JP4774318B2 - Manufacturing method of color filter - Google Patents

Description

  The present invention relates to an oxygen barrier film, a substrate, a pattern forming method, and a color filter manufacturing method using the same.

  As a method for forming a precise pattern of several μm to 100 μm, such as manufacturing a flat display such as a liquid crystal display and a plasma display, and manufacturing an electronic circuit, a photolithography method using a photosensitive resin is widely adopted.

  The photolithography method includes a process for forming a photosensitive resin film on a substrate such as glass, an exposure process for an optical pattern on the photosensitive resin film, and a development process. This photolithography method has high pattern overlay accuracy, and can be patterned on a large substrate exceeding 2 m.

  However, since the illuminance of exposure light decreases as the substrate becomes larger, it is necessary to improve the exposure sensitivity of the photosensitive resin film in order to maintain a desired process time.

  In order to increase the exposure sensitivity of the photosensitive resin film, for example, as described in Patent Documents 1 to 8, a method is known in which an oxygen blocking film is formed on the surface of the photosensitive resin film and then exposed. Specifically, by forming a water-soluble resin film that is oxygen-blocking and water-soluble, such as polyvinyl alcohol or polyvinylpyrrolidone, on the photosensitive resin film, the crosslinking reaction of the photosensitive resin film is performed. Suppressing diffusion of oxygen to be inhibited into the photosensitive resin film, thereby improving the sensitivity of the photosensitive resin film.

As a method for forming an oxygen barrier film, an aqueous polymer solution is applied onto a photosensitive resin film with a spin coater, a roll coater or the like, and the liquid film is dried by heating or the like. This photosensitive resin film is water-soluble, and is removed from the photosensitive resin film by being dissolved in a developer in a development process after exposure.
JP-A-5-119210 Japanese Patent Laid-Open No. 5-127011 Japanese Patent Laid-Open No. 5-134110 JP-A-5-210008 Japanese Patent Laid-Open No. 5-281408 JP-A-6-109911 Japanese Patent Laid-Open No. 11-288095 Japanese Patent Laid-Open No. 2005-3861

  However, the conventional patterning method has a problem that the exposure device and the photomask are contaminated by hydrogen chloride generated from the photosensitive resin. When the photomask is contaminated, the transmittance is reduced and common defects are generated. When the exposure device is contaminated, the yield and the operating rate are lowered, which causes a problem.

  The present invention has been made in view of the above problems, and an object thereof is to provide an oxygen barrier film, a pattern forming method, and a color filter manufacturing method capable of suppressing contamination of a photomask and an exposure device by hydrogen chloride. .

  The oxygen barrier film according to the present invention includes a water-soluble resin and a basic compound that forms a water-soluble compound by combining with hydrogen chloride.

Another oxygen barrier film according to the present invention includes a water-soluble resin and a compound represented by the following formula (1).

Here, R ₁ represents an optionally substituted alkyl group having 1 to 8 carbon atoms, R ₂ and R ₃ represent an optionally substituted alkyl group having 1 to 8 carbon atoms or hydrogen, R ₁ , R ₂ and R ₃ may be the same or different from each other.

  The board | substrate concerning this invention is equipped with the photosensitive resin layer formed on the board | substrate, and one of the above-mentioned oxygen interruption | blocking films | membranes formed on the photosensitive resin layer.

According to such an oxygen barrier film, hydrogen chloride generated from the photosensitive resin is combined with the basic compound or the compound of the formula (1) to form a water-soluble compound or a water-soluble R ₁ R ₂ R ₃ NHCl. . Accordingly, hydrogen chloride is hardly absorbed by the oxygen blocking film and released to the outside. In addition, since it is a water-soluble compound that is produced, it is easily dissolved in water (developer) during development and the like, and hardly adversely affects during development. Furthermore, since the oxygen blocking film contains a water-soluble resin, it is possible to prevent oxygen from diffusing into the photosensitive resin, and the sensitivity of the photosensitive resin can be improved.

Here, R ₁ of the compound of the formula (1) preferably has an OH group as a substituent.

  In this case, the basicity of this compound can be lowered, and the influence on the photosensitive resin can be suppressed. Moreover, water solubility is also improved.

  Moreover, the pattern formation method concerning this invention comprises the process of forming the above-mentioned oxygen barrier film on the photosensitive resin layer, and the process of exposing the said photosensitive resin film through an oxygen barrier film.

  Moreover, it is preferable to manufacture a color filter using the above-mentioned pattern formation method.

  ADVANTAGE OF THE INVENTION According to this invention, the oxygen interruption | blocking film | membrane, the board | substrate, the pattern formation method, and the manufacturing method of a color filter which can suppress the contamination to the photomask and exposure device by hydrogen chloride are provided.

(First embodiment)
A first embodiment according to the present invention will be described. FIG. 1 is a schematic configuration diagram showing a patterning process according to this embodiment.

  The patterning of the present invention includes at least a resist film forming step 2, an oxygen blocking film forming step 4, an exposure step 6, and a developing step 8.

(Resist film formation process)
In the resist film forming step, a photosensitive resin film (photoresist) 110 is formed on the substrate 100. For the formation of the photosensitive resin film, for example, a known resist film forming apparatus such as a spin coater, a spinless coater, a roll coater, or a dry film resist laminator can be used. In the case of a spin coater, the photosensitive resin film solution is spin-coated on the substrate 100 and dried. In the spinless coater, the photosensitive resin film solution is applied to the substrate 100 from a nozzle precisely processed into a slit shape. What is necessary is just to apply | coat, dry, and heat-process as needed.

(Material for photosensitive resin film)
The material of the photosensitive resin film 110 formed on the substrate 100 is not particularly limited. However, various known photosensitive resins that perform a photo-crosslinking reaction via a negative type, particularly a radical, particularly the oxygen-blocking of the present invention. The membrane can be used effectively.

(Negative photosensitive material)
The negative photosensitive resin is one in which the irradiated part of light is insolubilized and remains in the developer, and generally contains additives such as a binder polymer, a photopolymerizable compound, a photoreaction initiator, a solvent, and a dispersant. In addition, it is formed by applying and drying a mixture of a coloring material and a light shielding material as required.

(Photopolymerizable compound (crosslinking agent))
The photopolymerizable compound is a compound that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond.
The compound may be a monofunctional photopolymerizable compound or a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound. Examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. Examples of the bifunctional photopolymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like. Examples of the trifunctional or higher functional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. Examples include (meth) acrylate. A preferred photopolymerizable compound is dipentaerythritol hexa (meth) acrylate. The photopolymerizable compounds are used alone or in combination of two or more, but bifunctional or higher photopolymerizable compounds are preferably used. When two or more photopolymerizable compounds are used, at least one of them is used. It is preferable to use a bifunctional or higher photopolymerizable compound. The amount of the photopolymerizable compound used is usually 0.1 parts by mass or more and 70 parts by mass or less, preferably 1 part by mass or more and 60 parts by mass or less per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

(Binder polymer)
As the binder polymer, a colorant and a light-shielding agent can be dispersed, and a transparent resin that imparts a crosslinkable function by light irradiation to the colored composition layer together with other components is used. Examples of the binder polymer include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as benzyl (meth) acrylate, unsaturated carboxylic acid aminoalkyl ester compounds such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, etc. Carboxylic acid vinyl ester compounds, (meth) acrylonitrile, vinyl cyanide compounds such as α-chloroacrylonitrile, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3 Polymer of unsaturated carboxylic acid oxetane ester compounds such as-(meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, A melamine acrylate resin, a polyester resin, etc. are mentioned.

  As the binder polymer, monomers may be used alone or in combination of two or more. Examples of the copolymer include benzyl methacrylate / methacrylic acid copolymer, styrene / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, and 3-ethyl-3. -Methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid / styrene copolymer, and the like. In particular, a benzyl methacrylate / methacrylic acid copolymer is preferable. The content of the monomer unit having a carboxyl group in the copolymer is 5 to 50% by mass fraction, preferably 10 to 40%.

  The binder polymer preferably has a weight average molecular weight in the range of 5,000 to 400,000, more preferably in the range of 10,000 to 300,000 as determined by gel permeation chromatography (GPC) using polystyrene as a standard. . The binder polymer is generally used in a range of 5 to 90%, preferably 20 to 70% in terms of mass fraction with respect to the total solid content of the photosensitive resin.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include an active radical generator that generates an active radical when irradiated with light. Chlorine contained in the photopolymerization initiator, in particular, a photopolymerization initiator having a trichloromethyl group tends to be a hydrogen chloride source.
Examples of the photopolymerization initiator containing chlorine include thioxanthone compounds and triazine compounds. Examples of the thioxanthone compound include 2,4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. Examples of commercially available photopolymerization initiators include trade name “Irgacure-907” (acetophenone photopolymerization initiator, manufactured by Ciba Specialty Chemicals). These photopolymerization initiators can be used alone or in combination of two or more. The usage-amount of a photoinitiator is 1 to 30 mass parts normally with respect to 100 mass parts of total amounts of a binder polymer and a photopolymerizable compound, Preferably they are 3 to 20 mass parts. Note that materials other than the photopolymerization initiator, such as pigments, may contain chlorine. Therefore, the present invention can be carried out even when a photopolymerization initiator having no chlorine is used.

(Photopolymerization initiation aid)
The photopolymerization initiation assistant is a compound used in combination with the photopolymerization initiator to accelerate the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiation assistant include amine compounds and alkoxyanthracene compounds. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-dimethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- And bis (ethylmethylamino) benzophenone. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. A commercially available photopolymerization initiation assistant can also be used, and examples of the commercially available photopolymerization initiation assistant include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.). When the photopolymerization initiation assistant is used, the amount used is usually 10 mol or less, preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator. When the photopolymerization initiator and the photopolymerization initiation assistant are used, the total amount is usually 1 part by mass or more and 30 parts by mass or less, preferably 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound, preferably 3 parts by mass or more and 20 parts by mass or less.

(solvent)
Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol diethylene ether. Diethylene glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Alkylene glycol alkyl ether acetates such as ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, aromatic aliphatic ethers such as anisole, phenetole and methylanisole, acetone, Ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, methyl 2-hydroxyisobutyrate, cyclic such as γ-butyrolactone Examples include esters. These solvents can be used alone or in combination of two or more, and the content of the solvent in the photosensitive resin is usually 20% by mass to 90% by mass, preferably 50% by mass to 85% by mass. % To be used.

(Coloring agent)
When used as a transparent colored resin material or the like, a colorant is added. Dyes and pigments can be used as colorants, and organic and inorganic pigments can be used as pigments. Specifically, they are classified as pigments by the Color Index (published by The Society of Dyers and Colorists). The compound which is mentioned.

(Shading material)
When used as a black matrix, a light shielding agent is added. Examples of the light shielding material include organic pigments such as carbon, aniline black, and perylene compounds, and inorganic pigments such as titanium black and magnetite.

(Other additives)
Examples of other additives include fillers, polymer compounds other than binder polymers, surfactants, adhesion promoters, anti-aggregation agents, organic acids, and curing agents. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

(Oxygen barrier film formation process)
In the oxygen blocking film forming step 4, an oxygen blocking film 120 is formed on the substrate 100 coated with the photosensitive resin film 110. For the formation of the oxygen barrier film 120, for example, a known film forming apparatus such as a spin coater, a spinless (slit) coater, a roll coater, a curtain coater, a dry film resist laminator, or the like can be used. In the case of a spin coater, a polymer solution for forming an oxygen barrier film is spin-coated on a substrate and dried. In a spinless coater, a polymer of a photosensitive resin film is formed from a nozzle precisely processed into a slit shape. What is necessary is just to apply | coat a solution on a board | substrate, to dry, and to heat-process as needed. The average film thickness of the oxygen barrier film 120 is preferably 0.01 to 10 μm. In particular, from the viewpoint of eliminating the influence of light interference, the average film thickness is more preferably 0.01 to 0.1 μm. Here, the average film thickness of the oxygen barrier film is a portion of the oxygen barrier film after drying, which is a portion where normal patterning is performed, that is, a central portion excluding an edge portion. This is because the edge portion is raised compared to the central portion and the thickness is not uniform. The average thickness of the oxygen blocking film 120 can be easily obtained by measuring a plurality of points on the coated surface with a stylus type step gauge, an optical interference type film pressure gauge, a cross-sectional SEM photograph, or the like.
(Oxygen barrier film material)

  The oxygen barrier film 120 is a film mainly containing a water-soluble resin (water-soluble resin) and a basic compound. Specific examples of water-soluble resins that can be used as oxygen barrier films include, for example, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, and polyvinyl ether / maleic anhydride polymers. , Ethylene oxide polymer, ethyl cellulose, hydroxyethyl cellulose, cellulose such as water-soluble salt of carboxyethyl cellulose, water-soluble acrylic resin, etc., and mixtures of two or more thereof. Among these, oxygen barrier property, development removability From the viewpoint of the above, polyvinyl alcohol, and a mixture of polyvinyl alcohol and polyvinyl pyrrolidone are preferable. As the polyvinyl alcohol, a partially saponified type is preferable.

  As polyvinyl alcohol, it is preferable that a weight average molecular weight is 300-2400, and what is hydrolyzed 71-100 mol% is preferable. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124 (all trade names, manufactured by Kuraray Co., Ltd., saponification rate 97 to 98%), PVA- 203, PVA-204, PVA-205, PVA-210, PVA-220, PBA-224, PVA-217E (saponification rate 87-88%), PVA-405, PVA-420, (saponification rate 78) -82%), PVA-613 (saponification rate: 92-95%), and Gohsenol Goosefimmer LW (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). In addition, the last two digits × 100 of the three-digit numbers after PVA indicate the degree of polymerization.

  In the case of a mixture of polyvinyl alcohol and polyvinyl pyrrolidone, the mixing ratio of polyvinyl pyrrolidone to polyvinyl alcohol is not particularly limited and can be appropriately selected according to the purpose, but can be 50% by mass or less.

(Basic compound)
A basic compound is a compound that reacts with hydrogen chloride to form a water-soluble compound. The basic compound may be any compound that easily reacts with hydrogen chloride and thereby forms a water-soluble compound such as an ionic compound. Furthermore, it is desirable that it can be easily dispersed in the oxygen barrier film. The basic compound itself is preferably soluble in water.

Examples of the basic compound include amines, and those having the following structure are particularly preferable.

R ₁ is an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an iso-propyl group, a 1-butyl group, a 2-butyl group, or a 3-butyl group, or a C1-C1 having a substituent. Means an alkyl group of 8; R ₂ and R ₃ each represent an optionally substituted alkyl group having 1 to 8 carbon atoms or hydrogen, and R _1, R ₂ and R ₃ may be the same or different from each other. May be.

  In addition, as a kind of the substituent, a hydroxyl group (OH) group, an amino group, a carbonyl group, a carboxyl group, an alkenyl group, a phenyl group, a halogen such as chlorine, fluorine, bromine, or one or more of them is selected. It can be selected from an alkyl group having 1 to 3 carbon atoms. In particular, when it has a hydroxyl group, the basicity of the compound of formula (1) can be reduced, and adverse effects on the photosensitive resin can be suppressed.

Specifically, primary amine (H ₂ NR), for example, dodecylamine, tetradecylamine, hexanediamine, octadecylamine, lauryloxypropylamine, hexadecylamine, tridecylamine, phenylenediamine, undecylamine, tritylamine Etc.

Secondary amines (HNR ₂ ) such as di-ethanolamine, di-octylamine, methyl-octadecylamine, and di-phenylamine are also included.

Also included are tertiary amines (NR ₃ ), such as tri-ethanolamine, methyl-dioctylamine, tri-phenylamine, tri-dodecylamine, tri-benzylamine, tri-decylamine and the like.

  In particular, amines having an atmospheric pressure boiling point> 200 ° C. are preferable, and amines that do not have strong basicity to suppress reaction with the resist, particularly alcohol amines such as triethanolamine and diethanolamine are preferable.

  In addition, the ammonium salt produced | generated by reaction of an amine and hydrogen chloride is water-soluble.

  The content of the basic compound in the oxygen barrier film is preferably 0.05% or more and 20% or less, more preferably 0.1% or more and 5% or less by weight. If the addition amount of the basic compound is 0.05% or less, the effect of preventing the generation of hydrogen chloride tends to be low. Moreover, when the addition amount of a basic compound becomes 20% or more, it will become difficult to form a uniform coating film, and there exists a tendency for a drying rate to become slow.

(Application)
In the formation of the oxygen barrier film 120, an aqueous solution of the above-described water-soluble resin and basic compound is usually applied. More preferably, it is preferable to use an aqueous solution containing 0.2 to 3 wt% of the water-soluble resin and 0.1 to 5 wt% of the basic compound with respect to the dry weight of the water-soluble resin. In addition, it is also effective to add a surfactant to the water-soluble resin solution for forming the oxygen blocking film 120 as necessary in order to adjust the coating property and adhesion to the photosensitive resin film 110.

  The oxygen barrier film 120 is usually formed by applying a water-soluble resin solution on a substrate and drying it. The oxygen blocking film can be formed by spin coating, slit coating, or the like. An oxygen barrier film formed in a sheet shape in advance may be attached.

(Exposure process)
The exposure process is an apparatus that projects a predetermined light pattern on the photosensitive resin film 110 formed on the substrate 100 via the oxygen blocking film 120. The light pattern is not particularly limited, and various patterns can be employed. As the exposure apparatus, various known apparatuses can be used. For example, as shown in FIG. 2, the light from the light source 67 is shielded by a mask M to form a pattern, and this pattern is passed through the oxygen blocking film 120. As shown in FIG. 3, a pattern is formed by modulating light from a light source 67 with a spatial light modulator 68 without using a mask as shown in FIG. A so-called maskless exposure apparatus that projects onto the photosensitive resin film 110 via 120 may be used. The spatial light modulator 68 has a large number of light modulation elements 69 arranged in a matrix. Each light modulation element 69 has a first state in which light from the light source 67 is projected onto the photosensitive resin film 110 (state B1 in the drawing), and a second state in which light from the light source 67 is not projected onto the photosensitive resin film 110. The state (state B2 in the figure) can be switched, whereby a desired pattern can be projected onto the photosensitive resin film 110. Usually, the spatial light modulator 68 is controlled by a computer.

  As the spatial light modulator 68, a DMD (Digital Micro mirror Device) that changes the inclination of the reflection surface of the micro mirror (light modulation element 69) to switch between the first state and the second state, a reflective liquid crystal display LCOS (Liquid Crystal On Silicon) that realizes the first state and the second state by switching between reflection / non-reflection using an element (light modulation element 69), one light dot (pixel) composed of a plurality of ribbons Reflection of GLV (Grating Light Valve) elements that realize the first state and the second state by switching a large number of ribbon groups (light modulation elements 69) corresponding to 1 and switching the diffraction / non-diffraction by each ribbon group Type spatial light modulator or a transmissive spatial light modulator that realizes the first state and the second state by switching between transmissive and non-transmissive using a transmissive liquid crystal display element (light modulating element 62) Etc. can be used. In general, the area 68 a that can be drawn by one exposure is larger than the drawing area 110 a of the photosensitive resin film 110, so that the stage 66 on which the substrate 100 is placed is relatively positioned with respect to the spatial light modulator 68. It may be moved and exposed many times. At this time, it is also preferable that the region 68a is partially overlapped for exposure. As a result, multi-tone exposure is possible, and a continuous pattern without gaps can be suitably formed.

  The maskless exposure apparatus may be an exposure apparatus that directly draws a pattern by scanning a laser beam or the like.

  Such a maskless exposure system does not use an expensive photomask, so it can reduce manufacturing costs, and many advantages such as shortening the line switching time and shortening the time for new product development are expected. In many cases, the exposure takes time compared to the conventional exposure method, and the photosensitive resin film 110 is often required to have high sensitivity in order to shorten the process time. Therefore, the oxygen blocking film 120 is often required, and the merit of combining with the above-described oxygen blocking film forming apparatus is great.

  By this step, a latent pattern image is formed on the photosensitive resin film 110. As described above, since the photosensitive resin film 110 contains a chlorine-based compound as a photopolymerization initiator, hydrogen chloride (HCL) is often generated particularly in the exposure process. However, in the present embodiment, as described above, since the oxygen blocking film 120 contains a basic compound, the generated hydrogen chloride reacts with the basic compound to form a water-soluble compound. Therefore, it becomes difficult for this hydrogen chloride to corrode the exposure device, the photomask and the like. Further, since the oxygen blocking film suppresses the diffusion of oxygen into the photosensitive resin film 110, the sensitivity of the photosensitive resin film 110 is maintained at a high sensitivity, so that exposure can be performed efficiently and in a short time.

  The light that can be used for the pattern exposure of the present invention includes visible light, ultraviolet light, and the like, and is not particularly limited, but is particularly effective for a laser light source that easily causes interference. Lasers, excimer lasers, etc. can be listed. The wavelength of the laser light is preferably one having a wavelength of 290 to 430 nm, which has good compatibility with the photosensitive region of the photosensitive resin.

  As described above, the pattern forming method of the present invention can be particularly suitably applied to a method using a laser as a light source, and a method of printing a pattern at high speed via a mask or an aperture array, or an image formed by a spatial modulation element. It can be suitably applied to the baking method.

(Development process)
The developing process 8 is an apparatus for developing and patterning the photosensitive resin film 110. The developing device is not particularly limited, and various known developing devices can be used. For example, as shown in FIG. 1, a device can be used in which a predetermined developer is dropped from the shower head 8a onto the substrate 100 to bring the developer into contact with the exposed photosensitive resin film 110. The developer that has come into contact with the substrate 100 is collected by the collecting device 8b, and is again supplied to the shower head 8a by the pump 8c, and again comes into contact with the substrate 110, so that the developer is circulated and used effectively. . Note that the substrate 110 can be subsequently washed with water, dried, and heat-treated as necessary.

  Here, as the developer, a known alkaline aqueous solution for developing a photosensitive resin film is preferably used. Specifically, for example, an alkaline aqueous solution in which a hydroxide such as sodium or potassium, an inorganic alkali such as carbonate or hydrogen carbonate, an organic alkali such as organic ammonium or the like is dissolved can be used as the developer.

  Here, since the oxygen blocking film 120 is mainly formed of a water-soluble resin, when the developer is dropped onto the substrate 100, the oxygen blocking film 120 is dissolved in the developer and removed from the photosensitive resin film 110. . Therefore, the dropped developer comes into contact with the photosensitive resin film 110 without any problem, and the photosensitive resin film 110 is patterned. In addition, since a basic compound or a molecule in which a basic compound and hydrogen chloride are bonded is dissolved in water, there is no particular problem.

In this way, the photosensitive resin film 110 is patterned, and the pattern formation of the photosensitive resin is completed as shown in FIG.
By using the drawing machine of the present invention, it is possible to form a high-quality exposure pattern with a resolution comparable to that of batch exposure using a photomask and without unevenness. In addition, as a result of suppressing sublimates generated from the resist film such as hydrogen chloride, the operation rate of a photomask or an expensive large exposure machine can be significantly improved.

(Color filter manufacturing method)
Next, a manufacturing method of a color filter CF and a liquid crystal display LCD to which the above pattern forming method and exposure system are applied will be described with reference to FIG.

  The color filter CF partitions the transparent colored resin layers 73R, 73G, 73B, which are RGB subpixels as display units, and these transparent colored resin layers 73R, 73G, 73B on a transparent substrate 61 such as non-alkali glass. A black matrix 63 as a light shielding pattern is mainly formed.

  The black matrix 63 partitions the boundaries of the adjacent transparent colored resin layers 73R, 73G, and 73B to prevent color mixing, and requires extremely high pattern accuracy and uniformity. The shape of the black matrix 63 is generally a lattice shape or a stripe shape, but a refractive shape or a polygonal shape may be employed in order to increase the display resolution.

  The black matrix 63 may be a pattern obtained by patterning a thin film that is a combination of a light-shielding thin film made of metal such as chromium, molybdenum, and nickel and an anti-reflection film, and is also a light-shielding film in which carbon black, titanium compound, or ferrite compound is dispersed. The resin may be patterned. In the case of a light-shielding resin film having photosensitivity, this film may be directly patterned by a photolithographic method. In the case of a film having no photosensitivity, a photosensitive resin film is formed on the film, The black matrix 63 can be patterned by patterning the resin film and etching the non-photosensitive film using the patterned photosensitive resin film as a mask.

  In particular, when the black matrix 63 is manufactured using a photosensitive light-shielding resin film, the pattern forming method of the present invention can be suitably employed.

  In the opening of the black matrix 63, R (red), G (green), and B (blue) transparent colored resin layers 73R, 73G, and 73B are formed in a predetermined order.

  The transparent colored resin layers 73R, 73G, and 73B are formed in a pattern that covers the openings of the black matrix 63. For example, when one pixel is formed of RGB three-color stripes, the line width of the sub-pixel, that is, the opening width of the black matrix 63 is often about 1/3 of the pitch of one pixel.

  Such transparent colored resin layers 73R, 73G, and 73B can also be manufactured by patterning using a resist mask provided on the transparent colored resin layer. However, pattern formation using a transparent colored resin having photosensitivity is also described. The pattern forming method of the invention can be applied.

  If necessary, a transparent flattening film 80 for flattening the surface is provided on these transparent colored resin layers 73R, 73G, 73B, and further, a transparent conductive film serving as a common electrode for driving liquid crystal is provided thereon. A film 85 is formed.

  The transparent flattening film 80 is applied over the black matrix 63 / transparent colored resin layers 73R, 73G, 73B and fills the steps of the transparent colored resin layers 73R, 73G, 73B and the black matrix 63, and is suitable for a liquid crystal cell. It provides smoothness and prevents the elution of contaminants from the color filter CF. In addition, as for the transparent flattening film 80, it is necessary to use a photosensitive transparent flattening film when fine pattern formation is required according to the necessity of the liquid crystal cell design. Can be used.

  Further, columnar spacers 90 for adjusting the cell gap of the liquid crystal are formed on the transparent conductive film 85. The columnar spacer 90 can be formed by a photolithography method using the pattern used in the black matrix, the transparent colored resin layer, or the transparent flattening film, but the height accuracy and deformation characteristics are managed very strictly. Therefore, it is generally performed that a dedicated photosensitive resin layer is repeatedly applied and finished by a photolithography method using a dedicated pattern. The above patterning method can also be applied to these steps.

  In the case of a transflective liquid crystal, the optical path length in the liquid crystal cell is twice that of the transmissive region in the reflective region. For this reason, in order to simultaneously optimize the display characteristics of the transmissive display and the reflective display, a different cell gap may be formed for each of the reflective portion and the transmissive portion in the reflective / transmissive liquid crystal panel. In this case, a transparent resin pattern for adjusting the cell gap may be formed under the reflector. The patterning method described above can also be applied to this step.

  Then, the thin film transistor substrate TFT is disposed opposite to the color filter thus created, and the liquid crystal 220 is sealed between the alignment film 86 and the thin film transistor substrate TFT, thereby completing a liquid crystal display element as a flat display. To do. The thin film transistor substrate TFT has a pixel electrode 301 and an alignment film 387 on the lower surface of the thin film transistor element 300, and a polarizing film 315 is formed on the thin film transistor element 300.

  As described above, in the color filter CF, the patterning method of the present invention is used for patterning the black matrix 63, the transparent colored resin layers 73R, 73G, 73B, the transparent planarizing film 80, the transparent conductive film 85, the columnar spacer 90, and the like. Therefore, it is possible to manufacture a high-quality product with little unevenness. The pattern forming method described above can also be applied to a scattering layer, an alignment regulation structure, microlens formation, and the like.

  Furthermore, the pattern forming method of the present invention can be applied not only to a color filter for a liquid crystal display but also to a color filter for a flat display using a white organic EL light emitting element or the like.

  In addition, this invention is not limited to the said embodiment, A various application is possible. For example, the patterning method and the exposure system described above are not limited to the manufacture of color filters, but can be applied to the manufacture of electronic circuits such as LSI and various electronic circuits.

(Examples A1 to A4)
A light-shielding photosensitive resin material ((V259-BKIS-66: manufactured by Nippon Steel Chemical Co., Ltd.)) is applied to 370 × 470 mm non-alkali glass (Corning 1737, 0.7 t), and 90 mm on a hot plate. A light-shielding photosensitive resin film having a film thickness of 1.2 μm was formed by prebaking at a temperature of 110 ° C. for 110 seconds.

  Thereafter, an aqueous solution containing 3 wt% of diethanolamine and 1 wt% of polyvinyl alcohol (Poval 205 manufactured by Kuraray Co., Ltd.) was applied using a slit nozzle to form an oxygen blocking film having a thickness of 0.05 μm.

A lattice-shaped resin BM pattern was baked on the light-shielding photosensitive resin film through an oxygen barrier film using a proxy exposure machine at an exposure amount of 15 mJ / cm ² and an exposure gap of 60 μm.

  The light-shielding resin film after exposure was shower-developed at 23 ° C. for 80 seconds using an inorganic alkali developer (KOH 0.05%), and then subjected to droplet jet cleaning using a microjet cleaning device at a pressure of 10 MPa.

  After repeating the above operation for 100 sheets, the deposit on the surface of the photomask was observed and compared with the state before use, but no abnormality such as deposit was observed.

(Comparative Example A1)
A black matrix was formed in the same manner as in Example 1 except that the oxygen-blocking film was not formed on the light-shielding resin film of Example 1 and the exposure amount was 100 mJ / cm ² .

  After repeating the same operation over 100 sheets, a change in the surface state of the photomask was observed, and many deposits were observed.

(Examples B1 to B6, Comparative Example B1)
An average film thickness of 0.05 μm of a polyvinyl alcohol film containing 3% by weight of an amine compound listed in Table 1 on a glass substrate coated with a light-shielding resin film (resist film) having negative photosensitive characteristics. Formed with. The polyvinyl alcohol film was formed by applying a 1 wt% aqueous solution with a slit coater and drying in an air stream. In Comparative Example B1, no amine compound was used.

A lattice-like pattern was baked on the resist film formed with the polyvinyl alcohol film by a proximity exposure method (exposure gap 60 μm, exposure dose 400 mJ / cm ² ) through a photomask. After 100 operations were successively performed for each, the surface of the photomask was observed with a microscope, and the presence or absence of contamination on the mask surface was observed.

  From the results shown in FIG. 6, the contamination of the mask can be reduced by the basic compound, and particularly when the amine compound (Examples B1 to B4) having an atmospheric pressure boiling point of 200 ° C. or higher is added, the contamination of the mask is extremely well suppressed. It is understood that it can be done.

FIG. 1 is a schematic diagram showing an outline of a method for manufacturing a color filter according to the present embodiment. FIG. 2 is a schematic cross-sectional view showing the first exposure method. FIG. 3 is a schematic cross-sectional view showing a second exposure method. FIG. 4 is a schematic cross-sectional view of the substrate after the patterning tool. It is a top view of a cleaning device. FIG. 5 is a schematic cross-sectional view showing a color filter and an LCD. FIG. 6 is a table showing the conditions and results of Examples B1 to B6 and Comparative Example B1.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter manufacturing system, 100 ... Photosensitive resin film, 120 ... Oxygen blocking film, CF ... Color filter.

Claims (3)

Forming an oxygen blocking film on the photosensitive resin layer;
Exposing the photosensitive resin layer through the oxygen barrier film;
A color filter manufacturing method comprising a pattern forming method including:
The photosensitive resin layer contains a chlorine-based compound that generates hydrogen chloride in the exposure step ,
A method for producing a color filter, wherein the oxygen barrier film is an oxygen barrier film comprising a water-soluble resin and a basic compound that combines with hydrogen chloride to form a water-soluble compound. The manufacturing method of the color filter of Claim 1 whose said basic compound is a compound of following formula (1).

Here, R ₁ represents an optionally substituted alkyl group having 1 to 8 carbon atoms, R ₂ and R ₃ represent an optionally substituted alkyl group having 1 to 8 carbon atoms or hydrogen, R ₁ , R ₂ , and R ₃ may be the same as or different from each other. The method for producing a color filter according to claim 2, wherein R ₁ has an OH group as a substituent.

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