JP3109868B2 - Photocurable coloring composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition which is cured by light irradiation. This coloring composition is a coloring composition useful for producing, for example, a color filter for a liquid crystal display device, a color separation filter for printing, and the like.

[0002]

2. Description of the Related Art A resin which forms a film by being cured by light irradiation is known as a photocurable resin. After the photo-curable resin is applied, put a mask on it,
The mask is provided with a portion that transmits light and a portion that does not transmit light in advance, and light is irradiated from above the mask to cure the resin portion irradiated with the light, and the uncured portion remaining in the portion that does not transmit light Is used to remove the resin and form a resin film in a desired shape. As a film, a colorless, transparent and rigid one is desirable, and a photocurable resin that forms such a film is required.

[0003] It is known to produce colored images using photocurable resins. In order to form a colored image, a method of first curing a photocurable resin and then coloring the resin was used. The method is described in, for example, JP-A-58-199342. The publication teaches the use of a special acrylic copolymer as the photocurable resin.
The special copolymer has the general formula

[0004]

Embedded image And a monomer represented by the general formula

[0005]

Embedded image Or general formula

[0006]

Embedded image Is a binary copolymer obtained by copolymerizing a monomer represented by the following formula: The teaching teaches adding a diazo compound or azide compound to the binary copolymer to form a photocurable resin. Here, X is O or NH, Y is an acid group, R ₆ and R ₇ are hydrogen, a methyl group or an ethyl group, n is an integer of 1 to 3, R ₈ is a hydrogen or methyl group, and R ₉ is a carbon atom. It is said that two or three alkylene groups, R ₁₀ , R ₁₁ , and R ₁₂ represent hydrogen or an alkyl group having 1 to 4 carbon atoms.

In Japanese Patent Application Laid-Open No. 58-199342, as described above, the resin is colored after curing. That is,
Dissolve the above-mentioned photocurable resin in a solvent and apply it on the target object, put a mask on the application surface and shine light, cure the light-exposed parts, and cure the light-exposed parts. The film was left uncured, and the uncured portion was removed with a solvent to obtain a film, which was later colored with a dye. However, it is complicated to color the film after forming it. In addition, a special dye must be used to color the film, and the color must be darkened to form a color filter. Therefore, in order to dye a film having a thickness of, for example, about 2 microns to a deep color, for example, an optical density of 2 or more, the proportion of the compound of the formula (5) or (6) must be considerably increased. However, when the ratio is increased, the coating itself tends to be thermally decomposed, and when exposed to a high temperature, discoloration occurs due to the thermal decomposition, and the dye is discolored by the action of the decomposition product, resulting in inconvenience.

Therefore, a method has emerged in which a pigment is dispersed in a photocurable resin from the beginning instead of coloring the film with a dye after curing, and the pigment is cured. The method is described in, for example, JP-A-60-129938. This method is based on the principle that a mixture of an aldehyde having a styrylpyridinium group and polyvinyl alcohol is used as a photocurable resin, and a polyvinyl acetal compound is generated from the mixture to form a film. In this method, the pigment fine powder is dispersed in the above mixture to form a colored paint, and this paint is applied. Then, as described above, a mask is placed on the application surface, and light is irradiated to irradiate the light-irradiated portion. This is a method of curing, washing the uncured portion with water, and leaving a cured portion to obtain a colored film.

This method has the disadvantage that it is difficult to uniformly disperse the pigment in the polyvinyl acetal having a styrylpyridinium group, and it is therefore difficult to prepare a coating material itself. Further, since this polymer has a property close to that of polyvinyl alcohol, when the coating film of this paint is treated at a high temperature, it tends to turn brown or peel off from the substrate.

[0010] Japanese Patent Application Laid-Open No. 64-35417 discloses
It has been proposed to use a composition comprising a photosensitive resin having an acryloyl group and a pigment as a paint to form a colored image. This proposal is to make a paint by adding a polymerization initiator such as anthraquinone and a fine powder of pigment to a photosensitive resin such as triethylene glycol diacrylate, and put a mask on the coating surface of this paint, and shine light. Irradiate to partially cure the resin, remove the uncured portion with a solvent and develop,
This is a method of creating a colored image.

This method is harmful to the health of workers, may cause a fire, and requires special attention to waste liquid treatment, since an organic solvent must be used to make the paint. Had the disadvantage of having to do so. Further, the photosensitive resin having an acryloyl group,
In general, the polymerization reaction is easily inhibited by oxygen, so it is necessary to take special measures such as covering the coated surface with a polyvinyl alcohol film in order to avoid the influence of oxygen when irradiating light. Not so.

Japanese Patent Application Laid-Open No. 1-200353 discloses that
A photocurable colored composition comprising a polymer solution having a tetravalent covalent nitrogen, a dye compound, and a radiation-sensitive crosslinking agent is disclosed. In this case, the polymer having a tetravalent covalent nitrogen is represented by the general formula

[0013]

Embedded image It is said to have been obtained by polymerization of the monomer represented by Here, R ₁₃ is hydrogen or a methyl group, and R ₁₄ is 2
The valence organic group, Z, is an oxygen atom or an imino group.
Therefore, the monomer of the formula (8) is almost the same as the compound of the above (formula 7).

The polymer obtained from the monomer of the formula (8) taught by JP-A-1-200353 is difficult to disperse a dye compound, that is, a pigment, has poor adhesion to a glass substrate, and has a particularly high temperature. When heated to 200 ° C. or more, there was a disadvantage that the material became brown.

Japanese Patent Application Laid-Open (JP-A) No. 1-200353 discloses that the compound of the formula (8) is copolymerized with another unsaturated compound, conscious of the fact that the polymer of the compound of the formula (8) has difficulty in solubility. Mention that you may let them. In this case, copolymerization partners include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, esters such as methyl acrylate and ethyl methacrylate, vinyl aromatic compounds such as styrene and vinyl naphthalene, and N-vinylpyrrolidone. Examples include a wide range of compounds such as vinyl nitrogen-containing compounds such as 4-vinylpyridine, and it is described that only one of them may be used or two or more of them may be mixed and copolymerized. I have. However, what changes in the copolymerized properties other than solubility,
No confirmation has been made.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to provide a photocurable colored composition which eliminates the above-mentioned disadvantages of the conventional method. That is, both the photosensitive solution and the developing solution are photocurable resins in which water can be used as a solvent, and it is easy to disperse the fine powder of the pigment therein, and can be colored deeply with curing. The object is to provide a photocurable composition which adheres firmly to a glass substrate or the like and forms a transparent thin insoluble film.

[0017]

The inventor of the present invention has sought to achieve the above object by improving a photocurable resin. That is, a new photocurable resin is made, and a fine powder pigment and a photoreactivity imparting agent that have been used so far are added to this,
Attempts have been made to provide new compositions and thereby solve the above-mentioned problems.

Here, a new photocurable resin provided by the present inventors has a general formula

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

It is a copolymer produced by copolymerization of four kinds of monomers represented by the following formula. This copolymer has the property of being water-soluble. In the formula, n represents 1 or 2,
R ₁ , R ₃ and R ₄ are all hydrogen or a methyl group;
R ₂ is hydrogen or a carboxyl group, and X represents an ethylene group or a propylene group.

The above copolymers are unique in that they are water-soluble. Specifically, in general, a binary copolymer obtained by copolymerizing a monomer having a hydroxyl group (Formula 1) and a monomer having a carboxyl group (Formula 3) is However, when the terpolymer is obtained by copolymerizing a small amount of an amino group-containing monomer represented by the formula (4) into a terpolymer, the obtained terpolymer is Leads to water solubility. When dimethylacrylamide represented by the formula (2) is further copolymerized there, the obtained quaternary copolymer further increases water solubility and affinity for the pigment. Further, in order to obtain a stable pigment dispersion, it is desirable to disperse the pigment in advance with another water-soluble polymer (and a surfactant) and mix the pigment with the above copolymer. In this case, partially saponified polyvinyl acetate gives the best results in consideration of not only dispersibility but also photosensitivity. As described above, vinyl alcohol-based polymers have poor thermal stability and discoloration at high temperatures is remarkable, but the colored film obtained from the above copolymer, pigment and photoreactive agent almost discolors unexpectedly. Turned out not to be. The present invention has been completed based on the discovery of such facts.

(Summary of the Invention) The present invention relates to a water-soluble copolymer obtained by copolymerizing four types of monomers represented by the formulas (1) to (4), The gist of the present invention is a photocurable colored composition obtained by adding a photoreactivity imparting agent.

(Explanation of each requirement) The coloring composition according to the present invention is obtained by copolymerizing four kinds of monomers represented by (Formula 1), (Formula 2), (Formula 3) and (Formula 4). And a water-soluble copolymer (hereinafter, simply referred to as a copolymer). Among them, the monomer represented by (Formula 1) is, for example, 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate.

The monomer represented by the formula (2) is only dimethylacrylamide.

The monomers represented by the formula (3) are acrylic acid, methacrylic acid, maleic acid and fumaric acid. Among them, acrylic acid is most preferable from the viewpoint of water solubility.

The monomer represented by the formula (4) includes dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminoethylmethacrylamide,
Diethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, and diethylaminopropyl methacrylamide.

In order to copolymerize the monomers represented by the above (Formula 1), (Formula 2), (Formula 3) and (Formula 4), these monomers are dissolved in an appropriate solvent. And polymerize. As a solvent, an organic solvent such as methyl cellosolve or dimethylformamide can be used.
% Of acetic acid. Although a polymerization initiator is used for copolymerization, as a polymerization initiator for copolymerization in water, ammonium persulfate,
2,2'-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2'-azobis (2-amidinopropane) hydrochloride,
4'-azobis (4-cyanopentanoic acid), 2,2'-azobis {2-methyl-N [1,1-
Bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like.

Preferred copolymerization ratios of the monomers represented by the formulas (1) to (4) are as follows. First (Equation 1)
With respect to the monomer of the formula (5), this monomer is 5% in the copolymer.
When the content is 0% by weight or less, the photocurability of the photoreactivity imparting agent is reduced, and when the content is 80% by weight or more, the water solubility of the copolymer itself is reduced. Therefore, the monomer of the formula (1) preferably accounts for 50 to 80% by weight, more preferably 70 to 80% by weight in the copolymer.

Next, regarding the monomer of the formula (2),
If this monomer is less than 1% by weight in the copolymer, the effect is poor. Conversely, if it is more than 20% by weight, the hygroscopicity of the copolymer increases, and the strength of the film obtained from the copolymer decreases. descend. For this reason, the monomer of the formula (2) preferably accounts for 1 to 20% by weight in the copolymer, more preferably 5 to 16% by weight.

Further, the monomer of the formula (3) is effective in that the ratio of the pigment that can be added to the copolymer can be increased, and thus the thickness of the colored film can be reduced. However, the monomer of the formula (3) is contained in the copolymer in an amount of 0.1.
If the content is less than 1% by weight, the effect is poor. If the content is more than 3% by weight, the water solubility of the copolymer is reduced. Therefore,
The monomer of the formula (3) is preferably used in an amount of 0.1 to 3% by weight, particularly preferably 0.5 to 2% by weight.

Finally, the monomer of the formula (4) has a complementary relationship to the monomer of the formula (2). A good copolymer can be obtained by adding only a small amount of the monomer (a). When the monomer of the formula (4) is less than 1% by weight, its effect is poor, and when it is more than 10% by weight, the thermal stability of the copolymer decreases. For this reason, the monomer of the formula (4) is preferably contained in the copolymer in an amount of 1 to 5% by weight, more preferably 2 to 4% by weight.

The above copolymer may contain other monomers as optional components. Other monomers include acrylamide, methacrylamide, N-vinylpyrrolidone, diacetone acrylamide, tetrahydrofurfuryl acrylate, acrylamidoethyltrimethylammonium chloride, acrylamidoethyltriethylammonium chloride, acrylamidopropyltrimethylammonium chloride, acrylamidopropyltriethylammonium chloride Methacrylamidoethyltrimethylammonium chloride and methacrylamidoethyltriethylammonium chloride.

It is desirable to use methacrylamide among the optional components. Methacrylamide is water-soluble in nature, but it has a moderate hydrophobicity.
Even if the copolymer obtained by adding this is heat-treated at a high temperature,
This is because discoloration and coloring are less likely to occur, and rather, the degree of crosslinking is improved and the strength as a film is increased. The amount of methacrylamide added can be greater than that of the monomers represented by the formulas (2) to (4).
It can be.

The copolymerization of the monomers of the formulas (1) to (4) is carried out as follows. First, an aqueous acetic acid solution in which the monomers of the formulas (1) to (4) and the polymerization initiator are uniformly dissolved is prepared, and then the solution is added dropwise to a reactor containing water or acetic acid water while reacting. The vessel is heated and maintained at a suitable temperature to effect copolymerization. The temperature at this time varies depending on the type of the polymerization initiator, but is usually in the range of 70 to 90 ° C. Usually, the dropping is performed over several hours, and the temperature is maintained at the above temperature for several hours after the dropping to complete the copolymerization.

If the molecular weight of the copolymer thus obtained is too small, the resolution will be poor when it is used as a color filter. On the other hand, if the molecular weight is too large, it is difficult to dissolve the uncured portion and remove it from the cured portion after irradiating with light and curing. Therefore, the copolymer has a molecular weight of 10,10 in weight average molecular weight.
Suitably it is between 000 and 200,000.

In the present invention, any of organic pigments and inorganic pigments can be used. However, when it is used to make a color filter, it is preferable to use an organic pigment having a wide selection of transmitted light spectrum. Examples of organic pigments include phthalocyanine, condensed azo, perylene, anthraquinone, quinacridone, indanthrone, dioxazine, azo lake, benzimidazolone,
Various materials such as quinophthalones can be used.

The pigment is dispersed in the copolymer as a fine powder. As a fine powder, the size of the pigment particles will look turbid if they are larger than the wavelength of light of that color,
Preferably, the average particle size is less than 0.2 microns.
In order to disperse the pigment, it is preferable to previously disperse the pigment fine powder in an aqueous solution containing a dispersant, and to add and disperse the dispersion into an aqueous solution of a copolymer. A turbo mixer, a ball mill, an attritor, a bead mill, or the like is used to make a dispersion of the pigment fine powder.

As the dispersant used for dispersing the pigment, a surfactant and a water-soluble polymer are preferable. Among the water-soluble polymers, polyvinylpyrrolidone or vinylpyrrolidone / vinyl acetate copolymer well disperses the above-mentioned pigment, but in the composition according to the present invention, when a coating film is formed using this dispersant, The transparency of the obtained coating film may be poor or the color tone may change. In contrast, when a vinyl alcohol-based polymer is used as a dispersant, a composition having excellent pigment dispersibility and more excellent photoreactivity with a diazo resin than a vinylpyrrolidone-based polymer can be obtained. Can be

Particularly preferred vinyl alcohol-based dispersants are, for example, the following. Saponification degree 70-90
%, Is a partially saponified polyvinyl acetate having a molecular weight of 40,000 to 100,000. In addition, carboxylic acid or sulfonic acid derivatives of polyvinyl alcohol also have good pigment dispersibility, but they have the disadvantage of coloring when heated at high temperatures.

When the above-mentioned partially saponified polyvinyl acetate is used, its use amount is 10 to 200% by weight based on the pigment.
And The reason is that if the content is less than 10% by weight, the effect as a protective colloid is insufficient, and if it is more than 200 parts by weight, brown coloring is remarkably exhibited when heated to 200 ° C. or more. Among them, the amount of the partially saponified polyvinyl acetate is preferably 20 to 100% by weight based on the pigment.

In dispersing the pigment, a surfactant can be used alone as a dispersant as described above, but it is preferable to use the surfactant together with a water-soluble polymer. Among the surfactants, it is preferable to use a nonionic one.
Preferred surfactants are, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether and the like.

When a surfactant is used for dispersing the pigment, the amount of the surfactant is preferably 0.5 to 50% by weight based on the weight of the pigment. The reason is that at 0.5% by weight or less,
Because it is not possible to disperse the pigment sufficiently well,
On the other hand, when the content is 50% by weight or more, the film obtained from the composition becomes tacky and the stability of the image is reduced.

The pigment dispersed as described above is added to the copolymer. In this case, the pigment is added in an amount of 50 to 3 parts per 100 parts by weight of the copolymer.
00 parts by weight. In general, if the amount of the pigment is small, the degree of coloring is naturally insufficient, and if the amount is too large, on the other hand, the photosensitivity is reduced, and the film forming ability is reduced due to the lack of the resin, so that it is difficult to form a fine image. Become. However, the copolymer used in the present invention can form a fine image by increasing the amount of the pigment added. In the present invention, good results are obtained by using about 200 parts by weight of the pigment with respect to 100 parts by weight of the copolymer.

In the present invention, a water-soluble diazo resin or a water-soluble polyfunctional aromatic azide compound is used as a photoreactivity imparting agent for the copolymer. A diazo resin is a resin produced by adding and condensing formaldehyde to an aromatic diazonium compound. Examples of the aromatic diazonium compound include p-diazodiphenylaluminum and 2.5.
-Dimethoxy-4-p-tolylmercaptobenzenediazonium, 2.5-dimethoxy-4-morpholinobenzenediazonium and the like.

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
-Azidobenzar) acetone-2 sulfonic acid, 2,6
-Bis (4-azidobenzal) cyclohexanone-
2,2'-disulfonic acid, 2,6-bis (4-azidobenzal) acetone-2,2'-disulfonic acid and the like. These water-soluble diazo resins or water-soluble polyfunctional aromatic azide compounds are used in an amount of 5 to 30 parts by weight per 100 parts by weight of the copolymer.
It is preferred to use parts by weight.

The composition according to the present invention is usually used as an aqueous solution. To that end, an aqueous dispersion of the pigment fine powder is added to the aqueous solution of the copolymer as described above, and the mixture is stirred well and then mixed, and thereafter, photoreactivity such as a water-soluble diazo resin or a polyfunctional aromatic azide compound is imparted. Add the agent and stir well to dissolve. The aqueous solution thus obtained can be easily applied to glass or other substrates by a spin coater or a roll coater.

[0049]

According to the present invention, since a copolymer comprising the monomers of the formulas (1) to (4) is used, water is used as a solvent, a polymerization initiator is added thereto, and the mixture is heated.
Copolymers can be made easily. The copolymer thus produced has photocurability, can be obtained as an aqueous solution, and can easily disperse the fine powder pigment. Therefore, it can be used as it is as a photocurable paint. Therefore, in this case, there is no disadvantage or complexity due to the use of the organic solvent.
Further, since the composition of the present invention is added with a photoreactivity imparting agent such as a water-soluble diazo resin or a water-soluble polyfunctional aromatic azide compound, the photoreactivity imparting agent is irradiated with light to form the copolymer. Acts as a hardener to form a strong film. Furthermore, since this copolymer contains a hydroxyl group, a carboxyl group, and a substituted amino group, it has a high affinity for the pigment, and therefore,
Many pigments can be included, with which a densely colored film can be produced at once. Therefore, since the film can be made thin, a transparent electrode can be provided under the color filter layer, which is advantageous in the LCD manufacturing process. A protective coat layer is provided so that the color filter does not directly contact the liquid crystal.
When a high level of flatness is required as in the N-mode, the thin film thickness of the color filter is a great advantage. In general, a film which has been photocrosslinked with a diazo resin causes significant coloring at high temperatures, but the composition of the present invention has less coloring than expected. In addition, the copolymer is easily dissolved in water, and water can be used to remove uncured resin, so that development is easy. Therefore, the composition of the present invention is suitable for producing a color filter of a liquid crystal display element and a color separation filter of printing as a photocurable coloring composition.

In particular, when partially saponified polyvinyl acetate is used as a dispersant for the pigment in the present invention, since the above copolymer has a strong affinity for partially saponified polyvinyl acetate, a photoreactivity imparting agent is used. Is evenly crosslinked by
Produces transparent and strong colored images. Generally, partially saponified polyvinyl acetate has a tendency to be colored when heated, but when used in combination with the above-mentioned copolymer, there is no coloring, so that the color tone of the pigment is hardly impaired, and a beautiful color can be exhibited. .

[0051]

[Examples] The reason why the present invention is excellent will be specifically described below with reference to Examples and Comparative Examples. In the following, simply referring to parts or% means parts by weight or% by weight.

Example 1 (Preparation of composition) While passing nitrogen gas through a flask containing 200 parts of 10% aqueous acetic acid, maintaining the internal temperature at 80 ° C., and stirring well, the following monomer aqueous solution was used. Was added dropwise over 4 hours. 2-hydroxyethyl methacrylate 80 parts Dimethyl acrylamide 16 parts Acrylic acid 1 part Dimethylaminopropyl methacrylamide 3 parts Polymerization initiator (trade name V-501,4,4'-azobis (4-cyanopenta manufactured by Wako Pure Chemical Industries, Ltd.) Neuk) Acid 1 part 10% acetic acid aqueous solution 200 parts After the completion of the dropwise addition, the mixture was copolymerized with stirring at 80 ° C. for further 4 hours to obtain an aqueous solution of a copolymer having a pore diameter of 0.20.
The solution was filtered through a micron membrane filter, and the resulting aqueous solution was used as a photocurable resin.

Separately, the following formulations were made to make pigment dispersions. Phthalocyanine Blue 10 parts Surfactant (polyethylene glycol monooleyl ether) 0.1 part Partially saponified polyvinyl acetate (10% aqueous solution with 90% saponification degree and average degree of polymerization 2000) 100 parts

The above mixture was placed in a blender and stirred to such an extent that no large particles remained. It was transferred to an alumina pot filled with zirconia beads having a diameter of 1 mm and pulverized by a vibration mill. Thereafter, the mixture was further centrifuged at 12,000 rpm to remove coarse particles to prepare a pigment dispersion.

In the above, 10 parts of the aqueous copolymer solution obtained was added to
50 parts of a pigment dispersion and 31 parts of deionized water were further added, and a 10% aqueous solution of a diazo resin solution 2 sold by Shinko Giken Co., Ltd. as a diazo resin D-013 as a water-soluble diazo resin. The mixture was stirred with a magnetic stirrer for 2 hours to obtain a composition of the present invention.

(Use test of composition) The above composition was spin-coated on a glass plate at 1000 rpm and applied.
Dry in oven at 0 ° C. for 3 minutes. A photomask was overlaid on the surface of the coating film thus obtained, and an ultraviolet ray of 70 mJ / cm ² was irradiated from above using a super-high pressure mercury lamp. Then, when developed with 1% citric acid water at 25 ° C. for 1 minute,
A transparent blue image having a line width of 10 microns was obtained. After drying, the film thickness was measured by a surface roughness meter to be 0.4 μm. Therefore, this composition was suitable for obtaining such fine images. Next, this colored image plate was
When heated in an oven at a temperature of 1 ° C. for 1 hour, the light transmittance at 500 nm was reduced from 76% before heating to 74%, indicating that the heat resistance was good.

Example 2 This example is different from Example 1 in that the following monomer mixture was used for preparing an aqueous copolymer solution and the following formulation was used for preparing a pigment dispersion. A composition of the present invention was made in exactly the same manner as in Example 1, except that the following proportions were used to make the composition.

(Monomer mixture) 2-hydroxyethyl methacrylate 77 parts Dimethylacrylamide 8 parts Acrylic acid 1 part Dimethylaminopropylacrylamide 4 parts Methacrylamide 10 parts

(Blending of pigment dispersion) Chlorinated phthalocyanine green 10 parts Surfactant (polyethylene glycol phenyl ether) 0.1 part Partially saponified polyvinyl acetate (90% saponification degree, average polymerization degree 2000) 100 parts

(Mixing ratio of the composition) To 10 parts of the aqueous copolymer solution obtained above, 50 parts of the pigment dispersion and 31 parts of deionized water were added to obtain a water-soluble diazo resin as in Example 1. A 2% aqueous solution of a 10% diazo resin was added, and the remainder was treated exactly as in Example 1 to produce a composition of the present invention.

(Test for use of composition) The test was carried out in the same manner as in Example 1, except that the irradiation amount of ultraviolet rays was 240 mJ / cm ²
And As a result, a transparent line color image having a line width of 10 microns was obtained. After drying, the film thickness was measured to be 0.4 microns. Thus, the composition was suitable for making such fine images.

Example 3 An aqueous copolymer solution was prepared in the same manner as in Example 1 except that the following monomer composition was used. 2-hydroxyethyl methacrylate 77.5 parts Dimethyl acrylamide 10 parts Maleic acid 0.5 parts Dimethylaminopropyl methacrylamide 4 parts Methacrylamide 8 parts As in Example 1, a blue image containing phthalocyanine blue was prepared. , Photosensitivity and developability were not different from those of Example 1.

Comparative Example 1 In this comparative example, a pigment fine powder was added to a resin composition according to the teaching of JP-A-59-199342.
More specifically, an aqueous solution of the copolymer was prepared in the same manner as in Example 1 except that the following monomer mixture was used to prepare the copolymer. 2-hydroxyethyl methacrylate 83 parts Dimethylaminopropyl methacrylamide 7 parts Methacrylamide 10 parts Polymerization initiator (2,2'-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride) 1.2 parts Acetic acid 50 parts Deionization 350 parts of water

Separately, the following formulations were made to make pigment dispersions. Phthalocyanine blue 10 parts Surfactant (brand name Neugen EA-130T) 0.1 parts 10% aqueous solution of polyvinyl alcohol 100 parts

To 10 parts of the above aqueous copolymer solution, 45 parts of the above pigment dispersion, 30 parts of deionized water, and 2 parts of the same water-soluble diazo resin as used in Example 1 were added. Thereafter, the same treatment as in Example 1 was performed to obtain a photocurable colored composition, which was designated as Composition A.

To 10 parts of the above aqueous copolymer solution, 11 parts of the above pigment dispersion were added, and 2 parts of the same water-soluble diazo resin as used in Example 1 were added. A photocurable colored composition was obtained in exactly the same manner as described above, and this was designated as composition B.

Composition A was spin-coated on a glass plate in the same manner as in Example 1, irradiated with ultraviolet rays, and developed. As a result, most of the composition flowed out, and the remaining portion was porous and cloudy. Was.

Further, the composition B was similarly spin-coated,
When the film was irradiated with ultraviolet rays and developed, the resolution was good, but the thickness of the film obtained by drying was 1.2 μm. The fact that the film thickness of this comparative example was larger than that of Example 1 resulted in an unclear image. When this colored film was heated in an oven at 230 ° C. for 1 hour, 50
Since the light transmittance at 0 nm was reduced from 78% before heating to 59%, it was recognized that heat resistance was inferior.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/004 505 G03F 7/004 505 7/027 501 7/027 501 7/038 7/038 // C08F 220/28 C08F 220/28 ( 58) Field surveyed (Int.Cl. ⁷ , DB name) G03F 7/033 C08F 2/50 C08L 33/00 C09D 133/00 G02B 5/20 101 G03F 7/004 G03F 7/027 G03F 7/038 C08F 220 / 28

Claims (4)

(57) [Claims] 1. A compound of the general formula Embedded image Embedded image Embedded image A photocurable coloring composition obtained by adding a fine powder pigment and a photoreactivity imparting agent to a water-soluble copolymer produced by copolymerization of four types of monomers represented by the formula: Here, n represents 1 or 2, R ₁ , R ₃ and R ₄ all represent hydrogen or a methyl group, R ₂ represents hydrogen or a carboxyl group, and X represents an ethylene group or a propylene group. 2. A patent using a water-soluble copolymer obtained by adding and copolymerizing methacrylamide in addition to the four types of monomers represented by the formulas (1) to (4). The photocurable coloring composition according to claim 1. 3. A method according to claim 1, wherein the finely divided pigment is dispersed together with a surfactant and / or a water-soluble polymer and added as a dispersion. 3. The photocurable coloring composition described in 1. above. 4. The photocurable coloring composition according to claim 3, wherein the water-soluble polymer is partially saponified polyvinyl acetate.