JP2010163480A - Pigment dispersion composition, colored photosensitive composition, color filter, manufacturing method of color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a dispersion composition of a zinc phthalocyanine pigment exhibiting enhanced dispersibility and dispersion stability, to obtain a colored photosensitive composition exhibiting good stability with time and a large development latitude using the composition and to obtain a color filter exhibiting good color properties such as high color purity, high transmittance and high contrast. <P>SOLUTION: The pigment dispersion composition comprises (A) a zinc phthalocyanine pigment, (B) a dispersant containing a structural unit represented by general formula (b-1) below and (C) a resin having a polyester chain in the molecule. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a colored photosensitive composition containing the same, a color filter produced using the colored photosensitive composition, and a method for producing the color filter.

  The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a photopolymerization 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 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 having high color characteristics are demanded for color filters for image sensors (solid-state imaging devices).

  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. If the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, and the chromaticity and dimensional accuracy of the manufactured color filter are reduced, contrast is increased. There is a problem that it is significantly 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 in the exposure process. There is a tendency that the sensitivity is lowered and the alkali solubility in the developing process is lowered. Furthermore, 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. However, if the particle size of the pigment is made finer to improve the color characteristics, the surface area of the pigment particle becomes larger, so the cohesion between the pigment particles becomes stronger, and both dispersibility and dispersion stability at a high level are compatible. Is often difficult.

  In order to solve such problems, various pigment dispersants have been developed. Among these dispersants, a copolymer containing a macromonomer (an oligomer having an ethylenically unsaturated group at the end) is useful. By using the copolymer containing the macromonomer, the pigment particle size is small. It is disclosed that a pigment dispersion excellent in dispersion stability can be obtained (for example, see Patent Documents 1 and 2). However, since the copolymer containing the macromonomer described in the document does not have a functional group that promotes adsorption to the pigment, it does not function alone as a dispersant, and must be used in combination with another dispersant. There is a problem. In addition, when the copolymer containing the macromonomer is used as a dispersant, the thickening action seen in the polymer dispersant can be suppressed, but the dispersibility is reduced because the pigment is not sufficiently refined. There is a problem that it is not enough.

  In order to improve the dispersion stability of the pigment, a graft polymer having a partial structure of an organic dye (for example, see Patent Document 3), a graft polymer having a nitrogen-containing heterocyclic ring (for example, see Patent Document 4), and a cyclic imide group A graft polymer (for example, see Patent Document 5) is disclosed. Further, it is disclosed that a resin having an N-substituted maleimide and a urethane-based dispersant (for example, see Patent Document 6) or a graft copolymer having a nitrogen atom (for example, see Patent Document 7) are used in combination. . However, a pigment dispersion composition that is excellent in pigment dispersibility, fluidity, etc. and is soluble in an alkaline aqueous solution, and a colored photosensitive composition containing the pigment dispersion composition have not yet been provided. .

  On the other hand, in order to improve the color characteristics of the color filter, C.I. I. When using a copper halide phthalocyanine such as CI Pigment Green 36, it is necessary to increase the pigment concentration in the colored photosensitive composition. After forming a colored photosensitive layer containing the colored photosensitive composition on the substrate, exposure is performed. When developing and forming pixels, the latitude during development is narrow, and the pixel shape after development may be inversely tapered.

It has been proposed that a color filter with high brightness, high transmittance, and high color purity can be obtained using a green pigment other than a halogenated copper phthalocyanine (phthalocyanine having a central metal other than copper) (for example, a patent) Reference 8)), phthalocyanine having a central metal other than copper is poor in stability at the time of dispersion and over time, so a large amount of binder is required at the time of dispersion, and the development latitude of the colored photosensitive composition is narrow, indicating Unevenness may occur in the device.
Non-patent document 1 details zinc halide phthalocyanine, which is a kind of phthalocyanine having a central metal other than copper.
JP-A-8-259876 JP-A-10-339949 JP 2003-26950 A JP 2003-26949 A JP 2003-277673 A JP 2006-58821 A JP 2006-45262 A JP 2008-122478 A DIC Technical Review, 10, 46 (2004)

This invention makes it a subject to achieve the following objectives.
That is, an object of the present invention is to obtain a dispersion composition of a zinc phthalocyanine pigment having improved dispersibility and dispersion stability, and using this, a colored photosensitivity that has good temporal stability and a large development latitude. It is to obtain a composition.
Another object of the present invention is to obtain a color filter having a high color purity, a high transmittance, a high contrast and good color characteristics by using the colored photosensitive composition of the present invention. An object of the present invention is to obtain a liquid crystal display device having a high brightness and a clear image using this color filter.

  As a result of intensive studies, the inventors have (A) a zinc phthalocyanine pigment and (B) a dispersant containing a structural unit represented by the general formula (b-1) (hereinafter referred to as “specific dispersant”). And (C) a resin having a polyester chain in the molecule, the inventors have found that the above problems can be solved, and have completed the present invention. That is, the means for solving the problems are as follows.

<1> A pigment containing (A) a zinc phthalocyanine pigment, (B) a dispersant containing a structural unit represented by the following general formula (b-1), and (C) a resin having a polyester chain in the molecule. Dispersion composition.

In the general formula ^{(b-1), X} b is O or ^NR 25, ^{(R 25} is an alkyl group having 1 to 10 carbon atoms) ^{represents, R 21} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents an alkylene group having 1 to 10 carbon atoms or an arylene group.

<2> The dispersant containing the structural unit represented by (B) the general formula (b-1) is a dispersant further containing a structural unit represented by the following general formula (b-2) <1>. The pigment dispersion composition described in 1.

In the general formula ^{(b-2), R 21} has the same meaning as ^{R 21} in the general formula ^{(b-1), R 24} is an alkyl group having 1 to 10 carbon _{atoms, - (C n H 2n O} ) m - R ^26, _- represents a _{(OC n H 2n CO) l} -OR 26 - (C n H 2n CO 2) l -R 26 or -R ^29,. n is an integer of 1 to 10, and m and l are integers of 3 to 20. R ²⁶ is an alkyl group having 1 to 10 carbon atoms, and R ²⁹ is an alkylene group having 2 to 6 carbon atoms.

<3> The dispersant containing the structural unit represented by (B) general formula (b-1) is a dispersant containing 5 to 90% by mass of the structural unit represented by general formula (b-1). The pigment dispersion composition according to <1> or <2>.

<4> The resin having (C) the polyester chain in the molecule is a resin having a polyester chain represented by the following general formula (c) in the molecule: <1> to <3> The pigment dispersion composition as described.

In the general formula ^{(c), R 27} represents an alkylene group having 1 to 10 carbon ^{atoms, R 28} represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. r represents an integer of 3 to 80.

<5> The content of the dispersant containing the structural unit represented by (B) general formula (b-1) with respect to 100 parts by mass of the (A) zinc phthalocyanine pigment is in the range of 10 to 100 parts by mass < The pigment dispersion composition according to any one of 1> to <4>.

<6> The pigment dispersion composition according to any one of <1> to <5>, wherein the (A) zinc phthalocyanine pigment is a compound represented by the following general formula (a).

In general formula (a), X ^{21 to} X ³⁶ are each independently a hydrogen atom, a chlorine atom or a bromine atom. However, 8 or more of X ^{21 to} X ³⁶ are chlorine atoms or bromine atoms.
A pigment dispersion composition comprising (A) a zinc phthalocyanine pigment, (B) a dispersant containing a structural unit represented by the following general formula (b-1), and (C) a resin having a polyester chain in the molecule.

<7> A colored photosensitive composition comprising the pigment dispersion composition according to any one of <1> to <6>, a photopolymerizable compound, and a photopolymerization initiator.
<8> The colored photosensitive composition according to <7>, further comprising an alkali-soluble resin.

<9> The colored photosensitive composition according to <7> or <8>, which is for a color filter.
<10> A color filter having a colored pattern formed on the substrate using the colored photosensitive composition according to <9>.

<11> A photosensitive film forming step of forming the photosensitive film by applying the colored photosensitive composition according to <9> directly or via another layer to the substrate, and a pattern on the formed photosensitive film A color filter manufacturing method comprising: a colored pattern forming step of forming a colored pattern by sequentially performing exposure and development.
<12> A liquid crystal display device comprising the color filter according to <10>.

In the present invention, the nitrogen atom in the side chain of (B) the specific dispersant is adsorbed on the surface of the particulate (A) zinc phthalocyanine pigment, and functions as a protective colloid that improves dispersibility and dispersion stability. It seems to do. Further, this protective colloid layer and (C) a resin having a polyester chain in the molecule interact to improve dispersion stability.
In the coating process, between the resins having a polyester chain in the molecule and / or between the specific dispersant and the resin having the polyester chain in the molecule, the coating process having a high shear rate reduces the viscosity, It is estimated that uniformity is achieved.
Also in the development process, the resin having a polyester chain in the molecule has a high affinity with the developer, and the developer uniformly penetrates the colored photosensitive film, so that the development proceeds uniformly, thereby increasing the development latitude. Estimated.

According to the present invention, a dispersion composition of a zinc phthalocyanine pigment having improved dispersibility and dispersion stability can be obtained, and by using this, a colored photosensitive composition having good stability over time and a large development latitude. Can be obtained.
In addition, by using the colored photosensitive composition of the present invention, a color filter having high color purity, high transmittance, and high color characteristics with high contrast can be obtained. In addition, a liquid crystal display device with high brightness and clear images can be obtained.

  Hereinafter, the pigment dispersion composition, the colored photosensitive composition, the color filter, and the method for producing the color filter of the present invention will be described in detail.

<Pigment dispersion composition>
The pigment dispersion composition of the present invention comprises at least (A) a zinc phthalocyanine pigment, (B) a dispersant containing a structural unit represented by the general formula (b-1), and (C) a polyester chain in the molecule. It is a pigment dispersion composition containing resin which has.
That is, the pigment dispersion composition of the present invention is characterized by using a combination of a zinc phthalocyanine pigment, a specific dispersant, and a resin having a polyester chain in the molecule.
Hereinafter, each component which comprises the pigment dispersion composition of this invention is explained in full detail.

<(A) Zinc phthalocyanine pigment>
Since zinc phthalocyanine generally has 16 hydrogen atoms in the phthalocyanine ring, up to 16 of these hydrogen atoms can be substituted with bromine atoms and / or chlorine atoms. These halogen atoms may all be the same or different. When the number of substituents is constant, green becomes darker in the order of bromine atom> chlorine atom. When these hydrogen atoms are substituted with bromine atoms, for example, chlorine atoms, the number of bromine atoms is 0 to 16, the number of chlorine atoms is 0 to 16, and the number of hydrogen atoms is 0 to 16, in theory. A total of 136 types of substitution products can be produced.

In the present invention, the (A) zinc phthalocyanine pigment is a generic term for zinc halide phthalosinine represented by the following general formula (a), and X ^{21 to} X ³⁶ are each independently a hydrogen atom, a chlorine atom, or a bromine atom. The pigment which is is shown.
In the present invention, zinc halide phthalocyanine in which at least 8 or more of X ^{21 to} X ^{36 in} the general formula (a) are chlorine atoms or bromine atoms is preferable.

In the general formula (a), X ^{21 to} X ³⁶ each independently represent a hydrogen atom, a chlorine atom, or a bromine atom.

In the zinc phthalocyanine described above, eight or more of X ^{21 to} X ³⁶ are replaced with bromine atoms, thereby exhibiting a yellowish green color with high brightness, which is optimal for use in a color pixel pattern of a color filter. is there. In the present invention, zinc phthalocyanine substituted with 8 or more bromine atoms is most preferred.

  The average composition of zinc phthalocyanine can be easily obtained from mass spectrometry based on mass spectroscopy and halogen content analysis by flask combustion ion chromatography.

  The halogenated zinc phthalocyanine can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. More specific production methods are described in detail in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like.

  The zinc phthalocyanine pigment of the present invention preferably has an average primary particle size in the range of 10 nm to 40 nm. By using a zinc phthalocyanine pigment having an average primary particle diameter in this range, a colored photosensitive composition for a color filter having excellent dispersibility stability and coloring power, high brightness, and high contrast can be obtained.

  In addition, the average primary particle diameter in the present invention is a long one of 100 primary particles of zinc phthalocyanine pigment constituting the aggregate on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope. The average value of the diameter (major axis) and the shorter diameter (minor axis) is obtained and averaged.

  In obtaining a zinc phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 40 nm, it may be finely divided by any method, but it can easily suppress crystal growth and has a relatively large average primary particle diameter. In view of obtaining small pigment particles, it is preferable to employ a solvent salt milling treatment.

  The solvent salt milling means kneading and grinding a zinc phthalocyanine pigment, an inorganic salt, and an organic solvent. The zinc phthalocyanine pigment having a large particle diameter may be subjected to solvent salt milling after dry grinding. Specifically, a zinc phthalocyanine pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader and kneaded and ground therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  In obtaining a zinc phthalocyanine pigment having an average primary particle size in the range of 10 nm to 40 nm, it is preferable to increase the ratio of the amount of inorganic salt used to the amount of zinc phthalocyanine pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts, more preferably 7 to 15 parts, based on 1 part of zinc phthalocyanine pigment in terms of mass.

  As described above, it is preferable to use an organic solvent capable of suppressing crystal growth, as described above, and a water-soluble organic solvent can be suitably used as such an organic solvent, for example, diethylene glycol, glycerin, ethylene glycol. , Propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propano Le, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol.

  Although the usage-amount of the water-soluble organic solvent in this case is not specifically limited, 0.01-5 parts and 0.1-2 parts are preferable with respect to 1 part of zinc phthalocyanine pigments by mass conversion.

  30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 50-100 degreeC. The solvent salt milling time is preferably 5 to 20 hours, and more preferably 8 to 18 hours.

  In this way, a mixture containing a zinc phthalocyanine pigment, an inorganic salt, and an organic solvent as main components is obtained, and the organic solvent and the inorganic salt are removed from the mixture, and if necessary, a solid material mainly composed of the zinc phthalocyanine pigment. By washing, filtering, drying, pulverizing, etc., fine zinc phthalocyanine pigment powder can be obtained.

  As washing, either water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

  Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, but, for example, in the case of drying using a box dryer or a band dryer. When the pigment is in the form of a lamp or the like, it is carried out to break the pigment into powder, and examples thereof include pulverization with a mortar, hammer mill, disk mill, pin mill, jet mill and the like.

  Thus, a powder of zinc phthalocyanine pigment is obtained. The zinc phthalocyanine pigment used in the present invention has a property that the primary particles have a weaker cohesive force than the conventional copper halide phthalocyanine pigments and are more easily disintegrated. Therefore, the colored photosensitive composition for a color filter of the present invention has a high contrast.

  When the primary particles of the zinc phthalocyanine pigment of the present invention have an aspect ratio of 1 to 3 in the range of 1 to 3, the viscosity characteristics are improved in each application field and the fluidity becomes higher. In order to obtain the aspect ratio, as in the case of obtaining the average particle diameter of the primary particles as described above, the particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major diameter) and the shorter diameter (minor diameter) is obtained for 100 primary particles constituting the aggregate on the two-dimensional image, and the average value is calculated using these values. .

  The zinc phthalocyanine pigment of the present invention having an average primary particle diameter in the range of 10 nm to 40 nm can be obtained, for example, by the above-described method, but can also be purchased from Dainippon Ink & Chemicals, Inc.

<(B) Dispersant Containing Structural Unit Represented by General Formula (b-1)>
The dispersant (specific dispersant) including the structural unit represented by the general formula (b-1), which is one of characteristic components in the pigment dispersion composition of the present invention, will be described in detail.
The specific dispersant can function as a dispersant for the zinc phthalocyanine pigment in the pigment dispersion composition of the present invention.
First, the structural unit represented by the general formula (b-1) and matters related thereto will be described in detail.

In the general formula ^{(b-1), X} b is O or ^NR 25, ^{(R 25} is an alkyl group having 1 to 10 carbon atoms) ^{represents, R 21} represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms , R ²² and R ²³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents an alkylene group having 1 to 10 carbon atoms or an arylene group.

The ^{X b} in the general formula (b-1), (the alkyl group, alkyl group having 1 to 10 carbon atoms) oxygen atoms, monoalkylamino group is, preferably oxygen atom, ^{NR 25.} R ²⁵ represents an alkyl group having 1 to 5 carbon atoms. R ²¹ is preferably a hydrogen atom or a methyl group. R ²² and R ²³ are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L is preferably an alkylene group having 2 to 6 carbon atoms, or an arylene group such as a phenylene group or a naphthylene group.

  Moreover, as a preferable structural unit of general formula (b-1), they are (b-1-1) to (b-1-5) shown below.

  The specific dispersant of the present invention preferably contains a structural unit represented by the following general formula (b-2) in addition to the structural unit represented by the general formula (b-1).

In the general formula ^{(b-2), R 21} has the same meaning as ^{R 21} in formula ^{(b-1), R 24} is an alkyl group having 1 to 10 carbon _{atoms, - (C n H 2n O} ) m - R ²⁶ , — (C _n H _2n CO ₂ ) ₁ —R ²⁶ , or —R ²⁹ — (OC _n H _2n CO) 1 —OR ²⁶ is represented. n is an integer of 1 to 10, and m and l are integers of 3 to 20. R ²⁶ is an alkyl group having 1 to 10 carbon atoms, and R ²⁹ is an alkylene group having 2 to 6 carbon atoms.

The ^{R 24} in the general formula (b-2), the alkyl group having 1 to 8 carbon _{atoms, - (C n H 2n O} ) m -R 26, -R 29 - (OC n H 2n CO) l -OR 26 Is preferred. R ²⁶ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is preferably an integer of 2 to 5, l is preferably an integer of 5 to 15, and m is preferably an integer of 8 to 16.

  Preferred structural units of the general formula (b-2) include methyl methacrylate (b-2-1), ethyl methacrylate (b-2-2), butyl methacrylate (b-2-3), 2-ethylhexyl methacrylate. (B-2-4) and the following (b-2-5) to (b-2-7).

The content of the structural unit represented by the general formula (b-1) contained in the specific dispersant of the present invention is preferably in the range of 5 to 90% in terms of mass, more preferably in the range of 10 to 80%. More preferably, it is 15 to 50% of range.
Within this range, the dispersion stability is good and preferable.

Furthermore, when it contains the structural unit represented by general formula (b-2), it is preferable to contain in the range of 1-80 mass% in a specific dispersing agent, and it is preferable depending on containing 10-60 mass%.
Within this range, the dispersion stability and developability are improved, which is preferable.

  It is a preferred embodiment that the specific dispersant of the present invention further contains the following structural units in addition to the above general formula (b-1) and general formula (b-2).

  It is preferable that the specific dispersant further includes a structural unit derived from a monomer having an acid group. When the specific dispersing agent further contains a copolymer unit derived from a monomer having an acid group, when the pigment dispersion composition is applied to the colored photosensitive composition, it is excellent in the development removability of the unexposed area.

  Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  The specific dispersant may include only one type of structural unit derived from a monomer having an acid group, or may include two or more types.

  In the specific dispersant, the content of the structural unit derived from the monomer having an acid group is preferably 10 to 150 mgKOH / g, and particularly preferably 30 to 100 mgKOH / g. That is, from the viewpoint of dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition, the content of the structural unit derived from the monomer having an acid group is preferably 10 mgKOH / g or more. In addition, from the viewpoint of developability when producing a color filter with a colored photosensitive composition containing a pigment dispersion composition, the content of structural units derived from monomers having an acid group is 150 mgKOH / g or less. Preferably there is.

  The specific dispersant may further contain a structural unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired. As a result, compatibility with other dispersants or resins, solubility in solvents, and the like can be improved.

  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, chloro styrene, dichloro styrene, bromo styrene, 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.

Preferred structural units of the specific dispersant are those obtained by copolymerizing the above (b-1) and (b-2), and preferred compounds are shown below, but the present invention is not limited thereto. . The weight average molecular weights of the following compounds were all in the range of 10,000 to 20,000.
(B-1-1): (b-2-1) = 40: 60 (mass ratio),
(B-1-1) :( b-2-4) = 25: 55 (mass ratio),
(B-1-1) :( b-2-6) = 20: 50 (mass ratio),
(B-1-1) :( b-2-7) = 20: 50 (mass ratio),
(B-1-2) :( b-2-4) = 30: 70 (mass ratio)
(B-1-2) :( b-2-6) = 25: 55 (mass ratio),
(B-1-2): (b-2-7) = 20: 60 (mass ratio),
(B-1-4) :( b-2-1) = 30: 70 (mass ratio),
(B-1-4) :( b-2-4) = 20: 50 (mass ratio),
(B-1-4) :( b-2-7) = 20: 60 (mass ratio),
(B-1-5) :( b-2-4) = 30: 70 (mass ratio),
(B-1-5): (b-2-7) = 20: 60 (mass ratio),
(B-1-1): (b-2-7): Methacrylic acid = 20: 50: 5 (mass ratio),
(B-1-1): (b-2-4): methacrylic acid = 30: 55: 7 (mass ratio),
(B-1-2): (b-2-6): methacrylic acid = 20: 50: 5 (mass ratio),
(B-1-2): (b-2-7): Methacrylic acid = 20: 50: 5 (mass ratio)

  The preferred molecular weight of the specific dispersant is preferably in the range of 5000 to 50000 in terms of weight average molecular weight (Mw). In particular, the weight average molecular weight (Mw) is preferably in the range of 7000 to 30000.

  That is, from the viewpoint of the dispersibility and dispersion stability of the pigment contained in the pigment dispersion composition and the contrast of the color filter obtained by applying the pigment dispersion composition, the weight average molecular weight (Mw) of the specific dispersant Is preferably 5000 or more. Moreover, 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 dispersant is preferably 50000 or less.

  The content of the specific dispersant in the pigment dispersion composition of the present invention is preferably 10 to 100 parts by mass, more preferably 15 to 70 parts by mass, and 20 to 60 parts by mass with respect to 100 parts by mass of the zinc phthalocyanine pigment. Furthermore, it is a preferable range. When the specific dispersant is within this range, dispersibility and dispersion stability are improved, and a colored photosensitive composition using a pigment dispersion composition can be uniformly applied, and the effects of the present invention can be exhibited.

<(C) Resin having a polyester chain in the molecule>
The pigment dispersion composition of the present invention contains a resin having a polyester chain in the molecule.
The structure of the polyester chain in the resin having a polyester chain in the molecule is preferably one having 3 to 100 repeating units, more preferably 5 to 100, and still more preferably 5 to 60. is there.

  The structure of the repeating unit in the polyester chain is preferably a structure in which a diol compound and a dicarboxylic acid compound are condensed or a structure in which a lactone ring is subjected to ring-opening polymerization. Among these, a resin having a structure represented by the following general formula (c) in the molecule is preferable in terms of adsorptivity to the pigment, that is, dispersibility.

In the general formula ^{(c), R 27} represents an alkylene group having 1 to 10 carbon ^{atoms, R 28} represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. r represents an integer of 3 to 100.

In the general formula (c), R ²⁷ is more preferably an alkylene group having 2 to 5 carbon atoms, specifically an ethylene group, a propylene group, a pentylene group or the like.

Further, the molecular weight of the polyester chain is preferably 100 or more, more preferably 200 or more, and most preferably 200 or more and less than 6000 from the viewpoint of stability over time.
The resin having a polyester chain in the molecule is preferably a polymer compound having a non-polyester structure in the main chain and a polyester chain in the side chain, from the viewpoint of adsorptivity with the pigment, that is, dispersibility.

Specific examples of the resin having a polyester chain in the side chain include compounds obtained by reacting a polyalkyleneimine and a polyester compound described in, for example, JP-A Nos. 54-37082 and 61-174939. A compound in which the amino group of the side chain of polyallylamine described in Kaihei 9-169821 is modified with polyester, a graft polymer having a polyester type macromonomer described in JP-A-9-171253 as a copolymerization component, and JP Preferable examples include polyester polyol-added polyurethanes described in JP-A-60-166318.
Specific examples of the resin having a polyester chain in the main chain include a block polymer described in JP-A-6-239984, an aliphatic polyester compound described in JP-A-2003-306535, and the like.

  When these compounds contain a flexible polyester chain, the adsorptivity to the pigment increases, and the dispersibility can be further improved by using in combination with the specific dispersant. Furthermore, in the case where a colored photosensitive composition containing the pigment dispersion composition of the present invention is used as a resist solution to form a resist pattern (for example, when producing a colored pattern for a color filter), development in the development step Since the liquid permeability can be improved, a good resist pattern can be formed.

  Commercially available resins can be used as the resin having a polyester chain in the molecule, and these are also commercially available as dispersants. For example, Solsperse 24000GR, 28000, 32000, 38500 (manufactured by Nippon Lubrizol Co., Ltd.), Azisper PB711, PN411, PA111, PB821, PB822 (manufactured by Ajinomoto Fine Techno), EFKA4047, 4050 (manufactured by Efka Additives Japan), Is mentioned.

Among resins having a polyester chain in the molecule, from the viewpoint of adsorptivity with pigment, that is, dispersibility and stability over time, a compound obtained by reacting a polyalkyleneimine and a polyester compound, and a polyester type macromonomer as a copolymer component A graft polymer is preferable, and a compound obtained by reacting a polyalkyleneimine and a polyester compound is most preferable.
The resin having a polyester chain in the molecule may be used alone or in combination of two or more.

In the pigment dispersion composition, (C) the resin having a polyester chain in the molecule is, from the viewpoint of stability over time, the ratio of (B) specific dispersant: (C) the resin having a polyester chain in the molecule is in terms of mass. , Preferably in the range of 1: 0.1 to 1:10, more preferably in the range of 1: 0.3 to 1: 5, and in the range of 1: 0.5 to 1: 3. Is more preferable.
In addition, the content of the resin having a (C) polyester chain in the molecule in the pigment dispersion composition of the present invention is preferably 2 to 200 parts by mass, more preferably 6 to 200 parts by mass with respect to 100 parts by mass of the zinc phthalocyanine pigment. 100 mass parts and 10-60 mass parts are still more preferable ranges. (C) If the resin having a polyester chain in the molecule is in this range, the dispersion stability is improved and the viscosity is low, so that the coating uniformity is good, which is preferable.

<Solvent>
Examples of the solvent 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, and acetone. And solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, and xylene.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a colored photosensitive composition to be described later, from the viewpoint of handleability, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass. Can do.

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

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

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

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

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises at least the pigment dispersion composition of the present invention described above, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. May be included. Since this colored photosensitive composition contains the specific polymer described above and a dispersant having a polyester chain in the molecule, the pigment is kept in a well dispersed state in the composition, and good color characteristics are obtained. For example, when a color filter is configured, high contrast can be obtained.
Hereinafter, each component contained in the colored photosensitive composition of the present invention will be described in detail.

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

In the colored photosensitive composition for a color filter of the present invention, a zinc phthalocyanine pigment can be used alone, or a combination of a zinc phthalocyanine pigment and a conventionally known organic pigment can be used. The average primary particle diameter of conventionally known organic pigments used in combination is preferably in the range of 10 nm to 40 nm.
As a conventionally well-known organic pigment used in combination, a yellow pigment or a green pigment is preferable, and it is particularly preferable to use a yellow pigment in combination.

Examples of yellow pigments used in combination include C.I. I. Pigment YELLOW 83, 110, 138, 139, 150, 180, 185, and the like. The combined ratio of the zinc phthalocyanine pigment and the yellow pigment in the present invention is preferably 10 to 150 parts of the yellow pigment per 100 parts of the zinc phthalocyanine pigment in terms of mass.
Examples of the green pigment used in combination include C.I. I. Pigment GREEN 36, 7 and the like, but the color characteristics may be impaired, so the amount used is preferably 50 parts by mass or less, more preferably 30 parts by mass or less per 100 parts by mass of the zinc phthalocyanine pigment.

  In the colored photosensitive composition of the present invention, the total amount of the pigment containing a zinc phthalocyanine pigment is preferably 5 to 60% with respect to the total amount excluding the solvent in the colored photosensitive composition of the present invention. More preferably, it is -50%, and optimally it is 15-45%. By using the addition amount in this range, a color filter having excellent color characteristics, high contrast, and high luminance can be obtained.

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

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

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, 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 Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

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

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

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

  Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, 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 acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

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. ³¹ R ³² [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ^{_{], CH 2 = C (R 31}} ) (COOR 33) ^{[wherein, R 31} represents a hydrogen atom or an alkyl group of 1 to 5 carbon ^{atoms, R 33} is several alkyl group or C 1 to 8 carbon atoms 6 Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. is at least one, particularly _preferably CH ^{2 = CR} 31 ^{R 32} and / or ^{_{CH 2 = C (R 31)}} (COOR 33). These R ³¹ , R ³² and R ³³ are as defined above.

  As content of alkali-soluble resin in a coloring photosensitive composition, 1-20 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-15 mass%, Most preferably, it is 3 ˜12% by mass.

<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. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, 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 Sorbitol tetritaconate, etc. 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. And vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups. It is done.

CH ₂ ═C (R ^A ) COOCH ₂ CH (R ^B ) OH
(However, R ^A and R ^B 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 colored photosensitive monomers and oligomers, can also be used.

  About these photopolymerizable compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the performance design of a final coloring 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 further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

  Also, other components in the colored photosensitive composition such as binder polymer such as alkali-soluble resin, compatibility with photopolymerization initiator, etc. Is an important factor. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more.

In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.
The photopolymerizable compound is preferably used in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the nonvolatile components in the colored photosensitive composition. These may be used alone or in combination of two or more. In addition, the use method of the photopolymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface tackiness, and the like.

<Photopolymerization initiator>
The colored photosensitive composition of the present invention contains at least one photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent Publication No. EP88050A, benzophenones described in US Pat. No. 4,199,420 Aromatic thiol compounds, such as thioxanthones or acridine compounds described in Fr-2456541, compounds such as coumarins or lophine dimers described in JP-A-10-62986, JP-A-8- Sulfonium organoboron complexes described in Japanese Patent No. 015521 , Etc. can be mentioned.

  Among them, as the photopolymerization initiator, acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, lophine dimers series, A biimidazole type is preferred.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. Preferable examples include 4'-isopropyl-2-hydroxy-2-methyl-propiophenone.
Preferable examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy- Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone A preferred example is 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1.

  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 triazine photopolymerization initiator 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- Liazine, 4-Benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1, 3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 Preferred examples include 1,4-oxodiazole.
Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-(( Preferred examples include s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. .

Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like.
Preferable examples of the biimidazole-based photopolymerization initiator include 2-mercaptobenzimidazole and 2,2′-benzothiazolyl disulfide.

  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.

As a photoinitiator which can be used for this invention, it is not limited to the above photoinitiator, Another well-known thing 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, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.
Moreover, these photoinitiators can also be used together.

  As content of the photoinitiator in a coloring photosensitive composition, 0.1-15.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-10.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

  The colored photosensitive composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator (radical initiator) and increasing the photosensitive wavelength. The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 20% by mass with respect to the total solid content of the colored photosensitive composition from the viewpoints of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

  The colored photosensitive composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization of the photopolymerizable compound by oxygen.

  Examples of such co-sensitizers include amines such as MR Sander et al., "Journal of Polymer Society", Vol. 10, p. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).

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

<Solvent>
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent together with the above components.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionic acid 2-oxypropionic acid alkyl esters such as til, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy 2-methyl methyl propionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
A solvent may be used independently and may be used in combination of 2 or more type.

<Other ingredients>
In the colored photosensitive composition of the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, other fillers, the above general formula (1) or (2) Various additives such as a polymer compound other than the polymer compound and alkali-soluble resin represented, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

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

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  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.).

Fluorine-based organic compounds are particularly effective in preventing coating unevenness and thickness unevenness when, for example, a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
The addition amount of the fluorinated organic compound is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, with respect to the total mass of the pigment dispersion composition or the colored photosensitive composition. It is.

<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. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Surfactant>
The colored photosensitive composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include the MegaFac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and the Fluorad (registered trademark) series manufactured by 3M.

  In addition to the above, in the colored photosensitive composition, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Copolymers, acidic cellulose derivatives, polymers having hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; , Anionic surfactants, specifically phthalocyanine derivatives (commercial 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. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Examples of other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Sorbitan fatty acid esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, E Polymer dispersing agents such as KA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Zeneca); P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzoto Examples thereof include ultraviolet absorbers such as riazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

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

<Thermal polymerization inhibitor>
It is preferable to add a thermal polymerization inhibitor to the colored photosensitive composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, Benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  The colored photosensitive composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition of the present invention described above, and is necessary for this. Accordingly, it can be prepared by mixing an additive such as a surfactant.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described colored photosensitive composition of the present invention. The colored photosensitive composition of the invention is applied to the substrate directly or via another layer (preferably, applied by a coating method such as spin coating, slit coating, cast coating, roll coating) to form a photosensitive film. Then, the formed photosensitive film is exposed through a predetermined mask pattern, and after exposure, the uncured portion is developed and removed with a developing solution to develop a colored pattern (for example, a colored pixel) (for example, a colored pixel). The color filter can be most preferably manufactured.
Thereby, the color filter used for a liquid crystal display element and a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.
In this case, the radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.

  Drying (pre-baking) of the film with the colored photosensitive composition of the present invention applied (preferably applied) on the substrate is performed under conditions of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, an oven or the like. Can be done.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the colored photosensitive composition film 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.

  As said organic solvent, what was enumerated as the above-mentioned solvent which can be used when preparing the pigment dispersion composition or colored photosensitive composition of this invention is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 250 ° C.
Post-baking is heating after development for complete curing, and is usually performed at about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the above operation in accordance with the desired number of hues and sequentially repeating for each color, a color filter in which a cured film colored with a plurality of colors is formed can be produced.

  When the colored photosensitive composition of the present invention is applied to a substrate to form a film, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, Most desirably, the thickness is 1.0 to 2.5 μm.

  As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached thereto, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.

The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
Examples of other layers in the case where the colored photosensitive composition is applied to the substrate via another layer include a gas barrier layer and a solvent resistant layer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

(Synthesis of partially brominated zinc phthalocyanine)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride. For halogenation, 3.1 parts by mass of sulfuryl chloride, 3.7 parts by mass of anhydrous aluminum chloride, 0.46 parts by mass of sodium chloride, and 1 part by mass of zinc phthalocyanine were mixed at 40 ° C., and 2.2 parts by mass of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts by mass of a purified partially brominated zinc phthalocyanine crude pigment.
1 part by weight of this partially brominated zinc phthalocyanine crude pigment, 7 parts by weight of crushed sodium chloride, 1.6 parts by weight of diethylene glycol and 0.09 parts by weight of xylene were charged into a double-arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts by mass of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a partially brominated zinc phthalocyanine pigment.
The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) and contains an average of 10 bromines in one molecule, based on a halogen content analysis by mass spectrometry. It was.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

(Synthesis of polymer 1)
Dimethylaminoethyl methacrylate 30.0 g, ε-caprolactone 5 mol adduct of hydroxyethyl methacrylate (Placcel FM-5: manufactured by Daicel Chemical Industries, Ltd.) 70.0 g, n-dodecyl mercaptan 1.7 g and methoxypropylene glycol 233 g Is introduced into a three-necked flask purged with nitrogen, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 75 ° C. while flowing nitrogen into the flask. 0.67 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added thereto, and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 0.67 g of V-601 was further added and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours to obtain a 30% solution of polymer 1.
It was 13,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
The repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 30/70.

(Synthesis of polymer 2)
Dimethylaminoethyl methacrylate 25.0 g, 2-ethylhexyl methacrylate 55.0 g, benzyl methacrylate 20.0 g, n-dodecyl mercaptan 2.3 g and methoxypropylene glycol 233 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer ( The mixture is stirred with Shinto Kagaku Co., Ltd. (Three-One Motor) and heated to 75 ° C. while flowing nitrogen into the flask. To this was added 1.2 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.2 g of V-601 was further added and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours to obtain a 30% solution of polymer 2.
It was 12,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
The repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 25/55/20.

(Synthesis of Polymer 3)
Dimethylaminoethyl methacrylate 20.0 g, ε-caprolactone 5 mol adduct of hydroxyethyl methacrylate (Placcel FM-5: manufactured by Daicel Chemical Industries, Ltd.) 50.0 g, benzyl methacrylate 25.0 g, acrylic acid 5 g, n -1.6 g of dodecyl mercaptan and 233 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to ° C. To this, 1.0 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added, and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.0 g of V-601 was further added and the mixture was heated and stirred for 2 hours, and then heated to 90 ° C. and heated and stirred for 2 hours to obtain a 30% solution of polymer 3.
It was 12,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
Further, from titration with sodium hydroxide, the acid value per solid content was 40 mg KOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/50/25/5. .

(Synthesis of polymer 4)
Dimethylaminoethyl methacrylate 20.0 g, hydroxyethyl acrylate ε-caprolactone 10 mol adduct (Placcel FA-10L: manufactured by Daicel Chemical Industries, Ltd.) 50.0 g, benzyl methacrylate 25.0 g, acrylic acid 5 g, n -1.6 g of dodecyl mercaptan and 233 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to ° C. To this, 1.0 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added, and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.0 g of V-601 was further added, and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and stirred for 2 hours to obtain a 30% solution of polymer 4.
It was 12,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
Further, from titration with sodium hydroxide, the acid value per solid content was 40 mg KOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/50/25/5. .

Example 1
<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 stirred for 1 hour to prepare a mixed solution containing the pigment.
[Composition (1)]
-Partially brominated zinc phthalocyanine (the synthetic product) 150 parts-Dispersant: 100 parts of a 30% solution of the polymer 1-Resin having a polyester chain in the molecule: Ajisper PB711 (manufactured by Ajinomoto Fine Techno) 30 parts-Solvent: 720 parts of 2-acetoxy-1-methoxypropane

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 2 hours by a bead disperser Nano Ready Mill (manufactured by Imex Co., Ltd.) using 0.1 mmφ zirconia beads, and a green pigment dispersion composition (G1) Got.

<Evaluation of pigment dispersion composition>
The following evaluation was performed about the obtained pigment dispersion composition.
(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 after 1 week after dispersion (at room temperature) The viscosity η2 of the dispersion composition was measured and the degree of thickening was evaluated. The evaluation results are shown in Table 1 below. Here, a low viscosity indicates that the dispersibility and dispersion stability are good.

(Examples 2 to 4)
In Example 1, except that the specific dispersant (polymer 1) was replaced with the specific dispersants (polymer 2, polymer 3, and polymer 4) obtained in Synthesis Examples 2 to 4, respectively. In the same manner as in Example 1, green pigment dispersion compositions (G2), (G3), and (G4) were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 1)
In Example 1, the specific dispersant (polymer 1) was replaced with the following copolymer D-1 of methyl methacrylate and methacrylic acid (= 85/15 [mass ratio], weight average molecular weight: 15000). Except for this, a green pigment dispersion composition (G10) was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 2)
In Example 1, the specific dispersant (polymer 1) was prepared by adding methacrylic acid and terminal methacryloylated polymethyl methacrylate (AA-6: manufactured by Toagosei Co., Ltd.) copolymer D-2 (= 15/85 [mass ratio], A green pigment dispersion composition (G11) was prepared in the same manner as in Example 1 except that the weight average molecular weight was changed to 30000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

(Comparative Example 3)
In Example 1, the specific dispersant (polymer 1) was replaced with styrene and a terminal methacryloylated polymethyl methacrylate copolymer D-3 (= 15/85 [mass ratio], weight average molecular weight: 30000). Prepared a green pigment dispersion composition (G12) in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

(Comparative Example 4)
In Example 1, a resin having a polyester chain in the molecule, a copolymer D-1 (= 85/15 [mass ratio) of the following methyl methacrylate and methacrylic acid, which is a resin having no polyester chain in the molecule: The green pigment dispersion composition (G13) was prepared in the same manner as in Example 1 except that the weight average molecular weight was changed to 15000), and the same evaluation as in Example 1 was performed. The results are shown in Table 1 below.

(Example 5)
In Example 1, a copolymer D of a resin having a polyester chain in the molecule and an ε-caprolactone 2-mol adduct of methyl methacrylate and hydroxyethyl methacrylate (Placcel FM-2D: manufactured by Daicel Chemical Industries, Ltd.) -4 (= 85/15 [mass ratio], weight average molecular weight: 13000) A green pigment dispersion composition (G5) was prepared in the same manner as in Example 1 except that it was changed to that of Example 1. Was evaluated. The results are shown in Table 1 below.

(Example 6)
In Example 1, except that the resin having a polyester chain in the molecule was replaced with a polycaprolactone resin (Placcel H1P (weight average molecular weight: 10,000): manufactured by Daicel Chemical Industries, Ltd.), in the same manner as in Example 1, A green pigment dispersion composition (G6) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

  As is clear from Table 1, all of the pigment dispersion compositions of Examples using the polymers 1 to 4 which are specific dispersants according to the present invention have a low viscosity of the composition immediately after the dispersion, Even if it was made to change, the change of the viscosity was hardly seen. In contrast, Comparative Examples 1 to 3 using dispersants D-1 to D-3 not having the structure of the present invention and Comparative Example 4 using D-1 having no polyester chain are all viscosities immediately after dispersion. The viscosity was high, and the viscosity increased or gelled with time. It can be seen that the pigment dispersion composition dispersed with the specific dispersant of the present invention is excellent in dispersibility and dispersion stability.

(Example 10)
<Preparation of colored photosensitive composition>
The components described in the following composition (2) are further added to the pigment dispersion composition (G1) containing the green pigment obtained in Example 1, and the mixture is stirred and mixed. A composition (color resist solution) was prepared.
[Composition (2)]
Photopolymerizable compound: 80 parts of dipentaerythritol hexaacrylate Photoinitiator: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 parts-alkali-soluble resin: 2-acetoxy-1-methoxypropane solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) ( D-1, solid content 40%) 150 parts / solvent: 2-acetoxy-1-methoxypropane 1000 parts

<Evaluation of alkali developability, coatability, brightness, and contrast of colored photosensitive composition>
(Applicability)
The obtained colored photosensitive composition (color resist solution) is dried using a slit coating apparatus equipped with a slit head having a slit gap of 100 μm and an effective coating width of 540 mm, and the coating thickness after drying becomes 2.0 μm. A glass substrate having a width of 550 mm, a length of 650 mm, and a thickness of 0.7 mm is obtained by adjusting the gap between the slit and the substrate as described above and applying a colored photosensitive composition (color resist solution) obtained at a coating speed of 170 mm / second. The coated surface with a length of 640 mm was obtained.
After coating, the pressure was reduced to 67 Pa with a vacuum dryer, prebaked with a hot plate at 100 ° C. for 60 seconds, and then the coated surface was visually observed to evaluate the coating properties according to the following criteria.
◯: No patchy or streaky coating unevenness, foreign matter or repellency was observed.
X: Presence of spotted or streaky coating unevenness, foreign matter, and repellency was observed.

(Alkali developability)
The obtained colored photosensitive composition (color resist solution) was applied onto a 100 mm × 100 mm glass substrate (EAGLE2000, manufactured by Corning) so that the coating thickness after drying was 2.0 μm, and 90 ° C. In an oven for 60 seconds (pre-baking). Then, the mask exposure was performed at 100 mJ / cm ² (illuminance 20 mW / cm ² ), and the coated film after the exposure was covered with a 1% aqueous solution of an alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials). It rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer and form a pattern. The case where there was no chipping or peeling and a pattern similar to the exposure mask could be formed was marked as ◯, and the case where a pattern different from the exposure mask was formed was marked as x.

(Luminance: Y value)
About each of the produced colored filter board | substrate, Y value was measured as a brightness | luminance using MCPD-2000 by Otsuka Electronics Co., Ltd. When the y value was 0.42 (C light source), the Y value was larger than 68, and the smaller value was x. The measurement results are shown in Table 2 below.

(contrast)
A polarizing plate is placed on the colored resin film of the colored filter substrate, and the colored resin film is sandwiched between them. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are measured using BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. When the y value is 0.42 (C light source), the contrast is larger than 23000, and the smaller is x.

(Examples 11-15, Comparative Examples 10-13)
In Example 11, except that the green pigment dispersion (G1) was replaced with the pigment dispersions (G2 to G6, G10 to G13) obtained in Examples 2 to 6 and Comparative Examples 1 to 4, respectively. In the same manner as in Example 11, a colored photosensitive composition (color resist solution) was prepared and evaluated in the same manner as in Example 11. The results are shown in Table 2 below.

  As is apparent from Table 2, Examples 10 to 15 using the colored photosensitive composition obtained by the pigment dispersion composition using the polymers 1 to 4 of the specific dispersant according to the present invention have applicability. It was good, and there was no spotted or streaky coating unevenness, foreign matter or repellency. Further, a color filter having good developability and good brightness and contrast was obtained. On the other hand, Comparative Examples 10 to 13 using either the dispersant having no structure of the present invention or the resin having no polyester chain showed the presence of spotted or streaky coating unevenness, foreign matter, and repellency. It can be seen that the coloring filter obtained was poor in both brightness and contrast.

Claims (12)

A pigment dispersion composition comprising (A) a zinc phthalocyanine pigment, (B) a dispersant containing a structural unit represented by the following general formula (b-1), and (C) a resin having a polyester chain in the molecule. .

In the general formula ^{(b-1), X} b is O or ^NR 25, ^{(R 25} is an alkyl group having 1 to 10 carbon atoms) ^{represents, R 21} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. L represents an alkylene group having 1 to 10 carbon atoms or an arylene group. The dispersant (B) containing a structural unit represented by the general formula (b-1) is a dispersant further comprising a structural unit represented by the following general formula (b-2). Pigment dispersion composition.

In the general formula ^{(b-2), R 21} has the same meaning as ^{R 21} in the general formula ^{(b-1), R 24} is an alkyl group having 1 to 10 carbon _{atoms, - (C n H 2n O} ) m - R ^26, _- represents a _{(OC n H 2n CO) l} -OR 26 - (C n H 2n CO 2) l -R 26 or -R ^29,. n is an integer of 1 to 10, and m and l are integers of 3 to 20. R ²⁶ is an alkyl group having 1 to 10 carbon atoms, and R ²⁹ is an alkylene group having 2 to 6 carbon atoms.   The dispersant containing the structural unit represented by (B) the general formula (b-1) is a dispersant containing 5 to 90% by mass of the structural unit represented by the general formula (b-1). Or the pigment dispersion composition of Claim 2. The pigment according to any one of claims 1 to 3, wherein the resin (C) having a polyester chain in the molecule is a resin having a polyester chain represented by the following general formula (c) in the molecule. Dispersion composition.

In the general formula ^{(c), R 27} represents an alkylene group having 1 to 10 carbon ^{atoms, R 28} represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. r represents an integer of 3 to 80.   The content of the dispersant containing the structural unit represented by (B) the general formula (b-1) with respect to 100 parts by mass of the (A) zinc phthalocyanine pigment is in the range of 10 to 100 parts by mass. The pigment dispersion composition according to claim 4. The pigment dispersion composition according to any one of claims 1 to 5, wherein the (A) zinc phthalocyanine pigment is a compound represented by the following general formula (a).

In general formula (a), X ^{21 to} X ³⁶ are each independently a hydrogen atom, a chlorine atom or a bromine atom. However, 8 or more of X ^{21 to} X ³⁶ are chlorine atoms or bromine atoms.   The colored photosensitive composition containing the pigment dispersion composition of any one of Claims 1-6, a photopolymerizable compound, and a photoinitiator.   Furthermore, the coloring photosensitive composition of Claim 7 containing alkali-soluble resin.   The colored photosensitive composition according to claim 7 or 8, which is used for a color filter.   The color filter which has a coloring pattern which uses the coloring photosensitive composition of Claim 9 on a base material.   A photosensitive film forming step of forming the photosensitive film by applying the colored photosensitive composition according to claim 9 directly or via another layer to the photosensitive film, and pattern exposure and development on the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing steps.   A liquid crystal display device comprising the color filter according to claim 10.