TW201344350A - Colored photosensitive composition, color filter and production method thereof, and image display device - Google Patents

Abstract

A colored photosensitive composition is provided, which contains: (A) a dye, (B) a heteroalicyclic blocked isocyanate compound represented by general formula (3) as below, (C) a photopolymerization initiator, (D) a polymerizable compound, and (E) a polyfunctional secondary thiol compound containing two or more mercapto groups in a molecule.

Description

Coloring photosensitive composition, color filter, color filter manufacturing method, and image display device

The present invention relates to a coloring photosensitive composition, a color filter using the colored photosensitive composition, a method of producing a color filter, and a video display device.

In general, a liquid crystal display device is manufactured by separately producing a color filter substrate and a thin film-transistor (TFT) substrate, and sandwiching the liquid crystal to bond them. In this case, the color filter substrate is coated on a color filter (hereinafter also referred to as a color filter layer) formed in a layer shape, and an alignment film such as polyimide which is used to align the liquid crystal is applied. Therefore, the color filter layer must have resistance (NMP resistance) to a solvent having a strong polarity such as N-methylpyrrolidone (NMP) contained in the polyimide resin.

Further, in the color filter, the three colors are independent and the pixels per color are formed in a stripe shape or a mosaic shape. Therefore, a step is generated on the surface of the color filter layer, and therefore a resin film is used on the surface (hereinafter, the film is sometimes used in this case). It is called an "overcoat layer" as a planarization film. The resin film is also required to have NMP resistance similarly to the color filter layer.

In the TFT substrate, if a TFT is formed on the substrate, a step is generated on the surface. Therefore, a resin film (hereinafter referred to as an "interlayer insulating film" in some cases) is flattened thereon, and ITO is formed by a vacuum film forming method such as sputtering or vapor deposition. A film of indium tin oxide, a mixture of indium oxide and tin oxide. Usually, a positive resist is used to pattern ITO as a pixel electrode by photolithography, but at this time, the interlayer insulating film of the underlayer must have etching resistance (acid resistance) in order to etch ITO. . Here, it is more important that ITO is an inorganic substance and the resin film is an organic substance. Therefore, when the resin film is swollen or expanded by the peeling liquid, ITO cannot follow it, and a phenomenon of disconnection occurs. Therefore, it is of course required that the resin film is not peeled off by the peeling liquid, and it is required to be swollen and expanded less. As a stripping liquid (hereinafter sometimes simply referred to as "peeling liquid") used for peeling of the positive resist, a mixture of monoethanolamine (MEA) and dimethyl sulphoxide (DMSO) is used. . Further, since the resin film is sandwiched between the pixel electrode and the TFT, it is charged and becomes a cause of liquid crystal display failure. Therefore, it is an important required characteristic that the resin film is a low dielectric constant material.

Further, in a color filter of a color filter (COA) type, a color filter layer having the function of the interlayer insulating film is formed on the TFT. Therefore, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer are also required to have characteristics required for the interlayer insulating film, that is, low dielectric constant and peeling resistance. In order to meet these required characteristics, A resin coating is provided on the color filter layer as a protective layer.

In general, the NMP resistance used in the evaluation of the color filter is evaluated by the change in chromaticity before and after immersion for 10 minutes at 50 ° C. In contrast, the peeling resistance is due to 80 ° C. The swelling rate after immersion for 2 minutes was evaluated. Therefore, under such conditions, in general, the peeling resistance is strictly evaluated, and it is required to satisfy the peeling resistance.

As described above, in the COA method, in order to directly contact the resin film or the color filter with the pixel semiconductor, a low dielectric constant is required, and the interlayer insulating film also requires a low dielectric constant. In particular, in the COA method, the semiconductor for a pixel is directly in contact with the resin film or the color filter, and therefore it is important to have a low dielectric constant.

On the other hand, as a photosensitive composition for a color filter, a photosensitive composition for a color filter containing a triisocyanuric acid compound has been proposed (for example, see Japanese Patent Laid-Open No. Hei 10-333330 (Patent Document) 1)). The photosensitive composition is excellent in peelability from a cover film or the like, and prevents display unevenness due to stitches. However, in the photosensitive composition, there is also a problem that the peeling resistance of the peeling liquid or the like is low.

Further, as an example of the radically polymerizable compound, a photosensitive resin composition for image formation using a color filter such as a tris(hydroxy)ester of tris(hydroxyethyl)ester is proposed. For example, refer to Japanese Laid-Open Patent Publication No. 2003-177534 (Patent Document 2). However, the photosensitive resin composition is also low in peeling resistance to a peeling liquid or the like, and further improvement is expected.

Further, a photosensitive composition which improves the strength of a coating film after hardening by using a block isocyanate compound having an isomeric cyanate ring is further disclosed (for example, refer to Japanese Patent Laid-Open No. 2001-305726 Bulletin (Patent Document 3)). In addition to the above, a technique of improving heat resistance, chemical resistance, electrical insulation, and the like by using a blocked isocyanate compound is also described. However, for the purpose of solder resist, epoxy or epoxy acrylate is used in the composition, so that the blocked isocyanate is randomly separated from the OH group derived from epoxy or epoxy acrylate when the block is detached. In order to improve the solvent resistance, the solvent resistance is improved, but the low dielectric constant cannot be achieved (for example, refer to Japanese Laid-Open Patent Publication No. Hei 6-295060 (Patent Document 4), Japanese Patent Application Laid-Open No. Hei No. 8-234432 Japanese Patent Publication No. 2003-64236 (Patent Document 6)).

Moreover, with the trend of large-scale panels, 3D, and environmentalism in recent years, the demand for high-transmittance color filters has become very high. As a solution to this problem, attention is paid to dyes, dyes, and pigment blends as colored materials that achieve high transmittance in place of pigments.

For example, as a dye used for a coloring curable composition for a color filter, a pyrrolethymidine dye, a pyrimidine azo dye, a pyrazole azo dye, a dibenzopyran dye, or the like is used. A practical study of a compound of the above-mentioned dye precursors (for example, refer to Japanese Patent Laid-Open Publication No. 2008-292970 (Patent Document 7), Japanese Patent Laid-Open Publication No. 2007-039478 (Patent Document 8), and Japanese Patent Laid-Open No. 6 -230210 (Patent Document 9)).

In the method described in Patent Document 1 to Patent Document 6, when the peeling liquid property, the solvent resistance, and the low dielectric constant when forming a cured film such as an interlayer insulating film are used, the crosslinking density is obtained. When the solvent resistance is improved and the dielectric constant is improved, the dielectric constant is improved, and if the low dielectric constant is to be maintained, the epoxy group is not provided and the crosslinking density is low, so that the solvent resistance is insufficient.

Further, even in the methods described in Patent Documents 7 to 9, dyes generally have a tendency to suppress radical polymerization, and therefore, in a system using radical polymerization as a main curing means, it is easy to cause The dye after film formation caused by insufficient hardening is eluted in various treatment liquids (solvents) (solvent resistance is lowered), or the color shift between layers (effect on dielectric constant).

As described above, the present invention is a polymerizable composition containing a dye-containing resin film or a color filter which is highly resistant to a polar solvent and sufficiently satisfies both the high peeling resistance and the low dielectric constant. It has not been technically established so far.

The present invention has been made in view of the above, and an object thereof is to provide a colored photosensitive composition and a resin having a lower dielectric constant and a higher solvent resistance and peeling resistance than the colored photosensitive composition. a film and a color filter, the coloring photosensitive composition can form a dye containing a coloring material, has a low dielectric constant, and has high resistance to a solvent (including a solvent having a strong polarity) (solvent resistance) and A resin-resistant cured product (especially a resin film or a color filter) which is resistant to peeling liquid, can be cured at a low temperature, can be used to form a high-intensity color filter, and has excellent storage stability, and the object of the present invention is Achieve this goal.

The above problems can be achieved by the following means.

<1> A colored photosensitive composition comprising: (A) a dye, (B) a heteroalicyclic block isocyanate compound represented by the following formula (3), and (C) a photopolymerization initiator; D) a polymerizable compound, and (E) a polyfunctional thiol compound containing two or more thiol groups in one molecule,

In the formula (3), X represents a group derived from a terminal blocking agent, and Y represents a divalent linking group.

The colored photosensitive composition according to the above-mentioned item (1), wherein the (D) polymerizable compound is selected from the group consisting of a polymerizable compound represented by the following formula (1), and the following formula (2) At least one of the group consisting of the polymerizable compounds indicated:

In the general formulae (1) and (2), R ¹ each independently represents a substituent containing an ethylenic double bond, a substituent containing an epoxy group or a substituent having an OH group; and 3 in one molecule At least one of R ¹ represents a substituent containing an ethylenic double bond; and a plurality of R ^{1 's} may be the same or different.

<3> The colored photosensitive composition according to <1>, wherein the blocking agent is selected from the group consisting of methyl ethyl ketone oxime, acetone oxime, cyclohexanone oxime, methyl isobutyl ketone oxime, ε- A group consisting of caprolactam, γ-butylidene and β-propionamide.

<4> The colored photosensitive composition according to <1>, wherein the (A) dye is a metal-substituted compound having a structure represented by the following formula (I) and is coordinated to a metal atom or a metal compound:

In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

<5> The colored photosensitive composition according to <1>, wherein the (A) dye is a metal-substituted compound represented by the following formula (I-3):

In the formula (I-3), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amine group; Ma represents a metal atom or a metal compound; X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an aromatic group) a sulfonyl group, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkyl sulfonate) Amidino or arylsulfonyl), an oxygen atom, a sulfur atom, or a carbon atom; X ⁵ represents a group bondable to Ma, a represents 0, 1, or 2; R ⁸ and Y ¹ may also be bonded to each other The knot forms a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² can also be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

<6> A color filter comprising a coloring layer formed by using the coloring photosensitive composition according to any one of <1> to <5>.

<7> A method of producing a color filter, comprising: a colored layer forming step, wherein the colored photosensitive composition according to any one of <1> to <5> is applied onto a substrate to form a colored layer; In the exposing step, the colored layer is subjected to patterning exposure to form a latent image; and a developing step is performed to develop the colored layer on which the latent image is formed to form a pattern.

<8> An image display device comprising the color filter of <6>.

<9> An image display device comprising the use of any one of <1> to <5> on a substrate for driving a thin film transistor (TFT) liquid crystal display device A pixel formed by the colored photosensitive composition described in the section.

The colored photosensitive composition of the present invention contains (B) a heteroalicyclic block isocyanate compound having a triazine skeleton represented by the formula (3). When the blocked isocyanate compound is thermally hardened during post-baking, the group derived from the blocking agent is dissociated from the blocked isocyanate compound, and thus is derived from the NCO group derived from the blocked isocyanate compound and derived from the coloring. The urethanization reaction between the water contained in the photosensitive composition or the OH group or the like of the polymerizable compound increases the crosslinking density of the cured colored layer. Therefore, in addition to the low dielectric constant derived from the triazine skeleton, further lower dielectric constant is achieved. At the same time, it is presumed that the peeling resistance and solvent resistance are improved by promoting hardening.

However, it is also possible to have both a low dielectric constant and a hardening property in the case where the component (B) is not contained in the coloring photosensitive composition containing a dye. The colored photosensitive composition of the present invention contains (A) a dye and (E) a polyfunctional secondary thiol compound containing two or more mercapto groups in one molecule. The dye functions as a so-called "radical phagosome" which deactivates the generated radical polymerization terminal in the radical polymerization generally used in the photolithography method. Therefore, the exposure sensitivity is lowered, and the coating film cannot be sufficiently cured.

In the colored photosensitive composition of the present invention, this problem can be solved by introducing a thiol compound. The thiol compound generates a sulfur radical by a reaction of extracting hydrogen from a thiol group by a starting radical generated by a photopolymerization initiator, and promotes addition polymerization of an radical (ene-thiol reaction). Reduces the hardening inhibition caused by the dye. Moreover, it is presumed that it is also advantageous for the influence of oxygen suppression. use. However, since the thiol compound has high reactivity, it may cause gelation even if it is darkly reacted in a liquid storage state, but it is presumed that (E) a polyfunctional group containing two or more thiol groups in one molecule is used. The second-order thiol compound can be combined with sensitivity and storage stability.

Therefore, it is presumed that the colored photosensitive composition of the present invention can improve the dyeing of the dye after film formation in various treatment liquids (solvents) due to the poor color tone and color purity of the dye (the solvent resistance is lowered) ), or the problem of color shift between layers (effect on dielectric constant).

In addition, it is presumed that at least one selected from the group consisting of the polymerizable compounds represented by the general formula (1) and the general formula (2) and the (B) general formula are preferable as the (D) polymerizable compound. (3) A combination of a heteroalicyclic block isocyanate compound having a triazine skeleton, which can be subjected to radical polymerization of an ethylenic double bond due to light or heat, and a blocked isocyanate compound by heating When the block is detached, the NCO group is reacted with the ureido group of the OH group of the polymerizable compound to increase the crosslinking density.

According to the present invention, it is possible to provide a coloring photosensitive composition and a resin coating film and a color filter which have a lower dielectric constant and a higher solvent resistance and peeling resistance, which are formed using the colored photosensitive composition. The colored photosensitive composition can form a high-intensity color filter containing a dye as a colored material, and has a low dielectric constant and a higher tolerance to a solvent (including a solvent having a strong polarity) (solvent resistance). Resin-hardened resin (especially resin coating, color filter) Sheet), and excellent storage stability.

1‧‧‧Substrate

2‧‧‧Main electrode

3‧‧‧Protective electrode

4‧‧‧Chromium surface

Fig. 1 is a schematic view showing a main electrode and a guard electrode produced in the measurement of the relative dielectric constant.

<Coloring photosensitive composition>

The colored photosensitive composition of the present invention contains (A) a dye, (B) a heteroalicyclic block isocyanate compound represented by the following formula (3), (C) a photopolymerization initiator, and (D) polymerizability. The compound and (E) a polyfunctional secondary thiol compound containing two or more thiol groups in one molecule may optionally contain other components.

In addition, in the present specification, "~" indicates a range equal to or greater than the lower limit value and equal to or less than the upper limit value. Further, in the expressions in the specification, it is not described that the substituted and unsubstituted expressions also include a group having no substituent and a group having a substituent.

In the present specification, the term "all solids of the coloring photosensitive composition" means a total of the remaining components from which all of the components constituting the coloring photosensitive composition are removed.

Hereinafter, each component constituting the colored photosensitive composition of the present invention will be described in detail.

[(A) Dyes]

The colored photosensitive composition of the present invention contains a dye.

The dye is not particularly limited, and a pyrrolethymethylene group, a pyrazole azo system, an anilino azo system, a triphenylmethane system, an anthraquinone group, an anthrapyridone system, or a benzylidene group can be used as the chemical structure. , oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, dibenzo Dyes such as piperazine, phthalocyanine, benzopyran, and indigo.

Specific examples of such dyes include, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, and JP-A-6-11614. Japanese Patent Publication No. 2,592,207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, Japanese Patent Laid-Open No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-146215, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2002-14221, Japanese Patent Laid-Open No. Publication No. 2002-14222, Japanese Patent Laid-Open Publication No. Publication No. Hei No. Hei No. Hei. No. Hei. Japanese Patent Laid-Open No. 8-179120, Japanese Patent The dye described in JP-A No. 8-151531 or the like.

(The metal complex compound represented by the formula (I) is bonded to a metal atom or a metal compound)

Among the dyes, the dye suitable for the color-sensitive photosensitive composition of the present invention is preferably a metal-substituted compound having a structure represented by the following formula (I) and assigned to a metal atom or a metal compound (hereinafter referred to as "Dipyrromethene-based metal-miscible compound" and "pyrromethene-based dye").

In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

The monovalent substituent represents a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a linear, branched or cyclic alkyl group having a carbon number of 1 to 48, more preferably carbon). a linear, branched or cyclic alkyl group of 1 to 24, such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl , 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl a group, a 1-norbornyl group, a 1-adamantyl group, an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, such as a vinyl group, Allyl, 3-buten-1-yl), aryl (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having a carbon number of 6 to 24, such as phenyl or naphthalene a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2- Furanyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), decylalkyl (preferably carbon number) It is a 3 to 38 decyl group, more preferably a decyl group having a carbon number of 3 to 18, such as a trimethyl decyl group, a triethyl decyl group, a tributyl decyl group, a tert-butyl dimethyl decyl group. , a third hexyl dimethyl decyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having a carbon number of 1 to 48, more preferably an alkane having a carbon number of 1 to 24) An oxy group such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, dodecyloxy, and also cycloalkyloxy, Ring a pentyloxy group, a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having a carbon number of 6 to 48, more preferably an aryloxy group having a carbon number of 6 to 24, such as a phenoxy group, 1 -naphthyloxy),heterocyclicoxy (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazole -5-oxyl, 2-tetrahydropyranyloxy), decyloxy (preferably a decyloxy group having 1 to 32 carbon atoms, more preferably a decyloxy group having 1 to 18 carbon atoms) For example, trimethylnonyloxy, tert-butyldimethylstanoxy, diphenylmethylnonyloxy), mercaptooxy (preferably a decyloxy group having a carbon number of 2 to 48) More preferably, the decyloxy group having a carbon number of 2 to 24, such as an acetyloxy group, a pentyleneoxy group, a benzhydryloxy group, a decyloxy group, or an alkoxycarbonyl group Oxygen (preferably, the carbon number is 2~) An alkoxycarbonyloxy group of 48, more preferably an alkoxycarbonyloxy group having a carbon number of 2 to 24, such as an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and also a naphthenic group. An oxycarbonyloxy group, such as a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having a carbon number of 7 to 32, more preferably a carbon number of 7~) 24 aryloxycarbonyloxy, such as phenoxycarbonyloxy), Aminomethyl methoxyl (preferably an aminomethyl decyloxy group having a carbon number of 1 to 48, more preferably an amine carbaryloxy group having a carbon number of 1 to 24, such as N,N-dimethyl Base amine methyl decyloxy, N-butylamine methyl decyloxy, N-phenylamine methyl decyloxy, N-ethyl-N-phenylamine methyl decyloxy), amine sulfonium sulfonate a oxy group (preferably an sulfonyloxy group having a carbon number of 1 to 32, more preferably an sulfonyloxy group having a carbon number of 1 to 24, such as N,N-diethylamine sulfonate a mercaptooxy group, an N-propylaminesulfonyloxy group, an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having a carbon number of 1 to 38, more preferably a carbon number) Is an alkylsulfonyloxy group of 1 to 24, such as methylsulfonyloxy, hexadecanosulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy (more) Preferred is an arylsulfonyloxy group having a carbon number of 6 to 32, more preferably an arylsulfonyloxy group having a carbon number of 6 to 24, such as a phenylsulfonyloxy group, or a fluorenyl group ( Preferred is a fluorenyl group having a carbon number of from 1 to 48, more preferably a fluorenyl group having a carbon number of from 1 to 24, such as a methyl group, an ethyl group, a pentylene group, a benzamidine group, or a tetradecyl group. Base, cyclohexyl), alkoxycarbonyl ( Preferred are alkoxycarbonyl groups having 2 to 48 carbon atoms, more preferably alkoxycarbonyl groups having 2 to 24 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, Cyclohexyloxycarbonyl, 2,6-di-t-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl (preferably an aryloxycarbonyl group having a carbon number of 7 to 32, more Preferred is an aryloxycarbonyl group having a carbon number of 7 to 24, For example, phenoxycarbonyl), amine carbhydryl (preferably an aminomethyl thiol group having a carbon number of 1 to 48, more preferably an amine carbaryl group having a carbon number of 1 to 24, such as an amine carbaryl group, N,N-diethylamine, fluorenyl, N-ethyl-N-octylamine, decyl, N,N-dibutylamine, N-phenylamine, N-benzene a base amine methyl sulfhydryl group, N-methyl-N-phenylamine methyl sulfonyl group, N,N-dicyclohexylamine methyl fluorenyl group, an amine group (preferably an amine group having a carbon number of 32 or less, more Preferred are amine groups having a carbon number of 24 or less, such as an amine group, a methylamino group, an N,N-dibutylamino group, a tetradecylamino group, a 2-ethylhexylamino group, a cyclohexylamino group. An anilino group (preferably an anilino group having a carbon number of 6 to 32, more preferably an anilino group having a carbon number of 6 to 24, such as an anilino group or an N-methylanilino group) or a heterocyclic amino group ( Preferred are heterocyclic amine groups having 1 to 32 carbon atoms, more preferably heterocyclic amine groups having 1 to 18 carbon atoms, such as 4-pyridylamino group, and carbonamide. Preferred are carboxyamino groups having a carbon number of 2 to 48, more preferably carboguanamine groups having a carbon number of 2 to 24, such as acetaminophen, benzamidine, tetradecylamine, and the like. Pentamidine, cyclohexanide a ureido group (preferably a ureido group having a carbon number of 1 to 32, more preferably a ureido group having a carbon number of 1 to 24, such as a urea group, an N,N-dimethylureido group, or an N- a phenylureido group, a quinone imine group (preferably a quinone imine group having a carbon number of 36 or less, more preferably a quinone imine group having a carbon number of 24 or less, such as an N-succinimide group, N-o-phthalimido), alkoxycarbonylamino (preferably an alkoxycarbonylamino group having a carbon number of 2 to 48, more preferably an alkoxy group having a carbon number of 2 to 24) a carbonylamino group, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group, An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having a carbon number of 7 to 32, more preferably an aryloxycarbonylamino group having a carbon number of 7 to 24, such as a phenoxycarbonyl group; Amino), sulfonamide (preferably a sulfonamide having a carbon number of 1 to 48, more preferably a sulfonamide having a carbon number of 1 to 24, such as methanesulfonamido) Butanesulfonamido, benzenesulfonamido, hexadecanesulfonamido, cyclohexanesulfonamido, aminesulfonylamino (preferably) An amine sulfonylamino group having a carbon number of 1 to 48, more preferably an amine sulfonylamino group having a carbon number of 1 to 24, such as N,N-dipropylamine sulfonylamino group, N -ethyl-N-dodecylamine sulfonylamino), azo (preferably an azo group having a carbon number of 1 to 32, more preferably an azo having a carbon number of 1 to 24) a group such as a phenyl azo group, a 3-pyrazolylazo group, an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkyl group having 1 to 24 carbon atoms) Sulfur-based, such as methylthio, ethylthio, octylthio, cyclohexylthio), arylthio (preferably an arylthio group having a carbon number of 6 to 48, more preferably a carbon number of 6~) 24 arylthio group, such as phenylthio), heterocyclic thio group (preferably a heterocyclic thio group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18) a heterocyclic thio group such as a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group, an alkylsulfinyl group (preferably having a carbon number of 1 to 32) The alkylsulfinyl group, more preferably an alkylsulfinylene group having a carbon number of 1 to 24, such as a dodecylsulfinyl group, or an arylsulfinyl group (preferably, the carbon number is 6 to 32 arylsulfinylene, more preferably an arylsulfinyl group having a carbon number of 6 to 24, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably a carbon number) It is an alkylsulfonyl group of 1 to 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonate. Sulfhydryl, isopropylsulfonyl, 2-ethylhexylsulfonate Further, cetylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl (preferably an arylsulfonyl group having a carbon number of 6 to 48, more preferably An arylsulfonyl group having a carbon number of 6 to 24, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, an aminesulfonyl group (preferably an aminesulfonyl group having a carbon number of 32 or less, more Preferred are sulfonamides having a carbon number of 24 or less, such as sulfonyl, N,N-dipropylamine sulfonyl, N-ethyl-N-dodecylamsulfonyl, N- Ethyl-N-phenylamine sulfonyl, N-cyclohexylamine sulfonyl), sulfo, phosphonyl (preferably a phosphino group having a carbon number of 1 to 32, more preferably It is a phosphonium group having a carbon number of 1 to 24, such as a phenoxyphosphonium group, an octyloxyphosphonium group, a phenylphosphonium group, a phosphinylamino group (preferably a carbon number). It is a phosphinylamino group of 1 to 32, more preferably a phosphinylamino group having a carbon number of 1 to 24, such as a diethoxyphosphinylamino group or a dioctyloxyphosphinyl group. Amine).

When the above monovalent group is a group which can be further substituted, it may be further substituted by any of the above groups. Further, in the case of having two or more substituents, the substituents may be the same or different.

In the formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ may each independently bond to each other to form 5 members, 6 members, or 7 Ring of staff. Further, the ring formed has a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5-, 6-, or 7-membered compounds include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrolidine ring. The piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

In addition, the formed 5, 6 and 7 members of the ring can be further In the case of a substituent, it may be substituted by any of the substituents R; when substituted by two or more substituents, the substituents may be the same or different.

Further, in the case where R ⁷ is a halogen atom, an alkyl group, an aryl group or a heterocyclic group in the formula (I), the preferred range is the same as the above-mentioned halogen atom or alkane of R ¹ to R ⁶ . The preferred ranges of the aryl group, the aryl group or the heterocyclic group are the same.

In the formula (I), as the above R ¹ and R ⁶ , preferred among the above are an alkylamino group, an arylamino group, a carboxy oxime amino group, a ureido group, a quinone imine group, an alkoxycarbonyl group. Amino, sulfonylamino, more preferably carboxy oxime, ureido, alkoxycarbonylamino, sulfonylamino, more preferably carboxy oxime, ureido, alkoxycarbonylamine The sulfonium amide group is preferably a carboxy guanamine group or a ureido group.

In the formula (I), as the above R ² and R ⁵ , preferred among the above are an alkoxycarbonyl group, an aryloxycarbonyl group, an aminecarbamyl group, an alkylsulfonyl group, an arylsulfonyl group, Nitrile group, quinone imine group, amine carbaryl sulfonyl group, more preferably alkoxycarbonyl group, aryloxycarbonyl group, amine carbaryl group, alkyl sulfonyl group, nitrile group, quinone imine group, amine Further, a mercaptosulfonyl group is more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an aminecarbamyl group, a nitrile group, a quinone imido group, an amine formylsulfonyl group, and particularly preferably an alkoxy group. Carbonyl group, aryloxycarbonyl group, amine carbenyl group.

In the formula (I), as the above R ³ and R ⁴ , preferred among the above are substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted. The heterocyclic group is more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.

In the general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic substituted or unsubstituted carbon number of 1 to 12. The alkyl group, more specifically, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, a cyclohexyl group and a benzyl group; more preferably a branched chain having a carbon number of 1 to 12, or a cyclic substituted or unsubstituted alkyl group, and more specifically, for example, an isopropyl group, a cyclopropyl group, Isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl; further more preferably a substituted or unsubstituted alkyl group having a carbon number of 1 to 12, or more, more specific Examples thereof include an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (I), the aryl group in the case where R ³ and R ⁴ represent an aryl group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, more preferably It is a substituted or unsubstituted phenyl group.

When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group preferably includes a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, substituted or unsubstituted. Substituted 3-pyridyl, substituted or unsubstituted 2-pyridyl, substituted or unsubstituted 2-furyl, substituted or unsubstituted 2-pyrimidinyl, substituted or unsubstituted 2-benzothiazolyl, substituted or unsubstituted 1-imidazolyl, substituted or unsubstituted 1-pyrazolyl, substituted or unsubstituted benzotriazol-1-yl, Preferred are exemplified by substituted or unsubstituted 2-thienyl, substituted or unsubstituted 4-pyridyl, substituted or unsubstituted 2-furyl, substituted or unsubstituted 2-pyrimidine Base, substituted or unsubstituted 1-pyridyl.

Next, a metal atom or a metal compound which forms a dipyrromethene-based metal-miscible compound will be described.

As the metal or metal compound, any metal atom or metal compound which can form a complex compound may be any, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. . For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., also includes AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ a metal chloride such as GeCl ₂ , a metal oxide such as TiO or VO, or a metal hydroxide such as Si(OH) ₂ .

Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, and Cu are preferred from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and suitability of the self-aligning compound. , Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, and most preferably Fe, Zn, Cu, Co , B, or VO (V=O). Particularly preferred among these are Zn.

The dipyrromethene-based metal-doped compound in which the compound represented by the above formula (I) is bonded to a metal atom or a metal compound is preferably shown below. That is, in the general formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a cyano group, an alkoxy group, or the like. Aryloxy, heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminemethanyl, amine, anilino, heterocyclic amine, carboxy oxime, ureido, quinone, alkoxycarbonyl Amino, aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, or phosphinium decylamine And R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group or a heterocyclic oxy group. , mercapto, alkoxycarbonyl, aryloxycarbonyl, amine carbaryl, quinone imine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocycle a thio group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group, and each of R ³ and R ⁴ independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or a decane. Base, hydroxyl, cyano, alkoxy, aromatic , heterocyclic oxy, fluorenyl, alkoxycarbonyl, amine carbaryl, anilino, carboxy oxime, ureido, quinone imine, alkoxycarbonylamino, sulfonylamino, azo a base, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an amine sulfonyl group, or a phosphinium fluorenyl group, and R ⁷ represents a hydrogen atom, a halogen atom, or an alkane The group, the aryl group or the heterocyclic group, the metal atom or the metal compound means a form represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO.

A more preferred form of the dipyrromethene-based metal-doped compound is as follows. That is, in the above formula (I), R ¹ and R ⁶ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group or an alkoxycarbonyl group. , Aminomethyl, Amino, Heterocyclic Amine, Carboxylammonium, Urea, Iminoimine, Alkoxycarbonylamino, Aryloxycarbonylamino, Sulfonylamino, Azo, Alkylsulfonyl, arylsulfonyl, or phosphiniumamino, R ² and R ⁵ each independently represent alkyl, alkenyl, aryl, heterocyclyl, cyano, nitro, fluorenyl An alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbenyl group, a fluorenylene group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and R ³ and R ⁴ each independently represent a hydrogen atom. An alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a carbamoylamino group, a ureido group, a quinone imine group, an alkoxycarbonylamino group, Sulfonyl, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, or aminesulfonyl, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group Or a heterocyclic group, a metal atom or a metal compound means Zn Mg, Si, Pt, Pd, Cu, Ni, Co, or form B of VO.

A preferred form of the dipyrromethene-based metal-doped compound in which the compound represented by the above formula (I) is bonded to a metal atom or a metal compound is the following formula (I-1), formula (I) -2) and a compound represented by the formula (I-3).

In the above formula (I-1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group which can be bonded to Ma, and X ² represents a group necessary for neutralizing the charge of Ma. Further, X ¹ and X ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

Formula (I-1) in the R ¹ ~ R ⁶ in the general formula (I), the same meaning as R ¹ ~ R ^6, the preferred shape is also the same.

In the formula (I-1), Ma represents a metal atom or a metal compound, and The metal atom or the metal compound in the "compound compounded with the compound represented by the formula (I) on a metal atom or a metal compound" is synonymous, and the preferred range thereof is also the same.

Formula (I-1) R ⁷ in the general formula (I), the same meaning as R ^7, the preferred shape is also the same.

X ¹ in the formula (I-1) may be any group if it is a group capable of bonding to Ma, and examples thereof include water, alcohol (for example, methanol, ethanol, propanol), and the like, and metal chelate. "[1] Sakaguchi Takeshi, Ueno King Ping (1995, Nanjiang Hall), "Metal Chelate" [2] (1996), "Metal Chelate" [3] (1997), etc. The base of the recited compound. Among them, water, a carboxylic acid compound, an alcohol, an amine compound, and a guanamine compound are preferable in terms of production, and more preferred are water, a carboxylic acid compound, and a guanamine compound.

X ² in the formula (I-1) represents a group necessary for neutralizing the charge of Ma, and represents, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, and an aliphatic quinone imide (for example, Listed as dimercaptoimine, maleimide, pentaneimine, diethylamine, etc., preferably one of the valence groups of succinimide and maleimide, derived from aromatic A quinone imine or a heterocyclic quinone imide (for example, phthalimide, naphthyl imine, 4-bromophthalimide, 4-methylphthalic acid) Amine, 4-nitrophthalimide, naphthyl quinone imine, tetrabromophthalimide, etc., preferably phthalimide, 4-bromo-o-phenylene One of the valence groups of formazan and 4-methylphthalimide derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid) , 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-tert-butyl Benzoic acid or the like, preferably one of benzoic acid, 4-methoxybenzoic acid, salicylic acid, etc.) The base is derived from an aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, acetic acid, propionic acid, lactic acid, pivalic acid, caproic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, ten Diacid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyl octadecanoic acid, 2-hexyl decanoic acid, cyclopentylic acid, cyclohexylcarboxylic acid, 5-nor Terpene-2-carboxylic acid, 1-adamantanic acid, etc., preferably exemplified by one of valence groups of acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, stearic acid, etc. a dithiocarbamic acid (for example, a dimethyl thiocarbamic acid, diethyl dithiocarbamic acid, dibenzyl dithiocarbamic acid) valent group derived from a sulfonamide (Examples include benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide, and methotrexate, Preferably, one of the valent groups of benzenesulfonamide and mesylamine is derived from hydroxamic acid (for example, acetohydroxamic acid, octyl hydroxamic acid, phenyl hydroxamic acid) a valence group derived from a nitrogen-containing ring compound Intrauremone, 1-benzyl-5-ethoxyethyl carbazide, 1-allyl carbendazim, 5,5-diphenylethylene carbazide, 5,5-dimethyl- 2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, 1H-imidazole-4,5- Diethyl diformate, etc., preferably 1-benzyl-5-ethoxyethyl carbazide, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-di One of the valent groups of cyanoimidazole and 1H-imidazole-4,5-dicarboxylic acid diethyl ester.

Among them, in terms of production, preferred are a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic fluorenylene group, a sulfonic acid group, a nitrogen-containing ring compound. More preferably, it is a hydroxyl group, an aliphatic carboxylic acid group, or an aromatic hydrazine. Imino group, nitrogen-containing ring compound.

X ¹ and X ² in the formula (I-1) may be bonded to each other to form a ring of 5 members, 6 members, or 7 members together with Ma. The ring of the 5 members, 6 members, and 7 members formed may be a saturated ring or an unsaturated ring. Further, the ring of 5 members, 6 members, and 7 members may contain only a carbon atom and a hydrogen atom, or may be a hetero ring having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom.

In the above formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently The ground represents a hydrogen atom or a substituent. R ⁷ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound.

Formula (I-2) in the R ¹ ~ R ⁶ in the general formula (I), the same meaning as R ¹ ~ R ^6, the preferred shape is also the same.

The substituent represented by R ⁸ to R ¹³ in the formula (I-2) is synonymous with the substituent represented by R ¹ to R ⁶ of the compound represented by the formula (I), and the preferred embodiment thereof is also the same. When the substituent represented by R ⁸ to R ¹³ of the compound represented by the formula (I-2) is a group which may be further substituted, it may be substituted by any of the substituents R, and may be substituted by two or more. In the case of a substituent substitution, the substituents may be the same or different.

General formula R (I-2) ⁷ in the general formula (I), the same meaning as R ^7, the preferred shape is also the same.

R ¹⁴ in the formula (I-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and a preferred range of R ^{14 is} the same as the preferred range of the above R ⁷ . In the case where R ¹⁴ is a group which may be further substituted, it may be substituted by any of the substituents R, and when substituted by two or more substituents, the substituents may be the same or different.

In the formula (I-2), Ma represents a metal or a metal compound, and is synonymous with a metal atom or a metal compound in the "compound compound of the compound represented by the formula (I) on a metal atom or a metal compound". The preferred range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ in the formula (I-2) may be independently bonded to each other to form 5 members, 6 members, or 7 Saturated ring or unsaturated ring. The saturated or unsaturated ring formed is synonymous with a saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , and preferably the same.

In the above formula (I-3), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, Or a heterocyclic group. R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or Sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur An atom, or a carbon atom. X ⁵ represents a group which can be bonded to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members, or 7 members.

Formula (I-3) in the R ² ~ R ^5, and R ⁷ in the general formula (I), the R ² ~ R ^5, and R ⁷ is synonymous, the preferred shape is also the same.

In the formula (I-3), Ma represents a metal or a metal compound, and is synonymous with a metal atom or a metal compound in which a compound represented by the formula (I) is coordinated to a metal atom or a metal compound. The preferred range is also the same.

In the formula (I-3), R ⁸ and R ⁹ each independently represent an alkyl group (preferably a linear, branched, or cyclic alkyl group having a carbon number of 1 to 36, more preferably carbon). a linear, branched, or cyclic alkyl group of 1 to 12, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethyl a hexyl group, a dodecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, an alkenyl group (preferably an alkenyl group having a carbon number of 2 to 24, more preferably a carbon number of 2 to 12 alkenyl groups such as vinyl, allyl, 3-buten-1-yl), aryl (preferably an aryl group having 6 to 36 carbon atoms, more preferably a carbon number of 6) An aryl group of ~18, such as a phenyl group, a naphthyl group, a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, for example, 2 -thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl And an alkoxy group (preferably an alkoxy group having a carbon number of 1 to 36, more preferably an alkoxy group having a carbon number of 1 to 18, such as a methoxy group, an ethoxy group, a propoxy group, or a butyl group) Oxyl, hexyloxy, 2- a hexyloxy group, a dodecyloxy group, a cyclohexyloxy group, an aryloxy group (preferably an aryloxy group having a carbon number of 6 to 24, more preferably an aryloxy group having a carbon number of 1 to 18) , for example, phenoxy, naphthyloxy), alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably an alkylamino group having 1 to 18 carbon atoms, such as a Amino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, tert-butylamino group, third octylamino group , cyclohexylamino, N,N-diethylamino, N,N-dipropylamino, N,N-dibutylamino, N-methyl-N-ethylamino), aromatic Alkylamino group (preferably an arylamine group having a carbon number of 6 to 36, more preferably an arylamine group having a carbon number of 6 to 18, such as a phenylamino group, a naphthylamino group, N, N a -diphenylamino group, N-ethyl-N-phenylamino group, or a heterocyclic amine group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably a carbon number of 1) a heterocyclic amino group of ~12, such as 2-aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, 3-aminopyridyl).

In the formula (I-3), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a hetero group represented by R ⁸ and R ⁹ . When the cyclic amino group is a group which may be further substituted, it may be substituted by any of the substituents R, and when substituted by two or more substituents, the substituents may be the same or different.

In the formula (I-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom or a sulfur atom. Ra represents a hydrogen atom, an alkyl group (preferably a linear, branched, or cyclic alkyl group having a carbon number of 1 to 36, more preferably a linear or branched chain having a carbon number of 1 to 12, or A cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclo A pentyl group, a cyclohexyl group, a 1-adamantyl group, an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, such as a vinyl group or an allylic group). a group, a 3-buten-1-yl group, an aryl group (preferably an aryl group having a carbon number of 6 to 36, more preferably an aryl group having a carbon number of 6 to 18, such as a phenyl group or a naphthyl group) a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group having 1 to 12 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl , 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), fluorenyl (preferably having a carbon number of 1) More preferably a fluorenyl group of ~24, more preferably a fluorenyl group having a carbon number of 2 to 18, such as an ethyl group, a pentylene group, a 2-ethylhexyl group, a benzamidine group, a cyclohexyl group, or an alkane group. Sulfosyl group The alkylsulfonyl group having a carbon number of 1 to 24, more preferably an alkylsulfonyl group having a carbon number of 1 to 18, such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl a base, a cyclohexylsulfonyl group, an arylsulfonyl group (preferably an arylsulfonyl group having a carbon number of 6 to 24, more preferably an arylsulfonyl group having a carbon number of 6 to 18, for example Phenylsulfonyl, naphthylsulfonyl). Further, in the case where Ra may be substituted, it may be further substituted by a substituent, and when substituted by a plurality of substituents, the substituents may be the same or different.

X ³ and X ^{4 are} preferably each independently an oxygen atom or a sulfur atom, and X ³ and X ^{4 are} particularly preferably all oxygen atoms.

In the formula (I-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom or a carbon atom, and Rb has the same meaning as Ra in the X ³ .

Y ¹ and Y ^{2 are} preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ^{2 are} particularly preferably all NH.

In the formula (I-3), R ⁸ and Y ¹ may be bonded to each other such that R ⁸ , Y ¹ and a carbon atom together form a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxane). Pentane (dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, anthracene, benzofuran, benzothiophene), 6-membered ring (eg cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran) , dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline, or 7-membered ring (eg, cycloglycan) Alkane, hexamethyleneimine).

In the formula (I-3), R ⁹ and Y ² may be bonded to each other such that R ⁹ , Y ² and a carbon atom together form a ring of 5 members, 6 members, or 7 members. The ring of the five members, the six members, and the seven members formed may be a ring in which one of the bonds formed by R ⁸ and Y ¹ and a carbon atom is changed to a double bond.

In the general formula (I-3), when R ⁸ and Y ¹ and R ⁹ and Y ^{2 are} bonded to each other, the ring of 5 members, 6 members, and 7 members is a ring which can be further substituted, and can be When the substituent described in any of the substituents R is substituted by two or more substituents, the substituents may be the same or different.

In the formula (I-3), X ⁵ represents a group which may be bonded to Ma, and examples thereof are the same as those of X ² in the above formula (I-1). a represents 0, 1, or 2.

Preferred embodiments of the compound represented by the formula (I-3) are shown below. That is, R ² to R ⁵ , R ⁷ and Ma are each a preferred form of a complex comprising a compound represented by the formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are each independently NRa. (Ra is a hydrogen atom, an alkyl group, a heterocyclic group), or an oxygen atom, and Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom, or a carbon atom, and X ⁵ is via oxygen. a group in which an atom or a nitrogen atom is bonded, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other. A 5-member or 6-member ring is formed, and R ⁹ and Y ² are bonded to each other to form a 5-member, 6-member ring, and a represents a form of 0 or 1.

A more preferred form of the compound represented by the formula (I-3) is shown below. That is, R ² to R ⁵ , R ⁷ and Ma are each a preferred form of a complex comprising a compound represented by the formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms. Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded via an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ each independently represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Or an alkylamine group, or R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered or 6-membered ring, and a represents a form of 0 or 1.

The above formula (I-1), formula (I-) of the preferred form of the dipyrromethene-based metal-doping compound in which the compound represented by the formula (I) is bonded to a metal atom or a metal compound 2) and the compound represented by the formula (I-3), the compound represented by the above formula (I-3) is a particularly preferable form.

Specific examples of the dipyrromethene-based metal-substituted compound in which the compound represented by the above formula (I) used in the present invention is bonded to a metal atom or a metal compound are shown below. However, the present invention is not limited to these specific examples.

Further, in the exemplified compound 37 to the exemplified compound 39 described below, a/b and a/b/c represent the mass ratio of each constituent component.

In the exemplified compounds of the dipyrromethene-based metal-doping compound in which the compound represented by the formula (I) is bonded to a metal atom or a metal compound, the exemplified compound (40) to the exemplified compound (44) are also a general formula. An exemplary compound of (I-1), the exemplified compound (45) is also an exemplified compound of the formula (I-2), and the exemplified compound (1) to the exemplified compound (39) is also an exemplified compound of the formula (I-3) .

Further, in addition to the above-exemplified compounds, the exemplified compounds (Ia-3) to exemplified compounds (Ia-83) and the exemplified compounds (Ia-1) to exemplified compounds described in JP-A-2008-292970 may be mentioned. (IIa-20), exemplified compound (I-1) to exemplified compound (I-36), exemplified compound (II-1) to exemplified compound (II-11), and exemplified compound (III-1) to exemplified compound ( III-103), exemplified compound (I-1) described in Japanese Patent No. 3324279 The compound (I-1), the exemplified compound (I-13), and the exemplified compound (I-13) described in Japanese Patent Laid-Open No. Hei. No. Hei. -1) to exemplified compound (2-32), exemplified compound (3-1) to exemplified compound (3-32), exemplified compound (4-1) to exemplified compound (4-26), and exemplified compound (5- 1) - exemplified compound (5-26), exemplified compound (I-1) to exemplified compound (I-6) and exemplified compound (VII-1) described in JP-A-2005-77953 The exemplified compound (1-1) to the exemplified compound (1-45) described in Japanese Laid-Open Patent Publication No. Hei 11-352686, and the exemplified in Japanese Patent Laid-Open Publication No. 2000-19729 The compound (1-1) to the exemplified compound (1-50), and the exemplified compound (1-1) to the exemplified compound (1-45) described in JP-A-H11-352685, the formula (I) An example of a dipyrromethene-based metal-doping compound in which a compound represented by a compound is bonded to a metal atom or a metal compound.

The content of the dye (A) contained in the coloring photosensitive composition is preferably 2% by mass or more and 20% by mass or less based on the total stability of the pattern forming property or the coloring composition. It is preferably 2% by mass or more and 15% by mass or less.

(pigment)

The colored photosensitive composition of the present invention may further comprise a pigment as a colorant.

The pigment which can be preferably used in the present invention is exemplified by the following pigments. However, the invention is not limited to these pigments.

C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, CI pigment yellow 5, CI pigment yellow 6, CI pigment yellow 10, CI pigment yellow 11, CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, CI pigment yellow 15, CI pigment yellow 16, CI pigment yellow 17, CI Pigment Yellow 18, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 32, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 35: 1, CI Pigment Yellow 36, CI Pigment Yellow 36:1, CI Pigment Yellow 37, CI Pigment Yellow 37:1, CI Pigment Yellow 40, CI Pigment Yellow 42, CI Pigment Yellow 43, CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61 , CI Pigment Yellow 62, CI Pigment Yellow 63, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 77, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93 , CI Pigment Yellow 94, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109 , CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 115, CI Pigment Yellow 116, CI Yan Yellow 117, CI Pigment Yellow 118, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 123, CI Pigment Yellow 125, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 161, CI Pigment Yellow 162, CI Pigment Yellow 164, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Yellow 168, CI Pigment Yellow 169, CI Pigment Yellow 170, CI Pigment Yellow 171, CI Pigment Yellow 172, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 175, CI Pigment Yellow 176, CI Pigment Yellow 177, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 182, CI Pigment Yellow 185, CI Pigment Yellow 187, CI Pigment Yellow 188, CI Pigment Yellow 193, CI Pigment Yellow 194, CI Pigment Yellow 199, CI Pigment Yellow 213, CI Pigment Yellow 214, CI Pigment Orange 2, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17:1, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 52, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 60, CI Pigment Orange 61, CI Pigment Orange 62, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, etc., CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 14, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 41, CI Pigment Red 48:1, CI Pigment Red 4 8:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49, CI Pigment Red 49:1, CI Pigment Red 49:2, CI Pigment Red 52:1, CI Pigment Red 52:2 , CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 60:1, CI Pigment Red 63:1, CI Pigment Red 66, CI Pigment Red 67, CI Pigment Red 81:1, CI Pigment Red 81 : 2, CI Pigment Red 81:3, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90, CI Pigment Red 105, CI Pigment Red 112, CI Pigment Red 119, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 169, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 200, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 210, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 246, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 279, CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58, CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, CI Pigment Violet 37, CI Pigment Violet 42, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1 , CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, C.I. Pigment Blue 66, C.I. Pigment Blue 79, C.I. Pigment Blue 80, C.I. Pigment Black 1.

In particular, the colored photosensitive composition of the present invention comprises a metal-substituted compound having a structure represented by the above formula (I) and which is coordinated to a metal atom or a metal compound, that is, a dipyrromethene-based metal-containing compound as a dye. In the case of forming a blue coloring pattern, it is preferred to contain a blue pigment, in which case It is preferred to contain a phthalocyanine blue pigment as a pigment.

Suitable phthalocyanine blue pigments include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 75, and CI Pigment Blue 79, and the like. Among them, C.I. Pigment Blue 15:6 is excellent in heat resistance, light resistance, and contrast, and can be used more suitably.

The content of the pigment used in the coloring photosensitive composition of the present invention is preferably 20% by mass or more and 90% by mass or less, and more preferably 40% by mass or more based on the total content of the dye and the pigment. 70% by mass or less. By setting it as the range, the coloring photosensitive composition which is low in dielectric constant, and it is excellent in peeling liquid resistance and solvent resistance can be acquired, without the effect of this invention.

Further, in the colored photosensitive composition of the present invention, in addition to the phthalocyanine-based blue pigment, a violet pigment may be contained as a pigment for adjusting the chromaticity. By including a purple pigment, a deep blue color capable of achieving a high NTSC ratio can be provided.

As the purple pigment, C.I. Pigment Violet 19, C.I. Pigment Violet 23, and C.I. Pigment Violet 32 can be used. Among them, C.I. Pigment Violet 23 is more preferable from the viewpoints of obtaining brightness, light resistance, heat resistance, and high contrast.

The total content of the coloring agent of the dye (A) and the pigment is preferably 5% by mass or more and 40% by mass or less, more preferably 5% by mass or more, based on the total mass of the coloring photosensitive composition. Below mass%. By setting it as this range, it becomes easy to obtain the desired chromaticity, brightness, and film thickness.

(coated pigment)

The pigment used in the present invention is an organic pigment, and in the step of refining or dispersing the organic pigment, it is preferred to use a pigment obtained by coating an organic pigment with a polymer compound.

By coating the pigment with the polymer compound, the formation of the secondary aggregates is suppressed in the finely divided pigment, and the particles can be dispersed in the state of the primary particles. In other words, the dispersibility of the coated pigment is improved, and the dispersion stability of the dispersed primary particles is stably maintained.

Regarding the coating method of the polymer compound or the pigment used in the coating pigment, it is more preferable to use the treatment method described in paragraph number [0025] to paragraph number [0078] of JP-A-2009-1441269. And polymer compounds.

In the present invention, the pigment is preferably used by dispersing a pigment using at least one of dispersing agents to form a pigment dispersion composition. The same applies to the case of using the coated pigment as described above. By using the dispersant, the dispersibility of the pigment can be improved.

As the dispersant, for example, a known pigment dispersant or a surfactant can be suitably used.

Specific examples of the dispersant include a plurality of compounds, and examples thereof include an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic (co) polymer Polyflow No. 75, and a Polyflow No. .90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxygen Vinyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Nonionic surfactant such as sorbitan fatty acid ester; anionic surfactant such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100 EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by Sannopu Co., Ltd.) ) Polymer dispersants; Solsperse 3000, Solsperse 5000, Solsperse 9000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000 and other Solsperse dispersants (manufactured by Lubrizol Corporation, Japan) ); Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L7 2. Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123 (Manufactured by Asahi Chemical Co., Ltd. And IONNET S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, Disperbyk 103, Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 111, Disperbyk 112, Disperbyk 116, Disperbyk 130, Disperbyk 140, Disperbyk 142, Disperbyk 162 , Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 167, Disperbyk 170, Disperbyk 171, Disperbyk 174, Disperbyk 176, Disperbyk 180, Disperbyk 182, Disperbyk 2000, Disperbyk 2001, Disperbyk 2050, Disperbyk 2150 (Manufactured by BYK-CHEMIE) .

Other than this, an acryl-based copolymer is exemplified as an oligomer or a polymer having a polar group at a molecular terminal or a side chain.

The content of the dispersant is preferably from 1% by mass to 100% by mass, and more preferably from 3% by mass to 70% by mass based on the mass of the pigment.

Further, in view of the pigment dispersibility, it is preferred to prepare a pigment dispersion composition containing a pigment and a dispersant in advance when a pigment is added to the coloring photosensitive composition, and to disperse the pigment; A pigment derivative may be added as needed.

A pigment derivative into which a moiety having a affinity for a dispersing agent or a polar group is introduced is adsorbed on a surface of a pigment, and is used as a site of adsorption of a dispersing agent, whereby the pigment is dispersed in a state of fine particles in a pigment dispersion composition. . The colored photosensitive composition containing such a pigment dispersion composition can prevent re-agglomeration of the pigment, and therefore is effective in forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a matrix and an acidic group or a basic group or an aromatic group is introduced as a substituent in the matrix.

Specific examples of the organic pigment to be the parent skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoporphyrin pigments, and isoindolinones. Pigment, quinoline pigment, diketopylp Pyrrole pyrrole pigment, benzimidazolone pigment, and the like. Further, in general, a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a triazine or a quinoline which is not called a dye may be used as a matrix.

For the pigment derivative, Japanese Patent Laid-Open No. Hei 11-49974, Japanese Patent Laid-Open No. Hei 11-189732, Japanese Patent Laid-Open No. Hei 10-245501, Japanese Patent Laid-Open No. Hei. No. Hei. The pigments described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. derivative.

The content of the pigment derivative in the pigment dispersion composition is preferably from 1% by mass to 30% by mass, and more preferably from 3% by mass to 20% by mass based on the mass of the pigment. When the content is within the above range, the dispersion can be favorably dispersed while suppressing the viscosity, and the dispersion stability after dispersion can be improved. As a result, the colored photosensitive composition containing such a pigment dispersion composition has high transmittance, excellent color characteristics, and is suitable for producing a high-contrast color filter having good color characteristics.

The method of dispersing the pigment can be carried out, for example, by preliminarily mixing the pigment with a dispersing agent using a particle dispersing machine or the like, and then performing microdispersion by pre-dispersing with a homogenizer or the like, wherein the particle dispersing machine uses oxidation. Zirconium particles and the like.

[(B) Heteroalicyclic Block Isocyanate Compound]

The colored photosensitive composition of the present invention contains at least one of the heteroalicyclic block isocyanate compounds represented by the formula (3).

The heteroalicyclic block isocyanate compound is a compound in which three isocyanate groups (NCO groups) are blocked by a blocking agent, which contributes to a large degree of low dielectric constant, and blocks when thermally hardened. By detaching, the cross-linking reaction of the NCO group of the block and the OH group in the system (preferably, the OH group of the polymerizable compound) is released to increase the crosslinking density, and the peeling resistance can be more effectively performed. Liquid and solvent resistance are improved.

In the formula (3), X represents a group derived from a blocking agent. That is, it means that the hydrogen atom of the blocking agent is separated from one monovalent substituent which forms a bonding bond. Examples of the blocking agent include phenols, alcohols, decylamines, anthraquinones, diketones, thiols, ureas, imidazoles, esters (including urethanes), quinones, and amines. , indoleamines, diketones, etc. Among them, oximes and indoleamines are preferred from the viewpoints of storage stability and stability during prebaking.

Examples of the hydrazines include methyl ethyl ketone oxime, acetone oxime, cyclohexanone oxime, methyl isobutyl ketone oxime, etc., and examples of the internal guanamines are exemplified by ε-caprolactam. , γ-butyrolactam, β-propionalamine, etc., X may be derived from the capping agents The basis. Further, specific examples of the group derived from the terminal blocking agent include the following groups.

In the above formula, R ³ and R ⁴ are terminal groups constituting a group derived from ketoxime, and the ketone oxime is formed by a ketone structure represented by R ³ COR ⁴ , and the temperature at which the block is detached is determined by a ketoxime structure. Therefore, it is preferred to select it in consideration of stability or actual reaction temperature and the like. R ³ and R ^{4 are} derived from a blocking agent and are different, and examples thereof include a methyl group, an ethyl group, an isobutyl group, and a cyclohexyl group.

In the above formula (3), Y represents a divalent linking group. Examples of the divalent linking group represented by Y include a chain alkyl group, a cyclic alkyl group, an extended aryl group, and a divalent linking group obtained by combining these groups. The cyclic alkyl group and the extended aryl group may have a substituent. Specific examples include the following groups [(e-1) to (e-12)] and the like.

n: 1~10

The divalent linking group is preferably an aliphatic group or an alicyclic group in terms of heat-resistant discoloration and light resistance, and more preferably (e-1) or (e). -4), (e-6), (e-10), (e-11).

The heteroalicyclic block isocyanate compound represented by the above formula (3) is preferably a compound represented by the following formula (4).

In the above formula (4), R ² is a linking group of a diisocyanate forming OCN-R ² -NCO, and is synonymous with Y of the above formula (3). As the R ² , an aliphatic group or an alicyclic group is preferable in terms of light resistance and heat discoloration, and the aliphatic group, the alicyclic group and the Y of the above formula (3) are suitable. The aliphatic group or the alicyclic group represented by the same meaning (except for the above (e-1), (e-4), (e-6), (e-10) or (e-11)).

R ³ and R ⁴ are terminal groups constituting a group derived from ketoxime which is formed by a ketone structure represented by R ³ COR ⁴ , and a temperature at which the block is detached is determined by a ketone oxime structure, and therefore it is preferred. It is selected in consideration of stability or actual reaction temperature and the like. R ³ and R ^{4 are} derived from a blocking agent and are different, and examples thereof include a methyl group, an ethyl group, an isobutyl group, and a cyclohexyl group.

For example, using C as a solvent together with the methyl ethyl ketone oxime described above In a system such as diol monomethyl ether acetate, the temperature at which the block of methyl ethyl ketone oxime is separated is similar to the boiling point of the solvent, so that when the block is detached, it is evaporated together with the solvent, and the NCO group and the OH group can be made. The binding reaction proceeds rapidly.

Further, n represents an integer of 1 or more, and is preferably a low molecular weight in terms of developability or resolution, and is preferably an integer of 1 to 5. However, in the case of being constituted only by thermal hardening, developability and resolution are not problematic, and thus it is not necessary to be limited as described above.

Specific examples of the heteroalicyclic block isocyanate compound represented by the above formula (3) are shown below. However, it is not limited by these specific examples in the present invention.

The synthesis of the heteroalicyclic block isocyanate compound represented by the above formula (3) or (4) can be carried out by using a conventionally known method to have the formula (3) Or a three-isocyanate (NCO group) heteroalicyclic isocyanate compound having a structure corresponding to the formula (4) and a blocking agent. The amount of the blocking agent added is usually 1 equivalent or more and 2 equivalents or less, preferably 1.05 equivalent to 1.5 equivalents, per equivalent of the isocyanate group.

The content of the heteroalicyclic block isocyanate compound in the coloring photosensitive composition is preferably from 2% by mass to 70% by mass, and more preferably 5% by mass, based on the total mass of the coloring photosensitive composition. ~50% by mass. When the content is less than 2% by mass, the effect of improving the crosslinking density is small, and the peeling liquid resistance and the solvent resistance are insufficient, and when it exceeds 70% by mass, the development property or the resolution is generated. Inappropriate phenomenon.

Further, the amount of the heteroalicyclic block isocyanate compound is such that the number of NCO groups derived therefrom is the same as the number of OH groups contained in the polymerizable compound used in combination, or the number of all OH groups in the system. Alternatively, when the content of the heteroalicyclic block isocyanate compound is large, it is indispensable to increase the content of the OH-containing polymerizable compound.

[(C) Photopolymerization initiator]

The colored photosensitive composition of the present invention contains (C) a photopolymerization initiator.

The photopolymerization initiator is a compound which decomposes by light, and which initiates and promotes polymerization of the (D) polymerizable compound described later, and preferably has a sensitivity at a wavelength of ultraviolet rays.

The photopolymerization initiator is preferably a photopolymerization initiator having absorption at an exposure wavelength of ultraviolet rays, and may be used in combination with a sensitizing dye described later even when ultraviolet rays are not absorbed at a wavelength of ultraviolet rays. It has sensitivity at the wavelength of ultraviolet light. Further, the photopolymerization initiator may be used singly or in combination of two or more.

The photopolymerization initiator used in the present invention may, for example, be an organic halogenated compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxidation compound, an azo compound or a coumarin compound. An azide compound, a metallocene compound, a hexaaryldiimidazole compound, an organoboric acid compound, a disulfonic acid compound, an oxime ester compound, a phosphonium salt compound, a mercaptophosphine (oxide) compound.

Specific examples of the organic halogenated compound include, for example, "National Chemical Society Bulletin (Bull Chem. Soc. Japan)" 42, 2924 (1969), U.S. Patent No. 3,905,815, and Japanese Patent Publication No. Sho 46-4605. Japanese Patent Laid-Open No. Sho-48-36281, Japanese Patent Laid-Open Publication No. SHO-55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent Laid-Open No. 61-169835, and Japanese Patent Laid-Open No. 61 Japanese Laid-Open Patent Publication No. SHO-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and JP-A-63-298339 The compound described in the "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970), and the like, in particular, may be exemplified by a trihalomethyl group-substituted oxazole compound or a s-triazine compound.

Examples of the carbonyl compound include benzophenone and Michler's (Michler's). Ketone), 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxyl a benzophenone derivative such as benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2 -methyl-1-(4'-(methylthio)phenyl)-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl) Phenyl)-butanone-1,2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, 1,1,1-trichloromethyl-(p-butylphenyl)one, Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinyl phenylbutanone, thioxanthone, 2-ethyl thioxanthone, 2-isopropyl Thiolone, 2-chlorothiazinone, 2,4-dimethylthiaxanone, 2,4-diethylthiaxanone, 2,4-diisopropylthiaxanone, etc. A thioxanthone derivative, a paraben derivative such as p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester.

Examples of the hexaarylbiimidazole compound include various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Is 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5, 5'-tetraphenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (ortho) Chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(ortho-o-dichlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (neighbor Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole Wait.

The oxime ester compound can be listed in the British Chemical Society, JC Perkin II (1979) 1653-1660, British Chemical Society, JC Perkin II (1979) 156-162, photopolymer Compounds described in Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Laid-Open Publication No. 2000-66385, Japanese Patent Laid-Open Publication No. 2000-80068, and Japanese Patent Publication No. 2004- A compound or the like described in Japanese Patent No. 534797. As a specific example, Irgacure OXE-01, Irgacure OXE-02, etc. manufactured by Ciba Specialty Chemicals Co., Ltd. are suitable.

As a photopolymerization initiator, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzil dimethyl ketal compound, an α-hydroxyketone compound, An α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, a metallocene compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzothiazole compound, and a benzophenone system a group consisting of a compound, an acetophenone-based compound and a derivative thereof, a cyclopentadiene-benzene-iron complex compound and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound Compound.

More preferably, it is a trihalomethyltriazine-based compound, an α-aminoketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, and a diphenyl group. The ketone-based compound and the acetophenone-based compound are preferably selected from the group consisting of a trihalomethyltriazine-based compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone. A compound of at least one group consisting of compounds.

Hereinafter, the details of the oxime compound which is preferably used as a polymerization initiator in the present invention will be described.

The oxime compound which is preferable as a polymerization initiator in the present invention is an oxime ester compound represented by the following formula (5) or (6).

Further, in the present invention, the oxime ester compound as a photopolymerization initiator is preferably a compound represented by the following formula (A) from the viewpoints of self-sensitivity, stability over time, and coloration at the time of post-heating. .

In the formula (A), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ¹ represents -R, -OR, -COR, -SR, -CONRR', or -CN, R ² and R ³ each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these groups may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, the alkane One or more of the carbon atoms constituting the alkyl chain in the group and the aralkyl group may be substituted with an unsaturated bond, an ether bond or an ester bond, and R and R' may be bonded to each other to form a ring.

In the general formula (A), when the halogen atom in the case where X ¹ , X ² and X ³ represent a halogen atom, fluorine, chlorine, bromine or iodine, and X ¹ , X ² and X ³ represent an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a third pentyl group, and a hexyl group. Heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, C Alkynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxy A propyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, a perfluoroethyl group, a 2-(benzoxazole-2'-yl)vinyl group, and the like.

It is preferred that X ¹ , X ² and X ³ each represent a hydrogen atom, or X ¹ represents an alkyl group, and X ² and X ³ each represent a hydrogen atom.

In the general formula (A), the alkyl group represented by R and R' may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group or a butyl group. Base, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl , allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy , propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole- 2'-based) vinyl and the like.

Examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

Examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group.

Examples of the heterocyclic group represented by R and R' include a pyridyl group, a pyrimidinyl group, a furyl group, and a thienyl group.

Further, examples of the ring formed by bonding R and R' to each other include a piperidine ring and a morpholine ring.

Particularly preferred forms of R ² and R ³ which comprise R and R' described above are methyl, hexyl, cyclohexyl, -S-Ph, -S-Ph-Cl, and -S-Ph-Br, respectively. .

In the photopolymerization initiator, in the formula (A), a compound in which X ¹ , X ² and X ³ are each a hydrogen atom; R ¹ is a compound of an alkyl group, particularly a methyl group; and R ² is an alkyl group. In particular, a compound of a methyl group; and a compound wherein R ³ is an alkyl group, particularly an ethyl group, is particularly suitable as a photopolymerization initiator.

Therefore, preferred examples of the photopolymerization initiator represented by the above formula (A) include the compounds A to G exemplified below. However, the present invention is not limited by any of the following compounds.

The photopolymerization initiator represented by the formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

The compound represented by the formula (A) used in the present invention has an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a compound having an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly preferred are compounds with high absorbance at 308 nm and 355 nm.

The content of the (C) photopolymerization initiator is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 15% by mass, based on all the solid matter in the coloring photosensitive composition. Preferably, it is 3 mass% to 15 mass%. If it is this range, good sensitivity and pattern formation property can be obtained.

[(D) Polymerizable Compound]

The colored photosensitive composition of the present invention contains at least one of (D) a polymerizable compound.

Thus, the colored photosensitive composition of the present invention has a suitable hardening property. Sex.

The polymerizable compound which can be used in the present invention is a compound widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. Such compounds have, for example, the following chemical forms: monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Furthermore, it is preferable that the polymerizable compound is selected from the polymerizable compound represented by the formula (1) and the polymerizable property represented by the formula (2), which are described later, from the viewpoints of the liquid resistance and the solvent resistance. At least one of the compounds.

As an example of a monomer and a copolymer thereof, an ester or unsaturated of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) and an aliphatic polyol compound is used. An amide of a carboxylic acid and an aliphatic polyamine compound. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product of a polyfunctional isocyanate or an epoxy group, and a polyfunctional carboxy group can also be suitably used. An acid dehydration condensation reaction product or the like. Further, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an addition reaction product of a guanamine and a polyfunctional alcohol, an amine or a thiol, or a halogen group or A substituted carboxylic acid ester such as a toluenesulfonyloxy group or a substituted carboxylic acid ester of a decylamine and a polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like may be used instead of the above unsaturated carboxylic acid.

As a specific example of a monomer of an aliphatic polyol compound and an ester of an unsaturated carboxylic acid, an acrylate is present: ethylene glycol diacrylate, triethylene glycol dipropylene Acid ester, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, three Methylolpropane tris(propylene decyloxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol II Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate , sorbitol hexaacrylate, tris(propylene decyloxyethyl)isocyanate, polyester acrylate oligomer, ethylene oxide (EO) modification Triacrylate and the like.

The methacrylate is extended with butanediol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trishydroxyl Ethylene ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethyl Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [pair (3 -Methylacryloyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloyloxyethoxy)phenyl]dimethylmethane, and the like.

Iconic acid esters are ethylene glycol diconconate, propylene glycol diconconate, 1,3-butanediol diconconate, 1,4-butanediol diconcanate, and butyl Diol diconconate, pentaerythritol diconconate, sorbitol tetraconcanate, and the like. Butenoic acid esters include ethylene glycol bis-butyrate, butanediol dimethyl acrylate, pentaerythritol dimethyl acrylate, Wait.

Examples of the methacrylate include ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, sorbitol tetramethacrylate, and the like. The maleate ester is exemplified by ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate, and the like.

As an example of the other ester, an aliphatic alcohol ester described in Japanese Patent Laid-Open Publication No. Sho 57-47231, or Japanese Patent Laid-Open Publication No. SHO 57-196231, or Japanese Patent Laid-Open No. 59-5240 An amine group-containing ester described in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. Ester and the like.

Further, the above ester monomers may also be used in the form of a mixture.

Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6-hexamethylene Bis-propyleneamine, 1,6-hexamethylenebis-methylpropenylamine, diethylenetriaminetripropenylamine, xylylene bisacrylamide, exophthalene Bis-methyl methacrylamide and the like.

Other examples of the preferred amide-based monomer include a compound having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and specific examples thereof include a Japanese one. A polyisocyanate compound having two or more isocyanato groups in one molecule, which is described in the Japanese Patent Publication No. 48-41708, is added to a vinyl group-containing monomer having a hydroxyl group represented by the following formula (IV). The vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule.

General formula (IV) CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH

(wherein R ⁴ and R ⁵ each independently represent H or CH ₃ )

In addition, the urethane urethanes described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. The urethane-based urethane described in Japanese Patent Publication No. Sho 62-39417, Japanese Patent Publication No. Sho 62-39417, and JP-A-62-39418, the entire disclosure of which is incorporated herein by reference. Compounds are also suitable. In addition, an amine group structure or a thioether is contained in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A color-forming photosensitive composition having a very excellent photospeed can be obtained by adding an addition polymerizable compound.

Other examples include polyester acrylates described in each of the publications of JP-A-48-64183, JP-A-49-43191, and JP-A-52-30490. Resin and (meth)acrylic acid A multifunctional acrylate or methacrylate such as an epoxy acrylate obtained as such. Further, a specific unsaturated compound described in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Publication No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like described in the publication No. 25493. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 can be suitably used. Further, it can also be used as a photocurable monomer and oligomer in the Japanese Association of Associations, vol. 20, No. 7, and pages 300 to 308 (1984).

Further, examples thereof include bisphenol A diacrylate, bisphenol A diacrylate ethylene oxide modified product, trimethylolpropane triacrylate, and trimethylolpropane tris(propylene decyloxypropyl) ether. Trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate Ester, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene decyloxyethyl)isocyanate, pentaerythritol tetraacrylate oxirane modification As a preferred polymerizable compound, dipentaerythritol hexaacrylate ethylene oxide modified product, and the like, and a commercially available product is preferably a urethane oligomer UAS-10 or a urethane oligomer UAB- 140 (manufactured by Nippon Paper Chemical Co., Ltd.), DPHA (manufactured by Nippon Kasei Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

Further, as the polymerizable compound, it has a low dielectric constant and is resistant to peeling. From the viewpoint of the liquidity and the solvent resistance, it is more preferably at least one selected from the group consisting of a polymerizable compound represented by the following formula (1) and a polymerizable compound represented by the following formula (2).

At least one of the polymerizable compound represented by the following formula (1) and the polymerizable compound represented by the following formula (2) has an ethylenic double bond in the molecule, and thus is photopolymerizable or thermally polymerized. Sexually, has a triazine skeleton which contributes to a large degree of low dielectric constant, and has an OH group in the molecule (preferably, the number of OH groups in the molecule and the heteroalicyclic embedding described later having a triazine skeleton) A monomer having the same number or substantially the same number of NCO groups when the block of the isocyanate compound is detached (hereinafter also referred to simply as "monomer"). Therefore, in the photohardening, only a certain degree of polymerization is carried out by polymerization of the ethylenic double bond of the monomer, and in the case of further heat treatment after development, the OH group and the heteroalicyclic ring in the monomer are The NCO group of the blocked isocyanate compound is thermally crosslinked (urementation reaction) to increase the crosslinking density, and the peeling resistance and solvent resistance can be effectively improved, and the low dielectric constant can be obtained.

In the above formula (1) and formula (2), R ¹ each represents a substituent containing an ethylenic double bond or a substituent having an OH group, and at least one of a plurality of R ¹ in one molecule means At least one of the substituents of the ethylenic double bond represents a substituent having an OH group. Moreover, a plurality of R ¹ in the molecule may be the same or different.

The substituent having an ethylenic double bond is not particularly limited as long as it has a vinyl double bond, and examples thereof include the following substituent (b-1) to substituent (b-6) and a substituent (c). a substituent (c-14) and a group containing at least one of the substituents.

Further, in (b-3) to (b-6) and (c-6) to (c-12), n represents an integer of 1 to 30.

In the above, the substituent (b-1), the substituent (b-4), and the bifunctional substituent (that is, a substituent having two ethylenic double bonds), particularly the substituent (c-1)~ The substituent (c-3) [more preferably, the substituent (c-1)] is preferred.

Further, from the viewpoint of low dielectric constant, it is desirable that the polymerizable compound has a symmetrical structure, and from this viewpoint, it is preferred that a plurality of R ¹ in the molecule be responsible for the amine group A derived from the blocked isocyanate. The lowest OH group-containing substituent necessary for the formation of the acid ester bond is in the form of the same group.

The substituent containing an ethylenic double bond, if it contains a substituent selected from the substituent (b-1) to the substituent (b-6), and a bifunctional substituent (particularly a substituent (c-1) to a substituent At least one of (c-3)) may be present as a group containing the substituents, and the carbon number of the substituent having an ethylenic double bond is preferably 3~ 30, more preferably 3~15.

At least one of R ^{1 in} the molecule represents a substituent containing an OH group as described above. Further, as the polymerizable compound, a compound having an ethylenic double bond which does not have an OH group may be used in combination. Further, it is desirable to adjust so that the number of OH groups in the colored photosensitive composition and the number of NCO groups derived from the blocked isocyanate are the same number or substantially the same number. In this way, as a whole of the composition, the NCO group in which the block of the OH group and the heteroalicyclic block isocyanate compound is released is efficiently subjected to a crosslinking reaction (urethane bond), and the resistance can be more effectively improved. Stripping liquid and solvent resistance.

The substituent having an OH group is not particularly limited as long as it is a group having an OH group, and examples of the hydroxyl group (OH group) include, for example, the following substituent (d-1) to substituent (d-10). And a group comprising at least one of the substituents.

Further, in (d-3) to (d-6), n represents an integer of 1 to 30.

In the above, from the viewpoint of workability such as solvent solubility, a polymerizable compound represented by the formula (1) containing an alicyclic triazine skeleton is preferred. Further, from the viewpoint of self-developability or resolution, it is preferably a low molecular weight, preferably a The number of triazine skeletons in the molecule is one.

Preferred specific examples of the polymerizable compound represented by the above formula (1) and the polymerizable compound represented by the above formula (2) are listed below. However, the specific examples are not limited in the present invention.

In addition, as the (D) polymerizable compound, a component described in Paragraph No. [0031] to Paragraph No. [0061] of JP-A-2009-265630 can be cited from the viewpoint of low-temperature curability. Among them, the (D) polymerizable compound is preferably (1) to (20) and (M-1) to (M-8) shown below.

Further, in (1) and (11), n represents an integer of 1 to 30.

In the colored photosensitive composition of the present invention, the polymerizable compound may be used alone or in combination of two or more.

The content of the polymerizable compound in the coloring photosensitive composition is preferably determined by considering the mass ratio of the polymerizable compound to the alkali-soluble resin, the pattern formation property, and the dielectric constant property from the viewpoint of the self-developing property and the resolution. content. Specifically, the content of the polymerizable compound is preferably from 5% by mass to 55% by mass, more preferably from 10% by mass to 50% by mass, even more preferably 15% by mass of all the solid content of the coloring photosensitive composition. Mass%~45% by mass.

Further, the OH group in the polymerizable compound (monomer) selectively reacts with the NCO group of the block of the heteroalicyclic block isocyanate compound, and thus the ratio of OH equivalent to NCO equivalent (OH/NCO ratio) It is preferably 0.5 to 1.5, more preferably 0.75 to 1.25. By setting the ratio to the above range, the urethane bond can be completely terminated, thereby effectively increasing the crosslinking density. When the ratio is out of the above range, the crosslinking density is insufficient, and the peeling resistance and the solvent resistance are changed. Insufficient phenomenon. Further, the OH equivalent in the composition can be adjusted by the OH group-containing monomer and the OH group-free monomer within the above content range.

[(E) A polyfunctional thiol compound containing two or more sulfhydryl groups in one molecule]

The colored photosensitive composition of the present invention contains at least one of (E) a polyfunctional secondary thiol compound (hereinafter also simply referred to as "polyfunctional secondary thiol compound") containing two or more fluorenyl groups in one molecule.

Since the colored photosensitive composition of the present invention contains a polyfunctional secondary thiol compound, it is possible to improve the solvent resistance due to insufficient hardening caused by the dye or the color shift between the layers, and the coloring sensitivity can be obtained. The storage stability of the composition is improved.

The polyfunctional secondary thiol compound is not particularly limited as long as it has two or more mercapto groups in the molecule, and is preferably a compound having two to four mercapto groups in the molecule.

The molecular weight of the polyfunctional thiol compound is preferably 1,000 or less, more preferably 200 to 600.

Further, specific examples of the polyfunctional secondary thiol compound include Karenz MT (registered trademark) BD1, Karenz MT NR1, or Karenz MT PE1 (Showa Denko Co., Ltd.).

The content of the polyfunctional secondary thiol compound is preferably 10% by mass or less, and more preferably 1% by mass to 5% by mass based on the total amount of the solid matter in the coloring photosensitive composition.

When the content of the polyfunctional secondary thiol compound is within this range, a coloring photosensitive composition having the following properties can be provided: the coloring photosensitive composition has good sensitivity and good storage stability, and the obtained color filter is used. The pixel has good adhesion and no pattern defects, and has good electrical characteristics when used in a liquid crystal display device.

(sensitized pigment)

In the colored photosensitive composition of the present invention, the viewpoint of improving self-sensitivity It is preferable to add a sensitizing dye different from the structure of the dye (A). The sensitizing dye is a compound which promotes a radical generating reaction of a photopolymerization initiator component or a polymerization reaction of an ethylenically unsaturated compound caused thereby by exposure at an absorbable wavelength.

Such a sensitizing dye may, for example, be a known spectroscopic sensitizing dye or dye different from the (A) dye structure, or a dye or an organic pigment which absorbs light and interacts with a photopolymerization initiator.

Preferred examples of the spectroscopic dye or dye which can be used as the sensitizing dye in the present invention include polynuclear aromatics (for example, ruthenium, osmium, triphenylene) and dibenzopyrans (for example, fluorescein). Fluorescein, eosin, erythrosine, rhodamine B, rose bengal, cyanine (eg thiacarbocyanine, Oxacarbocyanine, merocyanine (eg, cyclamate, carbomerocyanine), thiazides (eg, thionine, methylene blue, toluidine blue) , acridines (such as acridine orange, chloroflavin, acriferlavin), phthalocyanines (such as phthalocyanine, metal phthalocyanine), porphyrin (such as tetraphenyl) Porphyrins, central metal-substituted porphyrins, chlorophylls (eg chlorophyll, chlorophyllin, central metal-substituted chlorophyll), metal complexes, terpenoids (eg hydrazine), squaraine compounds ( Squarylium) (such as squaraine compounds) and the like.

Examples of better spectroscopic sensitizing dyes or dyes are exemplified below.

The styrene-based dye described in Japanese Patent Laid-Open Publication No. Hei 37-13034, and the cationic dyes described in JP-A-62-143044; a quinoxalinium salt; a novel methylene blue compound described in Japanese Laid-Open Patent Publication No. SHO 64-33104; a scorpion described in Japanese Patent Laid-Open Publication No. SHO 64-56767; The benzoxanthene dyes described in Japanese Laid-Open Patent Publication No. 2-1714; the acridines described in Japanese Patent Laid-Open No. Hei 2-226148, and the Japanese Patent Publication No. Hei 2-226149; Japanese Patent Publication No. Sho. No. Sho. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a benzofuran dye; a conjugated ketone dye according to Japanese Laid-Open Patent Publication No. Hei No. Hei-2- 218-58; Fair 2-30 The azo cinnamic acid derivative described in the Japanese Patent Laid-Open Publication No. H-1-287105, and the Japanese Patent Laid-Open No. 62-31844, and the Japanese Patent Laid-Open No. 62 The dibenzopyran-based dye described in Japanese Laid-Open Patent Publication No. SHO-62-143043, and the aminostyryl ketone described in Japanese Patent Publication No. Sho 59-28325; The coloring matter described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2-244050, and the Japanese cyanine dye described in Japanese Patent Laid-Open Publication No. Hei 59-28326; A part of the cyanine dye described in Japanese Laid-Open Patent Publication No. Hei 59-89303; The benzopyrene dye described in Japanese Laid-Open Patent Publication No. Hei 8-334897.

Other preferred embodiments of the sensitizing dye include those belonging to the following group of compounds and having a maximum absorption wavelength at 350 nm to 450 nm.

Examples thereof include polynuclear aromatics (for example, ruthenium, osmium, and terphenyl), dibenzopyrans (for example, luciferin, ruthenium, erythrosine, rose red B, and rose bengal), and cyanines (for example). For example, thiacarbocyanine, oxacarbocyanine, merocyanine (eg, merocyanine, carbocyanine), thiazides (eg, thioindigo, methylene blue, toluidine blue), acridine (eg Acridine orange, chloroflavin, acriflavine), terpenoids (such as hydrazine), squaraine compounds (such as squaraine compounds).

The content of the sensitizing dye is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.5% by mass to 15% by mass based on the total amount of the solid matter in the coloring photosensitive composition.

In the above, each component contained as an essential component in the colored photosensitive composition of the present invention and a sensitizing dye which can be used arbitrarily will be described. In the colored photosensitive composition of the present invention, a resin, an organic solvent, a surfactant, or the like may be further added to the extent that the effects of the present invention are not impaired. The optional components are described below.

(resin)

The colored photosensitive composition used in the present invention can also contain a resin for the purpose of improving film properties, imparting development properties, and the like. Here, the resin means a polymerized substance such as an alkali-soluble resin, a thermosetting resin, a pigment coating resin, or a polymer dispersant. Compound. When it is considered to develop by alkali, it is preferred to contain at least an alkali-soluble resin.

Hereinafter, the alkali-soluble resin and the thermosetting resin among the resins will be described in detail. Further, when a pigment is used, a pigment coating resin or a polymer dispersing agent can be used for the purpose of improving the dispersibility of the pigment.

- alkali soluble resin -

The alkali-soluble resin used in the present invention can be suitably selected from the group consisting of a linear organic high molecular polymer and a molecule (preferably an acrylic copolymer or a styrene copolymer). An alkali-soluble resin having at least one base which promotes alkali solubility (for example, a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, etc.) in the molecule of the main chain.

The compound which is more preferably the above-mentioned alkali-soluble resin is exemplified by a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Publication No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho-58- The methacrylic acid copolymer and the acrylic acid copolymer described in each of the publications of Japanese Laid-Open Patent Publication No. SHO 59-53848 , ikonic acid copolymer, butenoic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and an acidic cellulose derivative having a carboxylic acid in a side chain, and a polymer having a hydroxyl group An acrylic resin such as a compound obtained by adding an acid anhydride.

The acid value is preferably in the range of 20 mgKOH/g to 200 mgKOH/g, preferably 30 mgKOH/g to 180 mgKOH/g, more preferably 50 mgKOH/g to 150 mgKOH/g.

The alkali-soluble resin used in the present invention is particularly preferably a copolymer of (meth)acrylic acid with another monomer copolymerizable therewith.

Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted by a substituent.

The alkyl (meth)acrylate and the aryl (meth)acrylate are CH ₂ =C(R)(COOR') [wherein R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R' represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms, and specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl). Propyl acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylic acid Phenyl ester, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl It is an alkyl group having 1 to 8 carbon atoms, hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like.

The vinyl compound is CH ₂ =CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms], specifically Examples thereof include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. .

The other monomer which can be copolymerized as described above may be used alone or in combination of two or more.

Among the above, benzyl (meth) acrylate / (meth) propyl is particularly suitable An olefinic acid copolymer or a multicomponent copolymer comprising benzyl (meth) acrylate/(meth)acrylic acid/other monomer.

Further, a resin having a polyalkylene oxide chain in a molecular side chain is also preferable as the alkali-soluble resin.

The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the ends of the chains are a hydrogen atom or a linear or branched alkyl group.

The repeating unit of the polyethylene oxide chain and the polypropylene oxide chain is preferably from 1 to 20, more preferably from 2 to 12.

The acrylic copolymer having a polyalkylene oxide chain in a side chain is preferably, for example, an acrylic copolymer containing a compound as a copolymerization component: polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(methyl). Acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, etc., and compounds whose terminal OH groups are blocked with an alkyl group, such as methoxypolyethylene glycol mono(meth)acrylic acid Ester, ethoxypolypropylene glycol mono(meth)acrylate, methoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, and the like.

The acrylic resin has an acid value in the range of 20 mgKOH/g to 200 mgKOH/g as described above. When the acid value is 200 mgKOH/g or less, the solubility of the acrylic resin to the alkali does not become excessively large, and it is possible to prevent the development range (development latitude) from becoming narrow. On the other hand, when it is 20 mgKOH/g or more, it is difficult to reduce the solubility in alkali, and it is possible to prevent the development time from being prolonged.

Moreover, in order to achieve coloring of the photosensitive composition, it is easy in the steps of coating and the like. In order to secure the film strength, the weight average molecular weight Mw (polystyrene equivalent value measured by the GPC method) of the acrylic resin is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

Further, in order to improve the crosslinking efficiency of the colored photosensitive composition usable in the present invention, it is preferred to use an alkali-soluble resin having a polymerizable group. The alkali-soluble resin having a polymerizable group may be used singly or in combination with an alkali-soluble resin having no polymerizable group.

The alkali-soluble resin having a polymerizable group can be used for a polymer having an aryl group, a (meth)acryl (meth) acryl, an aryloxyalkyl group or the like in a side chain. Such an alkali-soluble resin having a polymerizable double bond can be developed in an alkaline developing solution, and further has both photocurability and thermosetting property, which is preferable. Among them, a resin having an aryl group as a side chain polymerizable group has a high hardenability and a high heat decomposition resistance, and therefore is more preferable.

In the following, a preferred example of the alkali-soluble resin containing a polymerizable group is a compound containing an alkali-soluble group such as a COOH group or an OH group and a polymerizable double bond (a carbon-carbon unsaturated bond) in one molecule. It is not limited to the compounds shown below.

That is, you can list:

(1) by reacting an isocyanate group with an OH group in advance, leaving an unreacted isocyanate group, and a compound containing at least one (meth) acryloyl group and a carboxyl group-containing acrylic resin The resulting urethane modified acrylic resin containing a polymerizable double bond

(2) an unsaturated group-containing acrylic obtained by a reaction of a carboxyl group-containing acrylic resin with a compound having an epoxy group and a polymerizable double bond in a molecule Resin

(3) Acid side-chain epoxy acrylate resin

(4) An acrylic resin containing a polymerizable double bond obtained by reacting an OH group-containing acrylic resin with a dibasic acid anhydride having a polymerizable double bond.

Particularly preferred among the above are the resins of (1) and (2).

As a specific example, a copolymer having a OH group such as 2-hydroxyethyl acrylate, a COOH group-containing methacrylic acid, an acrylic or vinyl compound copolymerizable with the compounds, and the like may be used. The OH group is a compound obtained by reacting a reactive epoxy ring with a compound of a polymerizable double bond (for example, a compound such as glycidyl acrylate). In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group or an acrylonitrile group can also be used.

Further, a compound obtained by reacting a compound having an epoxy ring with an unsaturated carboxylic acid such as acrylic acid as described in JP-A-6-102,936, and JP-A-6-1- 6-1938, may be used. A reactant obtained by reacting with a saturated or unsaturated polybasic acid anhydride.

Examples of the compound having an alkali-soluble group such as a COOH group and a polymerizable double bond include, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (polyurethane acrylate containing COOH group) Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.; Viscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, PLACCEL CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.) Made); Ebecryl 3800 (made by Daicel Co., Ltd.) and so on.

The amount of addition in the case of using an alkali-soluble resin is preferably in the range of 3% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, based on all the solid content of the coloring photosensitive composition.

- Thermosetting resin -

When the coloring photosensitive composition is prepared, it is preferred to further add a thermosetting resin in addition to the above alkali-soluble resin. By using a thermosetting resin, the strength of the formed coloring layer can be improved, heat resistance can be improved, chemical resistance can be improved, and resistance to a peeling liquid or the like can be improved.

The thermosetting resin is preferably an epoxy resin, and examples of the epoxy resin include a bisphenol A type, a cresol novolac type, a biphenyl type, and an alicyclic epoxy compound, which are equal to a compound having two or more epoxy rings in the molecule.

For example, the bisphenol A type may be Epotohto YD-115, Epotohto YD-118T, Epotohto YD-127, Epotohto YD-128, Epotohto YD-134, Epotohto YD-8125, Epotohto YD-7011R, Epotohto ZX-1059, Epotohto YDF -8170, Epotohto YDF-170, etc. (above manufactured by Tohto Kasei Co., Ltd.), DENACOL EX-1101, DENACOL EX-1102, DENACOL EX-1103, etc. (above, manufactured by Changchun Chemical Co., Ltd.), PLACCEL GL-61 , PLACCEL GL-62, PLACCEL G101, PLACCEL G102 (manufactured by Daicel Chemical Industry Co., Ltd.), etc., in addition to bisphenol F type and bisphenol S type epoxy resin similar to these compounds. Compounds that can be used.

Further, an epoxy acrylate such as Ebecryl 3700, Ebecryl 3701, or Ebecryl 600 (manufactured by Daicel Co., Ltd.) can also be used.

Examples of the cresol novolak type include Epotohto YDPN-638, Epotohto YDPN-701, Epotohto YDPN-702, Epotohto YDPN-703, Epotohto YDPN-704 (above, manufactured by Tohto Kasei Co., Ltd.), DENACOL EM-125, etc. (manufactured by Nagase Chemical Co., Ltd.), the biphenyl type may be, for example, 3,5,3',5'-tetramethyl-4,4'-diglycidylbiphenyl, and the alicyclic epoxy compound may be exemplified by Celloxide 2021. Celloxide 2081, Celloxide 2083, Celloxide 2085, Epolead GT-301, Epolead GT-302, Epolead GT-401, Epolead GT-403, Epolead EHPE-3150 (above manufactured by Daicel Chemical Industries, Ltd.), Sun Tohto ST- 3000, Sun Tohto ST-4000, Sun Tohto ST-5080, Sun Tohto ST-5100, etc. (above by Dongdu Chemical Co., Ltd.), Epiclon 430, Epiclon 673, Epiclon 695, Epiclon 850S, Epiclon 4032 (above DIC Co., Ltd.) .

Further, 1,1,2,2-tetra(p-glycidoxyphenyl)ethane, tris(p-glycidoxyphenyl)methane, triglycidyltris(hydroxyethyl)isotrile can also be used. Polycyanate, diglycidyl phthalate, diglycidyl terephthalate, in addition to Epotohto YH-434, Epotohto YH-434L, as an amine epoxy resin, in bisphenol A A glycidyl ester obtained by modifying a dimer acid in a skeleton of an epoxy resin.

Among them, it is preferred that the "molecular weight/epoxy ring number" is 100 or more, and more preferably 130 to 500. When the "molecular weight/epoxy ring number" is small, the hardenability is high and hardening The shrinkage is large; and if it is too large, the hardenability is insufficient, the reliability is lacking, and the flatness is deteriorated and is not preferable.

Specific preferred compounds satisfying this condition include Epotohto YD-115, Epotohto 118T, Epotohto 127, Epotohto YDF-170, Epotohto YDPN-638, Epotohto YDPN-701, PLACCEL GL-61, PLACCEL GL-62, 3, 5 3',5'-tetramethyl-4,4'-diglycidylbiphenyl, Celloxide 2021, Celloxide 2081, Epolead GT-302, Epolead GT-403, Epolead EHPE-3150, and the like.

The amount of addition in the case of using a thermosetting resin is preferably in the range of 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, based on the total mass of the coloring photosensitive composition. It is 1% by mass to 10% by mass. When the amount is in this range, sufficient exposure sensitivity can be obtained without hindering photopolymerization, and thermal polymerization property can be imparted, so that high heat resistance and chemical resistance can be imparted, and the resist can be maintained. Storage stability of the liquid.

(Organic solvents)

The colored photosensitive composition of the present invention can be prepared by using an organic solvent. Further, the pigment dispersion composition or the ceria fine particle dispersion may be prepared by using an organic solvent.

The organic solvent used in the present invention is preferably an organic solvent having a boiling point of 110 ° C or more and 200 ° C or less from the viewpoints of coating property, suppressing nozzle clogging at the time of coating, and solvent removal property in producing a cured film. .

The organic solvent usable in the present invention may, for example, be an ester such as acetic acid. Ethyl ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, lactate Ester, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate Ester, ethyl ethoxyacetate, and alkyl 3-oxypropionate such as methyl 3-oxypropionate or ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc., methyl 2-oxypropionate, ethyl 2-oxypropionate, Alkyl 2-oxopropionates such as propyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate) , 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester, 2-oxy-2-methylpropionic acid methyl ester, 2-oxy-2-methylpropionic acid ethyl ester, 2 Methyl methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc., and methyl pyruvate, ethyl pyruvate, propyl pyruvate, B Methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butylene glycol diacetate, etc.; ethers, such as diethylene glycol Methyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ether Acetate, propylene glycol propyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diethyl Acid ester, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol N-butyl ether acetate, tripropylene glycol mono-n-butyl ether, tripropylene glycol methyl ether acetate, diethylene glycol Ethyl ether, etc.; ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; alcohols such as, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol mono-n-propyl ether , propylene glycol mono-n-butyl ether, aromatic hydrocarbons such as toluene, xylene, and the like.

Suitable among these are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid Ester, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, and the like.

The organic solvent may be used in combination of two or more kinds in addition to the above.

The content of the organic solvent in the coloring photosensitive composition of the present invention can be appropriately selected according to the purpose. From the viewpoint of coating properties, it is preferred that all the solid content of the colored photosensitive composition is 10% by mass. 30% by mass range.

(surfactant)

When the concentration of the pigment is increased, the thixotropy of the coating liquid is generally increased. Therefore, it is easy to apply or transfer the colored photosensitive composition on the substrate to form a colored photosensitive composition layer (colored layer coating film). Uneven thickness. In particular, in the formation of the colored photosensitive composition layer (colored layer coating film) by a slit coating method or the like, it is important to form a coating liquid for forming a photosensitive composition layer before drying to form a coating liquid. A film of uniform thickness. Therefore, it is preferred to contain a suitable surfactant in the colored photosensitive composition. The above surfactants can be cited as Japanese Patent Laid-Open The surfactant disclosed in Japanese Laid-Open Patent Publication No. Hei 11-133600 is a preferred surfactant.

As the surfactant for improving the coating property, a nonionic surfactant, a fluorine-based surfactant, an anthrone-based surfactant, or the like can be added.

Nonionic surfactants are preferably, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, poly Nonionic surfactants such as oxypropylene alkyl ethers, polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.

Specifically, there are polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene groups such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, and polyoxyethylene oleyl ether. Alkyl ethers; polyoxyethylene octyl phenyl ether, polyoxyethylene polystyrene ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyrene ether, polyoxyethylene oxime Polyoxyethylene aryl ethers such as phenyl ethers; polyoxyalkylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, polyoxygen A nonionic surfactant such as an alkyl sorbitan fatty acid ester.

Specific examples of such nonionic surfactants include Adeka Pluronic series, ADEKA NOL series, Tetronic series (above manufactured by ADEKA Co., Ltd.), EMULGEN series, and RHEODOL series (above by Kao shares limited) Company manufacturing), Eleminol series, NONYLPOL series, OCTAPOL series, DODECAPOL series, NEWPOL series (to It is manufactured by Sanyo Chemical Co., Ltd.), PIONIN series (above manufactured by Takemoto Oil Co., Ltd.), NISSAN NONION series (made by Nippon Oil Co., Ltd.), etc. These commercially available nonionic surfactants can be suitably used. A preferred HLB value is 8 to 20, and more preferably 10 to 17.

The fluorine-based surfactant can be suitably used as a compound having a fluoroalkyl group or a fluorine-extended alkyl group in at least any part of the terminal, the main chain and the side chain.

Specific commercial products are, for example, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F554, Megafac 780, Megafac 781, Megafac R30, Megafac R08 (manufactured by DIC Corporation), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (above manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above manufactured by Asahi Glass Co., Ltd.), Eftop EF351 , Eftop 352, Eftop 801, Eftop 802 (above, manufactured by JEMCO Co., Ltd.), and the like.

Examples of the anthrone-based surfactants include Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190 (above manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (the above is manufactured by Momentive Performance Materials Japan) and the like.

The surfactant is preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the coating liquid for forming the colored photosensitive composition layer. When the amount of the surfactant is more than 5 parts by mass, the surface roughness of the coating drying tends to occur, and the smoothness is easily deteriorated.

(other additives)

Further, in the colored photosensitive composition used in the present invention, in addition to the above components, various known additives may be further used as needed.

Hereinafter, such additives will be described.

When the alkali solubility of the uncured portion is promoted and the developability of the colored photosensitive composition is further improved, the addition of the organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less can be carried out. Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid; oxalic acid, malonic acid, and succinic acid; , glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, Aliphatic dicarboxylic acid such as methyl succinic acid, tetramethyl succinic acid or citraconic acid; tricarballylic acid, aconitic acid, camphoronic acid Aliphatic Tricarboxylic acid; benzoic acid, toluic acid, acrylic acid, 2,3-dimethylbenzoic acid (hemellitic acid), 3,5-dimethylbenzoic acid (mesitylenic acid) and other aromatic monocarboxylic acids; Aromatic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melophanic acid, pyromellitic acid, etc. Polycarboxylic acid; phenylacetic acid, phenoxyacetic acid, methoxyphenoxyacetic acid, hydrogenated atropic acid, hydrogenated cinnamic acid, mandelic acid, phenylsuccinic acid, atopic acid, cinnamic acid, methyl cinnamate Other carboxylic acids such as benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbellic acid, and the like.

(alkoxydecane compound)

In the colored photosensitive composition of the present invention, an alkoxydecane compound, particularly a decane coupling agent, can be used from the viewpoint of improving adhesion to a substrate.

The decane coupling agent preferably has an alkoxyalkyl group as a hydrolyzable group which can be chemically bonded to an inorganic material, and preferably exhibits affinity by interaction or formation of a bond with an organic resin (methyl group). And a propylene group, a phenyl group, a fluorenyl group, an epoxy decane, and more preferably a (meth) propylene propyl propyl trimethoxy decane.

The amount of addition in the case of using a decane coupling agent is preferably in the range of 0.2% by mass to 5.0% by mass, and more preferably 0.5% by mass to 3.0% by mass based on the total mass of the coloring photosensitive composition.

(common sensitizer)

The colored photosensitive composition used in the present invention preferably further contains a co-sensitizer as needed. In the present invention, the co-sensitizer has a sensitizing dye or a starter pair The sensitivity of the radiation is further increased, or the polymerization inhibition of the polymerizable compound due to oxygen is suppressed.

Examples of such a co-sensitizer include amines, for example, "Journal of Polymer Society", Vol. 10, p. 3173 (1972) by MRSander et al., Japanese Patent Publication No. 44-20189 Japanese Laid-Open Patent Publication No. SHO-52-82102, Japanese Patent Laid-Open No. SHO-52-134692, Japanese Patent Laid-Open Publication No. SHO 59-138205 The compound or the like described in Japanese Patent Laid-Open Publication No. SHO-63-33104, and the disclosure of Research Disclosure No. 33825, specifically, triethanolamine and p-dimethylaminobenzene. Ethyl formate, p-nonyldimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the co-sensitizer include a thioether such as a disulfide compound of JP-A-56-75643, and specific examples thereof include 2-mercaptobenzothiazole and 2-mercaptobenzoxazole. , 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, β-nonylnaphthalene, and the like.

Further, other examples of the co-sensitizer include an amino acid compound (for example, N-phenylglycine), and an organometallic compound (for example, tributyltin acetate) described in Japanese Patent Publication No. Sho 48-42965. A hydrogen compound (such as trithiane or the like) described in JP-A-H05-344727, and the like.

From the viewpoint of the improvement of the hardening speed by the balance between the growth rate of polymerization and the chain transfer, with respect to all the solid matter of the colored photosensitive composition, The content of the co-sensitizer is preferably in the range of 0.1% by mass to 30% by mass, more preferably in the range of 1% by mass to 25% by mass, still more preferably in the range of 1.5% by mass to 20% by mass. .

(polymerization inhibitor)

In the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during or during storage of the colored photosensitive composition, it is desirable to add a small amount of the thermal polymerization inhibitor.

The thermal polymerization inhibitor which can be used in the present invention may, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, or tert-butylcatechol ( T-butyl catechol), benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6- Tributylphenol), N-nitrosophenylhydroxylamine sulfonium salt, phenoxazine, phenothiazine, and the like.

The amount of the thermal polymerization inhibitor added is preferably from 0.01% by mass to 5% by mass based on the coloring photosensitive composition. Further, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenylamine may be added as needed, and it may be biased toward the photosensitive layer during drying after coating. The surface exists. The amount of the higher fatty acid derivative to be added is preferably from 0.5% by mass to 10% by mass based on the coloring photosensitive composition.

(Plasticizer)

Further, in the present invention, in order to improve the physical properties of the colored photosensitive composition, an inorganic filler, a plasticizer or the like may be added.

Plasticizers such as dioctyl phthalate and phthalic acid (dodecyl) ester, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triethylene sulfonate The glycerol or the like may be added in an amount of 10% by mass or less based on the total mass of the ethylenically unsaturated compound and the resin.

In the exposure to ultraviolet light or the like, the colored photosensitive composition of the present invention containing the above-mentioned components is cured with high sensitivity, is excellent in pattern formability, and has good shape and visible light transmittance, and is suitable for use in the coloring pattern. The color filter is formed in a colored pattern.

~ Modulation method of coloring photosensitive composition~

The colored photosensitive composition of the present invention can be prepared by (A) dye, (B) a heteroalicyclic block isocyanate compound represented by the following formula (3), and (C) photopolymerization. The initiator, (D) a polymerizable compound, and (E) a polyfunctional thiol compound containing two or more thiol groups in one molecule, and further mixed with a solvent as needed, using a desired mixer Mixing and dispersing the machine.

Further, the step of mixing and dispersing preferably comprises kneading dispersion followed by microdispersion treatment, but kneading dispersion may be omitted and only microdispersion treatment may be performed.

<Method of Manufacturing Color Filter>

Next, the color filter of the present invention and a method of manufacturing the same will be described.

The color filter of the present invention is constituted by using the colored photosensitive composition, and the color filter is composed of a coloring agent, and can be preferably formed on a substrate by photolithography.

Since the colored photosensitive composition of the present invention is used, the cured product (including the color filter) is excellent in transparency, particularly excellent in peeling resistance (including NMP resistance), solvent resistance, and low dielectric constant. In addition, it is excellent in light resistance and heat resistance (including heat-resistant discoloration), and has high development characteristics by using an alkaline aqueous solution. Therefore, it can be applied in various applications.

The color filter of the present invention is suitable for an insulating film of a protective film (protective layer) or a build-up board of an electronic component, in particular, an LCD for use, an interlayer insulating film for TFT, and a protective film for COA (flat (film) use, use of spacers, etc. Moreover, it can also be used as a solder resist associated with a printed substrate. In addition, since the various kinds of tolerances can be exhibited as a color filter material, it can be used as a so-called COA as disclosed in Fig. 1 and the like of Japanese Laid-Open Patent Publication No. Hei 9-311347, and can be suitably used as a color filter. A light sheet, that is, a color pixel containing a colored resin film. Further, since the various kinds of resistance are excellent, they can be applied to a normal color filter without a protective film, and it is expected that the steps of the color filter manufacturing step are shortened and the manufacturing is rationalized.

The color filter of the present invention can be formed by any method as long as it is a coloring layer (colored pattern) obtained by curing the colored photosensitive composition of the present invention.

Particularly preferably, the method for producing a color filter of the present invention comprises the steps of: a colored layer forming step of applying the colored photosensitive composition onto a substrate to form a colored layer; and an exposing step of patterning the colored layer Forming a latent image by exposure; and developing a step of developing the color layer on which the latent image is formed Into a pattern.

Further, in the method of producing a color filter of the present invention, it is particularly preferable to further provide a post-baking (post-heating) step, that is, heat-treating the colored pattern formed in the developing step. In the case of setting a multicolor coloring pattern, the post-baking step can also be performed after setting the coloring pattern of the last color.

In addition, a step of irradiating the colored pattern with ultraviolet rays (post exposure) may be provided between the developing step and the post-baking step.

Further, a color filter can be produced by a method such as the transfer method described in Japanese Laid-Open Patent Publication No. 2009-116078, or the ink jet method described in Japanese Laid-Open Patent Publication No. 2009-134263.

Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

First, a method of manufacturing a color filter for a liquid crystal display device which has been used from the prior art will be described, and then an effective color filter array (Color Filter on Array) is considered from the viewpoint of improving brightness and yield. A method of manufacturing a color filter for a liquid crystal display device of the COA) method will also be described.

[Manufacturing method of color filter]

- Colored layer forming step -

In the method for producing a color filter of the present invention, the coloring of the present invention is first performed by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet. The composition is applied to the substrate to form a colored layer, which is then pre-cured (prebaked) as needed to dry the colored layer.

Examples of the substrate include soda glass, alkali-free glass, borosilicate glass, quartz glass, and resin substrate used in a liquid crystal display device, and a charge coupled device (CCD) and a complementary metal used in a solid-state imaging device. An oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS), a photoelectric conversion element substrate in an organic CMOS, a germanium substrate, or the like.

Further, as a COA liquid crystal display device, a substrate for driving a liquid crystal display device of a thin film transistor (TFT) type is used.

Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or planarize the surface, an undercoat layer, an interlayer insulating film, or the like may be provided on the substrates as needed.

The prebaking conditions include heating at 70 ° C to 130 ° C for about 0.5 minutes to 15 minutes using a hot plate or an oven.

Further, the thickness of the coloring layer formed of the colored photosensitive composition can be appropriately selected as needed. In the color filter for a liquid crystal display device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 1.0 μm to 4.0 μm, and most preferably in the range of 1.5 μm to 3.5 μm. Further, in the COA liquid crystal display device color filter, the thickness of the pixel film is preferably in the range of 0.3 μm to 5.0 μm, more preferably in the range of 2.5 μm to 3.5 μm. Further, in the color filter for a solid-state imaging device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 0.3 μm to 2.5 μm, and most preferably in the range of 0.3 μm to 1.5 μm.

Further, the thickness of the colored layer is the film thickness after prebaking.

- Exposure step -

Then, in the method of producing a color filter of the present invention, for example, a coloring composition layer formed on a substrate is exposed through a photomask. The light or radiation to be applied in the exposure is preferably a g-line, an h-line, an i-line, a KrF light, or an ArF light, and particularly preferably an i-line. When the i-line is used for the irradiation light, it is preferable to irradiate with an exposure amount of 100 mJ/cm ² to 10000 mJ/cm ² .

Moreover, other exposure light sources can also use ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps. , the sun, etc.

Moreover, a laser light source can also be used for exposure, and an ultraviolet laser can be used as a light source.

The preferred illumination light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably 300 nm to 360, in terms of the wavelength of the resist. Ultraviolet laser with a wavelength in the range of nm. Specifically, in particular, a third harmonic (355 nm) of a Nd:YAG laser as a solid laser or a XeCl (308 nm) of a pseudo-molecular laser, XeF (353), which is large in output power and relatively inexpensive, can be suitably used. Nm).

The exposure amount of the colored layer is in the range of 1 mJ/cm ² to 100 mJ/cm ² , and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . When the exposure amount is in this range, it is preferable in terms of productivity in pattern formation.

The exposure apparatus is not particularly limited, and a commercially available exposure apparatus can be used by Callisto (manufactured by V Technology Co., Ltd.) or EGIS (manufactured by V Technology Co., Ltd.) or DF2200G (Great Japan Net) Screen stock Co., Ltd. manufactures) and so on. Further, it is also possible to suitably use a device other than the above.

The colored layer which has been exposed as described above can also be heated.

Further, in order to suppress oxidative fading of the colored material in the colored layer, exposure may be performed while circulating nitrogen gas in the chamber.

- development step -

Then, the colored layer after exposure is developed in a developing solution. Thereby, a colored pattern can be formed.

When the developer is a uncured portion (unexposed portion) in which the colored layer is dissolved and the hardened portion (exposed portion) is not dissolved, a combination of various organic solvents or an aqueous alkaline solution can be used. In the case where the developer is an alkaline aqueous solution, it is preferred to adjust the alkali concentration to pH 11 to 13, and more preferably to adjust the alkali concentration to pH 11.5 to 12.5. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethyl. An aqueous alkaline solution of ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene or the like.

In the color filter used in the COA liquid crystal display device, the developer is particularly preferably an organic alkaline developer from the viewpoint of damage to the circuit or the like of the underlayer.

The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The development temperature is preferably from 20 ° C to 40 ° C, more preferably from 20 ° C to 30 ° C.

Development can be performed by a puddle method, a shower method, a spray method, or the like.

Further, after development using an alkaline aqueous solution, it is preferred to wash with water.

Thereafter, in the method for producing a color filter of the present invention, the post-baking (post-heating) and/or ultraviolet irradiation (post-exposure) may be performed on the colored pattern formed by development as needed to promote coloring. Hardening of the pattern.

- UV irradiation (post exposure) step -

In the method for producing a color filter of the present invention, the colored pattern (pixel) formed by using the colored photosensitive composition may be exposed to light after irradiation with ultraviolet rays.

- post-baking (post-heating) steps -

It is preferable to further heat-treat the coloring pattern (or the coloring pattern subjected to post-exposure) which has been developed as described above. The colored pattern can be further cured by heat-treating the formed color pattern. This heat treatment can be performed, for example, by a heating plate, various heaters, an oven, or the like.

The temperature at the time of heat treatment is preferably from 100 ° C to 300 ° C, more preferably from 150 ° C to 250 ° C. Moreover, the heating time is preferably about 10 minutes to 120 minutes.

The colored pattern obtained as described above constitutes a pixel in the color filter. In the production of a color filter having a plurality of hues of pixels, the above-described steps and the optional ultraviolet (post exposure) step or post-baking may be repeated in accordance with the desired number of colors ( Late heating) steps.

In addition, the ultraviolet irradiation (post exposure) step or the post-baking (post-heating) step may be performed after the formation, exposure, and development of each of the monochromatic coloring composition layers (per color). All the color combinations of the expected number of colors After the formation, exposure, and development of the layer are completed, the ultraviolet irradiation (post exposure) step or the post-baking (late heating) step is collectively performed.

Hereinafter, details of a color filter which is a more preferable form of a color filter which is used as the coloring photosensitive composition of the present invention, a method for producing the same, and a production of the COA using the above will be described.

Examples of the TFT substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached to the glass, or solid-state photography. A photoelectric conversion element substrate used in a device or the like, for example, a germanium substrate or the like. In addition, it can also be a plastic substrate. Black matrices or black stripes separating the pixels are usually formed on the substrates.

A conventional TFT type LCD is produced by separately producing a TFT substrate and a color filter substrate, and sandwiching the liquid crystal to bond them. In this case, after the color filter is formed into a black matrix and each pixel, ITO is formed on the entire surface by a vacuum film formation method such as sputtering or vapor deposition. Therefore, the conventional TFT type LCD is usually used without patterning, and the underlying color filter does not need to be used in the case of peeling liquid resistance, low dielectric constant, and contact hole. Therefore, the fabrication of the TFT substrate and the production of the color filter are independently performed independently, and the individual progress is achieved. In the manufacturing technology of the TFT substrate, the manufacturing technology of the semiconductor is mainly used, but as the substrate is enlarged, there are a substrate transfer method, an exposure machine and an exposure method, a positive resist coating machine, and a coating method. Problems such as low dielectric constant of the interlayer insulating film, peeling resistance, and coating method. The colored photosensitive composition of the present invention can be suitably used as an interlayer insulating film of the TFT substrate.

However, in recent years, the use of monitors, televisions, and the like has been expanded. In order to increase the production efficiency year by year, the area of the substrate used in the mass production plant of the new construction has become larger, and the pixels and colors on the TFT side have been increased. The alignment of the pixels on the side of the filter becomes technically difficult. Therefore, if the black matrix is made thicker and the defect due to the positional shift is reduced, the aperture ratio is reduced and the screen is darkened. However, if the brightness of the backlight is increased in order to brighten the screen, various problems such as the life of the backlight, the problem of heat generation, and the problem of power consumption are generated.

For these reasons, a method called "COA method" for manufacturing a color filter on the TFT substrate side has been studied. Previously, the COA was formed by directly forming a color filter on the TFT as described above, so that substantially no alignment was required, and thus the black matrix could be thinned. Thereby, the aperture ratio can be increased without increasing the brightness of the backlight, thereby reducing the power consumption of the backlight. However, the COA method is a technique that has been attracting attention from the past, and since the color filter is directly formed on the TFT, it has the usual color filter, such as acid resistance, peeling resistance, low dielectric constant, and contact hole, which will be described later. The required characteristics that the light sheet material cannot correspond to have not been popularized.

In the method of manufacturing a COA color filter, a TFT film is usually formed on a substrate, and each pixel pattern is further formed to provide a color filter layer, and a light shielding film is usually formed on a portion opposed to the gate electrode. The film contains a metal film such as a chromium film or a coating film in which a black colorant such as carbon black is dispersed. Next, the pixel electrode corresponding to the gate electrode is further formed into a pattern on the color filter layer. The pixel electrode is formed by applying a positive photoresist to a metal oxide film formed by a vacuum film formation method such as sputtering, vapor deposition or the like by using a metal oxide such as ITO, tin oxide or indium oxide. law A pixel electrode pattern is formed. Further, after the pixel electrode is formed, the resist film remaining on the electrode is removed by the stripping solution. The removal of the resist cured film by the stripping liquid is usually carried out at a high temperature of approximately 100 ° C using an organic solvent having a high dissolving power, so that the color filter layer is destroyed. Therefore, in order to protect the color filter layer from the stripping liquid, a pixel protective film (protective layer) may be formed between the color filter layer and the pixel electrode. The colored photosensitive composition of the present invention contains a coloring agent and is also suitable for forming the color filter for COA. However, if it is used as a protective agent without a coloring agent, it can also be applied to a color filter for protecting the underlying layer.

Moreover, as a raw material of a plastic substrate, from the viewpoints of optical characteristics, heat resistance, mechanical strength, and the like, (1) amorphous polyolefin, (2) polyether oxime, (3) polypentamethyleneimine, (4) Polycarbonate, (5) polyethylene terephthalate, (6) polyethylene naphthalate, (7) norbornene polymer, (8) diphenylamine hydrazine as diamine component Polyimine, (9) a polyester comprising bisphenol fluorene and a dibasic acid. Preferred among these are (2) polyether oxime, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer. The raw materials are particularly preferred for LCD applications.

The characteristics required for the plastic substrate include low thermal expansion (prevention of deterioration in display accuracy accompanying hardening treatment when color filters are produced), gas barrier properties (to ensure liquid crystal stability), light transmittance, or optical isotropic properties. Characteristics, surface smoothness, etc. Regarding thermal expansion, it is preferred that the coefficient of thermal expansion is 10 ^-4 or less.

Further, the plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

Further, in the case of using a plastic substrate in a TFT substrate, performing a high temperature treatment of 400 ° C or higher in the annealing step becomes a bottleneck. Therefore, in order to avoid the temperature problem, a method of forming a TFT on a glass substrate or the like and then transferring the TFT onto the plastic substrate may be employed.

(Method for Manufacturing Color Filter for Liquid Crystal Display Device of COA Method)

The color filter for a COA liquid crystal display device can be produced by first applying a colored photosensitive composition of the present invention containing a colorant onto a TFT substrate to form a coating film of the colored photosensitive composition. The coating film is subjected to pattern exposure, alkali development, post-baking treatment, or the like to form respective pixels, and a transparent electrode (ITO) film is formed by sputtering on the respective pixels, and a positive photoresist is formed next. Coating a film, performing pattern exposure and development on the photoresist film, further etching necessary ITO to form a pixel electrode pattern, and then removing the photoresist film remaining on the pixel electrode pattern by a stripping solution .

The application of the colored photosensitive composition of the present invention to form a coating film can be carried out by spin coating (spin coating), slit coating, cast coating, roll coating, ink jet coating or the like. Cloth Method The colored photosensitive composition is applied onto a substrate directly or via another layer, and dried (prebaked) or the like. Further, drying (prebaking) of the colored photosensitive composition coated on the substrate can be carried out by heating at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven, or the like. . Further, in recent years, the size of the substrate has been increasing. Therefore, as a method of forming the coating film, slit coating is also effective, and the coating method is gradually becoming a general forming method.

The above coating film can be exposed by a predetermined mask pattern (pattern exposure) Light) only hardens the portion of the coating film that becomes a colored pattern. Particularly suitable radiation for exposure is ultraviolet rays such as g-line or i-line.

In the case of a negative type, an alkali development treatment is performed after the above pattern is exposed, whereby the unexposed non-hardened portion is eluted to the alkaline aqueous solution, and only the portion where the light is hardened remains. The developer suitable for the alkaline development treatment is preferably an organic alkaline developer which does not cause damage to the underlying circuit or the like. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

The base can be, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diaza An organic basic compound such as bicyclo-[5.4.0]-7-undecene is diluted with pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. An alkaline aqueous solution. Further, in the case of using a developer containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Further, the development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds.

After the above alkali development treatment, the remaining developer is washed and removed, dried, and then subjected to heat treatment (post-baking). The post-baking is a heat treatment for developing the hardening after development, and is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C. The post-baking treatment can be carried out by heating the heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heater so that the temperature of the coating film after development becomes the above condition. In addition, The post-baking treatment can also be carried out by any of continuous or batch type.

As described above, by using the coloring photosensitive composition of three colors of RGB, the above-described step of forming the coloring pattern of the RGB color is sequentially performed in this order, whereby a patterned hardened film containing a multicolor pixel, that is, a color filter can be formed. Light film.

(How to use color filter for liquid crystal display device of COA method)

The color filter formed by the above method can be used in a COA liquid crystal display device as described below. First, a transparent electrode (ITO) film is formed on the pixel of the color filter by sputtering, and a positive photoresist film having etching resistance is further formed thereon, and after pattern exposure and development are performed, A chemical such as hydrofluoric acid etches unnecessary ITO to form a pixel electrode. The photoresist used at this time must be a positive photoresist having etching resistance. Further, pattern exposure or development, etching, and the like, which are generally known, can be used without limitation.

Next, the positive resist remaining on the formed pixel electrode was quickly peeled off by a stripper. The peeling liquid can be a previously known peeling liquid without any particular limitation. For example, each of the publications of Japanese Patent Laid-Open No. Hei 51-72503, Japanese Patent Laid-Open No. Hei 57-84456, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. Various organic solvents disclosed in the above. A typical stripping solution is a mixed solvent of monoethanolamine (MEA) and dimethylarylene (DMSO). Further, by using an organic solvent heated to 60 ° C or higher as a peeling liquid, the time of the peeling step can be shortened, and the problem of development residue can be eliminated. The colored photosensitive composition of the present invention is particularly excellent in peeling resistance, and therefore, even if an organic solvent heated to 60 ° C or higher is used, The coating film is not peeled off by the color filter, or the resist film is removed without swelling or swelling.

The color filter of the present invention is generally disclosed in Fig. 1 of Japanese Laid-Open Patent Publication No. Hei 9-311347, and is used in various display devices such as a TFT liquid crystal display device.

The color filter obtained as described above is easy to align and can increase the aperture ratio, and thus is suitable for use in a COA type image display device. Further, since the coloring photosensitive composition of the present invention is used to form a pixel, the peeling resistance is high, and the yield is high, and the production efficiency is also high. Further, in general, the color filter is required to have good heat discoloration resistance, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance, and the like.

The color filter may have a structure in which only one layer of the pixel formed by the coloring photosensitive composition of the present invention is provided between the substrate and the pixel electrode, and the coloring photosensitive composition of the present invention may be used. The form of the two layers of the formed pixel and the pixel protective film formed on the film of the pixel.

The film thickness of the above pixel is preferably from 0.3 μm to 5.0 μm, more preferably from 0.5 μm to 3.5 μm. A thicker film of a pixel can achieve high chromaticity, but the resolution of the contact hole is deteriorated, so it must be balanced.

The film thickness of the above-mentioned pixel protective film is preferably 0.2 μm to 5.0 μm, more preferably 0.2 μm to 3.0 μm. Moreover, it is desirable that the above pixel protective film can flatten the step of the underlying pixel and have a smooth surface.

<Image display device>

The image display device of the present invention comprises the color filter of the present invention which is excellent in brightness and contrast.

Specific examples of the display device of the present invention include a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a mobile terminal such as a mobile phone, and a digital device. A display device such as a display device for a camera or a display device for a car navigation. Among these, as the object to which the color filter of the present invention is applied, a color display device is particularly preferable.

When the color filter of the present invention is used in an organic EL display device or a liquid crystal display device or the like, it is possible to display an image having high luminance, excellent spectral characteristics, and contrast.

[Liquid Crystal Display Device]

A liquid crystal display device using the color filter of the present invention will be described. For the definition of the liquid crystal display device or the organic EL display device or the details of each display device, for example, "electronic display device (sasaki Sasaki, Industrial Research Association, issued in 1990)", "display device (Ibuki Shunzhang) , Industrial Book Co., Ltd., issued in the first year of Heisei (1989), etc. Further, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Endowed by Natsuda, Ltd., Industrial Investigations Co., Ltd., issued in 1994)". The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

As a color filter of the present invention, especially for color film electricity It is effective for a liquid crystal display device of a Thin-Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field driving method such as In-plane Switching (IPS) or a multi-domain vertical alignment (MVA) is expanded. , or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching, FFS), and Reflective Optically Compensated Bend (R-OCB).

In particular, since the color filter of the present invention has a low dielectric constant, the effect of the present invention can be sufficiently exerted by being supplied to a COA liquid crystal display device.

In the COA liquid crystal display device, the required characteristics of the color filter layer must have a low dielectric constant and a peeling resistance in addition to the usual required characteristics, and the color filter of the present invention can satisfy the requirement. Some requirements.

In order to satisfy the required characteristics of the low dielectric constant, a resin film may be further provided on the color filter layer.

Further, in the coloring layer formed by the COA method, in order to electrically connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, it is necessary to form one side having a length of about 1 μm to 40 μm. Rectangular, or 1 μm in diameter ~40 μm Round or oval, or " The shape of the pixel cross section is a rectangular to tapered contact hole (guide path), and it is particularly preferable that the size of the via (that is, the length of one side) is 5 μm or less, by using the present invention. The colored photosensitive composition can form a conduction path of 5 μm or less. When the cross-sectional shape of the contact hole does not have a rectangular to a conical shape or the opening is insufficient, the disconnection or conduction failure of the transparent conductive film occurs, and the color filter is used for the image. In the case of the display device, there is a case where the display is defective. However, there is an advantage that the problem of the deterioration or collapse of the shape of the contact hole is suppressed by using the colored photosensitive composition of the present invention.

These image display methods are described, for example, in "EL, PDP, LCD Display - Technology and Market Trends - (Dongli Research Center Investigation and Research Department, issued in 2001)" on page 43 and the like.

In addition to the color filter of the present invention, the liquid crystal display device of the present invention includes various components such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. The color filter of the present invention can be applied to a liquid crystal display device including the known members.

For these components, for example, "'94 Liquid Crystal Display Peripherals, Chemicals Market (Ichishima Kentaro, CMC Co., Ltd., issued in 1994), "2003 LCD related market status and future prospects (volume) (Table It is described in "Fuji Chimera Research Institute, Inc., issued in 2003".

For backlighting, SID meeting Digest 1380 (2005) (A. Konno et al.) or Display Monthly, December 18, 2005 Pages ~ page 24 (Island Kang Yu), Display Monthly, December 2005 issue, page 25 ~ page 30 (Yumu Longming) and other records.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventionally known three-wavelength tube of a cold cathode tube, and in addition, by using red, green, and blue LED light sources ( RGB-LED) can provide a liquid crystal display device having high luminance and high color reproducibility as a backlight.

Further, the color filter of the present invention can be used for a solid-state imaging device such as a CCD or a CMOS. When used in a solid-state imaging device, it can provide a color filter having high luminance and good color decomposability.

[Method of Manufacturing Liquid Crystal Display Device]

Hereinafter, an example of a COA-type image display device (hereinafter also simply referred to as "COA") which is most suitable for use in a color filter formed using the color-sensitive photosensitive composition of the present invention is shown.

A usual color filter is provided on a glass substrate to be bonded to a TFT substrate. On the other hand, since the COA technology directly forms a color filter on a TFT substrate, it is necessary to consider the following aspects (i) to (iii) as compared with a usual color filter material.

(i) low dielectric constant

In the COA, a pixel electrode is directly disposed on the TFT, so that the voltage is directly applied to the color filter, so that the material of the color filter is required to be a low dielectric constant material.

(ii) Contact hole

In COA, the ITO wiring of the pixel electrode must be connected to the TFT provided below. Therefore, it is required to form the contact hole surely at the time of development.

(iii) peeling resistance

In COA, electrodes must be formed on each pixel. The electrode is formed by depositing ITO on the pixel by sputtering, patterning and etching the wiring by a positive resist, and secondly, removing the remaining layer by a high-temperature stripping solution of usually about 80 ° C. The type of resist is removed. Therefore, in the COA, in order to prevent the color filter or the like from being eroded by the peeling liquid and not swelled by the peeling liquid, it is impossible to follow the ITO and break the wire, and a low swelling ratio is required.

On the other hand, when a color filter is formed on a TFT substrate, the occurrence of a defective product in the color filter manufacturing step is also a defective product because it also includes a TFT substrate, and thus the risk is extremely high. However, in recent years, liquid crystal TVs have been used as a representative, and as the size of LCDs has increased, the size of manufactured substrates has also increased in size year by year. Further, since the injection time of the liquid crystal is also long, the liquid crystal injection method starts to become a dropping method. As described above, with the increase in the size of the substrate and the application of the liquid crystal dropping method, when the color filter is bonded to the TFT substrate, the alignment accuracy between the pixel of the color filter and the TFT is made strict. Correcting the positional deviation between the center portion and the peripheral portion of the substrate becomes very difficult.

In this respect, since the COA directly sets the pixels on the TFT, it is not necessary to worry about the positional deviation, and the opposite substrate sandwiching the liquid crystal is prepared by sputtering the substrate on which the ITO is entirely coated. Therefore, the degree of alignment needs to be the position of the sealant, and the work efficiency is drastically improved. As described above, the COA technology does not require alignment accuracy (looseness), and therefore has the advantage that the line width of the black matrix can be made very narrow, High aperture ratio and low power consumption of the backlight. As a result of various studies on COA as described above, there is a possibility that it will become a technology necessary for a large LCD substrate in the future. However, due to the risk of fabricating a color filter on a TFT as described above, and the inability to provide a color filter material that satisfies the requirements of (i) to (iii), the current situation has not yet been adopted. technology.

The colored photosensitive composition of the present invention can solve the problem of the color filter material for COA in view of the above, and the method of use can be used for each purpose.

That is, the most preferable method is a method of producing a color filter using the colored photosensitive composition of the present invention containing a colorant.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but it is not limited to the examples below. In addition, unless otherwise stated, "%" and "parts" are quality standards.

[Example 1]

(modulation of coloring photosensitive composition)

The coloring photosensitive composition of Example 1 was prepared by mixing and dissolving each of the following components.

Further, the blue pigment dispersion can be prepared as shown below.

12.8 parts of CI Pigment Blue 15:6 and 7.2 parts of a dispersing agent (Solsperse 5500 manufactured by Lubrizol Corporation, Japan) were mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill. A blue pigment dispersion is prepared.

(measurement and evaluation)

The coloring photosensitive composition of Example 1 obtained as described above was subjected to the following evaluation. The results are shown in Table 1 below.

- Determination of relative dielectric constant -

a) On a chrome-coated glass substrate (75 mm on one side and 0.3 μm on the chrome film), the rotation speed is adjusted so that the film thickness after hardening (post-baking) is 3.2 μm, by rotary coating The coloring photosensitive composition (1) to the coloring photosensitive composition (6) described in Table 1 below was applied to each of the cloths.

b) Next, the chromium-coated glass substrate on which the coating film was formed was placed on a hot plate, and prebaked at 100 ° C for 120 seconds to dry the solvent.

c) After prebaking, the coated film was irradiated with light at a exposure amount of 50 mJ/cm ² using a 2.5 kW ultrahigh pressure mercury lamp.

d) Next, a chrome-coated glass substrate on which a coating film was formed was subjected to heat curing (post-baking) at 220 ° C for 60 minutes by a hot air circulation dryer to prepare a test piece.

e) After the post-baking, the coating film at one corner of the test piece is peeled off to expose the surface of the chrome.

f) Next, the silver paste was spin-coated on the back side of the test piece and air-dried. Thereafter, the silver exposed surface of the surface is electrically connected (connected) to the silver paste coated surface of the back surface by the silver paste.

g) After drying, on the surface of the test film, a vacuum evaporation apparatus (trade name: ion sputter E1030, manufactured by Hitachi, Ltd.) is used, by Pt. In the Pd target, a main electrode 2 (inner circle) having a thickness of about 50 nm and a protective electrode 3 (outer circle) were formed on the test piece 1 in the manner shown in FIG. In addition, the test piece 1 is exposed in the e) Cut out the chrome surface 4.

h) After the electrode was produced, the thickness of the coating film of the portion of the test piece to which the electrode was not attached was measured by a stylus type surface shape measuring device (trade name: DEKTAK3, manufactured by Aiko Co., Ltd.).

i) Next, a dielectric test fixture 16451B and an electrode are mounted on a static capacitance measuring device (Precision Impedance Analyzer 4294A, manufactured by Agilent Technologies, Inc.), and further, the test piece in the above g) is mounted, and the measurement is applied at 1 kHz. Relative dielectric constant ε' at an AC voltage of 0.5 V. The evaluation was performed by the following criteria. The results are shown in Table 1.

[evaluation standard]

A: Relative dielectric constant ε'<3.0

B: Relative dielectric constant ε'3.0~5.0

C: Relative dielectric constant ε'>5.0

- peeling resistance -

The film thickness of the test piece was measured by the following procedures a) to e), and the swelling ratio was calculated, and the calculated value was used as an index for evaluating the peeling resistance. In the case where the peeling resistance is poor, when the film is immersed in the peeling liquid, the coating film is dissolved in the peeling liquid and peeled off from the substrate, and the film thickness cannot be measured. This case was evaluated as "C".

a) The film thickness (FT0) of the test piece obtained in d) of the [measurement of relative dielectric constant] was measured.

b) After the measurement, a mixture of monoethanolamine (MEA) and dimethyl hydrazine (DMSO) (MEA/DMSO = 7/3 by mass) was used as a stripping solution, and the above test piece was placed in a stripping solution at 80 ° C. Dip for 120 seconds.

c) filling the tank with a liquid of MEA/DMSO=7/3, further immersing in the impregnated test piece of the b), and thereafter on the stylus type surface shape measuring device (trade name DEKTAK3, Afco shares limited) A test piece in a state in which the peeling liquid covers the surface was placed on the test piece support table of the company, and the thickness of the coating film (FT1) (measurement of the film thickness of the swelled state of the peeling liquid) was measured.

d) filling the other tank with pure water, immersing the test piece swollen in the above c), leaving it for 1 night, replacing the stripping liquid contained in the coating film with water, and drying the test piece at 200 ° C The film thickness (FT2) was measured again for 30 minutes.

e) Using the FT0, FT1, and FT2 measured above, the swelling ratio and the film reduction rate of the test piece were calculated according to the following formula, and the peeling resistance was evaluated based on the following criteria. In addition, since (FT1-FT0) measures the apparent swelling of the peeling liquid, the film-reduced portion (FT2-FT0) eroded by the peeling liquid is corrected, and the actual swelling ratio is calculated, and the evaluation is performed by the following evaluation criteria. The results are shown in Table 1.

Actual swelling rate (%) = 100 × (FT1-FT2) / FT0

Membrane reduction rate (%) = 100 × (FT2-FT0) / FT0

[evaluation standard]

A: The actual swelling ratio is ≦40%, the film reduction rate is 5%, and the peeling resistance is good.

B: The actual swelling ratio is ≦40%, the film reduction rate is >5%, and the peeling resistance is within the allowable range.

C: The coating film is dissolved or peeled off, and the peeling resistance is poor.

- Chemical resistance (solvent resistance) -

Each of the colored photosensitive compositions was applied onto a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then baked at 90 ° C for 2 minutes on a hot plate to form a film thickness of 3.2. The color layer of μm. The resulting coloring layer was exposed to the entire surface by a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. with a cumulative irradiation amount of 50 mJ/cm ² (illuminance of 20 mW/cm ² ). Thereafter, the substrate was heated in an oven at 220 ° C for 1 hour to obtain a colored cured film.

The color of the obtained colored cured film was measured. Further, the substrate on which the cured film was formed was immersed in N-methyl-2-pyrrolidone having a temperature of 23 ° C for 20 minutes, and then the chromaticity of the colored cured film was measured, and ΔE*ab was used to calculate The chromaticity change caused by the immersion is 3 or less, and it can be said that the solvent resistance of the cured film is good.

[evaluation benchmark]

A: △E*ab before and after immersion is less than 2.0

B: △E*ab before and after immersion is 2.0 or more and 3.0 or less

C: △E*ab before and after immersion exceeds 3.0

- Stability over time -

The viscosity after the preparation was measured by an E-type viscometer (Tokyo instrument) at 25 ° C and 20 rpm, and the viscosity after storage at 40 ° C × 2 W in a constant temperature layer was evaluated by the following evaluation criteria. The results are shown in Table 1.

[evaluation benchmark]

A: The viscosity change before and after the passage of time is within ±5%

C: viscosity change before and after the passage of time exceeds ±5%

[Examples 2 to 18 and Comparative Examples 1 to 4]

The components constituting the composition of the first embodiment were changed to the components and amounts used in Table 1 or Table 2, and the same as in Example 1 to prepare Examples 2 to 18 and Comparative Examples 1 to Comparative Examples. 4 colored photosensitive composition.

Thereafter, various measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1 or Table 2.

The structures of the respective components used in Examples 1 to 18 and Comparative Examples 1 to 4 are as follows. Among the components shown below, the blocked isocyanate B2 is manufactured by the trade name BL4265, Sumika Bayer Urethane Co., Ltd., and the monomer M2 is a trade name M-315, manufactured by Toagosei Co., Ltd.

According to the results of Tables 1 and 2, it is understood that the colored photosensitive composition of the present invention has a low dielectric constant, is resistant to peeling liquid, and is excellent in storage stability. Further, it is understood that the colored photosensitive composition of the present invention can be cured by a low temperature of 180 degrees.

Further, when the first embodiment and the comparative example 4 are compared, it is understood that the colored photosensitive composition of the present invention containing a polyfunctional secondary thiol is excellent in stability over time, but a comparative example containing a polyfunctional primary thiol. 4 color-sensitive photosensitive composition Poor stability. It is presumed that the reason is that gelation occurs due to the reaction of the polyfunctional primary thiol with the monomer.

1‧‧‧Substrate

2‧‧‧Main electrode

3‧‧‧Protective electrode

4‧‧‧Chromium surface

Claims (9)

A colored photosensitive composition comprising: (A) a dye, (B) a heteroalicyclic block isocyanate compound represented by the following formula (3), (C) a photopolymerization initiator, and (D) polymerization a compound, and (E) a polyfunctional thiol compound containing two or more thiol groups in one molecule, (In the formula (3), X represents a group derived from a terminal blocking agent, and Y represents a divalent linking group). The colored photosensitive composition according to claim 1, wherein the (D) polymerizable compound is selected from the group consisting of a polymerizable compound represented by the following formula (1), and the following formula (2) At least one of the group consisting of the polymerizable compounds indicated: (In the general formulae (1) and (2), R ¹ each independently represents a substituent containing an ethylenic double bond, a substituent containing an epoxy group or a substituent having an OH group; and is present in one molecule; At least one of the three R ¹ represents a substituent containing an ethylenic double bond; a plurality of R ^{1 's} may be the same or different). The colored photosensitive composition according to claim 1, wherein the blocking agent is selected from the group consisting of methyl ethyl ketone oxime, acetone oxime, cyclohexanone oxime, methyl isobutyl ketone oxime, ε- A group consisting of caprolactam, γ-butylidene and β-propionamide. The colored photosensitive composition according to claim 1, wherein the (A) dye is a metal-substituted compound having a structure represented by the following formula (I) and is coordinated to a metal atom or a metal compound: (In the formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group). The colored photosensitive composition according to claim 1, wherein the (A) dye is a metal-substituted compound represented by the following formula (I-3): (In the formula (I-3), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, Or a heterocyclic group; R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. ;Ma represents a metal atom or a metal compound; X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or An arylsulfonyl group, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkyl group Sulfhydryl or arylsulfonyl), oxygen atom, sulfur atom, or carbon atom; X ⁵ represents a group bondable to Ma, a represents 0, 1, or 2; R ⁸ and Y ¹ may also Bonding to form a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members). A color filter comprising a coloring layer formed using the coloring photosensitive composition according to any one of claims 1 to 5. A method for producing a color filter, comprising: a colored layer forming step of applying a colored photosensitive composition according to any one of claims 1 to 5 to a substrate to form a colored layer; In the exposing step, the colored layer is subjected to patterning exposure to form a latent image; and a developing step is performed to develop the colored layer on which the latent image is formed to form a pattern. An image display device comprising the color filter of claim 6 of the patent application. An image display device comprising the coloring photosensitive composition according to any one of claims 1 to 5, which is formed on a substrate for driving a thin film transistor (TFT) liquid crystal display device. Picture.