JPH06148888A - Positive photosensitive material for formation of color filter - Google Patents

Abstract

PURPOSE:To obtain a color filter pattern of high resolution and to shorter processes and to obtain a thin film by using a positive photosensitive material consisting of thermosetting agent, dye, and photosensitive agent consisting of alkali soluble resin and 1,2-naphthoquinonediazide sulfonate. CONSTITUTION:This positive photosensitive material to form a color filter consists of polymer, photosensitive agent, thermosetting agent, dye, and solvent. The polymer used is an alkali-soluble resin. The photosensitive agent is 1,2- naphthoquinonediazide sulfonate. The thermosetting agent is such a compd. that can give heat resistance and solvent resistance to the photosensitive material by heat treatment after patterning. The alkali-soluble resin is not limited as far as it is soluble with a solvent and can form a film. It is preferable that the alkali-soluble resin is a vinylphenol polymer or novolac resin which is polymer condensate of phenols and aldehydes with addition of hydrogen and/or partly modified hydroxyl groups so that the resin maintains its transparency when heated again.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive material which can be used for forming a color separation color filter used for colorization of a solid-state image pickup device, a liquid crystal display device and the like. The present invention relates to a positive-type photosensitive material for forming a color filter, which realizes high resolution and can form a stable and uniform color filter pattern while simplifying the process.

[0002]

2. Description of the Related Art Conventionally, as a color separation color filter for colorizing a solid-state image pickup device, exposure is applied to a photosensitive film provided with photosensitivity by mixing a dichromate with a natural protein such as gelatin or casein. It is created by developing and forming a pattern, and then dyeing in a dyeing solution of each color. One example thereof is shown in FIGS. That is, a flattening layer is formed on a silicon substrate having an unevenness in which an image sensor is formed on a Si wafer (a). A photosensitive casein film is applied thereon, and only a desired portion where the first color is to be dyed is exposed to ultraviolet light through a photomask (b). Development is carried out to create a pattern for the first layer, and then it is immersed in a prescribed dyeing solution for dyeing to form a color pattern for the first color (c). After that, an intermediate film is applied to form a dyeing prevention layer (d). After that, the steps (b) to (d) are repeated several times to produce a color separation color filter (e).

As described above, in the conventional method, not only the number of steps is large and complicated, but also the thickness of the filter layer is several layers so that the film has to be a thick film.

Therefore, recently, various synthetic polymer type color filter materials have been studied as an alternative to natural proteins. Synthetic polymer systems have the characteristics of lot-to-lot variation, stability over time, and avoidance of the use of highly toxic chromium as a photosensitive component, which are problems in natural products, and gradually replace natural products. I am trying.

However, as in the case of natural products, current synthetic polymer systems require a step of dyeing after patterning by exposure and development, and the steps are still complicated. Furthermore, both natural protein and synthetic polymer systems are delicately controlled at the time of dyeing, and it is necessary to control conditions such as dyeing solution concentration, temperature, time and pH with extremely high accuracy in order to achieve a constant color tone.

Based on such a background, 1) Japanese Patent Laid-Open No. 4-1
In 28703, a color material in which a photosensitizer and a dye are dissolved in a resin is proposed, and an attempt is made to solve the above problems. Further, in 2) JP-A-3-230101, a color filter pattern is proposed. A microlens shape has been proposed which can be formed by a single layer that is not laminated, and the pattern itself has a light-collecting ability, and it is becoming possible to cope with thinning.

[0007]

However, in 1), although the material management and the pattern accuracy can be improved, the intermediate layer as the dye-proof film is required because the formed pattern is not cured. Therefore, the recent demand for thin film cannot be met. Further, in 2), since a natural protein is used in the pattern formation, a dyeing step is required, and a method for forming a single layer is that the lens pattern of the natural protein is protected by a photoresist or the like and dyed. The process of perforating only the parts and dyeing is inevitably complicated.

On the other hand, in the case of a liquid crystal display device, forming a color filter by the dyeing method has the same problems as in the case of a solid-state image pickup device. Further, in recent years, the pigment-dispersed color filter material, which is becoming mainstream, has a material configuration excellent in heat resistance together with a feature that a dyeing step can be omitted, but since it is a negative type photosensitive material, it has a sufficient resolution. It was a situation that I could not get it.

The present invention has been made in view of the above problems, and an object thereof is to realize high resolution in a solid-state image pickup device, a liquid crystal display device, etc., and to achieve thinning without the need for lamination. Another object of the present invention is to provide a positive-type photosensitive material that can be formed and can form a stable and uniform color filter pattern while simplifying the process.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that polymers,
The present invention has been completed by finding an optimum combination composition in a positive-type photosensitive material composed of a photosensitizer, a thermosetting agent, a dye and a solvent.

That is, the present invention relates to a polymer, a photosensitizer,
In a positive photosensitive material for forming a color filter, which comprises a thermosetting agent, a dye and a solvent, an alkali-soluble resin as the polymer, 1,2-naphthoquinonediazide sulfonic acid ester as the photosensitizing agent, and heat treatment after patterning as the thermosetting agent A positive-type photosensitive material for forming a color filter, which comprises a thermosetting agent capable of imparting heat resistance and solvent resistance.

The present invention will be described in more detail below.

The alkali-soluble resin in the present invention means
There is no particular limitation as long as it is soluble in a solvent and can form a film. This is because the binder as a light-sensitive material and the solubility in an alkali developing solution are imparted.

In particular, the alkali-soluble resin of the present invention has a maleic acid and / or (meth) acryl represented by the following general formula (1) or (2) in order to maintain transparency even when reheated. It is preferable that the resin is composed of a structural unit having a carboxylic acid component such as an acid.

[0015]

[Chemical 4]

[Wherein R ₁ represents hydrogen or a methyl group,
A is OA ₁ or NA ₂ A ₃ (A ₁ , A ₂ , and A ₃ are hydrogen, an alkyl group having 1 to 6 carbon atoms, and 6 to 1 carbon atoms, respectively)
An allyl group having up to 2 or an aralkyl group having 7 to 12 carbon atoms is shown. ), And k, l, and n are 0 or 1 respectively.
The above integers are shown, and m is an integer of 1 or more. ]

[0017]

[Chemical 5]

[In the formula, R ₁ represents hydrogen or a methyl group,
R ₂ and R ₃ each represent hydrogen, a methyl group, chlorine or bromine, A is OA ₁ or NA ₂ A ₃ (A ₁ , A ₂ and A ₃ are each hydrogen, an alkyl group having 1 to 6 carbon atoms, Represents an allyl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, x and y each represent an integer of 0 or 1 or more, and z represents an integer of 1 or more. ] In addition, as the alkyl group in the above formula, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, n-hexyl group, cyclohexyl group and the like,
Examples of the allyl group include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and the benzene ring may be substituted with a halogen such as chlorine and bromine, a nitro group, a cyano group and the like. Examples of the aralkyl group include benzyl group and phenethyl group, and the benzene ring may be substituted with halogen such as chlorine and bromine, nitro group and cyano group.

Further, the alkali-soluble resin is a hydrogenated product and / or a hydroxyl group of a novolak resin which is a vinylphenol polymer or a polycondensation product of a phenol and an aldehyde in order to maintain transparency even when reheated. It is preferable that the resin is a partially modified resin.

The method of hydrogenating the vinylphenol polymer or novolac resin is not particularly limited,
For example, JP-A-1-103604 and JP-A-2-425
4, JP-A-2-29751, and JP-A-2-29752.
No. etc. can be used for synthesis. The modification of the hydroxyl group of the vinylphenol polymer or novolac resin can be synthesized by a reaction such as alkylation, acylation, sulfonylation, glycidylation. For example, alkylation can be synthesized by reacting a resin with an alkyl halide under a basic catalyst, and similarly, glycidylation can be synthesized by reacting with epichlorohydrin or the like. Acylation and sulfonylation can be synthesized by reacting a resin with a carboxylic acid, a sulfonic acid, a carbonyl halide or a sulfonyl halide under an acid catalyst or a basic catalyst. The vinylphenol polymer can also be copolymerized with another radically copolymerizable monomer having a double bond. For example, methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, etc. Examples thereof include (meth) acrylic acid ester, acid amides such as acrylamide and methacrylamide, and styrene and acrylonitrile.

The thermosetting agent in the present invention can impart heat resistance and solvent resistance by heat treatment, and examples thereof include a melamine compound, a phenol compound, an azo compound, an isocyanate compound and an epoxy compound. To be

As the thermosetting agent having the above-mentioned characteristics, a melamine type curing agent and / or an epoxy type curing agent having a structural unit represented by the following general formula (3) is preferable.

[0023]

[Chemical 6]

[In the formula, W represents --NY ₅ Y ₆ {Y ₅ , Y ₆ are each hydrogen or --CH ₂ OZ (Z represents hydrogen or an alkyl group having 1 to 6 carbon atoms). } Or a phenyl group, and Y ₁ to Y ₄ are each hydrogen or —CH ₂ OZ.
(Z represents hydrogen or an alkyl group having 1 to 6 carbon atoms). ] As the alkyl group of Z in the above formula, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, n
Examples thereof include an amyl group, an isoamyl group, an n-hexyl group and a cyclohexyl group.

Specific examples of these thermosetting agents include, for example, melamine-based curing agents such as hexamethylolmelamine and alkylated hexamethylolmelamine, partially methylolated melamine and its alkylated products, tetramethylolbenzoguanamine and alkylated tetramethylol. Examples thereof include benzoguanamine, partially methylolated benzoguanamine and alkylated products thereof. The epoxy-based curing agent is a compound having an average of one or more epoxy groups in the molecule, and examples thereof include n-butyl glycidyl ether, 2-ethoxyhexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,
Glycidyl ethers such as neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, etc., 3,4-epoxycyclohexylmethyl (3,4 -Epoxycyclohexane) carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, bis (3,4-epoxy-)
Examples thereof include alicyclic epoxies such as 6-methylcyclohexylmethyl) adipate, dicyclopentadiene oxide, and bis (2,3-epoxycyclopentyl) ether.

When a melamine-based thermosetting agent and an epoxy-based thermosetting agent are used as the thermosetting agent, the melamine and epoxy thermosetting agents listed above may be used in appropriate combination.

The sensitizer used in the present invention is 1,2-naphthoquinonediazide sulfonic acid ester, which is for imparting a dissolution-inhibiting effect to the alkali developer in the unexposed area and a dissolution-accelerating effect in the exposed area. The ester component is not particularly limited as long as the properties can be maintained, but, for example, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,3,4,4 '. -Tetrahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, phenol, 1,3,5-trihydroxybenzene, methyl gallate, ethyl gallate, phenyl gallate and the like.

Further, it is preferable to add a curing aid to the positive photosensitive material of the present invention in order to complete the curing at a relatively low temperature in a short time. Here, the curing aid is not particularly limited as long as it has good storage stability and sufficient thermosetting property, and examples thereof include a latent thermal acid generator, a latent photoacid generator and a polycarboxylic acid. An acid anhydride, a polycarboxylic acid, an amine compound, a polyamine compound, etc. can be used. In particular, a latent thermal acid generator, a polycarboxylic acid anhydride, and a polycarboxylic acid are preferable because they have good storage stability, excellent curing characteristics, and are easy to handle. Specific examples of the thermal acid generator include organic halogen compounds and onium salts. Examples of the organic halogen compounds include trihalomethyl group-containing triazine compounds and oxadiazole compounds, and onium salts include allyldiazonium salts. , (Di) allyl iodonium salt, (di, tri) allyl sulfonium salt and the like can be used. Further, carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, etc. as aromatic, succinic anhydride as aliphatic,
Examples of maleic anhydride and the like include alicyclic groups such as methyl nadic acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Examples of the carboxylic acid include ring-opened products of the above acid anhydrides.

The dye in the present invention may be any dye that can be uniformly dissolved or dispersed in the light-sensitive material, is transparent to the light of the exposure wavelength at the time of patterning, and satisfies the spectral characteristics of each color after patterning. It is not particularly limited, and examples thereof include dyes and pigments.

The positive-working light-sensitive material of the present invention is composed of a polymer, a photosensitizer, a thermosetting agent, a dye and a solvent as described above, and is characterized by the combination thereof. That is, the polymer is a resin composed of a structural unit having a carboxylic acid component such as maleic acid and / or (meth) acrylic acid, a hydrogen of a novolac resin which is a vinylphenol polymer or a polycondensation product of phenols and aldehydes. By using an additive and / or a resin in which a part of the hydroxyl group is modified, it is alkali-soluble, has good transparency in the visible light region, is excellent in heat resistance and light resistance, and does not deteriorate in transparency. It is possible to faithfully reproduce the color tone originally shown by. By using 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitizer and mixing it with the above alkali-soluble resin, a high-resolution resist that does not swell in an alkali developing solution can be realized. Further, the thermosetting agent is necessary for maintaining the shape of the pattern, that is, for imparting heat resistance and solvent resistance.

In the positive-working photosensitive material of the present invention, the composition ratio of the polymer to the photosensitizer and the composition ratio of the polymer to the thermosetting agent can be variously changed within a range in which the characteristics can be maintained. The agent is preferably 5 to 30% by weight based on the solid content, and the photosensitizer is 10 to 30% by weight based on the solid content. Further, the dye can be dissolved or dispersed uniformly and can be mixed within the range of adjusting the color tone. Within this mixing ratio, a stable system having good adhesion, transparency, heat resistance due to curing, solvent resistance, and resist function can be maintained.

The positive-working light-sensitive material of the present invention is not particularly limited, but usually, the polymer, the photosensitizer, the thermosetting agent and the dye are put in an appropriate solvent so that the total solid content is 10 to 50% by weight. Obtained by dissolving. Examples of the solvent include ethylene glycol monoalkyl ether and its acetates, propylene glycol monoalkyl ether and its acetates, diethylene glycol mono- or dialkyl ethers, alkyl propionate and its alkoxys, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, acetic acid esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, ethyl lactate, diacetone alcohol, dimethylacetamide, dimethylformamide, N
Examples include -methylpyrrolidone and γ-butyrolactone. You may use these solvent individually or in mixture of 2 or more types. In addition, a nonionic, fluorine-based, or silicon-based surfactant may be added, if necessary. Further, other compatible additives may be added within the range in which the characteristics can be maintained.

The positive photosensitive material of the present invention can be used for forming a resist pattern by ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like, and has excellent sensitivity and resolution. In particular, because a color pattern can be created during pattern formation,
The process can be simplified and the process can be stabilized. Furthermore, by performing heat treatment after forming the pattern, a highly reliable pattern having excellent heat resistance and solvent resistance can be obtained, and thinning can be achieved because no lamination is required.

The method of using the positive photosensitive material of the present invention to form a resist pattern by irradiation with radiation is not particularly limited, and a conventional method can be used. For example, FIGS. 2A to 2F show an example of the present invention. As described above, the positive-type photosensitive material is prepared by uniformly mixing an alkali-soluble resin, a photosensitizer, a thermosetting agent and a dye in a solvent and filtering the mixture (for example, with a filter having a pore size of 0.1 to 1.0 μm). It is prepared by removing the insoluble matter. The positive type photosensitive material is applied onto the flattening layer formed on the image sensor (a). After that, exposure is performed by a reduction projection exposure device, a proximity aligner, a mirror projection, an electron beam exposure device or the like (b), and a resist pattern is formed by developing and rinsing (c). Examples of the developer include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n-butylamine. Secondary amines such as triethylamine, tertiary amines such as methyldiethylamine,
Aqueous solutions of alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline can be used. Furthermore, alcohols and surfactants may be added in appropriate amounts to the above alkaline aqueous solution before use. Coating, baking, exposure, development,
Other techniques such as rinsing can follow conventional methods in resist pattern formation for manufacturing integrated circuits and the like.

The resist pattern can be formed as described above. Next, the formed resist pattern is first
After exposing the entire surface with UV light to eliminate the absorption of the 1,2-naphthoquinonediazide sulfonate component, a predetermined temperature of 100 to 200 ° C, preferably 120 to 170 ° C on a hot plate or in a convection oven. By heat treatment for a predetermined time of about 1 to 30 minutes, thermosetting is possible (d). After that, (a) ~
By repeating the step (d) several times, it can be prepared without laminating the color separation color filter (e). At that time,
Considering the balance between fluidity and heat curing of the composition,
As shown in (f), the function as a microlens material can be provided.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Styrene / maleic anhydride copolymerized partial ester (copolymerization ratio 1/1, weight average molecular weight 5000 (GPC measured value,
Polystyrene conversion), 25 g of SMA (trademark) -17352) manufactured by Atochem Inc., 2, 3,
1,2-naphthoquinonediazide sulfonic acid ester of 4-trihydroxybenzophenone (triester form)
6.5 g, hexamethoxymethylol melamine (manufactured by Mitsui Cyanamid, Cymel (trademark) -303) 3.0
g, yellow dye (Kayaset (trademark) manufactured by Nippon Kayaku)
After mixing and dissolving 2.8 g of yellow K-CL) and 112 g of diethylene glycol dimethyl ether, 0.2 μ
m resist was filtered to prepare a resist solution.

Next, a resist solution having a thickness of 1.2 μm was formed by spin coating a resist solution on a silicon substrate.
Prebaking was performed on a hot plate at 0 ° C. for 90 seconds.
After that, a g-line reduction projection exposure apparatus (DSW-6300A,
GCA) and exposed to a 1% aqueous solution of tetramethylammonium hydroxide. Patterning is 40
It was possible to resolve 1 μmL / S at 0 mJ / cm ² .

Next, the obtained 5 μmL / S pattern is used as U
Whole surface exposure with V light (PLA-501, Canon) (LI
= 30), and then heated in an oven at 140 ° C for 30 minutes. After that, even if reheated at 200 ° C., no deformation of the pattern and no change in the light absorption property were observed. As for solvent resistance, no surface roughness was observed even when immersed in water, isopropyl alcohol, or diethylene glycol dimethyl ether.

Example 2 The dyes to be mixed were changed from yellow dyes to cyan dyes (Nippon Kayaku, Kayaset (trademark) Blue K-FL) or magenta dyes (Nippon Kayaku, Kayaset (trademark) Red K-). A resist solution was prepared in the same manner as in Example 1 except that it was changed to BL).

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, it was 350 mJ / cm ² for cyan system and 500 mJ for magenta system.
/ Cm ² was able to resolve 1 μmL / S, respectively.

The curing characteristics of the pattern are the same as in Example 1,
Deformation of the pattern after reheating at 200 ° C., change in absorption characteristics, and surface roughness after immersion in a solvent were not observed.

Example 3 A hydrogenated product of a p-vinylphenol polymer (weight average molecular weight 8000 (GPC measured value, converted to polystyrene), Marukain Petroleum, Marca Linker (trademark) PHC-82) was used as 2 parts.
5 g, 6.5 g of 1,2-naphthoquinonediazide sulfonic acid ester of 2,3,4-trihydroxybenzophenone (triester form), sorbitol tetraglycidyl ether (Nagase Kasei Kogyo Denacol (trademark) E)
X-611) 3.0 g, trimellitic anhydride 1.0 g,
2.8 g of a yellow dye (Nippon Kayaku, Kayaset (trademark) Yellow K-CL) and 112 g of diethylene glycol dimethyl ether were mixed and dissolved, and then filtered through a 0.2 μm filter to prepare a resist solution.

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, 500mJ
1 μmL / S could be resolved at / cm ² .

Whole surface exposure after pattern formation, heat treatment (1
With respect to the curing characteristics of the sample subjected to 70 ° C./5 minutes, hot plate), as in Example 1, no deformation of the pattern after reheating at 200 ° C., no change in absorption characteristics, and no surface roughness after immersion in solvent were observed.

Example 4 25 g of a methyl methacrylate / methacrylic acid copolymer (copolymerization ratio 85/15, weight average molecular weight 10000 (GPC measured value, converted to polystyrene)), 1 of 2,3,4-trihydroxybenzophenone , 2-naphthoquinonediazide sulfonic acid ester (triester form) 6.5 g,
Hexabutoxymethylol melamine (Mitsui Cyanamid, Mycoat (trademark) -506) 5.0 g, yellow dye (Nippon Kayaku, Kayaset (trademark) Yellow K)
-CL) 3.0 g and diethylene glycol dimethyl ether 112 g were mixed and dissolved, and then filtered through a 0.2 μm filter to prepare a resist solution.

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, 300 mJ
1 μmL / S could be resolved at / cm ² .

Next, the obtained 5 μmL / S pattern was U-shaped.
Whole surface exposure with V light (PLA-501, Canon) (LI
= 30), and then heated on a hot plate at 140 to 170 ° C. for 5 minutes. It was possible to obtain lens patterns with various curvatures according to each temperature. Further, after forming the lens pattern, even if heat treatment was performed at 200 ° C., no deformation of the pattern and no change in light absorption characteristics were observed. The solvent resistance was also good.

Example 5 A hydrogenated product of a p-vinylphenol polymer (weight average molecular weight 8000 (GPC measured value, converted to polystyrene), Maruka Linker (trademark) PHC-82 manufactured by Maruzen Petroleum Co., Ltd.) was used.
5 g, 6.5 g of 1,2-naphthoquinone diazide sulfonic acid ester of 2,3,4-trihydroxybenzophenone (triester form), hexamethoxymethylol melamine (manufactured by Mitsui Cyanamid, Cymel (trademark) -3)
03) 3.0 g, 5.0 g of blue pigment (manufactured by Dainichiseika, Chromophine (trademark) Cyanine Blue 4927) and 112 g of diethylene glycol dimethyl ether were uniformly mixed in a ball mill, and then filtered with a 0.5 μm filter. A resist solution was prepared.

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, 700 mJ
/ Cm ² was able to resolve 3 μmL / S.

Whole surface exposure after pattern formation, heat treatment (1
As for the curing characteristics of the sample subjected to the hot plate at 50 ° C. for 5 minutes, the deformation of the pattern after reheating at 200 ° C., the change in the absorption characteristics and the surface roughness after the immersion in the solvent were not observed, as in Example 1.

Example 6 A resist solution was prepared in the same manner as in Example 5 except that the pigment to be mixed was changed to a green pigment (Chromophine (trademark) Cyanine Green 2GN manufactured by Dainichiseika).

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, 700 mJ
/ Cm ² was able to resolve 3 μmL / S, respectively.

The curing characteristics of the pattern are the same as in Example 1,
Deformation of the pattern after reheating at 200 ° C., change in absorption characteristics, and surface roughness after immersion in a solvent were not observed.

Comparative Example 1 A resist solution was prepared by removing hexamethoxymethylolmelamine from Example 1.

Patterning was performed according to Example 1. 5
1 μmL / S could be resolved at 00 mJ / cm ² .

However, the curing characteristics of the pattern were insufficient, and the pattern flowed when heated at 200 ° C. Regarding the solvent resistance, when immersed in isopropyl alcohol or diethylene glycol dimethyl ether, surface roughness was observed and then dissolved.

Comparative Example 2 p-Vinylphenol Polymer (Weight Average Molecular Weight 8000
(GPC measurement value, converted into polystyrene), 25 g of Maruka Linker (trademark) MS-3P manufactured by Maruzen Sekiyu, 2,
6.5 g of 1,2-naphthoquinone diazide sulfonic acid ester of 3,4-trihydroxybenzophenone (triester form), sorbitol tetraglycidyl ether (Denacol (trademark) EX-61 manufactured by Nagase Kasei Kogyo Co., Ltd.)
1) 3.0 g, trimellitic anhydride 1.0 g, yellow dye (Nippon Kayaku, Kayaset (trademark) Yellow K-
CL) (2.8 g) and diethylene glycol dimethyl ether (112 g) were mixed and dissolved, and then filtered through a 0.2 μm filter to prepare a resist solution.

Using this resist solution, patterning was performed in the same manner as in Example 1. As a result, 250 mJ
1 μmL / S could be resolved at / cm ² .

Whole surface exposure after pattern formation, heat treatment (1
Regarding the curing characteristics of the sample subjected to 70 ° C./5 minutes, hot plate), pattern deformation after reheating at 200 ° C. and surface roughness after immersion in a solvent were not observed, but the absorption characteristics after reheating at 200 ° C. , For example, it decreased from 95% to 70% at 400 nm.

[0061]

As is apparent from the above description, in the present invention, a positive type photosensitive material composed of an alkali-soluble resin, a photosensitizer composed of 1,2-naphthoquinonediazide sulfonate, a thermosetting agent and a dye. Since a high resolution color filter pattern can be formed,
Moreover, it can be heat-cured by heat treatment, has excellent properties such as heat resistance, light resistance, solvent resistance, etc., and because it does not require a dyeing process, it is advantageous in shortening and managing the process, and heat-curing Since it does not need to be laminated, it can be made into a thin film, and is suitable as a color filter forming material for a color solid-state imaging device, a color liquid crystal display device and the like.

[Brief description of drawings]

FIG. 1 is a process explanatory diagram of a conventional method.

FIG. 2 is a process explanatory diagram when a positive photosensitive material of the present invention is used.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Silicon substrate 2 Flattening layer 3 Photosensitive casein film 4 Photomask 5 Ultraviolet light 6 Intermediate film 11 Positive photosensitive material 101 Color pattern of 1st color 102 Color pattern of 2nd color 103 Color pattern of 3rd color 201 After development of 1st color Color pattern 211 1st color after heat-curing color pattern 212 2nd color after heat-curing color pattern 213 3rd color after heat-curing color pattern 311 1st color after heat-curing color pattern 312 Having microlens function Color pattern after heat curing of the second color 313 Color pattern after heat curing of the third color having microlens function

Claims (6)

[Claims] 1. A positive photosensitive material for forming a color filter comprising a polymer, a photosensitizer, a thermosetting agent, a dye and a solvent, wherein an alkali-soluble resin is used as the polymer, and 1,2-naphthoquinonediazide sulfonate is used as the photosensitizer. A positive photosensitive material for forming a color filter, wherein a thermosetting agent capable of imparting heat resistance and solvent resistance by patterning and heat treatment is used as the thermosetting agent. 2. The alkali-soluble resin is represented by the following general formula (1):
Alternatively, the positive type photosensitive material for forming a color filter according to claim 1, comprising a structural unit represented by the general formula (2). [Chemical 1] [Wherein R ₁ represents hydrogen or a methyl group, A represents OA ₁ or NA ₂ A ₃ (A ₁ , A ₂ , and A ₃ are hydrogen, an alkyl group having 1 to 6 carbon atoms, and 6 carbon atoms, respectively). (Indicates an allyl group having up to 12 or an aralkyl group having 7 to 12 carbon atoms.)
Where k, l, and n each represent an integer of 0 or 1 or more, and m represents an integer of 1 or more. ] [Chemical 2] [In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ represent hydrogen, a methyl group, chlorine or bromine, respectively, and A is OA.
₁ or NA ₂ A ₃ (A ₁ , A ₂ and A ₃ each represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an allyl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms) .), X and y each represent an integer of 0 or 1 or more, and z represents an integer of 1 or more. ] 3. The alkali-soluble resin is a vinylphenol-based polymer or a novolak resin which is a polycondensation product of a phenol and an aldehyde, and / or a resin obtained by modifying a part of a hydroxyl group. The positive photosensitive material for forming a color filter according to claim 1. 4. The color filter forming agent according to claim 1, wherein the thermosetting agent is a melamine-based curing agent and / or an epoxy-based curing agent having a structural unit represented by the following general formula (3). Positive photosensitive material. [Chemical 3] [In the formula, W represents —NY ₅ Y ₆ {Y ₅ , Y ₆ are each hydrogen or —CH ₂ OZ (Z represents hydrogen or an alkyl group having 1 to 6 carbon atoms). } Or a phenyl group, and Y ₁
To Y ₄ each represent hydrogen or —CH ₂ OZ (Z represents hydrogen or an alkyl group having 1 to 6 carbon atoms). ] 5. A positive-type photosensitive material for forming a color filter, which further comprises a curing aid in the positive-type photosensitive material for forming a color filter according to claim 1. 6. The color filter forming composition according to claim 5, wherein the curing aid comprises at least one selected from a latent thermal acid generator, a polycarboxylic acid anhydride, and a polycarboxylic acid. Positive photosensitive material.