JP5283532B2 - Method for producing dye-containing curable composition, color filter, method for producing the same, and solid-state imaging device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a dye-containing curable composition capable of restraining generation of a film defect derived from a dye. <P>SOLUTION: The manufacturing method comprises a heating step of heating a dye solution prepared by blending at least an organic solvent-soluble dye and an organic solvent to 60-100&deg;C, a temperature lowering step of lowering the temperature of the dye solution after heating to a 20-40&deg;C range, and a blending step of further adding to the dye solution after the temperature lowering step a polymerization initiator and a polymerizable compound so as to be blended therewith within 12 hours from the termination of the temperature lowering operation. The content of the organic solvent-soluble dye with respect to the total mass is 30 mass% or more. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a dye-containing curable composition containing a dye, a color filter using the same, a method for producing the same, and a solid-state imaging device

  As a method for producing a color filter used for a liquid crystal display element (LCD or the like) or a solid-state image pickup element (CCD or CMOS), a pigment dispersion method is widely known.

  The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied on a glass substrate by a spin coater or a roll coater to form a coating film, and a colored pixel is formed by pattern exposure and development of the coating film. The color filter is obtained by repeating this operation for each color.

  In the case of producing a display element such as a liquid crystal display element or a solid-state imaging element by providing a color filter using a pigment, a pigment having a finer particle size is required from the viewpoint of improving contrast (for example, patents). Reference 1). This is due to a factor that the polarization axis rotates due to light scattering, birefringence, and the like by the pigment. If the pigment is not sufficiently refined, light is scattered and absorbed by the pigment, the light transmittance is lowered, the contrast is lowered, and further, the curing sensitivity at the time of pattern exposure is lowered.

  In particular, in color filters for solid-state image sensors, in recent years, further higher definition has been desired. Therefore, it is difficult to further improve the resolution with a conventional pigment dispersion system. That is, there is a problem that color unevenness occurs due to the influence of coarse pigment particles. Therefore, the pigment dispersion system is not suitable for applications requiring a fine pattern with a pixel size of 1.5 to 3.0 μm square, such as a solid-state imaging device.

  In response to such a situation, techniques for using dyes instead of pigments have been proposed. Further, in recent years, color filters used in solid-state imaging devices have been required to have thin colored patterns (for example, a thickness of 1 μm or less) from the viewpoint of improving image quality due to high light condensing properties and light color separation properties. Therefore, it is necessary to increase the dye density in terms of color density. On the other hand, it has been pointed out that when the concentration of the dye is increased, a coating defect due to the dye is likely to occur at the time of coating, such as crystallization of the dye, resulting in a decrease in yield when producing the color filter. In addition to coating defects, patterns can be easily peeled off at low exposure areas due to sensitivity reduction, and the relative amount of components that contribute to photolithographic properties decreases. There is also a problem that cannot be obtained.

  As methods for solving such problems, various methods have been proposed in the past, such as selecting the type of initiator and increasing the amount of initiator added (for example, see Patent Document 2).

JP 2000-321863 A Japanese Patent Laying-Open No. 2005-316012

  However, although problems such as pattern peeling, thermal sag, shape and color density can be solved to some extent, film defects caused by dyes (crystals, etc.) that are likely to occur when using a coating solution with a higher dye concentration should be eliminated. However, the decrease in the yield of products such as color filters has not been improved.

  The present invention has been made in view of the above, a method for producing a dye-containing curable composition capable of suppressing the occurrence of film defects caused by dyes, a color filter with few film defects and in which a decrease in yield is prevented, and An object of the present invention is to provide a solid-state imaging device excellent in the manufacturing method and color reproducibility, and to achieve the object.

Specific means for achieving the above object are as follows.
<1> A heating step of heating a dye solution in which at least an organic solvent-soluble dye and an organic solvent are mixed to 60 to 100 ° C, a temperature lowering step of lowering the temperature of the dye solution after heating to a range of 20 to 40 ° C, and a temperature lowering And a mixing step of further mixing the photopolymerization initiator and the polymerizable compound within 12 hours from the end of the temperature drop, and the content of the organic solvent-soluble dye in the total solid mass is It is a manufacturing method of the dye containing curable composition which produces the curable composition which is 30 mass% or more.

  <2> The method for producing a dye-containing curable composition according to <1>, wherein the organic solvent-soluble dye is a phthalocyanine dye.

  <3> A color filter formed using the dye-containing curable composition produced by the method for producing a dye-containing curable composition according to <1> or <2>.

  <4> After the dye-containing curable composition produced by the method for producing a dye-containing curable composition according to <1> or <2> is applied on a support, the coating film formed by coating is exposed. And a method for producing a color filter having a step of developing and forming a pattern.

  <5> A solid-state imaging device including the color filter according to <4>.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the dye containing curable composition which can suppress generation | occurrence | production of the film | membrane defect resulting from dye can be provided. Also,
ADVANTAGE OF THE INVENTION According to this invention, the color filter with few film defects and the fall of the yield was prevented, and its manufacturing method can be provided. further,
ADVANTAGE OF THE INVENTION According to this invention, the solid-state image sensor excellent in color reproducibility can be provided.

  Hereinafter, the manufacturing method of the dye-containing curable composition of the present invention will be described in detail, and the color filter of the present invention, the manufacturing method thereof, and the solid-state imaging device will be described in detail.

<Method for producing dye-containing curable composition>
The method for producing a dye-containing curable composition of the present invention is to produce a dye-containing curable composition containing an organic solvent-soluble dye in a relatively high proportion of 30% by mass or more with respect to the total solid mass. A heating step of heating a dye solution in which at least an organic solvent-soluble dye and an organic solvent are mixed to 60 to 100 ° C., a temperature lowering step of lowering the temperature of the dye solution after heating to a range of 20 to 40 ° C., and The dye solution is further provided with a mixing step of mixing the photopolymerization initiator and the polymerizable compound within 12 hours from the end of the temperature decrease.

  In the present invention, at the time of preparing the curable composition, a dye solution in which an organic solvent-soluble dye and an organic solvent are mixed is first heated in a predetermined temperature range, and then the temperature is decreased to a predetermined temperature range. If a photopolymerization initiator and a polymerizable compound are added before the time has elapsed, even if the dye concentration is 30% by mass or more of the total solid content, generation of particles due to crystallization of the dye occurs. Therefore, the coating defects can be prevented when the coating film is formed, and a film surface excellent in in-plane uniformity can be obtained. Thereby, for example, a decrease in product yield when a colored film such as a color filter is produced can be suppressed, and as a result, color reproducibility when an image is displayed can be improved.

-Heating process-
In the heating step, a dye solution obtained by mixing at least an organic solvent-soluble dye and an organic solvent is heated to 60 to 100 ° C. In the present invention, if the heating is not performed, there is no necessity for the temperature lowering treatment, and the dye is soluble in the organic solvent, but the surface treatment due to the generation of particles is prevented by adding the heat treatment. The In particular, when the temperature during heating is in the range of 60 to 100 ° C., the effect of preventing the occurrence of defects is great, and the in-plane uniformity can be more effectively improved.

If the heating temperature is less than 60 ° C., in-plane defects such as generation of particles due to crystallization of dye cannot be suppressed, and in the range exceeding 100, in-plane defects such as generation of particles due to crystallization of dye, etc. Can not be suppressed. Especially, as heating temperature, the range of 60-80 degreeC is more preferable.
There is no restriction | limiting in particular in the temperature increase rate at the time of a heating, What is necessary is just to select suitably.

  The heating time varies depending on the heating temperature, but it is preferable to carry out until the solution becomes transparent without becoming cloudy. Specifically, the range is from 1 to 60 minutes after reaching 60 ° C, and reaches 60 ° C. The range of 3 to 30 minutes is more preferable. Among them, the heating is preferably performed at 60 to 90 ° C. for 1 to 60 minutes after reaching 60 ° C., and more preferably at 70 to 80 ° C. for 3 to 30 minutes after reaching 70 ° C.

  The dye solution can be heated using, for example, a known heater such as a warm bath or a heat bath (for example, a water bath) using a heat medium such as water or oil, a heater, or a burner.

  The mixing ratio (d / s) of the organic solvent-soluble dye (d) and the organic solvent (s) in the dye solution in this step is not particularly limited, but is preferably in the range of 10/90 to 40/60. In this case, it is preferable that the total amount of the dye contained in the dye-containing curable composition, that is, an amount of 10% by mass or more with respect to the total mass of the dye-containing curable composition is included.

  Next, each component (an organic solvent soluble dye, an organic solvent, etc.) used for preparation of a dye solution will be described. The dye solution may contain other components such as an alkali-soluble binder, if necessary, in addition to the organic solvent-soluble dye and the organic solvent. However, from the viewpoint of increasing the reactivity by heating, it is preferable that the photopolymerization initiator and the polymerizable compound to be added in the subsequent step should be suppressed to less than 1% by mass with respect to the total mass of the dye solution, and are not included ( 0 (zero) mass%) is preferable.

(Organic solvent soluble dye)
The organic solvent-soluble dye is not particularly limited, and conventionally known dyes for color filters can be used. Examples of organic solvent-soluble dyes include triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo dyes. Can be mentioned. Preferable examples include phthalocyanine, pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone dyes.

  Specific examples include, for example, xanthene dyes, pyrazolone azo dyes, phthalocyanine dyes, pyridone azo dyes, triallylmethane dyes described in paragraphs [0027] to [0103] of JP-A-2006-276512. And the like. Also, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, U.S. Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828.

  As the dye in the present invention, a phthalocyanine-based dye is preferable in that particulate precipitates (particles) such as crystallization of the dye are easily generated and a coating defect preventing effect is remarkably obtained.

Examples of the phthalocyanine dyes include compounds represented by the following general formula (I).

In the general formula (I), R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ are each independently a sulfonic acid group or a base thereof, a sulfonamide group, or a substituted sulfamoyl group represented by the following general formula (a) Represents. i, j, k, and m each independently represent an integer of 0 to 2, and satisfy i + j + k + m ≦ 4.

R ¹⁷ HNSO ₂ −... General formula (a)
In the general formula (a), R ¹⁷ is an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, or a carbon number. An alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having 2 to 12 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a phenyl group, An alkylcarboxylalkyl group represented by the following general formula (a-1) and an alkyloxycarbonylalkyl group represented by the following general formula (a-2) are represented.

^{R 180 -CO-O-R 181} - ··· formula (a-1)
In General Formula (a-1), R ¹⁸⁰ represents an alkyl group having 2 to 12 carbon atoms, and R ¹⁸¹ represents an alkylene group having 2 to 12 carbon atoms.

^{R 190 -O-CO-R 191} - ··· formula (a-2)
In General Formula (a-2), R ¹⁹⁰ represents an alkyl group having 2 to 12 carbon atoms, and R ¹⁹¹ represents an alkylene group having 2 to 12 carbon atoms.

The sulfonic acid group represented by R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ in the compound represented by the general formula (I) may be unsubstituted or may have a substituent.

Examples of the compound represented by the general formula (I) include C.I. I. Solvent Blue 25 (C.I. Solvent Blue 25), C.I. I. Solvent Blue 55 (C.I. Solvent Blue 55), C.I. I. Solvent Blue 67 (C.I. Solvent Blue 67), C.I. I. Acid Blue 249 (C.I. Acid Blue 249), C.I. I. Direct Blue 86 (CI Direct Blue 86) and the like can be mentioned. These may be used singly or in combination of two or more.
The compound represented by the general formula (I) is a dye having an absorption maximum at a wavelength of 600 to 700 nm.

  In the case of forming a resist system that performs water or alkali development, at least one of acid dyes and derivatives thereof is preferable in that the binder and / or dye can be satisfactorily removed by development. In addition, it is also useful to select and use at least one of direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and derivatives thereof as appropriate. is there.

  The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer used for preparation of a composition or a development process. The salt is selected in consideration of all the required performances such as salt formation with a basic compound, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like. Specific examples of the acid dyes include those described in paragraph numbers [0040] to [0048] of JP-A No. 2004-295116.

When the acid dye is contained as a component of the composition, it may be better to use it as a derivative of the acid dye because the acid dye may not be sufficiently soluble in the organic solvent used for the preparation. As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of an acidic dye, or the like can be used. Although it will not specifically limit if it can melt | dissolve in the solution of the dye containing curable composition to be prepared, the solubility with respect to the developing solution used at the time of an organic solvent or image development processing, light absorbency, other in dye containing curable composition It is selected in consideration of all necessary performance such as interaction with components, light resistance, heat resistance and the like.
The salt of the acidic dye and the nitrogen-containing compound may be effective for improving the solubility of the acidic dye (providing solubility in an organic solvent) and improving the heat resistance and light resistance. In addition, about the nitrogen-containing compound which forms a salt with an acidic dye, and the nitrogen-containing compound which forms an amide bond with an acidic dye and obtains the sulfonamide body of an acidic dye, paragraph number [0051] of Unexamined-Japanese-Patent No. 2004-295116 Reference can be made to the descriptions of [0064].

  The content concentration of the organic solvent-soluble dye in the dye solution is 10 to 50 with respect to the total mass of the dye solution from the viewpoint that the dye solid content concentration in the dye-containing curable composition is a high concentration of 30% by mass or more. % By mass is preferable, and 15 to 40% by mass is more preferable. When the dye concentration in the dye solution prepared in this step is within the above range, a dye-containing curable composition having a solid concentration of 30% by mass or more and hardly causing coating defects during coating is prepared. can do.

(Organic solvent)
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each component and the coating property when the dye-containing curable composition is used, and particularly the solubility of the dye and the binder, the coating property, It is preferable to select in consideration of safety.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as 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 monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as toluene, Xylene and the like are preferred.

  When these organic solvents contain the solubility of a dye and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, the improvement of a coating surface shape, etc. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The organic solvent may be used in advance in the dye solution in an amount necessary for the finally obtained dye-containing curable composition, or a part of the organic solvent may be added in a later step. . From such a viewpoint, the preferable content of the organic solvent in the dye solution is 10 to 50% by mass with respect to the total mass of the dye solution, and more preferably, from the viewpoint of coatability when a dye-containing curable composition is used. From the above, the total solid concentration of the finally obtained dye-containing curable composition is 30 to 80% by mass, more preferably 40 to 75% by mass, and particularly 50 to 70% by mass. Is the amount to be.

-Cooling process-
In the temperature lowering process, the temperature of the dye solution heated in the heating process is decreased to a range of 20 to 40 ° C. After heating, the temperature is lowered to 20 to 40 ° C. in advance before adding a photopolymerization initiator, a monomer component, or the like, thereby increasing the effect of preventing defects and contributing to improvement of in-plane uniformity.

  When the temperature of the dye solution after cooling is lowered to less than 20 ° C., the dye precipitates in the solution, and when it stays in the range exceeding 40 ° C., the photopolymerization initiator and the polymerizability in the subsequent mixing step. When the compound is added, the reaction easily proceeds, and the stability over time when the dye-containing curable composition is obtained is lowered.

  From the viewpoint of obtaining a dye-containing curable composition in which the occurrence of coating defects is less likely to occur during coating, the temperature is preferably decreased in the range of 25 to 35 ° C. Moreover, there is no restriction | limiting in particular in the temperature fall rate at the time of temperature fall, What is necessary is just to select suitably.

  The temperature lowering process is performed, for example, by using a cooling bath (for example, a water bath) using a refrigerant such as water, a blower fan, a refrigerant circulation cooler, a chiller, or a Peltier element, or by leaving it in a predetermined temperature environment. be able to. Examples of the refrigerant circulation cooler include a refrigerant circulation system including a cooling pipe that circulates and circulates the refrigerant and exchanges heat with the refrigerant to cool the ink.

-Mixing process-
In the mixing step, the photopolymerization initiator and the polymerizable compound are further mixed into the dye solution having been cooled in the temperature decreasing step within 12 hours from the completion of the temperature decrease. By mixing the photopolymerization initiator and the polymerizable compound within 12 hours from the end of temperature decrease, the effect of preventing the occurrence of coating defects when the dye-containing curable composition is applied is improved, and excellent in-plane uniformity. Is obtained.

  The end of temperature reduction means the time when the temperature of the dye solution falls below 40 ° C. Therefore, after the temperature of the dye solution falls below 40 ° C., the temperature is adjusted so that the temperature is maintained within the temperature range of 20 to 40 ° C. for 12 hours from the time when the temperature falls below 40 ° C.

  From the viewpoint of more stably preventing surface defects, the mixing of the photopolymerization initiator and the polymerizable compound is preferably within 10 hours from the end of the temperature decrease, and more preferably within 5 hours from the end of the temperature decrease.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it can polymerize the following polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraph numbers [0070] to [0079] of JP-A No. 2004-295116. Among these, an oxime compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Among these, 2- (O-benzoyloxime) -1- [4- (phenylthio) is preferable in that a good pattern (particularly, the rectangular shape of the pattern in the case of a solid-state imaging device) can be obtained with a smaller exposure amount. Oxime-O- such as phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone Acyl compounds are particularly preferred, and specific examples include CGI-124 and CGI-242 (manufactured by Ciba Specialty Chemicals).

  The photopolymerization initiator can contain a sensitizer and a light stabilizer described in paragraph No. [0078] of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph No. [0081]. Moreover, you may use another well-known initiator other than said photoinitiator for the dye-containing curable composition of this invention.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the total solid content of the dye-containing curable composition (the total content in the case of 2 or more) is 3 to 20% by mass from the viewpoint of more effectively obtaining the effect of the present invention. Is preferable, 4-19 mass% is more preferable, and 5-18 mass% is especially preferable.

(Polymerizable compound)
Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.

  Examples of the monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these (Co) polymers of carboxylic acids, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (copolymers). ) Polymer. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group with monofunctional or polyfunctional alcohols, amines or thiols. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like. Further, as itaconic acid ester, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like. Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.
In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. A urethane compound etc. are mentioned.
^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH ... (A)
[However, in General Formula (A), R ⁴ and R ⁵ each independently represent H or CH ₃ . ]

  About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set in accordance with the final performance design of the dye-containing curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. In addition, from the viewpoint of increasing the strength of the cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). A method of adjusting both sensitivity and intensity by using them together is also effective. It is also polymerizable with respect to compatibility and dispersibility with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the dye-containing curable composition. The selection and use method of the compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more compounds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

  The content of the polymerizable compound in the total solid content of the dye-containing curable composition (in the case of two or more types) is not particularly limited, and from the viewpoint of more effectively obtaining the effects of the present invention. 10-80 mass% is preferable, 15-75 mass% is more preferable, 20-60 mass% is especially preferable.

  In the present invention, the content of the organic solvent-soluble dye in the total solid mass of the dye-containing curable composition is 30% by mass or more in terms of color density, but in the range of 30 to 80% by mass. From the viewpoint of making the film thinner and forming a thin film having a thickness of 1 μm or less (for example, a colored film (color filter) constituting a solid-state imaging device), 40 to 75% by mass is more preferable, and 50 to 70% by mass is particularly preferable.

(Other ingredients)
In addition to the above components, the dye-containing curable composition of the present invention may further contain other components such as an alkali-soluble binder and a crosslinking agent as long as the effects of the present invention are not impaired. In this case, other components may be added to the dye solution containing the organic solvent-soluble dye, or may be added together with the photopolymerization initiator in the subsequent mixing step, and in particular, the effects of the present invention are not impaired. From the viewpoint, a form added in the mixing step is desirable.

-Alkali-soluble binder-
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group and an acid anhydride added thereto, a polyhydroxystyrene resin, a polysiloxane resin, and poly (2-hydroxyethyl (meth) acrylate). ), Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

-Crosslinking agent-
Supplementally, a crosslinking agent may be used to obtain a highly cured film when the dye-containing curable composition is cured. Hereinafter, the crosslinking agent will be described.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 for melamine compounds, 2 for glycoluril compounds, guanamine compounds, and urea compounds. Although it is -4, Preferably it is 5-6 in the case of a melamine compound, and is 3-4 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 (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b).

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

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used singly or in combination of two or more.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Compounds obtained by methoxymethylating 1 to 3 methylol groups of methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned. Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene. Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.
Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used singly or in combination of two or more.

  In the present invention, it is not always necessary to contain a crosslinking agent. When it contains a crosslinking agent, the total content of the crosslinking agents (a) to (c) in the dye-containing curable composition varies depending on the material, but is based on the solid content (mass) of the curable composition. 1-70 mass% is preferable, 5-50 mass% is more preferable, 7-30 mass% is especially preferable.

-Other additives-
In the dye-containing curable composition of the present invention, various additives, for example, fillers, polymer compounds other than the above, nonionic, cationic, anionic surfactants, adhesion promoters, if necessary, Antioxidants, ultraviolet absorbers, aggregation inhibitors and the like can be blended. Examples of the various additives include those described in paragraph numbers [0155] to [0157] of JP-A No. 2004-295116.

  Further, when the alkali solubility in the non-exposed area is promoted and the developability of the dye-containing curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. A molecular weight organic carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In the present invention, among the above, the content of the dye with respect to the total mass of the dye-containing curable composition is 10 to 50% by mass, and the heating in the heating step is from 70 ° C. to 70 to 80 ° C. More preferably, the temperature of the dye solution after the temperature lowering in the temperature lowering step is 25 to 35 ° C., and the mixing in the mixing step is within 5 hours from the end of the temperature lowering.

The dye-containing curable composition of the present invention can be suitably used for forming a colored pixel such as a color filter used in a liquid crystal display (LCD), a solid-state imaging device (for example, CCD, CMOS, etc.) and the like.
The dye-containing curable composition of the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required. Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the effect of coarse particles in the pigment In the dye, when the amount of the dye occupying the entire composition is increased in order to increase the image density, a coating defect due to the dye (such as a crystal) is likely to occur. This is because when the pixel pattern is 2 μm or less, particularly 1.0 to 1.7 μm (further 1.0 to 1.5 μm), the coating defect becomes relatively large with respect to the pixel region, and the allowable defect width is small. The yield decreases due to narrowing, and in the case of a thin film having a thickness of 1 μm or less, the dye content is relatively high and particles are easily generated, and the generated defects are also conspicuous. Become prominent. In particular, when the thickness becomes 0.1 μm to 0.9 μm (further 0.1 μm to 0.7 μm), it appears more remarkably.
When such a color filter for a solid-state imaging device is formed, a pattern having good in-plane uniformity and excellent hue can be obtained by using the dye-containing curable composition of the present invention.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the dye-containing curable composition of the present invention described above is used. By using the dye-containing curable composition of the present invention, the occurrence of film defects (for example, crystallized particles (particles), etc.) caused by dyes after application can be suppressed, so that a high color density can be achieved with a thin film. Even in the case of (dye concentration), a color filter composed of a colored pattern with few coating defects and high in-plane uniformity can be produced.

  The method for producing a color filter of the present invention comprises a step of applying a dye-containing curable composition of the present invention on a support, exposing the coated film formed (for example, through a mask), and developing to form a pattern. Is provided. Specifically, the dye-containing curable composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation sensitive composition layer, A color filter can be suitably produced by forming a negative colored pattern by exposing through a predetermined mask pattern and developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  In the production of a color filter, a color filter having a desired hue can be produced by repeating the image forming step (and curing step if necessary) by the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

The exposure may be performed by any of a proximity method, a mirror projection method, and a stepper method. In particular, the exposure is performed by a stepper method (reduction projection exposure method using a reduction projection exposure machine). preferable. In the stepper method, a pattern is formed by performing exposure while varying the exposure amount stepwise, and the rectangularity of the pattern can be particularly improved when performing stepper exposure.
Moreover, as an exposure apparatus used for stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be used.

  Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

Any developer can be used as long as it has a composition that dissolves the dye-containing curable composition (uncured part) of the present invention but does not dissolve the irradiated cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned organic solvent used when preparing the dye-containing curable composition of this invention is mentioned. As the alkaline aqueous solution, for example, an alkaline aqueous solution obtained by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is suitable. Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline. , Pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans with water after image development.

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

<Solid-state imaging device>
The solid-state imaging device of the present invention is configured by providing the above-described color filter of the present invention. The color filter of the present invention is a colored pattern in which the occurrence of film defects is prevented by using the dye-containing curable composition of the present invention, and the solid-state imaging device provided with this color filter has excellent color reproducibility. Have.

The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
A support body has a plurality of photodiodes constituting a light receiving area of a CCD image sensor (solid-state imaging device) and a transfer electrode made of polysilicon or the like, and only the light receiving portion of the photodiode is placed on the photodiode and the transfer electrode. It has a light shielding film made of tungsten or the like having an opening, and has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, on the device protective film, This is a configuration having the color filter of the present invention. Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.

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

(Examples 1-15, Comparative Examples 1-18)
<Preparation of negative curable composition>
-Preparation of a negative curable composition of composition A-
Among the components in the following composition A, first, C.I. I. Solvent Blue 25 (dye) and cyclohexanone were mixed to prepare a dye solution. After starting the heating of the dye solution at the heating temperatures shown in Tables 2 to 3, water was added for 10 minutes from the temperature (° C.) in the table. It heated using the bath (heating process). Note that the negative curable compositions A11 and B4 are not heated. After completion of the heating, the dye solution in which the dye was dissolved was allowed to cool at room temperature (25 ° C.) (cooling step), and the temperature of the dye solution was lowered to the cooling temperatures shown in Tables 2 to 3 below. The temperature lowering rate at this time was 2 ° C./min. Subsequently, when the time shown in Tables 2 to 3 below has elapsed since the temperature of the dye solution reached 40 ° C. during the cooling process, oxime A, monomer A, and alkali-soluble binder A were added to the dye solution. Furthermore, 18 types of negative curable compositions A1 to A18 were prepared by stirring and dissolving, and using a dye as a colorant.
<Composition A of negative curable composition>
・ Cyclohexanone (organic solvent): 26g
・ Alkali-soluble binder A ... 3.0g
(Benzyl methacrylate / methacrylic acid (= 85/15 [molar ratio]) copolymer)
・ Monomer A (polymerizable compound) of the following structure: 2.0 g
Oxime A (2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (manufactured by Ciba Specialty Chemicals), photopolymerization initiator) 1.0g
・ C. I. Solvent Blue 25 (organic solvent-soluble dye) ... 4.0 g

-Preparation of a negative curable composition having compositions B to D-
In the preparation of the negative curable compositions A1 to A18 of the composition A, the types and amounts of the components and the preparation conditions (heating temperature, cooling temperature, time until charging) are changed as shown in Tables 1 to 3 below. Except having carried out, it carried out similarly to negative curable composition A1-A18, and prepared 15 types of negative curable compositions B1-B9, C1-C3, D1-D3 further.

<Production of color filter>
-Production of silicon wafer with undercoat layer-
A resist CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto a silicon wafer using a spin coater so as to have a film thickness of 2 μm, and is heated and dried at 220 ° C. for 1 hour to form a cured film. (Undercoat layer) was formed.

-Exposure and development of negative curable composition (image forming process)-
Next, using each of the negative curable compositions of compositions A to D prepared as described above, spin was performed on the obtained undercoat layer of the silicon wafer with the undercoat layer so that the dry film thickness was 1 μm. Coating was performed using a coater and prebaked at 100 ° C. for 120 seconds to form a colored film on the silicon wafer. With respect to this colored film, an exposure amount is obtained by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through a mask pattern in which square pixels of 2.0 μm are arranged in a 4 mm × 3 mm region on the substrate. It was exposed to light at an intensity 1200mW / cm ² at 100mJ / cm ^2. After the exposure, paddle development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by FUJIFILM Electronics Materials Co., Ltd.). Subsequently, it was rinsed with running water for 20 seconds and then spray-dried. Thereafter, post-baking was performed on a hot plate at 220 ° C. for 300 seconds to form a colored pattern on the silicon wafer.
As described above, a color filter for a solid-state imaging device was produced.

<Evaluation>
The following evaluation was performed about the color filter produced as mentioned above. The evaluation results are shown in Tables 2 to 3 below.

-1. Film defects (coating defects)
Foreign matter contained in the colored film before exposure / development after pre-baking is detected by the foreign matter evaluation apparatus Conplus III (manufactured by Applied Materials). From all the detected foreign matter, Foreign matters having a size of 1.0 μm or more were classified visually. The number of classified foreign matters having a maximum width of 1.0 μm or more (number per 1 cm ² ) was counted, and film defects were evaluated using the obtained value as an index. The foreign substance evaluation apparatus Conplus III has a different number of foreign substances depending on the state of the film. Therefore, it is necessary to check the in-plane uniformity of the film in advance when evaluating the foreign substance. For the group of coating films having in-plane uniformity within 100 nm, the number of foreign matters can be compared in the same row.

-2. In-plane uniformity
The film thickness of the colored film after exposure and development after pre-baking was measured using a non-contact type film thickness meter (FILMMETRICCSF-50, manufactured by Matsushita Techno Trading Co., Ltd.), and the in-plane uniformity of the colored film (range: Δ Value [μm] = Max−Min).

  As shown in Tables 2 to 3, in the examples, the number of defects was reduced, and a color filter excellent in in-plane uniformity could be produced. On the other hand, in the comparative example, the occurrence of surface defects appeared remarkably, and a uniform film could not be formed.

Claims (5)

A heating step of heating a dye solution obtained by mixing at least an organic solvent-soluble dye and an organic solvent to 60 to 100 ° C .;
A temperature lowering step of lowering the temperature of the dye solution after heating to a range of 20 to 40 ° C .;
A mixing step of further mixing a photopolymerization initiator and a polymerizable compound in the dye solution after the temperature decrease within 12 hours from the end of the temperature decrease;
And a method for producing a dye-containing curable composition for producing a curable composition having a content of the organic solvent-soluble dye in a total solid mass of 30% by mass or more.   The method for producing a dye-containing curable composition according to claim 1, wherein the organic solvent-soluble dye is a phthalocyanine dye.   The color filter formed using the dye-containing curable composition produced by the manufacturing method of the dye-containing curable composition of Claim 1 or Claim 2.   After the dye-containing curable composition produced by the method for producing a dye-containing curable composition according to claim 1 or 2 is coated on a support, the coated film formed by coating is exposed and developed. A method for producing a color filter comprising a step of forming a pattern.   A solid-state imaging device comprising the color filter according to claim 4.