JP2005202252A - Photosensitive coloring composition for solid-state imaging device color filter, solid-state imaging device color filter, solid-state imaging device and manufacturing method of solid-state imaging device color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition which has an extremely high sensitivity and is capable of precisely forming a fine pattern in an exposure process for forming a pattern. <P>SOLUTION: The photosensitive coloring composition for solid-state imaging device color filter contains at least a reactive monomer, a photopolymerization initiator, a colorant and an organic solvent, wherein the photopolymerization initiator comprises a compound expressed by the formula (1). In the formula (1), each of R<SP>1</SP>to R<SP>14</SP>is independently either of hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group and aliphatic group. Therein, the aromatic group and aliphatic group preferably contain a structure selected from branched structure and alicyclic structure, preferably contain, in the way of the group, one or more kinds selected from ether bond, ester bond, amino bond, amide bond, thioether bond and unsaturated bond and preferably contain, on the terminal of the group, one or more kinds selected from hydroxyl group, amino group, carboxyl group, halogen, carbonyl group and aromatic group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive coloring composition for a solid-state image sensor color filter, a solid-state image sensor color filter, and a method for producing the solid-state image sensor color filter that are preferably used in an image input device.

  Examples of the color filter include a color filter used for an image output device such as a liquid crystal display device, a color filter used for an image input device such as a solid-state imaging device, and the like. A typical example of a color filter structure used in a solid-state image sensor will be described with reference to FIG. An image pickup device substrate used for a CCD or a CMOS is usually formed on the surface of a silicone wafer 1, a signal transfer unit 2 formed on the silicone wafer 1, and the surface of the silicone wafer 1 between the signal transfer units 2. The light receiving unit (photoelectric conversion unit) 3 is configured. A planarizing film 4 made of a resin is provided on the entire surface of the imaging element base plate. Further, a combination of red, green and blue (RGB), a combination of cyan, magenta and yellow (CMY) or a combination of red, green and blue (RGB) in accordance with the spectral characteristics required for each light receiving portion on the planarizing film 4 located above the light receiving portion 3 Colored layers 5 of other colors are formed. A planarizing film 6 made of resin is provided on the entire surface of the colored layer 5, and a lens 7 is selectively provided at a position directly above the colored layer 5. Accordingly, a color pattern of RGB, CMY, or other colors is provided on the image pickup device substrate in accordance with the arrangement of the light receiving portions, and each light receiving device is formed. The unit size of each RGB, CMY, or other color coloring pattern is generally 10 μm square or less, and the structure is such that incident light can be color-separated with each pattern unit as one pixel. The pixel size of the color filter for the solid-state imaging device is much smaller than that of the color filter for the image output device.

  In order to record a high-definition image with a digital camera equipped with a solid-state image sensor, it is desirable to increase the number of effective recording pixels, that is, the number of light-receiving elements included in one solid-state image sensor as much as possible. In addition, with the spread of digital cameras mounted on mobile phones and the use of compact digital cameras, the solid-state imaging device itself is also becoming smaller. Therefore, in order to arrange more light receiving elements in a limited area, the coloring pattern formed corresponding to each light receiving element is also miniaturized. In addition, in order to efficiently capture light into the light receiving portion, the entire solid-state image sensor color filter including the colored layer has been made thinner, and as a result, the colored layer has been made thinner. Along with this, there is a tendency to increase the concentration of the colorant in the photosensitive coloring composition in order to maintain the absorption spectral characteristics even in the colored layer having a thin film thickness.

  Examples of the method for producing the colored layer portion of the color filter for a solid-state imaging device include a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, a dye dispersion method, and the like, such as spectral characteristics, durability, and pattern shape. A pigment dispersion method that exhibits a good balance of properties has been widely adopted. In addition, if the problem is caused by variations in the intensity of light incident on the light receiving part of the solid-state image sensor due to irregular reflection on the surface of the pigment particle, or noise within the pixel, this can be eliminated. In some cases, a method or a dye dispersion method is used. However, since dyes are less resistant to light, heat, water, and oxidizing environment than pigments, the structure of the dye changes due to these effects, and the resulting change in absorption spectral characteristics, that is, color change, is likely to occur. There is.

  In the pigment dispersion method, for example, a negative photosensitive coloring composition in which a pigment is dispersed is applied on a substrate and dried to form a coating film, and this coating film is exposed through a pattern mask or laser light. A color filter is produced by developing after selective exposure, such as direct drawing, by curing. In this case, since a negative photosensitive coloring composition is used, the exposed portion is cured in the exposure step, the unexposed portion is not cured, and only the unexposed portion is dissolved by the developer in the subsequent development step. Washed away and a cured pattern is formed.

  As is apparent from the above, the color pattern of the color filter for the solid-state image sensor is much smaller than that of the color filter for the image output device, and the miniaturization has progressed. It is also necessary to accurately form individual pattern units in accordance with the positions of these. Therefore, the exposure method for the photosensitive colored resin composition in the pattern forming process is also different from that for the color filter for the image output device. For example, in a color filter for a liquid crystal display, which is one of image output devices, a pattern can be formed by exposing with an aligner using a mask of the same size as the pattern. On the other hand, in a color filter for a solid-state imaging device, exposure is generally performed in which a mask pattern is reduced and projected by a lens using a stepper for semiconductor manufacturing that has high positional accuracy and is good at exposure of fine shapes. ing.

  Since the stepper projects a reduced size with a lens, if there is a width in the wavelength of light used, pattern projection faithful to the mask cannot be performed. Therefore, it is desirable to use a specific wavelength and make it as short as possible. Currently, steppers that are exposed to light having a wavelength of 436 nm, 365 nm, 248 nm, 193 nm, and the like have been put into practical use. As the exposure wavelength becomes smaller, it becomes possible to expose a fine pattern, but the price of the apparatus tends to increase. Since the pixel size of the color filter for the solid-state imaging device is relatively large compared to the pattern width of the semiconductor, at present, a 365 nm stepper which is high in output and relatively inexpensive in price is used for its manufacture. Most cases.

  The color filter has a role of selectively transmitting light of a desired wavelength by mixing and coloring a colorant such as a pigment or a dye. In the case of an image display medium such as a display, the wavelength required to transmit basically is between visible light (about 380 to 800 nm), and the color filter for the solid-state image sensor is also the type of image to be captured as data. Depending on the purpose of photographing and the purpose of photographing, in the case of a general digital camera or the like, it is often visible light. Due to such properties, the photosensitive coloring composition for forming a color filter itself is also capable of selectively transmitting and absorbing wavelengths in the visible light range corresponding to the spectral spectrum of the required color (RGB, CMY, etc.). If it has, it has little influence on the performance as a final solid-state imaging device, whether or not there is absorption in a region other than visible light.

  However, in the case of a negative photosensitive coloring composition in which a component not involved in the curing reaction such as a colorant or a polymer contained in the coating film absorbs irradiation light during patterning, the irradiation light is not sensitive. Since the coloring composition is not effectively used for curing, the coating film does not sufficiently cure. In particular, since the bottom of the coating is difficult for light to reach, poor curing occurs relatively strongly. Such a curing failure at the bottom of the coating film becomes more significant as the film thickness increases. In order to achieve the desired absorption spectral characteristics with a small film thickness, it is necessary to increase the concentration of the colorant in the photosensitive coloring composition and decrease the concentration of the component involved in the curing reaction. Therefore, even if the film thickness is small, the coating film may be insufficiently cured. In the state where the curing failure has occurred at the bottom of the coating film of the exposed part, even if the top of the coating film of the exposed part is sufficiently cured, the bottom of the coating is easily eroded by the developer during the development process, Adhesion between the exposed portion of the coating film and the underlying layer becomes insufficient, and a color pattern defect or shape defect is likely to occur. If the exposure time is made sufficiently long, curing failure at the bottom of the coating film can be prevented, but there is also a problem that the time required for production of the product becomes long.

  In the case of color filters for liquid crystal displays, because the pattern is relatively large, exposure is performed with light that is a mixture of multiple wavelengths using an equal-size mask, so that some wavelengths of the irradiated light do not contribute to the curing reaction Even if absorbed by the light, if the light having a wavelength applicable to the absorption wavelength region of the component involved in the curing reaction such as the polymerization initiator is transmitted, the curing of the photosensitive coloring composition proceeds, so that the above The problem is not so serious.

  However, in the case of a color filter for a solid-state imaging device, since exposure is generally performed using a stepper with light having high wavelength selectivity (which may have a certain wavelength distribution), absorption by components in the composition Greatly affects the curability. For example, when the coating film of the photosensitive coloring composition is exposed with light having a single wavelength of 365 nm, the wavelength of 365 nm is included in the components not involved in the curing reaction such as the colorant contained in the photosensitive coloring composition. If there is a component that absorbs light, poor curing at the bottom becomes noticeable. In particular, colorants (pigments, dyes, etc.) used to form green and blue pixels of commonly used color filters often have absorption at 330 to 370 nm. In the exposure using 365 nm light, the bottom portion is more likely to be hardened as the colored layer becomes thicker.

Furthermore, the color filter for a solid-state imaging device is generally required to have a fine pattern shape having a pattern shape of 10 μm square or less and a pattern film thickness of 0.2 μm to 1.6 μm. As the size of one pixel of the colored pattern becomes finer, the area that adheres to the substrate side becomes smaller, so the influence of erosion by the developer is greater, and as the thickness of the colored pattern increases, the pattern base becomes larger. Since the height of the pattern with respect to the area in close contact with the material side increases, the bottom is eroded by the developing solution during the developing process, and a phenomenon in which a colored pattern does not remain and flows with the developing solution tends to occur.
Moreover, since the coloring pattern formation process using a photosensitive coloring composition is generally performed in air, reaction inhibition by oxygen becomes a problem when curing is performed by radical reaction. Reaction inhibition due to oxygen occurs mainly on the surface of the coating film, causing a shape defect such as a pattern edge.

  In order to solve these problems, development of a photosensitive coloring composition that can sufficiently cure the coating film from the surface to the bottom with a small amount of light in the air that is actually exposed. Is desired.

  As a negative photosensitive composition, for example, Patent Document 1 discloses a negative colored photosensitive property obtained by stirring and dissolving a photosensitive resin composition and a dye using a photopolymerization initiator containing an o-acyloxime group. Composition, Patent Document 2, describes a photosensitive composition containing an oxime ester compound as a photoinitiator.

JP 2002-323762 A JP 2001-235858 A

In manufacturing a color filter for a solid-state imaging device, it is necessary to form a colored pattern accurately in accordance with the position of the light receiving device due to its properties. An object of the present invention is to provide a photosensitive coloring composition for a solid-state image sensor color filter with high sensitivity so that a fine color pattern of the solid-state image sensor color filter can be accurately formed with less irradiation energy.
In addition, the present invention provides a method for producing a solid-state image sensor color filter using the highly sensitive colored composition, a solid-state image sensor color filter having a colored layer formed using the colored composition, and the solid-state image sensor color filter. It aims at providing the solid-state image sensor provided with.

  In the photosensitive coloring composition for a solid-state image sensor color filter containing at least a reactive monomer, a photopolymerization initiator, a colorant, and an organic solvent, the present inventors have the following formula (1) as a photopolymerization initiator. It has been found that by using the photopolymerization initiator represented, the sensitivity of the photosensitive coloring composition is remarkably improved and the pattern forming ability is excellent. That is, the present invention provides a photosensitive coloring composition for a color filter of a solid-state imaging device that has good sensitivity, can be sufficiently cured with a small exposure amount, and can form a precise pattern. is there.

  The present invention includes at least a reactive monomer, a photopolymerization initiator, a colorant, and an organic solvent, wherein the photopolymerization initiator includes a compound represented by the following formula (1), It is the photosensitive coloring composition for element color filters.

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.

The photopolymerization initiator represented by the above formula (1) has high sensitivity. By using this photopolymerization initiator, the sensitivity of the photosensitive coloring composition is dramatically improved. It can be sufficiently cured even with a small exposure amount.
Further, since the photopolymerization initiator represented by the formula (1) has high sensitivity and is hardly susceptible to reaction inhibition by oxygen, the curing reaction sufficiently proceeds even at a deep position of the coating film, and the substrate or flat substrate The adhesion of the cured film to the chemical film or the like increases. Furthermore, since the photopolymerization initiator represented by the formula (1) is less susceptible to reaction inhibition by oxygen, the polymerization reaction proceeds rapidly even in the presence of oxygen, and the accuracy of the surface shape of the pattern, particularly the sharpness of the edge, is also improved. improves.
Therefore, by using the photopolymerization initiator of formula (1) in the photosensitive coloring composition, the adhesion of the coating film to the base and the accuracy of the surface shape of the pattern are simultaneously improved. As a result, solid-state imaging The fine and precise patterning property required for the element color filter can be obtained.

Of the photopolymerization initiators represented by the formula (1), compounds in which R ^{2 to} R ¹¹ are hydrogen are preferable, and in particular, R ^{2 to} R ¹¹ are hydrogen, R ¹ is a methyl group, and R ¹² is A compound in which an ethyl group, R ¹³ is a methyl group, and R ¹⁴ is a methyl group (formula (2)) efficiently generates radicals by irradiation with ultraviolet rays (330 to 370 nm as a guide) in the visible region, and is photosensitive. High sensitivity is given to the coloring composition. Since the compound of formula (2) is highly sensitive, a sufficient amount of polymerization initiating ability can be expressed by addition of a small amount, and the sensitivity is high when irradiated with ultraviolet rays close to the visible region, but a 1% solution of the initiator. Although it can be visually confirmed, it is very light yellow and the transparency of the initiator itself is high, so that it has little influence on the color of the photosensitive coloring composition and the resulting colored layer.
In particular, since the compound (2) has a large absorption intensity at 330 to 370 nm and a high quantum yield for the polymerization initiation reaction, the photosensitive coloring composition has an absorption at 330 to 370 nm. Even when it contains a colorant used to form a large number of green and blue pixels, the top of the photosensitive resin composition coating film is cured by light having a wavelength in the above range, and at the same time, at the bottom where only a small amount of light can reach. Has a high sensitivity that curing proceeds rapidly.

Since the photosensitive coloring composition according to the present invention can accurately form a very fine colored pattern, a fine processing of a pattern shape of 10 μm square or less and a film thickness of 0.2 μm or more and 1.6 μm or less is performed. It can be suitably used for a required color filter for a solid-state imaging device. In addition, the photosensitive coloring composition according to the present invention can be cured with a small amount of irradiation energy, and is less susceptible to reaction inhibition by oxygen. Since it is not necessary, there is an effect of reducing the complexity and cost of the process of forming the colored pattern.
Therefore, it is suitable for forming pixels of a color filter for a solid-state image sensor using this photosensitive coloring composition, and the obtained color filter is suitably used for a solid-state image sensor.

  The present invention is described in detail below. In the present invention, (meth) acryl means either an acrylic group or a methacryl group, and (meth) acryloyl means either an acryloyl group or a methacryloyl group. The light includes electromagnetic waves and radiation having wavelengths in the visible and non-visible regions, and the radiation includes, for example, microwaves and electron beams, and specifically refers to electromagnetic waves and electron beams having a wavelength of 5 μm or less. .

  The photosensitive coloring composition for a solid-state image sensor color filter of the present invention (hereinafter sometimes referred to as “photosensitive coloring composition”) contains at least a reactive monomer, a photopolymerization initiator, a colorant, and an organic solvent. The photopolymerization initiator includes a compound represented by the following formula (1).

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.
Therefore, first, each component blended in the photosensitive coloring composition of the present invention will be described.

  As the reactive monomer used in the present invention, a coating of a photosensitive coloring composition is formed on a substrate, and the coating is polymerized and cured when irradiated with light such as electromagnetic waves and radiation having wavelengths in the visible and invisible regions. Monomers and oligomers that can be made are included. As such a reactive monomer, monomers and oligomers having a photocurable functional group such as an ethylenically unsaturated bond can be used. In order to increase the crosslinking density, the reactive monomer preferably has two or more photocurable functional groups in one molecule.

  Specific examples of the monomer or oligomer containing an ethylenically unsaturated bond include the following polyfunctional acrylate monomers or oligomers, that is, (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; polyethylene glycol (Meth) acrylates of polyalkylene glycols such as polypropylene glycol; poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and their dicarboxylic acid modification Polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin and other oligo (meth) acrylates; both-end hydroxypoly-1,3-butadiene, both-end hydride In addition to di (meth) acrylates of hydroxylated polymers at both ends, such as xypolyisoprene and hydroxypolycaprolactone at both ends, tris [2- (meth) acryloyloxyethyl] phosphate, etc. may be mentioned. It is not limited to.

  More specifically, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, 1 , 4-butanediol diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythris Examples include tall tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate (DPHA), dipentaerythritol penta (meth) acrylate (DPPA), dipentaerythritol hexa (meth) acrylate and the like. be able to. Of these, poly (meth) acrylates of polyhydric alcohols having three or more valences and modified polybasic acid anhydrides thereof are preferable, and specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth). Examples thereof include, but are not limited to, acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  From the viewpoint of having alkali developability, those having an acidic functional group in the molecule may be used. For example, those having an acidic functional group and an ethylenically unsaturated bond, particularly those having one or more acidic functional groups and three or more ethylenically unsaturated bonds in one molecule (hereinafter referred to as “a trifunctional or more acidic polyfunctional group”). A functional acrylate monomer ”). The trifunctional or higher acid polyfunctional acrylate monomer has a role of improving the crosslinking density of the coating film and a role of improving the alkali developability, so even if a large amount of a colorant is added to the composition, The acidic polyfunctional acrylate monomer can be adjusted and improved without impairing the curability and developability of the photosensitive coloring composition.

The acidic functional group of the acidic polyfunctional acrylate monomer only needs to be capable of alkali development, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. From the viewpoint of properties, a carboxyl group is preferred.
As the above-described trifunctional or higher functional polyfunctional acrylate monomer, (1) a polyfunctional (meth) acrylate having a carboxyl group introduced by modifying a hydroxyl group-containing polyfunctional (meth) acrylate with a polybasic acid anhydride, Alternatively, (2) a polyfunctional (meth) acrylate having a sulfonic acid group introduced by modifying an aromatic polyfunctional (meth) acrylate with concentrated sulfuric acid or fuming sulfuric acid can be used.

  The reactive monomer is used in a ratio of 0.5 to 99.5 parts by weight, preferably 1 to 95 parts by weight, based on 100 parts by weight of the solid content in the photosensitive coloring composition. If the amount used is too small, sufficient photocurability cannot be obtained. If the amount used is too large, the ratio of the colorant becomes relatively low, and a sufficient coloring density cannot be obtained. Here, the solid content of the photosensitive coloring composition for a solid-state image sensor color filter includes all components except for the solvent, for example, a liquid monomer component.

  The photosensitive coloring composition of the present invention further includes a non-reactive polymer, a photocurable material, if necessary, together with the reactive monomer, in order to impart sufficient strength, durability, adhesion, etc. to the coating film. A reactive polymer such as a polymer and a thermosetting polymer, or a binder resin such as a thermosetting resin is used.

As the non-reactive polymer, it is possible to use a copolymer that does not include a photocurable functional group-containing unit such as an ethylenically unsaturated bond-containing unit, but includes an aromatic carbocyclic-containing unit, an ester group-containing unit, or the like. For example, a copolymer comprising two or more of the following monomers can be used: (meth) acrylic acid, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and styrene.
More specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer and the like can be exemplified.
Especially, when the said copolymer contains the structural unit provided with acidic functional groups, such as (meth) acrylic acid, it is preferable from the point by which alkali developability is provided to the said copolymer.

The photocurable polymer is preferably used because it has a photocurable property as well as a binder function. Such a photocurable polymer includes a photocurable functional group-containing unit such as the above-mentioned ethylenically unsaturated bond-containing unit as an essential constituent unit, and if necessary, an alcoholic hydroxyl group-containing unit, an aromatic group A copolymer containing a carbocyclic unit, an ester group-containing unit and the like is preferably used.
The molecular weight of the photocurable polymer is usually 1,000 to 100,000, preferably 1,000 to 50,000 in weight average molecular weight. When the weight average molecular weight is less than 1,000, the strength of the coating film becomes weak and the effect of adding a polymer cannot be obtained. When the weight average molecular weight is greater than 100,000, the solubility and developability may be deteriorated.

  As the thermosetting polymer or thermosetting resin, a compound having two or more thermosetting functional groups in one molecule is usually used, and an epoxy group is preferably used as the thermosetting functional group.

As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule (hereinafter sometimes referred to as “epoxy compound”) is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.
More specifically, bisphenol A type novolak epoxy resins such as trade name Epicoat 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and cresol novolac type epoxy resins such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) can be mentioned. .

  As an epoxy compound, a polymer having a relatively high molecular weight that is usually used as a binder component in order to impart adhesion, heat resistance, and alkali resistance to a cured film (hereinafter sometimes referred to as “binder epoxy compound”), In order to increase the crosslinking density of the cured film or to adjust the viscosity of the photosensitive coloring composition, the compound having a molecular weight smaller than that of the binder epoxy compound and having two or more epoxy groups in one molecule (hereinafter referred to as “multiple” You may use together a "functional epoxy compound".

  The average molecular weight of the binder epoxy compound is preferably 1,000 to 100,000, and particularly preferably 2,000 to 50,000, when expressed in terms of polystyrene-equivalent weight average molecular weight. If the molecular weight of the binder epoxy compound is less than 1,000, physical properties such as strength and solvent resistance required for the cured resin layer as the details of the color filter for the solid-state imaging device are likely to be insufficient. If it is larger than 100,000, the viscosity is likely to increase, the uniformity during coating on the substrate is impaired, and a large distribution tends to occur in the film thickness.

  On the other hand, the weight average molecular weight in terms of polystyrene of the polyfunctional epoxy compound is preferably 4,000 or less, particularly preferably 3,000 or less, on the condition that it is smaller than the binder epoxy compound combined therewith. In addition, a weight average molecular weight means the value calculated | required by polystyrene conversion using the gel permeation chromatography (For example, HLC-8029, Tosoh Corporation make) which used tetrahydrofuran as the developing liquid.

  The binder epoxy compound has a limit in the amount of epoxy that can be introduced into the copolymer molecule. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the photosensitive coloring composition, the epoxy group is replenished in the composition to increase the reactive site concentration of the epoxy, thereby increasing the crosslinking density. The polyfunctional epoxy compound can be appropriately selected from the polyvalent epoxy compounds described above.

  When the binder resin as described above is used together with the reactive monomer, the total amount of the reactive monomer and the binder resin is 1 to 99 parts by weight, preferably 5 to 100 parts by weight of the solid content in the photosensitive coloring composition. Used at a ratio of 95 parts by weight.

  As a photopolymerization initiator used for this invention, 1 type (s) or 2 or more types are selected and used from the compound group represented by following formula (1).

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.

By substituting halogen at one or two or more arbitrary positions of R ^{1 to} R ¹⁴ , it is possible to increase the cleavage reactivity of the compound of formula (1) at the time of light irradiation, and further improve the sensitivity. be able to. Examples of halogen include Br and Cl.
Moreover, the compound of Formula (1) is substituted by substituting a hydroxyl group, an amino group, a carboxyl group, a ketone group, an aromatic group, or an aliphatic group at one or two or more arbitrary positions of R ^{1 to} R ¹⁴ . The absorption spectrum can be changed, and the absorption wavelength characteristic can be adjusted according to the irradiation wavelength. Examples of the ketone group include those containing an alkyl group having 1 to 10 carbon atoms or an aromatic group having 5 to 14 carbon atoms. These alkyl groups and aromatic groups may have a substituent, or may have a structure other than hydrocarbon in the middle of the group.

The aromatic group is preferably an aromatic group having 5 to 20 carbon atoms, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a group containing a heteroatom other than a hydrocarbon such as a pyridyl group. Also mentioned.
As the aliphatic group, an aliphatic group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group. In addition to aliphatic hydrocarbon groups such as a group, an alkyl group such as an n-hexyl group, and an unsaturated hydrocarbon group such as an alkenyl group, groups containing hetero atoms other than hydrocarbons are also included.

  As a photoinitiator represented by Formula (1), the following are mentioned, for example.

Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-Methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-Methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-Methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Ethanone 1- [9-Methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Ethanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),
Propanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime)

Propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime]

Propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime]

Propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-Ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-Methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],
Propanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

  The photopolymerization initiator represented by the formula (1) has high sensitivity, and by using this photopolymerization initiator, the sensitivity of the photosensitive coloring composition is dramatically improved, and the reaction proceeds efficiently. As a result, it can be sufficiently cured even with a smaller exposure amount than usual. In addition, since the sensitivity is high, the curing reaction proceeds sufficiently even at a deep position in the coating film where only a small amount of light reaches, or even when the concentration of the colorant in the photosensitive coloring composition is high or the concentration of the curing component is small. Since the adhesiveness after curing with respect to the substrate or the flattening film as a base is increased, the pattern is difficult to flow during development, and a fine pattern shape can be accurately formed.

Such an improvement in sensitivity is particularly noticeable in exposure in the presence of oxygen. The photopolymerization initiator of formula (1) is less susceptible to reaction inhibition by oxygen, so that the polymerization reaction proceeds rapidly even in the presence of oxygen. Therefore, when forming a coating film using the photosensitive coloring composition of the present invention, there is no need to apply an oxygen blocking film on the coating film surface before exposure or to expose the coating film in a nitrogen atmosphere. The complexity of the process and the high cost can be avoided.
In addition, reaction inhibition due to oxygen occurs strongly on the surface of the coating film in contact with oxygen, and thus tends to affect the surface shape of the pattern, particularly the sharpness of the edges. On the other hand, since it becomes difficult to receive reaction inhibition by oxygen by using the photoinitiator of Formula (1) for the photosensitive coloring composition, the accuracy of the surface shape of the pattern is also improved.
Therefore, by using the photopolymerization initiator of the formula (1), the adhesion of the coating film to the base and the accuracy of the surface shape of the pattern are simultaneously improved. As a result, the fineness required for the solid-state image sensor color filter is improved. In addition, precise patterning properties can be obtained.

Of the compounds represented by the above formula (1), compounds in which R ^{2 to} R ¹¹ are hydrogen are preferable, and compounds in which R ^{2 to} R ¹¹ are hydrogen are R ¹ , R ¹² , R ^13. R ¹⁴ is preferably an aliphatic group having 1 to 3 carbon atoms.
Further, in the above formula (1), R ^{2 to} R ¹¹ are hydrogen, R ¹ is a methyl group, R ¹² is an ethyl group, R ¹³ is a methyl group, and R ¹⁴ is a methyl group. The compound represented efficiently generates radicals by irradiation with ultraviolet rays (330 to 370 nm as a guide) including i-line (365 nm) in the visible region, and gives high sensitivity to the photosensitive coloring composition.

  Initiators that are highly sensitive to irradiation with ultraviolet rays in the range of 330 to 370 nm generally have an absorption band also in the vicinity of 390 to 430 nm, and the initiator itself is often strongly colored yellow. However, although the compound of the formula (2) has high sensitivity when irradiated with ultraviolet rays in the range of 330 to 370 nm, for example, a solution in which an initiator is dissolved in about 1% in a solvent can be visually confirmed. It is light yellow and the transparency of the initiator itself is high. In addition, since it has high sensitivity, sufficient polymerization initiating ability can be expressed with a small amount of addition, so that there is little influence on the color of the photosensitive coloring composition and the resulting colored layer.

In addition, colorants such as pigments and dyes used in the green and blue photosensitive coloring compositions often absorb ultraviolet rays in the region close to the visible region, and coloring compositions containing these colorants. The amount of light that passes through the object coating is reduced. Therefore, when the photosensitive coloring composition of green and blue is irradiated with ultraviolet rays in a region close to the visible region, the sensitivity is often insufficient. On the other hand, since the compound of the above formula (2) has high sensitivity to ultraviolet rays in the region close to the visible region, the compound of formula (2) is blended as an initiator in the green and blue photosensitive coloring compositions. As a result, high sensitivity is obtained when ultraviolet rays are irradiated in a region close to the visible region, and the curing reaction proceeds sufficiently even at the bottom of the coating film and when the colorant concentration is high. Compared with other initiators such as Irgacure 907 (manufactured by Ciba Specialty Chemicals) which is often used in color filter applications, the compound (2) has a large absorption intensity of 330 to 370 nm such as 333 nm and 365 nm, and This is considered to be because the quantum yield related to the polymerization initiation reaction is high, and the reaction can be advanced by efficiently using light of 330 to 370 nm.
As a photoinitiator of Formula (2), commercial items, such as CGI242 (Ciba Specialty Chemicals), can be used, for example.

  In the present invention, together with the compound represented by the above formula (1), other photopolymerization initiators having an action of inducing radical polymerization reaction by causing cleavage or hydrogen abstraction reaction when irradiated with light, You may combine and use in the range which does not impair an invention field effect. When two or more kinds of initiators are used in combination, it is preferable to use those having absorption with respect to the exposure wavelength to such an extent that each initiator is not significantly inhibited by reaction.

  As other photopolymerization initiators, radical polymerization initiators can be used, for example, compounds that generate free radicals by the energy of ultraviolet rays, and derivatives such as benzophenone derivatives such as benzoin and benzophenone, or esters thereof; Xanthone and thioxanthone derivatives; halogen-containing compounds such as chlorosulfonyl, chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethylbenzophenones; triazines; fluorenones; haloalkanes; photoreducing dyes and reducing agents Redox couples; organic sulfur compounds; peroxides and the like. Preferred examples include ketone-based and biimidazole-based compounds. Specifically, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (manufactured by Ciba Specialty Chemicals), Darocur (Merck), Commercial products such as Adeka 1717 (Asahi Denka Kogyo), 2,2′-bis (o-chlorophenyl) -4,5,4′-tetraphenyl-1,2′-biimidazole (Kurokin Kasei) It is done. Other photopolymerization initiators can be used alone or in combination of two or more. When an initiator that does not absorb at the exposure wavelength is used, it is necessary to use a compound that absorbs at the exposure wavelength as a sensitizer.

  The blending amount of the photopolymerization initiator selected from the compound group represented by formula (1) is usually 0.5 to 100 parts by weight based on the total solid content in the photosensitive coloring composition for a solid-state image sensor color filter. 40 parts by weight, preferably 1 to 20 parts by weight.

  As the colorant used in the present invention, pigments and dyes can be used. As the pigment, organic pigments, inorganic pigments, extender pigments and the like can be used.

  Specific examples of organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), that is, the following Color Index (C.I. ) Some are numbered. For example, C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I.Pigment Yellow 16, C.I.Pigment Yellow 17, C.I.Pigment Yellow 20, C.I.Pigment Yellow 24, C.I.Pigment Yellow 31, g.P. Yellow 55, C.I. Pigment Yellow 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 65, C.I. Pigment Yellow 71, C.I. Pigment nt Yellow 73, C.I.Pigment Yellow 74, C.I.Pigment Yellow 81, C.I.Pigment Yellow 83, C.I.Pigment Yellow 93, C.I.Pigment Yellow 95, C.I.Pigment Yellow 95 97, C.I.Pigment Yellow 98, C.I.Pigment Yellow 100, C.I.Pigment Yellow 101, C.I.Pigment Yellow 104, C.I.Pigment Yellow 106, C.I.Pigment Yellow 108 CI Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. pigment Yellow 116, C.I. Pigment Yellow 117, C.I. Pigment Yellow 119, C.I. Pigment Yellow 120, C.I. Pigment Yellow 126, C.I. Pigment Yellow 127, C.I. 128, C.I.Pigment Yellow 129, C.I.Pigment Yellow 138, C.I.Pigment Yellow 139, C.I.Pigment Yellow 150, C.I.Pigment Yellow 151, C.I.Pigment 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Y llow 156, C.I.Pigment Yellow 166, C.I.Pigment Yellow 168, C.I.Pigment Yellow 175, C.I.Pigment Yellow 180, include C.I. Pigment Yellow 185 or the like.

  Examples of the orange pigment include C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 16. Pigment Orange 17, CI Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 38, C.I. Pigment Orange 38. C.I. Pigment Orange. 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 61 range 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, and the like.

  Examples of red pigments include CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, and CI Pigment Red 5. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 81, C.I. Pigment Red 122, .I.Pigment Red 209, C.I.Pigment Red 177, C.I.Pigment Red 254, and the like.

  Blue pigments include CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, and CI Pigment Blue. 60 etc. are mentioned.

  Examples of green pigments include CI Pigment Green 7, CI Pigment Green 36, and the like.

  Further, examples of the violet pigment include C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, and C.I. Pigment Violet 32. CI Pigment Violet 36, C.I. Pigment Violet 38, C.I. Pigment Violet 23:19, and the like.

  Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  Moreover, in order to improve heat resistance, what has a rigid chemical structure can be used. As what has a rigid structure, what has a phthalocyanine skeleton with a high bromination rate is mentioned, for example. Specifically, high brightness G pigments such as Monastral Green 6YC, 9YC, etc. (manufactured by Avisia Co., Ltd.), metals whose central metal is other than copper, such as Mg, Al, Si, Ti, V, Mn, Fe, High color purity G pigments made of different metal phthalocyanine pigments such as Co, Ni, Zn, Ge and Sn can be used.

When the colorant is a pigment, the particle size is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.1 μm or less. When the particle size of the pigment is larger than 0.5 μm, the dispersibility is poor and the particles are likely to aggregate, and the pigment particle is large with respect to the pattern size and film thickness. Due to the variation in light intensity between pixels, there is a high possibility that noise of an electric signal is generated.
The particle diameter here is the primary particle diameter of an actual pigment, and the maximum diameter and the minimum diameter were determined by dynamic scattering using Microtrac UPA (manufactured by Leed & Northrup).

  Examples of the dye include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes.

  Specific examples of the acid dye include C.I. I. Acid Red 6, C.I. I. Acid Red 11, C.I. I. Acid Red 26, C.I. I. Acid Red 60, C.I. I. Acid Red 88, C.I. I. Acid Red 111, C.I. I. Acid Red 186, C.I. I. Acid Red 215, C.I. I. AcidGreen 25, C.I. I. Acid Green 27, C.I. I. Acid Blue 22, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 78, C.I. I. Acid Blue 92, C.I. I. Acid Blue 113, C.I. I. Acid Blue 129, C.I. I. Acid Blue 167, C.I. I. Acid Blue 230, C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 25, C.I. I. Acid Yellow 36, C.I. I. Acid Yellow 38, C.I. I. Acid Yellow 42, C.I. I. Acid Yellow 44, C.I. I. Acid Yellow 72, C.I. I. Acid Yellow 78 etc. are mentioned.

  Specific examples of basic dyes include C.I. I. Basic Red 1, C.I. I. Basic Red 2, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Red 22, C.I. I. BasicRed 27, C.I. I. Basic Red 29, C.I. I. Basic Red 39, C.I. I. Basic Green 3, C.I. I. Basic Green 4, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9, C.I. I. Basic Blue 41, C.I. I. Basic Blue 66, C.I. I. Basic Violet 1, C.I. I. Basic Violet 3, C.I. I. Basic Violet 18, C.I. I. BasicViolet 39, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 23, C.I. I. Basic Yellow 25, C.I. I. Basic Yellow 28, C.I. I. Basic Yellow 41 etc. are mentioned.

  Specific examples of direct dyes include C.I. I. Direct Red 4, C.I. I. Direct Red 23, C.I. I. Direct Red 31, C.I. I. Direct Red 75, C.I. I. Direct Red 76, C.I. I. Direct Red 79, C.I. I. Direct Red 80, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 84, C.I. I. Direct Red 149, C.I. I. Direct Red 224, C.I. I. Direct Green 26, C.I. I. Direct Green 28, C.I. I. Direct Blue 71, C.I. I. Direct Blue 78, C.I. I. Direct Blue 98, C.I. I. Direct Blue 106, C.I. I. Direct Blue 108, C.I. I. DirectBlue 192, C.I. I. Direct Blue 201, C.I. I. Direct Violet 51, C.I. I. Direct Yellow 26, C.I. I. Direct Yellow 27, C.I. I. Direct Yellow 28, C.I. I. Direct Yellow 33, C.I. I. Direct Yellow 44, C.I. I. Direct Yellow 50, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 142, C.I. I. Direct Orange 26, C.I. I. Direct Orange 29, C.I. I. Direct Orange 34, C.I. I. Direct Orange 37, C.I. I. Direct Orange 72 etc. are mentioned.

  Specific examples of sulfur dyes include C.I. I. Sulfur Red 5, C.I. I. Sulfur Red 6, C.I. I. Sulfur Red 7, C.I. I. Sulfur Green 2, C.I. I. Sulfur Green 3, C.I. I. Sulfur Green 6, C.I. I. Sulfur Blue2, C.I. I. Sulfur Blue 3, C.I. I. Sulfur Blue 7, C.I. I. Sulfur Blue 9, C.I. I. Sulfur Blue 13, C.I. I. Sulfur Blue 15, C.I. I. Sulfur Violet 2, C.I. I. Sulfur Violet 3, C.I. I. Sulfur Violet 4, C.I. I. Sulfur Yellow 4 etc. are mentioned.

  Specific examples of vat dyes include C.I. I. Vat Red 13, C.I. I. VatRed 21, C.I. I. Vat Red 23, C.I. I. Vat Red 28, C.I. I. Vat Red 29, C.I. I. Vat Red 48, C.I. I. Vat Green 3, C.I. I. Vat Green 5, C.I. I. Vat Green 8, C.I. I. Vat Blue 6, C.I. I. Vat Blue 14, C.I. I. Vat Blue 26, C.I. I. Vat Blue 30, C.I. I. Vat Violet 1, C.I. I. Vat Violet 3, C.I. I. Vat Violet 9, C.I. I. Vat Violet 13, C.I. I. Vat Violet 15, C.I. I. Vat Violet 16, C.I. I. Vat Yellow 2, C.I. I. Vat Yellow 12, C.I. I. Vat Yellow 20, C.I. I. Vat Yellow 33, C.I. I. Vat Orange 2, C.I. I. Vat Orange 5, C.I. I. Vat Orange 11, C.I. I. Vat Orange 15, C.I. I. Vat Orange 18, C.I. I. Vat Orange 20 and the like.

  Specific examples of naphthol dyes include C.I. I. Azoic Coupling Component 2, C.I. I. Azoic Coupling Component 3, C.I. I. Azoic Coupling Component 4, C.I. I. Azoic Coupling Component 5, C.I. I. Azoic Coupling Component 7, C.I. I. Azoic Coupling Component 8, C.I. I. Azoic Coupling Component 9, C.I. I. Azoic Coupling Component 10, C.I. I. Azoic Coupling Component 11, C.I. I. Azoic Coupling Component 13, C.I. I. Azoic Coupling Component 32, C.I. I. Azoic Coupling Component 37, C.I. I. Azoic Coupling Component 41, C.I. I. Azoic Coupling Component 48 and the like.

  Specific examples of reactive dyes include C.I. I. Reactive Red 8, C.I. I. Reactive Red 22, C.I. I. Reactive Red 46, C.I. I. Reactive Red 120, C.I. I. Reactive Blue 1, C.I. I. Reactive Blue 2, C.I. I. Reactive Blue 7, C.I. I. Reactive Blue 19, C.I. I. Reactive Violet 2, C.I. I. Reactive Violet 4, C.I. I. Reactive Yellow 1, C.I. I. Reactive Yellow 2, C.I. I. Reactive Yellow 4, C.I. I. Reactive Yellow 14, C.I. I. Reactive Yellow 16, C.I. I. Reactive Orange 1, C.I. I. Reactive Orange 4, C.I. I. Reactive Orange 7, C.I. I. Reactive Orange 13, C.I. I. Reactive Orange 16, C.I. I. Reactive Orange 20 and the like.

  Specific examples of the disperse dye include C.I. I. Disperse Red 4, C.I. I. Disperse Red 11, C.I. I. Disperse Red 54, C.I. I. Disperse Red 55, C.I. I. Disperse Red 58, C.I. I. Disperse Red 65, C.I. I. DisperseRed 73, C.I. I. Disperse Red 54, C.I. I. Disperse Red 127, C.I. I. Disperse Red 141, C.I. I. Disperse Red 129, C.I. I. Disperse Red196, C.I. I. Disperse Red 210, C.I. I. Disperse Red 229, C.I. I. Disperse Red 354, C.I. I. Disperse Red 356, C.I. I. Disperse Blue 3, C.I. I. Disperse Blue 24, C.I. I. Disperse Blue 79, C.I. I. Disperse Blue 82, C.I. I. Disperse Blue 87, C.I. I. Disperse Blue 106, C.I. I. Disperse Blue 125, C.I. I. Disperse Blue 165, C.I. I. Disperse Blue 183, C.I. I. Disperse Violet 1, C.I. I. Disperse Violet 6, C.I. I. Disperse Violet 12, C.I. I. DisperseViolet 26, C.I. I. Disperse Violet 27, C.I. I. Disperse Violet 28, C.I. I. Disperse Yellow 3, C.I. I. Disperse Yellow 4, C.I. I. Disperse Yellow 5, C.I. I. Disperse Yellow 7, C.I. I. Disperse Yellow 23, C.I. I. Disperse Yellow 33, C.I. I. Disperse Yellow 42, C.I. I. Disperse Yellow 60, C.I. I. Disperse Yellow 64, C.I. I. Disperse Orange 13, C.I. I. Disperse Orange 29, C.I. I. Disperse Orange 30 etc. are mentioned.

  In order to increase the solubility of dyes in organic solvents, for example, acid dyes, basic dyes, etc. can be reacted with amines of primary amines such as n-propylamine, ethylhexylpropionate, etc. to form amine salt dyes, A sulfonamide group-containing dye or the like can also be obtained by reacting a sulfonic acid group such as a basic dye with an amine having a primary amine or higher as described above.

  Among the above colorants, examples of the colorant that is preferably used for forming a green pixel of a color filter include CI Pigment Green 7 and CI Pigment Green 36 green pigments. 1 type or 2 types can be selected and used. In addition, one or two of the above-mentioned green pigments may be selected from CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, and CI Pigment Yellow 13. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, etc. It can be combined with the above.

  Examples of the colorant that is preferably used for forming a blue pixel include CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, and CI Pigment. Blue pigments such as Blue 15: 6 and CI Pigment Blue 60 can be used, and one or more of them can be selected and used. In addition, one or more of the blue pigments may be combined with a violet pigment such as CI Pigment Violet 23:19.

  Examples of the colorant preferably used for forming a red pixel include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 81, and C.I. Pigment Red 122, CI Pigment Red 177, CI Pigment Red 209, C.I. Pigment Red 254, etc. are selected, and one or more of them are selected. Can be used.

In this invention, a coloring agent can be used individually or in mixture of 2 or more types.
The blending amount of the colorant is usually 3 to 80 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive coloring composition for a solid-state image sensor color filter. 40 parts by weight. When the blending amount of the colorant is less than 3 parts by weight, it becomes difficult to obtain the required absorption spectral characteristics. Moreover, when it exceeds 80 weight part, since the compounding quantity of a hardening component becomes relatively small with respect to the compounding quantity of a coloring agent, it becomes difficult to form the target pattern shape.

Examples of the organic solvent used in the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol and ethoxyethoxyethanol. Carbitol solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, etc .; Ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, methoxypropyl Cellosolve acetate solvents such as acetate, methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; methoxyethoxyethyl acetate Carbitol acetate solvents such as ethoxyethoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Aprotic amide solvents; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane These organic solvents are mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are preferably used. More preferably, MBA (acetate-3-methoxy _{butyl, CH 3 CH (OCH 3)} CH 2 CH 2 OCOCH 3), PGMEA ( propylene glycol monomethyl ether _{acetate, CH 3 OCH 2 CH (CH} 3) OCOCH 3), DMDG (Diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ), diethylene glycol methyl ethyl ether, or a mixture thereof can be used.

  These solvents may be used alone or in combination of two or more. In the present invention, the solid content concentration of the photosensitive coloring composition is adjusted to 5 to 70% by weight using a solvent.

  The photosensitive coloring composition according to the present invention further includes a sensitizer, a surfactant, a dispersant, an ultraviolet blocker, an ultraviolet absorber, a surface conditioner (leveling agent), or other components as necessary. May be blended.

  The dispersant is blended as necessary in order to disperse the colorant satisfactorily. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine and amines having a hydroxy group such as 1- (2-hydroxyethyl) piperazine, and the like, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide are listed. be able to.

  Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

  In addition, as commercially available dispersants, Shigenox-105 (trade name, manufactured by Hackol Chemical), Disperbyk-101, -130, -140, -160, -161, -162, and -163 -164, -165, -166, -170, -171, -182, -2000, -2001 (above, manufactured by Big Chemie Japan Co., Ltd.), EFKA-47,- 47EA, -48, -49, -100, -400, -450 (above, manufactured by EFKA CHEMICALS), Solsperse 12000, 13240, 11394, 17000, 20000, 24000GR, 24000SC , 27000, 28000, 33500 (manufactured by Zeneca Co., Ltd.), Ajisper PB711, 821, 822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

  Furthermore, when various surfactants are used in combination, the dispersion stability can be improved. Examples of the surfactant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether Examples include alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and polyethyleneimines.

  The product names of the surfactants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), Megafac (Dainippon Ink Chemical Co., Ltd.) )), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like.

  The sensitizer is blended in order to improve the sensitivity according to the light source for exposing the image. Examples thereof include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylaminobenzophenone, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate and the like.

  The photosensitive coloring composition for a solid-state image sensor color filter of the present invention is prepared by, for example, directly mixing the reactive monomer, photopolymerization initiator, and coloring agent, and other components such as a binder resin, if necessary, in an organic solvent. , Kneaders, roll mills, attritors, super mills, dissolvers, homomixers, sand mills and the like, and can be produced by dissolving or dispersing solid components by a known dispersion method.

  However, in the above method, a large amount of colorant may not be sufficiently dispersed in the solvent. Therefore, in advance, a colorant and, if necessary, a dispersant are mixed in a solvent to prepare a dispersed colorant dispersion, while a reactive monomer, a photopolymerization initiator, and a binder resin as necessary. It is preferable to prepare a clear resist solution in which other components are mixed, dispersed or dissolved with a solvent. And the photosensitive coloring composition excellent in colorant dispersibility is easily obtained by mixing the obtained colorant dispersion liquid and a clear resist liquid, and performing a dispersion process as needed.

  If the colorant dispersion is not prepared in advance, first add the colorant and, if necessary, the dispersant into the solvent, mix thoroughly, and stir to disperse the colorant, then start the reactive monomer and photopolymerization. By adding and mixing the remaining components including the colorant, not only the colorant dispersibility is not inhibited by the other compounding components in the colorant dispersion step, but also the stability is excellent.

  The solid-state image sensor color filter according to the present invention includes at least a colored layer on a substrate, and the colored layer can be formed using the photosensitive colored composition of the present invention.

  As an example of a method for manufacturing a solid-state image sensor color filter, first, a silicone wafer 1, a signal transfer unit 2 formed on the silicone wafer 1, and a surface of the silicone wafer 1 between the signal transfer units 2 are formed. An image sensor substrate composed of the light receiving unit 3 and the like is prepared. A planarizing film 4 made of a resin is provided on the entire surface of the imaging element substrate.

  Next, the photosensitive coloring composition of the present invention is applied onto the planarizing film 4 by an arbitrary coating method such as a spin coater, a roll coater, or a curtain coater to form a coating film and dried. After drying, the coating film of the irradiated portion is selectively cured by irradiating the coating film with light in a predetermined pattern.

In the exposure step, a mask pattern is reduced and projected by a lens using a semiconductor manufacturing stepper, and light is irradiated onto the surface of the coating film, whereby a predetermined position of the coating film can be selectively exposed and cured. As a light beam used for exposure, a light beam having a wavelength that causes a reaction of a photocurable component is appropriately selected from ultraviolet rays, electromagnetic waves, and radiation having wavelengths in the visible and invisible regions.
Irradiation energy required for curing is very low compared to conventional 1,000~6,000mJ / cm ² or so, may be about 50~3,000mJ / cm ^2. In addition, since the polymerization reaction can proceed even when exposure is performed in air containing oxygen, purging with an inert gas such as nitrogen, or coating the surface of the photosensitive coloring composition with an oxygen blocking film. There is no need to coat.

  In particular, when the compound represented by the formula (2) is used as an initiator, ultraviolet rays close to the visible region, for example, light having a wavelength of about 330 to 370 nm such as i-line (365 nm) is preferably used. High sensitivity is obtained. Since the compound of Formula (2) has high transparency, the color of the resulting colored layer is also good. Furthermore, even in a color composition in which sufficient sensitivity cannot be obtained at this irradiation wavelength, for example, a blue or green colored composition, high sensitivity can be obtained by using the compound of the formula (2).

  When the photosensitive coloring composition has an alkali developability, an unexposed portion is obtained by an immersion method, a spray method, or the like, using an alkali solution, and if the photosensitive coloring composition does not have an alkali developability, other developing solution such as a solvent or a surfactant solution. Is dissolved and developed to obtain a colored coating film having a predetermined pattern. After the development, the colored layer 5 can be formed usually by heating and post-baking. The colored layer is usually formed to a thickness of about 0.2 to 1.6 μm. When the thickness of the colored layer is less than 0.2 μm, it is necessary to increase the concentration of the colorant in the photosensitive coloring composition in order to achieve the target spectral characteristics. The concentration will be low. As a result, it becomes difficult to form a target pattern shape. Further, when the thickness of the colored layer is larger than 1.6 μm, when the photosensitive colored composition is applied onto the wafer, particularly when the coating method is a spin coater, the coating film is formed on the wafer. Since the thickness distribution becomes large, the target pattern height cannot be obtained on the entire surface of the wafer, which may result in a colored layer having uneven thickness.

The colored layer thus obtained has high sensitivity at the time of exposure, and reaction inhibition by oxygen hardly occurs. Therefore, in the irradiated part of the coating film, the polymerization proceeds sufficiently from the surface to a deep position and is cured. Therefore, even if the cured portion of the coating film has a fine colored pattern, it has high adhesion to the base and has a sharp surface shape, and therefore remains accurately after development. By using the photosensitive coloring composition of the present invention, specifically, a pixel portion having a pattern shape of 10 μm square or less per pixel and a film thickness of 0.2 μm or more and 1.6 μm or less can be formed. it can.
Therefore, a very accurate pixel pattern required for a solid-state image sensor color filter can also be formed using the photosensitive coloring composition of the present invention. In addition, the photosensitive coloring composition of the present invention can form a very accurate pixel pattern even when the colorant concentration in the photosensitive coloring composition is high or the concentration of the curing component is low. Further, it is possible to sufficiently cope with the thinning of the colored layer accompanying the thinning of the solid-state image sensor color filter.

Next, a planarizing film 6 made of a resin is formed on the colored layer 5, and a lens 7 is provided at a position directly above the light receiving portion 3 and the colored layer 5 to obtain a solid-state image sensor color filter. be able to.
The solid-state image sensor color filter thus obtained can be suitably used particularly for a solid-state image sensor such as a CCD or CMOS.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.

<Blue dispersion>
40 wt% mixture obtained by adding 30 wt% of pigment dispersant (Ajisper PB821, Ajinomoto Fine-Techno) to blue pigment (CI Pigment Blue 15: 6, Lionol Blue ES, manufactured by Toyo Ink) And 60 parts by weight of propylene glycol monomethyl ether acetate were mixed and dispersed.

<Violet dispersion>
40 parts by weight of a mixture obtained by adding 40% by weight of a pigment dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno) to purple pigment (CI Pigment Violet 23, Hosta Palm Violet RL, manufactured by Clariant), and propylene 60 parts by weight of glycol monomethyl ether acetate was mixed and dispersed.

Using the dispersion obtained above, a blue colored resin composition having the following composition was prepared.
<Blue resin composition>
Blue dispersion 25 parts by weight Violet dispersion 10 parts by weight Epicoat 157S70 (manufactured by Japan Epoxy Resin) 1.5 parts by weight MegaFac R-08MH (manufactured by Dainippon Ink and Chemicals) 0.04 parts by weight Methoxypropyl acetate 35 parts by weight 3 -Methoxybutyl acetate 7 parts by weight Multifunctional acrylate monomer (Sartomer SR399, manufactured by Nippon Kayaku)
3.4 parts by weight Styrene / benzyl methacrylate / acrylic acid / 2-hydroxymethyl acrylate / 2-methacryloyloxyethyl isocyanate copolymer (acid value: 70 mgKOH / g)
18 parts by weight

Example 1
0.6 g of the compound of the formula (2) (trade name CGI242, manufactured by Ciba Specialty Chemicals) was added as a photopolymerization initiator to 19.4 g of the blue-colored resin composition to obtain a photosensitive blue composition (1). .

(Example 2)
19.4 g of the blue resin composition, 0.5 g of the compound of the formula (2) (trade name CGI242, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and 4,4′-dimethylamino as a photosensitizer Benzophenone 0.1g was added and it was set as the photosensitive blue composition (2).

(Comparative Example 1)
To 19.4 g of the blue resin composition, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was used as a photopolymerization initiator. ) 0.5 g and 4,4′-dimethylaminobenzophenone 0.1 g as a photosensitizer were added to obtain a photosensitive blue composition (C1).

(resolution)
The obtained photosensitive resin composition was spin-coated on a glass substrate so as to have a film thickness of 1 μm when dried, and heated at 80 ° C. for 2 minutes to form a coating film of the photosensitive resin composition. A mask for forming a linear pattern with each line width of 1 μm, 3 μm, and 5 μm was brought into close contact with the coating film, and i-line (365 ± 10 nm) was selectively exposed from the mask side with the exposure amount shown in Table 1. After the exposure, a solution obtained by diluting an organic alkaline developer (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to 50% is developed by spraying for 15 seconds while rotating the coating film on a spin table, and then pure water. Was sprayed for 30 seconds, washed, and heated at 200 ° C. for 10 minutes. The pattern (1, 3, 5 μm) of the coating film was observed with an optical microscope, and the minimum value among the line widths on which the pattern was formed was defined as the resolution.

The photosensitive coloring compositions 1 and 2 (Examples 1 and 2) of the present invention were sufficiently cured at an exposure dose of 300 mJ / cm ² and had high resolution. On the other hand, the photosensitive coloring composition C1 (Comparative Example 1) is not sufficiently cured at an exposure amount of 300 mJ / cm ² , and the adhesiveness is insufficient because the irradiated part of the coating film was peeled off during development. confirmed. Therefore, when the exposure dose was 2000 mJ / cm ² , the photosensitive coloring composition C1 was cured and a pattern could be formed, but a large difference in sensitivity was recognized.

(Pattern formation test on wafer)
In addition, photosensitive coloring compositions 1 and 2 (Examples 1 and 2) were applied to a base material (with a light receiving portion provided every 3 μm) coated with an acrylic transparent thin film on a silicone wafer on which a solid-state imaging device was formed. Each was used to form a coating film as described above. The coating film was exposed to a pattern according to the position of the light receiving portion and developed. As a result, a very fine 3 μm dot pattern could be accurately formed. In addition, a 30 μm pattern for an LCD larger or larger than that could be produced without any problem.
On the other hand, when the photosensitive coloring composition C1 (Comparative Example 1) was similarly exposed at an exposure amount of 200 mJ / cm ² , curing was insufficient, and the irradiated portion of the coating film was completely peeled off from the substrate during development. Further, when the photosensitive coloring composition C1 (Comparative Example 1) was exposed at an exposure amount of 2000 mJ / cm ² , a 30 μm pattern for LCD could be formed, but a fine 3 μm dot pattern matched to the light receiving part of the solid-state imaging device. In the formation, curing was still insufficient, and a part of the pattern was peeled off during development.

It is typical sectional drawing about an example of a solid-state image sensor color filter.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Silicone wafer 2 ... Signal transfer part 3 ... Light-receiving part (photoelectric conversion part)
4 ... flattened film 5 ... colored layer 6 ... flattened film 7 ... lens

Claims (10)

For a solid-state image sensor color filter, comprising at least a reactive monomer, a photopolymerization initiator, a colorant, and an organic solvent, wherein the photopolymerization initiator contains a compound represented by the following formula (1): Photosensitive coloring composition.

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group. The photosensitive coloring composition for a solid-state image sensor color filter according to claim 1, wherein in the formula (1), R ^{2 to} R ¹¹ are hydrogen. The photosensitive coloring composition for a solid-state image sensor color filter according to claim 2, wherein, in the formula (1), R ¹ is a methyl group, R ¹² is an ethyl group, R ¹³ is a methyl group, and R ¹⁴ is a methyl group. Stuff.   The photosensitive coloring composition for solid-state image sensor color filters according to any one of claims 1 to 3, wherein the colorant is a pigment.   The photosensitive coloring composition for solid-state image sensor color filters according to any one of claims 1 to 3, wherein the colorant is a dye.   The photosensitive coloring composition for a solid-state image sensor color filter according to claim 1, which forms a blue pixel portion or a green pixel portion.   A solid-state imaging device comprising at least a colored layer on a substrate, wherein the colored layer is formed by curing the photosensitive colored composition according to any one of claims 1 to 6. Color filter.   The solid-state image sensor color filter according to claim 7, wherein the pattern shape is 10 μm square or less per pixel and the pattern film thickness is 0.2 μm or more and 1.6 μm or less.   A solid-state imaging device having the color filter according to claim 7. A solid-state imaging device comprising a step of applying the photosensitive coloring composition according to claim 1 to an imaging device substrate, an exposure step of exposing the photosensitive coloring composition to a predetermined pattern, and a step of developing after exposure. Production method.

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