JP5542316B2 - Pigment dispersion composition, colored photosensitive composition, color filter, liquid crystal display device, and solid-state imaging device - Google Patents

Description

  The present invention relates to a pigment dispersion composition, a colored photosensitive composition containing the pigment dispersion composition, a color filter having a colored region formed by the colored photosensitive composition, and a liquid crystal display using the color filter The present invention relates to an element and a solid-state imaging element.

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

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for use in image sensors (solid-state imaging devices) are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution.

  In response to the above requirements, the pigment contained in the colored photosensitive composition is dispersed in a finer state (good dispersibility), and is dispersed in a stable state (good dispersion stability). Is required. When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pixels formed by the photolithographic method, and there are many undeveloped residues (residues) on the substrate. There are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated. In addition, when the dispersion stability of the pigment is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored photosensitive composition is reduced, or the sensitivity in the exposure process. Or the alkali solubility in the development process is likely to be reduced. Further, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened. In order to improve color characteristics such as the contrast of color filters, it is effective to reduce the particle diameter of the pigment. However, if the particle diameter of the pigment is reduced, the surface area of the pigment particles increases, so the aggregation between the pigment particles It is often difficult to increase the strength and achieve both a high level of dispersibility and dispersion stability.

The following methods are known for miniaturization of pigment particles.
In general, the primary particles of the pigment are made fine by a method of kneading a pigment, a water-soluble inorganic salt, or a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader (a salt milling method). Are known. The obtained mixture of primary particles of fine pigment is put into water and stirred with a mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried to obtain a fine pigment as a secondary aggregate that is an aggregate of primary particles of the pigment. The dispersion step in a normal disperser such as a sand mill or a ball mill is a step of loosening a secondary aggregate that is an aggregate of primary particles of a pigment to obtain a dispersion close to the primary particles.

Although the primary particles of the fine pigment can be obtained by the above-described method, various pigment dispersants have been developed so far in order to improve the dispersibility and dispersion stability of the primary particles. Has been.
Among these pigment dispersants, for example, Patent Document 1 proposes an ω-carboxypolycaprolactone monomethacrylate copolymer for the purpose of obtaining high-definition pixels having good alkali developability.
For example, in Patent Document 2, for the purpose of improving dispersibility and alkali developability, a polymer structure of a vinyl compound such as styrene or alkyl (meth) acrylate is used as a graft chain, and a heterocyclic structure is included. A polymer compound having a side chain has been proposed.
However, even these methods cannot meet the demand for higher contrast from the market, and further higher dispersibility and dispersion stability in fine pigments have been desired.
JP 2004-287409 A JP 2003-238837 A

Then, this invention is made | formed in view of said point, and makes it a subject to achieve the following objectives.
That is, the first object of the present invention is that the finely divided pigment can be dispersed in the form of primary particles, and the dispersed primary particles of the pigment can be stably maintained. Another object of the present invention is to provide a pigment dispersion composition capable of forming a colored film excellent in the above.
In addition, a second object of the present invention is to provide a colored photosensitive composition that can form a colored cured film that includes the pigment dispersion composition and has excellent curing sensitivity, high strength, and excellent contrast. There is.
Furthermore, a third object of the present invention is a color filter that is formed using the colored photosensitive composition, has a high voltage holding property and contrast, and has a colored region with small color density unevenness and excellent color characteristics, An object of the present invention is to provide a liquid crystal display device and a solid-state imaging device provided with the color filter.

Means for solving the above-mentioned problems are as follows.
That is, the pigment dispersion composition of the present invention is
(A) When all the repeating units are 100% by mass, a high content containing at least 5% by mass of at least one repeating unit selected from the repeating units represented by any one of the following general formulas (I) and (II) A pigment dispersion composition comprising a molecular compound, (b) a pigment, and (c) an organic solvent.

In the general formulas (I) and (II), R ¹ , R ² , R ⁴ , and R ⁵ represent a hydrogen atom, R ³ and R ⁶ represent a hydrogen atom or a methyl group, and X ¹ and X ² each independently represents —C (═O) O—, —CONH—, or a phenylene group, and L ¹ and L ² each independently represent a single bond, —C ₂ H ₄ —, —C _{4 H 8 -, - C 2} H 4 O-C (= O) -C 2 H 4 -, _{or, -C 2 H 4 O-C} (= O) - cyclohexylene - represents, ^{Y 1} is O ² represents an oxygen atom, a sulfur atom, or —NH—, Y ² represents a single bond, —C (═O) O—, or —CONH—, and Z ¹ and Z ² each independently represent the following general formula (i) either consists of end groups alone selected ~ from the general formula (iv), to said distal end _{group, -C (= O) -NH-} C 2 H 4 O -, - C (= O) - , -C _{2 H 4 O -, - CH 2} CH (OH) CH 2 O-, or -CH ₂ - is composed by connecting, m and n each independently represents an integer of 2 to 8, p and q are , Each independently represents an integer of 5 to 60.

In the pigment dispersion composition of the present invention, it is preferable that (a) the polymer compound has an acid group in the side chain in the range of 50 mgKOH / g to 200 mgKOH / g.
It is also a preferred embodiment that (a) the polymer compound has a heterocyclic group composed of any one of the nitrogen-containing heterocyclic structures listed below in the side chain.
Nitrogen-containing heterocyclic structure: a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, an acridine ring, a phenothiazine ring, a phenoxazine ring, an acridone ring, base lens imidazole structure , Benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, cyclic imide structure Furthermore, the pigment dispersion composition of the present invention is preferably used for forming a colored region in a color filter.

The colored photosensitive composition of the present invention is characterized by containing the pigment dispersion composition of the present invention, a photopolymerizable compound, and a photopolymerization initiator.
Moreover, the color filter of this invention has a colored area | region formed with the coloring photosensitive composition of this invention on the board | substrate.
Furthermore, both of the liquid crystal display element and the solid-state image sensor of the present invention are characterized by including the color filter of the present invention.

Although the operation of the present invention is not clear, it is presumed as follows.
That is, (a) the polymer compound that functions as a pigment dispersant includes a repeating unit represented by either of the general formula (1) and the general formula (2), and has a specific graft chain structure. I understand that. This graft chain structure has low affinity with the pigment, but (c) the affinity with the organic solvent coexisting in the pigment dispersion composition is high. The graft chain portion can have a structure extending to the organic solvent side. That is, (a) the polymer compound in the present invention has a graft chain structure having a high affinity with the solvent, and therefore, when coexisting with (b) the pigment and (c) the organic solvent, the polymer compound has an extended structure, and the pigment surface It is considered that adsorption onto the organic solvent is efficiently performed, and as a result, it is considered that a stable dispersion state of the pigment can be maintained in the organic solvent.
On the contrary, in the graft chain structure having high affinity with the pigment and low affinity with the solvent, the graft chain part is adsorbed on the pigment surface, and the graft chain part may be extended to the organic solvent side. Can not. Therefore, the polymer compound having such a graft chain has a contracted structure when coexisting with the pigment and the organic solvent, and the adsorption to the pigment surface is not performed efficiently, resulting in the aggregation of the pigment. It is thought that it will end.

  In the ω-carboxypolycaprolactone monomethacrylate copolymer described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-287409), the graft chain end group is a highly interactive carboxyl group. Since the adsorption occurs or the structure of the polymer compound contracts, the effect of pigment dispersibility cannot be sufficiently exhibited.

  Furthermore, the (a) polymer compound in the present invention has a heterocyclic group in the side chain, which is a preferred embodiment, so that the heterocyclic structure and (b) the pigment have a strong electrostatic interaction. The polymer compound is strongly adsorbed on the surface, and the secondary aggregate can be effectively loosened to maintain a stable dispersion state.

In addition, a color filter having a colored region formed by using a colored photosensitive composition dispersed with (b) a pigment by (a) a polymer compound is a color filter in which the colored region (pixel portion) becomes cloudy under high temperature and high humidity. The problem that the colored region (pixel portion) becomes cloudy at the time of manufacturing the filter can also be solved. These problems are considered to occur as fine pigment particles in the filter aggregate and grow as crystals, and are more likely to occur as the primary particles of the pigment are finer.
In the present invention, as described above, (a) the polymer compound is used, and (b) the pigment dispersion composition in which the dispersibility of the pigment is improved, the (a) polymer compound is strong against the fine pigment. It is adsorbed and aggregation of pigment particles can be effectively suppressed even in the colored region (pixel portion). In addition, since (a) the polymer compound has a radically polymerizable or cationically polymerizable group at the graft chain terminal site, the light in the colored photosensitive composition is subjected to post-heating (baking) after exposure or development. Polymerization or crosslinking reaction with a polymerizable compound or the like can be performed, and aggregation of pigment particles can be effectively suppressed. As a result, it is considered that the problem that the colored region (pixel portion) becomes cloudy can be suppressed, and a colored region (pixel portion) having excellent contrast can be formed.

Furthermore, a color filter having a colored region formed by using a colored photosensitive composition dispersed with (b) a pigment by (a) a polymer compound also has an advantage of excellent liquid crystal voltage holding property. In general, the decrease in the voltage holding ratio of the liquid crystal is caused by the elution of low molecular components such as metal ions in the colored region (pixel portion) of the color filter. Therefore, when the metal ion concentration in the pixel portion is high. It is easy to generate.
In the present invention, (a) the radically polymerizable group or cationically polymerizable group at the graft chain end of the polymer compound causes a polymerization or crosslinking reaction with the photopolymerizable compound or the like in the colored photosensitive composition, and is dense and strong. A cured film is obtained. As a result, it is considered that the pixel portion of the color filter becomes a dense and strong cured film, the elution of metal ions can be effectively suppressed, and the voltage holding ratio is increased.

According to the present invention, a finely colored pigment can be dispersed in the form of primary particles, the primary particles of the dispersed pigment can be stably maintained, and a colored coating excellent in contrast Can be provided.
Another object of the present invention is to provide a colored photosensitive composition that can form a colored cured film that includes the pigment dispersion composition and has excellent curing sensitivity, high strength, and excellent contrast. .
Furthermore, a third object of the present invention is a color filter that is formed using the colored photosensitive composition, has a high voltage holding property and contrast, and has a colored region with small color density unevenness and excellent color characteristics, A liquid crystal display element provided with the color filter and a solid-state imaging element can be provided.

  Hereinafter, the pigment dispersion composition, the colored photosensitive composition, the color filter, the liquid crystal display device, and the solid-state imaging device of the present invention will be described in detail.

<Pigment dispersion composition>
The pigment dispersion composition of the present invention comprises (a) at least one selected from repeating units represented by any one of the following general formulas (I) and (II) when the total repeating units are 100% by mass . It contains a polymer compound containing 5% by mass or more of repeating units, (b) a pigment, and (c) an organic solvent.
Hereinafter, (a) the polymer compound, (b) the pigment, and (c) the organic solvent constituting the pigment dispersion composition of the present invention will be described.

  In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted means that what has a substituent is included with the thing which does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[(A) Polymer compound containing at least one repeating unit selected from repeating units represented by any one of general formulas (I) and (II)]
The pigment dispersion composition of the present invention comprises at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II) when the total repeating unit is 100% by mass. It is characterized by containing a polymer compound containing 5% by mass or more (hereinafter sometimes referred to as “specific polymer”).

In the general formulas (I) and (II), R ¹ , R ² , R ⁴ , and R ⁵ represent a hydrogen atom, R ³ and R ⁶ represent a hydrogen atom or a methyl group, and X ¹ and X ² each independently represents —C (═O) O—, —CONH—, or a phenylene group, and L ¹ and L ² each independently represent a single bond, —C ₂ H ₄ —, —C _{4 H 8 -, - C 2} H 4 O-C (= O) -C 2 H 4 -, _{or, -C 2 H 4 O-C} (= O) - cyclohexylene - represents, ^{Y 1} is O ² represents an oxygen atom, a sulfur atom, or —NH—, Y ² represents a single bond, —C (═O) O—, or —CONH—, and Z ¹ and Z ² each independently represent the following general formula (i) either consists of end groups alone selected ~ from the general formula (iv), to said distal end _{group, -C (= O) -NH-} C 2 H 4 O -, - C (= O) - , -C _{2 H 4 O -, - CH 2} CH (OH) CH 2 O-, or -CH ₂ - is composed by connecting, m and n each independently represents an integer of 2 to 8, p and q are , Each independently represents an integer of 5 to 60 .

R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
In the present ^{invention, R 1, R 2, R} 4, and as ^{R 5} is a hydrogen atom, the ^{R 3} and ^{R 6,} which takes a hydrogen atom or a methyl group, which pigment It is most preferable from the viewpoint of adsorption efficiency on the surface.

X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, in the present invention, it is required that it is —C (═O) O—, —CONH—, or a phenylene group, which is preferable from the viewpoint of adsorptivity to a pigment, and —C (═O) O— Is most preferred.

L ¹ and L ² each independently represents a single bond or a divalent organic linking group. Examples of the divalent organic linking group include a substituted or unsubstituted alkylene group, and a divalent organic linking group composed of the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
Among the above, in the present invention, L ¹ and L ² are each independently a single bond, —C ₂ H ₄ —, —C ₄ H ₈ —, —C ₂ H ₄ O—C (═O) —. It is required to be C ₂ H ₄ — or —C ₂ H ₄ O—C (═O) -cyclohexylene-.

Y ¹ represents an oxygen atom, a sulfur atom, or —NH—, and among them, an oxygen atom or —NH— is preferable from the viewpoint of adsorptivity to a pigment, and an oxygen atom is most preferable.
Y ² represents a single bond, —C (═O) O—, or —CONH—, and is —C (═O) O—, or X ² is — (C═O) O—. In this case, a single bond is preferable from the viewpoint of adsorptivity to the pigment.

Z ¹ and Z ² each independently represent a group containing any one of a carbon-carbon double bond, a carbon-carbon triple bond, and a cyclic ether. From the viewpoint of reactivity, these reactive partial structures are represented by A group contained as a terminal group is preferred.
In the present invention, the terminal group constituting the group represented by Z ¹ and Z ² needs to be selected from the following general formula (i) to general formula (iv), which is a polymerized crosslink It is preferable because the reaction is high.

Here, in the general formulas (i) to (iv), A represents a single bond, —C (═O) —, a phenylene group, or a methylene group.
R ^{10 to} R ¹⁵ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include the same monovalent organic groups as R ^{1 to} R ⁶ described above. In the present invention, R ^{10 to} R ¹⁵ are required to be a hydrogen atom or a methyl group, which is preferable from the viewpoint of a polymerization crosslinking reaction.
These terminal groups may constitute Z ¹ or Z ² alone, or may be combined with a linking group to constitute Z ¹ or Z ² . That is, these end groups are bonded to oxygen atoms in general formula (I) and general formula (II) directly or through a linking group. Here, as a linking group, —C (═O) —NH—C ₂ H ₄ O—, —C (═O) —, —C ₂ H ₄ O—, —CH ₂ CH (OH) CH ₂ O -, - CH ₂ - and the like.

In the present invention, it is preferable from the viewpoint of the polymerization crosslinking reaction that Z ¹ and Z ² include a terminal group represented by the general formula (i) or the general formula (iii).
In the case of a specific polymer in which Z ¹ and Z ² are a group containing a cyclic ether, a colored photosensitive composition to which a pigment dispersion composition containing the polymer is used is used. When forming, in the heating step (post-bake) after exposure and development, the cyclic ether reacts with other reactive groups (for example, carboxylic acid groups) to form a stronger cured film. There is also an advantage that you can.

  m and n each independently represents an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

  p and q each independently represent an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

The repeating unit represented by the general formula (I) or the general formula (II) is obtained by polymerizing a monomer represented by the following general formula (I-1) or the general formula (II-1), respectively. By copolymerizing, it is introduced as a repeating unit of the polymer compound. The repeating unit represented by the general formula (I) or the general formula (II) is obtained by polymerizing a monomer represented by the following general formula (I-2) or the general formula (II-2) or After synthesizing a polymer compound as a precursor by copolymerization, it contains any of a carbon-carbon double bond, a carbon-carbon triple bond, and a cyclic ether, and reacts with a hydroxyl group or a carboxyl group. by reacting a compound having a group may be introduced as a repeating unit of the high-molecular compound.

In the general formula (I-1), general formula (II-1), general formula (I-2), and general formula (II-2), R ^{1 to} R ⁶ are each independently a hydrogen atom, or Represents a monovalent organic group, X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, L ¹ and L ² each independently represent a single bond or a divalent organic linking group, Y ¹ represents an oxygen atom, a sulfur atom, or —NH—, and Y ² represents a single bond, —C (═O) O— or —CONH—, wherein Z ¹ and Z ² each independently represent a group containing any of a carbon-carbon double bond, a carbon-carbon triple bond, and a cyclic ether; m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

R ^{1 to} R ⁶ , X ¹ , X ² , L ¹ , L ^{2 in} General Formula (I-1), General Formula (II-1), General Formula (I-2), and General Formula (II-2) , Y ¹ , Y ² , Z ¹ , Z ² , m, n, p, and q are R ^{1 to} R ⁶ , X ¹ , X ² , L ^{1 in the} general formula (I) and the general formula (II). , L ² , Y ¹ , Y ² , Z ¹ , Z ² , m, n, p, and q, and preferred examples are also the same.

Here, examples of the compound containing any of a carbon-carbon double bond, a carbon-carbon triple bond, and a cyclic ether and having a group that reacts with a hydroxyl group or a carboxyl group include the following.
That is, (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic anhydride, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 3- Hydroxypropyl, ethyl 2- (meth) acrylate, glycidyl (meth) acrylate, allyl alcohol, allyl bromide, chloromethyl styrene, vinyl benzoic acid, propargyl alcohol, propargyl bromide, propargyl acid, glycidyl alcohol, glycidyl chloride , Oxetanyl alcohol, oxetanyl chloride.

  Although the preferable specific example of the repeating unit represented by general formula (I) or general formula (II) below is given to the following, this invention is not restrict | limited to these.

  The specific polymer in this invention should just contain at least 1 sort (s) of repeating units selected from the repeating unit represented by either general formula (I) and general formula (II), and contains only 1 type. It may be included or two or more types may be included.

  In the specific polymer, the content of the repeating unit represented by any one of the general formula (I) and the general formula (II) is not particularly limited, but the total repeating unit contained in the polymer is 100 masses. %, The repeating unit represented by any one of the general formulas (I) and (II) is preferably contained in an amount of 5% by mass or more, more preferably 50% by mass, and more preferably 50% by mass to 80%. More preferably, it is contained by mass%.

The specific polymer in the present invention is a single polymer having a functional group capable of adsorbing to the pigment in addition to the repeating unit represented by any one of the general formulas (I) and (II) for the purpose of enhancing adsorption to the pigment. A polymer compound containing a repeating unit derived from a monomer is preferable.
Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Among these, a monomer having an organic dye structure or a heterocyclic structure is preferable from the viewpoint of the adsorptive power to the pigment.

  The monomer having an organic dye structure or a heterocyclic structure is preferably one selected from the group consisting of a monomer represented by the following general formula (1), a maleimide, and a maleimide derivative. Among these, a monomer represented by the following general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic group.

The alkyl group represented by R ¹ in the general formula (1) is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. preferable.
When the alkyl group represented by R ¹ has a substituent, the substituent is preferably, for example, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group. As this alkoxy group, a C1-C5 thing is preferable and a C1-C3 thing is preferable.

Specific examples of preferable alkyl group represented by R ¹ in the general formula (1) include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n- Examples include a hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.
Among them, R ¹ is most preferably a hydrogen atom or a methyl group.

The divalent linking group represented by R ² in the general formula (1) is preferably an alkylene group or a divalent group containing an alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
When this alkylene group has a substituent, examples of the substituent include a hydroxy group.
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

As the divalent group containing an alkylene group represented by R ² in the general formula (1), two or more of the above alkylene groups linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom) It may be.
The divalent group containing an alkylene group represented by R ^2, the end towards which binds to Z in the alkylene group, -O -, - S -, - C (= O) O -, - CONH-, -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- A hetero atom selected from or a partial structure containing a hetero atom may be bonded.

Specific examples of the nitrogen-containing heterocyclic structure constituting the nitrogen-containing heterocyclic group represented by Z in the general formula (1) include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, and a triazole ring. , Tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure The thing which has is mentioned.
These nitrogen-containing heterocyclic structures may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, and an alkoxycarbonyl group. Is mentioned.

The nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Particularly preferred is a group having
Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea A structure and a cyclic imide structure are preferable, and a structure represented by the following general formula (2), (3), or (4) is particularly preferable.

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

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. As a combination of Y and Z, a combination (imidazolyl group) in which one of Y and Z is —N═ and the other is —NH— is preferable.

  In general formula (2), (3), or (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.
Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formula (2), (3), or (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and dispersion stability over time, and the general formula (2) Alternatively, in (4), a benzene ring is more preferable, and in general formula (3), a naphthalene ring is more preferable.

  In addition, the maleimide derivative in the present invention means a maleimide in which the N position is substituted with a substituent such as an alkyl group or an aryl group.

  Hereinafter, preferred specific examples (monomers M-1 to M-33) of the monomer represented by the general formula (1), maleimide, and maleimide derivatives are listed below, but the present invention is limited thereto. It is not a thing.

  The specific polymer in the present invention contains only one type of repeating unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives. It may be a thing and may contain 2 or more types.

In the specific polymer in the present invention, the content of the repeating unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivative is heavy. When the total repeating unit contained in the coalescence is 100% by mass, the content is preferably 5% by mass or more, and more preferably 10% by mass to 50% by mass.
That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, it is represented by the general formula (1). The content of polymerized units derived from one monomer selected from the group consisting of monomers, maleimides, and maleimide derivatives is preferably 5% by mass or more. Moreover, from the viewpoint of developability when producing a color filter with a colored photosensitive composition containing a pigment dispersion composition, the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives The content of polymerized units derived from one more selected monomer is preferably 50% by mass or less.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  It is preferable that the specific polymer in this invention contains the repeating unit derived from the monomer which has the above acidic groups. By including such a repeating unit, when the pigment dispersion composition of the present invention is applied to a colored photosensitive composition, the development removability of an unexposed portion is excellent.

The specific polymer in the present invention may contain only one type of repeating unit derived from a monomer having an acidic group, or may contain two or more types.
In the specific polymer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, repeating units derived from monomers having acidic groups The content of is preferably 50 mgKOH / g to 200 mgKOH / g.

  As a monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1 -(N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N -Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1 , 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

  The specific polymer in the present invention may further contain a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

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

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

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

A preferred embodiment of the specific polymer in the present invention includes at least a repeating unit represented by any one of the general formulas (I) and (II) and a repeating unit derived from a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least a repeating unit derived from a monomer having an organic dye structure or a heterocyclic structure, a repeating unit derived from the monomer represented by the general formula (1), and an acid And a repeating unit derived from a monomer having a group.
According to this embodiment, it is possible to provide a pigment dispersion composition having excellent pigment adsorption and excellent developability.

The preferred molecular weight of the specific polymer in the present invention is preferably in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30000, and the number average molecular weight (Mn) is in the range of 5000 to 15000.
That is, the weight average molecular weight (Mw) of the specific polymer is 1000 or more from the viewpoint of effectively loosening the secondary aggregate, which is an aggregate of primary particles of the pigment, or effectively weakening reaggregation. It is preferable that Further, from the viewpoint of developability when producing a color filter from a colored photosensitive composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 30000 or less.

The specific polymer in the present invention includes, for example, a monomer represented by the general formula (I-1) or the general formula (II-1), and other radical polymerizable compounds (such as those described above) as a copolymerization component. And various monomers), and can be produced by an ordinary radical polymerization method. Similarly, the polymer compound which is the precursor of the specific polymer is also composed of the monomer represented by the general formula (I-2) or the general formula (II-2) and other radical polymerizable compounds as a copolymerization component. It can be produced by a normal radical polymerization method using a compound (various monomers as described above).
In general, the radical polymerization method uses a suspension polymerization method or a solution polymerization method. Examples of the solvent used for synthesizing such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.
In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

  In the pigment dispersion composition of the present invention, the content of the specific polymer (a) is preferably a mass ratio of pigment: specific polymer = 1: 0.1 to 1: 2, more preferably 1: 0. 2 to 1: 1, and more preferably 1: 0.4 to 1: 0.7.

Furthermore, the pigment dispersion composition of the present invention may contain other polymer compound having a different structure from the above-mentioned (a) specific polymer, if necessary, within a range not impairing the effects of the present invention. You may use it simultaneously.
As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.
The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

[(B) Pigment]
As the (b) pigment in the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.
As the pigment, considering that the pigment dispersion composition of the present invention is used in the colored region of the color filter and preferably having a high transmittance, an organic pigment is preferable, and the particle size is as small as possible. It is preferable to use one.
Considering the handling properties of the pigment dispersion composition and the colored photosensitive composition containing the same, the average primary particle size of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 nm to 25 nm. When the particle diameter 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 the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.
However, the present invention is not limited to these.

Among these, the pigments that can be preferably used include the following.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1, 7

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations of organic pigments are shown below.
For example, as a red pigment, an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Alternatively, a perylene red pigment, an anthraquinone red pigment, and a diketopyrrolopyrrole red pigment can be mixed and used.
For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80 from the viewpoint of light transmittance and color purity from 400 nm to 500 nm. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

In addition, as the green pigment, a halogenated phthalocyanine pigment is used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. be able to.
For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoint of light transmittance of 400 nm to 450 nm and color purity. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

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

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

(Miniaturization of pigment)
In the present invention, if necessary, a pigment obtained by finely pulverizing the pigment as described above may be used.
In order to make the pigment finer, it is preferable to use a method including a step of preparing a liquid composition having a high viscosity together with a water-soluble organic solvent and a water-soluble inorganic salt and grinding the pigment.
In the present invention, it is more preferable to use the following method for refining the pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single By applying a strong shearing force by using a kneader such as a screw or twin screw extruder, the pigment in the mixture is ground, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a finer pigment.

Examples of the water-soluble organic solvent used for the above-mentioned miniaturization include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol, propylene glycolic monomethyl ether acetate and the like.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The amount of the water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferred amount is 1 to 10 times the mass. is there.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when a liquid composition containing a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is ground, a wet pulverizing apparatus such as the kneader described above may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, A pigment can be obtained.

In addition, when the above-described organic pigment is refined, by using a resin that is at least partially soluble in a water-soluble organic solvent in the liquid composition, the surface is coated with the resin. A processed pigment with little aggregation of the pigment can be obtained.
Here, as a resin that is used when obtaining a processed pigment and is at least partially soluble in a water-soluble organic solvent, a known resin used as a pigment dispersant can be used, but in the present invention, The aforementioned (a) specific polymer is preferably used.

  The content of the pigment (b) in the pigment dispersion composition of the present invention is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and still more preferably 10% by mass to 20% by mass.

[(C) Organic solvent]
The pigment dispersion composition of the present invention contains at least one (c) organic solvent.
Examples of the organic solvent used in the pigment dispersion composition of the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene and the like can be mentioned.
The amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc., but when used for the preparation of a colored photosensitive composition described later, from the viewpoint of handleability, it contains a pigment and the like. It can add so that solid content concentration may be 5 mass%-50 mass%.

[Other ingredients]
A pigment derivative is suitably used for the pigment dispersion composition of the present invention.
In the present invention, the pigment is made into fine particles by adsorbing the pigment derivative into which the part having affinity with the dispersant or the polar group is adsorbed on the surface of the processed pigment and using this as the adsorption point of the dispersant. It can be dispersed in the dispersion composition and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting adsorption of a polymer dispersant such as a specific polymer by modifying the pigment surface.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments.
In addition, the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.

  Examples of the pigment derivative in the present invention include JP-A Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, and JP-A. Those described in JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, and the like can be used.

When a pigment derivative is used in the pigment dispersion composition of the present invention, the amount used is preferably in the range of 1% by mass to 80% by mass with respect to the pigment, and 3% by mass to 65% by mass. More preferably, it is in the range of 5% by mass to 50% by mass. When the content is within this range, the pigment can be favorably dispersed while keeping the viscosity low, and the dispersion stability after dispersion can be improved.
By applying this pigment dispersion composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

  In the pigment dispersion composition of the present invention, a dispersant such as a surfactant can also be used.

(Preparation of pigment dispersion composition)
The pigment dispersion composition of the present invention can be prepared by passing through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, the pigment dispersion composition of the present invention includes, for example, (a) a specific polymer, (b) a pigment, (c) an organic solvent, a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic wave. Using a disperser or the like, fine dispersion can be performed with beads made of glass or zirconia having a particle diameter of 0.01 mm to 1 mm.
In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.

  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, and the method described herein can also be applied to the present invention.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises the above-described pigment dispersion composition of the present invention, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. Depending on, other components may be included.
Hereinafter, each component contained in the colored photosensitive composition of the present invention will be described in detail.

(Pigment dispersion composition)
The colored photosensitive composition of the present invention is constituted by using at least one kind of the above-described pigment dispersion composition of the present invention. The details of the pigment dispersion composition of the present invention constituting the colored photosensitive composition are as described above.
As content of the pigment dispersion composition in the colored photosensitive composition of this invention, content of a pigment is 5 mass%-70 mass% with respect to the total solid (mass) of a colored photosensitive composition. The quantity which becomes is preferable, and the quantity used as the range of 15 mass%-60 mass% is more preferable. When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.

[Photopolymerizable compound]
The colored photosensitive composition of the present invention contains at least one photopolymerizable compound.
The photopolymerizable compound that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer 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, isocyanuric acid There are EO-modified triacrylate and the like.

  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.

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 (a) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

Formula (a)
_{CH 2 = C (R) COOCH} 2 CH (R ') OH
(However, R and R ′ each 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 photopolymerizable composition excellent in the 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.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the performance design of the final colored photosensitive composition.
For example, it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.

In addition, the selection of the addition polymerization compound with respect to the compatibility and dispersibility with other components in the colored photosensitive composition (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, and colorants (pigments)) The usage method is an important factor, and for example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like. The addition polymerizable compound is preferably used in the range of 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass with respect to the non-volatile component in the colored photosensitive composition. These may be used alone or in combination of two or more. In addition, as for the method of using the addition polymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.

(Photopolymerization initiator)
Examples of the photopolymerization initiator constituting the colored photosensitive composition of the present invention include halomethyloxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428. Active halogen compounds such as halomethyl-s-triazine described in U.S. Publication No. 4, etc., and aromatic carbonyls such as ketals, acetals, or benzoin alkyl ethers described in US Pat. Compounds, aromatic ketone compounds such as benzophenones described in U.S. Pat. No. 4,199,420, (thio) xanthones or acridine compounds described in French Patent No. 2456741, JP-A-10-62986 Compounds such as coumarins or lophine dimers described in JP-A-8-0155; Sulfonium organic boron complexes such as 1 JP, and the like.

  As the photopolymerization initiator in the present invention, acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, oxadiazole, coumarin), acridine, biimidazole An oxime ester type is preferable.

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

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

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. it can.

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

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

  Examples of the active halogen compound (triazine-based, oxadiazole-based, coumarin-based) 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- (di) Ethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl -5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl-5 -A No-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- Preferable examples include 5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

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

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

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

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

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

[Alkali-soluble resin]
The colored photosensitive composition of the present invention preferably contains an alkali-soluble resin. By containing the alkali-soluble resin in the colored photosensitive composition, the pattern forming property can be further improved when the colored photosensitive composition is applied to pattern formation by a photolithography method.

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

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. 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 the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and 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 particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.

  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 suitable thing of alkali-soluble resin in this invention, the copolymer of (meth) acrylic acid and the other monomer copolymerizable with this is mentioned especially. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (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 represents 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. And the like.

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. At least one selected from the group consisting of CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  As content in the coloring photosensitive composition of alkali-soluble resin, 1 mass%-30 mass% are preferable with respect to the total solid of this composition, More preferably, they are 1 mass%-25 mass%. Especially preferably, it is 2 mass%-20 mass%.

〔solvent〕
In general, the colored photosensitive composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, etc. Is preferred.
You may use a solvent in combination of 2 or more types besides using independently.

[Other ingredients]
In the colored photosensitive composition of the present invention, if necessary, other than a sensitizing dye, an epoxy resin, a fluorinated organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the above alkali-soluble resin. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor.

[Sensitizing dye]
A sensitizing dye may be added to the colored photosensitive composition of the present invention as necessary. The sensitizing dye can accelerate the radical generating reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

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

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

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

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

(In General Formula (XIV), A ¹ represents a sulfur atom or —NR ⁶⁰ —, R ⁶⁰ represents an alkyl group or an aryl group, and L ⁰¹ represents the basicity of the dye in combination with adjacent A ¹ and the carbon atom. Represents a non-metallic atomic group forming a nucleus, R ⁶¹ and R ⁶² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁶¹ and R ⁶² are bonded to each other to form an acidic nucleus of the dye W may represent an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, ^{-L 02} - are connected via a bond by wherein ^{-L 02} -. Is -O- or -S- In addition, W is synonymous with that shown in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or —NR ⁶⁹ —, L ⁰³ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁶⁹ represents an alkyl group or an aryl group.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁷³ —, and R ⁷³ represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. L ⁰⁴ and L ⁰⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and a carbon atom, and R ⁷¹ and R ⁷² are each independently These are monovalent non-metallic atomic groups and can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

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

(In General Formula (XVIII), A ⁵ represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —, and Y represents An oxygen atom, a sulfur atom, or ═N (R ⁷⁴ ), each of R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ independently represents a hydrogen atom or a monovalent non-metallic atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ⁷⁴ , R ⁷⁵ , and R ⁷⁶ represent a monovalent non-metallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ⁷⁴ , R ⁷⁵ and R ⁷⁶ will be specifically described. Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

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

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

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

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

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

Specific examples of preferred substituted alkyl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ obtained by combining the above substituents with an alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, Xoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N- Methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N -Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group , Methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl Group, p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl Group, etc. can be mentioned.

Specific examples of preferred aryl groups as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of the preferable substituted aryl group as R ⁷⁴ , R ⁷⁵ , or R ⁷⁶ include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ⁷⁵ and R ⁷⁶ include a substituted or unsubstituted alkyl group. A more preferred example of R ⁷⁴ includes a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, ^{A 5} will be described in the general formula (XVIII). A ⁵ represents an aromatic ring or a heterocyclic ring which may have a substituent, and specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ⁷⁴ in formula (XVIII). , R ⁷⁵ , or R ⁷⁶ may be the same as those exemplified in the above description.
Among them, preferable A ⁵ includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A ⁵ includes an aryl group having an amino group.

Next, Y in the general formula (XVIII) will be described. Y is a nonmetallic atom or a nonmetallic atomic group directly bonded to the nitrogen-containing heterocycle in the general formula (XVIII) via a double bond, and represents an oxygen atom, a sulfur atom, or = N (R ⁷⁴ ).
Moreover, X in general formula (XVIII) represents an oxygen atom, a sulfur atom, or -N ( ^R74 )-.

  Next, the compound represented by the following general formula (XVIII-1), which is a preferred embodiment of the compound represented by the general formula (XVIII) used in the present invention, will be described.

In General Formula (XVIII-1), A ⁵ represents an aromatic ring or a hetero ring that may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ⁷⁴ ) —. R ⁷⁴ , R ⁷⁷ , and R ⁷⁸ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A ⁵ and R ⁷⁴ , R ⁷⁷ , or R ⁷⁸ are each aliphatic or aromatic. They can be joined to form a family ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In general formula (XVIII-1), A ⁵ and R ⁷⁴ have the same meanings as in general formula (XVIII), R ⁷⁷ is R ⁷⁵ in general formula (XVIII), and R ⁷⁸ is R in general formula (XVIII). ^It is synonymous with ⁷⁶ . Ar represents an aromatic ring or a hetero ring having a substituent, and has the same meaning as A ⁵ in formula (XVIII).
However, as a substituent that can be introduced into Ar in the general formula (XVIII-1), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (For example, —SOCH ₃ , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

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

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

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

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

(Epoxy resin)
In the colored photosensitive composition of the present invention, an epoxy resin can be used as a thermal polymerization component in order to increase the strength of the formed coating film.
The epoxy resin 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 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) Similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above made by Tohto Kasei), Denacol EM-125, etc. (above made by Nagase Kasei), biphenyl type As alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl, 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 and the like (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

(Fluorine organic compounds)
The colored photosensitive composition of the present invention contains a fluorine-based organic compound, thereby improving liquid characteristics (particularly fluidity) when used as a coating liquid, and improving coating thickness uniformity and liquid-saving properties. be able to.
In other words, a colored photosensitive composition containing a fluorine-based organic compound reduces the interfacial tension between the surface to be coated and the coating liquid, improves the wettability to the surface to be coated, and improves the coating property to the surface to be coated. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

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

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

In particular, the fluorine-based organic compound is effective in preventing coating unevenness and thickness unevenness when forming the thin coating film using the colored photosensitive composition of the present invention. Furthermore, it is also effective when the colored photosensitive composition of the present invention is applied to slit coating that easily causes liquid breakage.
The addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. is there.

(Thermal polymerization initiator)
It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds.
Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxide. Examples thereof include oxydicarbonate.

(Surfactant)
Various surfactants may be added to the colored photosensitive composition of the present invention from the viewpoint of improving coatability. As the surfactant, various nonionic, cationic, and anionic surfactants can be used in addition to the above-mentioned fluorine-based surfactant.
Among these, the above-described nonionic surfactants are preferably fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

Specific examples of cationic surfactants include phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

(Other additives)
In addition to the above, various additives can be added to the colored photosensitive composition of the present invention.
Specific examples of additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, and hydroxyl group Alkali-soluble resins such as those obtained by adding acid anhydride to polymers, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, Polymer dispersing agents such as EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Industrial Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco); Solsparse 3000, 5000, 000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 , F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2-hydroxy UV absorbers such as phenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.

In addition, when the alkali solubility of the uncured part is promoted and the developability of the colored photosensitive composition is further improved, the colored photosensitive composition of the present invention is added with an organic carboxylic acid, preferably a molecular weight of 1000 or less. It is preferable to add a low molecular weight organic carboxylic acid.
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.

Further, a thermal polymerization inhibitor may be added to the colored photosensitive composition of the present invention.
Examples of the thermal polymerization inhibitor 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-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

  The colored photosensitive composition of the present invention is a photopolymerizable compound, a photopolymerization initiator, and, if necessary, an alkali-soluble resin, a solvent, and a surface active agent, compared to the pigment dispersion composition of the present invention described above. It can be prepared by adding an additive such as an agent.

Since the colored photosensitive composition of the present invention contains the pigment dispersion composition of the present invention, it is excellent in pigment dispersibility and color characteristics.
Therefore, it is preferably used to form a colored region of a color filter that requires good color characteristics.

<Color filter>
The color filter of the present invention is characterized by having a colored region formed on the substrate by the above-described colored photosensitive composition of the present invention.
Here, the coloring region includes both a three-color or four-color coloring pattern (pixel portion) and a black matrix.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.

A method for producing the color filter of the present invention will be described.
First, the colored photosensitive composition of the present invention is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and the like. The coating film which consists of an adhesive composition is formed (application | coating process). Thereafter, the coating film is exposed through a predetermined mask pattern (exposure process). After the exposure, the uncured portion of the coating film is developed and removed with a developer (development process). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, 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 disposed is used. In addition, it is possible to produce a color filter by forming a colored pattern using the colored photosensitive composition of the present invention.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, 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 the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the colored photosensitive 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, Slit nozzle coating method) is preferable.
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, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Further, the solid content of the colored photosensitive composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.

When forming the coating film by the coloring photosensitive composition of this invention on a board | substrate, as thickness (after prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying conditions are such that 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 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C. using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

[Exposure process]
In the exposure step, the coating film made of the colored photosensitive composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
In manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used is a pattern for forming a pixel (colored pattern) as well as a through hole or a U-shaped depression. The thing in which the pattern for forming is provided is used.

[Development process]
In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the colored photosensitive 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 used for development include the solvents described above that can be used when preparing the colored photosensitive composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001% by mass to 10% by mass, preferably 0 An alkaline aqueous solution dissolved so as to be 0.01 mass% to 1 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. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After the rinse treatment, draining and drying are performed, and then a heat treatment of about 200 ° C. to 250 ° C. is usually performed.
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 steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

The application of the colored photosensitive composition of the present invention has been described mainly with respect to the application to the color pattern of the color filter, but also for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored photosensitive composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

<Liquid crystal display device, solid-state imaging device>
The liquid crystal display element and the solid-state image sensor of the present invention comprise the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

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

<Synthesis of specific polymer>
[Synthesis Example 1: Synthesis of specific polymer (P-1)]
Into a 500 mL three-necked flask, 171.2 g of ε-caprolactone, 8.6 g of methacrylic acid, and 0.2 g of 2,6-di-t-butyl-4-methylphenol were introduced and dissolved while stirring while blowing nitrogen. Thereto was further added 0.1 g of monobutyltin oxide and heated to 100 ° C. After 8 hours, it was confirmed by gas chromatography that the raw materials had disappeared from the mixed solution, and then cooled to room temperature, and 100 mL of N-methyl-2-pyrrolidone was added to dissolve the mixed solution. DBU 18.0g was added there, and after stirring at room temperature for 30 minutes, allyl bromide 12.1g was further injected | thrown-in.
Thereafter, the mixed solution was heated to 60 ° C., and after 6 hours, the raw material disappeared from the mixed solution by gas chromatography, and then cooled to room temperature. And the reaction liquid mixture was thrown in into 1 L of water, and the crystal | crystallization was deposited. The precipitated crystals were collected by filtration and dried to obtain 180.0 g of monomer (X-1) having the following structure. The structure of the monomer (X-1) was confirmed by NMR and IR.

Subsequently, in a 500 mL three-neck flask, 75.0 g of monomer (X-1), 10.0 g of monomer M-11, 15.0 g of methacrylic acid, 2.4 g of dodecyl mercaptan, and 1-methoxy-2-propanol 233.0 g was introduced, and the mixture was heated and stirred at 75 ° C. while blowing nitrogen. To this, 0.55 g of 2,2′-azobis (isobutyric acid) dimethyl was added and stirred with heating at 75 ° C. for 2 hours. After 2 hours, 0.55 g of 2,2′-azobis (isobutyric acid) dimethyl was further added, and the mixture was stirred with heating at 75 ° C. for 2 hours. After 2 hours, after heating and stirring at 90 ° C. for 2 hours, a 30% solution of the specific polymer (P-1) was obtained.
The weight average molecular weight of the obtained specific polymer (P-1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and found to be 19000.

[Synthesis Example 2: Synthesis of specific polymer (P-2)]
Into a 500 mL three-necked flask, 228.2 g of ε-caprolactone, 8.6 g of methacrylic acid, and 0.2 g of 2,6-di-t-butyl-4-methylphenol were introduced and dissolved while stirring while blowing nitrogen. Thereto was further added 0.1 g of monobutyltin oxide and heated to 100 ° C. After 8 hours, it was confirmed by gas chromatography that the raw material had disappeared from the mixed solution, and then cooled to room temperature, and 100 mL of N-methyl-2-pyrrolidone was added and dissolved. DBU 18.0g was added there, and it stirred at room temperature for 30 minutes, Then, epibromohydrin 13.1g was further injected | thrown-in.
Thereafter, the mixed solution was heated to 50 ° C., and after 6 hours, the raw material disappeared from the mixed solution by gas chromatography, and then cooled to room temperature. The reaction mixture was poured into 1 L of water to precipitate crystals. The precipitated crystals were collected by filtration and dried to obtain 234.0 g of monomer (X-2) having the following structure. The structure of the monomer (X-2) was confirmed by NMR and IR.

Subsequently, in a 500 mL three-necked flask, 75.0 g of monomer (X-2), 10.0 g of monomer M-11, 15.0 g of methacrylic acid, 2.0 g of dodecyl mercaptan, and 1-methoxy-2-propanol 233.0 g was introduced, and the mixture was heated and stirred at 75 ° C. while blowing nitrogen. To this was added 0.60 g of 2,2′-azobis (isobutyric acid) dimethyl, and the mixture was heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.60 g of 2,2′-azobis (isobutyric acid) dimethyl was further added, and the mixture was stirred with heating at 75 ° C. for 2 hours. After 2 hours, after heating and stirring at 90 ° C. for 2 hours, a 30% solution of the specific polymer (P-2) was obtained.
It was 21,000 as a result of measuring the weight average molecular weight of the obtained specific polymer (P-2) by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.

[Synthesis Example 3: Synthesis of specific polymer (P-3)]
Into a 500 mL three-necked flask, 114.1 g of ε-caprolactone, 13.0 g of 2-hydroxyethyl methacrylate, and 0.2 g of 2,6-di-t-butyl-4-methylphenol were introduced and dissolved with stirring while blowing nitrogen. . Thereto was further added 0.1 g of monobutyltin oxide and heated to 100 ° C. Six hours later, gas chromatography confirmed that the raw material had disappeared from the mixture, and then cooled to room temperature to obtain 127.0 g of monomer (X-3) having the following structure. The structure of the monomer (X-3) was confirmed by NMR and IR.

Subsequently, in a 500 mL three-neck flask, 78.0 g of monomer (X-3), 10.0 g of monomer M-11, 12.0 g of methacrylic acid, 2.3 g of dodecyl mercaptan, and 1-methoxy-2-propanol 233.0 g was introduced, and the mixture was heated and stirred at 75 ° C. while blowing nitrogen. To this, 0.66 g of 2,2′-azobis (isobutyric acid) dimethyl was added and heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.66 g of 2,2′-azobis (isobutyric acid) dimethyl was further added, and the mixture was stirred with heating at 75 ° C. for 2 hours. After 2 hours, the mixture was heated and stirred at 100 ° C. for 2 hours. After cooling to room temperature, 9.5 g of 2-methacryloyloxyethyl isocyanate and 0.1 g of monobutyltin oxide were added, and the mixture was heated and stirred at 60 ° C. Six hours later, after confirming disappearance of the raw material by NMR, 22.5 g of 1-methoxy-2-propanol was added to obtain a 30% solution of the specific polymer (P-3).
It was 23,000 as a result of measuring the weight average molecular weight of the obtained specific polymer (P-3) by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material.

The monomer M-11 used in the synthesis examples refers to those mentioned as preferred specific examples of the monomer represented by the general formula (1), maleimide, and maleimide derivatives.
Moreover, specific polymer (P-4)-(P-20) and comparative polymer (C-1)-(C-4) are specific polymer (P-1)-(P-3). It was synthesized in the same manner as the synthesis of

  Tables 1 to 4 below show the structures, weight average molecular weights, and acids of the specific polymers (P-1) to (P-20) and comparative polymers (C-1) to (C-4). It shows about the value.

[Examples 1 to 5, Comparative Examples 1 and 2]
<Preparation 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 (average primary particle size: 24 nm) 100 parts (a) Specific polymer or comparative polymer (10% by mass solution) described in Table 8 below 150 parts 1-methoxy-2-propyl acetate 600 Part

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 4 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.5 mmφ zirconia beads to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
The obtained pigment dispersion composition was evaluated in the following (1) and (2). The results are summarized in Table 8.

(1) Viscosity measurement and evaluation For the obtained pigment dispersion composition, using an E-type viscometer, the viscosity η1 of the pigment dispersion composition immediately after dispersion and the pigment dispersion composition after 1 week at room temperature after dispersion The viscosity η2 of the product was measured and the degree of thickening was evaluated. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. This sample was placed between two polarizing plates, the amount of transmitted light was measured when the polarization axis was parallel and when the polarization axis was parallel, and the ratio was taken as contrast. 512 color display 10.4 “size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka”). Here, a high contrast indicates that the pigment is uniformly dispersed in a highly refined state, and thus the transmittance, that is, the coloring power is high.

  From the results shown in Table 8, it can be seen that (a) the pigment dispersion composition of the example containing the specific polymer has higher contrast, lower initial viscosity, and less increase in viscosity over time than the comparative example. .

[Examples 6 to 10, Comparative Examples 3 and 4]
<Preparation of pigment dispersion composition>
The components of the following composition (2) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 5 hours to prepare a mixed solution containing the pigment.

[Composition (2)]
・ C. I. Pigment Green 36 (average primary particle size: 17 nm) 100 parts (a) Specific polymer or comparative polymer (10% by mass solution) described in Table 9 below 180 parts 1-methoxy-2-propyl acetate 600 Part

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.1 mmφ zirconia beads to obtain a pigment dispersion composition.

<Evaluation of pigment dispersion composition>
About the obtained pigment dispersion composition, it carried out similarly to Example 1, and evaluated said (1) and (2). The results are summarized in Table 9.

  From the results shown in Table 9, it can be seen that (a) the pigment dispersion composition of the example containing the specific polymer has higher contrast, lower initial viscosity, and less thickening over time than the comparative example. .

[Examples 11 to 16, Comparative Examples 5 to 7]
<Preparation of pigment dispersion composition>
The components of the following composition (3) 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 (3)]
・ C. I. Pigment Red 254 (average primary particle size: 25 nm) 110 parts ・ (a) Specific polymer or comparative polymer (10% by mass solution) described in Table 10 below 150 parts 1-methoxy-2-propyl acetate 500 Part

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 4 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.5 mmφ zirconia beads to obtain a pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained as described above, the following colored photosensitive composition was prepared.

Pigment dispersion composition 2000 parts Dipentaerythritol hexaacrylate (photopolymerizable compound) 100 parts 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di ( 20 parts of trichloromethyl) -S-triazine (photopolymerization initiator) / propylene glycol monomethyl ether acetate of benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) Solution (solid content 30%) (alkali-soluble resin) 400 parts 1-methoxy-2-propyl acetate (solvent) 390 parts

<Production and Evaluation of Color Filter Using Colored Photosensitive Composition>
(1) Exposure sensitivity The prepared colored photosensitive composition (color resist solution) on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) has an x value of 0.650 as an index of color density. And then dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface 10mJ ^/ cm ² ~500mJ ^/ cm 2 of at various exposure amounts (illuminance 20 mW / cm ²⁾ of the coating film exposed, alkali development the coating film after exposure liquid CDK-1 (Fuji Film Electronics Materials The product was covered with a 1% aqueous solution, and the product was allowed to stand for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored region) for the color filter on the glass substrate. A filter substrate (color filter) was produced.
Here, the minimum exposure amount in which the film thickness after development of the region irradiated with light in the above exposure process was 95% or more with respect to the film thickness 100% before exposure was evaluated as the exposure sensitivity. The results are shown in Table 10 below.

<Evaluation of colored photosensitive composition and color filter>
Subsequently, the produced colored photosensitive composition and colored filter substrate (color filter) were evaluated as follows. The results are summarized in Table 10 below.

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

  A polarizing plate is placed on the colored pattern of the color filter thus obtained, the colored pattern is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using a BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. Larger values indicate higher contrast.

(3) Solubility in alkali developer and evaluation of suspension in alkali developer 150 ml beaker with 100 g of 10% aqueous solution of alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) Measure.
On the other hand, the colored photosensitive composition was applied on a 100 mm × 100 mm glass substrate (trade name: manufactured by 1737 Corning) so as to have a film thickness of 2.5 μm and dried (prebaked) in an oven at 90 ° C. for 60 seconds. The glass was cut so that the sample had a size of 25 mm × 100 mm, and two of them were superposed so that the coated surface was on the outside, thereby preparing a measurement sample.
The measurement sample is dipped in the developer prepared as described above and the up-and-down operation of drawing it out is repeated 20 times, and the solubility of the coating film after pre-baking and the presence or absence of the suspension in the developer are visually observed. It was judged.
The immersion time in the developer was 1 second to 2 seconds per time.

The evaluation index is as follows. Here, the larger the index number, the better the developability of the coating film.
-Evaluation index-
5: The coating film is completely dissolved in the vertical movement 1 to 10 times, and there is no suspension in the alkaline developer 4: The coating film is completely dissolved in the vertical movement 11 to 20 times, and in the alkaline developer No suspension 3: The coating film is completely dissolved in 1 to 10 times in the vertical motion, but there is a suspension in the alkaline developer 2: The coating film is completely dissolved in 11 to 20 times in the vertical motion. There is a suspension in the developer 1: The coating film is insoluble even after 20 vertical movements

  From the results shown in Table 10, it can be seen that the colored photosensitive compositions of the examples have higher exposure sensitivity and higher solubility of the coating film in the alkaline developer than the comparative examples. Moreover, it turns out that the color filter of an Example has high contrast compared with a comparative example.

[Examples 17 to 23, Comparative Examples 8 to 10]
<Preparation of pigment dispersion composition>
Components of the following composition (4) are mixed, and the number of revolutions is 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.

[Composition (4)]
・ C. I. Pigment Red 254 (average primary particle size: 25 nm) 120 parts C.I. I. Pigment Red 177 (average primary particle size: 22 nm) 20 parts. (A) Specific polymer or comparative polymer (10% by mass solution) described in Table 11 below 240 parts. 25 parts of pigment derivative B having the following structure. 600 parts of 1-methoxy-2-propyl acetate

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 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 pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained as described above, the following colored photosensitive composition was prepared.

Pigment dispersion composition 2100 parts Dipentaerythritol hexaacrylate (photopolymerizable compound) 80 parts 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di ( 50 parts of trichloromethyl) -S-triazine (photopolymerization initiator) / propylene glycol monomethyl ether acetate of benzyl methacrylate / methacrylic acid (= 75/35 [mass ratio]) copolymer (weight average molecular weight: 10,000) Solution (solid content 30%) (alkali-soluble resin) 300 parts 1-methoxy-2-propyl acetate (solvent) 390 parts

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

<Evaluation of colored photosensitive composition and color filter>
About the produced colored photosensitive composition and colored filter substrate (color filter), as in Example 11, (1) exposure sensitivity, (2) contrast, and (3) solubility in alkali developer, and alkali The suspension in the developer was evaluated. In addition, (4) voltage holding ratio was also evaluated as follows. The results are summarized in Table 11 below.

(4) Voltage holding ratio On the glass substrate with ITO electrode (trade name: 1737, manufactured by Corning), the thickness of the colored photosensitive composition obtained by the above-described method after drying is 2.0 μm. It was applied and dried (prebaked) in an oven at 90 ° C. for 60 seconds. Thereafter, exposure is performed at 100 mJ / cm ² without using a mask (illuminance is 20 mW / cm ² ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C. and subjected to heat treatment (post-baking) for 30 minutes in an oven at 230 ° C. Thereby, the glass substrate in which the colored cured film was formed was obtained.
Next, the glass substrate on which this colored cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then manufactured by Merck & Co., Inc. Liquid crystal MJ9711189 (trade name) was injected to produce a liquid crystal cell.

Subsequently, after putting a liquid crystal cell into a 70 degreeC thermostat for 48 hours, the voltage holding rate of the liquid crystal cell was measured by Toyo Technica Co., Ltd. liquid crystal voltage holding rate measuring system VHR-1A type (brand name).
The voltage holding ratio is a value of a voltage applied at a liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds.
The conditions for measuring this voltage holding ratio are as follows.

-Measurement conditions-
・ Distance between electrodes: 5μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
-Applied voltage pulse width: 16.67 msec

The evaluation index is as follows. Here, it can be seen that the larger the index number, the higher the voltage holding ratio and the better the electrical characteristics.
-Evaluation index-
5: 90% or more 4: 85% or more and less than 90% 3: 80% or more and less than 85% 2: 75% or more and less than 80% 1: less than 75%

  From the results shown in Table 11, it can be seen that the colored photosensitive compositions of the examples have higher exposure sensitivity and better solubility of the coating film in the alkaline developer than the comparative examples. In addition, it can be seen that the color filter of the example has a higher contrast, a higher voltage holding ratio, and better electrical characteristics than the comparative example.

[Examples 24-29, Comparative Examples 11-13]
<Preparation of pigment dispersion composition>
The components of the following composition (5) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And stirred for 4 hours to prepare a mixed solution containing the pigment.

[Composition (5)]
・ C. I. Pigment Blue 15: 6 (average primary particle size: 22 nm) 85 parts C.I. I. Pigment Violet 23 (average primary particle size: 26 nm) 15 parts, 15 parts of pigment derivative B having the above structure, 200 parts of (a) specific polymer or comparative polymer (10% by mass solution) described in Table 12 below 600 parts of 1-methoxy-2-propyl acetate

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.5 mmφ zirconia beads to obtain a pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained as described above, the following colored photosensitive composition was prepared.

Pigment dispersion composition 2000 parts Dipentaerythritol hexaacrylate (photopolymerizable compound) 100 parts 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di ( 30 parts of trichloromethyl) -S-triazine (photopolymerization initiator) propylene glycol monomethyl ether acetate of benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) Solution (solid content 30%) (alkali-soluble resin) 400 parts 1-methoxy-2-propyl acetate (solvent) 390 parts

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

<Evaluation of colored photosensitive composition and color filter>
About the produced colored filter substrate (color filter), as in Example 11, (1) exposure sensitivity, (2) contrast, and (3) solubility in alkali developer, and suspension in alkali developer The product was evaluated. In addition, as in Example 17, (4) voltage holding ratio was also evaluated. The results are summarized in Table 12 below.

  From the results shown in Table 12, it can be seen that the colored photosensitive compositions of the examples have higher exposure sensitivity and better solubility of the coating film in the alkaline developer than the comparative examples. In addition, it can be seen that the color filter of the example has a higher contrast, a higher voltage holding ratio, and better electrical characteristics than the comparative example.

[Examples 30 to 35, Comparative Examples 14 to 16]
<Preparation of pigment dispersion composition>
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 Green 36 (average primary particle size: 16 nm) 70 parts C.I. I. Pigment Yellow 150 (average primary particle size: 26 nm) 30 parts (a) Specific polymer or comparative polymer (30% by mass solution) described in Table 13 below 280 parts 1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads, 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 pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained as described above, the following colored photosensitive composition was prepared.

Pigment dispersion composition 2000 parts Dipentaerythritol hexaacrylate (photopolymerizable compound) 100 parts 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di ( 30 parts of trichloromethyl) -S-triazine (photopolymerization initiator) propylene glycol monomethyl ether acetate of benzyl methacrylate / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000) Solution (solid content 30%) (alkali-soluble resin) 400 parts 1-methoxy-2-propyl acetate (solvent) 390 parts

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

<Evaluation of colored photosensitive composition and color filter>
About the produced colored filter substrate (color filter), as in Example 11, (1) exposure sensitivity, (2) contrast, and (3) solubility in alkali developer, and suspension in alkali developer The product was evaluated. In addition, as in Example 17, (4) voltage holding ratio was also evaluated. The results are summarized in Table 13 below.

  From the results shown in Table 13, it can be seen that the colored photosensitive compositions of the examples have higher exposure sensitivity and better solubility of the coating film in the alkaline developer than the comparative examples. In addition, it can be seen that the color filter of the example has a higher contrast, a higher voltage holding ratio, and better electrical characteristics than the comparative example.

[Examples 36 to 38, Comparative Examples 17 to 19]
<Preparation of resist solution>
Components of the following composition were mixed and dissolved to prepare a resist solution.

[Composition of resist solution]
Propylene glycol monomethyl ether acetate 19.20 parts Ethyl lactate 36.67 parts Benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio = 60/22/18) copolymer 40% propylene glycol Monomethyl ether acetate (PGMEA) solution 30.51 parts ・ Dipentaerythritol hexaacrylate 12.20 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.0061 parts ・ Fluorine surfactant (F-475, Dainippon Ink and Chemicals, Inc.) Industrial Co., Ltd.) 0.83 parts TAZ-107 (Midori Chemical Co., Ltd.) 0.586 parts

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

<Preparation of pigment dispersion composition>
Components of the following composition (7) 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 (7)]
-100 parts of pigment described in Table 14-(a) Specific polymer or comparative polymer (10% by mass solution) described in Table 14 180 parts-750 parts of 1-methoxy-2-propyl acetate

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 3 hours with a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads to obtain a pigment dispersion composition.

<Preparation of colored photosensitive composition>
Using the pigment dispersion composition obtained above, stirring and mixing were performed to obtain the following composition to prepare a colored photosensitive composition solution.

Pigment dispersion composition 1000 parts CGI-124 20 parts (Ciba Specialty Chemicals Co., Ltd .; oxime photopolymerization initiator)
・ Dipentaerythritol hexaacrylate (photopolymerizable compound) 20 parts ・ TO-756 (manufactured by Toagosei Co., Ltd., photopolymerizable compound) 35 parts ・ Propylene glycol monomethyl ether acetate 20 parts

<Production and Evaluation of Color Filter Using Colored Photosensitive Composition>
The colored photosensitive composition prepared as described above was applied onto the undercoat layer of the silicon wafer with an undercoat layer obtained by the above-described method, thereby forming a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), various range of 50mJ ^/ cm ² ~1200mJ ^/ cm 2 pattern at a wavelength of 365nm through 1.5μm square Island pattern mask The exposure amount was as follows.
Thereafter, the silicon wafer substrate on which the coating film after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Material). Paddle development was carried out at 23 ° C. for 60 seconds to form a colored pattern (colored region) on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the center of rotation to the shower nozzle to perform a rinsing treatment, and then spray-dried.

(Evaluation of film strength and substrate adhesion)
The colored pattern obtained as described above was observed for pattern defects. From this result, the film strength of the colored pattern and the substrate adhesion of the colored pattern were evaluated.
The evaluation criteria are as follows. The evaluation results are shown in Table 14.
-Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

(Evaluation of uneven color)
The luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the ratio of pixels with a deviation from the average within ± 5% to the total number of pixels. The evaluation criteria are as follows.
First, the colored photosensitive composition prepared as described above was applied onto the undercoat layer of the silicon wafer with an undercoat layer obtained by the above-described method, thereby forming a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.

With respect to the monochromatic colored cured film thus obtained, the colored cured film surface was irradiated with light from the optical microscope side, and the reflection state was observed with an optical microscope provided with a digital camera with a magnification of 1000 times. The digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels and photographed the surface of the colored cured film in a reflective state. The photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format. The colored cured film surface was photographed for 20 arbitrarily selected regions.
In addition, the digitally converted data was stored by digitizing the captured image as a density distribution of 256 gradations from 0 to 255 for each of the three primary colors of RGB.

Next, the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 μm square on the actual substrate, and the luminance in one partition was averaged.
In this example, since an image of 1000 times optical was captured with a 1.28 million pixel digital camera, 2 μm on the actual substrate was 2 mm on the captured image, and the image size on the display was 452 mm × 352 mm. The total number of sections in one area was 39976.

  For all the sections in each region, an arbitrary luminance and the average luminance of all adjacent sections adjacent to it were measured. A partition having a difference of 5 or more from the average brightness of adjacent partitions is recognized as a significant difference partition, and the average total number of significant difference partitions in all regions and the average total number of significant difference partitions in all regions are the total number of partitions (39976). The ratio of the total to the total) was calculated.

The evaluation criteria are as follows. The evaluation results are shown in Table 14.
-Evaluation criteria-
○: Deviation from the average is less than 2% △: Deviation from the average is 2% or more and less than 5% ×: Deviation from the average is 5% or more

  From the results shown in Table 14, it can be seen that the colored pattern obtained from the colored photosensitive composition of the example does not cause color unevenness and is superior in substrate adhesion as compared with the comparative example.

When the liquid crystal display element provided with the color filter obtained in the said Examples 11-35 was produced, the obtained liquid crystal display element is excellent in contrast, and there is no generation | occurrence | production of a color nonuniformity, and it has favorable image display performance. I understood.
Moreover, when a solid-state imaging device provided with a color filter obtained from the colored photosensitive composition of Examples 36 to 38 was produced, the obtained solid-state imaging device had no color unevenness and had excellent color separation. It was found to have performance.

Claims (8)

(A) When all the repeating units are 100% by mass, a high content containing 5% by mass or more of at least one repeating unit selected from the repeating units represented by any of the following general formulas (I) and (II) A pigment dispersion composition comprising a molecular compound, (b) a pigment, and (c) an organic solvent.

(In the general formulas (I) and (II), R ¹ , R ² , R ⁴ , and R ⁵ represent a hydrogen atom, R ³ and R ⁶ represent a hydrogen atom or a methyl group, and X ¹ and X ² each independently represents —C (═O) O—, —CONH—, or a phenylene group, and L ¹ and L ² each independently represent a single bond, —C ₂ H ₄ —, —C _{4 H 8 -, - C 2} H 4 O-C (= O) -C 2 H 4 -, _{or, -C 2 H 4 O-C} (= O) - cyclohexylene - represents, ^{Y 1} is Represents an oxygen atom, a sulfur atom, or —NH—, Y ² represents a single bond, —C (═O) O—, or —CONH—, and Z ¹ and Z ² each independently represent the following general formula (i) either consists of end groups alone selected ~ from the general formula (iv), to said distal end _{group, -C (= O) -NH-} C 2 H 4 O -, - C (= O) - , _-C 2 H _{4 O -, - CH 2 CH} (OH) CH 2 O-, or -CH ₂ - is composed by connecting, m and n each independently represents an integer of 2 to 8, p and q are, Each independently represents an integer of 5 to 60.)

(In general formula (i) to general formula (iv), A represents a single bond, —C (═O) —, a phenylene group, or a methylene group. Also, R ^{10 to} R ¹⁵ are each independently Represents a hydrogen atom or a methyl group.)   The pigment dispersion composition according to claim 1, wherein the polymer compound (a) has an acid group in a side chain in a range of 50 mgKOH / g to 200 mgKOH / g. The said (a) polymer compound has a heterocyclic group comprised by either one of the nitrogen-containing heterocyclic structures listed below in the side chain. A pigment dispersion composition.
Nitrogen-containing heterocyclic structure: a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, an acridine ring, a phenothiazine ring, a phenoxazine ring, an acridone ring, base lens imidazole structure , Benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, cyclic imide structure   It is used for formation of the colored area | region in a color filter, The pigment dispersion composition of any one of Claims 1-3 characterized by the above-mentioned.   A colored photosensitive composition comprising the pigment dispersion composition according to any one of claims 1 to 3, a photopolymerizable compound, and a photopolymerization initiator.   A color filter comprising a colored region formed of the colored photosensitive composition according to claim 5 on a substrate.   A liquid crystal display device comprising the color filter according to claim 6.   A solid-state imaging device comprising the color filter according to claim 6.