JP5642402B2 - Color filter, manufacturing method thereof, and solid-state image sensor - Google Patents

Description

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

  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. A large amount of dye must also be added when the molar absorption coefficient of the dye is low.

  On the other hand, it has been pointed out that when the dye concentration is increased, when heat treatment is performed after film formation, a phenomenon of color transfer is likely to occur between adjacent colored patterns having different hues or between stacked and overlapping layers. In addition to color migration, the pattern can be easily peeled off in low exposure areas due to sensitivity reduction, and the relative amount of components contributing to photolithographic properties is reduced. There is also a problem that the concentration cannot be obtained.

  In relation to such problems, various methods have been proposed in the past, such as selecting the type of initiator and increasing the amount of initiator added (see, for example, Patent Document 2). In addition, a method for producing a color filter is disclosed in which polymerization is performed with the exposure temperature raised by irradiating the colored pattern with light while heating the substrate after forming the colored pattern, thereby increasing the polymerization rate of the system. (For example, refer to Patent Document 3). Furthermore, a method for producing a color filter is disclosed in which light irradiation is performed between the development process and the heat treatment to prevent shape deformation of the color filter (see, for example, Patent Document 4).

JP 2000-321863 A Japanese Patent Laying-Open No. 2005-316012 Patent No. 3309514 JP 2006-258916 A

  However, although problems such as pattern peeling, thermal sag, shape and color density have been solved to some extent, when using a coating solution with increased dye concentration, color migration that tends to occur during heat treatment, that is, between adjacent pixels or The fact is that even the color transfer phenomenon between the upper and lower layers in the laminated structure has not been solved. There is also a problem that light resistance is lowered.

  The present invention has been made in view of the above, and a color filter manufacturing method that can suppress color transfer to adjacent pixels and upper and lower layers in a laminated structure and can produce a color filter excellent in light resistance, and An object is to provide a color filter and a solid-state imaging device that are light-resistant and excellent in color reproducibility, and an object is to achieve the object.

Specific means for achieving the above object are as follows.
<1> A dye-containing negative curable composition containing at least a polymerizable group-containing dye represented by the following general formula (I), a photopolymerization initiator, a polymerizable compound, and an organic solvent is coated on a support, A film forming process for forming a coating film, a pattern forming process for exposing and developing the coating film to form a pattern, and an irradiation illuminance [mW / cm ² ] of light having a wavelength of 275 nm or less to the pattern after development . The amount of irradiation light [mJ / cm ² ] is 10 times or more of the exposure amount [mJ / cm ² ] in the exposure before development , when the ultraviolet light is 5% or more and 25% or less of the integrated irradiation illuminance of all wavelength light in the ultraviolet light. ] , And a heat treatment process for heat-treating the pattern after the ultraviolet irradiation.

In the general formula (I), Dye represents a dye residue, L represents a divalent linking group, n represents an integer of 0 to 5, m represents an integer of 1 or more, and Z represents the general formula. The group represented by (IIa) or the general formula (IIb) is represented. R ¹ represents a hydrogen atom or an alkyl group, R ² represents a substituent, and p represents an integer of 0 to 4. * Represents a linking site.

<2> The method for producing a color filter according to <1>, wherein the exposure before development in the pattern forming step is performed with i-line .
<3> The irradiation illuminance [mW / cm ² ] of wavelength light of 275 nm or less contained in the ultraviolet light irradiated in the ultraviolet irradiation step is 10% of the integrated irradiation illuminance of all wavelength light in the ultraviolet light. 1> or the method for producing a color filter according to <2>.
<4> integral irradiation illuminance in the ultraviolet irradiation step, a 200 mW / cm ² or more der Ru before SL <1> to the method for producing a color filter according the to any one of <3>.
<5> The color filter according to any one of <1> to <4>, wherein an irradiation light amount in the ultraviolet irradiation step is 15 to 100 times an exposure amount before development in the pattern forming step. It is a manufacturing method.
<6> integral irradiation illuminance in the ultraviolet irradiation step, a 250 mW / cm ² or more 2000 mW / cm ² or less is the <1> to the method for producing a color filter according to any one of the <5>.
<7> The above <1> to <6>, wherein the content of the polymerizable group-containing dye is 30% by mass to 80% by mass with respect to the total solid content of the dye-containing negative curable composition. The method for producing a color filter according to any one of the above.
<8> The above <1> to <6>, wherein the content of the polymerizable group-containing dye is 50% by mass to 70% by mass with respect to the total solid mass of the dye-containing negative curable composition. The method for producing a color filter according to any one of the above.
<9> The method for producing a color filter according to any one of <1> to <8>, wherein the photopolymerization initiator is an oxime compound.
< 10 > A color filter produced by the method for producing a color filter according to any one of <1> to < 9 >.
< 11 > A solid-state imaging device including the color filter according to < 10 >.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the color filter which can suppress the color transfer to the upper and lower layers in an adjacent pixel and laminated structure, and can produce the color filter excellent in light resistance can be provided. Also,
ADVANTAGE OF THE INVENTION According to this invention, the color filter and solid-state image sensor which were excellent in light resistance and color reproducibility can be provided.

It is a schematic sectional drawing which shows the structural example of the color filter produced in the Example.

  Hereinafter, the method for producing a color filter of the present invention will be described in detail, and the color filter of the present invention and a solid-state imaging device including the same will be described in detail through the description.

The method for producing a color filter of the present invention comprises (A) a polymerizable group-containing dye represented by the following general formula (I) as a colorant, (B) a photopolymerization initiator, (C) a polymerizable compound, and (D) A dye-containing negative curable composition containing at least an organic solvent is coated on a support, a film forming step for forming a coating film, and the coating film thus formed is exposed and developed to form a pattern. a pattern forming step of, in the pattern after development, a UV irradiation step of irradiating ultraviolet light exposure amount [mJ / cm ^2] of 10 times or more of the irradiation light amount of the exposure before development [mJ / cm ^2], And a heat treatment step of performing a heat treatment on the pattern after the ultraviolet irradiation.

  In the present invention, the colorant used in the coating solution for forming the coating film contains a dye having a specific structure having a polymerizable group, and after the pattern exposure and development, the pattern formed by exposure / development is heat-treated. Before, a step of irradiating ultraviolet rays (hereinafter sometimes abbreviated as UV) is provided, and the amount of UV light irradiation is set to 10 times or more of the exposure amount at the time of pattern exposure. Since movement of dyes that are easy to move (especially yellow dyes and magenta dyes) can be suppressed, color transfer between different colored resin layers (ie, colored pixels) and between upper and lower layers can be suppressed, and the light resistance of the color filters (colored pixels) Can also improve performance. This is remarkable in the case of a color filter for a solid-state imaging device having a structure in which different color resin layers (colored pixels) are adjacent to each other. Thereby, the color reproducibility at the time of image display improves, and high color reproducibility can be maintained over a long period of time.

-Film formation process-
The film forming step includes (A) a polymerizable group-containing dye represented by the general formula (I) as a colorant, (B) a photopolymerization initiator, (C) a polymerizable compound, and (D) an organic solvent. A dye-containing negative curable composition is applied onto a support to form a coating film.

  Application of the dye-containing negative curable composition is performed by applying the dye-containing negative curable composition containing the components (A) to (D) onto the support by spin coating, cast coating, roll coating, or the like. And drying to form a radiation-sensitive composition layer.

  The thickness of the layer to be formed is preferably in the range of 0.1 to 3 μm, and more preferably in the range of 0.2 to 1 μm from the viewpoint of thinning of the color filter for the solid-state imaging device and color reproducibility. A range of 0.3 to 0.7 μm is more preferable.

  As the support, for example, soda glass used for liquid crystal display elements, Pyrex (registered trademark) glass, quartz glass and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for imaging elements, Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS) substrate. 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.

(A) Polymerizable group-containing dye The dye-containing negative curable composition of the present invention contains at least one polymerizable group-containing dye represented by the following general formula (I). Since this dye tends to stay in the intended film due to the polymerization reaction of the polymerizable group in the molecule, even when heat is applied after patterning, movement to adjacent pixels and upper and lower layers, that is, coloring is prevented. As a result, each pixel can be colored to a desired hue, the hue and contrast of the display image are improved, and the color reproducibility is improved. In addition, light resistance is improved, and an image with high color reproducibility can be displayed over a long period of time.

  In the general formula (I), Dye represents a dye residue, and L represents a divalent linking group. N represents an integer of 0 to 5, and m represents an integer of 1 or more.

The dye residue represented by Dye is a residue obtained by removing a group such as hydrogen in the molecule of a conventionally known dye, and may have any dye skeleton. Examples of the dye residue include triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrazoleazo, anilinoazo, pyrazolotriazoleazo, pyridoneazo, pyrazoloazoleazomethine, Examples include residues derived from dyes having chemical structures such as pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, and anthrapyridone. Among them, from the viewpoint of achieving a higher improvement effect in terms of prevention of color transfer and light resistance, residues derived from pyrazole azo series, anilino azo series, pyrazolo triazole azo series, pyridone azo series, anthraquinone series, anthrapyridone series dyes are present. In particular, the substitution position of the following formula [“-(L) _n —Z” is A, B ¹ , B ² (B ¹ and B ² are = CR ¹ -and —CR ² =, respectively, as described later. In some cases, any of R ¹ , R ² ), R ⁵ , R ⁶ and G may be used. * Represents a bond of “— (L) _n —Z”. ] The dye residue represented by this. Details of each group of the dye residue will be described later.

The divalent linking group represented by L is preferably a divalent aliphatic group, aromatic group, heterocyclic group, sulfamoyl group, carbamoyl group, or acylamino group. These linking groups may be further substituted with the substituents mentioned for G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) described later. L is preferably a divalent aliphatic group.

  N represents an integer of 0 to 5, and is preferably an integer of 1 to 3 in terms of color value. m represents an integer of 1 or more, and is more preferably 1 to 3 in terms of stability over time.

Z represents a group represented by the following general formula (IIa) or the following general formula (IIb). When there are a plurality of Z, they may be the same or different.

R ¹ in the general formula (IIa) represents a hydrogen atom or an alkyl group. Moreover, R < ² > in the said general formula (IIb) represents a substituent, p represents the integer of 0-4. * Represents a linking site.

In general formula (IIa), R ¹ represents a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. In general formula (IIb), R ² represents a substituent. Examples of the substituent include groups listed as G, R ¹ , R ² , R ⁵ , and R ⁶ in general formula (1) described later. The preferred embodiments are also the same. p represents an integer of 0 to 4, preferably p is 0 or 1, and more preferably p is 0.

  In the present invention, among the polymerizable group-containing dyes represented by the general formula (I), a dye monomer represented by the following general formula (1) (hereinafter referred to as “the dye monomer of the present invention”). Is preferred). This dye monomer has a polymerizable group, and when used in the method for producing a color filter of the present invention, it can suppress the occurrence of color transfer between colored pixels and has heat fastness and light fastness. In addition, since high sensitivity, high resolution, and high transmittance characteristics can be imparted, when it is contained in a colored curable composition, images with good temporal stability, high heat resistance and light resistance (particularly yellow and magenta). Image). Thereby, the color filter excellent in light resistance and heat resistance can be obtained.

In the general formula (1), A represents a 5-membered or 6-membered heterocyclic diazo residue of Component A-NH _2. Examples of the heteroatom in the heterocyclic ring of the heterocyclic diazo component include N, O, and S. The heterocycle is preferably a nitrogen-containing 5-membered heterocycle, and the heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. Preferable examples of the heterocyclic ring in A include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Each heterocyclic group may further have a substituent. Especially, as said A, the pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring, and benzothiazole ring which are represented with the following general formula (a)-(f) are preferable.

R ^{7 to} R ²⁰ in the general formulas (a) to (f) represent the same groups as the substituents G, R ¹ , and R ² described later. Of the general formulas (a) to (f), a pyrazole ring represented by the general formulas (a) and (a ′) and an isothiazole ring represented by the general formula (b) are preferable. The pyrazole ring represented by (a ′) is most preferable.

In the general formula (1), B ¹ represents a nitrogen atom or = CR ^1- , and B ² represents a nitrogen atom or -CR ² =. However, both B ¹ and B ² are not nitrogen atoms. Examples of ^{B 1} and ^{B 2,} each = CR ¹ - and CR ² = is more preferable that represent. Moreover, the position of the double bond of = CR ¹ -or -CR ² = represented by B ¹ and B ² is determined by the structure of the 6-membered ring formed by including this.

R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms. R ⁵ and R ⁶ may further have a substituent. The details of the aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group will be described later. Preferable examples of R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group. R ⁵ and R ⁶ are more preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group. R ⁵ and R ⁶ are most preferably a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Each group may further have a substituent.

In the general formula (1), G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl. Group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group; alkyl group, aryl An amino group substituted by a group or a heterocyclic group; acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group , Arylthio group A heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, each group may be further substituted. Details of the groups represented by G, R ¹ and R ² will be described later.

Preferred examples of the group represented by G include a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group; an alkyl group, an aryl group, or a heterocyclic group. An amino group substituted by a cyclic group; an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, and a heterocyclic thio group are more preferable. Includes a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group; an amino group substituted with an alkyl group, an aryl group, or a heterocyclic group; or an acylamino group.
Among these, as G, a hydrogen atom, an aliphatic group, an alkylamino group, an arylamino group, and an amide group are most preferable. Each group may further have a substituent.

Preferable groups represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, and a cyano group. Each group may further have a substituent.
In the general formula (1), R ¹ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a 5- to 6-membered ring.
Preferred examples of the substituent in the case where each group represented by A, R ¹ , R ² , R ⁵ , R ⁶ , and G further has a substituent include the groups listed for G, R ¹ , and R ² “-(L) _n -Z” and the like.

The dye monomer represented by the general formula (1) has “-(L) _n -Z” at any position on the groups A, R ¹ , R ² , R ⁵ , R ⁶ and G in the molecule. At least one group selected from the polymerizable groups represented by. In the present invention, the position where the polymerizable group represented by "-(L) _n -Z" is introduced may be any ^{one of} A, R ¹ , R ² , R ⁵ , R ⁶ , and G. Of course, these groups may be introduced into further substituted groups.
In the general formula (1), as the position where the polymerizable group represented by the “— (L) _n —Z” is introduced, on the heterocyclic ring represented by A, G, R ⁵ , R ⁶ , In addition, a group substituting for G, a group substituting for R ⁵ and a group substituting for R ⁶ are preferred, and more preferably, on the pyrazole ring when A is a pyrazole ring represented by the general formula (a) And R ⁷ , R ⁸ , R ⁹ is substituted with a substituent, or G, R ⁵ , R ⁶ , and G are substituted with R ⁵ A group substituted on the group R ⁶ .

The group represented by G, R ¹ , R ² , R ⁵ or R ⁶ in the general formula (1) will be described in detail.
Throughout this specification, “aliphatic group” means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch or may form a ring. Moreover, it is preferable that the carbon atom number of the said aliphatic group is 1-20, and it is more preferable that it is 1-16. The aryl moiety in the aralkyl group and substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of the aliphatic group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2- Mention may be made of phenethyl, vinyl and allyl groups.
Throughout this specification, “aromatic group” means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, and particularly preferably phenyl. The number of carbon atoms in the aromatic group is preferably 6-20, and more preferably 6-16. Examples of aromatic groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.
In the present specification, the “heterocyclic group” includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. When the heterocyclic group has a substituent, examples of the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, and an ionic hydrophilic group. Etc. are included. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, and 2-furyl group.

In the general formula (1), examples of the halogen atom represented by G, R ¹ or R ² include a fluorine atom, a chlorine atom and a bromine atom.

The carbamoyl group represented by G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. When the carbamoyl group has a substituent, examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

In the general formula (1), the alkoxycarbonyl group represented by G, R ¹ , R ² , R ⁵ and R ⁶ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms. When the alkoxycarbonyl group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The aryloxycarbonyl group represented by G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms. When the aryloxycarbonyl group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The acyl group represented by G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms. When the acyl group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

In the general formula (1), the alkoxy group represented by G, R ¹ and R ² includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As said alkoxy group, a C1-C12 alkoxy group is preferable. When the alkoxy group has a substituent, examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, hydroxyethoxy group, and 3-carboxypropoxy group.

In the general formula (1), the aryloxy group represented by G, R ¹ and R ² includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms. When the aryloxy group has a substituent, examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

In the general formula (1), the acyloxy group represented by G, R ¹ and R ² includes an acyloxy group having a substituent and an unsubstituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 12 carbon atoms. When the acyloxy group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

In the general formula (1), the carbamoyloxy group represented by G, R ¹ and R ² includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. When the carbamoyloxy group has a substituent, examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

The “alkoxycarbonyl” group in the alkoxycarbonyloxy group represented by G, R ¹ and R ² in the general formula (1) is the same as the above-described alkoxycarbonyl group. As for the aryloxycarbonyloxy group, the “aryloxycarbonyl” group is the same as the above-mentioned aryloxycarbonyl group.

In the general formula (1), the amino group substituted with an alkyl group, aryl group or heterocyclic group represented by G, R ¹ and R ² may further have a substituent, but an unsubstituted amino group Does not contain groups. The alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms. When the alkylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 12 carbon atoms. When the arylamino group has a substituent, examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chloroanilino group.
Furthermore, examples of the heterocyclic amino group include a pyrrolidinylamino group, a piperidinylamino group, a pyrrolinylamino group, and a pyridinylamino group.

In the general formula (1), the acylamino group represented by G, R ¹ and R ² includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. When the acylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

In the general formula (1), the ureido group represented by G, R ¹ and R ² includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. When the ureido group has a substituent, examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

In the general formula (1), the sulfamoylamino group represented by G, R ¹ and R ² includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. When the sulfamoylamino group has a substituent, examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino.

In the general formula (1), the alkoxycarbonylamino group represented by G, R ¹ and R ² includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms. When the alkoxycarbonylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The aryloxycarbonylamino group represented by G, R ¹ and R ² in the general formula (1) includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. When the aryloxycarbonylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The alkyl and arylsulfonylamino groups represented by G, R ¹ and R ² in the general formula (1) include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. . The alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 12 carbon atoms. When the alkylsulfonylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the alkylsulfonylamino group include a methanesulfonylamino group.
The arylsulfonylamino group is preferably an arylsulfonylamino group having 6 to 12 carbon atoms. When the arylsulfonylamino group has a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the arylsulfonylamino group include N-phenylmethanesulfonylamino group, benzenesulfonylamino group, and 3-carboxybenzenesulfonylamino group.

In the general formula (1), the alkyl, aryl and heterocyclic thio groups represented by G, R ¹ and R ² include an alkyl, aryl and heterocyclic thio group having a substituent and an unsubstituted alkyl, aryl and heterocyclic ring. A thio group is included. The alkyl and heterocyclic thio groups are preferably those having 1 to 12 carbon atoms, and the arylthio groups are preferably those having 6 to 12 carbon atoms. When the alkyl, aryl and heterocyclic thio groups have a substituent, examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group and a 2-pyridylthio group, respectively.

Examples of the alkyl and arylsulfonyl groups represented by G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) include a methanesulfonyl group and a phenylsulfonyl group, respectively.
Examples of the alkyl and arylsulfinyl groups represented by G, R ¹ and R ² in the general formula (1) include a methanesulfinyl group and a phenylsulfinyl group, respectively.

The sulfamoyl group represented by G, R ¹ , R ² , R ⁵ and R ⁶ in the general formula (1) includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. When the sulfamoyl group has a substituent, examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

  Examples of the “ionic hydrophilic group” include a sulfonic acid group, a carboxylic acid group, a sodium sulfonate group, a potassium sulfonate group, a lithium sulfonate, a sodium carboxylate group, a potassium carboxylate group, and a lithium carboxylate group. Can be mentioned.

In the general formula (1), the group represented by “— ((L) _n —Z) _m ” is as described above in the description of the general formula (I), and the preferred embodiments are also the same. .

  Of the dye monomers represented by the general formula (1), a compound represented by the following general formula (3) is preferable.

In the general formula (3), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ¹ is preferably an electron withdrawing group having a σ _p value of 0.30 to 1.0. Specific examples of preferred groups as Z ¹ include the electron-withdrawing substituents described later. Among them, an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, Preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms. An alkylsulfonyl group having 1 to 12 carbon atoms and an arylsulfonyl group having 6 to 18 carbon atoms are particularly preferable, and a cyano group is most preferable.

In the general formula (3), R ¹ , R ² , R ⁵ , R ⁶ , L, Z, n, m are synonymous with those in the general formula (1).
In the general formula (3), R ³ and R ⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl and aryl. A sulfonyl group or a sulfamoyl group is represented. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl group, and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable.
In the general formula (3), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
In the general formula (3), Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Among these, Q is preferably a group consisting of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Among these, an aromatic group and a heterocyclic group are particularly preferable as the 5- to 8-membered ring represented by Q. As the nonmetallic atom necessary for forming the 5- to 8-membered ring, a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom are preferable. Specific examples of the 5- to 8-membered ring include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole. And a ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an oxane ring, a sulfolane ring, and a thiane ring.

Each group (Z ¹ , Z ² , Q, R ³ , R ⁴ ) described in the general formula (3) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (1), the groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups.

Here, Hammett's substituent constant σ _p value used in the present specification will be described in relation to the substituent Z ¹ .
Hammett's rule was found in 1935 by L. L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the Hammett's rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean, “Lange's and book of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). However, even if each substituent is limited or specified by Hammett's substituent constant σ _p in the present invention, it is not limited to only a substituent having a known value that can be found in the above-mentioned book. Also included are substituents that fall within the range when measured based on Hammett's law. As for the “Hammett's substituent constant σ _p ” in the present invention, the σ _p value is used for a substituent that is not a benzene derivative, regardless of the substitution position, as a measure of the electron effect of the substituent.

Hammett substituent constant σ As an electron withdrawing group having a _p value of 0.60 or more, a cyano group, a nitro group, an alkylsulfonyl group (for example, methanesulfonyl group), an arylsulfonyl group (for example, benzenesulfonyl group) As an example.
Examples of the electron withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m -Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), Mention may be made of halogenated alkyl groups (for example trifluoromethyl).
In addition to the above, an electron-attracting group having a Hammett substituent constant σ _p value of 0.30 or more includes an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl) , Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy group), halogenated alkylthio groups (for example, difluoromethylthio) ) An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with two or more electron-withdrawing groups having a σ _p value of 0.15 or more; and a heterocycle (eg, 2-benzo Oxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) It is possible.
Further, specific examples of the electron withdrawing group having a σ _p value of 0.20 or more include a halogen atom in addition to the above.

A particularly preferred combination of substituents as the dye monomer (azo dye) represented by the general formula (1) is any combination of two or three or more of the following (i) to (v).
(I) R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group, and more preferably a hydrogen atom, an aryl group, or a heterocyclic group. A sulfonyl group, most preferably a hydrogen atom, an aryl group, or a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms.
(Ii) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an amide group, more preferably a hydrogen atom, a halogen atom, an amino group or an amide group, most preferably a hydrogen atom. An amino group or an amide group.
(Iii) A is preferably a pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring, or benzothiazole ring, more preferably a pyrazole ring or isothiazole ring, and most preferably a pyrazole ring.
(Iv) ^{B 1} and ^{B 2} are each ^-CR 1 =, - CR ² = a and, and these ^R 1, ^{R 2} are each preferably a hydrogen atom, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, An alkyl group, a hydroxyl group, and an alkoxy group are preferable, and a hydrogen atom, a cyano group, a carbamoyl group, and an alkyl group are more preferable.
(V) As the substitution position of the polymerizable group represented by Z, on the 5-membered or 6-membered heterocyclic ring represented by A, or on the substituent of any of G, R ⁵ and R ⁶ More preferably, it is more preferable that A is a substituent substituted on the pyrazole ring in the case where it is a pyrazole ring or a substituent represented by G, R ⁵ or R ⁶ .

  In addition, about the preferable combination of substituents of the compound represented by the general formula (1), a compound in which at least one of various substituents is the above-described preferable group is preferable, and more various substituents are the above-described preferable groups. Are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  Specific examples (dyes a-1 to h-8) of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to the following examples.

  Regarding the method for synthesizing the compound represented by the general formula (1), the methods described in paragraph numbers [0083] to [0094] of JP-A-2005-281329 can be referred to.

  In the dye-containing negative curable composition of the present invention, other known dyes are contained together with the polymerizable group-containing dye represented by the general formula (I) as long as the effects of the present invention are not impaired. May be.

  The content of the polymerizable group-containing dye represented by the general formula (I) in the dye-containing negative curable composition is 30 masses in terms of color density with respect to the total solid mass of the composition. % Or more, more preferably in the range of 30 to 80% by mass. Furthermore, from the viewpoint of forming a thin film and forming a thin film of 1 μm or less (for example, a colored film (color filter) constituting a solid-state imaging device). % By mass is more preferable, and 50 to 70% by mass is particularly preferable.

(B) Photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one 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 halomethyl oxadiazole 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 [0077] 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]. In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph [0079] of the same publication may be used in the dye-containing negative curable composition.

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 negative curable composition (total content in the case of two or more) is 3 to 20 from the viewpoint of more effectively obtaining the effects of the present invention. % By mass is preferable, 4 to 19% by mass is more preferable, and 5 to 18% by mass is particularly preferable.

(C) Polymerizable compound The dye-containing negative curable composition of the present invention contains at least one 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] dimethylmethane bis - [p- (methacryloxyethoxy) phenyl] dimethylmethane. 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. Those having an aromatic skeleton described in JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. 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.
Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane 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 Compounds and the like.
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 negative 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. In addition, for compatibility with other components (for example, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the dye-containing negative curable composition, dispersibility, The selection and use method of the polymerizable compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds 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 negative curable composition (total content in the case of 2 or more types) is not particularly limited, and is a viewpoint for obtaining the effect of the present invention more effectively. Therefore, 10 to 80% by mass is preferable, 15 to 75% by mass is more preferable, and 20 to 60% by mass is particularly preferable.

(D) Organic solvent The dye-containing negative curable composition in the present invention contains at least one 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 a dye-containing negative curable composition is used, and in particular, the solubility of the dye and the binder, coating Is preferably selected in consideration of safety and safety.

  Examples of the organic solvent 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 content of the organic solvent in the dye-containing negative curable composition is preferably such that the total solid content in the composition is 10 to 80% by mass, and more preferably 15 to 60% by mass.

(E) Other components In addition to the above components, the dye-containing negative curable composition 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. Good.
-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.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and a weight of 2000 to 1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

  The acid value of the alkali-soluble binder is preferably 50 to 300 mgKOH / g, more preferably 75 to 200 mgKOH / g, and particularly preferably 80 to 160 mgKOH / g. When the acid value is within the above range, a development residue hardly remains at the time of pattern formation, and the coating uniformity is good.

-Crosslinking agent-
Supplementally, a crosslinking agent may be used to obtain a highly cured film when the dye-containing negative curable composition is cured.
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.
For details such as specific examples of the crosslinking agent, the description of paragraph numbers [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

-Other additives-
For the dye-containing negative curable composition, various additives such as fillers, polymer compounds other than the above, various surface activities such as fluorine-based, nonionic-based, cationic-based, anionic-based, and silicone-based as necessary. An agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a polymerization inhibitor and the like can be blended. Examples of the various additives include those described in paragraph numbers [0155] to [0156] of JP-A No. 2004-295116.

(Polymerization inhibitor)
In the dye-containing negative curable composition of the present invention, it is desirable to add a polymerization inhibitor. By adding a small amount of a polymerization inhibitor, unnecessary thermal polymerization of the polymerizable compound during production or storage of the curable composition can be prevented.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol). ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the total mass of the curable composition.

(Surfactant)
By adding various surfactants to the colored photosensitive composition of the present invention, coatability can be further improved. As the surfactant, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
In particular, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when used as a coating liquid can be further improved, and the uniformity of coating thickness and the liquid-saving property can be further improved. That is, when the photosensitive resin composition contains a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and The coating property of is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F780, F781 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), CW-1 (manufactured by GENECA), etc. It is done.

Examples of the cationic surfactant include a phthalocyanine derivative (commercially available product: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) heavy. Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. Rate, sorbitan fatty acid esters (pluronics L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF).
Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

Furthermore, as the silicone surfactant, for example, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, SH29PA, SH30PA, SH8400 manufactured by Toray Silicone Co., Ltd., TSF manufactured by Toshiba Silicone Co., Ltd. -4440, TSF-4300, TSF-4445, TSF-444 (4) (5) (6) (7) 6, TSF-4460, TSF-4452, Shin-Etsu Silicone KP341, Big Chemie BYK323 , BYK330 and the like.
The surfactants may be used alone or in combination of two or more.

  In addition, when promoting alkali solubility in the non-exposed region and further improving the developability of the dye-containing negative curable composition, the composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. An 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.

-Pattern formation process-
In the pattern forming step, the coating film formed by coating is exposed and developed to form a pattern. In the production of a color filter, a color filter having a desired hue can be produced by repeating exposure and development together with the application in the film forming step for a desired number of hues. In addition, every time the formation, exposure, and development of a single color coating film are completed (for each color), an ultraviolet irradiation process and / or a heat treatment process described later may be performed. After the exposure and development are completed, the ultraviolet irradiation process and the heat treatment process described later may be performed collectively.

As light or radiation used for exposure at the time of pattern formation, ultraviolet rays such as g-line, h-line and i-line are preferable. 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.

Although there is no restriction | limiting in particular as an exposure amount at the time of exposure at the time of pattern formation, 50-1000mJ / cm < ² > is preferable.

Development can be performed using a developer. Any developer may be used as long as it is composed of a composition that dissolves the dye-containing negative curable composition (uncured part) but does not dissolve the irradiated cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As an organic solvent, the above-mentioned organic solvent used when preparing a dye-containing negative curable composition 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.

-UV irradiation process-
Ultraviolet irradiation process, the pattern after performing a developing process in the pattern formation step, ultraviolet light 10 times more light quantity of the exposure amount [mJ / cm ^2] in the exposure process before development [mJ / cm ^2] Irradiate (UV light). Between the development process in the pattern formation step and the heat treatment described later, the pattern (dye-containing negative curable composition) after development is irradiated with UV light for a predetermined time, so that the color when heated later It is possible to effectively prevent migration, and light resistance is improved.

As a light source for irradiating UV light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp, or the like can be used. Among them, the irradiated ultraviolet light includes light having a wavelength of 275 nm or less, and the irradiation illuminance [mW / cm ² ] of the light having a wavelength of 275 nm or less is 5% or more with respect to the integrated irradiation illuminance of all the wavelength light in the ultraviolet light. The thing which can irradiate the light which is is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

The integrated irradiation illuminance is a curve drawn with the illuminance at each spectral wavelength (radiant energy passing through a unit area per unit time; [mW / m ² ]) as the vertical axis and the light wavelength [nm] as the horizontal axis. The sum (area) of the illuminance of each wavelength light included in the irradiated light.

Irradiation with UV light is performed as an irradiation light amount [mJ / cm ² ] that is 10 times or more of the exposure amount at the time of exposure in the pattern forming step. If the amount of irradiation light in this step is less than 10 times, color transfer between colored pixels and between upper and lower layers cannot be prevented, and light resistance also deteriorates.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

In this case, the integrated irradiation illuminance in the irradiated ultraviolet light is preferably 200 mW / cm ² or more. When the integrated irradiation illuminance is 200 mW / cm ² or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. Among them, preferred is ^{250~2000mW / cm 2, 300~1000mW / cm} 2 is more preferable.

-Heat treatment process-
In the heat treatment process, the pattern after the ultraviolet irradiation in the ultraviolet irradiation process is heat-treated. The formed pattern can be further cured by heating (for example, so-called post-baking).

  The heat treatment can be performed by a method capable of heating a pattern, such as a hot plate, various heaters, and an oven.

  The temperature of the heat treatment is preferably from 160 to 260 ° C, more preferably from 180 to 220 ° C, in terms of efficient curing. Although the heat treatment time varies depending on the heating temperature, it is generally preferably 3 to 10 minutes. Among these, it is more preferable to carry out at a temperature of 160 to 220 ° C. for 3 to 10 minutes.

Even if the dye-containing negative curable composition in the present invention adheres to, for example, the nozzle of the coating apparatus discharge section, the piping section of the coating apparatus, the inside of the coating apparatus, etc., it can be easily cleaned and removed using a known cleaning liquid. Can do. In this case, in order to perform more efficient cleaning removal, it is preferable to use the solvent contained in the curable composition of the present invention as the cleaning liquid.
JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A and the like can also be suitably used as the cleaning liquid for cleaning and removing the curable composition in the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid with respect to the dye-containing negative curable composition, a surfactant related to the present composition described above may be added to the cleaning liquid.

  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 in particular, 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. In particular, it is suitable for applications such as a high-resolution CCD element or CMOS exceeding 1 million pixels. 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 hue change caused by the color shift A large impact. Further, in the case of a thin film having a thickness of 1 μm or less (especially 0.1 to 0.9 μm, and further 0.1 to 0.7 μm), the dye content is relatively high, and between colored pixels and between upper and lower layers. The color transfer of appears. Therefore, when a color filter for a solid-state imaging device is formed using a dye as a colorant, a pattern having particularly high color reproducibility and excellent light resistance can be obtained.

  The solid-state imaging device of the present invention is configured by providing the color filter of the present invention. The color filter of the present invention has high light resistance by avoiding color transfer between colored pixels and between upper and lower layers as described above, and a solid-state imaging device equipped 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 obtained according to the present invention and functions as a solid-state imaging device. For example, the following configuration can be given. That is, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a CCD image sensor (solid-state imaging device) is provided on a support, and the photodiodes receive light on the photodiodes and transfer electrodes. A light-shielding film made of tungsten or the like having an opening only in a part, and a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. Further, the color filter of the present invention is provided.
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.

(Examples 1-19, Comparative Examples 1-13)
<Preparation of negative curable composition>
-Preparation of curable composition A-
Among the components in the following composition A, a dye solution is prepared by mixing the exemplified compound a-2 described above (polymerizable group-containing dye represented by formula (I)) and cyclohexanone. Oxime A, monomer A, and alkali-soluble binder A were added and dissolved by stirring to prepare a negative curable composition A using a dye as a colorant.
<Composition A>
-Exemplary compound a-2 described above (polymerizable group-containing dye represented by formula (I)) ... 5.0 g
・ Cyclohexanone (organic solvent): 26g
・ Alkali-soluble binder A ... 2.0g
(Benzyl methacrylate / methacrylic acid (= 85/15 [molar ratio]) copolymer, weight average molecular weight: 17000, acid value: 96 mgKOH / g)
・ Monomer A (polymerizable compound) of the following structure: 2.0 g
・ Oxime A ・ ・ ・ 1.0g
(2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (manufactured by Ciba Specialty Chemicals); photopolymerization initiator)

-Preparation of negative curable compositions BJ-
In the preparation of the negative curable composition A, the negative curable composition B˜ was the same as the negative curable composition A except that the types of components were changed as shown in Table 1 below. J was prepared.

<Production of color filter>
-Production of silicon wafer with undercoat layer-
Resist CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; base clearing agent) is applied on a silicon wafer using a spin coater so as to have a film thickness of 2 μm, and dried by heating at 220 ° C. for 1 hour. Thus, a cured film (undercoat layer) was formed.

-Exposure and development of negative curable compositions-
Next, using each of the negative curable compositions A to J prepared as described above, a spin coater is formed on the undercoat layer of the obtained silicon wafer with an undercoat layer so that the dry film thickness becomes 1 μm. And then prebaked at 100 ° C. for 120 seconds to form a colored film on the silicon wafer. With respect to this colored film, 2.0 μm square pixels are respectively arranged in a 4 mm × 3 mm region on the substrate through an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.), and the following table. It exposed with an exposure amount shown in ² [mJ / cm 2] at an illuminance 1000 mW / cm ² (integral irradiation illuminance). After exposure, paddle development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Electronics Materials Co., Ltd.) to form a pattern. Subsequently, it was rinsed with running water for 20 seconds and then spray-dried. Thereafter, the entire silicon wafer on which the pattern was formed was irradiated with ultraviolet rays at a dose [mJ / cm ² ] shown in Table 2 below using a high-pressure mercury lamp. After irradiation, post-baking treatment was performed on a hot plate at 220 ° C. for 300 seconds to form a colored pattern on the silicon wafer. In addition, the wavelength light of 275 nm or less contained in the irradiation light from a high pressure mercury lamp is 10%.
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 Table 2 below.

-1. Color transfer
Apply the CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; foundation clearing agent) to the colored pattern forming surface of the color filter produced as described above so that the dry film thickness is 1 μm, and let it dry. Then, after forming a transparent film as shown in FIG. 1, heat treatment was performed at 200 ° C. for 5 minutes. After heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The ratio [%] of the absorbance value of the obtained transparent film to the absorbance of the colored pattern similarly measured before heating was calculated and used as an index for evaluating the color transfer.

-2. Light resistance
The color filter produced as described above was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux · h). After irradiation, the ΔE ^* ab value of the color difference before and after irradiation was measured. A smaller ΔE ^* ab value indicates better light resistance, and it is particularly preferable that the ΔE ^* ab value is 10 or less.

  As shown in Table 2, in the examples, the occurrence of color transfer due to the heat treatment was drastically suppressed, and the light resistance could be greatly improved. On the other hand, in the comparative example, the color transfer could not be prevented and the light resistance was inferior.

Claims (11)

A dye-containing negative curable composition containing at least a polymerizable group-containing dye represented by the following general formula (I), a photopolymerization initiator, a polymerizable compound, and an organic solvent is coated on a support, and a coating film is formed. A film forming step to be formed;
A pattern forming step of exposing and developing the coating film to form a pattern;
UV light having an irradiation illuminance [mW / cm ² ] of light having a wavelength of 275 nm or less is 5% or more and 25% or less of the integrated irradiation illuminance of all wavelengths in the ultraviolet light is exposed to the pattern after development. An ultraviolet irradiation step of irradiating with an irradiation light amount [mJ / cm ² ] of 10 times or more of an exposure amount [mJ / cm ² ] in
A heat treatment step of performing heat treatment on the pattern after ultraviolet irradiation;
The manufacturing method of the color filter which has this.


[Wherein Dye represents a dye residue, L represents a divalent linking group, n represents an integer of 0 to 5, m represents an integer of 1 or more, and Z represents the general formula (IIa) or The group represented by the general formula (IIb) is represented. R ¹ represents a hydrogen atom or an alkyl group, R ² represents a substituent, and p represents an integer of 0 to 4. * Represents a linking site. ] The method for producing a color filter according to claim 1, wherein exposure before development in the pattern forming step is performed with i-line. Irradiation illuminance [mW / cm] of wavelength light of 275 nm or less included in the ultraviolet light irradiated in the ultraviolet irradiation step ² Is 10% of the integrated irradiation illuminance of all wavelength light in ultraviolet light. The method for producing a color filter according to claim 1 or 2. The integral irradiation illuminance in the ultraviolet irradiation step, 200 mW / cm ² or more der Ru請 Motomeko 1 to the method for producing a color filter according to any one of claims 3. The method for producing a color filter according to any one of claims 1 to 4 , wherein an irradiation light amount in the ultraviolet irradiation step is 15 times to 100 times an exposure amount in exposure before development in the pattern forming step. . The integral irradiation illuminance in the ultraviolet irradiation step, 250 mW / cm ² or more 2000 mW / cm ² or less color manufacturing method of the filter according to any one of claims 1 to 5 is. The content of the polymerizable group-containing dye, with respect to the total solid mass of the dye-containing negative curable composition, any one of claims 1 to 6 or less 80% by weight to 30% by weight The manufacturing method of the color filter as described in 2. The content of the polymerizable group-containing dye, with respect to the total solid mass of the dye-containing negative curable composition, any one of claims 1 to 6 is 70 wt% or less than 50 wt% The manufacturing method of the color filter as described in 2. The photopolymerization initiator, the method for producing a color filter according to any one of claims 1 to 8 is an oxime compound. Color filter produced by the method for producing a color filter according to any one of claims 1 to 9. A solid-state imaging device comprising the color filter according to claim 10 .