KR20230092727A - Photosensitive coloring composition for blue color filter, color filter, and solid-state imaging device using the same, and liquid crystal display device - Google Patents

Abstract

The present invention is to provide: a photosensitive coloring composition for a blue color filter that has excellent viscosity characteristics and dispersion stability, and is excellent in alkali developability and a pattern formation property independent of an exposure amount even in a thin film; a color filter; and a solid-state imaging element and a liquid crystal display device using the same. A photosensitive coloring composition for a blue color filter contains a coloring agent (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E), wherein the coloring agent (A) contains a blue pigment (A1) or a purple pigment (A2), the content of the coloring agent (A) is 45-70 mass% in the total non-volatile content, the dispersion resin (B) contains a dispersion resin (B1) having an amine value of 70 to 150 mgKOH/g, and the polymerization initiator (D) contains at least one photopolymerization initiator selected from the group consisting of general formula (1) and general formula (2).

Description

Photosensitive coloring composition for blue color filter, color filter, solid-state imaging device using the same, and liquid crystal display device

The present invention relates to a photosensitive coloring composition for a blue color filter suitable for production of a color filter used for a liquid crystal display device, a solid-state imaging device, and the like.

A solid-state imaging device represented by C-MOS (Complementray Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc., additively mixes B (blue), G (green), and R (red) on the light-receiving element. It is common to perform color separation by arranging color filters each having primary color filter segments. In recent years, the area per pixel tends to decrease due to miniaturization and high pixelation of solid-state imaging devices, and thinning of color filters used in solid-state imaging devices is strongly desired.

In addition, even if the color filter is thinned, the shape of the spectral wavelength is required to be the same as before. If so, it becomes necessary to increase the density|concentration of the colorant contained in the pixel of a color filter. For that purpose, it is necessary to increase the concentration of the colorant in the photosensitive coloring composition used for producing the color filter.

However, in order to increase the concentration of the colorant in the photosensitive coloring composition, it is necessary to reduce other components, causing problems with the stability of the photosensitive coloring composition. Therefore, coexistence with thinning was a subject.

In addition, when the concentration of the colorant contained in the photosensitive coloring composition increases, the solubility of the coating film in an alkaline developer tends to decrease remarkably, so that residue is generated on the substrate or light-shielding layer of the unexposed area during development. there is a problem with In addition, although the pigment contained in the photosensitive coloring composition tends to be further and further refined with high color reproduction of the color filter, it is effective to use a dispersion resin having a high amine value in order to stably disperse the finely divided pigment. However, when a dispersion resin having a high amine value is used, development itself with an alkaline developer becomes difficult.

Therefore, as a solution to the problem of high concentration of colorant, developability, and residue on the substrate or light-shielding layer of the unexposed part during development, Patent Document 1 indicates that the content of the colorant is 30% of the total non-volatile matter. A coloring composition using a specific photopolymerizable monomer at ~ 60% by mass is disclosed. Patent Document 2 discloses a photoinitiator having a specific structure.

Japanese Unexamined Patent Publication No. 2009-92839 Japanese Unexamined Patent Publication No. 2009-134289

When the photosensitive coloring composition of Patent Document 1 is applied to a coloring composition in which the content of the coloring agent is 45% by mass or more in the total non-volatile matter, the adhesion of the pixel pattern is poor and there is a problem of pixel defects.

The photosensitive coloring composition using the specific initiator of Patent Document 2, for example, using a stepper exposure apparatus to increase the exposure amount can ensure the adhesion of the pixel pattern, but there is a problem that a lot of development residue remains. Therefore, there was a problem that the pixels could not be formed into thin films when the amount of the photopolymerization initiator was increased to expose the pixel patterns with a low exposure amount.

An object of the present invention is to provide a photosensitive coloring composition for a blue color filter having excellent viscosity characteristics and dispersion stability, excellent alkali developability even in a thin film, and excellent pattern formation property independent of exposure amount.

The present invention is a photosensitive coloring composition for a blue color filter comprising a colorant (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E),

The colorant (A) contains a blue pigment (A1) and a purple pigment (A2),

The content of the coloring agent (A) is 45% by mass to 70% by mass in the total non-volatile matter,

The dispersion resin (B) includes a dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g,

The acid value of the alkali-soluble resin (C) is 80 mgKOH/g to 180 mgKOH/g,

The photopolymerization initiator (D) relates to a photosensitive coloring composition for blue color filters containing at least one photopolymerization initiator selected from the group consisting of the following general formula (1) and general formula (2).

[Tue 1]

In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ represents an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and adjacent substituents bond to each other to form an aliphatic ring or An aromatic ring may be formed. R ₄ represents a nitro group, an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and is bonded to adjacent substituents, You may form an aliphatic ring or an aromatic ring.

In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent.

In addition, the present invention is the photosensitive coloring composition for blue color filters, wherein the content of the polymerizable compound having an average number of functional groups of 3 to 4 in the polymerizable unsaturated group is 50% by mass or more based on the total amount of the polymerizable compound (E). It is about.

Further, the present invention relates to a color filter characterized by comprising a blue filter formed of the photosensitive coloring composition for a blue color filter on a base material.

Further, the present invention relates to a solid-state imaging device including the color filter.

Moreover, this invention relates to the liquid crystal display device provided with the said color filter.

According to the present invention, it is possible to provide a photosensitive coloring composition for a blue color filter having excellent viscosity characteristics and dispersion stability, excellent alkali developability even in a thin film, and excellent pattern formation property independent of exposure amount. In addition, the present invention can provide a color filter, a solid-state imaging device using the color filter, and a liquid crystal display device.

Terms used in the present invention are defined. In the case of notation as "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate" or "(meth)acrylamide", unless otherwise specified, , "acryloyl and/or methacryloyl", "acryl and/or methacryl", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide", respectively. and/or methacrylamide”. "C.I." enumerated in this specification means a color index (C.I.). The resist pattern which can be formed from the photosensitive coloring composition for color filters is also called a pixel and a filter segment. A monomer refers to an unreacted state, and a monomeric unit refers to a state constituting a part of a copolymer after polymerization of a monomer.

The photosensitive coloring composition for a blue color filter of the present invention (hereinafter also referred to as a coloring composition) includes a coloring agent (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E). ),

The colorant (A) contains a blue pigment (A1) and a purple pigment (A2),

The content of the coloring agent (A) is 45% by mass to 70% by mass in the total non-volatile matter,

The dispersion resin (B) includes a dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g,

The acid value of the alkali-soluble resin (C) is 80 mgKOH/g to 180 mgKOH/g,

The photopolymerization initiator (D) contains at least one kind of photopolymerization initiator selected from the group consisting of the following general formula (1) and general formula (2).

[Tue 2]

In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ represents an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and adjacent substituents bond to each other to form an aliphatic ring or An aromatic ring may be formed. R ₄ represents a nitro group, an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and is bonded to adjacent substituents, You may form an aliphatic ring or an aromatic ring.

In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent.

In the present invention, the dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g of the dispersion resin (B) and an acid value of the alkali-soluble resin (C) of 80 mgKOH/g to 180 mgKOH/g, and at least one photopolymerization initiator selected from the group consisting of general formula (1) and general formula (2) of the photopolymerization initiator (D). When the amine titer of the dispersion resin (B) is within a specific range, the viscosity stability improves, but on the other hand, the alkali developability deteriorates. Then, developability improves by making the acid value of alkali-soluble resin (C) used together into a specific range. Further, in addition to both viscosity stability and alkali developability, the pattern formability is also improved due to the synergistic effect with the photopolymerization initiator (D). In this way, a photosensitive coloring composition for a blue color filter having preferable viscosity stability and alkali developability, little exposure dose dependence of pattern formation property, and excellent adhesion is obtained.

[Colorant (A)]

The coloring agent (A) in the coloring composition of this invention can form a blue color filter by containing a blue pigment (A1) and a purple pigment (A2). The coloring agent (A) may contain pigments other than the blue pigment (A1) and the purple pigment (A2) as needed.

(Blue Pigment (A1))

The blue pigment (A1) is, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17 , 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 64, 66, 67, 68, 71, 72, 73, 74 , 75, 76, 78, 79 and the like. Among these, C.I. Pigment Blue 15:3, 15:4, and 15:6, which are unsubstituted phthalocyanine pigments having a transmissive region in a short wavelength region, are preferable from the viewpoints of coloring power and pattern formation.

(Purple Pigment (A2))

The purple pigment is, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25 , 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. Pigment Violet 23, which is a dioxazine pigment, is preferable from the viewpoints of coloring power and pattern formation.

A coloring agent (A) can be used individually or in combination of 2 or more types.

The mass ratio of the blue pigment (A1) and the purple pigment (A2) is preferably A1:A2 = 90:10 to 55:45, and more preferably 80:20 to 60:40.

The content of the coloring agent (A) is preferably 45 to 70% by mass, more preferably 47 to 65% by mass, and 48 to 60% by mass in 100% by mass of the non-volatile matter of the coloring composition, from the viewpoint of thin film formation and developability. more preferable

(miniaturization of organic pigments)

It is preferable to micronize and use an organic pigment. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution/precipitation methods can all be used. Among these, salt milling treatment by a kneader method, which is one type of wet grinding, is preferable. As for the average primary particle diameter calculated|required by TEM (transmission electron microscope) of a micronized pigment, 5-90 nm is preferable. Moreover, as for an average primary particle diameter, from a viewpoint of dispersibility and coloring power, 10-70 nm is more preferable.

The salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt (eg, sodium chloride), and a water-soluble organic solvent in a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or the like. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading mechanically while heating. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt at the time of salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution, and a sharp particle size distribution.

It is preferable to add resin to the salt milling treatment from the viewpoint of coloring strength and dispersion stability. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified by natural resins. Among these, those that are solid at room temperature and insoluble in water are preferable, and those that are partially soluble in the above organic solvent are preferable. The amount of resin used is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the coloring agent (A).

It is preferable to add a pigment derivative (a) to the salt milling treatment from the viewpoint of dispersion stability and coloring strength. The amount of the dye derivative (a) used is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the organic pigment.

<Removal of metal>

When a specific metal element exists in a large amount as an impurity other than the constituent component of a pigment in a coloring composition, dispersion stability over time is impaired. In addition, there are cases where heat resistance is lowered and sensitivity is lowered. In addition, a color filter created using this may have a foreign matter, and as a result, it is easy to cause a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as a specific metal element) contained in the photosensitive coloring composition is 500 mass ppm or less.

300 mass ppm or less is more preferable, and, as for the total amount of the said specific metal element, 200 mass ppm or less is especially preferable. Moreover, although the lower limit of the total amount of a specific metal element is not specifically limited, 1 mass ppm or more is preferable and 5 mass ppm or more is more preferable. If it is within the above range, a photosensitive coloring composition capable of forming a color filter with reduced cost, excellent storage stability, and less generation of foreign matter and lowering of brightness is obtained.

It is preferable that it is respectively 100 mass ppm or less, respectively, and, as for the quantity of each specific metal element contained in the photosensitive coloring composition, it is more preferable that it is respectively 50 mass ppm or less.

In addition, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, etc., which constitute the pigment, are preferably small in terms of impurities that do not become constituent components of the pigment, and can be removed in the same way as specific metal elements. In addition, since Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed from materials (for example, catalysts) used in the manufacturing process of various raw materials of the photosensitive coloring composition, they are removed as much as possible.

As a method for removing the colorant (A) or mixed metal from the device in the manufacturing process, Japanese Patent Laid-Open No. 2010-83997, Japanese Patent Laid-Open No. 2018-36521, Japanese Patent Laid-Open No. 7-198928, Japanese Patent A method by water washing according to Unexamined Patent Publication No. 8-333521, Japanese Unexamined Patent Publication No. 2009-7432, or the like, or a method such as removal of magnetic foreign matter by a magnet described in Japanese Unexamined Patent Publication No. 2011-48736, or the like.

Content of a specific metal element can be measured by inductively coupled plasma emission spectrometry (ICP).

<Dye derivative (a)>

The photosensitive coloring composition of the present invention may contain a pigment derivative (a). When the pigment derivative is adsorbed on the surface of the organic pigment, the surface of the organic pigment has polarity and is easily compatible with the dispersion resin, thereby further improving the dispersibility of the organic pigment. A pigment derivative is a compound which has an acidic group, a basic group, a neutral group, etc. in the organic pigment residue. Dye derivatives, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group or a phosphoric acid group, and compounds having a basic substituent such as tertiary amino group at the terminal of these amine salts, sulfonamide groups, phenyl groups or phthals and compounds having neutral substituents such as midalkyl groups.

Organic pigments, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threnic pigments, metal complex pigments, azo, disazo, polyazo Azo pigments, such as these, etc. are mentioned.

Diketopyrrolopyrrole pigment derivatives are disclosed in Japanese Patent Laid-Open No. 2001-220520, WO2009/081930 pamphlet, WO2011/052617 pamphlet, WO2012/102399 pamphlet, Japanese Patent Laid-Open No. 2017-156397, phthalocyanine-based pigment derivatives , Japanese Patent Laid-Open No. 2007-226161, WO2016/163351 Pamphlet, Japanese Patent Laid-Open No. 2017-165820, Japanese Patent No. 5753266, anthraquinone-based pigment derivatives, Japanese Patent Laid-Open No. 63-264674, Japan Japanese Unexamined Patent Publication No. Hei 09-272812, Japanese Unexamined Patent Publication No. Hei 10-245501, Japanese Unexamined Patent Publication No. Hei 10-265697, Japanese Unexamined Patent Publication No. 2007-079094, WO2009/025325 pamphlet, quinacridone-based pigment derivatives , Japanese Patent Laid-Open No. 48-54128, Japanese Patent Laid-Open No. 03-9961, Japanese Patent Laid-Open No. 2000-273383, dioxazine-based pigment derivatives, Japanese Patent Laid-Open No. 2011-162662, thiazine indigo-based pigment Derivatives are Japanese Patent Laid-Open No. 2007-314785, triazine-based pigment derivatives are Japanese Patent Laid-Open No. 61-246261, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2003-165922, Japanese Patent Laid-Open Publication No. 2003-168208, Japanese Unexamined Patent Publication No. 2004-217842, Japanese Unexamined Patent Publication No. 2007-314681, benzoisoindole-based pigment derivatives, Japanese Unexamined Patent Publication No. 2009-57478, quinophthalone-based pigment derivatives, Japanese Japanese Unexamined Patent Publication No. 2003-167112, Japanese Unexamined Patent Publication No. 2006-291194, Japanese Unexamined Patent Publication No. 2008-31281, Japanese Unexamined Patent Publication No. 2012-226110, naphthol-based pigment derivatives, Japanese Unexamined Patent Publication 2012-208329, Japanese Unexamined Patent Publication No. 2014-5439, azo dye derivatives, Japanese Unexamined Patent Publication No. 2001-172520, Japanese Unexamined Patent Publication No. 2012-172092, acidic substituents, Japanese Unexamined Patent Publication No. 2004-307854, basic substituents, The dye derivatives described in Japanese Unexamined Patent Publication No. 2002-201377, Japanese Unexamined Patent Publication No. 2003-171594, Japanese Unexamined Patent Publication No. 2005-181383, and Japanese Unexamined Patent Publication No. 2005-213404 are exemplified. In addition, although these documents sometimes describe a pigment derivative as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, etc., a compound having a substituent such as an acidic group, a basic group, or a neutral group at the organic pigment residue described above. Silver is synonymous with a pigment derivative.

A pigment derivative can be used individually or in combination of 2 or more types.

The amount of use of the pigment derivative is preferably from 1 to 100 parts by mass, more preferably from 3 to 70 parts by mass, still more preferably from 5 to 50 parts by mass, based on 100 parts by mass of the organic pigment.

The pigment derivative is adsorbed on the surface of the pigment by adding the pigment derivative to the organic pigment and performing micronization treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., and the case where the pigment derivative is not added In comparison, the primary particles of the pigment can be further refined.

By adding a color derivative to an organic pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the color derivative is adsorbed on the surface of the pigment and the surface of the pigment has polarity to promote adsorption of the resin type dispersant. do. Thereby, the compatibility with other components improves, and the dispersion stability and aging viscosity stability of the photosensitive coloring composition are improved.

[Dispersion Resin (B)]

Dispersion resin (B) contains dispersion resin (B1) whose amine value is 70 mgKOH/g - 150 mgKOH/g.

(dispersion resin (B1))

The dispersion resin (B1) is a basic dispersion resin. The dispersion resin (B1) is preferably a copolymer in which a monomer containing a basic group-containing monomer is radically polymerized, for example. As for the basic group of dispersion resin (B1), a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium base group are mentioned.

As for the molecular structure of dispersion resin (B1), a random polymer and a block polymer are mentioned. Among these, a block polymer is preferable. Examples of the block polymer include an AB block structure, which is a block structure including a site having a basic group adsorbed to the colorant (A), and an ABA block structure (adsorption block in which either the A block or the B block has a basic group). The block portion having no basic group block is a highly solvent-soluble portion that is not adsorbed to the colorant (A), and contributes to dispersion stability as a steric repulsive portion of the colorant (A).

The amine titer of the dispersion resin (B1) is 70 to 150 mgKOH/g, more preferably 70 to 120 mgKOH/g. When the amine value is in the range of 70 to 150 mgKOH/g, the acid-base interaction with the alkali-soluble resin used in the present invention improves the dispersion stability of the colorant (A), while the developability is also compatible.

The dispersion resin (B1) preferably has one or more basic group-containing monomer units selected from the group represented by the following general formula (3), general formula (4), and general formula (5) in order to obtain basicity, , It is more preferable to contain two or more types of these, and it is still more preferable to contain units represented by general formulas (3) and (4). Accordingly, it is difficult to depend on the exposure amount, and good pattern formability is easily obtained.

[Tue 3]

In formula (3), R ₁ to R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and 2 of R ₁ to R ₃ Two or more may be bonded to each other to form an annular structure. R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.

R ₁ to R ₃ in the general formula (3) are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and a methyl group or an ethyl group. , a propyl group, a butyl group and a benzyl group are particularly preferred.

In Formula (4), R ₅ and R ₆ independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R ₅ and R ₆ combine with each other to form a cyclic structure, can also R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

R ₅ and R ₆ in the general formula (4) are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferred.

In formula (5), R ₇ represents a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ₁₂ , and R ₁₂ represents a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 12 carbon atoms, or an acyl group, and R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently A methyl group, an ethyl group, or a phenyl group is shown. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

Examples of the alkyl group having 1 to 18 carbon atoms in R ₇ in the general formula (5) include linear, branched, and cyclic alkyl groups. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group, etc. are mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

Examples of the aralkyl group of 7 to 12 carbon atoms include a group in which an aryl group of 6 to 10 carbon atoms and an alkyl group of 1 to 8 carbon atoms are bonded. Examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a 2-phenylpropan-2-yl group.

Moreover, as for an acyl group, a C2-C8 alkanoyl group and an aroyl group are mentioned, for example. For example, an acetyl group, a benzoyl group, etc. are mentioned.

Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is still more preferred.

In general formulas (3), (4), and (5), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ₁₃ -, -COO- R ₁₄ - (provided that R ₁₃ and R ₁₄ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms); and the like. Among these, -COO-R ₁₄ - is preferable. In the above formula (9), Y ^- of the counter anion includes, for example, Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like .

The quaternary ammonium base-containing monomers forming the general formula (3) include, for example, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acrylo Alkyl (meth)acrylate-based quaternary ammonium salts such as yloxyethyldimethylbenzylammonium chloride and (meth)acryloyloxyethylmethylmorpholinoammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, ) Alkyl (meth) acryloylamide-based quaternary ammonium salts such as acryloylaminoethyltriethylammonium chloride, (meth)acryloylaminoethyldimethylbenzylammonium chloride, dimethyl diallylammonium methyl sulfate, and trimethylvinylphenylammonium Chloride etc. are mentioned.

Tertiary amine group-containing monomers forming the general formula (4) include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N - (meth)acrylates having a tertiary amino group such as dimethylaminopropyl (meth)acrylate and N,N-diethylaminopropyl (meth)acrylate;

N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl ( (meth)acrylamides having tertiary amino groups such as meth)acrylamide;

etc. can be mentioned.

Examples of the monomer forming the general formula (5) include compounds represented by the following formulas (5-1) to (5-11).

[Tuesday 4]

In formulas (5-1) to (5-11), R ₄ represents hydrogen or a methyl group.

Among these, 2,2,6,6-tetramethylpiperidylmethacrylate (a compound in which R ₄ is a methyl group in the formula (5-1)), 1,2,2,6,6-pentamethylp Peridyl methacrylate (a compound in which R ₄ is a methyl group in the formula (5-2)) is preferable, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferable.

The dispersion resin (B1) may contain amino group-containing monomer units other than the monomer units represented by general formulas (3), (4) and (5).

The content of the basic group-containing monomer unit is preferably from 20 to 70% by mass, and more preferably from 30 to 65% by mass, based on all the monomers of the dispersion resin (B1). When used in an appropriate amount, an appropriate amine titer is obtained and the dispersion stability is improved.

Other monomers forming the other monomer units contained in the dispersion resin (B1) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate , butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl ( straight-chain or branched alkyl (meth)acrylates such as meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate;

Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate Alkyl (meth)acrylates;

heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate;

(meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl Ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol Monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxy polyethylene glycol-polypropylene glycol (meth) acrylate, such as (poly) Alkylene glycol monoalkyl ether (meth)acrylates;

Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate , paracumylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxy (poly)alkylene glycol (meth)acrylates having an aromatic ring such as polypropylene glycol (meth)acrylate and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate;

3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyl (meth)acrylates having an alkyloxysilyl group such as trimethoxysilane;

Fluoroalkyl (meth)acrylic such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate rates; (meth)acryloxy-modified polydimethylsiloxanes (silicone macromers);

(meth)acrylamide, dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine, etc. of N-substituted (meth)acrylamides; And nitriles, such as (meth)acrylonitrile, etc. are mentioned.

Moreover, styrenes, such as styrene and (alpha)-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; And fatty acid vinyls, such as vinyl acetate and vinyl propionate, etc. are mentioned.

(meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethylphthalate, 2-(meth)acryloyloxypropylphthalate, 2-( Carboxyl groups such as meth)acryloyloxyethylhexahydrophthalate, 2-(meth)acryloyloxypropylhexahydrophthalate, β-carboxyethyl(meth)acrylate, and ω-carboxypolycaprolactone(meth)acrylate A containing monomer is mentioned.

Dispersion resin (B1) can be used by forming a salt with an acidic compound. As for the said acidic compound, a phosphoric acid compound and a sulfonic acid compound are mentioned.

Examples of the phosphoric acid compound include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate and the like.

Examples of the sulfonic acid compound include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, and monon-propylsulfuric acid. A hydrate such as p-toluenesulfonic acid monohydrate may also be used.

Among these, a phosphoric acid compound is preferable from the viewpoint of suppressing foreign matter.

The weight average molecular weight of the dispersion resin (B1) is preferably 1,000 to 100,000 in terms of polystyrene from the viewpoint of dispersion stability.

The content of the dispersion resin (B1) is preferably from 0.5% by mass to 50% by mass, and more preferably from 1% by mass to 30% by mass in the total non-volatile matter of the coloring composition from the viewpoint of dispersion stability.

The dispersion resin (B) may further contain at least one of a phosphoric acid-based dispersion resin (B2) and a carboxylic acid-based dispersion resin (B3).

(Phosphoric acid-based dispersion resin (B2))

The phosphoric acid-based dispersion resin (B2) is a resin having a phosphoric acid bond [(-O) ₃ P=O] in the molecule. A preferable example is a phosphoric acid-based dispersion resin represented by any of the following (B2-1) or (B2-2), for example.

[Phosphoric Acid Dispersion Resin (B2-1)]

The phosphoric acid-based dispersion resin (B2-1) is a resin represented by the following general formula (6).

(HO-) _3-n -PO-(OR ¹ ) _n Formula (6)

(In formula (6), R ¹ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2)

Since the phosphoric acid-based dispersion resin represented by the general formula (6) has a large effect of suppressing the re-agglomeration of the pigment after dispersion, a color filter having less foreign matter and excellent transparency can be produced.

The phosphoric acid-based dispersion resin represented by the general formula (6) is produced by, for example, using a monoalcohol as an initiator, ring-opening addition of a cyclic ester (first step), followed by phosphoric acid esterification (second step) It is desirable to do

Monoalcohol is a compound having one hydroxyl group in its molecule, and any of primary, secondary and tertiary alcohols can be used. Monoalcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, hexadecyl alcohol and the like. Among these, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferable.

In the first step, a polyester residue having a hydroxyl group at one end can be synthesized by ring-opening addition polymerization of ε-caprolactone, which is a cyclic ester, using a monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, by introducing monoalcohol, ε-caprolactone, and a polymerization catalyst into a reactor connected to a dehydration tube and a condenser under a nitrogen stream. In the case of using a low-boiling monoalcohol, it can be reacted under pressure using an autoclave. For the reaction, a non-solvent or an appropriate dehydrating solvent such as toluene or xylene may be used. The solvent used in the reaction may be removed by an operation such as distillation after completion of the reaction, or may be used as a part of the product as it is.

The reaction temperature in the first step is preferably 120°C to 220°C, and more preferably 160°C to 210°C. When the reaction is carried out at an appropriate temperature, a reactant is efficiently obtained while suppressing side reactions.

1-50 mol is preferable, and, as for the number of moles of epsilon caprolactone added with respect to 1 mol of monoalcohols, 3-20 mol is more preferable. When reacted in an appropriate ratio, a dispersion resin having an appropriate molecular weight is obtained.

The polymerization catalyst is, for example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodine, tetrabutylammonium iodine, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethyl Quaternary ammonium salts such as ammonium iodine, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, quaternary phosphonium salts such as benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, potassium acetate, organic carboxylates such as sodium acetate, potassium benzoate and sodium benzoate, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and Zinc compounds, such as zinc chloride, etc. are mentioned.

In the second step, a polyester residue having a hydroxyl group at one end is reacted with a phosphate esterification agent such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, or phosphorus oxychloride, for example, to obtain a compound represented by the general formula (6) A phosphoric acid-based dispersion resin can be obtained. Among these phosphoric acid esterification agents, one or more phosphoric acid esterification agents selected from the group consisting of orthophosphoric acid, polyphosphoric acid and phosphorus pentoxide are preferable because there is no by-product such as hydrochloric acid gas and no special equipment is required. Among them, polyphosphoric acid having an orthophosphoric acid equivalent content of 116% by mass is preferable.

The addition ratio of the phosphate esterification agent is preferably 0.5 to 1.5, more preferably 1.0 to 1.3, and still more preferably 1.05 to 1.2, in terms of the molar ratio of phosphorus atoms in the phosphoric acid esterification agent to the hydroxyl groups of the polyester residue having a hydroxyl group at one end. do. When reacted in an appropriate ratio, a dispersion resin with few by-products is obtained.

The reaction temperature in the second step is not particularly limited, but is preferably from 40°C to 130°C, more preferably from 50°C to 110°C, still more preferably from 60°C to 100°C. When the reaction is conducted at an appropriate temperature, a dispersion resin containing less unreacted substances and less by-products is obtained.

It is preferable that the molar ratio of the dispersion resin represented by General formula (6) of a phosphoric acid ester of n=1 and a phosphoric acid ester of n=2 is 100:0 - 100:30 from a dispersible viewpoint.

In addition, it is preferable that the dispersion resin represented by general formula (6) has a structure in which R ¹ is represented by general formula (6-1) below.

-(R ¹¹ -COO-) _m -R ¹² Formula (6-1)

(In formula (6-1), R ¹¹ represents a lactone residue, R ¹² represents a monoalcohol residue, and m represents an integer of 1 to 50)

In general formula (6-1), for example, when R ¹ is a polycaprolactone residue, pigment dispersibility and dry solubility become good, which is preferable. As for the number average molecular weight of a polycaprolactone residue, 300-10,000 are preferable.

[Phosphoric Acid Dispersion Resin (B2-2)]

The phosphoric acid-based dispersion resin (B2-2) is a dispersion resin that is a copolymer of a phosphoric acid group-containing monomer and other monomers, and is described in, for example, Japanese Patent Laid-Open No. 2003-253078 and Japanese Unexamined Patent Publication No. 2008-161737 am.

(Carboxylic Acid Dispersion Resin (B3))

The carboxylic acid-based dispersion resin (B3) is a resin having a dispersing ability containing a carboxy group (-COOH) in the molecule. As a preferable example, it is the carboxylic acid type dispersion resin represented by any of the following (B3-1) or (B3-2).

[Carboxylic Acid Dispersion Resin (B3-1)]

The carboxylic acid-based dispersion resin (B3-1) is a polyester portion having a carboxy group formed by reacting an acid anhydride group in at least one acid anhydride selected from the group of tetracarboxylic acid dianhydride and tricarboxylic acid anhydride with a hydroxyl group in a hydroxyl group-containing compound. And, it is resin containing the vinyl polymer part formed by radically polymerizing a monomer.

First, the polyester part will be explained. A polyester part is a site|part where a plurality of ester groups derived from the reaction of an acid anhydride group and a hydroxyl group exist.

Tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane -2-Acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2- Dicarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride such as bicyclo[2.2.2]-octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, ethylene glycol dianhydride Mellitic acid ester, propylene glycol dianhydrous trimellitic acid ester, butylene glycol dianhydrous trimellitic acid ester, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'- Biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetra Carboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furan Tetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4' -Biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenyl) phthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalenesuccinic acid dianhydride. Among these, aromatic tetracarboxylic dianhydride is preferable from the viewpoint of adsorbability to a pigment.

Tetracarboxylic dianhydride is not limited to the above exemplary compounds, and may have any structure as long as it has two acid anhydride groups. These may be used alone or in combination. Since tetracarboxylic dianhydride forms a dispersion resin having two carboxyl groups in one unit of tetracarboxylic dianhydride by reaction with a hydroxyl group-containing compound, it is preferable as a component of the dispersion resin of the present invention from the viewpoint of pigment adsorption. do.

Examples of the tricarboxylic acid anhydride include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

Aliphatic tricarboxylic acid anhydrides include, for example, 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1 , 2-anhydride, 1,3,4-cyclopentane tricarboxylic acid anhydride, etc. are mentioned.

Aromatic tricarboxylic acid, for example, benzene tricarboxylic acid anhydride (1,2,3-benzene tricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzene tricarboxylic acid anhydride], etc.), naphthalene tricarboxylic acid anhydride (1 ,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride, etc.), 3,4,4 '-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3,2'-biphenyl tricarboxylic acid anhydride, 3, 4,4'-biphenylmethane tricarboxylic acid anhydride or 3,4,4'-biphenylsulfone tricarboxylic acid anhydride; and the like. Among these, aromatic tricarboxylic acid anhydrides are preferable from the viewpoint of adsorbability to pigments.

The molar ratio between the acid anhydride group in at least one acid anhydride selected from tetracarboxylic acid anhydride and tricarboxylic acid anhydride and the hydroxyl group in the hydroxyl group-containing compound is preferably acid anhydride group/hydroxyl group = 0.5 to 1.5. When reacted at an appropriate ratio, it is easy to obtain a dispersion resin having good dispersibility.

The hydroxyl group-containing compound is preferably a polyol such as a diol having a plurality of hydroxyl groups among monools and polyols. The hydroxyl group in the polyol functions as a bonding origin with the vinyl polymer moiety.

Examples of the polyol serving as the origin of bonding with the vinyl polymer moiety include compounds having two hydroxyl groups and one thiol group in the molecule and at least one hydroxyl group-containing compound selected from the group consisting of vinyl polymers containing single-terminal hydroxyl groups. For example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2 -Mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2, 2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc. are mentioned.

As for carboxylic acid type dispersion resin (B3-1), the following carboxylic acid type dispersion resin (B3-1-1) or (B3-1-2) is more preferable.

<<Carboxylic Acid Dispersion Resin (B3-1-1)>>

The vinyl polymer portion of the carboxylic acid-based dispersion resin (B3-1-1) is a monomer unit containing at least one thermal crosslinkable group selected from the group consisting of a hydroxyl group, an oxetane group, a tert-butyl group, and a block isocyanate group, and a carboxy group It is a dispersion resin containing a containing monomeric unit.

(i-1) [hydroxyl group-containing monomer]

The hydroxyl group-containing monomer is a (meth)acrylate-based monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3) or 4)-hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α- such as ethyl-α-hydroxymethylacrylate hydroxyalkyl acrylate;

A (meth)acrylamide-based monomer having a hydroxyl group, for example, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2- N-(hydroxyalkyl)(meth)acrylamides such as hydroxybutyl)(meth)acrylamide;

Vinyl ether monomers having a hydroxyl group, for example, 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, 2-(or 3- or 4-)hydroxybutyl vinyl ether, etc. hydroxyalkyl vinyl ether;

Allyl ether monomers having a hydroxyl group, for example, 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, 2-(or 3- or 4-)hydroxybutyl allyl ether, etc. Hydroxyalkyl allyl ether is mentioned.

In addition, alkylene to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether Monomers to which oxides and/or lactones are added are also preferred. The alkylene oxide is preferably, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and a combination of two or more of these. Any of random and/or block may be sufficient as the coupling|bonding form at the time of using 2 or more types of alkylene oxide together. As the lactone, for example, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination of two or more of these are used. Both alkylene oxide and lactone may be added.

(i-2) [oxetane group-containing monomer]

Examples of the oxetane group-containing monomer include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl]alkyloxetane. Among them, (3-ethyloxetan-3-yl)methyl methacrylate and the like are preferred. As for a commercial item, ETERNACOLL OXMA ((3-ethyloxetan-3-yl) methyl methacrylate) (made by Ube Industries, Ltd.) is mentioned, for example.

(i-3) [tert-butyl group-containing monomer]

Examples of the t-butyl group-containing monomer include t-butyl methacrylate and t-butyl acrylate.

(i-4) [block isocyanate group-containing monomer]

Block isocyanate group-containing monomers include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylic acid, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. can be heard Commercially available products include, for example, Karenz MOI-BM (methacrylic acid 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl) (manufactured by Showa Denko K.K.), Karenz MOI-BP (2-[( 3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko K.K.); and the like.

The content of the thermally crosslinkable group-containing monomer unit is preferably 5 to 90% by mass, and more preferably 20 to 60% by mass, based on all the monomer units. When it is 5% by mass or more, it becomes possible to obtain a colored composition having excellent resistance due to a crosslinking effect, and when it is 90% by mass or less, the dispersion stability of the composition is improved.

(ii) [Carboxyl Group-Containing Monomer]

Examples of the carboxy group-containing monomer include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among these, (meth)acrylic acid is preferable because of its good copolymerizability and easy availability.

(iii) [other monomers]

Other monomers can be used for the vinyl polymer portion of the carboxylic acid-based dispersion resin (B3-1-1).

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, iso Alkyl (meth)acrylates, such as bornyl (meth)acrylate;

aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate;

Heterocyclic (meth)acrylates, such as tetrahydrofurfuryl (meth)acrylate;

Alkoxy polyalkylene glycol (meth)acrylates, such as methoxy polypropylene glycol (meth)acrylate and ethoxy polyethylene glycol (meth)acrylate;

(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloyl N-substituted (meth)acrylamides such as morpholine;

amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile.

In addition, styrenes such as styrene and α-methyl styrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, vinyl acetate, vinyl propionate, etc. Fatty acid vinyls of are also mentioned.

<<Carboxylic Acid Dispersion Resin (B3-1-2)>>

The carboxylic acid-based dispersion resin (B3-1-2) is a resin having a polymerizable unsaturated group in the vinyl polymer portion.

The method for producing the carboxylic acid-based dispersion resin (B3-1-2) is, for example, glycidyl methacrylate and a polymer having a hydroxyl group or a carboxy group and a reaction product, methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxy group Reactants with and the like can be mentioned. As for carboxylic acid type dispersion resin (B3-1-2), the dispersion resin of Unexamined-Japanese-Patent No. 2011-157416 is mentioned, for example.

[Carboxylic Acid Dispersion Resin (B3-2)]

The carboxylic acid-based dispersion resin (B3-2) is a dispersion resin represented by the following general formula (7), and is specifically, a dispersion resin described in Japanese Unexamined Patent Publication No. 2007-140487.

(HOOC-) _m -R ² -(-COO-[-R ⁴ -COO-] _n -R ⁵ ) _t Formula (7)

(In formula (7), R ² is a tetravalent tetracarboxylic acid compound residue, R ⁵ is a monoalcohol residue, R ⁴ is a lactone residue, m is 2 or 3, n is an integer from 1 to 50, t is (4- m))

[Alkali Soluble Resin (C)]

The coloring composition in this invention contains alkali-soluble resin (C) from a viewpoint of film-formability, coating-film resistance, developability, and pattern formation property.

The alkali-soluble resin (C) is preferably a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed. Moreover, as for transmittance|permeability, 95 % or more is more preferable. The alkali-soluble resin (C) is preferably a thermoplastic resin or an active energy ray-curable resin if classified according to its main curing method. The active energy ray-curable resin preferably has a thermosetting functional group. In addition, alkali-soluble resin (C) can be used individually or in combination of 2 or more types.

The content of the alkali-soluble resin (C) is preferably 2 to 40 parts by mass, and more preferably 5 to 25 parts by mass in 100% by mass of the non-volatile content of the coloring composition from the viewpoint of film formability and resistance of the coating film.

(thermoplastic resin)

Resin species of the thermoplastic resin include, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. can Among these, an acrylic resin having an acidic group, an α-olefin/(anhydride)maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/(anhydride)maleic acid copolymer is preferable, and an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer are more preferable.

(active energy ray curable resin)

The alkali-soluble resin (C) is preferably an active energy ray-curable resin having a polymerizable unsaturated group from the viewpoint of coating film resistance. In particular, by using a resin into which a polymerizable unsaturated group has been introduced by the methods (i) and (ii) shown below, when a coating film is formed by exposure to active energy rays, the resin is three-dimensionally crosslinked, thereby increasing the crosslinking density and increasing the coating film resistance. this gets better

(Method (i))

Method (i) is, for example, an addition reaction of a carboxy group of a monocarboxylic acid monomer having a polymerizable unsaturated group to a side chain epoxy group of a copolymer obtained by copolymerizing an epoxy group-containing monomer and another monomer, and furthermore, to the resulting hydroxyl group, There is a method of introducing a polymerizable unsaturated group and a carboxyl group by reacting a polybasic acid anhydride.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxybutyl (meth)acrylic acid. rate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, from a reactive viewpoint with the monocarboxylic acid monomer of the following process, glycidyl (meth)acrylate is preferable.

Monocarboxylic acid monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, cyano substituents, etc. A monocarboxylic acid etc. are mentioned.

Polybasic acid anhydrides include, for example, tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like, and these may be used alone or in combination of two or more. It is also possible to hydrolyze the remaining anhydride groups using tricarboxylic acid dianhydrides such as trimellitic acid dianhydride or using tetracarboxylic dianhydride such as pyromellitic acid dianhydride as necessary, such as increasing the number of carboxy groups. . Moreover, if tetrahydrophthalic anhydride or maleic anhydride having a polymerizable unsaturated group is used as the polybasic acid anhydride, the polymerizable unsaturated group can be further increased.

As a method similar to method (i), for example, an epoxy group-containing monomer is subjected to an addition reaction to a part of the side chain carboxy group of a copolymer obtained by copolymerizing a monocarboxylic acid monomer and one or more other monomers, thereby adding a polymerizable unsaturated group and a carboxy group. There is a way to introduce

(Method (ii))

As method (ii), there is a method of reacting the isocyanate group of the isocyanate group-containing monomer with the side chain hydroxyl group of a copolymer obtained by copolymerizing a monomer of a monocarboxylic acid monomer or another monomer using a hydroxyl group-containing monomer.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate , hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε- Polyester mono(meth)acrylates to which caprolactone and/or poly12-hydroxystearic acid are added can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the point of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. can be heard

Examples of the monomer constituting the alkali-soluble resin include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate rate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl ( meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxy poly (meth)acrylates such as propylene glycol (meth)acrylate or ethoxypolyethylene glycol (meth)acrylate, or (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N- (meth)acrylamides such as diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, styrene, or styrene such as α-methylstyrene vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.

Alternatively, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy -4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3- Phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4 -Aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate , N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butylate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2- Benzoimidazolyl) phenyl] maleimide, N-substituted maleimides such as 9-maleimide acridine, EO modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylation Phenyl acrylate, ethylene oxide (EO) modified (meth)acrylate of phenol, EO or propylene oxide (PO) modified (meth)acrylate of paracumylphenol, EO modified (meth)acrylate of nonylphenol, nonylphenol PO modified (meth)acrylate etc. are mentioned.

In addition, a carboxy group-containing monomer can be used. Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, ε-caprolactone addition acrylic acid, ε-caprolactone addition methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

In addition, a hydroxyl group-containing monomer can be used. The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate or hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, ( poly) ε-caprolactone, and/or (poly) ester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added; and the like.

Moreover, a phosphoric acid ester group containing monomer is also mentioned. The phosphoric acid ester group-containing monomer is, for example, a monomer obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the hydroxyl group-containing monomer.

Monomers used for the synthesis of alkali-soluble resin (C) may be used singly or in combination of two or more.

Alkali-soluble resin (C) can use together an alkali-soluble resin having a polymerizable unsaturated group and an alkali-soluble resin having no polymerizable unsaturated group in order to adjust the degree of curing of the coating film.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, and more preferably 4,000 or more and 20,000 or less, from the viewpoint of alkali development solubility. Moreover, as for the value of Mw/Mn, 10 or less are preferable. With an appropriate weight average molecular weight (Mw), adhesion to the substrate is improved and solubility in alkali development is improved.

The acid value of the alkali-soluble resin (C) is preferably 80 mgKOH/g to 180 mgKOH/g, more preferably 90 to 170 mgKOH/g, and 95 to 163 mgKOH/g in order to obtain alkali development solubility. this is more preferable An appropriate acid value improves alkali development solubility, reduces residue, improves pattern shape, and improves adhesion to a substrate.

Alkali-soluble resin (C) can be used individually or in combination of 2 or more types.

[Photoinitiator (D)]

The photopolymerization initiator (D) contains at least one kind of photopolymerization initiator selected from the group consisting of general formula (1) and general formula (2), which are oxime ester compounds.

[Tuesday 5]

In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ represents an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and adjacent substituents bond to each other to form an aliphatic ring or An aromatic ring may be formed. R ₄ represents a nitro group, an alkyl group of 20 or less carbon atoms which may have a substituent, an alkoxy group of 20 or less carbon atoms which may have a substituent, or an aryl group of 20 or less carbon atoms which may have a substituent, and is bonded to adjacent substituents, You may form an aliphatic ring or an aromatic ring.

In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent.

Specific examples D-1 to D-9 of the photopolymerization initiator (D) represented by Formula (1) or Formula (2) are shown below. In addition, this invention is not limited to these.

[Table 1]

The symbols in the tables represent Me: methyl group, Et: ethyl group, and Bu: butyl group.

Commercially available products of the photopolymerization initiators represented by the general formulas (1) and (2) are, for example, ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl. ]-, 1-(O-acetyloxime) (IRGACURE OXE02) (manufactured by BASF Japan Ltd.), NCI-831, NCI-930 (all manufactured by ADEKA CORPORATION), TRONLY TR-PBG-304 (Changzhou Tronly New Electronic Materials Co ., manufactured by Ltd.) and the like.

A photoinitiator (D) can be used individually or in combination of 2 or more types.

The content of the photopolymerization initiator (D) is preferably from 0.2 to 20 parts by mass, more preferably from 0.5 to 10 parts by mass, from the viewpoint of photocurability and developability, based on 100% by mass of the non-volatile content of the coloring composition. When it contains an appropriate amount, the adhesiveness of a pattern improves.

[Polymerizable compound (E)]

The polymerizable compound (E) is a monomer (monomer) or an oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (E) include acid group-containing monomers, urethane bond-containing monomers, and other monomers. The number of polymerizable unsaturated groups of the polymerizable compound (E) is one or more, preferably two or more, and more preferably three or more. Moreover, the upper limit of the number of said polymerizable unsaturated groups is 20 pieces.

As for the acid group of an acid group containing monomer, a sulfonic acid group, a carboxy group, a phosphoric acid group, etc. are mentioned.

Examples of acid group-containing monomers include esterified products of poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acids, and dicarboxylic acids; Esterified substances of polyhydric carboxylic acids and monohydroxyalkyl (meth)acrylates, and the like are exemplified. Specific examples include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. monoester products containing free carboxyl groups of monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as the like and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and phthalic acid; Propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, Tricarboxylic acids such as benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Oligoester products containing free carboxy groups with monohydroxy monoacrylates or monohydroxy monomethacrylates such as the like are exemplified.

(urethane bond-containing monomer)

The urethane bond-containing monomer is, for example, polyfunctional urethane acrylate obtained by reacting polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, (meth)acrylate obtained by reacting polyfunctional isocyanate with alcohol and further having a hydroxyl group Polyfunctional urethane acrylate obtained by making a reaction, etc. are mentioned.

(meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Rate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate rate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy group-containing compound and carboxyl ( meth) acrylate reactants, hydroxyl group-containing polyol polyacrylate, and the like.

As for polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc. are mentioned.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, rate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate )Acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylol Propane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, Neo Pentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine Various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid ester, epoxy (meth)acrylate, and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentachloride Erythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned.

Commercially available products of the polymerizable compound (E) are, for example, available from TOAGOSEI CO., LTD. Manufacturing Aronix M309, M321, M350, M315, M305, M450, M408, M400, M402, M510, M520 and the like.

A polymeric compound (E) can be used individually or in combination of 2 or more types.

The content of the polymerizable compound (E) is preferably from 1 to 50% by mass, more preferably from 2 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition.

The average number of functional groups of the polymerizable unsaturated groups of the photopolymerizable monomer (E) is preferably 3 to 5, more preferably 3 to 4. Moreover, 50 mass % or more is preferable in the polymeric compound (E) whole quantity, and, as for content of the polymeric compound of 3-4 average functional groups, 60 mass % or more is more preferable. In addition, the upper limit of the content of the polymerizable compound having 3 to 4 average functional groups is 100% by mass in the total amount of the polymerizable compound (E). When 50 mass % or more of a polymeric compound having an average functional group number of 3 to 4 is contained, the photocurability and developability of the coloring composition are improved.

Examples of the polymerizable compound having an average functional group number of 3 include trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, and EO-modified trimethylolpropane tri(meth)acrylate. PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol triacrylate succinic acid modified product, pentaerythritol triacrylate phthalic acid modified product, Isocyanuric-acid EO modified triacrylate etc. are mentioned.

Examples of the polymerizable compound having an average functional group number of 4 include pentaerythritol tetraacrylate.

(thermosetting compound (F))

The coloring composition of the present invention may further contain a thermosetting compound (F). By including a thermosetting compound, when producing a color filter, it reacts at the time of baking a filter segment, and the crosslinking density of a coating film improves. As a result, heat resistance is improved, pigment aggregation is suppressed during the firing, and coloring power is improved.

Examples of the thermosetting compound (F) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, an epoxy compound and an oxetane compound are preferable.

[Epoxy compound (F-1)]

Epoxy compounds, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde , cinnamaldehyde, etc.), phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl Polymers with diisopropenyl biphenyl, butadiene, isoprene, etc.), polycondensates with phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols ( Polycondensates with benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyl dimethanol, α, α, α', α'-biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls ( α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) polycondensates, polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, Heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like are exemplified.

Commercially available products include, for example, Epikote 807, Epikote 815, Epikote 825, Epikote 827, Epikote 828, Epikote 190P, Epikote 191P (above is a trade name; manufactured by Yuka Shell Epoxy K.K.), Epikote 1004, Epikote 1256 (above is a trade name; JER TECHMORE VG3101L (trade name: manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name: manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name: manufactured by JER), JER 157S65, 157S70 ( Product name: manufactured by JER Corporation), EPPN-201 (brand name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (above product names; manufactured by JER Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN- 1020 (above trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above trade names; manufactured by Daicel Corporation), DENACOL EX-211, 212, 252, 313, 314, 321, 411, 421 . can be heard

The content of the epoxy compound is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass in 100% by mass of the non-volatile matter of the coloring composition. When mixed in an appropriate amount, coloring power and heat resistance are improved.

[Oxetane compound (F-2)]

The said oxetane compound is a compound which has an oxetane group. Examples of the oxetane compound include a monofunctional oxetane compound, a bifunctional oxetane compound, and a trifunctional or higher functional oxetane compound.

The monofunctional oxetane compound is, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxy Methyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane Cetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, etc. are mentioned.

Specific examples include OXE-10 and OXE-30 manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., TOAGOSEI CO., LTD. Manufacture OXT-101, OXT-212, etc. are mentioned.

The bifunctional oxetane compound is, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3- Oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methylether , Di[1-ethyl(3-oxetanyl)]methylether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl- 3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl ]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(3- Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4 -bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) Ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified Hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F(3-ethyl -3-oxetanylmethyl) ether etc. are mentioned.

As a specific example, Ube Industries, Ltd. Manufacturing, OXBP, OXTP, TOAGOSEI CO., LTD. Manufacture OXT-121, OXT-221, etc. are mentioned.

The trifunctional or higher functional oxetane compound, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritolpentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3 -Oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritolpentakis(3-ethyl-3-oxetanylmethyl) ) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (for example, oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) or polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 40 parts by mass, based on 100 parts by mass of the non-volatile matter of the coloring composition. When the content of the oxetane compound is within the above range, an excellent coating film having good water staining and high chemical resistance can be obtained.

A melamine compound refers to the compound which has a melamine ring structure. The melamine compound is preferably a methylol type or an ether type, and a melamine compound having an average of 5.0 or more in the number of methylol groups and/or ether groups per melamine ring is more preferable. When a melamine compound is used in an appropriate amount, coloring power is improved and resistance to N-methylpyrrolidone is also improved.

Commercial products are, for example, NIKALAC MW-30 HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS -001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (manufactured by SANWA CHEMICAL CO., LTD.), CYMEL 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Cytec Industries Inc.), and the like.

Among these, NIKALAC MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS- in which the number of methylol groups and/or ether groups per melamine ring is 5.0 or more on average. 21, MS-11, MW-24X, MX-45 (manufactured by SANWA CHEMICAL CO., LTD.) CYMEL 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Cytec Industries Inc.), etc. It is preferable in terms of increasing the density.

A thermosetting compound (F) can be used individually or in combination of 2 or more types.

(curing agent)

In the coloring composition of the present invention, a curing agent (curing accelerator) may be used in combination as necessary in order to assist curing of the thermosetting compound (F). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. The curing agent may be, for example, an amine compound (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), block isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives, bicyclic amines Deine compounds and salts thereof (e.g. imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole sol, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.) ), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2 -Vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc. ) and the like.

A hardening|curing agent can be used individually or in combination of 2 or more types.

The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (F).

[Organic Solvent (G)]

The coloring composition of the present invention may contain an organic solvent (G).

The organic solvent (G) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3 -Butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3 ,5-trimethylcyclohexanone, 3-ethoxyethylpropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3 -Methoxybutanol, 3-methoxybutylacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n -Butyl alcohol, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-dichlorotoluene Ethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether , ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Methyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl Ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, Methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters and the like can be given. Among these, from the viewpoint of dispersibility of organic pigments and solubility of alkali-soluble resins, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Alcohols, such as glycol acetates, benzyl alcohol, and diacetone alcohol, and ketones, such as cyclohexanone, are preferable.

Organic solvent (G) can be used individually or in combination of 2 or more types.

The viscosity of the coloring composition of the present invention at 25°C is preferably less than 50 mPa·S, more preferably less than 15 mPa·S, and still more preferably 10 mPa·S or less, from the viewpoint of coatability. The viscosity can be adjusted by blending the organic solvent (P) or the like.

[sensitizer (H)]

The photosensitive coloring composition of this invention can contain a sensitizer (H).

The sensitizer (H) is, for example, unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphor-quinone, benzoin derivatives, fluorene derivatives, naphtha polymethine pigments such as toquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives; Cridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporpyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetrapyrine derivatives, anurene derivatives, spiro Pyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or mihiraketone derivatives, α-acyloxyesters, acyloxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrene quinone, camphor-quinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'- Bis (diethylamino) benzophenone etc. are mentioned.

Among these, thioxanthone derivatives, mihiraketone derivatives, and carbazole derivatives are preferable, and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4- Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis( Ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like are more preferable.

A sensitizer (H) can be used individually or in combination of 2 or more types.

Commercially available products include, for example, "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone). Manufactured by Chemark Chemical), etc. are mentioned.

The content of the sensitizer (H) is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (F) from the viewpoint of photocurability and developability.

[Thiol chain transfer agent (I)]

The photosensitive coloring composition may contain a thiol chain transfer agent (I). When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, during radical polymerization after light irradiation, thiol radicals that are less susceptible to inhibition of polymerization by oxygen are generated, and the sensitivity of the photosensitive coloring composition is improved.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). Moreover, as for a thiol type chain transfer agent, what has 4 or more SH groups is more preferable. When the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. Cionate, trimethylolpropanetrithioglycolate, trimethylolpropanetrithiopropionate, trimethylolpropanetris(3-mercaptobutyrate), pentaerythritol tetrakithioglycolate, pentaerythritol tetrakithiopropio nate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N- dibutylamino)-4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane trithiopropionate, and pentaerythritol tetrakisthio Propionate can be mentioned.

A thiol type chain transfer agent can be used individually or in combination of 2 or more types.

1-10 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive coloring composition, and, as for content of a thiol type chain transfer agent, 2-8 mass % is more preferable. When contained in an appropriate amount, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the surface of the film.

[Polymerization inhibitor (J)]

The photosensitive coloring composition may contain a polymerization inhibitor (J). This prevents exposure due to the diffracted light of the mask during photolithography exposure, making it easy to obtain a good pattern shape.

The polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3 -Ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butyl Alkyl catechol compounds such as catechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol; Nol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n- Alkylresorcinol compounds such as butylresorcinol, 2-t-butylresorcinol and 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di- Alkylhydroquinone compounds such as t-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, trioctylphosphine oxide, triphenyl and phosphine oxide compounds such as phosphine oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucine.

As for content of a polymerization inhibitor, 0.01-0.4 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive coloring composition. When an appropriate amount is contained, it becomes easy to obtain a favorable pattern shape.

[Ultraviolet rays absorbent (K)]

The photosensitive coloring composition may contain a ultraviolet absorber (K). The ultraviolet absorber (K) is an organic compound having an ultraviolet ray absorbing function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicyl A rate organic compound etc. are mentioned.

Examples of benzotriazole-based compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2- [2-Hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethylacetate and 95% benzenepropanoic acid, 3-( 2H-benzotriazol2-yl)-(1,1-dimethylethyl)-4-hydroxy, a mixture of C7-9 branched and straight chain alkyl esters, 2-(2H-benzotriazol2-yl)-4, 6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3, 3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2- (2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4 -(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol2-yl) -6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(meta acryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol2-yl)phenyl] propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol2-yl)phenyl]propionate.

Commercial products are made by BASF Japan Ltd. Manufactured by TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA CORPORATION Manufactured by ADEKASTAB LA-29, LA-31 RG, LA-32, LA-36, CHEMIPRO KASEI KAISHA , LTD. Manufactured by KEMISORB71, 73, 74, 79, 279, Otsuka Chemical Co., Ltd. Manufacture RUVA-93 etc. are mentioned.

The triazine compound is, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2 -[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol; The reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester; 2,4-bis "2-hydroxy-4-butoxyphenyl" -6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2 -(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. there is.

Commercial products are CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMISORB 102, BASF Japan Ltd. Manufacture TINUVIN 400, 405, 460, 477, 479, 1577ED, ADEKA ADEKASTAB LA-46, LA-F70, SUN CHEMICAL COMPANY LTD. Manufacture CYASORB UV-1164 etc. are mentioned.

Benzophenone compounds, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 Water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone , 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

Commercial products are CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMISORB 10, 11, 11S, 12, 111, SHIPRO KASEI KAISHA, LTD. Manufactured by SEESORB 101, 107, ADEKA CORPORATION Manufactured by ADEKASTAB 1413, SUN CHEMICAL COMPANY LTD. Manufacture UV-12 etc. are mentioned.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert butylphenyl salicylate.

As for content of a ultraviolet absorber (K), 0.1-10 mass % is preferable in 100 mass % of the non-volatile matter of a coloring composition. When an appropriate amount is contained, it becomes easy to obtain a favorable pattern shape. Moreover, when a sensitizer (H) is included, content of a photoinitiator (F) includes content of a sensitizer (H).

[Antioxidant (L)]

The photosensitive coloring composition may contain an antioxidant (L). The antioxidant can prevent the photopolymerization initiator or thermosetting compound contained in the photosensitive coloring composition from being yellowed due to oxidation by thermal curing or a thermal process when not ITO, thereby suppressing a decrease in transmittance of the film. In particular, when the organic pigment concentration of the photosensitive coloring composition is high, since the content of the photopolymerizable compound (E) is relatively reduced, the film is likely to be yellowed when the amount of the photopolymerization initiator is increased or a combination of a thermosetting compound is used. Therefore, by including an antioxidant, yellowing due to oxidation at the time of a heating process can be prevented, and the fall of the transmittance|permeability of a film can be suppressed.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferable from the viewpoint of coexistence of the transmittance and sensitivity of the coating film.

Hindered phenolic antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4; 6(1H,3H,5H)-trione, 1,1,3-tris(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene -Bis(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5 -Di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)- 2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t- Butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, 3,5-di-t-butyl-4-hydroxybenzylphos Calcium salt of phonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybis Ethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4 -Hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2, 5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2' -methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like.

Commercially available products are ADEKASTAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA CORPORATION, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KEMINOX101, 179, 76, 9425, BASF Japan Ltd. Manufacturing IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, SUN CHEMICAL COMPANY LTD. Manufacture Cyanox CY-1790, CY-2777, etc. are mentioned.

The hindered amine antioxidant is, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) Dill) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine-4 -yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, succinic acid Polycondensate of dimethyl and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3- Tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2 ,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexane Esters of acids, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino} -1,3,5-triazine-2-yl] -4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy) -4-piperidinyl)ester, reaction product of 1,1-dimethylethylhydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5 -bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate, poly[[6-morph Polyno-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6 -tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2, 2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino- and N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

Commercially available products are ADEKASTAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F manufactured by ADEKA CORPORATION. , LA-502XP, CHEMIPRO KASEI KAISHA, LTD. Manufactured by KAMISTAB29, 62, 77, 94, BASF Japan Ltd. Manufacturing Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100, SUN CHEMICAL COMPANY LTD. Production CYASORB UV-3346, UV-3529, UV-3853 and the like.

Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2'-methylene-bis(4 , 6-di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4 ,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4 -Di-t-butylphenyl)-4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl Isooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di( 2,4-di-t-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis( 3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5- Di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl) )-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-dit-butyl-6-methylphenyl) phosphite.

Commercially available products are ADEKASTAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA CORPORATION, and BASF Japan Ltd. Manufactured by IRGAFOS168, Clariant Chemicals Ltd. Manufacture HostanoxP-EPQ etc. are mentioned.

The sulfur-based antioxidant is, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propio nate], 3,3'-thiobispropionate ditridecyl, 2,2-thio-diethylenebis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2 , 4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc. are mentioned.

Commercially available products are ADEKASTAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, CHEMIPRO KASEI KAISHA, LTD. Manufacture KEMINOXPLS etc. are mentioned.

Antioxidant (L) can be used individually or in combination of 2 or more types.

As for content of antioxidant (L), 0.5-5.0 mass % is preferable in 100 mass % of the non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

[Leveling agent (M)]

The photosensitive coloring composition may contain a leveling agent. Accordingly, the wettability to the substrate and the drying property of the film are further improved during film formation. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

A leveling agent (M) can be used individually or in mixture of 2 or more types.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile matter of the photosensitive coloring composition. By being in this range, the coating property of the photosensitive coloring composition, the pattern adhesiveness, and the balance of transmittance improve more.

[Storage Stabilizer (N)]

The photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. The storage stabilizer (N) is, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, Organic phosphines, such as tetraphenyl, phosphite, etc. are mentioned. As for content of a storage stabilizer (N), 0.1-10 mass parts is preferable with respect to 100 mass parts of organic pigments (A).

[adhesion improver (O)]

The photosensitive coloring composition may contain an adhesion improver. As a result, the adhesion between the film and the substrate is further improved. Moreover, it becomes easy to form a pattern with a narrow width by the photolithography method. Adhesion improvers include, for example, silane coupling agents and the like.

Adhesion improver (O), for example, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane Epoxysilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinyl Aminosilanes such as hydrochloride of benzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, p - Styryls such as styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc. Silane coupling agents, such as isocyanates of , are mentioned.

The content of the adhesion improver is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent (A). When an appropriate amount is contained, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is further improved.

<Method for producing colored composition>

The method for producing the colored composition of the present invention is a mixture of a colorant (A), a pigment derivative, a dispersion resin (B), and an alkali-soluble resin (C), followed by two-roll mill, three-roll mill, ball mill, and horizontal sand It can be prepared by dispersing using various dispersing means such as a mill, a vertical sand mill, an annular bead mill, or an attritor. When two or more types of colorants (A) are used, dispersion treatment may be carried out separately. Further, using the colorant (A) and the pigment derivative, micronization treatment may be performed in advance, and dispersion treatment may be performed.

30-200 nm is preferable and, as for the average dispersed particle diameter (secondary particle diameter) of the blue pigment (A1) and the purple pigment (A2) in the coloring composition of this invention, 40-200 nm is more preferable. If it is this range, the photosensitive coloring composition with high dispersion stability will be obtained.

The average dispersed particle diameter (secondary particle diameter) measurement method uses, for example, Nikkiso Co., Ltd. Microtruck UPA-EX150 employing a dynamic light scattering method (FFT power spectrum method), and particle permeability is measured in an absorption mode. , making the particle shape nonspherical and making D50 the average diameter are mentioned. The diluting solvent for measurement is preferable because it is easy to obtain results with little variation when the organic solvent used for dispersion is used and the sample treated with ultrasonic waves is measured immediately after sample preparation.

<Method for producing photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, a dispersion is prepared by dispersing a coloring agent (A), a dispersion resin (B), and the like. Then, the alkali-soluble resin (C), the photopolymerization initiator (D), and the polymerizable compound (E) are blended with the dispersion, and it can be produced by stirring and mixing. In addition, the timing of blending each material is arbitrary. Further, the dispersing step may be performed a plurality of times.

Examples of the disperser that performs the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

The photosensitive coloring composition of the present invention is mixed with coarse particles of 5 µm or more, preferably 1 µm or more, more preferably 0.5 µm or more, by means such as centrifugal separation, filtration with a sinter filter or membrane filter. It is desirable to remove the foreign matter that has been removed. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 micrometer or less.

The content of the coloring agent (A) in the photosensitive coloring composition of the present invention is preferably 45 to 70% by mass, more preferably 46 to 65% by mass, based on 100% by mass of the total non-volatile content, from the viewpoint of developability and thinning. , more preferably 48 to 60% by mass.

The photosensitive coloring composition has a viscosity at 25°C of preferably less than 50 mPa·S, more preferably less than 15 mPa·S, and particularly preferably 10 mPa·S or less, from the viewpoint of coatability.

<Moisture content in the photosensitive coloring composition>

It is preferable that content of the water contained in the photosensitive coloring composition of this invention is 2 mass % or less in the photosensitive coloring composition.

When the content of said water is set, the photosensitive coloring composition is excellent in dispersion stability and sensitivity even after aging storage.

In addition, the content of water contained in the photosensitive coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, and if the moisture content is sufficiently small within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method of producing a photosensitive coloring composition while blowing in a dry inert gas, a method of dehydrating by introducing molecular sieves after production, and the like are exemplified. Among them, a method of manufacturing while blowing a dry inert gas is preferable.

The water content can be measured by known methods such as the Karl Fischer method.

<Amount of toluene in the photosensitive coloring composition>

The photosensitive coloring composition of the present invention may contain toluene. As for content of toluene, 0.1-10 mass ppm is preferable in the photosensitive coloring composition. 9 mass ppm or less is preferable, as for the upper limit of content of toluene, 8 mass ppm or less is more preferable, and 7 mass ppm or less is still more preferable. The lower limit is preferably 0.2 ppm by mass or higher, more preferably 0.3 ppm by mass or higher, and still more preferably 0.4 ppm by mass or higher.

<Color Filter>

The color filter of the present invention includes a substrate and a blue color filter segment formed of a photosensitive coloring composition. It is preferable that the color filter segment used together with the blue color filter segment has a red filter segment and a green filter segment.

The substrate includes a transparent substrate and a reflective substrate. As for a transparent substrate, a glass substrate is mentioned, for example. As for a reflective substrate, the board|substrate using an aluminum electrode or a metal thin film as a reflective surface is mentioned, for example.

[Production method of color filter]

The color filter of the present invention comprises: a step of coating the photosensitive coloring composition of the present invention on a substrate to form a colored layer; a step of exposing the colored layer to light in a pattern through a mask; It can be obtained by the process of forming a colored pattern by doing.

Moreover, you may provide the process of drying the said colored layer (pre-bake process) and the process of thermosetting the said color pattern (post-bake) as needed.

Hereinafter, the manufacturing method of the color filter of this invention is demonstrated in detail.

(Process of forming a colored layer)

In the step of forming a colored layer, the photosensitive coloring composition of the present invention is coated on a substrate by rotary coating, roll coating, slit coating, flow coating, or inkjet coating, and, if necessary, an oven, hot plate, etc. is used, and dried (prebaked) at a temperature of 50 to 120° C. for 10 to 120 seconds.

As for the said board|substrate, the board|substrate in which imaging elements, such as CCD and CMOS, are provided on a glass substrate or a silicon substrate, for example is mentioned. On the board|substrate, you may provide an undercoat layer as needed.

(Process of exposure in pattern form)

In an exposure process, a specific pattern is exposed through a mask using exposure apparatuses, such as a stepper, for example for a colored layer. In this way, a cured film is obtained.

For exposure, for example, ultraviolet rays such as g-line, h-line, and i-line are preferably used.

In addition, as for exposure, the pulse exposure of an ultraviolet-ray is also preferable, as shown below.

<Pulse Exposure of Ultraviolet Rays>

Pulsed exposure of ultraviolet rays includes an excimer laser that generates laser light using a mixed gas of a noble gas such as argon, krypton, or xenon, and a halogen gas such as fluorine or chlorine. Depending on the combination of the type of the mixed gas, the oscillation wavelength is different, and there are 193 nm (ArF), 248 nm (KrF), 308 nm (XeCl), 351 nm (XeF), and the like. Pulse exposure of ultraviolet rays in the present specification is preferably a pulse exposure of an excimer laser with a wavelength of 193 nm (ArF) and 248 nm (KrF), and more preferably 248 nm (KrF). An excimer laser has a pulse width of several tens of ns, a cross section of a beam reflects the shape of a discharge region, and oscillates a rectangular beam with high output. In addition, there are devices that can generate pulse energy up to several thousand mJ. Excimer lasers are used in the field of laser processing because they are suitable for batch processing of a relatively large area with high irradiation intensity, rather than processing that focuses a beam on a single point.

In general, an excimer laser is a laser that uses emission light from excimer molecules that exist in a very short time when a mixed gas is excited, and the ground level of excimer is in a dissociated state. Therefore, since the base molecular density is always zero and it is a very good laser medium, pixels with excellent surface morphology can be formed.

The film thickness of the cured film is preferably 1.0 µm or less, more preferably 0.2 to 0.8 µm, and still more preferably 0.2 to 0.6 µm.

(development process)

By subjecting the cured film to an alkali development treatment, the colored layer of the unirradiated portion in the exposure step is eluted into the aqueous alkali solution, leaving only the cured portion.

The developer is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline , pyrrole, piperidine, and alkaline compounds such as 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developing solution is preferably from 0.001 to 10% by mass, and more preferably from 0.01 to 1% by mass.

11-13 are preferable and, as for the pH of alkaline developing solution, 11.5-12.5 are more preferable. If the alkali concentration is within the above range, the pattern roughness and peeling can be more effectively suppressed, and the remaining film rate can be further improved. In addition, a decrease in the development speed and generation of development residues can be further suppressed.

The developing method includes, for example, a dip method, a spray method, a paddle method, and the like, and the temperature is preferably 15 to 40°C. After alkali development, it is preferable to wash with pure water.

Then, after drying, heat treatment (post-bake) is preferably performed to fully cure the cured film. The heating temperature of post-baking is preferably 100 to 300°C, more preferably 150 to 250°C. Moreover, as for heating time, 2 minutes - about 1 hour are preferable, and 3 minutes - about 30 minutes are more preferable.

The color filter of the present invention can be suitably used for solid-state imaging devices such as CCD and CMOS, and is particularly suitable for high-resolution CCDs and CMOS devices exceeding 1 million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving unit of each pixel constituting a CCD or CMOS and a microlens for condensing light.

<Solid-state imaging device>

The solid-state imaging device of the present invention includes the color filter. The solid-state imaging device of the present invention includes, for example, the following structures.

On a substrate, a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, and the photodiode and the photodiode on the transfer electrode A device protective film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving part on the light-shielding film, and on the device protective film, the color filter of the present invention is a configuration with

Further, a configuration having a concentrating unit (for example, a micro lens, the same applies below) on the device protective layer and below the color filter (closer to the substrate), or a configuration having a condensing unit on the color filter may be used. .

The color filter of the present invention can also be used not only for the solid-state image sensor, but also for image display devices such as liquid crystal display devices and organic EL display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with good color tone and excellent display characteristics.

Example

Hereinafter, Examples and Comparative Examples are shown to explain the present invention in more detail. However, the present invention is not limited to the examples. In addition, "part" is a "mass part", and "%" is a "mass %".

Prior to Examples, each measurement method will be described.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), and amine value (mgKOH/g) of the resin are as follows.

(Average Molecular Weight of Dispersion Resin and Alkali-Soluble Resin)

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the dispersion resin and the alkali-soluble resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by TOSOH CORPORATION) as a device, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two lines for both fillers, and the oven temperature is 40 ° C. Measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent composed of 1 wt% of the above eluent, and 20 microliters of the sample was injected. Molecular weight is a polystyrene conversion value.

(Acid value of dispersion resin and alkali-soluble resin)

80 ml of acetone and 10 ml of water were added to the dispersion resin and 0.5 to 1 g of the alkali-soluble resin solution, stirred to dissolve uniformly, and a 0.1 mol/L KOH aqueous solution was used as a titrant, and an automatic titration apparatus ("COM-555" HIRANUMA Co., Ltd.) was titrated using, and the acid value (mgKOH/g) was measured. Then, the acid value per non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of the non-volatile content of the resin solution.

(amine value of basic dispersion resin)

The amine titer of the basic dispersion resin is a value obtained by converting the non-volatile content of the total (mgKOH/g) measured in accordance with the method of ASTM D 2074.

<Production example of coloring agent (A)>

(micronized phthalocyanine blue pigment (A1-1))

100 parts of phthalocyanine-based blue pigment C.I. Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by TOYOCOLOR CO., LTD.), 800 parts of pulverized salt, and 100 parts of diethylene glycol were mixed with a stainless steel 1 gallon kneader (Inoue Seisakusho Co. , Ltd.), and kneaded at 70°C for 12 hours. This mixture was added to 3000 parts of hot water, stirred with a high-speed mixer for about 1 hour while heating at about 70 ° C to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80 ° C for 24 hours. , 98 parts of blue micronized pigment (A1) was obtained.

(micronized phthalocyanine blue pigment (A1-2))

90 parts of phthalocyanine-based blue pigment C.I. Pigment Blue 15:6 (manufactured by TOYOCOLOR CO., LTD. "LIONOL BLUE ES"), 10 parts of pigment derivative (a-1) represented by formula (8) were added, and pulverized table salt 800 part and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70°C for 12 hours. This mixture was added to 3000 parts of hot water, stirred with a high-speed mixer for about 1 hour while heating at about 70 ° C to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80 ° C for 24 hours. , 98 parts of blue micronized pigment (A1) was obtained.

(micronized dioxazine-based purple pigment (A2))

120 parts of dioxazine-based purple pigment C.I. Pigment Violet 23 ("FastVioletRL" manufactured by Clariant), 1600 parts of pulverized salt, and 100 parts of diethylene glycol were put into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) , and kneaded at 90°C for 18 hours. This mixture was added to 5000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 70 ° C to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then dried at 80 ° C for 24 hours. , 118 parts of purple micronized pigment (A2) were obtained.

(Dye derivative (a))

(a-1):

chemical formula (8)

[Tue 6]

(a-2): Solsperse 5000 (manufactured by Lubrizol Japan Ltd.: phthalocyanine acid color derivative)

<Method for producing basic dispersant (B1)>

(Basic dispersion resin (B1-1) solution)

50 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were introduced into a reaction apparatus equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, and the mixture was heated at 50°C while flowing nitrogen. was stirred for 1 hour, and the inside of the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride and 133 parts of methoxypropyl acetate as catalysts were added, and the temperature was raised to 110° C. under a nitrogen stream to polymerize the first block (block B). Initiated. After polymerization for 4 hours, the polymerization solution was sampled, the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 61 parts of methoxypropyl acetate, 20 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of benzyl chloride salt of dimethylaminoethyl methacrylate were introduced into this reaction apparatus, and the temperature was 110°C. - Stirred while maintaining under a nitrogen atmosphere, and the reaction was continued. After 2 hours from the introduction of dimethylaminoethyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion of the second block (A block) was 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature. The polymerization was stopped by cooling to . As a result of the GPC measurement, the Mw12000 of the polymer and the molecular weight distribution Mw/Mn were 1.2, and the reaction conversion rate was 98.5%. In this way, basic dispersion resin (B1-1) having an amine value per non-volatile matter of 71.4 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate ( PGMAc) was added to prepare an acrylic block copolymer (B1-1) solution.

(Preparation of basic dispersion resin (B1-2 to B1-7) solution)

Except having used the raw materials and charged amount described in Table 2, it synthesize|combined in the same way as (B1-1), and obtained the solution of basic dispersion resin (B1-2) - (B1-7).

The amine value and weight average molecular weight of each basic dispersion resin were as shown in Table 2.

[Table 2]

MMA; Methyl methacrylate

nBA; n-butyl acrylate

HEMA; Hydroxyethyl methacrylate

DM; Dimethylaminoethyl methacrylate

DMAPMA; N,N-Dimethylaminoethyl (meth)acrylamide

LA-82; 1,2,2,6,6-pentamethylpiperidyl methacrylate

DE; Diethylaminoethyl methacrylate

DMC; Benzyl chloride salt of DM

DMAPMAC; Benzyl chloride salt of DMAPMA

LA-82C; Benzyl chloride salt of LA-82C

DEC; Benzyl chloride salt of DE

<Manufacture example of phosphoric acid-based dispersion resin (B2)>

(Phosphoric acid-based dispersion resin (B2-1) solution)

186 parts of lauryl alcohol, 571 parts of ε-caprolactone monomer, and 0.6 part of tetrabutyl titanate were introduced into a reaction vessel equipped with a nitrogen gas introduction pipe, condenser, and stirrer, and after substitution with nitrogen gas, the mixture was heated at 120°C for 3 hours. It was heated and stirred. Disappearance of the caprolactone monomer was confirmed by an RI detector of GPC (gel permeation chromatography) using tetrahydrofuran as an eluent. After cooling to 40°C or lower, it is mixed with 84.5 parts of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, the temperature is gradually raised, and heated at 80°C for 6 hours while stirring, the number average molecular weight of R1 is 760, n=1 and 2 A phosphoric acid-based resin type dispersant (B2-1) having an abundance ratio of 100:12 was obtained. By adjusting the non-volatile content with propylene glycol monomethyl ether acetate, a phosphoric acid-based dispersion resin (B2-1) solution having a non-volatile content of 30% and an acid value per non-volatile content of 166 mgKOH/g was obtained.

(Phosphoric acid-based dispersion resin (B2-2) solution)

A thermometer, cooling pipe, nitrogen gas inlet pipe, and stirring device were attached to a separable four-necked flask, and 1,500 parts of cyclohexanone were added, the temperature was raised to 80 ° C, the inside of the reaction vessel was substituted with nitrogen, and then methyl methacrylate was added in the dropping tube. 120 parts, n-butyl methacrylate 210 parts, 2-hydroxyethyl methacrylate 90 parts, methacrylic acid 60 parts, paracumylphenol ethylene oxide modified acrylate (manufactured by TOAGOSEI CO., LTD. "Aronix M-110 ]) A mixed solution of 120 parts, 6 parts of acid phosphoxyethyl methacrylate, and 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion|finish of dripping, reaction was continued for further 3 hours, and the phosphoric acid type dispersion resin (B2-2) solution of 30% of non-volatile matter and a weight average molecular weight of 24,000 was obtained.

<Manufacture example of carboxylic acid type dispersion resin (B3)>

(Carboxylic acid-based dispersion resin (B3-1) solution)

In a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, methacrylic acid 10 parts, methyl methacrylate 100 parts, i-butyl methacrylate 70 parts, benzyl methacrylate 20 parts, propylene glycol monomethyl ether 50 parts of acetate were introduced and substituted with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. It heated up at 90 degreeC, and reacted for 7 hours, adding the solution which added 0.1 part of 2,2'- azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed that 95% reacted by non-volatile content measurement. 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was heated at 100°C. It was reacted for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and propylene glycol monomethyl ether acetate was added and diluted so that the non-volatile content was 30% by measurement of the non-volatile content, acid value 70 mgKOH / g , A solution of a carboxylic acid-based dispersion resin (B3-1) having a weight average molecular weight of 8,500 was obtained.

(Carboxylic acid-based dispersion resin (B3-2) solution)

62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were introduced into a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, followed by substitution with nitrogen gas. , It heated and stirred at 120 degreeC for 4 hours. After confirming that 98% had reacted by non-volatile matter measurement, 73.3 parts of pyromellitic anhydride was added and it was made to react at 120 degreeC for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydrides were half esterified, and the reaction was terminated. It adjusted with propylene glycol monomethyl ether acetate, and obtained the carboxylic acid type dispersion resin (B3-2) solution of 30% of a non-volatile matter. The acid value of the obtained carboxylic acid-based dispersion resin (B3-2) was 49 mgKOH/g.

(Carboxylic Acid Dispersion Resin (B3-1-1) Solution)

3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of propylene glycol monomethyl ether acetate, dimethylbenzylamine in a reaction tank equipped with a gas inlet pipe, condenser, stirring blades, and thermometer 0.1 part was added. After replacing with nitrogen gas, the inside of the reaction vessel was heated at 120°C to react for 4 hours, and then at 80°C for 2 hours. In addition, 30 parts of tert-butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, 10 parts of propylene glycol monomethyl ether acetate was prepared, and 0.2 part of 2,2'-azobisisobutyronitrile was divided into 15 times and added every 30 minutes while maintaining the inside of the reaction vessel at 80°C. Non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers had reacted. In the non-volatile matter measurement, propylene glycol monomethyl ether acetate was added and diluted so that the non-volatile matter was 30%, and a carboxylic acid-based dispersion resin (B3-1-1 with an acid value of 51 mgKOH / g and a weight average molecular weight (Mw) of 24,000 per non-volatile matter) ) solution was obtained.

(Carboxylic acid-based dispersion resin (B3-1-2) solution)

108 parts of 1-thioglycerol, 174 parts of pyromellitic acid anhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.2 part of monobutyltin oxide as a catalyst were added to a reaction vessel equipped with a gas inlet tube, thermometer, condenser and stirrer, After substituting with nitrogen gas, it was made to react at 120 degreeC for 5 hours (1st process). It was confirmed by the measurement of the acid value that 95% or more of the acid anhydrides were half esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate were added, and the inside of the reaction vessel was heated to 80 ° C. to obtain 2,2'-azobis (2,4-dimethylvalero Nitrile) 1.2 parts were added and it reacted for 12 hours (2nd process). It was confirmed that 95% reacted by non-volatile content measurement. Finally, 500 parts of the 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were added, and IR based on the isocyanate group The reaction was performed until disappearance of the peak at 2270 cm ^-1 was confirmed (third step). After confirmation of peak disappearance, the reaction solution was cooled and adjusted with propylene glycol monomethyl ether acetate to obtain a carboxylic acid-based dispersion resin (B3-1-2) solution containing 30% of a non-volatile matter. As for the acid value of obtained carboxylic acid type dispersion resin (C2-1-2), 1,593 and the weight average molecular weight of 68 mgKOH/g and unsaturated double bond equivalent were 13,000.

<Manufacture example of alkali-soluble resin (C)>

(Preparation of alkali-soluble resin solution (C-1))

196 parts of cyclohexanone was introduced into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was substituted with nitrogen, In the dropping tube, 44.9 parts of n-butyl methacrylate, 15.6 parts of 2-hydroxyethyl methacrylate, 14.5 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by TOAGOSEI CO., LTD.) ) A mixture of 25 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. An alkali-soluble resin solution (C-1) was obtained. The weight average molecular weight (Mw) was 26000.

(Preparation of alkali-soluble resin solution (C-2))

207 parts of cyclohexanone were introduced into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was substituted with nitrogen, In the dropping tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by TOAGOSEI CO., LTD.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, And a mixture of 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, reaction was continued for further 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, after stirring while stopping nitrogen gas and blowing dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.) 6.5 Part, the mixture of 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was dripped at 70 degreeC over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 ° C. for 20 minutes, and the non-volatile content was measured, and cyclohexanone was added so that the non-volatile content was 20% by mass in the previously synthesized resin solution, and alkali-soluble resin A solution (C-2) was prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of alkali-soluble resin (C-3 to C-6) solution)

Except having used the raw materials and charged amount described in Table 3, it synthesize|combined in the same way as (C-1), and obtained the solution of basic dispersion resin (C-3) - (C-6).

[Table 3]

nBA: n-butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

M110: paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by TOAGOSEI CO., LTD.)

MOIs; 2-methacryloyloxyethyl isocyanate

MMA: methyl methacrylate

BzMA; Benzyl methacrylate

MAAs; methacrylic acid

(Preparation of alkali-soluble resin (C-7) solution)

333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet pipe, the atmosphere in the flask was changed from air to nitrogen, the temperature was raised to 100°C, and benzyl meta 70.5 g (0.40 mol) of acrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Company, Ltd.), and A solution obtained by adding 3.6 g of azobisisobutyronitrile to a mixture of 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and further stirring was continued at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0.9 g and 0.145 g of hydroquinone were introduced into the flask, the reaction was continued at 110°C for 6 hours, and the reaction was terminated when the acid value of the nonvolatile matter reached 1 mgKOH/g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added, and it was made to react at 120 degreeC for 3.5 hours, and the photosensitive transparent resin solution of acid value 80 mgKOH/g was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether so that the non-volatile content was 20% by mass in the previously synthesized photosensitive transparent resin solution An alkali-soluble resin (C-7) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 12,000.

(Preparation of alkali-soluble resin (C-8) solution)

35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of V-59 (azo polymerization initiator manufactured by Wako Pure Chemical Corporation) were introduced into a reaction vessel, and the temperature was raised to 80° C. under a nitrogen atmosphere. Then, 6.79 parts of benzyl methacrylate, 5.67 parts of N-phenylmaleimide, 3.38 parts of styrene, and 10.5 parts of methacrylic acid were added dropwise over 2 hours, followed by further stirring for 4 hours to obtain a polymerization reaction liquid. Further, to this polymerization reaction solution, 25.5 parts of propylene glycol monomethyl ether acetate was added, and 0.05 part of p-methoxyphenol and 0.09 part of tetraethylammonium chloride were added and dissolved, and then 10.3 parts of (3,4-epoxycyclohexyl)methyl acrylate Part was added dropwise, and it was made to react at 85 degreeC for 32 hours, and the alkali-soluble resin which has an ethylenically unsaturated group in a side chain was obtained. Next, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass, and an alkali-soluble resin (C-8) solution was obtained. When the weight average molecular weight by GPC of resin P4 obtained in this way was 29000 in terms of polystyrene and further neutralization titration with KOH was performed, the acid value was 100 mgKOH/g. The reaction rate of (3,4-epoxycyclohexyl)methylacrylate with carboxylic acid was 46% by mass from the acid value before and after the reaction.

(Preparation of alkali-soluble resin (C-9) solution)

35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, and 1.5 parts of V-59 (azo polymerization initiator manufactured by Wako Pure Chemical Corporation) were introduced into a reaction vessel, and the temperature was raised to 80° C. under a nitrogen atmosphere. Then, 9.5 parts of benzyl methacrylate, 6.5 parts of methyl methacrylate, 3.5 parts of 2-hydroxyethyl methacrylate, and 10.7 parts of methacrylic acid were added dropwise over 2 hours and stirred for 4 hours to obtain a polymerization reaction liquid. Furthermore, after adding 25.5 parts of propylene glycol monomethyl ether acetate to this polymerization reaction liquid, adding 0.05 part of p-methoxyphenol and 0.3 part of triphenylphosphine and dissolving, 17.5 parts of (3,4-epoxycyclohexyl)methyl acrylate Part was added dropwise, and it was made to react at 85 degreeC for 24 hours, and the alkali-soluble resin (C-9) solution which has an ethylenically unsaturated group in a side chain was obtained. When the weight average molecular weight by GPC of resin P6 obtained in this way was 18000 in terms of polystyrene and further neutralization titration by KOH was performed, the acid value was 50 mgKOH/g. The reaction rate of (3,4-epoxycyclohexyl)methylacrylate with carboxylic acid was 66% by mass from the acid value before and after the reaction.

(Preparation of alkali-soluble resin (C-10) solution)

207 parts of cyclohexanone were introduced into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device in a separable four-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was substituted with nitrogen, In the dropping tube, 37.5 parts of methacrylic acid, 27.5 parts of methyl methacrylate, 5.0 parts of n-butyl methacrylate, 18.0 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile The mixture was added dropwise over 2 hours. After completion of the dropwise addition, reaction was continued for further 3 hours to obtain a copolymer resin solution. Next, with respect to the entire amount of the obtained copolymer solution, after stirring while stopping nitrogen gas and blowing dry air for 1 hour, after cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.) 12.0 Part, the mixture of 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was dripped at 70 degreeC over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution.

After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight, alkali-soluble resin (C-10) A solution was prepared. The acid value was 220 mgKOH/g and the weight average molecular weight (Mw) was 17,600.

Properties of the obtained alkali-soluble resin are shown in Table 4.

[Table 4]

<Preparation of coloring composition>

(Coloring composition (PB-1))

After stirring and mixing the following raw materials to be uniform, using zirconia beads with a diameter of 0.5 mm, dispersed in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) for 3 hours, and then (孔徑) It filtered with a 1.0 micrometer filter, and produced the coloring composition (PB-1). The organic solvent (G-1) is propylene glycol monomethyl ether acetate.

Micronized phthalocyanine blue pigment (A1-1) : 13.5 parts by mass

Pigment Derivative (A3-2) : 1.5 parts by mass

Basic dispersion resin (B1-1) solution : 10.0 parts by mass

Organic solvent (G-1) : 75.0 parts by mass

(Coloring composition (PB-2 to 26))

Coloring compositions (PB-2 to 26) were produced in the same manner as the coloring composition (PB-1), except that the material species and mass were changed as shown in Table 5.

[Table 5]

<Preparation of photosensitive coloring composition>

[Example 1]

(Photosensitive coloring composition (PR-1))

The following raw materials were mixed and stirred, and filtered through a filter having a pore diameter of 1.0 µm to obtain a photosensitive coloring composition (PR-1). Content of a coloring agent (A) is 50 mass % of all non-volatile matter.

Coloring composition (PB-1) : 30.65 parts by mass

Coloring composition (PB-19) : 10.01 parts by mass

Alkali-soluble resin (C-1) solution : 7.19 parts by mass

Photopolymerization initiator (D-1) : 0.75 parts by mass

Photopolymerizable monomer (E-1) : 1.28 parts by mass

Epoxy compound (F-1) : 0.02 parts by mass

Oxetane compound (F-2) : 0.02 parts by mass

Sensitizer (H) : 0.02 parts by mass

Thiol chain transfer agent (I) : 0.02 parts by mass

Polymerization inhibitor (J) : 0.02 parts by mass

UV absorber (K) : 0.02 parts by mass

Antioxidants (L) : 0.02 parts by mass

Leveling agent (M) : 0.67 parts by mass

Storage Stabilizer (N) : 0.02 parts by mass

Silane coupling agent (O) : 0.02 parts by mass

organic solvent (G) : 49.27 parts by mass

[Examples 2 to 63, Comparative Examples 1 to 6]

(Photosensitive coloring composition PR-2 to PR-69)

Photosensitive coloring compositions (PR-2 to 69) were produced in the same manner as in Example 1, except that the material species and mass were changed as shown in Table 6. Content of a coloring agent (A) is 50 mass % of all non-volatile matter.

In addition, about each raw material, it is as follows.

(Photoinitiator (D))

Photopolymerization initiators (D-1) to (D-9): previously described

(D-10) Photopolymerization initiator of formula (2): Irgacure OXE01 (manufactured by BASF Japan Ltd.)

(D-11) photopolymerization initiator of formula (1): TRONLY TR-PBG-345 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.)

(Polymerizable compound (E))

(E-1) trimethylolpropane triacrylate: 3 polymerizable unsaturated groups

[Aronix M309 (manufactured by TOAGOSEI CO., LTD.)]

(E-2) A mixture of dipentaerythritol penta and hexaacrylate: 5 to 6 polymerizable unsaturated groups

[Aronix M402 (manufactured by TOAGOSEI CO., LTD.)]

(E-3) polybasic acidic acrylic oligomer: with carboxy group, 3 polymerizable unsaturated groups

[Aronix M510 (manufactured by TOAGOSEI CO., LTD.)]

(E-4) polybasic acidic acrylic oligomer: with carboxy group, 5 polymerizable unsaturated groups

[Aronix M520 (manufactured by TOAGOSEI CO., LTD.)]

(E-5) caprolactone-modified dipentaerythritol hexaacrylate: 6 polymerizable unsaturated groups

[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(Epoxy compound (F-1))

(F-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2′-bis(hydroxymethyl)-1-butanol

[EHPE-3150 (manufactured by Daicel Corporation)],

(F-1-2) Sorbitol glycidyl etherized epoxy compound

[DENACOL EX611 (manufactured by Nagase Chemtex Corporation)],

(F-1-3) triglycidyl isocyanurate

As described above, (F-1-1) to (F-1-3) were mixed in equal amounts, respectively, to obtain an epoxy compound (F-1).

(oxetane compound (F-2))

3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane

[Aronoxetane OXT-221 (manufactured by TOAGOSEI CO., LTD.)]

(sensitizer (H))

(H-1) 2,4-diethylthioxanthone

[KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]

(H-2) 4,4'-bis (diethylamino) benzophenone

[CHEMARK DEABP (manufactured by Chemark Chemical)]

In the above, (H-1) and (H-2) were mixed in equal amounts, respectively, to obtain a sensitizer (H).

(thiol chain transfer agent (I))

(I-1) Trimethylolethanetris (3-mercaptobutylate)

[TEMB (manufactured by Showa Denko K.K.)]

(I-2) Trimethylolpropanetris (3-mercaptobutylate)

[TPMB (manufactured by Showa Denko K.K.)]

(I-3) pentaerythritol tetrakis (3-mercaptopropionate)

[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]

(I-4) trimethylolpropanetris (3-mercaptopropionate)

[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]

(I-5) tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]

As described above, (I-1) to (I-5) were mixed in equal amounts to obtain a thiol-based chain transfer agent (I).

(Polymerization inhibitor (J))

(J-1) 3-methylcatechol

(J-2) Methylhydroquinone

(J-3) t-butylhydroquinone

As described above, each of (J-1) to (J-3) was mixed in the same amount to obtain a polymerization inhibitor (J).

(ultraviolet ray absorbent (K))

(K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl phenyl) -1,3,5-triazine

[TINUVIN400 (manufactured by BASF Japan Ltd.)]

(K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol

[TINUVIN900 (manufactured by BASF Japan Ltd.)]

As described above, each of (K-1) to (K-2) was mixed in equal amounts to obtain a UV absorber (K).

(Antioxidant (L))

(L-1) pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate

(L-2) dioctadecyl 3,3'-thiodipropanoate

(L-3) tris[2,4-di-(t)-butylphenyl]phosphine

(L-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate

(L-5) p-octylphenyl salicylic acid

In the above, each of (L-1) to (L-5) was mixed in the same amount to obtain an antioxidant (L).

(Leveling agent (M))

(M-1) "BYK-330" manufactured by BYK-Chemie Inc.

(M-2) "MEGAFACE F-551" manufactured by DIC Corporation

(M-3) "EMULGEN 103" manufactured by Kao Corporation

As mentioned above, each 1 part of (M-1) - (M-3) was mixed, and the mixed solution which melt|dissolved in 97 parts of propylene glycol monomethyl ether acetate was used as the leveling agent (M).

(storage stabilizer (N))

(N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol

(“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)

(N-2) triphenylphosphine

("TPP" manufactured by HOKKO SANGYO Co., LTD.)

In the above, (N-1) to (N-2) were mixed in equal amounts to obtain a storage stabilizer (N).

(adhesion improver (O))

(O-1) 3-glycidoxypropyltriethoxysilane

[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

(O-2) 3-methacryloxypropyltriethoxysilane

[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

(O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane

[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

(O-4) 3-mercaptopropyltrimethoxysilane

[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

As described above, (O-1) to (O-4) were mixed in equal amounts to obtain a silane coupling agent (O).

(organic solvent (G))

(G-1) 30 parts of propylene glycol monomethyl ether acetate

(G-2) cyclohexanone 30 parts

(G-3) 10 parts of ethyl 3-ethoxypropionate

(G-4) 10 parts of propylene glycol monomethyl ether

(G-5) 10 parts of cyclohexanol acetate

(G-6) 10 parts of dipropylene glycol methyl ether acetate

In the above, (G-1) to (G-6) were respectively mixed in the above parts by mass to obtain a solvent (G).

[Table 6-1]

[Table 6-2]

<Evaluation of photosensitive coloring composition>

About the obtained photosensitive coloring composition, evaluation regarding viscosity stability, alkali developability, pattern formation property, and exposure change was performed by the following method. Table 6 shows the evaluation results.

(Viscosity stability evaluation)

The initial viscosity on the next day after preparing the photosensitive coloring composition and the viscosity with time at 40 ° C. for 1 week, accelerated over time, were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. It was measured under the same conditions as 50 rpm. From the values of this initial viscosity and the viscosity with the passage of time, the rate of change in viscosity with the passage of time was calculated from the following formula, and the dispersion stability was evaluated. 3 or more can be used without problems in practical use. Formula: [rate of change in viscosity with time] = ｜([initial viscosity] - [viscosity with time])/[initial viscosity]｜ × 100

5: change rate less than 5%

4: change rate of 5% or more and less than 10%

3: change rate of 10% or more and less than 15%

2: change rate of 15% or more and less than 20%

1: change rate of 20% or more

(Evaluation of alkali developability)

On a 6-inch silicon wafer, a resist solution for a planarization film (“HL-18s” manufactured by NIPPON STEEL CORPORATION) was coated by spin coating, heated on a hot plate at 100° C. for 6 minutes, and then heated in an oven at 230° C. for 1 hour. , the coating film was cured to obtain a silicon wafer with a flat film Next, the photosensitive coloring composition was coated on the flattening film by spin coating so that the film thickness after drying was 0.5 μm, and it was applied on a hot plate at 100 ° C. After prebaking for 10 minutes, pattern exposure was performed at an exposure amount of 3000 J/m2 through a photomask for forming 1.0 μm square pixels at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.). The coating film after exposure was subjected to paddle development with an organic alkali developer After paddle development, it was washed with pure water by a spin shower for 20 seconds, the water droplets remaining on the wafer were blown with high-pressure air, the substrate was naturally dried, and square pixels A pattern was formed and the surface of the unexposed portion washed out by development was observed with a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech), and alkali developability was judged by the presence or absence of residues. can be used without problems in practice.

5: No residue at 1 minute development time

4: Residue is slightly visible at 1 minute of developing time

3: A little residue is seen at 1 minute of developing time

2: Residue visible at 1 minute development time

1: Severe residue is seen at 1 minute of developing time

(pattern formation)

Through the photomask of 1.0 micrometer square, the exposure amount performed pattern exposure of 3 levels of 1500 J/m<2>, 3000 J/m<2>, and 4500 J/m<2>. Next, a test substrate was formed in the same procedure as in the above alkali developability test, and pattern pixels were observed with a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Tech). 3 or more can be used without problems in practical use.

5: No pixel defects out of 50 pattern pixels

4: 1 or more but less than 3 pixel defects out of 50 pattern pixels

3: 3 or more but less than 6 pixel defects out of 50 pattern pixels

2: 6 or more but less than 10 pixel defects out of 50 pattern pixels

1: 10 or more pixel defects out of 50 pattern pixels

(adhesion evaluation)

On a 6-inch silicon wafer, a resist liquid for planarization film HL-18s (manufactured by NIPPON STEEL CORPORATION) was applied with a spin coater, and heat treatment was performed on a hot plate at 100° C. for 6 minutes as a prebake. Furthermore, it was treated in an oven at 230°C for 1 hour to cure the coated film to form a 0.5 µm flattening film.

Next, the obtained photosensitive composition was applied onto a silicon wafer with a planarization film by a spin coater, and heat-treated for 1 minute on a hot plate at 100°C as a pre-bake.

Next, using an i-line stepper FPA-5510iZ (manufactured by Canon Inc.), a square pixel pattern mask having mask dimensions of 0.8, 1.2, 1.6, and 2.0 µm squares when forming a pixel pattern was focused through a mask. Exposure was performed at a distance of -0.3 µm, respectively. Exposure was performed at an exposure amount of 1000 J/m 2 . The coated film after exposure was developed for 1 minute with an organic alkali developer OD210 (manufactured by Adeka Corporation), washed with water with a paddle for 1 minute, and the substrate was dried by spin drying. After developing and washing with water, a blue pattern was obtained.

The resulting blue pattern was heat-treated on a hot plate at 230°C for 4 minutes to form a cured film of a blue pattern, and the resolution of the pattern was evaluated according to the following criteria.

5: 0.8 μm pattern remaining (adhering)

4: 1.2 μm pattern remaining (adhering)

3: 1.6 μm pattern remaining (adhering)

2: 2.0 µm pattern remaining (adhering)

1: No pattern remains

[Table 7-1]

[Table 7-2]

Claims (5)

A photosensitive coloring composition for a blue color filter comprising a colorant (A), a dispersion resin (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a polymerizable compound (E),
The colorant (A) contains a blue pigment (A1) and a purple pigment (A2),
The content of the coloring agent (A) is 45% by mass to 70% by mass in the total non-volatile matter,
The dispersion resin (B) includes a dispersion resin (B1) having an amine value of 70 mgKOH/g to 150 mgKOH/g,
The acid value of the alkali-soluble resin (C) is 100 mgKOH/g to 150 mgKOH/g,
The photopolymerization initiator (D) is a photosensitive coloring composition for blue color filters containing at least one kind of photopolymerization initiator selected from the group consisting of the following general formula (1) and general formula (2).
[Tue 1]

(In general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 4 or less carbon atoms. R ₃ is an alkyl group having 20 or less carbon atoms which may have a substituent, and an alkoxy group having 20 or less carbon atoms which may have a substituent represents a group or an aryl group having 20 or less carbon atoms which may have a substituent, which may be bonded to adjacent substituents to form an aliphatic ring or an aromatic ring R ₄ is a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent; A C20 or less alkoxy group which may have a substituent or a C20 or less aryl group which may have a substituent is shown, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring.
In the general formula (2), R ₅ to R ₇ each independently represent an alkyl group having 4 or less carbon atoms which may have a substituent). According to claim 1,
The photosensitive coloring composition for blue color filters in which content of the polymerizable compound having 3 to 4 average functional groups of the polymerizable unsaturated group is 50% by mass or more with respect to the total amount of the polymerizable compound (E). The color filter provided with the blue filter formed from the photosensitive coloring composition for blue color filters of Claim 1 or 2 on a base material. A solid-state imaging device comprising the color filter according to claim 3. A liquid crystal display device comprising the color filter according to claim 3.