KR20060049026A - Colored curable composition, color filter and manufacturing method thereof - Google Patents

Abstract

It is an object of the present invention to provide a colored curable composition and a color filter having good yellow color, high light fastness, high heat fastness, and excellent stability over time.

The compound represented by the following general formula (Y1) is contained [Ry ₁ : aliphatic group, aryl group, heterocyclic group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfonate Pamoyl group; Ry ₂ : H, aliphatic group, aryl group, heterocyclic group; Ry ₃ , Ry ₄ : a substituent; Vm = 1-3, yn = 0-2 (ym + yn = 1-3), yp = 0-5].

Description

Colored curable composition, color filter, and its manufacturing method {COLORED CURABLE COMPOSITION, COLOR FILTER AND MANUFACTURING METHOD THEREOF}

The present invention relates to a color curable composition suitable for forming a color filter for use in a liquid crystal display device or a solid state image pickup device, a color filter using the color curable composition, and a manufacturing method thereof.

A color filter formed on an element for colorizing a solid state image pickup device or a liquid crystal display device, the color filter consisting of a yellow filter layer, a magenta filter layer, and a cyan filter layer formed adjacent to each other on the same plane of a substrate, or a red filter layer, and a green filter layer. And a color filter composed of a blue filter layer are known. And a band-shaped pattern or a mosaic pattern is formed of these filter layers.

As a method of manufacturing the color filter as described above, various methods have been proposed so far. Especially, the so-called color resist method which repeats the process of patterning by exposing and developing the photosensitive resin composition containing a pigment | dye for predetermined number of times is widely practiced.

The color resist method is a method of producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable in light, heat, and the like because the pigment is used. In addition, since the patterning is performed by the photolithography method, the positional accuracy is also sufficient, making it a preferred method for the production of color filters for large screens and high-precision color displays.

When producing a color filter by the pigment dispersion method which disperse | distributes a pigment as mentioned above, a radiation-sensitive composition is apply | coated on a glass substrate using a spin coater, a roll coater, etc., and a coating film is formed and this coating film is pattern-exposed By developing, a colored pixel is obtained, and the color filter is obtained by performing this operation to the desired number of colors. As a pigment dispersion method, the negative photosensitive composition which uses a photopolymerizable monomer and a photoinitiator as alkali-soluble resin is known (for example, refer patent documents 1-8, 12, and 13).

However, in recent years, higher precision has been demanded in color filters for solid state image pickup devices. However, in the conventional pigment dispersion system as described above, the resolution is not improved and color deviation due to coarse particles of the pigment is generated. Therefore, the pigment dispersion system is not suitable for applications requiring a fine pattern such as a solid state imaging device. Did.

The use of dye is conventionally proposed about such a problem (for example, refer patent documents 9-10). There is also a positive photosensitive composition (see Patent Documents 11 to 12, for example). However, the dye-containing curable composition has the following problems, and further improvement has been required. In other words,

(1) Generally, dyes are inferior in heat resistance and light resistance to pigments, and have insufficient fastness.

(2) When the dye absorption coefficient of the dye is low, a large amount of dye must be added, and in this case, other components such as the polymerizable compound, the binder, and the photopolymerization initiator in the curable composition must be relatively reduced. The curability at the time of hardening, the heat resistance of the hardened hardened part, the developability of a nonhardened part, etc. may fall.

(3) The dye often exhibits interaction with other components in the curable composition, and it is difficult to control the developability (soluble) of the hardened part and the non-hardened part.

Thus, in the dye conventionally used for the photosensitive composition, in particular, the fastness may not be sufficiently satisfied, the solubility in the photosensitive composition is low, and the dye may be precipitated in the liquid or in the state of the coating film formed. It was also difficult to contain dye at a high concentration.

On the other hand, it is known that yellow dye and cyan dye are used for the green filter array of a color filter (for example, refer patent document 10). However, the pyridone azo dye used has insufficient heat resistance and light resistance.

In addition, in the case of the color filter which consists of a yellow filter layer, a magenta filter layer, and a cyan filter layer, the yellow pigment used for a yellow filter layer improved the fastness, color, etc. which were better.

Patent Document 1: Japanese Patent Application Laid-open No. Hei 1-102469

Patent Document 2: Japanese Patent Application Laid-Open No. Hei1-152499

Patent Document 3: Japanese Patent Application Laid-Open No. 2-181704

Patent Document 4: Japanese Patent Application Laid-Open No. 2-199403

Patent Document 5: Japanese Patent Application Laid-Open No. 4-76062

Patent Document 6: Japanese Patent Application Laid-Open No. 5-273411

Patent Document 7: Japanese Patent Application Laid-Open No. 6-184482

Patent Document 8: Japanese Patent Application Laid-Open No. 7-140654

Patent Document 9: Japanese Patent Application Laid-open No. Hei 6-75375

(Patent Document 10) Japanese Patent Publication No. 2002-14221

(Patent Document 11) Japanese Patent Publication No. 7-111485

(Patent Document 12) Japanese Patent Application Laid-Open No. 2002-14223

(Patent Document 13) Japanese Patent Application Laid-Open No. 2002-14220

As described above, the dye-containing curable composition is useful in applications such as solid-state imaging devices that require high precision and uniform color, but it does not reach the stability of color density or color of the dye, such as fading, and in particular, The improvement of the fastness, such as heat resistance and light resistance, has become a subject. Further, the dye was low solubility, and the improvement of dye precipitation property with low stability over time when the liquid preparation or the coated film was in the state was also one of the problems.

This invention is made | formed in view of the said subject, Comprising: It aims at providing the coloring curable composition which yellow color is good, heat fastness and light fastness, and is excellent in stability with time, and also the color and transmittance characteristic are favorable. An object of the present invention is to provide a color filter composed of yellow, excellent in color fastness and light fastness, and a method of manufacturing a color filter which enables production by high productivity of the color filter. Let it be the subject of invention.

According to the present invention, various dye compound derivatives having good color and high fastness to light and heat have been examined in detail. As a result, certain specific pyrimidine azo dyes (dyes) have particularly improved fastness including heat resistance and light resistance. Based on the findings, a colored curable composition, a color filter, and a method for producing the same are provided, and the above object is achieved. The specific means for achieving the said subject is as follows.

It is a colored curable composition containing at least 1 sort (s) of the compound represented by <1> following General formula (Y1).

In General Formula (Y1), Ry ₁ represents an aliphatic group, an aryl group, a hetirocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group. a represents, Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, Ry ₃ and Ry ₄ represents a substituent independently. Ry ₁ and Ry ₂ may be bonded to each other to form a 5- to 7-membered ring together with the nitrogen atom to which Ry ₁ and Ry ₂ are bonded (imide ring may be used). ym represents the integer of 1-3, and some Ry <_1> and Ry <_2> may mutually be same or different, respectively. yn represents the integer of 0-2, and some Ry <_3> may mutually be same or different. ym + yn is an integer of 1-3. yp represents the integer of 0-5, and some Ry <_4> may mutually be same or different, and when they are adjacent, they may combine with each other and may form the 5- or 7-membered ring.

<2> It is a color filter characterized by containing at least 1 sort (s) of the compound represented by the following general formula (Y1).

In General Formula (Y1), Ry ₁ represents an aliphatic group, an aryl group, a hetirocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group. a represents, Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, Ry ₃ and Ry ₄ represents a substituent independently. Ry ₁ and Ry ₂ may be bonded to each other to form a 5- to 7-membered ring together with the nitrogen atom to which Ry ₁ and Ry ₂ are bonded (imide ring may be used). ym represents the integer of 1-3, and some Ry <_1> and Ry <_2> may mutually be same or different, respectively. yn represents the integer of 0-2, and some Ry <_3> may mutually be same or different. ym + yn is an integer of 1-3. yp represents the integer of 0-5, and some Ry <_4> may mutually be same or different, and when they are adjacent, they may combine with each other and may form the 5- or 7-membered ring.

<3> It has a process of apply | coating the coloring curable composition as described in said <1> on a support body, exposing through a mask, developing, and forming a pattern shape.

Hereinafter, the coloring curable composition of this invention, a color filter, and its manufacturing method are demonstrated in detail.

[Color curable composition]

The colored curable composition of this invention contains the compound represented by the general formula (Y1) shown below as a pigment | dye (henceforth also called "azo dye concerning this invention"), Preferably it is a binder and radiation sensitive It consists of a compound and a polymerizable monomer. Moreover, generally, it can also comprise using a solvent and can also comprise using other components, such as a crosslinking agent, as needed.

By using the azo dye which concerns on this invention, the coloring curable composition of this invention is not only excellent in fastness but also high sensitivity, high resolution, and a high transmittance characteristic can also be achieved.

Compound represented by general formula (Y1)

The colored curable composition of this invention contains at least 1 sort (s) of the compound (azo dye which concerns on this invention) represented by following General formula (Y1). This azo dye has a good yellow color with high transmittance characteristics, has no sedimentation over time when it is in the state of a liquid preparation or a coated coating film, and is excellent in stability, and particularly has excellent resistance to heat and light.

In this specification, the "aliphatic" may be linear, branched, or cyclic, and any of saturated and unsaturated may be sufficient as the aliphatic site | part, For example, it contains an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group, Unsubstituted or substituted by a substituent. In addition, any of a monocyclic ring and a condensed ring may be sufficient as "aryl" in this specification, and may be unsubstituted or may be substituted by the substituent. In the present specification, the "hetero ring" means that the heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, or an oxygen atom) in the ring, and any of a saturated ring and an unsaturated ring may be used. And any of the condensed rings may be used, or may be unsubstituted or substituted with a substituent.

In the present invention, the "substituent" may be a group which can be substituted, and for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an imide group, an azo group, an acyloxy group, an acylamino group, an aliphatic oxy group, or an aryl jade. Time period, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfo Neyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, aryl amino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxy Carbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, heterocyclic thio, hydroxy group, cyano , Sulfo group, nitro group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, dia A ryloxy phosphinyl group etc. are mentioned.

Hereinafter, each group in the said general formula (Y1) is demonstrated in detail.

In General Formula (Y1), Ry ₁ represents an aliphatic group, an aryl group, a heterocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Indicates. Further, Ry ₁ in this case is more than one, a plurality of Ry ₁ may be the same or different.

The aliphatic group represented by Ry ₁ may be unsubstituted or may have a substituent, may be saturated or unsaturated, an aliphatic group having 1 to 25 carbon atoms is preferable, and an aliphatic group having 1 to 12 carbon atoms is more preferable. For example, a methyl group, an ethyl group, a vinyl group, an allyl group, an ethynyl group, isopropenyl group, 2-ethylhexyl group, 3-methoxypropyl group, 2-methoxyethyl group, etc. are mentioned.

The aryl group represented by Ry ₁ above, may be a substituent which may have a non-substituted, preferably an aryl of 6-16 carbon atoms total, more preferably an aryl group 6 to 12 carbon atoms in total few. For example, a phenyl group, 4-nitrophenyl group, 4-methylphenyl group, etc. are mentioned.

As the heterocyclic group represented by Ry ₁ , saturated or unsaturated may be used, and a heterocyclic group having 5 to 7 members and having 2 to 15 carbon atoms (more preferably 2 to 12 carbon atoms) is preferable. For example, 2-pyridyl group, 3-furyl group, 2-piperidyl group, etc. are mentioned. Moreover, you may have a substituent.

As the carbamoyl group represented by Ry ₁ , carbamoyl groups having 1 to 12 carbon atoms are preferable, and carbamoyl groups having 1 to 10 carbon atoms are more preferable. For example, a dimethyl carbamoyl group, an ethoxy ethyl carbamoyl group, etc. are mentioned.

The aliphatic oxycarbonyl group represented by Ry ₁ above, may be a substituent which may have an unsubstituted, saturated may be may be an unsaturated, and the aliphatic oxy group having 2 to 16 carbon atoms in total preferably, than the aliphatic oxy group of a total carbon number of 2 to 12 desirable. For example, a methoxycarbonyl group, butoxycarbonyl group, etc. are mentioned.

As the aryloxycarbonyl group represented by Ry ₁ above, it may be a substituent which may have a non-substituted, preferably an aryloxycarbonyl group having a carbon number of 7-17 in total, and more preferably an aryloxycarbonyl group of 7 to 15 carbon atoms total. For example, a phenoxycarbonyl group etc. are mentioned.

As the acyl group represented by the Ry _1, may be either aromatic or aliphatic, preferably an acyl group of 2 to 15 carbon atoms total, more preferably an acyl group having 2 to 10 carbon atoms in total. For example, an acetyl group, pivaloyl group, a benzoyl group, etc. are mentioned.

The aliphatic sulfonyl group represented by Ry ₁ may be unsubstituted or may have a substituent, preferably an aliphatic sulfonyl group having 1 to 15 carbon atoms in total, and more preferably an aliphatic sulfonyl group having 1 to 12 carbon atoms in total. For example, a methane sulfonyl group, butane sulfonyl group, a methoxy ethane sulfonyl group, etc. are mentioned.

As the arylsulfonyl group represented by Ry ₁ above, may be a substituent which may have a non-substituted, preferably an arylsulfonyl of 6 to 20 total carbon atoms, more preferably an aryl sulfonyl of the total number of carbon atoms 6-12. For example, a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group, etc. are mentioned.

The sulfamoyl group represented by Ry ₁ may be unsubstituted or may have a substituent, preferably a sulfamoyl group having 0 to 18 carbon atoms, and more preferably a sulfamoyl group having 0 to 12 carbon atoms. For example, a sulfamoyl group, a dimethyl sulfamoyl group, etc. are mentioned.

In General Formula (Y1), Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. The aliphatic group, aryl group, and heterocyclic group represented by this Ry ₂ are the same as the aliphatic group, aryl group, and heterocyclic group represented by said Ry ₁ , respectively, and each preferable form is also the same. In addition, if Ry ₂ have more than two, a plurality of Ry is ₂ or different gatahdo.

In General Formula (Y1), Ry ₃ and Ry ₄ each independently represent a substituent. In addition, ₃ Ry, Ry ₄ is the case where two or more, plural Ry _3, plural Ry ₄ is gatahdo or different, respectively.

The substituent represented by Ry _{3 may} be a substitutable group, and examples thereof include groups exemplified in the above-mentioned "substituents", and preferably an aliphatic group, an aryl group, a heterocyclic group, an acyl group, or an acyl. Oxy group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic thio group, arylthio group, hydroxy group, sulfo group, halogen atom and the like.

The substituent represented by the above Ry ₄ may be any substitutable group, and examples thereof include groups exemplified in the above-mentioned "substituents", and preferably an aliphatic group, an aryl group, a heterocyclic group, an acyl group, or an acyl. Oxy group, acylamino group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, sulf Pamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic thio group, arylthio group, sia Furnace group, sulfo group, nitro group, carboxyl group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbo Bamoylsulfamoyl group.

In addition, when a plurality of Ry ₄ are adjacent to, for example, bonded to adjacent carbon atoms, they may be bonded to each other to form a 5- to 7-membered ring. Examples of the ring include a naphthalene ring and a quinoline ring. Etc. can be mentioned.

The Ry ₁ and Ry ₂ may be bonded to each other to form a 5- to 7-membered ring together with the nitrogen atom (N) to which the Ry ₁ and Ry ₂ are bonded. As said ring, imide rings, such as a piperidine ring, a pyrrolidine ring, a morpholine ring, etc., and succinic acid imide, are mentioned, for example.

The inter alia, in that it can save more than the effect of the present invention, the Ry ₁ is an aliphatic group, an aryl group, a carbamoyl group, an aliphatic oxycarbonyl group, or acyl form is preferable, an aliphatic group, an aryl group, an aliphatic oxy The form which is a carbonyl group or an acyl group is more preferable, and the form which is an aliphatic group is the most preferable. About each of these groups, the specific group mentioned above is mentioned as a more preferable thing.

Similarly, in the point which can utilize the effect of this invention more, the form which Ry ₂ is a hydrogen atom or an aliphatic group is preferable, and the form which is a hydrogen atom is more preferable. In the same manner, the Ry ₃ is preferably an aliphatic group, an aryl group, an aliphatic oxy group, an aryloxy group, an aliphatic thio group, or an arylthio group, and is preferably an aliphatic group or an aliphatic group. More preferred are those which are oxy or aliphatic thio groups. In the same manner, in order to further utilize the effects of the present invention, Ry ₄ represents an aliphatic group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, and aliphatic group. The form which is a sulfonamide group, an aryl sulfonamide group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, a cyano group, a sulfo group, a nitro group, a carboxyl group, a carbamoylamino group, a sulfamoylamino group, or a halogen atom is preferable, Aliphatic group, aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, sulfamoyl group, cyano group, nitro group, or a form which is a halogen atom is more preferable, and aliphatic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, sulfamoyl group Most preferred is a cyano group or a halogen atom. About each of these groups, the specific group mentioned above is mentioned as a more preferable thing.

In the general formula (Y1), the ym is preferably 3 or 2, yn is preferably 0 or 1, and yp is an integer of 0 to 3, in order to further utilize the effects of the present invention. desirable.

Among the compounds represented by the above general formula (Y1), compounds represented by the following general formula (Y2) (azo dyes according to the present invention) are preferred in view of more efficient use of the effects of the present invention.

In the general formula (Y2), yq and yr each independently represent an integer of 0 to 2, and yq + yr satisfies 1 or 2. In the point which can show the effect of this invention more effectively, 0 or 1 is preferable for said yq, and 1 or 2 for yr is preferable.

In addition, the same as if in the general formula _{(Y2) Ry 1, Ry 2} , Ry 3, Ry 4, and yp, respectively, the general formula (Y1) of the same form is also preferred.

Moreover, from the viewpoint which can effectively utilize the effect of the present invention, among the compounds represented by the general formula (Y2), the compound represented by the following general formula (Y3) (azo dye according to the present invention) is preferable.

Ry ₁ , Ry ₂ , Ry ₄ , and yp in the general formula (Y3) are the same as those in the general formulas (Y1) to (Y2), respectively, and preferred embodiments thereof are also the same. In Formula (Y3), Ry ₅ represents a hydrogen atom, Ry ₃ , or -N (Ry ₁ ) Ry ₂ , wherein Ry ₁ to Ry ₃ also represent Formulas (Y1) to (Y2). It is the same as the case in, and the preferable form is also the same.

In addition, if Ry ₅ represents a -N (Ry ₁₎ Ry _2, the general formula (Y3) may be the same as the other or different -N (Ry ₁₎ Ry ₂ in.

As said Ry ₅ , the form of a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, or -N (Ry ₁ ) Ry ₂ is preferable at the point which can utilize the effect of this invention more, and a hydrogen atom, Particularly preferred is an aliphatic group or a form of -N (Ry ₁ ) Ry ₂ . About each of these groups, the specific group mentioned above is mentioned as a more preferable thing.

In order to more effectively utilize the effects of the present invention, in the general formula (Y3), Ry ₁ represents an aliphatic group, an aryl group, an aliphatic oxycarbonyl group, or an acyl group, and Ry ₂ represents a hydrogen atom or an aliphatic group. Ry ₅ is a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic thio group, or -N (Ry ₁ ) Ry ₂ , and the Ry ₄ is an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, A sulfamoyl group, a cyano group, a nitro group, or a halogen atom is preferable, and Ry ₁ is an aliphatic group, Ry ₂ is a hydrogen atom, and Ry ₅ is a hydrogen atom, an aliphatic group, or -N ( Ry ₁ ) Ry ₂ , wherein Ry ₄ is an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, a sulfamoyl group, a cyano group, a nitro group, or a halogen atom.

Hereinafter, the specific example (example compound Y-1 to Y-48) of the compound (azo dye) represented by the said General Formula (Y1)-(Y3) is shown. However, in this invention, it is not limited to these.

Synthesis Example

Next, the synthesis example of the compound (azo dye) represented by the said General formula (Y1) is explained in full detail with reference to the following scheme as an example the synthesis | combination of the azo dye Y-1 which is the said exemplary compound.

<Synthesis of Intermediate Product B>

First, while 58.1 g (0.450 mol) of 2-ethylhexylamine was stirred at 20 degreeC, the compound A 16.3g (0.100 mol) was added gradually at 25 degrees C or less. Thereafter, the reaction solution was heated up to 130 ° C and stirred for 3 hours. Then, the temperature of the reaction solution was lowered to room temperature, and 200 ml of ethyl acetate and 200 ml of water were added. The ethyl acetate phase was extracted, washed twice with 200 ml of water, and dried over magnesium sulfate. After magnesium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure to obtain a viscous liquid. The obtained viscous liquid was purified by silica gel column chromatography to obtain 42.0 g of an intermediate product B which was a pale yellow viscous liquid (yield 95.9%).

<Synthesis of Azo Dye Y-1>

Next, 50 ml of water and 15 ml of concentrated hydrochloric acid were added to 8.6 g (0.050 mol) of Compound C. After addition, while stirring at 3 degrees C or less, the solution which melt | dissolved 3.6 g (0.052 mol) of sodium acetate in 10 ml of water was further dripped over 10 minutes (The liquid after completion of dripping is called "the reaction liquid of compound C."). ). Separately from this, a solution in which 22.0 g (0.497 mol) of the intermediate B was dissolved in a mixed solution of 80 ml of methanol and 8.4 ml of pyridine was prepared. And after stirring at 10 degrees C or less to the obtained solution, the "reaction liquid of compound C" obtained above was dripped over 20 minutes. The reaction solution after the dropwise addition was stirred for 1 hour at 20 ° C, and then poured into a mixed solution of 150 ml of ethyl acetate and 150 ml of water, extracted, and the extracted ethyl acetate phase was washed twice with 200 ml of water again, and magnesium sulfate It was dried using. After magnesium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure to obtain a yellow viscous liquid. The obtained yellow viscous liquid was purified by silica gel column chromatography, and crystallized with acetonitrile to obtain azo dye Y-1 (19.5 g) as yellow crystals (yield 74.1%).

Moreover, also about said other exemplary compound, it can synthesize | combine similarly to the above by changing into a desired compound according to the target azo dye.

As a density | concentration in the total solid component of the colored curable composition of the azo dye which concerns on this invention, although it changes with molecular weight and molar extinction coefficient, 0.5-80 mass% is preferable, 0.5-60 mass% is more preferable, 0.5- 50 mass% is especially preferable.

Compounds represented by the above general formulas (Y1) to (Y3) (azo dyes according to the present invention) record color images used in solid-state image pickup devices such as CCDs and CMOS, and displays such as LCDs and PDPs. It can use suitably for the color filter to reproduce, or the curable composition for producing these color filters.

The color filter of this invention can be produced by any method as long as it is a form which can be comprised using the compound represented by the said General Formula (Y1)-(Y3), For example, it contains the azo dye which concerns on this invention. The process of preparing a curable composition, apply | coating the prepared curable composition on a support body, exposing through a mask, developing, for example, in the case of negative type, removes an unhardened part (unexposed part), and forms a pattern image ( If necessary, the color filter of the present invention can be preferably produced by repeating the desired color number so as to constitute a desired color. Specifically, it mentions later.

-bookbinder-

The colored curable composition of this invention can contain at least 1 sort (s) of a binder. Although it will not specifically limit, if it is alkali-soluble as a binder which concerns on this invention, What is chosen from a viewpoint of heat resistance, developability, water availability, etc. is preferable.

The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution. Examples of such linear organic polymers include polymers having a carboxylic acid in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Laid-Open No. 59-71048, and the like. And maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and particularly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful. In addition, an acid anhydride is added to the polymer which has a hydroxyl group, etc., polyhydroxy styrene resin, polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide , Polyvinyl alcohol and the like are also useful.

Moreover, you may copolymerize the monomer which has a hydrophilic group, and as an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-metholacrylamide, Secondary and tertiary alkylacrylamides, dialkylaminoalkyl (meth) acrylates, morpholino (meth) acrylates, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole , Methyl (meth) acrylate, ethyl (meth) acrylate, branched or straight propyl (meth) acrylate, branched or straight butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like are used. And copolymerizing the same.

In addition to the above, as the monomer having a hydrophilic group, a tetrahydrofurfuryl group, a phosphate site, a phosphate ester site, a quaternary ammonium salt site, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid or a site thereof, and a morphonylethyl group Monomers are also useful.

Moreover, from a viewpoint of improving crosslinking efficiency, you may have a polymeric group in a side chain, and the polymer etc. which have an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful. Examples of the polymers having these polymerizable groups include KS Resist-106 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), Cychrom P series (manufactured by Daicel Kagaku Kogyo Co., Ltd.), and the like.

Moreover, alcohol soluble nylon, the polyether of 2, 2-bis (4-hydroxyphenyl) propane, an epichlorohydrin, etc. are also useful from a viewpoint of raising the intensity | strength of a hardened film.

Among the various binders described above, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance, and from the viewpoint of developability control, acrylic type Resin, acrylamide type resin, and acryl / acrylamide copolymer resin are preferable. As said acrylic resin, the copolymer which consists of a monomer chosen from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., and KS resist-106 (Osaka Yuki Kagaku) High School Co., Ltd., the Cychrom P series (made by Daicel Kagaku Kogyo Co., Ltd.), etc. are preferable.

As the binder in the present invention, an alkali-soluble phenol resin can also be used. The said alkali-soluble phenol resin can be used suitably when the coloring curable composition of this invention is comprised positively, For example, a novolak resin, a vinyl polymer, etc. are mentioned.

As said novolak resin, what is obtained by condensing phenols and aldehydes in presence of an acidic catalyst is mentioned, for example. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol A, and the like. Phenols can be used individually or in combination of 2 or more types. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.

As a specific example of the said novolak resin, the condensation product of methacresol, paracresol, or a mixture thereof and formalin is mentioned.

Novolak resin may adjust molecular weight distribution using means, such as a fractionation. Moreover, you may mix low molecular weight components which have phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ , more preferably a 2000 to 1 × 10 ⁵ polymer, more preferably 5000 to 5 × 10 ⁴ . Polymers are particularly preferred.

As content in the colored curable composition of this invention of a binder, 10-90 mass% is preferable with respect to the total solid of the said composition, 20-80 mass% is more preferable, 30-70 mass% is especially preferable. .

-Cross-linking system-

In the present invention, the compound (azo dye) represented by the general formula (Y1) described above is used, and the curing reaction of the film proceeds more highly than the conventional one, and a film having good curability is obtained. It is also possible to obtain a highly cured film. It is useful from the viewpoint of achieving high resolution of the colored curable composition of the present invention.

The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, the crosslinking agent in (a) an epoxy resin, (b) a methrol group, an alkoxymethyl group, and an acyloxymethyl group can be used. A phenol compound substituted with at least one group selected from a melamine compound, a guanamine compound, a glucoluril compound, or a urea compound, (c) a metyrol group, an alkoxymethyl group, and an acyloxymethyl group substituted with at least one group selected, A naphthol compound or a hydroxy anthracene compound is mentioned. Especially, polyfunctional epoxy resin is especially preferable.

As said (a) epoxy resin, as long as it has an epoxy group and has crosslinkability, any may be sufficient, for example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, Bivalent glycidyl group containing butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxy biphenyl diglycidyl ether, phthalic acid diglycidyl ester, N, N- diglycidyl aniline, etc. Low molecular compounds, trivalent glycidyl group-containing low molecular compounds represented by trimethylolpropane triglycidyl ether, trimetholphenol triglycidyl ether, TrisP-PA triglycidyl ether and the like, pentaerythritol tetraglyci A tetravalent glycidyl group-containing low molecular compound represented by dil ether, tetramethyrol bisphenol A tetraglycidyl ether, and the like, dipentaerythritol pentagle Low molecular weight compounds containing polyhydric glycidyl groups, such as cydyl ether and dipentaerythritol hexaglycidyl ether, 1,2 of polyglycidyl (meth) acrylate and 2,2-bis (hydroxymethyl) -1-butanol And a diglycidyl group-containing high molecular compound represented by -epoxy-4- (2-oxyranyl) cyclohexane adduct.

As a number substituted by the metharol group, the alkoxy methyl group, and the acyloxy methyl group contained in the said crosslinking agent (b), it is 2-6 in the case of a melamine compound, 2-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound. However, in the case of a melamine compound, it is preferably 5-6, in the case of a glycoluril compound, a guanamine compound, and a urea compound.

Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of the above (b) are generally referred to as compounds (metholol-containing compounds, alkoxymethyl group-containing compounds, or acyloxymethyl group-containing compounds) according to (b). There is work to do.

The metyrol group-containing compound according to (b) is obtained by heating the alkoxymethyl group-containing compound according to (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid and methanesulfonic acid in alcohol. The acyloxymethyl group-containing compound according to (b) is obtained by mixing and stirring the metyrol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, the specific example of the compound which concerns on (b) which has the said substituent is given.

As said melamine compound, for example, a compound or a mixture of 1 to 5 methoxymethylated hexamethylolmelamine, hexamethoxymethylmelamine, hexametholmelamine metholol group, hexamethoxyethylmelamine, hexaacyloxy The compound, the mixture, etc. which 1-5 of the metyrol groups of methyl melamine and hexamethol melamine were acylated are mentioned.

As said guanamine compound, the compound or its mixture, tetramethoxyethylguar which methoxymethylated 1-3 methyrol groups of tetrametholguanamine, tetramethoxymethylguanamine, and tetrametholguanamine, for example The compound which carried out acyloxymethylation of 1-3 methyrol groups, such as namin, tetraacyloxymethyl guanamine, and tetramethyrol guanamine, or its mixture, etc. are mentioned.

As said glycoluril compound, the compound in which methoxymethylated 1-3 of the methirol groups of tetrametholglycoluril, tetramethoxymethylglycoluril, and tetrametholglycoluril, or its mixture, tetramethylolglycol, for example is mentioned. The compound which carried out acyloxymethylation of 1-3 of the methyrol groups of usyl, or its mixture, etc. are mentioned.

As said urea compound, the compound which carried out the methoxymethylation of 1-3 methyrol groups of tetrametholurea, tetramethoxymethylurea, tetrametholurea, or its mixture, tetramethoxyethylurea, etc. are mentioned, for example. have.

The compound according to (b) may be used alone or in combination.

The crosslinking agent (c), that is, a phenolic compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a metyrol group, an alkoxymethyl group, and an acyloxymethyl group, is heated as in the case of the crosslinking agent (b). The crosslinking suppresses intermixing with the overcoated photoresist and further increases the film strength.

Hereinafter, these compounds may be generally called a compound (metholol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (c).

As the number of the metyrol group, the acyloxymethyl group, and the alkoxy methyl group contained in the crosslinking agent (c), at least two are required per molecule, and from the viewpoints of thermal crosslinkability and storage stability, two positions and four of the phenol compounds serving as skeletons Preferred are compounds in which all of the positions are substituted. Moreover, the naphthol compound and the hydroxyanthracene compound which become a skeleton are also preferable in which the ortho position and para position of an OH group are substituted. The 3 or 5 position of the phenol compound serving as the skeleton may be unsubstituted or may have a substituent. Moreover, also in a naphthol compound, it may have an substituent other than the ortho position of OH group even if it is unsubstituted.

The methirol group-containing compound according to the above (c) uses a compound whose ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, which is sodium hydroxide, potassium hydroxide, ammonia, It is obtained by reacting with formalin in the presence of a basic catalyst, such as tetraalkylammonium hydroxide.

The alkoxymethyl group-containing compound according to (c) is obtained by heating the metyrol group-containing compound according to (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid and the like in alcohol.

The acyloxymethyl group-containing compound according to (c) is obtained by reacting the metyrol group-containing compound according to (c) with acyl chloride in the presence of a basic catalyst.

As a skeletal compound in a crosslinking agent (c), the phenolic compound, the naphthol compound, the hydroxyanthracene compound, etc. which are unsubstituted in the ortho position or para position of a phenolic OH group are mentioned, for example, each of phenol and cresol Bisphenols, such as an isomer, 2.3- xylenol, 2, 5- xylenol, 3, 4- xylenol, 3, 5- xylenol, bisphenol A, 4,4'-bishydroxy biphenyl, TrisP-PA (manufactured by Honshu Kagaku Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

As a specific example of the said crosslinking agent (c), the compound which methoxymethylated 1-2 methyrol groups of a trimethol phenol, a tri (methoxymethyl) phenol, and a trimethol phenol, a trimethol-3- cresol, and a tri ( Dimethol cresols, such as the compound which methoxymethylated 1-2 methyrol groups, such as a methoxymethyl) -3- cresol and a trimethol-3- cresol, and 2, 6- dimethyrol-4- cresol, and tetramethol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylation of 1 to 3 methrol groups of tetramethyrol bisphenol A, tetramethyrol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4, Methoxymethylated 1 to 5 metholol groups of 4'-bishydroxybiphenyl, hexametholol of TrisP-PA, hexamethoxymethyl body of TrisP-PA, and hexametholol body of TrisP-PA, Bishydroxymethyl naphthalene diol etc. are mentioned.

Moreover, as a hydroxy anthracene compound, 1, 6- dihydroxy methyl-2, 7- dihydroxy anthracene etc. are mentioned, for example.

Moreover, as an acyloxymethyl group containing compound, the compound etc. which carried out the acyloxymethylation of the metyrol group of the said metyrol group containing compound partially or fully, etc. are mentioned, for example.

Preferred among these compounds are hexametholol or trimethylol phenol, bishydroxymethyl-p-cresol, tetramethol bisphenol A, TrisP-PA (manufactured by Honshu Kagaku Kogyo Co., Ltd.) or these metirol groups. The phenol compound substituted by both an alkoxy methyl group and a metyrol group and the alkoxy methyl group is mentioned.

The compounds according to these (c) may be used alone or in combination.

When it contains a crosslinking agent in this invention, as total content in the colored curable composition of the said crosslinking agents (a)-(c), although it changes with a raw material, it is 1-70 mass% with respect to solid content (mass) of the said composition. Is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

Polymerizable Monomer

The colored curable composition of this invention can be comprised preferably by containing at least 1 sort (s) of a polymerizable monomer. A polymerizable monomer is mainly contained when a colored curable composition is comprised in negative form. Moreover, it can further contain with the photoinitiator mentioned later in the positive type system containing the naphthoquinone diazide compound mentioned later, In this case, the hardening degree of the pattern formed can be promoted more.

This polymeric monomer is useful at the point which can achieve high sensitivity and high resolution of the colored curable composition of this invention by using it with the photoinitiator mentioned later. Hereinafter, a polymeric monomer is demonstrated.

As said polymerizable monomer, the compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure is preferable, As an example, polyethyleneglycol mono (meth) acrylate, polyethyleneglycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and methacrylates such as acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocy (Meth) acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin or trimetholethane, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034 , Urethane acrylates described in Japanese Patent Application Laid-open No. 51-37193, Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication Polyfunctional acrylates and methacrylates, such as polyester acrylates described in each of Japanese Patent Application No. 52-30490, epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof; have. In addition, Japan Adhesion Society Vol. 20, No7, pages 300 to 308 are mentioned as photocurable monomers and oligomers.

As content in the colored curable composition of the said polymerizable monomer, 0.1-90 mass% is preferable with respect to solid content of the said composition, 1.0-80 mass% is more preferable, 2.0-70 mass% is especially preferable.

Radiation-sensitive compounds

The colored curable composition of this invention can be comprised preferably by containing at least 1 sort (s) of a radiation sensitive compound. The radiation-sensitive compound according to the present invention is a compound capable of causing chemical reactions such as radical generation, sporadic generation, and base generation to radiation such as UV, deep UV, visible light, infrared light, and electron beam, but the alkali For the purpose of insolubilizing the soluble resin with an alkaline developer by insolubilizing the soluble resin by a reaction such as crosslinking, polymerization, or decomposition of an acidic group, polymerization of a polymerizable monomer or oligomer coexisting in the coating film, crosslinking of a crosslinking agent, and the like. Is used.

This radiation sensitive compound is useful from the viewpoint of achieving high sensitivity and high resolution of the colored curable composition of the present invention.

When a colored curable composition is comprised by negative type, a photoinitiator is included and when it is comprised by positive type, a naphthoquinone diazide compound contains as an essential component, respectively.

Photoinitiator etc.

First, the photoinitiator used when it comprises in a negative type is demonstrated. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable monomer (monomer having a polymerizable group). However, the photopolymerization initiator is preferably selected from the viewpoints of characteristics, starting efficiency, absorption wavelength, availability, and cost. Moreover, you may further contain in the positive type system containing a naphthoquinone diazide compound, and in this case, the hardening degree of the pattern formed can be promoted more.

As the photoinitiator, at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl substituted coumarin compound, a tropine dimer, a benzophenone compound, an acetophenone compound and the like Derivatives, cyclopentadiene-benzene-iron complexes, salts thereof, oxime compounds and the like.

As an active halogen compound which is the said halomethyloxadiazole type compound, the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound of Unexamined-Japanese-Patent No. 57-6096, etc., 2-trichloro Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(p-methoxystyryl) -1,3,4-oxadiazole, etc. are mentioned.

As an active halogen compound which is the said halomethyl-s-triazine type compound, the vinyl-halomethyl-s-triazine compound of Unexamined-Japanese-Patent No. 59-1281, 2- of Unexamined-Japanese-Patent No. 53-133428 is mentioned. (Naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound Can be.

As another embodiment, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylene Dioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-p-methoxystyryl-s-tri Azine, 2- (naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis- Trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphtho -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphtho-1-yl] -4,6-bis-trichloro Methyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Butoxyethyl) -naphtho-1-yl] -4,6-bis- Richloromethyl-s-triazine, 2- (2-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl -s-triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s-triazine , 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N -Di (chloroethyl) aminophenyl 2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN- Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylamino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro -pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycar Bonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine , 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro- pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri Azine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Tyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro- pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( o-chloro-pN-ethoxycarbonylmethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- (o-bro -pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) made by Midori Kagaku Co., Ltd., PANCHIM company make T series (e.g., T-OMS, T-BMP, TR, TB, etc.), Chiba Specialty Chemicals Co., Ltd. Ilgacua series (e.g., Ilgacua 369, Ilgacua 784, Ilgacua 651, Family) Cure 184, Ilcure Cure 500, Ilcure Cure 1000, Ilcure Cure 149, Ilcure Cure 819, Ilcure Cure 261, etc., DaroCrera Series (e.g., 3rd Daccure 117), 4,4'-bis (diethylamino) -Benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorphenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenyl Imidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyfe ) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4 , 5-diphenylimidazolyl dimer, benzoin isopropyl ether and the like are also useful.

In the colored curable composition of this invention, other well-known photoinitiators other than the said photoinitiator can be used together. Specifically, the bisinal polyketolaldonyl compound described in US Pat. No. 2,367,660, the α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670, and the acyl inether described in US Pat. No. 2,448,828. , Aromatic acyloin compounds substituted with α-hydrocarbons as described in US Pat. No. 2,722,512, polynuclear quinone compounds as described in US Pat. Nos. 3,046,127 and 2,951,758, and triallylimidazole as described in US Pat. No. 3,549,367. A combination of an immer / p-aminophenyl ketone and the benzothiazole compound / trihalomethyl-s-triazine compound described in JP-A-51-48516.

As for content in the colored curable composition of the said photoinitiator, 0.01-50 mass% is preferable with respect to solid content (mass) of the said polymerizable monomer, 1-30 mass% is more preferable, 1-20 mass% Particularly preferred. When the said content is less than 0.01 mass%, superposition | polymerization may become difficult to progress, and when it exceeds 50 mass%, a polymerization rate will become large, but molecular weight may become low and a film strength may weaken.

A sensitizer and a light stabilizer can be used together for the said photoinitiator.

Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluolinone, 2-chloro-9-fluolinone, 2-methyl-9-fluolenonon, 9-anthrone, 2-bro Parent-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6 -Dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridon, 10 -Butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino Benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone and the like, and benzothiazole-based compounds described in JP-A-51-48516, such as tinubin 1130 and copper 400 Can be mentioned.

In addition to the above, it is also preferable to add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone , 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like useful.

Naphthoquinone diazide compound

Next, the naphthoquinone diazide compound used when constructing a positive type is demonstrated. A naphthoquinone diazide compound is a compound which has at least 1 o-quinone diazide group, For example, o-naphthoquinone diazide-5-sulfonic acid ester and o-naphthoquinone diazide-5-sulfonic acid amide and o-naphthoquinone diazide-4-sulfonic acid ester, o-naphthoquinone diazide-4-sulfonic acid amide, and the like. These esters and amide compounds are known to known methods using, for example, phenol compounds described in general formula (I) in Japanese Patent Application Laid-Open No. 2-84650 and Japanese Patent Application Laid-Open No. 3-49437. It can manufacture.

Moreover, when forming a colored curable composition positively, it is the thing which melt | dissolves the said binder and the said crosslinking agent in the ratio of about 2-50 mass%, and about 2-30 mass% of the total solid added to a solvent normally, respectively. desirable. Moreover, as for each content of the said naphthoquinone diazide compound and the said pigment, the ratio of about 2-30 mass% and about 2-50 mass% is preferable with respect to the mass of the solution which melt | dissolved the said binder and a crosslinking agent, respectively.

-solvent-

In preparing the colored curable composition of the present invention, a solvent may generally be contained. The solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored curable composition, but is preferably selected in consideration of solubility, applicability, and safety of the binder.

As a specific example of a solvent, ester, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl Esters, methyl lactate, ethyl lactate, methyl oxy acetate, ethyl oxy acetate, butyl oxy acetate, methyl methoxy acetate, ethyl methoxy acetate, butyl butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate and the like; 3-oxypropionic acid alkyl esters, such as methyl 3-oxypropionate and ethyl 3-oxypropionate, for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropionic acid Ethyl and the like; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate and 2-methoxypropionic acid Propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-e Ethyl oxy-2-methylpropionate and the like; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetacetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; Ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons, for example, toluene, xylene, and the like are preferable.

Among the above, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

Various additives

To the colored curable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, and the like can be blended as necessary.

Specific examples of the various additives include fillers such as glass and alumina; Polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactants such as nonionic, cationic and anionic systems; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Adhesion promoters such as hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane ; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; And aggregation inhibitors such as sodium polyacrylate.

In addition, when promoting alkali solubility of the portion to be removed (non-hardened portion in the case of negative type) and further improving developability of the colored curable composition of the present invention, the composition is preferably an organic carboxylic acid, preferably The low molecular weight organic carboxylic acid with a molecular weight of 1000 or less can be added.

Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetate, enanthic acid, and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sublinic acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethylsuccinic acid, sheet Aliphatic dicarboxylic acids such as laconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconic acid and canforonic acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemeric acid, and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; And other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamilidene acetic acid, cumalic acid, and unbelic acid. .

The colored curable composition of the present invention is for forming colored pixels such as color filters used in liquid crystal displays (LCDs), solid-state imaging devices (e.g., CCDs, CM0S, etc.), printing inks, inkjet inks, and As production uses, such as a coating material, it can use preferably.

<< color filter and manufacturing method thereof >>

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

In the manufacturing method of the color filter of this invention, the coloring curable composition of this invention mentioned above is used. The color filter of this invention uses the coloring curable composition of this invention mentioned above, and apply | coats this coloring curable composition on a support body by coating methods, such as a rotary coating, a flexible coating, and a roll coating, and forms a radiation sensitive composition layer. The layer can be most preferably produced by exposing the layer through a predetermined mask pattern and developing with a developer to form a negative or positive colored pattern (image forming step). At this time, if necessary, a curing step of curing the formed colored pattern by heating and / or exposure can be provided. As light or radiation used at this time, particularly ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used. Moreover, when a colored curable composition is comprised positively, the process of post-baking a coloring pattern after an image formation process can also be provided.

In the production of a color filter, in the case of a negative type, the image forming process (and a curing step if necessary) is repeated in accordance with a desired number of colors. In the case of a positive type, the image forming process and the post bake are the desired number of colors. By repeating according to, a color filter composed of a desired number of colors can be produced.

As the support, for example, soda glass, pyrex (R) glass, quartz glass used for liquid crystal display devices and the like and a transparent conductive film attached thereto, a photoelectric conversion device substrate used for an imaging device, for example, a silicon substrate, etc. Or a complementary metal oxide film semiconductor (CMOS). These supports may be provided with black stripes separating each pixel.

If necessary, a primer layer may be formed on these supports in order to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

As a developing solution used for the manufacturing method of the color filter of this invention, as long as it melt | dissolves the uncured part of the colored curable composition of this invention, and a hardened part consists of a composition which does not melt | dissolve, any can be used. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used. As said organic solvent, the above-mentioned solvent used for preparation of the colored curable composition of this invention is mentioned.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, for example. The concentration of the alkaline compounds such as seed, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001-10% by mass, preferably 0.01-1% by mass The alkaline aqueous solution which melt | dissolves so that it will become preferable is preferable. Moreover, when the developing solution which consists of such alkaline aqueous solution is used, it wash | cleans with water after developing in general.

The color filter of the present invention can be used for solid-state image pickup devices such as liquid crystal display devices and CCDs, and is particularly preferable for high resolution CCD devices and CMOS devices having more than 1 million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises CCD, and the microlens for condensing.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

Example 1

1) Preparation of resist solution (negative type)

Propylene glycol monomethyl ether acetate (PGMEA); Part 5.20

Ethyl lactate (EL)... Part 52.6

·bookbinder… Part 30.5

[41% EL solution of methacrylic acid benzyl / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (copolymerization ratio [molar ratio] = 60/20/20)]

Dipentaerythritol hexaacrylate... Part 10.2

Polymer inhibitor (p-methoxyphenol)... 0.006part

Fluorine-based surfactants; 0.80part

(F-475, Dainippon Ink & Chemicals Co., Ltd. product)

TAZ-107 (manufactured by Midori Kagaku Co., Ltd .; photopolymerization initiator). 0.58part

Were mixed and dissolved to prepare a resist solution.

2) Fabrication of glass substrate with primer layer

After ultrasonically cleaning the glass substrate (Corning 1737) with 0.5% NaOH water, water washing and dehydration baking (200 ° C / 20 minutes) were performed. Subsequently, the resist solution obtained in the above 1) was applied onto the cleaned glass substrate using a spin coater so as to have a film thickness of 2 μm, and dried at 220 ° C. for 1 hour to form a cured film (primer layer).

3) Preparation of dye resist solution (color curable composition [negative type])

9.4 g of the resist solution obtained in the above 1) and 0.95 g of the above-described exemplary compound Y-1 (the compound represented by the above general formula (Y1)), which is an azo dye according to the present invention, are mixed and dissolved to dissolve the dye resist solution (color curing curability). A solution of the composition [negative type]) was prepared.

4) Exposure and development of dye resist solution (image formation)

The dye resist solution obtained in the above 3) was applied onto the primer layer of the glass substrate on which the primer layer obtained in the above 2) was formed using a spin coater so as to have a film thickness of 1.0 μm, and prebaked at 100 ° C. for 120 seconds.

Subsequently, the coating film was irradiated with an exposure dose of 500 mJ / cm 2 through a mask having a line width of 20 μm at a wavelength of 365 nm using an exposure apparatus. After irradiation, it developed on 25 degreeC and the conditions for 40 second using developing solution CD-2000 (made by Fujifilm Arch). After rinsing with running water for 30 seconds, it spray-dried.

As mentioned above, the yellow pattern preferable as yellow color which comprises a color filter was obtained.

5) Evaluation

The storage stability over time of the dye resist solution prepared above, and the heat resistance and light resistance of the coating film apply | coated and formed on the glass substrate using the dye resist solution were evaluated as follows. The evaluation results are shown in Table 1 below.

Storage stability over time

After storing the dye resist solution for 1 month at room temperature, the degree of precipitation of the foreign matter in the solution was visually evaluated according to the following criteria.

〔Criteria]

(Circle): Precipitation was not confirmed.

(Triangle | delta): Precipitation was confirmed slightly.

X: Precipitation was confirmed.

Heat resistance

The glass substrate coated with the dye resist solution was mounted on a 200 ° C. hot plate to be in contact with the substrate surface and heated for 1 hour, and then the color difference (ΔEab value) before and after heating with a colorimeter MCPD-1000 (manufactured by Otsuka Denshi Co., Ltd.). Was measured and evaluated according to the following criteria. The smaller the value of ΔEab, the better the heat resistance.

〔Criteria〕

○: ΔEab value <5

Δ: 5≤ΔEab value≤10

×: ΔEab value> 10

Light resistance

A glass substrate coated with a dye resist solution was irradiated with a xenon lamp at 50,000 ux for 20 hours (1 million ux · h equivalent), and then measured as a color difference (ΔEab value) before and after irradiation to measure light resistance. It evaluated according to the following criteria. The smaller the value of ΔEab, the better the light resistance.

〔Criteria〕

○: ΔEab value <3

Δ: 3≤ΔEab value≤10

×: ΔEab value> 10

(Examples 2 to 10)

In the preparation of the dye resist solution of Example 1, the yellow pattern was changed in the same manner as in Example 1 except that the azo dye according to the present invention was changed (but equimolar) as shown in Table 1 below. It formed and performed similar evaluation. The evaluation results are shown in Table 1 below.

(Comparative Examples 1-2)

In the preparation of the dye resist solution of Example 1, the azo dye according to the present invention was changed (but equimolar) as shown in Table 1 below. A pattern was formed and the same evaluation was performed. The evaluation result is shown in following Table 1 with the result of an Example.

Table 1

As shown in Table 1 above, in the examples using the azo dye according to the present invention, the colored curable compositions prepared in solution were excellent in storage stability over time in comparison with the comparative examples using dyes other than these. The yellow pattern formed using this colored curable composition showed good heat resistance and light resistance.

Example 11

1) Preparation of colored curable composition [positive type]

The following composition was mixed and dissolved, and the solution-like colored curable composition [positive type] was prepared.

Ethyl lactate (EL)... Part 30

Resin P-1... Part 3.0

Naphthoquinone diazide compound N-1... Part 1.8

Hexamethoxy metholated melamine (crosslinking agent). 0.6 part

TAZ-107 (manufactured by Midori Kagaku Co., Ltd.). Part 1.2

F-475... 0.0005parts

(Fluorinated Surfactant; Dainippon Ink & Chemicals Co., Ltd.)

Exemplary compound Y-3 of the azo dye according to the present invention. 1.5

(Compound represented by General Formula (Y1))

Synthesis of Resin P-1

70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of 2-hydroxyethyl methacrylate, and 600 g of 2-methoxypropanol were charged into a three-necked flask, and agitated, reflux condenser, and thermometer were attached. Then, catalytic amount of polymerization initiator V-65 (made by Wako Pure Chemical Industries, Ltd.) was added at 65 degreeC under nitrogen stream, and it stirred for 10 hours. The obtained resin solution was dripped at 20 L (liter) ion-exchange water, stirring severely, and white powder was obtained. This white powder was vacuum-dried at 40 degreeC for 24 hours, and 145g of resin P-1 was obtained. As a result of measuring this molecular weight by GPC, it was weight average molecular weight Mw = 28,000 and number average molecular weight Mn = 11,000.

Synthesis of naphthoquinone diazide compound N-1

42.45 g of Trisp-PA (manufactured by Honshu Kagaku Co., Ltd.), 61.80 g of o-naphthoquinone diazide-5-sulfonyl chloride, and 300 ml of acetone were added to a three-necked flask, and 24.44 g of triethylamine was added at room temperature. Dropped over time. After completion of the dropwise addition, the mixture was stirred for another 2 hours, and then poured into the reaction solution while stirring in a large amount of water. The precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum dried at 40 ° C. for 24 hours to obtain a photosensitive naphthoquinone diazide compound N-1.

2) Exposure, development (image formation) of colored curable composition

A glass substrate on which a primer layer was formed was prepared in the same manner as in Example 1, and the colored curable composition prepared in the same manner as in Example 1 was applied, prebaked, irradiated, developed, and rinsed on the glass substrate on which the primer layer was formed. The spray drying was carried out to obtain a yellow pattern, and then the pattern was heated at 180 ° C. for 5 minutes (post bake). The yellow pattern formed showed a good profile of the rectangular shape.

Subsequently, the storage stability of the dye resist solution prepared above and the heat resistance and light resistance of the coating film formed on the glass substrate using the dye resist solution were evaluated in the same manner as in Example 1, and as in the case of the negative type described above. , Storage stability, and light resistance and heat resistance were all good.

(Examples 12 to 21)

In addition to changing the glass substrate of Examples 1-10 into a silicon wafer substrate, the operation similar to Examples 1-10 was performed and the coating film was formed on the silicon wafer substrate. Subsequently, the developer was exposed to a square pattern of 2 μm × 2 μm at an exposure dose of 500 mj / cm 2 using an i-line reduced projection exposure apparatus, and using a developer diluted with 60% of CD-2000 (manufactured by Fujifilm Arch). It developed at 60 degreeC for 60 second. Then, after rinsing with running water for 30 seconds, it spray-dried. By the above, the pattern preferable as a color filter for CCDs whose square cross section is substantially rectangular and whose profile is favorable was obtained.

According to the present invention, it is possible to provide a colored curable composition having good color of yellow, high heat and light fastness, and excellent stability with time. According to the present invention, there is provided a color filter composed of yellow with good color and transmittance characteristics, and excellent in color fastness and light fastness, and a method of manufacturing a color filter which enables production by high productivity of the color filter. Can be.

Claims (3)

At least 1 type of compound represented by the following general formula (Y1) is contained, The colored curable composition characterized by the above-mentioned.

(In General Formula (Y1), Ry ₁ represents an aliphatic group, an aryl group, a hetirocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and Ry ₃ and Ry ₄ each independently represent a substituent, wherein Ry ₁ and Ry ₂ are bonded to each other so that Ry ₁ and Ry ₂ are bonded; Or a ym may represent an integer of 1 to 3, and a plurality of Ry ₁ and Ry ₂ may be the same as or different from each other, and yn is an integer of 0 to 2 And a plurality of Ry ₃ may be the same as or different from each other ym + yn is an integer of 1 to 3. yp represents an integer of 0 to 5, and a plurality of Ry ₄ may be the same as or different from each other, May be bonded to each other to form a 5-membered to 7-membered ring.) The color filter containing 1 or more types of compounds represented by the following general formula (Y1).

(In General Formula (Y1), Ry ₁ represents an aliphatic group, an aryl group, a hetirocyclic group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Ry ₂ represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group, and Ry ₃ and Ry ₄ each independently represent a substituent, wherein Ry ₁ and Ry ₂ are bonded to each other so that Ry ₁ and Ry ₂ are bonded; Or a ym may represent an integer of 1 to 3, and a plurality of Ry ₁ and Ry ₂ may be the same as or different from each other, and yn is an integer of 0 to 2 And a plurality of Ry ₃ may be the same as or different from each other ym + yn is an integer of 1 to 3. yp represents an integer of 0 to 5, and a plurality of Ry ₄ may be the same as or different from each other, May be bonded to each other to form a 5-membered to 7-membered ring.) After apply | coating the coloring curable composition of Claim 1 on a support body, it has the process of exposing through a mask, developing, and forming a pattern image, The manufacturing method of the color filter characterized by the above-mentioned.