.

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.

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.

As the use of the colored polymerizable composition of the present invention containing the (A) pigment dispersion, the description has mainly focused on the use for a color filter, but the formation of a black matrix that isolates each colored pixel constituting the color filter. It can also be applied to.
The black matrix is formed by exposing and developing the pigment dispersion composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-baking as necessary to promote film curing. Can be formed.

  The colored polymerizable composition of the present invention is excellent in dispersion stability of the pigment, is cured with high sensitivity, and is excellent in developability. Therefore, even when the pigment is contained at a high concentration, it is a thin layer and A colored region having excellent color characteristics can be formed with high resolution, and is particularly useful for forming a colored region of a color filter, and its application range is wide.

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.
Unless otherwise specified, “%” and “parts” are based on mass.
(Synthesis Example 1: Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 85 ° C., the inside of the reaction vessel was purged with nitrogen, 13.5 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 8.5 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.8 parts of dimethyl 2,2′-azobis (2-methylpropionate) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 15000 and an acid value of 2.9 mmol / g.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 1 was prepared.

(Synthesis Example 2: Preparation of acrylic resin solution 2)
Into a reaction vessel, 800 parts of propylene glycol monomethyl ether acetate was heated to 100 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 60.0 parts of styrene, 80.0 parts of methacrylic acid, 68.0 parts of methyl methacrylate Part, Toa Gosei Co., Ltd. macromonomer AA-6, 62.0 parts, azobisisobutyronitrile 9.0 parts was added dropwise over 1 hour to carry out the polymerization reaction. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. Was about 33000 and an acid value of 3.44 mmol / g was obtained.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acrylic resin solution 2 was prepared by adding acetate.

(Synthesis Example 3: Preparation of acrylic resin solution 3)
A weight average molecular weight obtained by adding 10 parts by weight of glycidyl methacrylate and 1 part by weight of tetraethylammonium bromide to the acrylic resin solution 2 obtained in Synthesis Example 2 and stirring at 90 ° C. for 2 hours to introduce a double bond group into the side chain. Was about 34000 and an acid value of 3.1 mmol / g was obtained.
A predetermined amount of propylene glycol monomethyl ether acetate was added to the previously synthesized acrylic resin 3 solution to prepare an acrylic resin solution 3 having a nonvolatile content of 20% by weight.

(Synthesis Example 4: Preparation of acrylic resin solution 4)
Polyacrylic acid / methyl methacrylate (weight ratio 50/50) of propylene glycol monomethyl ether acetate having a weight average molecular weight of 10,000 and an acid value of 6.9 mmol / g is added to 30% by weight of glycidyl methacrylate and 1 part by weight of tetraethylammonium bromide. In addition, the mixture was stirred at 90 ° C. for 3 hours to obtain a solution of acrylic resin 4 having a weight average molecular weight of 12000 and an acid value of 4.1 mmol / g, in which a double bond group was introduced into the side chain.
A predetermined amount of propylene glycol monomethyl ether acetate was added to the previously synthesized acrylic resin 4 solution in the same manner as in Synthesis Example 2 to prepare an acrylic resin solution 4 having a nonvolatile content of 20% by weight.

(Synthesis Example 5: Preparation of comparative acrylic resin C1 solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 85 ° C., the inside of the reaction vessel was purged with nitrogen, 13.5 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 3.5 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.8 parts of dimethyl 2,2′-azobis (2-methylpropionate) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of acrylic resin C1.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Comparative resin solution C1 was prepared. The weight average molecular weight was 15000, and the acid value of this resin C1 was 1.41 mmol / g.

(Examples 1-5, Comparative Example 1)
<Preparation 1 of pigment dispersion composition>
The components of the following composition (1) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
[Composition (1)]
・ C. I. Pigment Red 254 75 parts C.I. I. Pigment Yellow 139 25 parts Acrylic resin solution shown in Table 1 (solid content 20% by mass) 280 parts 1-methoxy-2-propyl acetate 630 parts Specific pigment derivative or comparative compound shown in Table 1 8 parts

Subsequently, the mixed solution (A to F) obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain red pigment dispersions (A to F).
The structures of (a-1) specific pigment derivatives (Y-1) to (Y-4) and comparative compound (H-1) according to the present invention described in Table 1 below are shown below. In addition, the acrylic resins 1 and 2 and the comparative resin C1 which are (a-3) specific acid value polymers used in the following Examples and Comparative Examples are those obtained in Synthesis Examples 1 to 5.

<Evaluation of pigment dispersion>
The obtained pigment dispersions (A to D) and comparative pigment dispersions E and F according to the present invention were evaluated as follows.
(1) Viscosity measurement and evaluation Using the E-type viscometer, the viscosity η ¹ of the pigment dispersion immediately after dispersion and 1 week after dispersion (at room temperature of 25 ° C. to 28 ° C.) and the viscosity was measured eta ² of the pigment dispersion after to assess the extent of thickening by calculating the difference. If the difference between the viscosity η ² after 1 week and the viscosity η ¹ after dispersion is 5 (mPa · s) or less, the dispersion stability is good. The results are shown in Table 1 above.
As is apparent from Table 1, (a-2) specific pigment derivatives and (a-3) pigment dispersions A to D prepared containing a specific acid value polymer, and (a-2) specific pigment derivatives The comparative dispersion E containing the comparative resin C was excellent in dispersion stability, but (a-2) the comparative dispersion F not containing the specific pigment derivative deteriorated with time. I understand that

Hereinafter, an example in which a colored polymerizable composition containing a colorant is prepared for forming a color filter for use in a solid-state imaging device will be described.
[Production of silicon substrate with undercoat layer]
Components of the following composition (2) were mixed and dissolved to prepare a resist solution for the undercoat layer.
<Composition (2)>
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
-36.67 parts of ethyl lactate-30.51 parts of binder polymer [40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)]
Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
Photopolymerization initiator 0.586 parts (TAZ-107 (trihalomethyltriazine photopolymerization initiator),
(Midori Chemical Co., Ltd.)

  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 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

1-1. Preparation of Colored Polymerizable Composition (Coating Solution) The following components were further added to the pigment dispersion obtained by the dispersion treatment, followed by stirring and mixing to prepare a curable composition solution.
-(A) Pigment dispersion (dispersion listed in Table 2) 100 parts by mass-DPHA (manufactured by Nippon Kayaku Co., Ltd.) 4.0 parts by weight-Polymerization initiator (compounds listed in Table 2) 0.5 parts by weight Unit in which allyl methacrylate / methacrylic acid / hydroxyethyl methacrylate / methacrylic acid is reacted with glycidyl methacrylate

[Mol ratio, 25/25/25/25, weight average molecular weight 45,000:
(C) component] 1.0 part by weight / surfactant (trade name: Tetranic 150R1, BASF) 0.2 part by weight / solvent: 100 parts by weight PGMEA (B) polymerization initiator (I The structures of (-1) to (I-3) are shown below.

[Production and Evaluation of Color Filter Using Colored Polymerizable Composition]
-Pattern formation and sensitivity evaluation-
The colorant-containing curable composition prepared in Examples 1 to 5 and Comparative Example 1 was applied onto the silicon substrate with the undercoat layer to form a curable composition layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.6 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), exposure through a Island pattern mask having a pattern of 1.4 μm square at a wavelength of 365 nm is 1.4 μm having the same size as the mask pattern The exposure was performed at various exposure amounts of 50 to 1600 mJ / cm ² so that a four-sided island pattern was obtained. Here, an exposure amount of 50 mJ / cm ² was measured by a light illuminance system, and the exposure amount was changed with reference to the exposure amount, and an integrated exposure amount (mJ / cm ² ) was obtained to obtain sensitivity. A smaller value indicates that a fine pattern with a high resolution can be formed with a low exposure amount and is highly sensitive. The results are shown in Table 2 above.
Thereafter, the silicon wafer substrate on which the irradiated coating film 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). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. Thereafter, using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation), the formed 1.4 μm square colored pattern and its peripheral portion were observed at a magnification of 20,000. In the exposure process, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability. The results are shown in Table 2 above.

  As is clear from Table 2, according to the colored polymerizable compositions of Examples 1 to 5 according to the present invention, a highly sensitive and fine colored region can be formed, and no residue is present after development. It turns out that it is excellent in the developability of an unexposed part. On the other hand, it turns out that it replaces with (a-3) specific acid value polymer which concerns on this invention, and is inferior in developability in the comparative example 1 using comparative resin C1.

(Examples 6 to 8, Comparative Example 2)
<Preparation 2 of pigment dispersion>
Components of the following composition (3) were mixed and kneaded and dispersed with two rolls to prepare mixed solutions (F to I) containing pigments.
[Composition (3)]
・ C. I. Pigment Green 36 50 parts by mass / C.I. I. Pigment Yellow 150 50 parts by mass, resin 200 parts by mass, Solsperse 32000GR (manufactured by Nippon Lubrizol Corporation; polyester-based dispersant)
20 parts by mass / solvent: propylene glycol methyl ether acetate 520 parts by mass / the following (a-2) specific pigment derivative or comparative compound (compound described in Table 3) 6 parts by weight

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ Solvent: Propylene glycol methyl ether acetate (PGMEA)
350 parts by mass The structures of (a-1) specific pigment derivatives (Y-5) to (Y-7) and a comparative compound (H-2) according to the present invention described in Table 3 below are shown below.

<Evaluation of pigment dispersion>
With respect to the obtained pigment dispersions (GI) and comparative pigment dispersion J according to the present invention, the dispersion stability was evaluated in the same manner as the pigment dispersions A to F. The results are shown in Table 3 above.
As apparent from Table 3, the pigment dispersions G to I prepared by including (a-2) the specific pigment derivative and (a-3) the specific acid value polymer were excellent in dispersion stability. .

Hereinafter, an example in which a curable composition containing a colorant is prepared for forming a color filter for use in a solid-state imaging device will be described.
<Preparation of silicon substrate with undercoat layer>
Components of the following composition (4) were mixed and dissolved to prepare a resist solution for the undercoat layer.
<Composition (4)>
Propylene glycol monomethyl ether acetate 19.20 parts (PGMEA: solvent)
-36.67 parts of ethyl lactate-30.51 parts of binder polymer [40% PGMEA solution of benzyl methacrylate / methacrylic acid (molar ratio = 75/25)]
Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound)
・ Polymerization inhibitor (p-methoxyphenol) 0.0065 part ・ Fluorosurfactant 0.80 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
-Photopolymerization initiator [said polymerization initiator (I-1)] 0.50 parts

  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 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

2-1. Preparation of Colored Polymerizable Composition (Coating Solution) The following components were further added to the pigment dispersion obtained by the dispersion treatment, followed by stirring and mixing to prepare a curable composition solution.
-(A) Pigment dispersion [dispersion shown in Table 4] 100 parts by mass-3.8 parts by weight of pentaerythritol tetraacrylate-0.5 parts by weight of the polymerization initiator shown in Table 4-benzyl methacrylate / methacrylic acid (mol ratio) 70/30, weight average molecular weight 70,000) 0.7 parts by weight Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by weight Solvent: PGMEA 100 parts by weight

  About the curable composition layer of the said composition, the colored area | region which consists of a curable composition was formed on the silicon substrate like Example 1, and it was set as the colored pattern of a color filter, and performance evaluation was performed similarly. The results are shown in Table 4 below.

  As apparent from Table 4, according to the colored polymerizable compositions of Examples 6 to 8 according to the present invention, a highly sensitive and fine colored region can be formed, and no residue is present after development. It turns out that it is excellent in the developability of an unexposed part. On the other hand, it turns out that it replaces with (a-3) specific acid value polymer which concerns on this invention, and it is inferior to developability in the comparative example 2 using the (A) pigment dispersion J using the comparative resin C1.

(Examples 9 to 11 and Comparative Example 3)
<Preparation of pigment dispersion>
Components of the following composition (6) 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 (6)]
・ C. I. Pigment red 254 50 parts C.I. I. 50 parts of Pigment Red 177 200 parts of resin listed in Table 5 BYK111 (by Big Chemie; phosphate ester dispersant) 10 parts listed below (a-2) specific pigment derivative or comparative compound (compound described in Table 5) 4 parts 1-methoxy-2-propyl acetate 820 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a red pigment dispersion (K to N).
(A-1) Specific pigment derivative (Y-6) according to the present invention described in Table 5 below is the same as described above. The structures of specific pigment derivatives (Y-8), (Y-9) and comparative compound (H-3) are shown below.

<Evaluation of pigment dispersion>
With respect to the obtained pigment dispersions (K to M) and comparative pigment dispersion N, the dispersion stability was evaluated in the same manner as the pigment dispersions A to F. The results are also shown in Table 5.
As apparent from Table 5, the pigment dispersions K to M prepared by including (a-2) the specific pigment derivative and (a-3) the specific acid value polymer were excellent in dispersion stability. .

Hereinafter, an example in which a curable composition containing a colorant is prepared for forming a color filter for use in a liquid crystal display element will be described.
<Preparation of curable composition (coating liquid)>
The following components were further added to the dispersion-treated pigment, and the mixture was stirred and mixed to prepare a curable composition solution.
-100 parts by weight of the above pigment dispersion (described in Table 6)-3.8 parts by weight of dipentaerythritol pentaacrylate-1.5 parts by weight of the polymerization initiator described in Table 6-Benzyl methacrylate / methacrylic acid (mol ratio, 70 / 30, weight average molecular weight 70,000) 0.7 parts by weight, surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by weight, solvent: PGMEA 100 parts by weight (B) polymerization described in Table 6 Initiator (I-3) is the compound described above. The polymerization initiator (I-4) is “4-benzoxolane-2,6-di (trichloromethyl) -s-triazine”, and the polymerization initiator (I-5) is S-1 / It is a mixture of Z-1 / K-1 weight ratio 5/2/3.

<Production of color filter>
3-2. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).
(Slit application conditions)
Gap at the opening of the coating head tip: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

3-3. Exposure and development After that, the photocurable coating film was exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kw ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film was developed by Fuji Film Electronics. It was covered with a 1% aqueous solution of Alkali developer CDK-1, manufactured by Materials, and allowed to stand for 40 seconds.

3-4. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the photocuring treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, the colored region which consists of a resin film was formed on the glass substrate, and it was set as the colored pattern of the color filter.

[Performance evaluation]
The exposure amount required for curing the curable composition coating film (colored layer) formed on the glass substrate using the colored polymerizable composition prepared as described above was measured in the same manner as in Example 1, and a sensitivity standard was obtained. It was. A smaller value indicates higher sensitivity. The results are shown in Table 6 above.
Further, after the separately formed colored layer (20 μm square) was exposed at an exposure amount of 100 mJ / cm ² , development and post-baking were performed under the above conditions, and the formed colored region and its peripheral portion were the same as in Example 1. Observation was performed under conditions to confirm the presence or absence of residues in the non-image area. The results are shown in Table 6 above.

  As is apparent from Table 6, according to the colored polymerizable composition of the present invention, a highly sensitive and fine colored region can be formed, and there is no residue after development. It turns out that it is excellent. On the other hand, it turns out that it is inferior to developability in the comparative example 3 using the pigment dispersion liquid N which does not contain (a-3) specific acid value polymer which concerns on this invention.

Claims (5)

  (A) at least (a-1) pigment, (a-2) a compound having a pigment nucleus structure and an amino group in the molecule, and (a-3) an acid value of 2.9 mmol / g to 7 mmol / g A colored polymerizable composition comprising a pigment dispersion containing the polymer of (B), (B) a polymerization initiator, and (C) a polymerizable compound.   2. The colored polymerizable composition according to claim 1, wherein the compound (a-2) having a pigment mother nucleus structure and an amino group in the molecule is a compound having at least one of an amide structure and a urea structure. Composition.   The colored polymerizable composition according to claim 1 or 2, wherein the compound (a-2) having a pigment mother nucleus structure and an amino group in the molecule is a compound having a heterocyclic structure. .   A color filter comprising a colored region formed by using the colored polymerizable composition according to any one of claims 1 to 3.   A solid-state imaging device comprising the color filter according to claim 4.