JPH05127382A - Photosetting colored composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting composition capable of being cured and deeply colored, firmly adhering to a glass substrate, etc., and forming a transparent and thin insoluble film by using a special copolymer as a photosetting resin. CONSTITUTION:Three kinds of the monomers shown by formulas I, II and III are coplymerized, and a fine-powder pigment and a photochemical reaction initiator are added to the obtained copolymer to form a photosetting colored composition. In the fomulas, R1, R2 and R4 are hydrogen or methyl, R3 is hydrogen or carboxyl, A is -CH2-CH2- or -CH2-CH2-CH2-, and B is -N=(R5)2 or -N<+>identical(R5)3X. In this case, R5 is methyl or ethyl, and X is hydrogen or other anionic groups. The copolymer thus formed has a photosetting property and is obtained as an aq. soln., and the copolymer can be used as a photosetting paint.

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 irradiation with light. This coloring composition is a coloring composition useful for making, for example, a color filter for a liquid crystal display device or a color separation filter for printing.

[0002]

2. Description of the Related Art A resin that is cured by irradiation with light to form a film is known as a photocurable resin. After the photo-curing resin is applied, a mask is placed on the resin, and the mask is provided with a portion that transmits light and a portion that does not transmit light in advance. It is used to remove the uncured resin remaining in the resin and form a resin film in a desired shape. Since it is desirable that the film is colorless and transparent and tough, a photocurable resin is required to form such a film.

It is known to make colored images using photocurable resins. JP-A-60-129738 proposes to use a polyvinyl acetal compound obtained by acetalizing polyvinyl alcohol with an aldehyde having a styrylpyridinium group as a photocurable resin to form a colored image. The proposal is
A fine powder of a pigment is dispersed in a polyvinyl acetal compound to form a coating, and the coating is applied and the above-mentioned mask is placed on the coated surface, light is irradiated to cure the exposed portion, and the uncured portion is treated with water. It is a method of washing away with and leaving a cured part afterwards.

This method has a drawback in that it is difficult to uniformly disperse the pigment in the polyvinyl acetal having a styrylpyridinium group, and thus it is difficult to prepare the paint itself. Further, since this polymer has properties close to those of polyvinyl alcohol, when the coating film of this paint was treated at a high temperature, it tended to peel off from the substrate.

Further, JP-A-64-35417 discloses
It is proposed that a composition comprising a photosensitive resin having an acryloyl group and a pigment be used as a paint to form a colored image. The proposal is to add a polymerization initiator such as anthraquinone and a fine powder of pigment to a photosensitive resin such as triethylene glycol diacrylate to prepare a paint, put a mask on the coating surface of the paint, and apply light. Irradiate to partially cure the resin, remove the uncured portion with a solvent and develop,
It is to make a colored image.

[0006] This proposal is harmful to the health of workers because of the fact that an organic solvent must be used for the paint, and in some cases, there is a risk of fire, and special attention must be paid to waste liquid treatment. It had the drawback that it had to be. Further, the photosensitive resin having an acryloyl group is
Since the polymerization reaction is generally apt to be inhibited by oxygen, it is necessary to take special measures such as coating the coated surface with a polyvinyl alcohol film in order to avoid the effect of oxygen when irradiating with light, and therefore the work is easy. It had the drawback of not being.

In addition, Japanese Patent Laid-Open No. 58-199342 proposes to use a special acrylic copolymer as a photocurable resin. Special copolymer is a general formula

[0008]

[Chemical 5] A monomer represented by

[0009]

[Chemical 6] Or

[0010]

[Chemical 7] It is a binary copolymer obtained by copolymerizing with a monomer represented by. This proposal teaches that a diazo compound or an azide compound is added to this binary copolymer to prepare a photocurable resin. Here, X is O or NH, Y is an acid group, R ₁ , R ₂
Is H, CH ₃ or C ₂ H ₅ , n is an integer of 1 to ₃ , R ₃ is H or CH ₃ , and R ₄ is an alkylene group having 2 or 3 Cs,
R ₅ , R ₆ and R ₇ are said to represent H or an alkyl group having 1 to 4 carbon atoms.

According to this proposal, in order to color the resin thus obtained, it must be dyed with a special dye later,
In addition, in order to make a color filter, it is necessary to dye deeply, but if a coating with a film thickness of about 2 microns is to be dyed at a high density, for example, an optical density of 2 or more, (Equation 5) or (Equation 6) Although the concentration of the compound must be considerably high, it has a drawback that the polymer itself is discolored by thermal decomposition at high temperature and the dye is discolored by the action of decomposition products.

Further, Japanese Patent Laid-Open No. 1-2003353 discloses that
Disclosed is a photocurable colored composition comprising a polymer solution having tetravalent covalent nitrogen, a dye compound, and a radiation-sensitive crosslinking agent. In that case, the polymer having a tetravalent covalent nitrogen has the general formula

[0013]

[Chemical 8] It is said that it is obtained by polymerizing the monomer represented by. Here, R ₈ is hydrogen or a methyl group, and R ₉ is 2
A valent organic group, Z is an oxygen atom or an imino group.
Therefore, the monomer of formula (7) is almost the same as the compound of formula (6).

The polymer obtained from the monomer of the formula (7) taught in JP-A-1-200353 is difficult to disperse the dye compound, that is, the pigment, and the adhesiveness to the glass substrate is inferior. When it is heated to 200 ° C. or higher, it has a drawback that it becomes brownish.

Japanese Unexamined Patent Publication No. 1-2003353 discloses that a polymer of a compound of the formula (7) has a difficulty in solubility, and thus a compound of the formula (7) is copolymerized with another unsaturated compound. It mentions that it may be done. In this case, the 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 vinylnaphthalene, 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 but two or more may be mixed and copolymerized. ing. However, what was copolymerized
It has not been confirmed at all what properties other than solubility change.

[0016]

SUMMARY OF THE INVENTION The present invention has been made in order to provide a photocurable coloring composition which eliminates the above-mentioned drawbacks of conventional methods. That is, it is a photo-curable resin in which water can be used as a solvent for both the photosensitive solution and the developing solution, and it is easy to disperse a fine powder of a pigment in the photo-curable resin, and it is possible to color deeply with curing. The object of the present invention is to provide a photocurable composition capable of firmly adhering to a glass substrate or the like and forming a transparent thin insoluble film.

[0017]

The gist of the present invention is to use a special copolymer as a photocurable resin. Further, the present invention, when curing the copolymer by irradiation of light, the presence of a photoreactivity imparting agent such as a water-soluble diazo resin or a water-soluble polyfunctional aromatic azide compound as a curing agent. It is the essence. Further, the present invention is
It is also the essence to contain fine pigment powder in a dispersed state therein. Here, the special copolymer is

[0018]

[Chemical 1]

[0019]

[Chemical 2]

[0020]

It is a water-soluble copolymer prepared by copolymerizing three kinds of monomers represented by the following formula. In the formula, R ₁ , R ₂ and R ₄
Are hydrogen or methyl group, R ₃ is hydrogen or carboxyl group, A is —CH ₂ —CH ₂ —, or —C
H ₂ —CH ₂ —CH ₂ — group, and B is

[0021]

It is a group. Here, R ₅ represents a methyl group or an ethyl group, and X represents a halogen or other anion group.

The above copolymers are unique in that they are water soluble. More specifically, a monomer containing a hydroxyl group (Formula 1) and a monomer containing a carboxyl group (Formula 3)
The binary copolymer obtained by copolymerizing the above-mentioned monomer is generally insoluble in water in many cases, but a small amount of the amino group or quaternary ammonium group represented by (Formula 2) is present therein. Upon introduction, it was found that the obtained terpolymer became water-soluble. The present invention has been completed based on such confirmation.

[0023]

SUMMARY OF THE INVENTION The present invention provides a water-soluble copolymer prepared by copolymerizing three kinds of monomers represented by the above-mentioned (formula 1), (formula 2) and (formula 3), in the form of fine powder. The present invention relates to a coloring composition containing a pigment and a photoreactivity imparting agent.

[0024]

[Explanation of each requirement] The coloring composition according to the present invention comprises a water-soluble copolymer prepared by copolymerizing three kinds of monomers of (Formula 1), (Formula 2) and (Formula 3). I'm out. Among these, the monomer represented by (Formula 1) is, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

The monomer represented by the formula (2) is a compound containing an amino group or a quaternary ammonium group substituted with an alkyl group. Among them, compounds containing an amino group include, for example, dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide. It's an amide. The compound containing an ammonium group is, for example, acrylamidoethyltrimethylammonium chloride, acrylamidoethyltriethylammonium chloride, acrylamidopropyltrimethylammonium chloride, acrylamidopropyltriethylammonium chloride, methacrylamidoethyltrimethylammonium chloride,
Methacrylamidoethyltriethylammonium chloride, methacrylamidopropyltrimethylammonium chloride and methacrylamidopropyltriethylammonium chloride.

The monomers represented by the formula (3) are acrylic acid, methacrylic acid, maleic acid and fumaric acid.

In order to copolymerize the monomers represented by the above (formula 1), (formula 2) and (formula 3), these monomers are dissolved in a suitable solvent and polymerized. An organic solvent such as methyl cellosolve or dimethylformamide may be used as the solvent, 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′-dimethyleneisobutylamidine) 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} or the like can be used.

Preferred copolymerization ratios of the monomers represented by (Formula 1), (Formula 2) and (Formula 3) are as follows.
The monomer represented by (Formula 1) preferably accounts for 60 to 90% by weight of the copolymer. The reason is that if the amount of the monomer of the formula (1) is less than 60% by weight, the water-solubility, photocrosslinking property and adhesive force to the base material of the resulting copolymer are lowered, and conversely 90% by weight. This is because the water solubility of the copolymer deteriorates when the content is more than%.

The monomer represented by the formula (2) preferably accounts for 0.5 to 10% by weight in the copolymer, and particularly preferably 1 to 5% by weight. The reason is that when the amount of the monomer of formula (2) is less than 0.5% by weight, it becomes difficult to make the copolymer water-soluble,
On the other hand, if it is more than 10% by weight, the thermal stability of the obtained copolymer is lowered.

The monomer represented by the formula (3) preferably accounts for 0.1-5% by weight of the copolymer, and more preferably 0.5-3% by weight. The reason is that when the amount of the monomer of the formula (3) is less than 0.1% by weight, it becomes difficult to disperse the pigment in the copolymer. This is because the water solubility of the coalesced product decreases, and even if the uncured product is removed with an aqueous acetic acid solution after being cured by irradiation with light, for example, it cannot be easily removed.

The above copolymer may contain a small amount of another monomer as an optional component. Examples of the other monomer include acrylamide, methacrylamide, N-vinylpyrrolidone, diacetone acrylamide, tetrahydrofurfuryl acrylate, and glycerin monoacrylate.

Among the optional components, it is desirable to use methacrylamide. Although methacrylamide is water-soluble by nature, it also has moderate hydrophobicity, so
Even if the copolymer obtained by adding this is heat-treated at high temperature,
This is because discoloration or coloration is less likely to occur, and on the contrary, the degree of crosslinking is improved and the strength of the film is increased. The amount of methacrylamide added may be greater than that of the monomer represented by (Formula 2) or (Formula 3), and may be 0-20% by weight.

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. So the copolymer is
Its molecular weight is 10,000 to 20 in terms of weight average molecular weight.
A value of 10,000 is suitable.

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

The pigment is dispersed in the copolymer in the form of fine powder. As a fine powder, if the size of the pigment particles is larger than the wavelength of the light of that color, it looks cloudy,
The average particle size is preferably 0.5 micron or less.
In order to disperse the pigment, it is preferable to previously disperse the fine pigment powder in an aqueous solution containing a dispersant, and to add this dispersion to the aqueous solution of the copolymer and mix them. A turbo mixer, a ball mill, an attritor, a bead mill, or the like is used to prepare a dispersion of fine pigment powder. As the dispersant, a surfactant or a water-soluble polymer can be used.
However, it is necessary to use a nonionic or cationic active surfactant. This is because the monomer represented by (Formula 2) is cationic. It is particularly preferable to use a nonionic one. As the water-soluble polymer, it is preferable to use partially saponified polyvinyl acetate, polyvinyl alcohol in which a cationic group is partially introduced, or polyvinyl pyrrolidone.

The amount of the pigment added to the copolymer is 50 to 200 parts by weight based on 100 parts by weight of the copolymer. Generally, when the amount of the pigment is too small, the coloring degree is naturally insufficient, and when the amount is too large, the photosensitivity is lowered and the film forming ability is lowered due to the shortage of the resin content. It gets harder. However, the copolymer used in the present invention can add a pigment additive 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 the photoreactivity-imparting agent for the copolymer. The diazo resin is a resin made by adding formaldehyde to an aromatic diazonium compound and condensing it. Examples of aromatic diazonium compounds include p-diazodiphenylaluminum, 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 azido 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, 2,6-bis (4-azidobenzal) acetone-2,2'-disulfonic acid and the like. The water-soluble diazo resin or the water-soluble polyfunctional aromatic azide compound is used in an amount of 5-30 parts by weight based on 100 parts by weight of the copolymer.
It is preferable to use parts by weight.

The composition according to the present invention is usually used as an aqueous solution. As described above, an aqueous dispersion of pigment fine powder is added to an aqueous solution of a copolymer as described above and mixed well, and a photoreactivity-imparting agent such as a water-soluble diazo resin or a polyfunctional aromatic azide compound is added and dissolved. Let The aqueous solution thus obtained can be easily applied onto glass or another substrate by a spin coater or a roll coater.

[0040]

According to the present invention, (Equation 1) and (Equation 2)
And a copolymer consisting of the monomers of formula (3) is used,
A copolymer can be easily prepared by using water as a solvent and adding a polymerization initiator thereto and heating. The copolymer produced in this way has photocurability, is obtained as an aqueous solution, and can disperse the fine powdery pigment easily. Therefore, it can be used as it is as a photocurable coating material. Therefore, in this case, there is no disadvantage and no trouble due to the use of the organic solvent. Further, since the composition of the present invention contains a photoreactivity-imparting agent such as a water-soluble diazo resin or a polyfunctional aromatic azide compound, the photoreactivity-imparting agent is added to the copolymer by irradiation with light. It acts as a curing agent and forms a strong coating. Furthermore, since this copolymer has a zwitterionic property containing a hydroxyl group and a carboxyl group and a substituted or unsubstituted amino group or a quaternary ammonium group, it has a high affinity for pigments, Many pigments can be included, with which a deeply colored film can be produced all at once. Therefore, the film can be made thin, and a more clear image can be provided when used for processing the ITO electrode. Moreover,
Since this copolymer is zwitterionic, it is easily dissolved in water, and since water can be used to remove the uncured resin, development is easy. Therefore, the composition of the present invention is suitable as a photocurable coloring composition for producing color filters for liquid crystal display devices and color separation filters for printing.

The advantages of the present invention will be specifically described below with reference to Examples and Comparative Examples. In the following, simply parts or% means parts by weight or% by weight.

[0042]

Example 1

[Preparation of Composition] The following monomer aqueous solution was added dropwise over 4 hours while thoroughly stirring at 85 ° C. while passing nitrogen gas through a flask containing 150 parts of deionized water and 50 parts of acetic acid. Acrylic acid 2 parts 2-hydroxyethyl methacrylate 84 dimethylaminopropyl methacrylamide 4 methacrylamide 102, 2'-azobis (N, N'-dimethylene 1.2 isobutylamidine) hydrochloride (polymerization initiator) deionized water 200 85 Copolymerization was carried out at 0 ° C for 4 hours with stirring to obtain an aqueous solution of the copolymer. An aqueous solution obtained by filtering this with a membrane filter having a pore size of 0.20 μm was used as a photocurable resin.

The following formulations were made to separately make pigment dispersions. Phthalocyanine Bull-hydrogenated cake (pigment content 48%) 100 parts Surfactant (trade name Neugen EA-130T) 155% polyvinyl alcohol aqueous solution 300

The above mixture was placed in a blender and stirred until 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. Further, centrifugation was carried out at 12000 rpm to remove coarse particles to prepare a pigment dispersion.

To 10 parts of the photocurable resin aqueous solution obtained above, 45 parts of pigment dispersion was added, and further 30 parts of water was added,
0.2 parts of water-soluble diazo resin sold by Shinko Giken Co., Ltd. under the name of diazo resin D-13 was added, mixed well in a mixer, and then the pore size was 0.8 μm.
The composition of the present invention was obtained by filtering with a filter of m.

[0046]

[Use test of composition] The above composition was applied on a glass plate at 2000
Spin coating was performed at rpm, a photomask was overlaid, and an ultraviolet ray of 65 mJ / cm ² was irradiated onto the photomask using an ultrahigh pressure mercury lamp. After that, when developed with 2% acetic acid water, the line width is 10μ.
m was reproduced. The film thickness after drying was 0.4 μm.
The light transmittance at 460 nm was 70%. After heating the colored plate in an oven at 230 ° C. for 1 hour, the light transmittance was measured and found to be 68%. Therefore, this composition was suitable for obtaining such fine images.

[0047]

Example 2

[Preparation of Composition] This example 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. The composition was made. Acrylic acid 1 part 2-hydroxyethyl methacrylate 86 dimethylaminopropyl acrylamide 3 methacrylamide 10

[0048]

[Composition Use Test] Exposure and development were carried out in the same manner as in Example 1, and as a result, a clear image was obtained in the same manner as in Example 1.

[0049]

Comparative Example 1 This comparative example was carried out without using the carboxyl group-containing monomer represented by the formula (3) among the monomers used in the present invention. Specifically, an aqueous solution of a photocurable resin was prepared in exactly 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 Methacrylamide 10 Polymerization initiator (same as in Example 1) 1.2 Acetic acid 50 Water 350

Using the resin aqueous solution and using the same pigments and the like as used in Example 1, compositions corresponding to the following two kinds of the present invention compositions A and B were prepared. A composition B composition Resin aqueous solution 10 parts 10 Pigment dispersion 45 11 Water 30-Diazo resin 0.2 0.2

The composition A was spin-coated on a glass plate in the same manner as in Example 1, irradiated with ultraviolet rays, and developed. Most of the composition flowed out, and the remaining part was porous and turbid. Was there.

On the other hand, when the composition B was spin-coated in the same manner, irradiated with ultraviolet rays and developed, the resolution and the light transmittance were about the same as in Example 1, but the film obtained by drying was The thickness was 1.2 μm. The larger film thickness of this comparative example than that of Example 1 made the image unclear.

After heating the above colored plate in an oven at 230 ° C. for 1 hour, the light transmittance at 460 nm was measured and found to be 60%, which was considerably discolored compared to 71% before heating. ..

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 7/027 // G03F 3/00 Z 7818-2H

Claims (2)

[Claims] 1. A general formula: [Chemical 2] [Chemical 3] A photocurable coloring composition obtained by adding a fine powdery pigment and a photoreactivity-imparting agent to a copolymer produced by copolymerizing three kinds of monomers represented by Here, R ₁ , R ₂ , and R ₄ are all hydrogen or a methyl group, R ₃ is a hydrogen or a carboxyl group, and A is —CH ₂ —CH ₂ — or —CH ₂
A —CH ₂ —CH ₂ — group and B is It is a base. In this case, R ₅ represents a methyl group or an ethyl group, and X represents a halogen or other anionic group. 2. As the copolymer, (formula 1), (formula 2),
The photocurable composition according to claim 1, characterized in that a copolymer obtained by adding methacrylamide and copolymerizing the monomer together with the monomer represented by the formula (3) is used. Coloring composition.