JPH05323607A - Aqueous colored resist material, method for developing the same and production of color filter - Google Patents

Abstract

PURPOSE:To provide a colored resist material contg. a photosetting resin, pigment powder and a dispersant and using water as a solvent in production, application and development. CONSTITUTION:This colored resist material contains a photosetting resin, pigment powder and a dispersant. The photosetting resin is a copolymer consisting of 2-hydroxyethyl methacrylate, (meth)acrylamide and dialkylaminopropyl (meth) acrylamide or further contg. unsatd. carboxylic acid and having >=70wt.% 2- hydroxyethyl methacrylate content. The dispersant is partially saponified polyvinyl acetate. An aq. soln. contg. 2-6C carboxylic acid which is solid at ordinary temp. is used as a developer. A surfactant and/or acetylene glycol may further be added to the developer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous colored resist material, a developing method thereof and a color filter manufacturing method. More specifically, according to the present invention, a mask is overlaid on the coated surface of the colored photosensitive resin, and light is irradiated,
The present invention relates to a water-based colored resist material for exposing a colored image after curing an irradiated portion and then removing an uncured portion, a developing method using such a colored resist material, and a method for producing a color filter by this developing method. It is a thing.

[0002]

2. Description of the Related Art Resist materials, also called photosensitive resins, are widely used in making today's electronic machinery. Among them, the colored resist material is said to be necessary for making a color filter for a liquid crystal display device, a color separation filter for printing, or the like.

The above-mentioned color filter is manufactured by providing a large number of fine regions having different hues on a transparent substrate in close proximity to each other. In order to closely provide a number of such fine areas of different colors, apply a photosensitive coating, that is, a resist material on a transparent substrate for each color, and contact a mask that makes only the areas to be colored transparent, Irradiate
A difference in solubility is caused between a portion irradiated with light and a portion not irradiated with light, and then this is brought into contact with a developing solution to remove the easily soluble portion, thereby forming a resin film only in a region to be colored, It depends on the method.

Previously, a method of later dyeing the resin film thus formed was used for displaying an image. However, it is not only difficult to dye the resin film after it has been formed, but a special dye must be used to color the resin film later, and it is not possible to color it later. There is a drawback that it is difficult to deepen the coloring. Especially, the resin film is originally 1-2
It must be as thin as a micron, and it is preferred that it be as thin as possible.
It was extremely difficult to deeply color such a thin resin film later.

Therefore, the pigment is dispersed in the resist material from the beginning without dyeing the film after curing.
A method of curing this has come to be used. The method is described in, for example, JP-A-60-129738. This publication uses a mixture of an aldehyde containing a stilbazolinium group and polyvinyl alcohol as a photocurable resin, and a pigment is dispersed in this mixture, which is then applied onto a substrate to form a photocurable resin. It teaches that a colored image is obtained by partially irradiating the resin to insolubilize it.

The method taught by Japanese Patent Laid-Open No. 129738/1985 has the advantage that water can be used as a solvent for the photocurable resin, in addition to the advantage that coloring afterwards is unnecessary and coloring is possible in a dark color. have. The fact that water can be used brings about great advantages in that not only the cost of the solvent is low, but also the working environment is improved and the solvent recovery device is not required. However, in this method, since the mixed solvent of water and isopropyl alcohol is used for developing the cured resin, the advantage that water can be used as the solvent is halved.

Further, Japanese Patent Laid-Open No. 64-35417 discloses
It has been proposed to use a composition composed of a photosensitive resin having an acryloyl group and a pigment as a resist material.
This proposal teaches that a compound such as triethylene glycol diacrylate is used as a photosensitive resin, to which a polymerization initiator such as anthraquinone and a fine powder pigment are added to form a colored resist material. However, this proposal has a drawback that an organic solvent must be used when the colored resist material is applied to the substrate.

Further, Japanese Laid-Open Patent Publication No. 1-200353 discloses
A polymer solution having tetravalent covalent nitrogen, a pigment,
A photocurable coloring composition comprising a photosensitive cross-linking agent is disclosed. The polymer solution disclosed in this publication has an advantage that water can be used as a solvent and water can also be used for development after curing. However, this solution has a drawback that it is difficult to disperse the pigment therein, and the adhesiveness to the glass substrate is poor, and the solution has a high temperature such as 20 ° C.
It had the drawback of being colored brown when heated above 0 ° C.

[0009]

As described above, the colored resist materials proposed so far are manufactured by the following process.
It is often necessary to use an organic solvent either in the process of applying this or in the process of developing it, and even if it is rarely proposed to use an organic solvent, it lacks the performance as a colored resist material. It was a thing. Therefore, the present inventor has attempted to provide a colored resist material which can be used without using an organic solvent and has sufficient performance.
That is, not only water can be used as a solvent when manufacturing a colored resist material, but also water can be used as a solvent when applying this, and it is also developed when developing after being cured by irradiation with light. An attempt was made to provide a colored resist material which can use water as a liquid and which can easily disperse a pigment and can be colored in a dark color.

[0010]

The present inventor searched what should be used as a photocurable resin. For that purpose, copolymers with various compositions were prepared and the experiment using this as a resist material was repeated. As a result, they have found that it is suitable to use a water-soluble acrylic polymer as a raw material for the resist material. Particularly, a copolymer obtained by copolymerizing at least three kinds of monomers of 2-hydroxyethyl methacrylate, (meth) acrylamide, and dialkylaminopropyl (meth) acrylamide, in which 2-hydroxyethyl methacrylate is It has been found that when a copolymer that accounts for 70% by weight or more of the copolymer is used as a resist material, one satisfying the above problems can be obtained.

Particularly, when the above-mentioned three kinds of monomers are copolymerized, a carboxyl group-containing monomer such as acrylic acid is present therein as a fourth component, and at least four kinds of monomers are copolymerized. It has been found that, when polymerized and 2-hydroxyethyl methacrylate accounts for 70% by weight or more of the copolymer, the copolymer becomes more suitable as a resist material.

When the above-mentioned copolymer is used as a resist material, the saponification degree is 70-for dispersing the pigment.
It has been found that it is necessary to use 85 mol% of partially saponified polyvinyl acetate (X) as a dispersant and disperse the fine powder pigment with this dispersant in order to obtain a good colored resist material.

Further, when developing the above aqueous colored resist material, it was found that an aqueous solution of carboxylic acid having 2 to 6 carbon atoms which is solid at room temperature, such as citric acid, can be used as a developing solution. .. In particular, when a developer prepared by adding a surfactant to the above-mentioned carboxylic acid aqueous solution is used, the surfactant works in cooperation with the carboxylic acid to obtain a clear image in which the uncured colored resist material is completely removed. It was found that Further, when acetylene glycol is further added to this developer, not only the surface of both the image portion and the non-image portion is cleaned and the image becomes clearer, but also a large amount of air bubbles generated in the developing process are erased. It has been found that development becomes easy. The present invention has been completed based on such knowledge.

The present invention is a copolymer (V) comprising (a) 2-hydroxyethyl methacrylate, (b) acrylamide or methacrylamide, and (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide. Then, the copolymer (V) in which 2-hydroxyethyl methacrylate (a) accounts for 70% by weight or more is used as a resist material, and a partially saponified polyvinyl acetate (with a saponification degree of 70-85 mol% ( The main point is to provide an aqueous colored resist material obtained by adding a fine powdery pigment (Y) dispersed in water in (X) and a photoreactivity imparting agent (Z).

The present invention also provides the above (a) and (b).
A copolymer (W) obtained by further adding an unsaturated carboxylic acid to the three monomers of (c) and copolymerizing the four monomers.
And a copolymer (W) in which 2-hydroxyethyl methacrylate (a) accounts for 70% by weight or more.
As a resist material, and an aqueous colored resist material obtained by adding a fine powdery pigment (Y) dispersed in water with the partially saponified polyvinyl acetate (X) and a photoreactivity imparting agent (Z) to the resist material. It is what

Furthermore, the present invention also includes a method of developing using the above-mentioned aqueous colored resist material. The method uses the above-mentioned copolymer (V or W) as a resist material,
An aqueous colored resist material obtained by adding a fine powdery pigment (Y) dispersed in water with partially saponified polyvinyl acetate (X) and a photoreactivity imparting agent (Z) to this is used on a substrate. After coating and covering the coated surface with a mask to irradiate light to partially cure the colored resist material, the uncured resist material is removed with a carboxylic acid-containing aqueous solution that has 2 to 6 carbon atoms and is solid at room temperature. Then, the colored resist material is developed.

Further, the present invention is characterized in that, in the above-mentioned developing method, a surfactant is added to a carboxylic acid-containing aqueous solution used as a developing solution, thereby removing the uncured resist material and developing. The method of developing a colored resist material is also included. Furthermore, the present invention is characterized by adding acetylene glycol together with a surfactant to a carboxylic acid-containing aqueous solution used as a developing solution, and removing the uncured resist material by the resulting developing solution to develop the colored resist. It also includes the method of developing the material.

The aqueous colored resist material according to the present invention contains, as a resist material, a copolymer (V) composed of at least three kinds of acrylic monomers. Here, the three kinds of acrylic monomers are (a) 2-hydroxyethyl methacrylate, (b) acrylamide or methacrylamide, (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide. Among the copolymers, 2-hydroxyethyl methacrylate of (a) above is required to account for 70% by weight or more.

Further, the aqueous colored resist material according to the present invention comprises a copolymer (W) containing an unsaturated carboxylic acid as a fourth component in addition to the above three kinds of acrylic monomers as a resist material. When it does, it becomes a better colored resist material.

The 2-hydroxyethyl methacrylate of (a) above is

[0021]

[Chemical 1] Is a compound represented by. This compound is a water-soluble compound and has the property of easily polymerizing in water.

The above-mentioned (b) acrylamide or methacrylamide has the general formula

[0023]

[Chemical 2] Is a compound represented by. Here, R ₁ is H or CH ₃ . This compound is also water-soluble and has the property of easily polymerizing in water.

The above-mentioned (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide has the general formula

[0025]

[Chemical 3] Is a compound represented by. Where R ₂ is the above (Equation 2)
Is the same as H or CH ₃ , and Q is

[0026]

[Chemical 4] R ₃ represents CH ₃ or C ₂ H _5, and the compound represented by the formula (3) is also water-soluble and has a property of polymerizing in water.

In the present invention, the acrylic monomers belonging to the above (a), (b) and (c) are essential, but in addition to them, a small amount of another water-soluble monomer is contained as the fourth component. The copolymer can be used as the resist material. Among the fourth components, the unsaturated carboxylic acid (d) exerts a particularly remarkable effect. Here, the unsaturated carboxylic acid (d) is
General formula

[0028]

[Chemical 5] Is a compound represented by. In the formula, R ₄ is H or a carboxyl group, and R ₅ is hydrogen or a methyl group. That is, unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, and fumaric acid. All of these acids are water-soluble and have the property of polymerizing in water.

In order to copolymerize the above-mentioned acrylic monomers (a), (b) and (c) or the unsaturated carboxylic acid (d) added thereto, these monomers can be copolymerized. Polymerize by dissolving in a suitable solvent. As the solvent, an organic solvent such as methyl cellosolve or dimethylformamide can be used, but water is preferably used. A polymerization initiator is used for the copolymerization, and as the polymerization initiator for the copolymerization in water, ammonium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutylamine) hydrochloride, 2, 2'-azobis (2-amidinopropane) hydrochloride, 4,
4'-azobis (4-cyanopentanoic acid),
2,2′-azobis {2-methyl-N [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like can be used.

The copolymerization ratio required in the copolymer is
It is that 2-hydroxyethyl methacrylate of (a) accounts for 70% by weight or more in the copolymer. Therefore, the total amount of the monomers (b), (c) and (d) is 30% by weight or less. The reason for this is that if the amount of the monomer (a) is less than 70% by weight, the water-solubility, photocurability and adhesive strength of the resulting copolymer to the substrate will decrease.

When the amount of the monomer (a) is more than 90% by weight in the copolymer, the water solubility of the copolymer is lowered. Therefore, an organic solvent is added to water during the polymerization. It is necessary to add acetic acid. However, when acetic acid is added, there is a drawback that acetic acid emits a strong odor and the working environment is deteriorated.

Among the acrylic monomers, (b) acrylamide or methacrylamide is 5 to 2 in the copolymer.
It is preferable to make up 0% by weight. Among them, it is particularly preferable to occupy 10 to 15% by weight. The reason for this is that when the amount of the monomer (b) is less than 5% by weight, the developability when the copolymer is irradiated with light to be cured becomes poor, and it is difficult to disperse the pigment in the copolymer. Because it will be. On the contrary, if the amount of the monomer (b) is more than 20% by weight, the heat resistance and chemical resistance of the obtained copolymer after curing will be deteriorated.

Among the acrylic monomers, (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide is one of the copolymers.
Occupy 20% by weight, especially 3 to 1
It preferably accounts for 0% by weight. The reason is (c)
If the amount of the monomer is less than 1% by weight, it becomes difficult to disperse the pigment in the copolymer, and the water solubility is also decreased. On the contrary, if it is more than 20% by weight, the copolymer is cured. It is because the heat resistance and the chemical resistance after the heat treatment are deteriorated.

The resist material used in the present invention is, in addition to the above acrylic monomers of (a), (b) and (c),
It may be copolymerized by including other monomer as the fourth component. The amount of the other monomer as the fourth component must be 5% by weight or less of the copolymer. The reason is that if the amount is 5% by weight or less, the fourth component usually rarely largely changes the properties of the copolymer.

When the carboxylic acid represented by the formula (5) is used as the fourth component, the obtained copolymer is particularly suitable as an aqueous colored resist material. That is, the copolymer in which the carboxylic acid represented by (Formula 5) is introduced is
This is because it is easy to disperse the fine powder pigment in it, and when it is heated, it brings about an advantage that it is difficult to be colored brown or the like.

The carboxylic acid represented by the formula (5) preferably accounts for 0.1-5% by weight of the copolymer,
Especially, it is preferable to occupy 0.5 to 3% by weight. The reason is that when the carboxylic acid of the formula (5) is less than 0.1% by weight, the advantage of easily dispersing the pigment in the copolymer does not appear, and conversely, when it is more than 5% by weight. , The water solubility of the copolymer decreases, and it is difficult to remove the uncured product with an aqueous solution, especially after removing it with an aqueous solution of carboxylic acid after curing by irradiating light. Is.

If the molecular weight of the copolymer is too small, it will be
The resolution is poor. On the contrary, if the molecular weight is too large,
After curing by irradiating light, it becomes difficult to dissolve the uncured portion and remove it from the cured portion. Therefore, the copolymer has a weight average molecular weight of 10,000 to 200,00.
A value of 0 is suitable.

In the present invention, both organic pigments and inorganic pigments can be used. However, when a color filter is to be produced, it is preferable to use an organic pigment having a wide selection of transmitted light spectrum. As organic pigments,
Various materials such as phthalocyanine type, azo type, perinone type, anthraquinone type, quinacridone type, indanthrone type, dioxazine type and thioindigo type can be used.

The pigment is dispersed as a fine powder in the copolymer. The fine powder preferably has a particle size of 0.5 micron or less. The reason is that if the size of the pigment particles is larger than the wavelength of the color light, the transmitted light will appear cloudy.

To disperse the finely divided pigment in the copolymer, the fine pigment powder is previously dispersed in an aqueous solution containing a dispersant, and this dispersion is added to and mixed with the aqueous solution. Is preferred. A turbo mixer, a ball mill, an attritor, a beads mill, or the like is used for mixing. As the dispersant, it is common to use a water-soluble polymer and a surfactant. As the water-soluble polymer, partially saponified polyvinyl acetate, polyvinyl alcohol in which a cationic group is partially introduced, polyvinylpyrrolidone, etc. are generally used. In the present invention, the degree of saponification is particularly 70-85 mol%. Select and use polyvinyl acetate.

In general, when partially saponified polyvinyl acetate is used as a dispersant, it is required that the degree of saponification is within the range of 50 to 90 mol%. There is. However, in the present invention, those having a saponification degree within the range of 70 to 85 mol% are particularly selected and used. The reason is that when a saponification degree of 70 mol% or less is used, not only is the cloud point low, the restrictions on the operating temperature increase, but also after formation of a copolymer film and irradiation with light, This is because it was confirmed that the development becomes difficult when the cured copolymer is removed with an aqueous solution and the development is attempted. It was also confirmed that when the saponification degree exceeds 85 mol%, the storage stability of the copolymer solution in which the pigment is dispersed is deteriorated.

The partially saponified polyvinyl acetate used as the dispersant is generally required to have a weight average molecular weight of 20,000 to 100,000. However, in the present invention, it is preferable to select and use one having a weight average molecular weight of 40,000 to 100,000. The reason is that when a partially saponified polyvinyl acetate having a weight average molecular weight of less than 40,000 is used, the compatibility between the partially saponified polyvinyl acetate and the copolymer becomes poor, and thus the storage stability of the pigment dispersion becomes poor. The reason is that the efficiency of photocrosslinking by the diazo resin becomes poor.

When a surfactant is used as a dispersant for dispersing the pigment, a nonionic or ionic dispersant is used as the dispersant when the copolymer coexisting therein is made of only acrylic monomers. However, when the copolymer is made of an acrylic monomer and a carboxylic acid, a nonionic one must be used as the dispersant. The reason is that since the copolymer contains a cationic component, the anionic activator is not so preferable, and the nonionic one is better.

The amount of the pigment added to the copolymer (V or W) is 50 to 200 parts by weight based on 100 parts by weight of the copolymer. When the amount of the pigment is too small, of course, the degree of coloring is insufficient, and when the amount is too large, the photosensitivity is decreased and
Since the film-forming ability is reduced due to the lack of the copolymer, it becomes difficult to form a fine image.

In the present invention, a water-soluble diazo resin or a water-soluble polyfunctional aromatic azide compound is used as a substance which imparts photoreactivity to the copolymer (V or W). Diazo resin,
It is a resin made by adding formaldehyde to an aromatic diazonium compound and condensing it. Examples of the aromatic diazonium compound include p-diazodiphenylamine, 2,5-dimethoxy-4-p-tolylmercaptobenzenediazonium and 2,5-dimethoxy-4-.
Such as morpholinobenzenediazonium.

The polyfunctional aromatic azide compound is an aromatic compound having two or more azide groups in one molecule. For example, 4,4'-diazidostilbene-
Sodium 2,2'-disulfonate, 2,6-bis (4
-Azidobenzal) acetone-2-sulfonic acid, 2,
6-bis (4-azidobenzal) cyclohexanone-
2,2'-disulfonic acid and the like. The water-soluble diazo resin or water-soluble polyfunctional aromatic azide compound is preferably used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the copolymer.

The aqueous colored resist material according to the present invention may be prepared by adding a finely divided pigment dispersion liquid prepared by dispersing the above partially saponified polyvinyl acetate in water to the above copolymer (V or W) aqueous solution. It is made by mixing and mixing with a photoreactivity-imparting agent to dissolve it. The water-based colored resist material thus produced is used by coating it on glass or another substrate with a spin coater, a roll coater or the like.

In the method for developing a colored resist material according to the present invention, after applying the colored resist material as described above,
A mask is overlaid on the surface of the coated object, the surface is covered with a mask, and light is irradiated from above to cure the part exposed to the light,
After making the unexposed part uncured, the coated product is contacted with a developing solution to wash the coated product with the developing solution to remove the uncured copolymer, leaving only the cured part a colored part. To develop. The operations within the range described here have been performed conventionally.

The developing method of the colored resist material according to the present invention is particularly different in the composition of the developing solution used therein. That is, it means that the developing solution uses water as a solvent, and that the developing solution contains a carboxylic acid having 2 to 6 carbon atoms and solid at room temperature.
In addition, the developer may further contain a surfactant. On top of that, the developer may additionally contain acetylene glycol.

The carboxylic acid which can be contained in the developer is a solid having 2 to 6 carbon atoms at room temperature. The reason for limiting the number of carbon atoms to 2 to 6 is that it was confirmed that those having such a range generally dissolve well in water, and that the aqueous solution dissolves the above copolymer well. Further, the reason why the solid material is limited to the solid material at room temperature is that the solid material does not volatilize to give off a pungent odor and the working environment is not deteriorated.

The concentration of the carboxylic acid contained in the developing solution needs to be changed depending on the method of bringing the developing solution into contact with the coating material of the copolymer. For example, when developing by a dipping method such as immersing a coated material in a developing solution and shaking it, it is necessary to increase the concentration of the developing solution, but it is necessary to spray the developing solution onto the coated material. With the spray method, the concentration of the developer can be reduced. Generally speaking, the concentration of carboxylic acid in the developer is preferably 0.01 to 3% by weight.

Examples of carboxylic acids that can be used are malic acid, citric acid, oxalic acid, tartaric acid, malonic acid, adipic acid, maleic acid, fumaric acid, succinic acid and the like.

As the surfactant added to the developing solution, it is preferable to use anionic or nonionic surfactants. Among them, it is particularly preferable to use an aromatic anion type. Examples of preferred surfactants include anionic ones such as sodium dodecylbenzene sulfonate, sodium isopropylnaphthalene sulfonate, and sodium diphenyl ether disulfonate, and examples of nonionic ones include polyoxyethylene nonylphenyl ether. , Polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and the like.

When an aqueous solution in which only the above-mentioned surfactant is dissolved is used as a developer, the uncured portion is hardly dissolved. When an aqueous solution in which only the above-mentioned carboxylic acid is dissolved is used as a developing solution, most of the uncured portion is dissolved but some insoluble matter remains, which appears as image stains. On the other hand, when a developing solution in which a surfactant and a carboxylic acid coexist is used, the uncured portion is peeled off in a scaly form and development can be easily performed. In this respect, the combined use of the carboxylic acid and the surfactant brings about a remarkable effect.

When acetylene glycol is further added to the above-mentioned developing solution, due to the strong penetrating action and washing action of acetylene glycol, very small amounts of pigment fine particles and uncured resin film adhered are completely removed, and an image is obtained. The surface of both the part and the non-image part becomes clean, and the image becomes clearer. At the same time, the defoaming action of acetylene glycol enables easy and reliable development as described below.

Generally, when developing industrially, a spray method is adopted. This is because the spray method allows the use of a low-concentration developing solution and provides an image with less surface roughness. However, when developing by a spray method, if a surfactant is included in the developer, the developer generates a large amount of bubbles, which makes it difficult to develop and also reduces the cleaning effect, resulting in a clear image. Will not be obtained. This becomes remarkable especially when an anionic surface active agent is used. In order to prevent this, an antifoaming agent has been used so far. However, when an antifoaming agent is used, it adheres to and remains on the surface of the image, which causes a problem such as blurring of the image. For example,
When a silicone compound was used as the defoaming agent, such an adverse effect occurred.

On the other hand, when acetylene glycol is added to the above-mentioned developing solution, the acetylene glycol exerts a defoaming function in addition to a washing function, so that the developing solution can be prevented from foaming during the developing process. Therefore, the development becomes easy and surely possible.

Acetylene glycol is

[0059]

[Chemical 6] However, it also includes a derivative in which the hydroxyl group therein is etherified by the addition of ethylene oxide. Therefore, the acetylene glycol that can be used in the present invention has the general formula

[0060]

[Chemical 7] Is a compound represented by. Here, m and n are 0 or a positive integer, and m + n is 30 or less. Among these, it is preferable that m + n is 3 or more. It is preferable to add acetylene glycol to a concentration of 0.01 to 1% by weight in the developing solution.

The preferred specific addition ratios of the solid carboxylic acid, the surfactant and the acetylene glycol differ depending on the developing method. For example, in the method of vibrating the coated material in the developing solution to develop, the concentration of each of the above additives in the developing solution is increased, but in the spray method, the concentration is decreased. However, the total concentration range including all of them is as follows: 0.1 to 1 part by weight of solid carboxylic acid, 0.1 to 1 part by weight of surfactant, and 100 to 100 parts by weight of developer, and acetylene. The amount of glycol is preferably 0.002 to 0.1 part by weight.

[0062]

According to the present invention, the above-mentioned (a),
Since the copolymer of (b) and (c) consisting of the acrylic monomer is used and the monomer of (a) occupies 70% by weight or more in the copolymer, water is used as a solvent. A copolymer can be easily prepared by adding a polymerization initiator to and heating. The copolymer thus prepared has photocurability and can be applied as an aqueous solution. Moreover, since this polymer contains a hydroxyl group, an amide group, a substituted amino group, or a quaternary ammonium group, and further contains a carboxyl group in some cases,
Since it has a high affinity for the pigment, it is possible to easily disperse the pigment in this copolymer aqueous solution and to include a large amount of the pigment. Therefore, it is possible to easily make the coloring deep and dark by just applying it, and thus to reduce the thickness of the coating film. This also applies to the copolymers obtained by adding the unsaturated carboxylic acid (d) to the acrylic monomers (a), (b) and (c).

Further, according to the present invention, since the partially saponified polyvinyl acetate having a saponification degree of 70 to 85 mol% is used for dispersing the pigment in the above copolymer, the pigment is stable in water for a long period of time. Therefore, the colored dispersion has an advantage that the life of the colored dispersion is long.
Further, since this dispersion contains a photoreactivity-imparting agent, the photoreactivity-imparting agent acts as a curing agent for the copolymer upon irradiation with light, and thus can be used as a resist material. ing.

Moreover, since this copolymer can be produced using water as a solvent as described above, not only the cost of the solvent is low but also the risk of fire is eliminated when the colored resist material is produced. Benefits include better environment and no need for solvent recovery equipment. The colored resist material according to the present invention brings the above-mentioned benefits.

According to the developing method of the present invention,
In addition to the advantage derived from the colored resist material itself as described above, the advantage that water can be used as a solvent is further increased. That is, according to the method of the present invention, water can be used as a solvent even when the colored resist material is applied, and water can be used as a developer when developing after irradiation with light. Can be left unused, thus improving the working environment as described above,
The benefits such as the need for solvent recovery equipment are even greater.

Furthermore, since an aqueous solution containing a carboxylic acid having 2 to 6 carbon atoms and being solid at room temperature is used during development, the working environment during development is good, and development is easy and reliable. Therefore, the image becomes clearer. Specifically, carboxylic acid has 2 carbon atoms.
Since it is limited to 6 or less, it is generally easy to dissolve in water and the uncured colored resist material can be easily removed. Further, since the carboxylic acid is limited to solid at room temperature, Volatilization of carboxylic acid is small and therefore the working environment is improved. Further, since the above-mentioned carboxylic acid is used, the cured coating film has good thermal stability, and the coating film is less colored even when heated, and therefore a clear image is provided. The method of the present invention provides the above-mentioned benefits during development.

Further, in the developing method according to the present invention, when the surfactant is added to the developing solution together with the above-mentioned carboxylic acid, it becomes easier to remove the uncured colored resist material, which is excellent. An image is obtained. That is, when each of the carboxylic acid and the surfactant is used alone as a developing solution, the uncured colored resist material is only gradually dissolved. The colored resist material peels off like a scale and can be easily developed,
Moreover, the image thus obtained becomes clear and stable.

Further, in the developing method according to the present invention, when acetylene glycol is added to the developer together with the carboxylic acid and the surfactant, the surface of both the image portion and the non-image portion becomes more clean and the image becomes clear. .. Further, despite the addition of the surfactant to the developing solution, the developing solution does not foam in the course of development, and therefore the developing operation is facilitated and the developing can be carried out efficiently. The present invention brings such a great benefit.

[0069]

EXAMPLES Specific examples of the present invention will be described below with reference to examples. In the following, simply parts or% means parts by weight or% by weight.

[0070]

Example 1 This example is an example using a copolymer consisting of acrylic monomers only.

[0071]

[Preparation of colored resist material] The following monomer aqueous solution was added dropwise to a flask containing 200 parts of 10% acetic acid water over 4 hours while thoroughly stirring at 70 ° C while passing nitrogen gas. 2-hydroxyethylmethacrylate 85 parts methacrylamide 10 dimethylaminopropylmethacrylamide 5 polymerization initiator (Wako Pure Chemical Industries, Ltd. trade name V-50) 1 acetic acid 20 water 180 Then, stirring was continued at 70 ° C. for 4 hours for further reaction. ..
25 parts of water was added to 75 parts of this reaction solution, and the mixture was filtered through a filter having a pore size of 0.2 μm to obtain an aqueous solution as a photocurable copolymer. When the composition was examined by infrared absorption spectrum, it contained 84.2% by weight of 2-hydroxyethyl methacrylate.

To make a separate pigment dispersion, the following formulation was made. 10% aqueous solution of partially saponified polyvinyl acetate (Gosenol KM-11, manufactured by Nippon Kasei Chemical Co., Ltd.) having a degree of saponification of 78 mol% and an average degree of polymerization of 1000 100 parts polyoxyethylene monooleyl ether 5 blue pigment (phthalocyanine blue) 20 zirconia The above formulation was placed in a bead mill filled with beads and stirred for 2 hours. After the bubbles disappeared, the mixture was filtered with a filter having a pore size of 1 μm to obtain a pigment dispersion.

Aqueous solution 1 of the photocurable copolymer obtained above
15 parts of pigment dispersion was added to 0 parts, and 35 parts of water was added.
Further, 0.15 part of the water-soluble diazo resin was added, and the resulting mixture was gently stirred in the mixer. Thus, the colored resist material according to the present invention was obtained.

[0074]

[Image preparation] The above-mentioned colored resist material was poured onto a glass plate, spin-coated at 1000 rpm, dried at 70 ° C for 3 minutes, covered with a photomask, and irradiated with ultraviolet rays of 100 mJ / cm ² from above with a high-pressure mercury lamp. did.

After that, it was immersed in a developing solution and rocked at 30 ° C. for 3 minutes to develop. As the developer, an aqueous solution of 1 part citric acid and 99 parts deionized water was used. When washed with water and dried, a blue transparent image having a film thickness of 0.6 μm was obtained. In this image, both a concave image and a convex image having a line width of 10 μm were clearly formed.

[0075]

Example 2

[Preparation of Colored Resist Material] In this Example, a colored resist material was prepared in the same manner as in Example 1 except that the following monomer mixture was used to prepare the copolymer in Example 1. made. 2-Hydroxyethyl methacrylate 80 parts Methacrylamide 4 dimethylaminopropyl acrylamide 6 Dimethyl acrylamide 6 The composition of the obtained copolymer was examined by infrared absorption spectrum. As a result, the copolymer was found to have 2-hydroxyethyl methacrylate of 79.5 wt. % Included.

[0076]

[Image Producing] In this example, an image was obtained by the same processing as in Example 1 except that the composition of the developing solution in Example 1 was changed to the following and the developing operation was changed as follows.

As a developing solution, DL-malic acid 0.05
Part, an aqueous solution of 100 parts of deionized water was used. As the developing operation, the above developing solution was heated to 30 ° C. and sprayed for 2 minutes for development.

As a result, an image of almost the same quality as in Example 1 was obtained.

[0079]

Example 3 This example is an example using a copolymer composed of an acrylic monomer and an unsaturated carboxylic acid.

[0080]

[Preparation of colored resist material] 30 parts acetic acid, 17 deionized water
Pass the nitrogen gas into a flask containing 0 parts at 80 ° C.
The following monomer aqueous solution was added dropwise over 4 hours with thorough stirring. 2-hydroxyethyl acrylate 85 parts methacrylamide 10 dimethylaminopropyl methacrylamide 4 acrylic acid 1 polymerization initiator [4,4′-azobis (4-cyanopentanoic acid)] 1 acetic acid 30 deionized water 170 and then 80 ° C. The reaction was continued for 4 hours with stirring.
To 60 parts of this reaction solution was added 40 parts of deionized water, and the pore size was 0.
The aqueous solution obtained by filtering with a 2 μm filter was used as a photocurable copolymer. When the obtained copolymer was examined by infrared absorption spectrum, the copolymer contained 84.2% by weight of 2-hydroxyethyl acrylate.

To make a separate pigment dispersion, the following formulation was made. Partially saponified vinyl acetate having a saponification degree of 78 mol% and an average degree of polymerization of 1000 (Nippon Gosei Kagaku KK, Gohsenol KM-11) 6% aqueous solution 50 parts Polyoxyethylene oleyl ether (HLB20) 0.5 Blue pigment (phthalocyanine blue) 6 The above mixture was put in a bead mill and stirred for 2 hours, and then coarse particles were removed by centrifugation to obtain a pigment dispersion.

Aqueous solution 4 of the photocurable copolymer obtained above
To 0 parts, add 100 parts of pigment dispersion and add 3 parts of deionized water.
4 parts and 10% diazo resin aqueous solution (Shinko Giken, D
-013) 6 parts and the resulting mixture was slowly stirred in a mixer for 2 hours to obtain a colored resist material according to the present invention.

[0083]

[Image Preparation] The above colored resist material was poured onto a glass plate, spin-coated at 1000 rpm and dried to obtain a coating film having a film thickness of 0.7 μm. A photomask for resolution test is placed on this coating film, and 80 mJ /
Irradiated with UV of cm ² .

After that, it was immersed in a developing solution, shaken for 2 minutes, then pulled up and washed with deionized water. As the developing solution, an aqueous solution containing 1.5 parts of malic acid, 1.5 parts of a surfactant (Perex NBL manufactured by Kao Corporation), and 97 parts of deionized water was used. At the time of development, the uncured portion was peeled off in a scale in the developer, and the uncured portion was easily removed. The image thus developed had an image in which a concave image and a convex image having a line width of 10 μm were clearly distinguishable, and no stain was found on the concave portion.

[0085]

Example 4 In this example, a colored resist material was spin-coated on a glass surface under exactly the same conditions as in Example 3, irradiated with ultraviolet rays, and then only the developing step was changed.

As a developing solution, 0.02 part of citric acid, 0.02 part of a surfactant (Perex SSH manufactured by Kao Corporation),
An aqueous solution consisting of 100 parts of deionized water was used. The developing operation was carried out by spraying a developing solution at 30 ° C. for 2 minutes. At the time of development, the uncured portion was peeled off in a scale in the developer, and the uncured portion was easily removed. The image thus obtained was clear and good with the same quality as in Example 3.

[0087]

Example 5 In this example, the copolymer obtained in Example 1 was used, to which a red pigment dispersion, a green pigment dispersion,
And blue pigment dispersion were added separately, and these were separately coated on a glass plate to form the above-mentioned three colored images as separate layers to prepare a color filter. The details are as follows.

A mixture of chromophthal red and disazo yellow is used as the red pigment, a mixture of phthalocyanine chloride and disazo yellow is used as the green pigment, and a mixture of phthalocyanine blue and oxazine violet is used as the blue pigment. Using.

A green resist material was obtained in exactly the same manner as in Example 1 except that the above green pigment was used instead of the blue pigment phthalocyanine blue used in Example 1. This green resist material is poured onto a glass plate having a diameter of 70 mm, and spin coated at 800 rpm for 90 seconds,
It was dried at 70 ° C. for 3 minutes. After that, pixel size 80x80
A photo mask having a size of 10 μm and a pixel size of 10 μm was overlaid, and ultraviolet rays of 500 mJ / cm ² were irradiated using a contact aligner (SUSS MJB 3HP).

Then, a developing solution at 25 ° C. (Perex N
It was immersed in an aqueous solution containing 1% BL and 1% malic acid) and shaken for 2 minutes. It was washed with water and dried at 100 ° C. for 10 minutes to obtain a green transparent image having a film thickness of 0.70 μm.

Further, except that the above-mentioned blue pigment was used instead of the green pigment, a blue resist material was prepared in exactly the same manner as the case where the green resist material was prepared, and the blue resist material obtained above was used as the green resist material. It was poured on the transparent image, spin coated and dried in the same way as for the green resist material,
Only the exposure dose was changed to 100 mJ / cm ² , and the film thickness was 0.1.
A 60 μm blue transparent image was obtained.

Furthermore, except that the above-mentioned red pigment was used instead of the green pigment, a red resist material was prepared in exactly the same manner as when the green resist material was prepared, and this red resist material was obtained by the above-mentioned blue method. It was poured onto a transparent image, spin-coated and dried in the same manner as in the case of the green resist material, but the exposure amount was changed to 300 mJ / cm ² , and a red transparent image with a film thickness of 0.68 was obtained. Thus, a glass plate provided with three color transparent images was used as a color filter.

This color filter had a good transmitted light spectrum and luminous intensity. Attach a cellophane adhesive tape with a width of 24 mm on the image surface of this filter,
The test of peeling in the 0 degree direction was repeated 5 times, but the image did not peel off. This confirmed that the image was firmly attached to the glass plate.

A protective coating material (polyimide coating material PSI-G-463 manufactured by Chisso Co., Ltd.) is formed on the image.
0) and spin coating at 1000 rpm,
It was baked at 180 ° C. Furthermore, 200 ℃ on this surface
When ITO was sputtered to a thickness of about 1500 angstroms, no abnormality was found. From this, it was confirmed that the obtained product was excellent as a color filter.

[0095]

Example 6 In this example, the ultraviolet irradiation product obtained in Example 1 was treated with a developer containing acetylene glycol to obtain an image. The details are as follows.

As the developing solution, an aqueous solution having the following composition was used. DL-malic acid 0.1 part Surfactant [Kao Corp., Perex NBL] 0.1 Acetylene glycol (Nisshin Chemical Industry Co., Ltd. 0.01 Surfynol 104, compound represented by the above formula 6) Yes, it is a compound corresponding to m = n = 0 in formula 7.) Deionized water 100

The colored resist material obtained in Example 1 was poured onto a glass plate and spin-coated in exactly the same manner as in Example 1,
After drying and irradiating with ultraviolet rays, the developing solution is pressurized to 2
It was developed by spraying at Kg / cm ² for 2 minutes.

Compared with the case of Example 1, in Example 1, the developing solution foamed in the developing process, the number of bubbles increased with the passage of time, and finally the bubbles overflowed from the developing tank. In the case of Example 6, the developing solution did not foam, so that the development was easy. In addition, this Example 6
Compared with the developer obtained in Example 1, the developed product obtained in Example 1 had better image breakage, no stain was observed on the glass surface of the non-image area, and the image surface was more glossy. It became a certain aspect.

[0099]

Example 7 In this example, a colored resist material was spin-coated on a glass surface under the same conditions as in Example 3, irradiated with ultraviolet rays, and then only the developing step was changed.

As the developing solution, an aqueous solution containing carboxylic acid, a surfactant and acetylene glycol was used.
More specifically, 1 part of DL-malic acid as a developer, 1 part of a surfactant (manufactured by Kao Corporation, Perex NBL), acetylene glycol (manufactured by Nissin Chemical Co., Surfynol 104, a compound represented by the above formula 6). Which is a compound corresponding to m = n = 0 in the formula 7.) 0.1 part, deionized water 97.9
Part of an aqueous solution was used to immerse the ultraviolet irradiation product in this developing solution, shake it for 2 minutes, then pull it up and wash with deionized water.

When the image after development was observed with a microscope,
Concave lines and convex lines having a line width of 10 μm were clearly formed, and no trace of the colored resist material remained on the uncured portion was observed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical location C09D 129/04 PEU 6904-4J 133/14 PFY 7921-4J G02B 5/20 101 7348-2K G03F 7 / 004 505

Claims (6)

[Claims] 1. A copolymer (V) comprising (a) 2-hydroxyethyl methacrylate, (b) acrylamide or methacrylamide, and (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide, Among them, the copolymer (V) in which 2-hydroxyethyl methacrylate (a) accounts for 70% by weight or more is used as a resist material, and the saponification degree is 70%.
An aqueous colored resist material comprising a fine powdery pigment (Y) dispersed in water using -85 mol% partially saponified polyvinyl acetate (X) and a photoreactivity imparting agent (Z). 2. (a) 2-hydroxyethyl methacrylate, (b) acrylamide or methacrylamide, (c) dialkylaminopropyl acrylamide or dialkylaminopropyl methacrylamide,
(D) A copolymer (W) containing an unsaturated carboxylic acid, in which the 2-hydroxyethyl methacrylate (a) accounts for 70% by weight or more, is used as a resist material. An aqueous coloring obtained by adding a fine powdery pigment (Y) dispersed in water with a partially saponified polyvinyl acetate (X) having a saponification degree of 70-85 mol% and a photoreactivity imparting agent (Z) Resist material. 3. A partially saponified polyacetic acid having a saponification degree of 70-85 mol% as a resist material, wherein the copolymer (V) according to claim 1 or the copolymer (W) according to claim 2 is used as a resist material. A fine powdery pigment (Y) dispersed in water with vinyl (X),
An aqueous colored resist material containing a photoreactivity-imparting agent (Z) is used, which is applied to the surface of a substrate, the coated surface is covered with a mask, and light is irradiated to partially cure the colored resist material. After that, the uncured resist material is removed by an aqueous solution containing a carboxylic acid having 2 to 6 carbon atoms and which is solid at room temperature, and a method for developing a colored resist material. 4. A partially saponified polyacetic acid having a saponification degree of 70-85 mol% as a resist material, wherein the copolymer (V) according to claim 1 or the copolymer (W) according to claim 2 is used as a resist material. A fine powdery pigment (Y) dispersed in water with vinyl (X),
An aqueous colored resist material containing a photoreactivity-imparting agent (Z) was used, and this was applied to the surface of the substrate, the coated surface was covered with a mask, and light was irradiated to partially cure the colored resist material. After that, the uncured resist material is removed with an aqueous solution containing a surfactant and a carboxylic acid having 2 to 6 carbon atoms and which is solid at room temperature, to develop a colored resist material. 5. A partially saponified polyacetic acid having a saponification degree of 70-85 mol% as a resist material, which is the copolymer (V) according to claim 1 or the copolymer (W) according to claim 2. A fine powdery pigment (Y) dispersed in water with vinyl (X),
An aqueous colored resist material containing a photoreactivity-imparting agent (Z) was used, and this was applied to the surface of the substrate, the coated surface was covered with a mask, and light was irradiated to partially cure the colored resist material. After that, the uncured resist material is removed with an aqueous solution containing a surfactant, a carboxylic acid having 2 to 6 carbon atoms and being solid at room temperature, and acetylene glycol. .. 6. The method of developing according to any one of claims 3 to 5, wherein a red color on a glass substrate,
A method for producing a color filter, which comprises successively forming green and blue resist material layers.