JPH0760265B2 - Photosensitive composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive composition which can be favorably used as a dye resistant layer of an organic color filter or the like.

[Conventional technology]

There are roughly two ways to install a color filter.

For example, a color separation organic color filter is directly manufactured on a solid-state image pickup device in which a photodetector and the like are provided on a silicon wafer (hereinafter referred to as "direct-attach type").

A solid-state image sensor and a color-separating organic color filter are individually manufactured, and they are aligned with each other and bonded with an appropriate adhesive or the like (hereinafter referred to as "bonding type").

The photosensitive composition of the present invention is particularly useful when applied to a direct-attaching type color filter which is considered to be excellent in mass productivity.

When manufacturing a direct-attached color filter, the surface of the solid-state image sensor is flattened, and a polymer layer (hereinafter referred to as “flattened” layer) is used to obtain a color filter without distortion.
Apply. After that, provide a photosensitive material layer for forming the dyed layer on it, and then provide a patterned resist on the dyed layer and dye the exposed part of the dyed layer to form the dyed layer. The post resist is peeled off, and then the next dyed layer is formed in the same manner. (A method in which a single dyed layer is dyed separately into a plurality of dyed portions.) The dyed layer is exposed to a predetermined pattern, developed and dyed to form a dyed layer, and then a transparent dye resistant insulating layer And then the next dyed layer is formed thereon in the same manner.

The above method has a problem such as color bleeding at the boundary of each dyed portion, and the method is generally used.

In the color filter obtained by the above method,
The choice of dye resistant insulation layer is important.

The dye-resistant insulating layer serves as a dye-resistant layer of the dyed layer of the first color that has already been dyed when dyeing the second and subsequent colors.
It plays an important role in preventing color bleeding with time between the dyed layers of the finished color filter. Further, the dyeing resistant insulating layer is basically required to have good dyeing resistance, adhesion to the substrate and the dyeing layer, colorless transparency, development resistance, and coating property.

However, it is difficult to select one that satisfies all of these properties. That is, for example, as the layer to be dyed, a water-soluble photosensitive material such as a mixture of gelatin, casein, grey, polyvinyl alcohol, etc. and dichromate is usually used, and a water-soluble dye is used for dyeing. To be done. Therefore, as the dye-resistant insulating layer, a highly lipophilic one is required from the viewpoint of dyeing resistance, but when a highly hydrophilic one is required from the viewpoint of adhesiveness with the dyeing layer. This is because the contradictory properties are required.

The present inventors have found a photosensitive composition containing a polymer having a repeating unit represented by the following formulas (I) and (II) and a sensitizer as a photosensitive polymer which has solved such a contradiction, and have previously proposed it. (Japanese Patent Application No. 60-21044).

(In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group,
R ³ represents a hydrogen atom or a phenyl group, R ⁴ represents a hydrogen atom,
It represents a phenyl group or a cyano group, and R ⁵ and R ⁶ represent a hydrogen atom, a halogen atom, a nitro group or a methoxy group. ) [Problems to be Solved by the Invention] The polymer as described above is represented by a compound represented by the following formula (III), that is, a glycidyl ester of acrylic acid or a glycidyl ester of methacrylic acid and the following formula (IV). A compound, that is, a reaction product of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate represented by the following formula (VI) and cinnamic acid chloride represented by the following formula (VII) or a derivative thereof is treated with azobisisobutyronitrile, A compound obtained by radical copolymerization according to a known method using a radical initiator such as benzoyl peroxide.

(In the formula, R ^{1 to} R ⁶ have the same meanings as described above, and X represents a halogen atom.) However, the compound represented by the formula (VII) is extremely susceptible to hydrolysis and thus is contained in the air during storage. It is hydrolyzed by the generated water, or is hydrolyzed by the trace amount of water contained in the system when it is reacted with 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. In the compound described above, usually a small amount of formula (V), The cinnamic acid represented by or its derivative is contained as an impurity. Since this impurity is similar to the property of the compound represented by the formula (IV), it is the actual situation that it cannot be sufficiently removed by a usual operation such as washing with alkaline water.

When the polymerization reaction is carried out with the acid still contained in the monomer, the glycidyl group of the compound represented by the formula (III) undergoes a cross-linking reaction due to the catalytic action of the acid during the reaction. If not, the acid is incorporated into the produced polymer because it is difficult to decompose with the polymer under normal conditions.

The resin thus obtained has a poor storage stability and undergoes a slight gelation in a few days to a few weeks, and for example, when it is passed through a photosensitive solution composition to prepare a 0.2 μm filter. There were problems such as clogging and frequent paper replacement.

[Means for solving problems]

As a result of various studies to solve the above-mentioned drawbacks, the present inventors have found that when reacting the compounds represented by the formulas (III) and (IV), the concentration of the acid in the reaction system is 1 × 10 ⁻³ mol. The present invention has been completed by finding that a photosensitive resin having significantly improved storage stability can be produced by carrying out the polymerization under the condition of / l or less.

That is, the gist of the present invention is at least the following formulas (I) and (II) (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and R ³
Represents a hydrogen atom or a phenyl group, R ⁴ represents a hydrogen atom, a phenyl group or a cyano group, and R ⁵ and R ⁶ represent a hydrogen atom, a halogen atom, a nitro group or a methoxy group. ) A photosensitive composition comprising a polymer having a repeating unit represented by the formula) and a sensitizer, wherein the polymer comprises a compound represented by the following formulas (III) and (IV) at an acid concentration of 1 in the reaction system. A photosensitive composition which is obtained by polymerization under the condition of × 10 ^-3 mol / l or less.

(In the formula, R ^{1 to} R ⁶ have the same meanings as described above.).

The present invention will be described in more detail.

The compound represented by the formula (III) is a glycidyl ester of acrylic acid and a glycidyl ester of methacrylic acid, and commercially available ones can be conveniently used.

Next, the compound represented by the formula (IV) can be obtained by synthesizing according to the following formula.

That is, hydroxyethyl acrylate or hydroxyethyl methacrylate (VI) is reacted with cinnamic acid halide or its derivative (VII) in the presence of a base in a solvent. The base is for capturing hydrochloric acid generated as the reaction progresses, and any base can be used, but usually a tertiary organic amine such as triethylamine, a heterocyclic basic compound such as pyridine, or tetramethylammonium. Quaternary ammonium hydroxide such as hydroxide, strong organic base such as diazabicycloundecene, and inorganic base such as sodium hydroxide and sodium carbonate are preferably used. These bases do not always have to exist in a solution state and may exist in a suspended state.

Examples of the solvent include tetrahydrofuran (THF),
Ether solvents such as dioxane and diethyl ether,
Ketone-based solvents such as acetone, methyl ethyl ketone and cyclohexane, hydrocarbons such as pentane and hexane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloroethane, and basic solvents with low nucleophilicity such as pyridine are used as bases. Can also be used for the same purpose.

The reaction is carried out at -10 ° C to + 80 ° C, preferably -5 ° C to + 50 ° C. Since this reaction is a highly exothermic reaction, it is usually possible to mix the whole mixture at once (VII) or to add a base afterwards and control the reaction by the dropping rate. The reaction time may be controlled as described above by balancing the dropping time with heat removal. After the dropping is completed, the reaction is completed for 1 to 5 hours. It is convenient that the intended product can be taken out by separately removing the hydrochloride formed after the reaction and further distilling it or when using a water-soluble solvent, by adding water to phase-separate the product.

This crude product is a corresponding acid that was usually present as an impurity in the starting acid halide (VII) or a trace amount of the corresponding acid produced by hydrolysis of (VII) with water that was present in a trace amount in the solvent (about 1%), it is difficult to completely remove the corresponding acid even after repeated washing with alkaline water, and if it is used for polymerization as it is, it will cause a decrease in storage stability of the produced polymer. One of the methods for completely removing the acid is to pass the crude product through a column of a porous inorganic carrier such as silica gel or alumina. Any developing solvent may be used as long as the acid developing speed is sufficiently slow, but hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and benzene, halogenated hydrocarbons such as chloroform and methylene chloride, or mixed solvents thereof, etc. Is preferably used.

The thus obtained (IV) and (III) and, if necessary, other monomers are mixed and dissolved in a solvent, and polymerization is carried out using a radical initiator.

The solvent is not particularly limited as long as it has a sufficiently small radical chain transfer constant and is neutral, but aromatic hydrocarbons such as benzene and toluene, ether solvents such as tetrahydrofuran and dioxane, ketone solvents such as acetone and methyl ethyl ketone. Alcohol solvents such as methanol and ethanol are preferably used.

As the radical initiator, peroxides such as benzoyl peroxide and t-butylperoxide, and azo initiators such as azobisisobutyronitrile are preferably used.

The concentration of the acid present in the reaction system is 1 × 10 ⁻³ mol / l or less, preferably 1 × 10 ⁻⁴ mol / l or less. (IV)
This condition can be easily achieved by synthesizing and purifying by the method described above.

Although the reaction temperature and the reaction time vary depending on the initiator and solvent used, the reaction is usually carried out at 30 ° C to 150 ° C, preferably 40 ° C to 130 ° C for 1 hour to 30 hours, preferably 3 hours to 20 hours.

After completion of the reaction, a poor solvent such as m-hexane or n-pentane may be added to the reaction solution to precipitate the polymer, or the solvent may be removed by distillation to isolate the polymer. If necessary, the polymer may be further purified by a reprecipitation method or the like.

The polymer of the present invention has a composition of 3% in tetrahydrofuran (THF).
The intrinsic viscosity at 0 ° C is usually 0.05 to 3 dl / g, and preferably 0.
A range of 1 to 2.0 dl / g, particularly preferably 0.2 to 1.5 dl / g is suitable. Various known sensitizers can be used. For example, anthrone, benzophenone, phenanthrene, Michler-ketone, 2-nitrofluorene, 5-nitroacenaphthene, chrysene, p-nitroaniline, 2-benzoylmethylene-3-methylnaphthothiazoline, 2-dibenzoylmethylene-3-methyl. Naphthothiazoline, benzyl, N-acetyl-4-nitro-
So-called triplet sensitizers such as 1-naphthylamine and anthraquinone are preferably used. As the amount of sensitizer,
0.1 to 20% by weight of polymer, preferably 0.5 to 10
Weight percent is used.

Usually, a solvent that dissolves both the polymer and the sensitizer, for example, ethyl cellosolve, a cellosolve solvent such as methyl cellosolve, an ester solvent such as butyl acetate, or dimethylformamide (DMF), dimethyl sulfoxide (DMSO), It is dissolved in a solvent such as N-methylpyrrolidone to serve as a photosensitive solution. The sensitizer itself often has a yellow color because of the sensitizer contained in it.However, a thin film is formed on the substrate by spin coating, casting, or the dip method, and visible light / near-ultraviolet light is used. If exposed and developed, the sensitizer can be easily washed out to obtain a colorless and transparent polymer layer.

Hereinafter, an example of a color filter using the photosensitive composition of the present invention will be described in more detail with reference to the drawings.

1 (a) to 1 (j) are explanatory views showing an example of a manufacturing process of a direct-attaching type color filter.

In the figure, 1 is a silicon wafer, 2 is a light detecting portion, 3 is a protective film, 4 is a flattening layer, 5 is a layer to be dyed, 6 is a mask, 7 is a dye resistant insulating layer, 8 is a bonding pad, and 9 is a pad. The dyed layer and 10 are surface layers, respectively.

In the case of a direct-attaching type color filter, the color filter is directly provided on the surface of the solid-state image pickup device, and the solid-state image pickup device as the base is, for example, a silicon wafer 1 as shown in FIG. 2 is provided, and a protective film 3 made of phosphorus glass, quartz or the like is provided on the upper surface thereof. Other than the above, the solid-state image sensor is provided with a scanning line, a light-shielding film, etc., which are omitted in the drawing.

The color filter of the present invention is formed on the upper surface of the solid-state image pickup device as described above, and will be described in the order of steps.

First, the flattening layer 4 is coated on the protective film 3 of the solid-state image sensor to a thickness of about 0.2 to 2.0 μ. As the flattening layer, it is preferable to use the same one as the dyeing resistant insulating layer 7 described later. This layer flattens the surface of the photodetection portion, facilitates formation of the dyed layer 5, the dye-resistant insulating layer 7, and the like, and also the dyed layer 5
It is possible to reduce color stains and the like due to unevenness in thickness. Then, a predetermined bonding pad 8 or the like is processed on the flattening layer 4 {FIG. 1 (b)}.

The material of the flattening layer 4 and the method of processing the bonding pad 8 will be described later in detail together with the description of the dye-resistant insulating layer 7.

Then, on the flattening layer 4, gelatin, casein, grill,
A mixture of a water-soluble polymer such as albumin or a synthetic polymer such as polyvinyl alcohol and a dichromate such as ammonium dichromate is applied to form a photosensitive material layer for forming the dyed layer 5. {FIG. 1 (c)}.

The photosensitive material layer for constituting the dyed layer 5 is usually 0.
It is provided to be 1 to 2 μ.

Then, the photosensitive material layer for forming the dyed layer 5 is exposed through a mask 6 having a predetermined pattern {FIG. 1 (d)}. The photosensitive material for forming the layer to be dyed 5 is usually made to have photosensitivity in the range of 440 to 380 nm, and therefore, it is exposed by using a high pressure mercury lamp having a wavelength in such a region as a light source.

Then, it is developed with water to form a portion constituting the dyed layer 5 having a predetermined pattern {Fig. 1 (e)} and dyed with a first color dye having a predetermined spectral characteristic according to a known method. The dyed layer 5 is formed.

Then, a photosensitive resin composition for forming the dye-resistant insulating layer 7 is coated {FIG. 1 (f)}. In the present invention, in order to form the dye-resistant insulating layer 7, in the present invention, a composition containing a copolymer having units represented by the formulas (I) and (II) and a sensitizer is used as a dyed layer. 5 is formed and then applied {FIG. 1 (f)} and exposed using a mask 6 having a predetermined pattern, that is, a pattern and the like in which a portion forming a bonding pad portion is made light opaque. {FIG. 1 (g)}. At the time of exposure, a high-pressure mercury lamp having a wavelength that the sensitizer has absorption may be used. In the exposed composition, the energy absorbed by the sensitizer is transferred to the cinnamoyl group in the polymer, and the cinnamoyl group in an excited state forms a cyclobutane ring with two molecules to cause crosslinking and insolubilization. .

Then, by developing with a suitable developing solution such as ethyl cellosolve or methyl ethyl ketone, or a mixture of these with benzyl alcohol or N-methylpyrrolidone, the unexposed portion corresponding to the bonding pad portion is eluted. The dye-resistant insulating layer 7 (filter portion) that has been processed and has the sensitizer eluted by the development is obtained, and the dye-resistant insulating layer 7 becomes colorless and transparent {FIG. 1 (h)}. Even when the present photosensitive composition is used for the flattening layer 4, the transparent flattening layer 4 having the bonding pad 8 and the like processed can be obtained by the same operation.

Then, a photosensitive substance for forming a dyed layer is provided on the dye resistant insulating layer 7 in the same manner as described above, and exposed and developed to form a dyed layer portion having a predetermined pattern. Then, the second dyed layer 9 is formed by dyeing with a second color dye having a predetermined spectral characteristic {FIG. 1 (i)}.

Such an operation may be repeated to form another layer to be dyed through the dye-resistant insulating layer.

As the layer to be dyed, three types of three primary color systems of red, green and blue may be used, or three types of complementary color systems of cyan, green and yellow may be used. At this time, for example, the second yellow dyed layer may be formed so as to partially overlap the first cyan dyed layer, and the third color green color may be obtained at the overlapped portion.

Usually, a surface layer 10 is provided on the uppermost layer to be dyed in order to smooth the surface or protect the dyed layer.

The surface layer 10 is required to have strength, transparency, adhesion to the intermediate layer and the dyeing layer, and workability such as a bonding pad portion, and any material that satisfies the requirements may be used.
You may use the photosensitive composition mentioned above.

The surface layer 10 is usually provided so as to have a film thickness of 0.1 to 2 .mu.m, and is exposed and developed to perform a predetermined bonding pad or the like {FIG. 1 (j)}.

As described above, the color filter of the present invention can be obtained, but the flattening layer or the dye-resistant insulating layer of the color filter of the present invention has complete dye resistance, and adheres to the substrate or the dye layer. Therefore, it is possible to obtain a clear image.

In the present invention, the above-mentioned special photosensitive composition is used as the flattening layer and / or the dye-resistant insulating layer, but in the present invention, at least one layer comprising the above-mentioned photosensitive composition is provided, and Other resin layers or the like may be used and may be appropriately selected and determined according to the application. However, in view of the physical properties of the photosensitive composition, it is preferable to use it as a dye-resistant insulating layer rather than a flattening layer. Other photosensitive resins include polyglycidyl methacrylate, polymethyl methacrylate,
Various materials such as polymethyl isopropenyl ketone, methyl methacrylamide, polyhexafluorobutyl methacrylate, polypten-1-sulfone can be used.

〔Example〕

 The present invention will be described in more detail with reference to the following examples.

Example 1 [Synthesis of Monomer] 33 g of hydroxyethyl methacrylate and 24 g of pyridine are dissolved in 84 ml of tetrahydrofuran. Cinnamic acid chloride
A solution of 50 g of tetrahydrofuran in 50 ml is added dropwise to the above solution over 30 minutes while stirring.

The reaction temperature at this time is controlled to be 5 to 10 ° C. After the dropping is completed, the reaction is performed at the above temperature for 4 hours to complete the reaction.

Pyridine hydrochloride formed after the reaction is removed by passing. Then, 300 ml of demineralized water is added to the separated reaction solution to cause phase separation with the product.

Then, tetramethylammonium hydroxide 1
Repeated washing 3 times with 300% aqueous solution, then 300 ml of demineralized water
The crude product can be taken out by repeating the washing three times.

The yield at this time is 36.0 g (yield 55%).

20 g of the above crude product is applied to a silica gel (500 g) column, developed with a chloroform / n-hexane (= 4/1 wt) mixed solvent, and purified. The effluent is analyzed by thin layer chromatography to collect the fractions in which no cinnamic acid is found at all, and the developing solvent is removed by distillation under reduced pressure to obtain the desired product.

Yield 11.5 g (57.5%) [Synthesis of polymer] 19.5 g of glycidyl methacrylate and 10.7 g of the above-mentioned minnamoyloxyethyl methacrylate were added to p-dioxane 150.
Dissolve in ml and bubble with nitrogen for 30 minutes. Then, the mixture was heated to 60 ° C. while maintaining a nitrogen atmosphere, 037 g of azobisisobutyronitrile was added, and the mixture was reacted at 60 ° C. for 6 hours. The acid and base concentrations in the reaction system were 1 × 10 ⁻⁴ mol / l or less.

After completion of the reaction, the reaction mixture was added dropwise to 450 ml of n-hexane to precipitate a polymer, and the precipitated polymer was separated, dissolved in 95 ml of acetone and added dropwise to 300 ml of methanol to reprecipitate, and then dried under reduced pressure. .

Yield 25.4g (84.1%) ηsp / c = 0.54 (THF at 30 ℃ C =
0.2g / dl) [Preparation of sensitizer] 1.4g of polymer synthesized with Synthetic Agent 1 to 2-dibenzoylmethylene-3-methylnaphthothiazoline 42mg as a sensitizer
And dissolve in cyclohexanone to make the total 10 g, 0.2
The solution was passed through a Millipore filter of μ to obtain a photosensitive solution. This photosensitizing solution is applied on a silicon wafer with a 2-inch φ oxide film (SiO ₂ 5000Å) to a thickness of 1.0μ by the spin coating method (2500 rpm), and the sensitivity, resolution and adhesiveness are described below. I evaluated it. For dyeing resistance and transparency, use 0 instead of a silicon wafer.
Evaluation was performed on a glass substrate made of 5 mm thick temperax in the same manner as in the case of a silicon wafer.

(1) Sensitivity ... Eastman Kodak Co., Ltd. No.2
After exposure with a mask aligner MA-10 manufactured by Mikasa Co., Ltd. using a step plate, the mixture was exposed to 1: 1 with a 7: 1 (vol / vol) mixed solvent of methyl isobutyl ketone and isopropyl alcohol.
Spray development was carried out for 1 minute, followed by rinsing with methyl isobutyl ketone for 1 minute. The film thickness of each obtained step was measured with a film thickness meter α-step manufactured by Tencor Co., Ltd. to prepare a sensitivity curve, and the sensitivity was determined by having an irradiation energy amount giving a residual film rate of 80%.

(2) Resolving power ...... An image obtained after exposure and development was performed using an optical microscope (X500) in the same manner as in the sensitivity evaluation using a resolution test chart manufactured by Totopan Co., Ltd. and a mask aligner MA-10 manufactured by Mikasa Co., Ltd. The resolution was defined as having the smallest line-and-space width that was observed and observed.

(3) Transparency: Mask aligner MA manufactured by Mikasa Co., Ltd.
After exposure on the whole surface using -10, after development spectrophotometer made by Hitachi Ltd.
228 was used to determine the spectral transmittance from 380 to 780 nm.

(4) Dyeing resistance: The same substrate as that for which transparency was evaluated was dyed yellow or cyan under the same conditions as those of a color filter to be followed, and after rinsing, the spectral transmittance was evaluated in the same way as when transparency was evaluated. I asked.

(5) Adhesion property ... Adhesive tape (cellophane tape) was adhered well by finger pressure and peeled off to evaluate adhesiveness with glass. Further, a dyed layer of gelatin was formed on the upper surface of the flattening layer in the same manner as in Example, and the adhesive strength was evaluated with the adhesive tape as in the above. The evaluation criteria are as follows.

◯: No peeling at all ×: Some peeling was observed (6) Storage stability: 0.2 μm was again applied to check the progress of gelation, and the number of days after which gelation became impossible due to clogging I asked. The results are summarized in Table 1.

Comparative Example A cinnamoyloxyethyl methacrylate crude product was obtained in the same manner as in Example 1. As a result of acid-base titration of this product, it was found to contain about 2% by weight of cinnamic acid. This product was directly copolymerized with glycidyl methacrylate in the same manner as in Example 1 without purification. The acid concentration in the reaction system was 8 × 10 ⁻³ mol / l, and the base concentration was 10 ⁻⁴ mol / l. The resulting polymer was used as a photosensitive solution and evaluated in the same manner as in the examples. The results are summarized in Table 1.

Example 2 A photosensitive composition prepared in the same manner as in Example 1 was spin-coated to a film thickness of 2 μm on a solid-state imaging device substrate composed of a large number of photodetection units and a drive circuit for driving them. Then, a resin layer for forming the flattening layer was formed. The applied resin layer was yellowish. Using a mask aligner MA10 type {Mikasa Co., Ltd.} equipped with a high pressure mercury lamp through a mask having a predetermined pattern such as a bonding pad on the resin layer forming this flattening layer.
20 ° C after exposure with an energy amount of 300 mm / cm ³
Of methyl isobutyl ketone and isopropyl alcohol
Spray development was performed for 1 minute with a 7: 1 (vol / vol) mixed solvent. Further, a rinse with methyl isobutyl ketone was performed for 1 minute.
The flattening layer obtained by processing the obtained bonding / pad parts was a transparent layer in which the yellow color disappeared.

Then, post-baking was performed at 150 ° C. for 15 minutes to perform thermal curing.

Then, an aqueous solution of gelatin-ammonium dichromate (10: 1, weight ratio) was applied onto this flattening layer by spin coating so as to have a film thickness of 1 μ to form a photosensitive material layer for forming a layer to be dyed. Formed. The photosensitive material layer forming the layer to be dyed was exposed through a mask having a predetermined pattern using the same apparatus as above with an energy amount of 200 millijure / cm ² , and then developed with water at 45 ° C. for 1 minute. Then
The gelatin film was cured by heating at 120 ° C for 15 minutes.

Soak for 1 minute at 75 ℃ in an approximately 0.1% aqueous solution of "Kayanol N5G" (manufactured by Nippon Kayaku Co., Ltd.) (Kayanol is a trade name of Nippon Kayaku Co., Ltd.) whose pH is adjusted to 4 with acetic acid. Dyeing treatment was performed to form a layer to be dyed.

Then, a photosensitive composition having the same composition as that of the flattening layer was formed to a film thickness of 0.5.
The coating was spin coated to give a thickness of μ, and exposed, developed and cured in the same manner as in the flattening layer to form a transparent dyeing resistant insulating layer which was processed in the bonding pad and the like.

Then, a gelatin-ammonium dichromate layer was formed on the dye-resistant insulating layer in the same manner as described above, exposed and developed in the same manner as described above, and then adjusted to pH 4 with acetic acid, "Diacron Turkis Blue". GF "(manufactured by Mitsubishi Kasei Co., Ltd.)
About {Diacron is a registered trademark of Mitsubishi Kasei Co., Ltd.}
A dyed layer was formed by dyeing with a 0.3% aqueous solution at 75 ° C. for 1 minute.

Next, the same photosensitive composition as that of the flattening layer was applied as a protective film by spin coating so as to have a film thickness of 0.5 μ, exposed under the same conditions as described above, and developed and bonded.
A solid color image pickup device was obtained in which a transparent surface layer on which a pad portion or the like was processed was formed and a color filter was directly attached.

〔The invention's effect〕

Thus, according to the composition of the present invention, excellent dyeing resistance, good adhesion to the substrate and the dyeing layer, good visibility, colorless transparency to near ultraviolet rays, and the like, and further processing using visible light rays and near ultraviolet rays. Possible dye resistant insulation layers can be formed.

[Brief description of drawings]

1 (a) to 1 (j) are explanatory views showing an example of a manufacturing process of a direct-attaching type color filter. In the figure, 1 is a silicon wafer, 2 is a light detecting part, 3 is a protective film, 4 is a flattening layer, 5 is a dyed layer, 6 is a mask, 7 is a dye resistant insulating layer, 8 is a bonding pad, and 9 is a bonding pad. Represents a layer to be dyed, and 10 represents a surface layer.

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Claims (3)

[Claims] 1. At least the following formulas (I) and (II): (In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, and R ³
Represents a hydrogen atom or a phenyl group, R ⁴ represents a hydrogen atom, a phenyl group or a cyano group, and R ⁵ and R ⁶ represent a hydrogen atom, a halogen atom, a nitro group or a methoxy group. ) A photosensitive composition comprising a polymer having a repeating unit represented by the formula) and a sensitizer, wherein the polymer comprises a compound represented by the following formulas (III) and (IV) at an acid concentration of 1 in the reaction system. A photosensitive composition which is obtained by polymerization under the condition of × 10 ^-3 mol / l or less. (In the formula, R ^{1 to} R ⁶ are as defined above.) 2. The photosensitive composition according to claim 1, wherein the acid is represented by the following formula (V). (In the formula, R ^{3 to} R ⁶ are as defined above.) 3. A compound represented by the formula (IV) obtained by reacting a compound represented by the following formula (VI) and a compound represented by the following formula (VII) and then purifying with a porous inorganic carrier. The photosensitive composition according to claim 1, which is (In the formula, R ^{2 to} R ⁶ have the same meanings as described above, and x represents a halogen atom.)