JP2006010911A - Colored photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive composition capable of reducing the degree of increase in film thickness and the degree of increase in viscosity when applied after long-term storage. <P>SOLUTION: The colored photosensitive composition comprises a dye, a photosensitizing agent, a curing agent, a solvent and compounds represented by formulae (I) and (II), wherein a content of the compounds is 1-12 mass% based on the amount of the colored photosensitive composition. In the formula (I), R<SP>1</SP>represents alkyl. In the formula (II), R<SP>2</SP>-R<SP>4</SP>each independently represents H, alkyl or aryl, and the alkyl and aryl may be substituted by hydroxyl or alkyl, provided that one of R<SP>2</SP>-R<SP>4</SP>represents a group other than H. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a colored photosensitive composition.

  Colored photosensitive compositions are widely used as raw materials for forming pixels, which are constituent units of color filters used in color liquid crystal display devices and image sensors. As the colored photosensitive composition, for example, those containing a dye, an alkali-soluble resin and a photosensitizer are known, and those containing a curing agent in addition to these are also known (see, for example, Patent Document 1). ).

  In order to form a pixel using the colored photosensitive composition, for example, there is a method in which a layer made of the colored photosensitive composition is formed on the surface of the substrate, and the layer is exposed by irradiating light through a mask. Are known. By treating the colored photosensitive composition layer after exposure with a developer, the exposed area of the colored photosensitive composition layer exposed to light is dissolved in the developer, and the unexposed area is dissolved. The pixel remains without being formed. By repeating the same operation while changing the color of the pigment contained in the colored photosensitive composition, pixels of each color corresponding to the three primary colors can be sequentially formed to obtain a color filter (see, for example, Patent Document 2). ).

  However, some colored photosensitive compositions containing a dye and a melamine-based curing agent increase the film thickness at the time of coating due to an increase in the viscosity of the composition during storage. The cause of the increase in viscosity is not clear, but is thought to be due to condensation between the curing agents or bonding between the curing agent and other substances contained in the composition. As a result, when the coating thickness of the colored photosensitive composition is increased, the increased thickness may cause a colored photosensitive composition that does not dissolve in the developer even when irradiated with light rays in exposure. Even if dissolved during development, the post-development pattern line width may become thick, and it may be difficult to form pixels with the intended pattern. For this reason, the photosensitive composition using a dye has a problem that pixels cannot be formed with an expected exposure amount. (For example, refer to Patent Document 3).

  In general, when a resist is used, its applicability often becomes a problem. The problem of applicability is that there is a problem with film thickness uniformity in the wafer plane. The problem of film thickness uniformity means that when the film thickness is measured at a plurality of points within the wafer surface, the film thickness value fluctuates despite being within the same wafer. If there is a problem in the film thickness uniformity, the film thickness uniformity in the wafer surface becomes worse and a phenomenon called coating unevenness occurs. Since the pattern formation state has changed in the coating unevenness portion as compared with other portions where the film thickness is uniform, the yield decreases.

JP-A-7-268236, page 2, right column, lines 21-22 Japanese Patent Laid-Open No. 7-306309, page 11, right column, lines 28-35 JP, 2002-196482, A, page 2, right column, line 34-page 2, right column, line 40

Therefore, the present inventors diligently studied to develop a colored photosensitive composition having a small degree of increase in coating thickness after long-term storage. In the process, it was found that when the compound represented by formula (I) was added to the composition, the degree of increase in the coating film thickness during coating was reduced.
Further, as a result of further studies, a film obtained by applying a colored photosensitive composition after long-term storage by using a compound represented by the formula (II) in addition to the compound represented by the formula (I). It was found that the degree of increase in thickness and the degree of increase in viscosity could be reduced, leading to the present invention.

  That is, the present invention includes a dye, a photosensitizer, a curing agent, a solvent, a compound represented by formula (I) and a compound represented by formula (II), and the content of the compound represented by formula (I) is A colored photosensitive composition having a mass fraction of 1 to 12% by mass with respect to the photosensitive composition, a pixel obtained using the colored photosensitive composition, a color filter having the pixel, and the above An image sensor including a color filter is provided.

[In Formula (I), R ¹ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.
In formula (II), R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclohexane having 3 to 6 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is represented. The hydrogen atom on the alkyl group, the hydrogen atom on the cycloalkyl group, and the hydrogen atom on the aryl group may be substituted with a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. However, at least one of R ^{2 to} R ⁴ represents a group other than a hydrogen atom. ]

  The colored photosensitive composition of the present invention has the same coating thickness as that immediately after the preparation because there is little increase in the coating thickness at the time of coating caused by the increase in viscosity during storage even after storage for a long time. Represents film thickness. That is, regardless of the storage period, it can be the same as the case where the colored photosensitive composition immediately after the adjustment is used.

  The colored photosensitive composition of the present invention contains a dye. The dye is not particularly limited as long as it can be dissolved in an organic solvent used in the photosensitive composition and can form a pixel of a color filter. For example, C.I. I. Solvent Yellow 4 (hereinafter, CI Solvent Yellow is omitted and only numbers are described. Other dye types and hues are also omitted) 14, 15, 23, 24 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Solvent Red 45, 49, C.I. I. Solvent Orange 2, 7, 11, 15, 26, 56, C.I. I. Solvent blue 35, 37, 59, 67 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. Acid Yellow 17, 29, 40, 76, C.I. I. Acid Red 91, 92, 97, 114, 138, 151, C.I. I. Acid Orange 51, 63, C.I. I. Acid Blue 80, 83, 90, C.I. I. Examples include dyes such as Acid Green 9, 16, 25, and 27. The dye used in the present invention is not limited to the exemplified dyes.

The dyes of the colored photosensitive composition of the present invention include amine salts of acidic dyes represented by formulas (i) to (vii) and sulfones of acidic dyes represented by formulas (viii) to (ix). Amide compounds can also be used.

D- (SO ₃ ⁻ ) _m (C _n H _{2n + 1} N ⁺ H ₃ ) _m (i)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₂ N ⁺ H ₂ } _m (ii)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₃ N ⁺ H} _m (iii)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) ₄ N ⁺ } _m (iv)
D- (SO ₃ ⁻ ) _m (C _e H _{2e + 1} OC _f H _2f N ⁺ H ₃ ) _m (v)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) (PhCH ₂ ) ₂ N ⁺ H} _m (vi)
D- (SO ₃ ⁻ ) _m {(C _n H _{2n + 1} ) Py ⁺ } _m (vii)
_{D - [{SO 2 NH (} C n H 2n + 1)} p] [(SO 3 L) q] (viii)
D-[{SO ₂ NH (C _e H _{2e + 1} OC _f H _2f )} _p ] [(SO ₃ L) _q ] (ix)

[In formulas (i) to (ix), D represents a dye matrix.
m represents an integer of 1 or more and 20 or less.
n represents an integer of 1 or more and 20 or less.
e and f each independently represents an integer of 1 or more and 10 or less.
Ph represents a phenyl group.
Py represents a pyridine ring residue or a methylpyridine ring residue connected to C _n H _{2n + 1} by a nitrogen atom.
p represents an integer of 1 to 8.
q represents an integer of 0 or more and 8 or less.
L represents a hydrogen atom or a monovalent cation. ]

Specific examples of D include an azo dye matrix, a xanthene dye matrix, an anthraquinone dye matrix, a triphenylmethane dye matrix, and a phthalocyanine dye matrix.
m preferably represents an integer of 1 to 10, more preferably an integer of 1 to 8.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 8.
e and f each independently preferably represent an integer of 1 to 8, more preferably an integer of 1 to 6.
Py preferably represents a methylpyridine ring residue.
p preferably represents an integer of 1 to 6, more preferably an integer of 1 to 5.
q preferably represents an integer of 0 to 6, more preferably an integer of 0 to 5.
Examples of the monovalent cation in L include lithium ions, sodium ions, potassium ions, quaternary ammonium ions such as (C ₂ H ₅ ) ₃ HN ⁺ , and preferably sodium ions.

  The content of the dye in the colored photosensitive composition of the present invention is a mass fraction with respect to the solid content of the colored photosensitive composition, preferably 5 to 70% by mass, more preferably 5 to 50% by mass. . When the content of the dye is in the above range, it is preferable because the color density is sufficient as a color filter and the film loss during development tends to be small.

  Examples of the photosensitive agent used in the colored photosensitive composition of the present invention include ester compounds of a phenol compound and an o-naphthoquinonediazide sulfonic acid compound. Here, examples of the phenol compound include di, tri, tetra, and pentahydroxybenzophenone, and compounds represented by the formulas (41) to (51).

  Examples of the o-naphthoquinone diazide sulfonic acid compound include o-naphthoquinone diazide-5-sulfonic acid and o-naphthoquinone diazide-4-sulfonic acid.

  Specifically, the photosensitive composition in the present invention is an ester of 2,3,4,4′-tetrahydroxybenzophenone and o-naphthoquinonediazide-5-sulfonic acid, a compound represented by the formula (41) And o-naphthoquinonediazide-5-sulfonic acid ester, a compound represented by formula (42) and o-naphthoquinonediazide-5-sulfonic acid ester, a compound represented by formula (43) and o-naphtho Esters with quinonediazide-5-sulfonic acid, compounds with formula (44) and o-naphthoquinonediazide-5-sulfonic acid, compounds with formula (45) and o-naphthoquinonediazide-5 Esters with sulfonic acid, compounds with formula (46) and o-naphthoquinonediazide-5-sulfonic acid, compounds with formula (47) and o- Esters with phtoquinonediazide-5-sulfonic acid, compounds with formula (48) and o-naphthoquinonediazide-5-sulfonic acid, compounds with formula (49) and o-naphthoquinonediazide-5 -Ester with sulfonic acid, ester of compound represented by formula (50) and o-naphthoquinonediazide-5-sulfonic acid, compound represented by formula (51) and o-naphthoquinonediazide-5-sulfonic acid An ester of a compound represented by formula (41) and o-naphthoquinonediazide-4-sulfonic acid, an ester of a compound represented by formula (42) and o-naphthoquinonediazide-4-sulfonic acid, a formula Ester of a compound represented by (43) and o-naphthoquinonediazide-4-sulfonic acid, a compound represented by formula (44) and o-naphthoquino Esters with diazide-4-sulfonic acid, esters with a compound represented by formula (45) and o-naphthoquinonediazide-4-sulfonic acid, compounds with a formula (46) and o-naphthoquinonediazide-4- Esters of sulfonic acid, compounds of formula (47) and o-naphthoquinonediazide-4-sulfonic acid, compounds of formula (48) and o-naphthoquinonediazide-4-sulfonic acid Ester, ester of compound represented by formula (49) and o-naphthoquinonediazide-4-sulfonic acid, ester of compound represented by formula (50) and o-naphthoquinonediazide-4-sulfonic acid, formula ( 51) and an ester of o-naphthoquinonediazide-4-sulfonic acid, preferably a compound represented by formula (41) and o- Esters with naphthoquinonediazide-5-sulfonic acid, compounds with formula (43) and o-naphthoquinonediazide-5-sulfonic acid, compounds with formula (51) and o-naphthoquinonediazide-5 -Esters with sulfonic acid, esters with 2,3,4,4'-tetrahydroxybenzophenone and o-naphthoquinonediazide-5-sulfonic acid. Moreover, the photosensitive agent used for the colored photosensitive composition of this invention is not restricted to the said compound, The photosensitive agent used for i line | wire photoresist can be used.

  Content of a photosensitive agent is a mass fraction with respect to solid content of a coloring photosensitive composition, Preferably it is 20-50 mass%, More preferably, it is 30-45 mass%. It is preferable that the content of the photosensitizer is in the above-mentioned range since both the residual film ratio after development at the time of pattern formation and the exposure time at the time of pattern formation tend to be good.

  As the curing agent used in the colored photosensitive composition of the present invention, a curing agent that is cured by heating is used. Examples of the curing agent include compounds represented by the formula (III).

[In the formula (III), 6 R ^{5 s} are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a 3 to 10 carbon atoms. Represents a cycloalkyl group. However, at least two of the six R ⁵ are not hydrogen atoms. ]

  Examples of the linear alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Examples thereof include an n-nonyl group and an n-decanyl group, preferably a methyl group, an ethyl group and an n-propyl group, and more preferably a methyl group.

  Examples of the branched alkyl group having 3 to 10 carbon atoms include an isopropyl group and a group represented by the following structural formula.

  Among them, the branched alkyl group having 3 to 10 carbon atoms is preferably an isopropyl group, a sec-butyl group, or a tert-butyl group, and more preferably an isopropyl group.

  Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group, preferably a cyclobutyl group, a cyclopentyl group, A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, More preferably, a cyclohexyl group is mentioned.

R ⁵ is preferably a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or a carbon number. Examples thereof include 3 to 4 branched alkyl groups, and particularly preferably a methyl group.

  Specific examples of the compound represented by the formula (III) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine, preferably hexamethoxymethyl melamine.

  Content of a hardening | curing agent is a mass fraction with respect to solid content of a coloring photosensitive composition, Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. When the content of the curing agent is in the above range, the mechanical strength when the formed color filter pattern is heat-cured is sufficient, and the film thickness of the color filter is less likely to occur in the development process, resulting in uneven color of the image. It is preferable because it hardly occurs.

  The colored photosensitive composition of the present invention contains a compound represented by the formula (I).

[In Formula (I), R ¹ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. ]

Examples of the linear alkyl group having 1 to 10 carbon atoms include the same groups as described above. Examples of the branched alkyl group having 3 to 10 carbon atoms include the same groups as described above. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and preferably a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. More preferably, a cyclohexyl group is mentioned.
R ¹ is preferably methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, sec-butyl, tert-butyl and the following: More preferred are methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group, sec-butyl group and tert-butyl group.

R ¹ in formula (I) and R ⁵ in formula (III) preferably represent the same group.

When methanol in which R ¹ is a methyl group is used as the compound represented by formula (I), it is preferable to use hexamethoxymethylmelamine in which R ⁵ represents a methyl group as the compound represented by formula (III). .

  The content of the compound represented by the formula (I) is 1 to 12% by mass, preferably 3 to 10% by mass, more preferably 5 to 5% by mass with respect to the colored photosensitive composition. 9% by mass. When the amount of the compound represented by formula (I) is within the above range, the change in viscosity can be suppressed when the colored photosensitive composition is stored, and the coating surface is uneven when coated on the substrate. Is difficult to observe and is preferable.

  The colored photosensitive composition of the present invention contains a compound represented by the formula (II).

[In the formula (II), R ^{2 to} R ⁴ each independently represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a carbon atom having 3 to 6 carbon atoms. A cycloalkyl group or an aryl group having 6 to 12 carbon atoms is represented. The hydrogen atom of the alkyl group, the hydrogen atom of the cycloalkyl group, and the hydrogen atom of the aryl group may be substituted with a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. However, at least one of R ^{2 to} R ⁴ represents a group other than a hydrogen atom. ]

The alkyl group having 1 to 6 carbon atoms in R ² to R ^4, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, hexyl and the like, preferably methyl group, ethyl Group and propyl group.
As a C3-C6 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group etc. are mentioned, for example, Preferably a cyclohexyl group is mentioned.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group.

  Specific examples of the compound represented by the formula (II) include N-methylamine, N-ethylamine, N-cyclohexylamine, N, N-dimethylamine, N, N-diethylamine, N, N-methylphenyl. Preferred examples include amine, N, N-methylcyclohexylamine, trimethylamine, triethylamine, methyldiphenylamine, dimethylcyclohexylamine, methylphenylcyclohexylamine, triphenylamine, p-aminophenol, 3-amino-1-propanol. Are p-aminophenol, methyldicyclohexylamine, 3-amino-1-propanol, and the like.

  Content of the compound represented by Formula (II) is a mass fraction with respect to solid content of a coloring photosensitive composition, Preferably it is 0.02-5 mass%, More preferably, it is 0.1-4 mass%. It is. When the content of the compound represented by the formula (II) is in the above range, the ratio of change in film thickness during coating before and after storage tends to be small, and the decrease in the residual film ratio tends to be small, which is preferable.

  Moreover, the sum of the content of the compound represented by the formula (I) and the content of the compound represented by the formula (II) is a mass fraction with respect to the colored photosensitive composition, preferably 3 to 12 masses. %, More preferably 4 to 10% by mass. When the sum of the content of the compound represented by the formula (I) and the content of the compound represented by the formula (II) is in the above range, the ratio of the film thickness change during coating before and after storage is small, Moreover, there is a tendency that the decrease in the development residual film ratio tends to be small, which is preferable.

Examples of the solvent used in the colored photosensitive composition of the present invention include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, N -Methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, N, N-dimethylformamide, cyclohexanone, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, ethyl pyruvate, ethyl lactate, etc., preferably propylene glycol monomethyl Examples include ether, N, N-dimethylformamide, and ethyl lactate, and more preferable examples include N, N-dimethylformamide and ethyl lactate.
These solvents may be used alone or in combination of two or more. Content of a solvent is a mass fraction with respect to the photosensitive composition, and is 60-80 mass% normally.

  The colored photosensitive composition of the present invention may contain an alkali-soluble resin as long as the effect is not impaired. The alkali-soluble resin is a resin that can be dissolved in an alkaline developer, and the same alkali-soluble resin as that used in a normal photosensitive resin composition can be used. Examples of the alkali-soluble resin include novolak resins and vinyl phenol resins, and novolak resins are preferable. Examples of the novolak resin include a novolak resin obtained by condensing p-cresol and formaldehyde, a novolak resin obtained by condensing p-cresol and m-cresol and formaldehyde, and the like. Examples of the vinyl phenol resin include polyvinyl phenol and styrene-vinyl phenol copolymer.

  In the colored photosensitive composition of the present invention, since the degree of increase in film thickness during coating during storage is reduced, a color filter is produced by a process of patterning the colored photosensitive composition to form pixels. For example, even with a colored photosensitive composition after storage, pixels can be formed under the same conditions as immediately after adjustment. Furthermore, since the colored photosensitive composition of the present invention has good coating properties, it is not necessary to pay special attention to coating properties during coating.

  In order to pattern using the colored photosensitive composition of the present invention, a layer made of the colored photosensitive composition of the present invention is formed over the entire surface of the substrate in the same manner as usual, and a mask is formed on the layer. The exposure may be performed by irradiating with a light beam through the.

  The substrate may be a glass plate or the like, or a silicon wafer or the like. The silicon wafer may have a solid-state imaging device such as a charge coupled device formed on the surface thereof. In order to form the colored photosensitive composition layer of the present invention on such a substrate, the colored photosensitive composition may be applied by a method such as spin coating as usual.

  As the light beam, for example, i-line (wavelength 365 nm), g-line, ArF, KrF can be used, and i-line is preferably used. The exposure can be performed using a normal exposure machine. An optical lens may be disposed between the mask and the colored photosensitive composition layer. The optical lens is used, for example, to collect light rays that have passed through the mask and form pixels having a size smaller than that of the mask.

  Since the mask is provided with a region that transmits light and a region that blocks light, the colored photosensitive resin composition layer includes a region that is exposed to light and exposed and a region that is not irradiated with light.

  After exposure, by treating the colored photosensitive composition layer with a developer, the exposed area of the colored photosensitive composition layer exposed to light is dissolved in the developer, and the area not irradiated with light. Remains without melting and constitutes a pixel.

As the developer, the same developer as that usually used for developing the photosensitive composition can be used, and a commercially available developer can also be used. As the developer, an alkaline aqueous solution is preferably used. In order to perform the treatment with the alkaline aqueous solution, for example, the photosensitive composition layer after exposure may be immersed in an alkaline aqueous solution together with the substrate.
After treating with an alkaline aqueous solution, the pixel is obtained by washing with water and drying.

  Such pixels are colored with a dye contained in the colored photosensitive composition. Further, the pattern is the same as the region that shields the light beam of the mask, and may be, for example, a band shape or a mosaic shape.

  When a colored photosensitive composition containing a curing agent is used, after processing with a developing solution, the obtained pixel is usually cured by heating to improve its mechanical strength. Can do.

  Next, by changing the color of the dye contained in the colored photosensitive composition and repeating the same operation as described above, corresponding color pixels can be sequentially formed to obtain a color filter.

  The color filter thus obtained is useful as a color filter for color liquid crystal display devices and image sensors.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

Example 1
(Preparation of colored photosensitive composition 1)
The following components were mixed, and the mixture was filtered through a membrane filter (pore diameter: 0.1 μm) to obtain a colored photosensitive composition 1.

C. I. Solvent Blue 67 (Dye) 16 parts by mass N, N′bis (1-methyl-3-phenylpropyl) -4,4′-bis (5-hydroxy-3-methyl-1-phenyl-1H-pyrazole-4- Ylazo) bisphenyl-2,2′disulfonamide (dye) 1 part by mass 1-benzoyl-6- [2- (1-methyl-3-phenylpropylsulfamoyl) anilino] -4- (4-pentylphenyl)- 3H-dibenz [f, i, j] isoquinoline-2,7-dione (dye) 1 part by mass 1-4- (7-hydroxy-2,4,4-trimethyl-2-chromanyl) resorcinol (bis, tris) -(6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonate) and 4- (7,8-dihydroxy-2,4,4-trimethyl-2-chromanyl) pyro Roll (mono, bis, tris, tetrakis, pentakis) (6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonate) (photosensitizer) 11 parts by mass 4- [1 ', 2' , 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol tris (6-diazo-5,6- Dihydro-5-oxo-1-naphthalenesulfonate) (photosensitive agent) 32 parts by mass hexamethoxymethylmelamine (curing agent) 35 parts by mass methanol (compound represented by formula (I)) 24 parts by mass 3-amino-1 -Propanol (compound represented by formula (II)) 0.1 parts by mass ethyl lactate (solvent) 266 parts by mass N, N-dimethylformamide (solvent) 15 parts by mass

(Evaluation)
(1) Thickness of the colored photosensitive composition layer immediately after preparation of the colored photosensitive composition The colored photosensitive composition 1 immediately after preparation obtained above is spin-coated on a silicon wafer at a rotational speed of 2300 rpm. And a coating film was obtained. The coating film was heated at 100 ° C. for 1 minute, and the solvent in the colored photosensitive composition 1 was volatilized and removed to form a colored photosensitive composition layer. The thickness of the resulting colored photosensitive composition layer, film thickness meter is determined using the model number;; VM-800J Dainippon Screen Co., Ltd.], and the thickness thereof was set to FT _0. Then, the colored photosensitive composition layer is exposed by being irradiated with i-line (wavelength 365 nm) through a mask for obtaining a strip-shaped pattern using an exposure machine [Nikon NSR 1755i7A; manufactured by Nikon Corporation]. After the exposure, the colored photosensitive composition layer after exposure is immersed in a developer (3% tetramethylammonium hydroxide aqueous solution) maintained at 23 ° C. for 1 minute, developed, washed with water, dried, and the line width is increased. A blue pixel formed in a band-like pattern having a thickness of 50 μm was formed.

(2) Thickness of the colored photosensitive composition layer after storage of the colored photosensitive composition The colored photosensitive composition 1 obtained as described above is placed in a brown glass bottle capable of shielding visible light, and at room temperature. After stored for 4 weeks, using the same method as described above, the colored photosensitive composition layer is formed, its thickness is the FT _1.

(3) Rate of change in thickness of the resulting colored photosensitive composition layer before and after storage of the colored photosensitive composition From the thicknesses FT ₀ and FT ₁ obtained above, the colored photosensitive composition is calculated according to the calculation formula (4). The rate of change (R) in the thickness of the composition layer was calculated. The results are shown in Table 1.

_{R = FT 1 / FT 0 (} 4)

Comparative Example 1
A colored photosensitive composition 2 was obtained in the same manner as in Example 1 except that methanol and 3-amino-1-propanol were not used, and the colored photosensitive composition layer was evaluated in the same manner as in Example 1. The rate of change in thickness (R) was calculated. The results are shown in Table 1.

Example 2
(Preparation of colored photosensitive composition 3)
The following components were mixed, and the mixture was filtered through a membrane filter (pore diameter: 0.1 μm) to obtain a colored photosensitive composition 3.

5-hydroxy-N- (1-methyl-3-phenylpropyl) -1- [4- (1-methyl-3-phenylpropylsulfamoyl) phenyl] -4- [4- (1-methyl-3-phenylpropiyl) Rusulfamoyl) phenylazo] -1H-pyrazole-3-carboxamide (dye) 7 parts by mass 1- [4- (1-methyl-3-phenylpropylsulfamoyl) phenyl] -4- [4- (1-methyl- 3-phenylpropylsulfamoyl) phenylazo] -5-hydroxy-1H-pyrazole-3-carboxylic acid (dye) 11 parts by mass N, N′bis (1-methyl-3-phenylpropyl) -4,4′-bis (5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-ylazo) bisphenyl-2,2′disulfonamide (dye) 15 mass 4- (7-hydroxy-2,4,4-trimethyl-2-chromanyl) resorcinol (bis, tris)-(6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonate) and 4- (7,8-dihydroxy-2,4,4-trimethyl-2-chromanyl) pyrogallol (mono, bis, tris, tetrakis, pentakis) (6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfo Nert) (photosensitive agent) mixture 31 parts by mass 2,3,4,4′-tetrahydroxybenzophenone (mono, bis, tris, tetrakis, pentakis)-(6-diazo-5,6-dihydro-5-oxo- 1-naphthalenesulfonate) (photosensitive agent) 10 parts by mass hexamethoxymethylmelamine (curing agent) 26 parts by mass methanol (formula represented by formula (I) Compound) 31 parts by mass 3-amino-1-propanol (compound represented by formula (II)) 0.1 parts by mass ethyl lactate (solvent) 143 parts by mass N, N-dimethylformamide (solvent) 75 parts by mass

(Evaluation)
(1) Thickness of the colored photosensitive composition layer immediately after the preparation of the colored photosensitive composition 3 The colored photosensitive composition 3 immediately after the preparation obtained above is spin-coated on a silicon wafer at a rotational speed of 1700 rpm. Was applied to obtain a coating film. The coating film was heated at 100 ° C. for 1 minute, and the solvent in the colored photosensitive composition 3 was volatilized and removed to form a colored photosensitive composition layer. The thickness of the resulting colored photosensitive composition layer, film thickness meter is determined using the model number;; VM-800J Dainippon Screen Co., Ltd.], and the thickness thereof was set to FT _0.

(2) Thickness of the colored photosensitive composition layer after storage of the colored photosensitive composition 3 The colored photosensitive composition 3 obtained above is placed in a brown glass bottle that can shield visible light, and in after being stored for two weeks, using the same method as described above, the colored photosensitive composition layer is formed, its thickness is the FT _1.

(3) The rate of change in thickness (R) was determined in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2
A colored photosensitive composition layer 5 was obtained in the same manner as in Example 2 except that methanol and 3-amino-1-propanol were not used, and the colored photosensitive composition layer was evaluated in the same manner as in Example 2. The rate of change in thickness (R) was determined. The results are shown in Table 2.

Example 3
FIG. 1 shows an example of creating an image sensor. First, a photoelectric conversion element is formed on the silicon wafer surface (light receiving portion 5). Subsequently, on the surface of the silicon wafer, there are a transfer path (transfer path 6) through which electrons generated by the photoelectric conversion element are transmitted, an electrode (transfer electrode 4), and a film (light-shielding film 7) that blocks light incident thereon. It is formed. Further, after these are formed, an insulating film (insulating film 8) is formed. A color filter is formed on the solid-state imaging element forming substrate (substrate on which the light receiving portion 5, the transfer electrode 4, the transfer path 6, the light shielding film 7, and the insulating film 8 are formed on the surface of the silicon wafer) formed in this manner. In this process, a planarization film layer (planarization film 3) is formed for the purpose of planarizing the substrate surface. Next, a colored photosensitive composition for forming green pixels of the colored photosensitive composition of the present invention is applied onto the substrate (FIG. A), and pattern exposure is performed through a mask ( FIG. B), the pattern 11 is formed by dissolving the region 11 which has been dissolved in the developer by the subsequent exposure of the colored photosensitive composition applied, with the developer. Thereafter, heat curing is performed to form a desired green pixel (FIG. C). Next, this process is repeated for the red pixel and the blue pixel, and three color pixels are formed on the same plane of the solid-state imaging element formation substrate (FIG. F). Further, an on-chip lens (on-chip lens 9) for efficiently condensing light incident on the photoelectric conversion element (light receiving unit 5) is formed (FIG. G), and an image sensor is formed.

  Since the colored photosensitive composition of the present invention is excellent in terms of storage stability and coatability, it can be used in the production of a color filter, and the color filter is preferably used in an image sensor.

An example of creating an image sensor is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1; Silicon wafer substrate 2; Planarization film | membrane 3; Transfer electrode 4; Light-receiving part 5; Transfer path 6; Light-shielding film 7; Insulating film 8; On-chip lens 9: Color filter Mask pattern sectional drawing 10: Irradiation exposure 11: Exposure Part G; green pixel R; red pixel B; blue pixel

Claims (9)

A dye, a photosensitive agent, a curing agent, a solvent, a compound represented by formula (I) and a compound represented by formula (II), wherein the content of the compound represented by formula (I) is a colored photosensitive composition The colored photosensitive composition which is 1-12 mass% in mass fraction with respect to a thing.

[In Formula (I), R ¹ represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.
In formula (II), R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclohexane having 3 to 6 carbon atoms. An alkyl group or an aryl group having 6 to 12 carbon atoms is represented. The hydrogen atom on the alkyl group, the hydrogen atom on the cycloalkyl group, and the hydrogen atom on the aryl group may be substituted with a hydroxyl group or an alkyl group having 1 to 6 carbon atoms. However, at least one of R ^{2 to} R ⁴ represents a group other than a hydrogen atom. ] At least one of R ^{2 to} R ⁴ represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a hydrogen atom on the alkyl group, the cyclo The colored photosensitive composition according to claim 1, wherein at least one hydrogen atom among the hydrogen atom on the alkyl group and the hydrogen atom on the aryl group represents a group substituted with a hydroxyl group.   2. The colored photosensitive composition according to claim 1, wherein the content of the compound represented by the formula (II) is 0.02 to 5% by mass with respect to the colored photosensitive composition in terms of mass fraction.   The sum of the content of the compound represented by formula (I) and the content of the compound represented by formula (II) is 3 to 12% by mass with respect to the colored photosensitive composition. The colored photosensitive composition according to claim 1. The colored photosensitive composition according to claim 1 or 2, wherein the curing agent is a compound represented by the formula (III).

[In the formula (III), 6 R ^{5 s} are each independently a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a 3 to 10 carbon atoms. Represents a cycloalkyl group. However, at least two of the six R ⁵ are not hydrogen atoms. ] The colored photosensitive composition according to claim 5, wherein R ¹ and R ⁵ represent the same substituent.   The pixel obtained using the colored photosensitive composition in any one of Claims 1-6.   A color filter having the pixel according to claim 7. An image sensor comprising the color filter according to claim 8.

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