JPH08262728A - Photosensitive resin composition and pattern forming method using same - Google Patents

Abstract

PURPOSE: To shorten exposure time and to enhance the productivity of a color filter, etc., by incorporating polysilane having a specified wt. average mol.wt. and soluble in an org. solvent, an optical radical generating agent, an oxidizing agent, specified silicone oil and an org. solvent. CONSTITUTION: This resin compsn. contains polysilane having a wt. average mol.wt. of >=10,000 and soluble in an org. solvent, an optical radical generating agent, an oxidizing agent, silicone oil represented by the formula and an org. solvent. In the formula, each of R<1> -R<6> is 1-10C optionally halogen or glycidyl substituted aliphatic hydrocarbon, 6-12C optionally halogen substituted aromatic hydrocarbon or 1-8C alkoxy, each of (m) and (n) is an integer and m+n>=1. Network polysilane is preferably used as the polysilane in consideration of mechanical strength as a photosensitive material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition and a pattern forming method using the same.

[0002]

2. Description of the Related Art A color filter is used for color display of a liquid crystal display using a liquid crystal as an optical shutter. So far, the present inventors have developed a method for manufacturing a color filter utilizing photolysis of organic polysilane.

For example, JP-A-5-273410 discloses a method of immersing a metal alkoxide containing a dye or a pigment in a colored sol as a raw material. Further, JP-A-5-47782 discloses a method of pattern electrodeposition using an electrodeposition liquid containing a dye or pigment on a polysilane-irradiated portion on a transparent conductive film.

[0004]

However, these methods using polysilane have a problem that exposure for a long time is required. The present invention solves the above problems, and thereby can provide a simple and highly productive method for producing a color filter.

[0005]

The present invention comprises: a) a polysilane which is soluble in an organic solvent and has a weight average molecular weight of 10,000 or more. B) a photoradical generator and an oxidant.

[0006]

Embedded image

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are an aliphatic hydrocarbon group which may be substituted with a halogen or glycidyl group having 1 to 10 carbon atoms, carbon Number 6 ~
It is a group selected from the group consisting of an aromatic hydrocarbon group which may be substituted with 12 halogens and an alkoxy group having 1 to 8 carbon atoms, and may be the same or different. m and n are integers and satisfy m + n ≧ 1. ] A photosensitive resin composition containing a silicone oil having a structure shown by d) an organic solvent, and a photosensitive material obtained by applying the composition onto a substrate and drying the composition.

The present invention includes: A) coating the photosensitive resin composition on a substrate and drying,
A step of forming a photosensitive layer, B) a step of forming a latent image of a colored pattern by selectively exposing the photosensitive layer: and C) a dye or a portion of the exposed portion on which the latent image of the colored pattern is formed. A step of coloring with a coloring liquid containing a pigment;

In the present invention, D) another coloring is carried out at least once in the same manner as the coloring step except that latent images having different coloring patterns are formed on the photosensitive layer, and different dyes or pigments are used. Provided is a multicolor pattern forming method further including a step, and a color filter obtained by the method.

In the present invention, A ') a step of applying the above-mentioned photosensitive resin composition on a substrate and drying it to form a photosensitive layer, B') selectively exposing the photosensitive layer to form a pattern. A step of forming a latent image having a pattern: and C ′) a step of immersing or applying the exposed portion on which the latent image having a pattern is formed in a sol of a metal oxide containing no pigment or dye; The above object is achieved by the above.

<Photosensitive resin composition> The photosensitive resin composition of the present invention comprises: a) a weight average molecular weight of 10 which is soluble in an organic solvent.
It contains more than 000 polysilanes, b) photoradical generators and oxidants, c) silicone oils and d) organic solvents.

A ) Polysilane The polysilane used in the present invention may be a network or chain polysilane. In consideration of mechanical strength as a photosensitive material, network polysilane is preferable. The network form and the chain form are distinguished by the bonding state of Si atoms contained in polysilane. Network polysilane is the number of bonded Si atoms
It is a polysilane containing a Si atom whose (bond number) is 3 or 4. On the other hand, in chain polysilane, the number of Si atoms bonded to adjacent Si atoms is two. Since the valence of Si atoms is usually 4, if the number of bonds among Si atoms present in polysilane is 3 or less, it is bonded to a hydrocarbon group, an alkoxy group or a hydrogen atom in addition to the Si atom. .
Examples of such a hydrocarbon group include an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with halogen, and 6 carbon atoms.
-14 aromatic hydrocarbon groups are preferred. Specific examples of the aliphatic hydrocarbon group include a methyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a chain-like one such as a trifluoropropyl group and a nonafluorohexyl group,
And cycloaliphatic groups such as cyclohexyl group and methylcyclohexyl group. Further, specific examples of the aromatic hydrocarbon group include a phenyl group, a p-tolyl group, a biphenyl group and an anthracyl group. Examples of the alkoxy group include those having 1 to 8 carbon atoms.
Specific examples include a methoxy group, an ethoxy group, a phenoxy group and an octyloxy group. Of these, a methyl group and a phenyl group are particularly preferable in view of ease of synthesis.

In the case of network-like polysilane, the Si atom whose number of bonds with adjacent Si atoms is 3 or 4 is
5-50 of the total number of Si atoms in the network polysilane
% Is preferable. If it is less than 5%, the effect of the present invention may not be obtained, and if it exceeds 50%, solubility may be problematic. This value can be determined by measuring the nuclear magnetic resonance spectrum of silicon.

The polysilane in the present specification includes a mixture of network-shaped and chain-shaped polysilane. In that case, the content rate of the above Si atom,
Calculated by the average of the network and chain polysilanes.

The polysilane used in the present invention is a halogenated silane compound in the presence of an alkali metal such as sodium in an organic solvent such as n-decane or toluene.
It can be produced by a polycondensation reaction by heating to 80 ° C. or higher.

In the case of the network-like polysilane, it is composed of an organotrihalosilane compound, a tetrahalosilane compound and a diorganodihalosilane compound, and the organotrihalosilane compound and the tetrahalosilane compound are 5 mol% or more and 50 mol% of the total amount. By heating and polycondensing the halosilane mixture of less than 1%, the target network polysilane is obtained. Here, the organotrihalosilane compound serves as a Si atom source having 3 bonds with adjacent Si atoms, and one tetrahalosilane compound has a Si atom source having 4 bonds with adjacent Si atoms. Become. The network structure can be confirmed by measuring an ultraviolet absorption spectrum or a nuclear magnetic resonance spectrum of silicon.

On the other hand, in the case of chain polysilane, a plurality or a single diorganodichlorosilane is used,
It can be produced by the same reaction as in the case of network polysilane.

The halogen atom contained in each of the organotrihalosilane compound, the tetrahalosilane compound and the diorganodihalosilane compound used as the raw material of polysilane is preferably a chlorine atom. Examples of the substituent other than the halogen atom which the organotrihalosilane compound and the diorganodihalosilane compound have include the above-mentioned hydrocarbon group, alkoxy group or hydrogen atom.

These network-like and chain-like polysilanes are soluble in organic solvents and have a weight average molecular weight of 10
It is not particularly limited as long as it is 000 or more. Considering the use as a photosensitive material, the polysilane used in the present invention needs to be soluble in an organic solvent having a vaporizing property.
Preferred as such an organic solvent is one having 5 to 5 carbon atoms.
12 hydrocarbons, halogenated hydrocarbons and ethers.

Examples of hydrocarbons include pentane, hexane, heptane, cyclohexane, n-decane, n-dodecane, benzene, toluene, xylene and methoxybenzene. Examples of halogenated hydrocarbons include carbon tetrachloride, chloroform, 1,2-dichloroethane,
Examples include dichloromethane and chlorobenzene. Examples of ether type include diethyl ether, dibutyl ether, and tetrahydrofuran. The weight average molecular weight of polysilane is preferably 10,000 or more. This is because if it is less than 10,000, the effect of the present invention cannot be obtained.

B) Photoradical Generator and Oxidizing Agent The photoradical generator that can be used in the present invention is not particularly limited as long as it is a compound that generates a halogen radical by light, but 2,4,6-tris (trihalomethyl) ) -1,3,5-Triazine and its 2-position, or its 2- and 4-position-substituted compounds, phthalimidotrihalomethanesulfonate and its compound having a substituent on the benzene ring, and naphthalimidotrihalomethanesulfonate Examples thereof include compounds having a substituent on the benzene ring thereof. The substituents that these compounds have are aliphatic and aromatic hydrocarbon groups that may have a substituent.

On the other hand, the oxidizing agent usable in the present invention is not particularly limited as long as it is a compound which serves as an oxygen supply source, and examples thereof include peroxides, amine oxides and phosphine oxides. A combination of a trichlorotriazine-based photo radical generator and a peroxide as an oxidant is preferable.

The addition of the photoradical generator and the oxidant is
It utilizes the fact that the Si-Si bond is efficiently cleaved by the halogen radical and that oxygen is easily inserted. Further, by adding a soluble dye such as a coumarin-based dye, a cyanine-based dye, or a merocyanine-based dye, it is possible to generate a halogen radical by photoexcitation of the dye. All of these contribute to the improvement of the sensitivity of polysilane to light.

C) Silicone Oil The silicone oil used in the present invention has the formula:

[0025]

Embedded image

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are aliphatic hydrocarbon groups which may be substituted with halogen having 1 to 10 carbon atoms or glycidyloxy groups, It is a group selected from the group consisting of an aromatic hydrocarbon group having 6 to 12 carbon atoms and an alkoxy group having 1 to 8 carbon atoms and may be the same or different. m and n are integers, and m + n ≧
1 is satisfied. ] Is shown.

Specific examples of the aliphatic hydrocarbon group contained in this silicone oil include chain groups such as methyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, trifluoropropyl group and glycidyloxypropyl group. And cycloaliphatic groups such as cyclohexyl group and methylcyclohexyl group. Further, specific examples of the aromatic hydrocarbon group include a phenyl group, a p-tolyl group and a biphenyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a phenoxy group and an octyloxy group.

The types of R ^{1 to} R ⁶ and the values of m and n are not particularly important and are not particularly limited as long as they are liquid at room temperature and compatible with polysilane and an organic solvent.
In consideration of compatibility, it is preferable that the polysilane used has the same group as the hydrocarbon group. For example, when a phenylmethyl type polysilane is used as the polysilane, it is preferable to use the same phenylmethyl type or diphenyl type silicone oil. Further, among R ¹ to R ^6, at least two such that an alkoxy group having 1 to 8 carbon atoms, silicone oil having two or more alkoxy groups per molecule can be used as a crosslinking agent. Examples thereof include methylphenyl methoxy silicone and phenyl methoxy silicone containing 15 to 35% by weight of an alkoxy group.

The molecular weight is 10,000 or less, preferably 3
Those of 000 or less are preferably used. Further, those having a viscosity at 25 ° C. of 200 cps or less, preferably 50 cps or less are suitably used.

D) Organic Solvent The organic solvent used in the present invention is preferably the one described in a) polysilane.

The composition of the photosensitive resin composition of the present invention is 1 to 30 parts by weight of a photoradical generator, 1 to 30 parts by weight of an oxidizing agent, and 5 to 100 parts by weight of a silicone oil based on 100 parts by weight of polysilane. . When a dye is further added, it is preferably 1 to 20 parts by weight with respect to 100 parts by weight of polysilane. On the other hand, the total concentration of the organic solvent is 5 to
Used to be 15% by weight. In the present invention, since the silicone oil that functions as a compatibilizing agent for the polysilane and the photoradical generator and the oxidizing agent is used, the photoradical generator and the oxidizing agent should be contained in a large amount as compared with the case where the silicone oil is not used. Is possible.

<Photosensitive Material> A photosensitive material is obtained by applying the above-mentioned photosensitive resin composition onto a substrate and drying it. As the base material, a glass plate, a metal plate, a plastic plate or the like may be used depending on the application, but a transparent substrate must be used when a color filter is manufactured. Examples of the transparent substrate include a glass plate, a quartz plate, a polyethylene terephthalate film, a polyolefin film, and an acrylic film. Among these, it is particularly preferable to use a glass plate as the substrate. At that time, the thickness of the substrate changes depending on the strength of the material used. For example, when a glass plate is used, a glass plate having a thickness of 0.6 to 1.2 mm is preferable from the viewpoint of strength as a color filter material. Further, if necessary, a light shielding film (black matrix) of metallic chromium may be previously patterned on the substrate.

The coating method on the substrate is not particularly limited as long as a polysilane layer having a uniform thickness can be formed, and any method known to those skilled in the art can be used. Generally, it is preferable to use the spin coating method. The polysilane layer formed on the substrate preferably has a dry thickness in the range of 0.1 to 10 μm. The photosensitive material thus obtained can be used as a color filter or a ceramic thin film.

<Colored Pattern Forming Method> The colored pattern forming method of the present invention comprises: A) a step of applying the above-mentioned photosensitive resin composition on a substrate and drying it to form a photosensitive layer; and B) selecting the photosensitive layer. To form a latent image of the colored pattern by exposing the exposed portion to light, and C) a step of coloring the exposed portion on which the latent image of the colored pattern is formed with a coloring liquid containing a dye or a pigment.

When forming a multicolor pattern,
Further, D) includes another coloring step which is performed at least once in the same manner as the coloring step except that latent images having different coloring patterns are formed on the photosensitive layer and different dyes or pigments are used. .

Step A) This step has the same contents as those described above for the photosensitive material.

Step B) The second step is to selectively expose the photosensitive layer to form a latent image of a colored pattern on the exposed portion. Ultraviolet rays are generally used for the exposure. Figure 1
This step is shown in (a). That is, a patterned mask 103 is superposed on the photosensitive material 104 composed of the substrate 101 and the polysilane layer 102 obtained in the step A), and the ultraviolet rays 110 are irradiated there.

The ultraviolet ray used in the present invention has a wavelength of 250 to 400 nm which is the σ-σ * absorption region of polysilane. This irradiation is 0.01 to 1 J / c per 1 μm of polysilane layer thickness.
It is performed with a light amount of m ² , preferably 0.1 to 0.5 J / cm ² . Irradiation light amount is reduced coloration and less than 0.01 J / cm ^2, the generation of pinholes is increased exceeds a 1 J / cm ^2. Ultraviolet light sources include high pressure and ultra high pressure mercury lamps, xenon lamps, metal halide lamps, and He-
Cd laser, Ar laser, YAG laser, excimer laser, etc. can be used.

The Si-Si bond existing in the polysilane layer is cleaved by ultraviolet irradiation to generate Si-OH (silanol group). Therefore, a latent image having silanol groups corresponding to the pattern is formed on the irradiated photosensitive material.

C) Step The third step is a step of coloring the exposed portion of the photosensitive layer on which the latent image of the coloring pattern is formed with a coloring liquid containing a dye or a pigment. As a coloring method in this step, a sol-gel coloring method, a dyeing method, an electrodeposition method and a silane coupling method can be used, but from the viewpoint of heat resistance of the obtained material,
A sol-gel coloring method or a silane coupling method is preferable. The sol-gel coloring method will be described in detail below.

Sol-Gel Coloring Method In the sol-gel coloring method, a sol of a metal oxide containing a dye or a pigment is used as a coloring liquid. In the present specification, the “metal oxide sol” refers to one obtained by polycondensing one or more kinds of metals through oxygen and forming a sol in a suitable solvent. For example, in the case of silicon, Called silica sol.

As the raw material of the metal oxide sol, those generally used in the sol-gel method can be used. That is,
Si, Zr, Pb, Ti, Ba, Sr, Nb, K, Li, Ta, In, Sn, Z
n, Y, Cu, Ca, Mn, Fe, Co, La, Al, Mg, V alkoxides, acetylacetonates, acetates, metal organic compounds such as amines, soluble inorganic salts such as nitrates, or oxide fine particles A dispersion is used. Among these, it is preferable to use an Si alkoxide, which is easy to handle, as a raw material. The sol is formed by making the above raw materials into a solution with a solvent such as alcohol and conducting a polycondensation reaction using a catalyst such as an acid or a base.

For example, when synthesizing a metal oxide sol using tetraethoxysilane as an alkoxide of Si, a dye or pigment is mixed with a solution of tetraethoxysilane dissolved in a mixed solution of ethanol and water. rear,
Add hydrochloric acid and stir at room temperature. Thereby, tetraethoxysilane is hydrolyzed and dehydrated and condensed to obtain a homogeneous silica sol. Further, the mixing of the dye or pigment may be performed after forming the sol.

The composition is tetraethoxysilane 100
20 to 200 parts by weight of ethanol, 50 to 200 parts by weight of water, 0.01 to 3 parts by weight of hydrochloric acid, and 0.5 to 25 parts by weight of dye or pigment are preferable with respect to parts by weight.

The dyes or pigments which can be used in the present invention are all those which can be dissolved or dispersed in an alcohol solution of a metal alkoxide and which can interact with a metal oxide sol. It is considered that such dyes or pigments are adsorbed on the photosensitive material by interacting with silanol groups formed in the polysilane layer upon irradiation with ultraviolet rays. As a result, the photosensitive material is colored according to the exposure pattern.

Such dyes include basic dyes, oil-soluble dyes and disperse dyes. Examples of CI Nos. Of dyes that can be preferably used in the present invention are shown below.

As the basic dye, basic red
(Basic Red) 12, Basic Red 27, Basic
Basic Violet 7, Basic Violet 10, Basic Violet 40, Basic Blue 1, Basic Blue 7, Basic Blue 7, Basic Blue 26, Basic Blue 77, Basic Green 1 and Basic Yellow (Ba
sic Yellow) 21.

As the oil-soluble dye, Solvent Red
(Solvent Red) 125, Solvent Red 132, Solvent Red 83, Solvent Red 109, Solvent Red
Examples include Blue (Solvent Blue) 67, Solvent Blue 25, Solvent Yellow 25, Solvent Yellow 89, and Solvent Yellow 146. As a disperse dye, Disperse Red
60, Disperse Red 72, Disperse Blue (D
Examples include isperse Blue) 56, Disperse Blue 60, and Disperse Yellow 60. Of these, metal-containing oil-soluble dyes, which are particularly excellent in heat resistance and light resistance, are suitable as color filter materials.

On the other hand, pigment C. which can be preferably used in the present invention.
As an example of I.No., Pigment Yell
ow) 83, Pigment Yellow 110, Pigment Yellow 139, Pigment Red 53: 1, Pigment Red 177, Pigment Red 221, Pigment Violet 23, Pigment Violet 37, Pigment Violet -Blue (Pigment Blue) 15, Pigment Blue 15: 3, Pigment Blue 15: 6, Pigment Green (Pigment Green) 7, Pigment Green 36, Pigment Black 7 are mentioned.

The pigment may be dispersed once in an alcohol solution of a metal alkoxide and then made into a sol, or may be dispersed in the sol solution. At the time of dispersion, it is desirable to use a nonionic surfactant and disperse particles to a particle size smaller than the wavelength of visible light.

The exposed portion of the photosensitive material is colored by coating or immersing the thus obtained metal oxide sol containing a dye or a pigment. This is because the exposed portion of the photosensitive material has a silanol group as described above, and adsorption (gelation) occurs due to the interaction between the silanol group and the metal oxide sol containing the dye or pigment. Is considered to be. Also, in the case of a metal oxide sol in which a pigment is dispersed, particles of the metal oxide are adsorbed on the surface of the pigment, and when coloring is performed using the metal oxide sol in which the pigment is dispersed, The presence of the pigment can be confirmed by a transmission electron microscope.
From this, it can be confirmed that the pigment having the metal oxide particles adsorbed on the surface is diffused inside through the fine pores present in the exposed portion of the photosensitive layer.

The application can be carried out using an air spray, an airless spray, a roll coater, a curtain flow coater, a meniscus coater or the like.
On the other hand, the dipping is performed by filling a coloring liquid in a tank of a size capable of completely dipping the photosensitive material. The coating method is preferable because the management of the coloring liquid is easy and the amount of the coloring liquid used is small.

It is also possible to add to the metal oxide sol an aprotic organic solvent which swells the polysilane layer, such as acetonitrile, dioxane and tetrahydrofuran, in order to increase the coloring speed and the coloring concentration. These are preferably 1 to 1 in the metal oxide sol.
It may be contained in an amount of 20% by weight. When the content of the solvent exceeds 20% by weight, the polysilane layer is partially redissolved, and the surface of the resulting colored photosensitive material may be disturbed.

The colored photosensitive material thus obtained is dried after removing the metal oxide sol containing the dye or pigment. As a removing method, a method of washing with water, a method of blowing off with an air blow, or the like can be used.

Drying is generally preferably carried out at 100 ° C. or higher for 10 minutes to 1 hour, but the drying conditions can be changed within a range that does not adversely affect the transparent substrate, dye or pigment used. For example, when the glass substrate is used as a transparent substrate and contains a pigment, it can be dried at 200 ° C. for 30 minutes or more. In this drying process, it is expected that gelation due to dehydration reaction will proceed further and the dye or pigment will be trapped in the SiO ₂ crosslinked film. In particular, when silicone oil having two or more alkoxy groups in one molecule is used as the silicone oil, the crosslinking reaction proceeds and the heat resistance of the obtained pattern colored portion is improved.

It is considered that this makes it possible to obtain a colored film which is less likely to be eluted in an organic solvent or the like, and which is not colored in this portion in another coloring step and which has excellent resistance.

By the first pattern coloring step as described above,
As shown in FIG. 1B, a monochromatic pattern-colored photosensitive material 104 'is obtained.

Coloring Method Other than Sol-Gel Coloring Method As a coloring method other than the sol-gel coloring method, there are a dyeing method, an electrodeposition method and a silane coupling method.

In the dyeing method, an exposed portion of the photosensitive material is colored by applying or dipping an aqueous solution of a dye as a coloring liquid. It is considered that this is because the dye interacts with the silanol group generated in the exposed portion and is adsorbed. The aqueous dye solution preferably contains 0.1 to 5% by weight of the dye. As the dye, those described in the sol-gel coloring method can be used. Further, lower alcohol may be added in an amount of 1 to 30% by weight in order to enhance the solubility of the dye, and an aprotic organic solvent as described in the sol-gel coloring method may be included. Dyeing conditions such as dyeing temperature and dyeing time can vary depending on the desired dyeing concentration and the type and amount of dye used. The dyed photosensitive material is dried after removing the dye aqueous solution. As a method for removing, a method of washing with water, a method of blowing off with an air blow, or the like can be used as in the sol-gel coloring method. The drying may be carried out by leaving it indoors, but it is preferable to compulsorily dry it by heating at 50 to 100 ° C. for 5 to 30 minutes.

In the electrodeposition method, an electrodepositable solution containing a dye or a pigment is used as a coloring liquid. As the electrodepositable solution, those well known to those skilled in the art such as anionic and cationic resins and micelle electrolytic solution can be used.

The anionic resin is a resin having an acid group neutralized with a base, and the resin is preferably a (meth) acrylic acid copolymer or an oil-free polyester resin.
On the other hand, the cationic resin is obtained by neutralizing a resin having a basic group with an acid, and a (meth) acrylic acid ester copolymer is preferable as the resin.

On the other hand, the micellar electrolytic solution is an aqueous micellar solution of a charged surfactant. The surfactant may be positively or negatively charged, and examples of the positively charged may include benzalkonium chloride, lanolin fatty acid aminopropylethyldimethylammonium salt, tetraalkylammonium salt and imidazolinium. Examples thereof include salts and alkyldimethylbenzyl ammonium salts. Examples of negatively charged compounds include aliphatic carboxylates, alkylbenzene sulfonates, sulfosuccinates, and the like.

The dyes and pigments that can be used in the electrodeposition method include, in addition to those described in the sol-gel coloring method, direct dyes and acid dyes. As a direct dye, Direct Yellow4
4, Direct Red (Direct Red) 23, direct
Red 79, Direct Blue 25, Direct Blue 86, Direct Green
n) 59 and the like.

Acid yellow dyes (A
cid Yellow) 38, Acid Yellow 99, Acid Violet 49, Acid Blue (Acid B)
lue) 40, Acid Blue 83, Acid Green (Aci
d Green) 25, Acid Green 18 and the like.

An electrodepositable solution containing a dye or pigment is prepared as follows. That is, in the case of an anionic or cationic resin, by neutralizing the resin having an acid group or a basic group into an aqueous solution or an aqueous dispersion, and by dissolving or dispersing a dye or a pigment therein,
The desired coloring liquid can be obtained. When a pigment is used, it is preferable to disperse it so that the particle diameter is 0.4 μm or less. After that, it is diluted with water so that the pigment concentration becomes 3 to 20%, and a solvent is added if necessary to obtain a solution capable of electrodeposition. Further, a thermosetting type electrodepositable solution can be prepared by adding an amino resin or a blocked isocyanate known as a curing agent for electrodeposition coatings. In addition, a silane coupling agent or colloidal silica may be contained in the electrodepositable solution in order to react with the silanol groups generated in the ultraviolet irradiation portion of polysilane to form a crosslinked structure. On the other hand, in the case of a water-soluble dye, the dispersing step is not necessary, but in the case of an oil-soluble dye or a disperse dye, it is necessary to disperse and atomize it like the pigment.

On the other hand, in the case of the micelle electrolytic solution,
A coloring liquid is prepared by adding the above-mentioned surfactant and dye or pigment to an aqueous medium, mixing them, and dispersing them if necessary. The concentration of the surfactant is not particularly limited,
It is preferably at or above the limit micelle concentration. In order to form a crosslinked structure with the silanol group of the polysilane layer,
The above-mentioned silane coupling agent and colloidal silica can be used in combination. Supporting electrolytes such as alkali metal sulfates or acetates may be added as needed to adjust the electrical conductivity.

Unlike the other coloring methods, in the electrodeposition method, it is necessary to use a glass plate having a transparent electrode made of ITO or a conductive polymer as a transparent substrate. The glass plate on which the transparent electrode has been formed, which has undergone the above steps A) and B), is immersed in the above electrodepositable solution. A colored pattern is formed on the polysilane layer of the latent image by electrodeposition of the transparent electrode as a cathode or an anode. Removal of the colored liquid after electrodeposition is performed by washing with water, blowing off with an air blow, or the like.

When the resin used in the electrodepositable solution has a crosslinking ability, it may be dried according to the crosslinking reaction conditions. When the resin used in the electrodepositable solution does not have a cross-linking ability, or when it does not contain a resin and consists of a pigment and a surfactant, it is preferably dried at 80 ° C. for 10 minutes or longer.

The final coloring method is the silane coupling method. In this method, a pigment aqueous dispersion containing a silane coupling agent is used as the coloring liquid. Although known silane coupling agents can be used, it is preferable to use methoxysilane- and ethoxysilane-based coupling agents. As the pigment, those described in the sol-gel coloring method can be used.

The pigment aqueous dispersion containing a silane coupling agent is 1 to 25 parts by weight of a nonionic surfactant, 1 to 25 parts by weight of a silane coupling agent, and 100 parts by weight of a pigment.
Water and, if necessary, water-miscible organic solvent 150-250
It is adjusted by dispersing parts by weight using glass beads or the like. Since the silane coupling reaction generally proceeds in the presence of an acid, it is preferable to acidify the coloring liquid with hydrochloric acid or the like.

The pigment aqueous dispersion containing the silane coupling agent is applied to or dipped in the exposed photosensitive material, and the coloring liquid is removed and then dried, whereby the silane coupling reaction proceeds and the exposed pattern is formed. Coloring is made accordingly. For other details, the contents described in the sol-gel coloring method can be referred to.

Step D) Through the steps A) to C), the photosensitive material is colored in a single color. In order to obtain a material having a plurality of colors such as a color filter, further different coloring is required. Therefore, the fourth step is to perform the second and subsequent colors on the monochromatic photosensitive material obtained through the steps C).

As shown in FIG. 1C, the mask film 103
To form a latent image of a different colored pattern on the polysilane layer using a mask film 113 instead of, and the same as the above steps B) and C) except using a dye or pigment different from the one used previously. As a result, as shown in FIG. 1 (d), a photosensitive material 104 ″ that is patterned in two colors is obtained. The mask film 113 used here is generally polysilane as shown in FIG. 1 (c). It has a mask pattern which covers the colored pattern portions of the layer in steps B) and C) and exposes the uncolored portions.

Further, if desired, as shown in FIG. 1 (e), instead of the mask film 113, a mask film 123 is used.
As shown in FIG. 1 (f), three colors are formed in the same manner as in the second color coloring step, except that latent images having different coloring patterns are formed on the polysilane layer by using Patterned filter material on 10
4 "'is obtained. The mask film 123 used here
In general, as shown in FIG.
It has a mask pattern that covers the colored pattern portions of the second color and the second color and exposes the uncolored portions.

By repeating such steps, it is possible to fabricate a filter which is further colored in multiple colors. Further, in this step D), the entire surface is exposed without using a mask film, so that the portion other than the colored pattern portion of the first color can be colored.

The term "forming latent images of different colored patterns" in the present specification means that latent images of completely the same colored pattern are not formed in each pattern coloring step, and they do not necessarily overlap each other. It is not limited to forming a colored pattern. Further, the term “using different dyes or pigments” in the present specification means that at least 1 is used in each pattern coloring step.
It refers to the use of coloring liquids having different hues containing different types of dyes or pigments, and some of the dye or pigment compositions used in the coloring liquids may overlap in each step.

Since the patterned portion of the polysilane layer which has been once colored and dried has almost no silanol groups, it is difficult to be dyed with other dyes or pigments in the subsequent coloring step.
Therefore, the method of the present invention hardly causes the problem of color mixing.
When the dyeing method is used as the coloring method, it is preferable to sequentially perform the coloring from the dye having a high adsorption rate in order to ensure the prevention of color mixture of the coloring pattern. The size of the adsorption rate of the dye that can be used in the present invention is determined by silica gel chromatography. On the other hand, by using the electrodeposition method as a coloring method and as a color mixing prevention method when using a micelle electrolyte solution as a coloring solution, the oxidation potential of the pigment to be used is measured by voltammetry, and the pigment having a high oxidation potential is colored. Is mentioned.

<Color Filter> The color filter of the present invention uses three colorants containing dyes or pigments corresponding to the three primary colors of RGB in the method for forming a colored pattern including the above steps A) to D). It can be obtained by further forming a black matrix or a black stripe. The black matrix and the black stripe can be colored with a black dye or a black pigment as the fourth color following the RGB three primary colors. Alternatively, a transparent substrate in which the black matrix and the black stripes are previously patterned may be used.

<Thin Film Pattern Forming Method> In the thin film pattern forming method of the present invention, A ') a step of coating and drying the above-mentioned photosensitive resin composition on a substrate to form a photosensitive layer, B') the photosensitive layer A step of forming a latent image in a pattern by selectively exposing the layer, and C ') the exposed portion on which the latent image of the colored pattern is formed, a sol of a metal oxide containing no pigment or dye. It includes a step of dipping or coating.

A ′) step and B ′) step These two steps have the same contents as the A) step and B) step of the above-mentioned colored pattern forming method, respectively.

Step C ′) In this step, the exposed portion on which the patterned latent image is formed is immersed or coated in a sol of metal oxide. The sol of metal oxide used here is The difference from the step C) of the above-mentioned colored pattern forming method is that it contains no pigment or dye. As the sol of the metal oxide, those described in the sol-gel coloring method in step C) of the coloring pattern forming method can be used.

A pattern is formed on the exposed portion of the photosensitive material by applying or immersing the above exposed portion in a sol of metal oxide. It is considered that this is because, as described above, adsorption (gelation) occurs due to the interaction between the silanol groups generated in the exposed portion and the metal oxide sol particles.

When the metal oxide sol contains a functional portion or a functional compound, these portions or compounds are incorporated into the photosensitive layer as the metal oxide sol particles are adsorbed. A thin film having is obtained.

When the function expression for this adsorption is performed,
The following three ways are possible. First, if the metal oxide sol particles themselves contain functional atoms or functional functional groups,
The second is a case where a functional particulate material that can be adsorbed to the photosensitive layer coexists with the metal oxide sol particles, and the last is a case where a functional material that can dissolve in the metal oxide sol coexists. Of course, these two or more kinds may be combined to exhibit the function.

Examples of the functional atom include a fluorine atom and the like. Examples of the functional functional group include an alkyl group, which is a hydrophobic group, and a carboxyl group, a sulfo group, an acidic hydroxyl group, an amino group, which are groups having ion exchangeability. By forming a sol containing many of these functional atoms or functional functional groups and adsorbing it to the photosensitive layer, for example, when a fluorine atom is used, the water repellent portion is patterned on the photosensitive layer. You can

Examples of the functional particulate material include copper and silver particles. When silica sol is used as the metal oxide sol, these functional particulate materials are dispersed using silica sol, or once dispersed using a nonionic surfactant, they are mixed at the time of silica sol preparation. This allows the silica sol particles and the functional particulate material to coexist. In this case, the particle size of the functional particulate material needs to be 500 nm or less, preferably 200 nm or less. If the particle diameter exceeds 500 nm, the particles cannot be fixed because they cannot diffuse to the irradiated portion of the photosensitive layer even when immersed in the sol solution. This particle size can be measured by a usual centrifugal sedimentation method. When the silica sol particles and the functional particulate material coexist, it is generally considered that the silica sol particles are adsorbed on the surface of the functional particulate material. The adsorption of silica sol particles on the surface of the functional particles can be confirmed by measuring the zeta potential. For example, the zeta potential when dispersed using a nonionic surfactant stabilizes at -5 to -25 mV. It is considered that this is due to the presence of silanol groups on the surface of the functional particulate material due to the adsorption of silica sol. By adsorbing the thus-produced material on the photosensitive layer, copper or silver can be patterned and contained in the photosensitive layer.

On the other hand, as the functional material which can be dissolved in the metal oxide sol, a material which is soluble in water or alcohol and has a property of interacting with the silanol group of silica sol can be used. As the functional material, polyvinyl alcohol, polyethylene glycol, a polymer having an alcoholic hydroxyl group such as cellulose, poly (2-methyl-2-
Oxazoline), poly (N-vinylpyrrolidone), poly (N, N-
Polymers containing amide groups such as dimethyl acrylamide) are suitable. When these materials are contained in the photosensitive layer, the flexibility by gelling at a temperature at which the material does not decompose, and the gelation at a temperature at which the material decomposes,
Porosity and other functions can be imparted by utilizing the pores remaining after the material is decomposed.

The application can be carried out using an air spray, an airless spray, a roll coater, a curtain flow coater, a meniscus coater, or the like.
On the other hand, the dipping is carried out by filling the bath with a metal oxide sol solution in a tank having a size capable of completely dipping the photosensitive material. The coating method is preferable because the solution can be easily managed and the amount of the sol solution used can be small.

It is also possible to add an aprotic organic solvent such as acetonitrile, dioxane and tetrahydrofuran which swells the polysilane layer into the metal oxide sol in order to increase the adsorption rate and the color density. These are preferably 1 to 1 in the metal oxide sol.
It may be contained in an amount of 20% by weight. If the content of the solvent exceeds 20% by weight, partial re-dissolution of the polysilane layer may occur, which may cause disorder on the surface of the resulting patterned photosensitive material.

The patterned photosensitive material thus obtained is dried after removing the metal oxide sol solution. As a removing method, a method of washing with water, a method of blowing off with an air blow, or the like can be used.

Drying is generally preferably carried out at 100 ° C. or higher for 10 minutes to 2 hours, but the drying conditions can be changed within a range that does not adversely affect the substrate used and the functional material contained therein. For example, when a glass substrate is used and the metal oxide sol is silica sol, the organic substituent is eliminated by drying at 400 ° C. or higher to obtain a metal oxide thin film.

By the steps A ′) to C ′), as shown in FIG.
As shown in (3), a desired patterned thin film forming laminate 104 ′ is obtained. If unevenness is required on the glass surface like the pre-group of optical disk substrate, then
By exposing the entire surface as shown in (c) and decomposing and removing the remaining photosensitive layer, a patterned thin film having irregularities is obtained as shown in FIG. 2 (d). As a method of removing the unnecessary photosensitive layer, there are a method of volatilizing by heating and a method of removing using a solvent. When removing by heating, 1 above 200 ℃
Heating for 0-60 minutes is sufficient. In this case, the metal oxide sol particles do not have to have functionality.

By repeating the steps B ') to C') by changing the exposed portion and using a metal oxide sol solution having a different composition, it is possible to easily pattern thin films having different functions on the same substrate. Is possible.

[0094]

The present invention will be further described by the following examples, but the present invention is not limited thereto.

Preparation Example 1 Preparation of Linear Polysilane A 1000 ml flask equipped with a stirrer was charged with 400 ml of toluene and 13.3 g of sodium. The contents of this flask were heated to 111 ° C in a yellow room where ultraviolet rays were blocked,
Sodium was finely dispersed in toluene by high speed stirring. Phenylmethyldichlorosilane 51.6 here
Polymerization was performed by adding g and stirring for 3 hours.
Then, excess sodium was inactivated by adding ethanol to the obtained reaction mixture. After washing with water, the separated organic layer was put into ethanol to precipitate polysilane. The crude polysilane obtained was reprecipitated from ethanol three times to obtain a linear polymethylphenylsilane having a weight average molecular weight of 24,000.

Preparation Example 2 Preparation of network-like polysilane The same operation as in Preparation Example 1 was carried out except that the amount of phenylmethyldichlorosilane was changed from 51.6 g to 42.1 g, and 4.1 g of tetrachlorosilane was newly added. A network polymethylphenylsilane having a weight average molecular weight of 11,600 was obtained.

Example 1 Production of Photosensitive Resin Composition and Photosensitive Material Using the Same (1) 100 parts by weight of linear polysilane obtained in Preparation Example 1, TSR-1
65 (Methylphenyl methoxy silicone with a molecular weight of 930, manufactured by Toshiba Silicone) 10 parts by weight, TAZ-110 (2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5
-Triazine, manufactured by Midori Kagaku Co., Ltd.) and BTTB (3,
15 parts by weight of 3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, manufactured by NOF CORPORATION) was dissolved in 1215 parts by weight of toluene to obtain a photosensitive resin composition. The photosensitive resin composition was spin-coated on a quartz substrate so that the absorption at 335 nm in the ultraviolet region of polysilane was 1.5 in absorbance.
A photosensitive material was obtained.

Example 2 Production of Photosensitive Resin Composition and Photosensitive Material Using the Same, Part 2 The amount of TSR-165 was changed from 10 parts by weight to 30 parts by weight, and the amount of toluene was changed from 1215 parts to 1395 parts. Example 1 except that
The same operation as above was performed to obtain a photosensitive resin composition and a photosensitive material.

Example 3 Preparation of Photosensitive Resin Composition and Photosensitive Material Using the Same, Part 3 The amount of TSR-165 was changed from 10 parts by weight to 50 parts by weight, and the amount of toluene was changed from 1215 parts to 1615 parts. Example 1 except that
The same operation as above was performed to obtain a photosensitive resin composition and a photosensitive material.

Example 4 Production of Photosensitive Resin Composition and Photosensitive Material Using the Same Part 4 TSR-165 amount was changed from 10 parts by weight to 100 parts by weight and toluene amount was changed from 1215 parts to 2115 parts Example 1 except that
The same operation as above was performed to obtain a photosensitive resin composition and a photosensitive material.

Example 5 Production of Photosensitive Resin Composition and Photosensitive Material Using It 5 TSR-165 10 parts by weight of X-40-2171 (phenyl methoxy silicone having a molecular weight of 790, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 The same operation as in Example 1 was carried out except that parts by weight were used to obtain a photosensitive resin composition and a photosensitive material.

Example 6 Production of Photosensitive Resin Composition and Photosensitive Material Using the Same, Part 6 TSR-165 10 parts by weight instead of 10 parts by weight of KR-213 (methylphenyl methoxy silicone having a molecular weight of 640, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight The same operation as in Example 1 was carried out except that parts were used to obtain a photosensitive resin composition and a photosensitive material.

Comparative Example 1 100 parts by weight of the linear polysilane obtained in Preparation Example 1 was dissolved in 900 parts by weight of toluene, and a quartz substrate was used so that the absorption at 335 nm in the ultraviolet region of polysilane would be 1.5. A photosensitive material was obtained by spin coating on top.

Comparative Example 2 A photosensitive material was obtained in the same manner as in Example 1 except that TSR-165 was not used and the amount of toluene was changed from 1215 parts by weight to 1115 parts by weight.

Evaluation of Sensitivity of Photosensitive Material Using an ultra-high pressure mercury lamp CL-50-200A (500W) made by Nippon Batteries,
Measure the time until the absorbance at 335 nm of polysilane is 0.75, which is half the value before irradiation by irradiation with ultraviolet rays,
This was defined as sensitivity. A spectrophotometer MCPD-1000 manufactured by Otsuka Electronics was used for measuring the absorbance. The results are summarized in Table 1.

[0106]

[Table 1] Example Silicone Silicone amount Sensitivity (s) (parts by weight) Example 1 TSR-165 10 12 Example 2 TSR-165 30 10 Example 3 TSR-165 50 8 Example 4 TSR-165 100 6 Implementation Example 5 X-40-2171 50 6 Example 6 KR-213 50 5 Comparative Example 1 * ¹ − −60 Comparative Example 2 − − 15 * 1 Polysilane only

Example 7 Production of Photosensitive Resin Composition and Photosensitive Material Using the Same (7) 100 parts by weight of linear polysilane obtained in Preparation Example 1, TSR-1
65 (Methylphenyl methoxy silicone having a molecular weight of 930, manufactured by Toshiba Silicone) 50 parts by weight, TAZ-110 (2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine, 10 parts by weight, manufactured by Midori Kagaku, BTTB (3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone,
15 parts by weight of Nippon Oil & Fats and 3,3'-carbonylbis (7-
5 parts by weight of diethylaminocoumarin (manufactured by Kodak) was dissolved in 1620 parts by weight of tetrahydrofuran to obtain a photosensitive resin composition. This photosensitive resin composition was spin-coated on a quartz substrate so that the absorption of polysilane in the ultraviolet region at 335 nm was 1.5, and a photosensitive material was obtained. This photosensitive material is irradiated with ultraviolet rays, and the time until the absorbance of polysilane at 335 nm becomes 0.75, which is half the value before irradiation, is
It was 45 seconds. In addition, the ultraviolet irradiation uses the ultra-high pressure mercury lamp CL-50-200A (500W) made by Nippon Battery, and 440n by the filter.
The light less than m was cut. A spectrophotometer MCPD-1000 manufactured by Otsuka Electronics was used for the measurement of the absorbance.

Comparative Example 3 The same operation as in Example 3 was carried out except that TSR-165 was not used and the amount of tetrahydrofuran was changed from 1625 parts by weight to 1175 parts by weight. Of polysilane in this case
The time required for the absorbance at 335 nm to reach half the value before irradiation was 110 seconds.

Comparative Example 4 Except that TSR-165 and 3,3′-carbonylbis (7-diethylaminocoumarin) were not used and the amount of tetrahydrofuran was changed from 1625 parts by weight to 1130 parts by weight.
The same operation as in Example 3 was performed. In this case, the time required for the absorbance at 335 nm of polysilane to reach half the value before irradiation was 460 seconds.

The use of the silicone oil in the present invention was intended to compatibilize the polysilane with the photoradical generator and the oxidizing agent, but it was confirmed that the photoreactivity was improved by including the silicone oil. . It is presumed from the fact that the photoreaction of the polysilane in the solution is several times to several tens of times faster than that in the solid state. That is, the polysilane layer is softened by containing the silicone oil. It is considered that the reaction in the solid became closer to the reaction in the solution due to the softening, and the photoreactivity was increased.

Preparation Example 3 Preparation of Coloring Liquid Used in Sol-Gel Coloring Method 168 g of tetraethoxysilane, methyltriethoxysilane
84 g, ion-exchanged water 250 g and ethanol 96 g were put into a 1000 cc beaker, and 35% concentrated hydrochloric acid 1.92 g was added with stirring using a magnetic stirrer. When stirring was continued for 15 minutes while maintaining the liquid temperature at 20 ° C, a transparent and homogeneous silica sol was obtained. 56 g of this silica sol, 1 ion-exchanged water
39 g and 50 g of red AQ-866 (manufactured by Mikuni pigment), which is a nonionic pigment paste for color filters, were placed in a 300 cc beaker, stirred for 30 minutes, and then 40 g of ethanol was added to prepare a sol for red coloring.

Also, instead of red AQ-866, green
AQ-016 (manufactured by Mikuni dye), blue AQ-010 (manufactured by Mikuni dye) and black AQ-022 (manufactured by Mikuni dye) were used to prepare sols for green coloring, blue coloring and black coloring, respectively.

Preparation Example 4 Preparation of Coloring Liquid Used in Staining Method 2 g of Victoria Blue BH (basic dye manufactured by Hodogaya Chemical Co., Ltd.), 178 g of ion-exchanged water and 20 g of acetonitrile were mixed to prepare a blue staining liquid. Astrafloxin FF (basic dye manufactured by Hodogaya Chemical Co., Ltd.) (2 g), ion-exchanged water (178 g) and acetonitrile (20 g) were mixed to prepare a red dyeing solution. A green dyeing solution was prepared with 1 g of brilliant basic cyanine 6GH (basic dye manufactured by Hodogaya Chemical Co., Ltd.) and 1.4 g of yellow 7GLH (basic dye manufactured by Hodogaya Chemical Co., Ltd.).

It was confirmed by silica gel chromatography that the order of adsorption rates of the obtained three kinds of staining solutions was blue, red, and green.

Preparation Example 5 Preparation of Coloring Liquid Used in Electrodeposition Method CI Pigment Red 177 80 g, CI Pigment Yellow 83
A mixture of 20 g, 30 g of polycarboxylic acid surfactant Caribbon B (manufactured by Sanyo Kasei) and 300 g of ion-exchanged water was dispersed for 10 hours using a sand mill. Ion-exchanged water was added to the dispersion after pressure filtration to prepare a pigment concentration of 10%. Further, acetonitrile was added so that the content thereof would be 10% of the whole to prepare a red coloring electrodeposition solution. CI Pigment Green 36 80 g and CI Pigment Yellow 83 20 g as pigments for electrodeposition liquid for green coloring
Was prepared by the same procedure. In addition, CI Pigment Blue 15 80 g was used as the pigment for the blue coloring electrodeposition liquid.
And CI Pigment Violet 23 20 g were prepared by a similar procedure. Further, a black coloring electrodeposition liquid was prepared by the same procedure using CI Pigment Black 7 100 g as a pigment.

Preparation Example 6 Preparation of Coloring Liquid Used in Silane Coupling Coloring Method CI Pigment Red 177 80 g, CI Pigment Yellow 83
Using a sand mill, a mixture of 20 g, nonionic surfactant Nonipol 300 (manufactured by Sanyo Kasei) 30 g, silane coupling agent KBM-403 20 g, and ion-exchanged water 300 g was used with a sand mill.
Time dispersed. Ion-exchanged water was added to the dispersion after pressure filtration to prepare a pigment concentration of 3.5%. Further, acetonitrile was added so that its content was 10% of the whole, and then the pH was adjusted to 2.5 with hydrochloric acid to prepare a red coloring liquid. A green coloring solution was prepared by the same procedure, using CI Pigment Green 36 80 g and CI Pigment Yellow 83 20 g as pigments.

Also, the blue coloring liquid was used as a pigment with CI Pigment Blue 15 80 g and CI Pigment Violet 2
Prepared by a similar procedure using 3Og. In addition, CI pigment black 7 is used as a pigment with the black coloring liquid.
Prepared by the same procedure using 100 g.

Example 8 Production of Photosensitive Resin Composition for Forming Colored Pattern and Photosensitive Material Using the Same Part 1 100 parts by weight of network polymethylphenylsilane obtained in Preparation Example 2, TSR-165 (molecular weight 930 Methyl phenyl methoxy silicone, made by Toshiba Silicone) 50 parts by weight, TAZ
-110 (2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine, Midori Kagaku) 10 parts by weight, and BTTB (3,3 ', 4,4 15 parts by weight of'-tetra- (t-butylperoxycarbonyl) benzophenone, manufactured by NOF CORPORATION) was dissolved in 1575 parts by weight of toluene to obtain a photosensitive resin composition for forming a colored pattern. This photosensitive resin composition for forming a colored pattern was spin-coated on a 5 cm × 5 cm glass substrate for liquid crystal and dried at 80 ° C. for 10 minutes to obtain a photosensitive material having a film thickness of 2.0 μm.

Example 9 Production of Color Filter Using Sol-Gel Coloring Method A 90 μm × 90 μm color filter red pixel pattern was formed on the photosensitive material obtained in Example 8.
An inch-square negative mask was overlaid, and this laminate was exposed to ultraviolet rays having a light intensity of 0.2 J / cm ² using an ultrahigh pressure mercury lamp. After removing the negative mask, the filter material on which a latent image was formed was added to the colored sol solution for red obtained in Preparation Example 2
Soaked for a minute. Then, it was washed with water and dried at 100 ° C. for 10 minutes.

Next, instead of the negative mask used above,
A negative mask on which a blue pixel pattern of a color filter was formed was overlaid on the red pixels by 20 μm and exposed to light to form a latent image. After forming the latent image, the same operation as for red was performed using the colored sol for blue obtained in Preparation Example 3 to perform the second color coloring. Similarly, the negative color mask having the green pixel pattern of the color filter and the green colored sol obtained in Preparation Example 3 were used to perform the third color coloring. Finally, exposure was performed without using a negative mask, and the unexposed portion having a width of 20 μm existing between pixels of each color was exposed. Coloring was performed using the black coloring sol obtained in Preparation Example 3 to form a light-shielding film between pixels to obtain a color filter.

It was confirmed that the obtained color filter had no color mixture. In addition, the spectral transmittance of this color filter was measured using a spectrophotometer MCPD-1000 manufactured by Otsuka Electronics. R: 5% (wavelength 510 nm), G: 8% (wavelength 450 n
m), 7% (wavelength 650 nm), and B: 4% (wavelength 600 nm).

Comparative Example 5 A photosensitive material was obtained in the same manner as in Example 8 except that TSR-165 was not used and the amount of toluene was changed from 1575 parts by weight to 1115 parts by weight. A color filter was obtained by performing the same operation as in Example 9 except that the photosensitive material obtained here was used instead of the photosensitive material obtained in Example 8, but the coloring state was insufficient. It was The spectral transmittance of this color filter is R: 32% (wavelength 510nm), G: 3
6% (wavelength 450 nm) and B: 23% (wavelength 600 nm).

Example 10 Production of Photosensitive Material Containing Black Matrix The photosensitive resin composition for forming a colored pattern obtained in Example 8 was placed on a glass substrate for liquid crystal having a 5 cm × 5 cm metallic chromium light-shielding film. It was spin-coated and dried at 80 ° C. for 10 minutes to obtain a photosensitive material having a film thickness of 2.0 μm.

Example 11 Preparation of Photosensitive Material for Electrodeposition Method Instead of a glass substrate for liquid crystal having a metal chromium light-shielding film,
A photosensitive material was obtained in the same manner as in Example 10, except that the liquid crystal glass substrate with ITO was used.

Example 12 Production of Color Filter Using Staining Method On the photosensitive material obtained in Example 10, a 90 μm × 90 μm color filter blue pixel pattern was formed 3
An inch-square negative mask was overlaid, and this laminate was exposed to ultraviolet rays having a light intensity of 0.2 J / cm ² using an ultrahigh pressure mercury lamp. After removing the negative mask, the filter material on which the latent image was formed was immersed in the blue dyeing solution obtained in Preparation Example 4 for 2 minutes. Then, it was washed with water and dried at 100 ° C. for 10 minutes.

Next, instead of the negative mask used above,
A negative mask on which a red pixel pattern of a color filter was formed was overlapped with a blue pixel of 20 μm horizontally, and then exposed to form a latent image. After forming the latent image, the red dyeing solution obtained in Preparation Example 4 was used to perform the same operation as that for blue.
Coloring was performed. Similarly, a negative mask in which a green pixel pattern of the color filter was formed and the green dyeing solution obtained in Preparation Example 4 were used to perform the third color coloring to obtain a color filter. The spectral transmittance of this color filter is R: 6% (wavelength 510 nm), G: 8% (wavelength
450 nm), 7% (wavelength 650 nm), and B: 4% (wavelength 600 nm).

Example 14 Production of Color Filter Using Electrodeposition Method Red pixel pattern of 90 μm × 90 μm color filter was formed on the photosensitive material obtained in Example 11 3
An inch-square negative mask was overlaid, and this laminate was exposed to ultraviolet rays having a light intensity of 0.2 J / cm ² using an ultrahigh pressure mercury lamp. After removing the negative mask, the filter material on which a latent image was formed was dipped in the red coloring electrodeposition solution obtained in Preparation Example 5 and electrodeposited at a constant voltage of 50 V for 30 seconds. Then, it was washed with water and dried at 100 ° C. for 10 minutes.

Next, instead of the negative mask used above,
A negative mask on which a blue pixel pattern of a color filter was formed was overlaid on the red pixels by 20 μm and exposed to light to form a latent image. After the latent image was formed, the blue coloring electrodeposition solution obtained in Preparation Example 5 was used to carry out the same operation as for red to give a second color. Similarly, the negative color mask having the green pixel pattern of the color filter and the green coloring electrodeposition liquid obtained in Preparation Example 5 were used to perform the third coloring. Finally, exposure was performed without using a negative mask, and the unexposed portion having a width of 20 μm existing between pixels of each color was exposed. The black electrodeposition liquid obtained in Preparation Example 5 was used for electrodeposition to form a light-shielding film between pixels to obtain a color filter. The spectral transmittance of this color filter is R: 7% (wavelength 510 nm), G: 5% (wavelength
It was 450 nm), 4% (wavelength 650 nm), and B: 5% (wavelength 600 nm).

Example 15 Production of Color Filter Using Silane Coupling Method Instead of the sol for red coloring, green coloring, blue coloring and black coloring obtained in Preparation Example 3, obtained in Preparation Example 6. A color filter was obtained in the same manner as in Example 9 except that the obtained red, green, blue and black coloring liquids were used. The spectral transmittance of this color filter is R: 6% (wavelength 510 nm), G:
8% (wavelength 450nm), 7% (wavelength 650nm), B: 5% (wavelength 600nm)
nm).

Example 16 Application by Airless Spray Instead of dipping in a sol solution for 2 minutes, a wet film thickness of 50 is obtained.
A color filter was obtained by performing the same operations as in Example 9 except that the coating was performed using an airless spray so that the thickness became μm. This color filter exhibited the same performance as that obtained in Example 9.

Example 17 Coating with a doctor blade Instead of immersing in a sol solution for 2 minutes, a wet film thickness of 50
A color filter was obtained by performing the same operations as in Example 9 except that coating was performed using a doctor blade so that the thickness became μm. This color filter exhibited the same performance as that obtained in Example 9.

Preparation Example 7 Preparation of Silica Sol Used for Thin Film Pattern Forming Method 13 g of tetraethoxysilane, 20 g of ethanol, and 13 g of ion-exchanged water were placed in a 200 cc beaker and stirred with a magnetic stirrer while using 0.1% of 35% concentrated hydrochloric acid. g was added. After keeping the liquid temperature at 30 ° C. and stirring for 2 hours, 43 g of ion-exchanged water and 10 g of acetonitrile were added to obtain a silica sol.

Example 18 Thin Film Pattern Forming Method The photosensitive resin composition obtained in Example 3 was used to measure 5 cm in length × 5 in width.
A glass substrate having a size of cm × 0.11 cm was coated with a spin coater so that the dry film thickness was 2 μm. A quartz photomask was overlaid on the obtained thin film pattern forming laminate and exposed to ultraviolet rays having a light intensity of 0.2 J / cm ² . Preparation Example 7: Laminated body on which a latent image is formed after removing the photomask
It was immersed in the sol for 5 minutes. After dipping, wash with water and then at 200 ℃ for 3
A patterned thin film of silica gel was obtained by drying for 0 minutes. Further, this thin film pattern-formed laminate was irradiated with ultraviolet rays at a light amount of 0.2 J / cm ^{2 over} the entire surface without using a mask. When this was dried at 200 ° C. for 30 minutes, the photosensitive layer portion other than the silica gel pattern formed by the first exposure was volatilized and decomposed, and a concavo-convex pattern of a thin film of silica gel was formed on the glass substrate. Further, by calcining this at 600 ° C. for 30 minutes, this silica gel was changed to a glass of perfect silicon oxide. When measuring the uneven profile with a Japanese vacuum surface shape measuring device Dectak 3ST, the height is 0.5 μm.
It was confirmed that the pregrooves were formed. As described above, according to the thin film pattern forming method, it becomes possible to process fine irregularities on the glass surface without using a stamper method or an etching method.

Comparative Example 6 The procedure of Example 18 was repeated using the 10 wt% toluene solution of the polysilane obtained in Preparation Example 1 instead of the photosensitive resin composition obtained in Example 3. However, a sufficient uneven pattern could not be obtained.

[0135]

EFFECTS OF THE INVENTION The photosensitive resin composition of the present invention has dramatically improved photoreactivity as compared with the conventional polysilane type. Therefore, the exposure time can be shortened and the productivity of color filters and the like can be improved.

[Brief description of drawings]

FIG. 1 is a process drawing schematically showing a method for forming a colored pattern of the present invention.

FIG. 2 is a process drawing schematically showing another method for forming a colored pattern of the present invention.

[Explanation of symbols]

 101 ... Substrate, 102 ... Polysilane layer, 103 ... Mask.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G03F 7/26 521 G03F 7/26 521 (72) Inventor Takeshi Imamura 19 Ikedanaka-cho, Neyagawa-shi, Osaka No. 17 In Japan Paint Co., Ltd. (72) Inventor Iwao Sumiyoshi No. 19 Ikedanaka-cho, Neyagawa City, Osaka Prefecture No. 17 In Japan Paint Co., Ltd.

Claims (15)

[Claims] 1. A) a polysilane soluble in an organic solvent and having a weight average molecular weight of 10,000 or more b) a photoradical generator and an oxidizer c) a formula: ## STR1 ## [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are an aliphatic hydrocarbon group which may be substituted with a halogen or glycidyl group having 1 to 10 carbon atoms, and 6 to 6 carbon atoms. 12 aromatic hydrocarbon groups optionally substituted by halogen, having 1 to 1 carbon atoms
A group selected from the group consisting of 8 alkoxy groups,
They may be the same or different. m and n are integers and satisfy m + n ≧ 1. ] A photosensitive resin composition containing a silicone oil having a structure shown by d) an organic solvent. 2. The photosensitive resin composition according to claim 1, further comprising a dye. 3. The photosensitive resin composition according to claim 1, wherein at least two of R ^{1 to} R ⁶ of the silicone oil are alkoxy groups having 1 to 8 carbon atoms. 4. The photosensitive resin composition according to claim 1, wherein the polysilane is a network polysilane. 5. A photosensitive material obtained by applying the photosensitive resin composition according to claim 1 on a substrate and drying it. 6. A) a step of applying a photosensitive resin composition according to claim 1 on a substrate and drying it to form a photosensitive layer, B) a colored pattern by selectively exposing the photosensitive layer. Forming a latent image of the above, and C) a step of coloring the exposed portion on which the latent image of the colored pattern is formed with a coloring liquid containing a dye or a pigment; 7. A coloring step which is performed at least once in the same manner as the coloring step except that D) a latent image having a different coloring pattern is formed on the photosensitive layer and a different dye or pigment is used. A method for forming a colored pattern, which further comprises: 8. The method for forming a colored pattern according to claim 6, wherein the coloring step (C) includes a method of applying the photosensitive layer to the coloring liquid. 9. The coloring pattern forming method according to claim 6, wherein the coloring step (C) includes a method of immersing the coloring liquid in the photosensitive layer. 10. In the coloring step (C), a transparent electrode is used as a transparent substrate, and an electrodepositable solution containing a dye or a pigment is used as a coloring liquid to carry out coloring by electrodeposition. The method for forming a colored pattern according to claim 1. 11. The method for forming a colored pattern according to claim 6, wherein the coloring liquid is a sol of a metal oxide containing a dye or a pigment. 12. The method for forming a colored pattern according to claim 6, wherein the coloring liquid is an aqueous solution of a dye. 13. The method for forming a colored pattern according to claim 6, wherein the coloring liquid contains a silane coupling agent and a surfactant. 14. A color filter obtained by the method for forming a colored pattern according to claim 7. 15. A ') a step of applying a photosensitive resin composition according to claim 1 on a substrate and drying it to form a photosensitive layer, B') selectively exposing the photosensitive layer, A step of forming a patterned latent image; and C ') a step of immersing or applying the exposed portion having the patterned latent image formed thereon in a sol of a metal oxide containing no pigment or dye. Pattern formation method.