JP2878865B2 - Method for producing photocurable colored resin 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 method for producing a photocurable colored resin composition which can be used for producing a color filter and the like.

[0002]

2. Description of the Related Art Color filters are used in color television receivers and photographing machines. This is one in which colorants are arranged in a mosaic or stripe shape on a transparent substrate.

[0003] To make such a color filter,
Photocurable resins have been used. Previously, a photo-curable resin was applied uniformly on a transparent substrate, a photomask with a stripe or mosaic pattern was placed on top of this, and exposed to light to cure the exposed parts, The remaining uncured portions were removed, leaving the resin in stripes or mosaics, and the resin portions were later dyed.

[0004] However, if the resin is cured and then dyed on the substrate, color unevenness occurs, and the process becomes longer to prevent dyeing and color mixing. Further, since the heat resistance of the dye is low, the dye is easily discolored at high temperatures. Therefore, an improved method has been proposed in which the pigment is dispersed in a resin and colored.

When the method of mixing the pigment powder in the photocurable resin in advance is adopted, it is necessary to disperse the pigment fine particles uniformly and stably for a long time in the resin. Therefore, in providing a photocurable colored resin composition, it has been a major problem how to uniformly and stably disperse pigment fine particles in a resin.

Japanese Patent Application Laid-Open No. Hei 1-200353 proposes using a resin containing a quaternary ammonium group in order to uniformly and stably disperse the pigment powder. That is, the above publication discloses a photocurable colored resin composition in which a pigment and a photocuring agent are added to a polymer solution containing a quaternary ammonium group. As the polymer containing a quaternary ammonium group, for example, a polymer of an acrylic compound containing a trialkylammonium group is used.

However, as described in the above publication, the resin containing a quaternary ammonium group did not have good dispersibility of the pigment powder, and also had poor adhesiveness and heat resistance of the resin. More specifically, a compound containing a quaternary ammonium group has a cationic surface activity, and a cationic compound has a dispersing ability lower than that of an anionic or nonionic compound as a whole. I have. In addition, since a compound containing a quaternary ammonium group acts as a coagulant rather than a dispersant for a pigment powder having a negative charge, it cannot be used for a pigment powder having a negative charge. Had the drawback. Furthermore, a resin containing a quaternary ammonium group needs to contain a large amount of a quaternary ammonium group in order for the resin to exhibit good dispersibility. There was a drawback that.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocurable colored resin composition in which a pigment powder is uniformly and stably dispersed by using a resin which does not have the above-mentioned difficulties and disadvantages. Is what you do.

[0009]

The inventor of the present invention has disclosed a monomer (A) having a polyoxyalkylene group and a polymerizable allyl group, such as polyoxyethylene (2-allyl-4-nonylphenyl) ether. ) And a copolymer of an active hydrogen such as 2-hydroxyethyl methacrylate and a monomer (B) having a polymerizable acryloyl group, and a diazo resin or an azide compound added to a photocurable composition. As a resin, I proposed earlier. Such a photocurable resin has excellent pigment dispersibility, and generally exhibits better heat resistance and adhesiveness than the above-described resin containing a quaternary ammonium group.

As a result of further study on the above-mentioned photocurable resin composition, the inventor of the present invention has found that when a specific production process is performed to produce the above-mentioned resin composition, it is far more difficult to follow a general production method. It has been found that a colored composition having excellent dispersibility of the pigment powder can be obtained. Here, the ordinary production method is a method in which the monomer (A) and the monomer (B) are first copolymerized, and the pigment powder is dispersed in the obtained polymer. Here, the specific manufacturing process means that the pigment powder is first dispersed in a solution of the monomer (A), and only the monomer (A) is polymerized in the presence of the pigment powder. This is a method in which a polymer of the monomer (B) is added to this polymer solution, and this is used as a photocurable resin. The present invention has been completed based on such findings.

According to the present invention, a pigment powder is dispersed in an aqueous solution of a polymerizable monomer (A) containing a polymerizable unsaturated group and a polyoxyolefin group, and then a polymerization initiator is added thereto. The monomer (A) is polymerized, and thus a pigment-containing polymer aqueous solution is first prepared, and a polymer of the polymerizable monomer (B) containing a polymerizable unsaturated group and active hydrogen is added thereto, A gist of the present invention is a method for producing a photocurable colored resin composition, which comprises adding a photoreactivity imparting agent.

[0012]

[Description of each requirement] Monomer (A) used in the present invention
Is a polymerizable compound containing a polymerizable unsaturated group and a polyoxyolefin group. The polymerizable unsaturated group is a vinyl group, an allyl group, an allylphenyl group, an acryloyl group,
It means a vinylphenyl group, a propenylphenyl group or the like. The polyoxyolefin group means a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a polyoxyethylene polyoxypropylene group, or the like. Specific compounds belonging to the monomer (A) include, for example, polyoxyethylene (meth) acrylate, polyoxyethylene polyoxypropylene (meth)
Acrylate, polyoxyethylene polyoxytetramethylene (meth) acrylate, polyoxypropylene polyoxytetramethylene (meth) acrylate, polyoxyethylene- (2-allyl-4-nonylphenyl) ether, and the like.

The monomer (B) that can be used in the present invention is a polymerizable compound containing a polymerizable unsaturated group and active hydrogen. The polymerizable unsaturated group means a vinyl group, an acryloyl group, an allyl group, etc., similarly to the above-mentioned monomer (A). In addition, the compound containing active hydrogen refers to a compound containing a hydroxyl group, an amino group, and an amide group. Specific examples of the monomer (B) include 2-
These are hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, (meth) acrylamide, diacetone acrylamide, and N-vinylpyrrolidone.

The pigment which can be used in the present invention is in the form of a powder. The degree of the powder should be as fine as possible
It is desirable that the particle size is equal to or less than μm and the particle size is uniform. The pigment may be inorganic or organic. As the organic substance, various substances such as phthalocyanine, azo, quinacridone, perinone, anthraquinone, indanthrone, dioxazine, and thioindigo can be used.

The polymerization of the monomer (A) or the monomer (B) is carried out by
This is performed in a nitrogen atmosphere. Further, in order to polymerize the monomer (A) or the monomer (B), a polymerization initiator is used.
As the polymerization initiator, a water-soluble one selected from known polymerization initiators is used. The polymerization initiator that can be used in the present invention is, for example, ammonium persulfate, 2,2 ′
-Azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 4,4'-azobis (4-cyanopentanoic acid), 2,2 '-(azobis (2-methyl-N [1,1- Bis (hydroxymethyl)
-2-hydroxyethyl] propionamide.
These polymerization initiators are used in an amount of 0.1% based on the total amount of the monomers.
-5% by weight, preferably 0.2-1% by weight is used.

In the present invention, first, an aqueous solution of the monomer (A) is prepared, and the pigment powder is dispersed therein. Since the monomer (A) contains a polyoxyolefin group, it is well dissolved in water and has properties as a surfactant. Therefore,
First, an aqueous solution of the monomer (A) is prepared, and then the pigment powder is added thereto, whereby the pigment powder can be easily dispersed. In order to further disperse the pigment powder, a mixer or a mill is used. For example, the dispersion obtained above is placed in a rotary mixer and stirred to crush large lumps, then transferred to a bead mill and stirred until particles of 1 μm or more are almost gone. Glass, steel, or ceramic globules can be used as a medium for the bead mill, but it is preferable to use partially stabilized zirconia beads. This is because the strength of the zirconia beads is high and does not contaminate the solution.

The monomer (A) may be polymerized singly or may be copolymerized with another water-soluble monomer. Other monomers include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycerin mono (meth) acrylate,
(Meth) acrylamide, dimethylacrylamide, diacetone acrylamide, dimethylaminopropyl (meth) acrylamide, (meth) acrylic acid, N-vinylpyrrolidone, and the like can be used. These other monomers are used in an amount of not more than the monomer (A) by weight.

The monomer (A) is represented by the following structural formula.
It is a compound represented by the following general formula.

Embedded image

Here, 1, m, and n are integers from 0 to 25, and have a relationship of 10 ≦ 1 + m + n ≦ 25. Also, R
Is an acryloyl group, a methacryloyl group, an alkylallylphenyl group, a styryl group, an isopropenyl group or the like.

According to the present invention, the polymerization of the monomer (A) is carried out in water. However, the water is not limited to pure water, and may be an aqueous solvent containing another organic solvent.
Alcohol and acetone can be used as the organic solvent. When a large amount of an organic solvent is used, a polymer or copolymer of the produced monomer (A) may be precipitated. In such a case, acetic acid is a good organic solvent because the addition of acetic acid in an aqueous solvent can lead to the dissolution of the polymer or copolymer.

In the present invention, in order to polymerize the monomer (A), a polymerization initiator is added to an aqueous solution of the monomer (A) in which the pigment powder is dispersed, and stirring is continued while passing nitrogen. What is necessary is just to heat up. In this way, by heating for several hours,
The monomer (A) is polymerized or copolymerized to form a polymer (A). If the resulting solution contains lumps therein, remove the lumps by centrifugation or filtration.

According to the present invention, the polymer (B) obtained from the monomer (B) is added to the aqueous solution of the polymer (A) obtained as described above. The polymer (B) can be produced from the monomer (B) in the same manner as in the polymerization of the monomer (A). That is, the polymer (B) can be produced by adding the polymerization initiator to the aqueous solution of the monomer (B) and heating while continuing to stir while passing nitrogen. The aqueous solution of the polymer (B) thus obtained may contain large agglomerates therein. In such a case, the mixture is filtered through a filter having a pore size of 0.2 to 0.5 μm in order to remove agglomerates, and used for the next use.

The polymer (B) is not limited to one obtained by polymerizing the monomer (B) alone, but may be a copolymer of the monomer (B) and another monomer. You may. The other monomer copolymerized with the monomer (B) is substantially the same as the other monomer copolymerized with the monomer (A). That is, as other monomers copolymerized with the monomer (B), tetrahydrofurfuryl (meth) acrylate, (meth) acrylamide, diacetone acrylamide, N-vinylpyrrolidone, dimethylaminopropyl (meth) acrylamide, (Meth) acrylic acid or the like can be used. These other monomers are not more than the amount of the monomer (B) by weight.

In the present invention, a photoreactivity imparting agent is added to the aqueous solution of the pigment-containing polymer (A) together with the polymer (B). The photoreactivity imparting agent is a photo-crosslinking agent that performs a cross-linking reaction by extracting active hydrogen from a polymer containing active hydrogen, and a photo-crosslinking agent, which is used as a polyfunctional monomer or a polymer having a double bond in a side chain. Photopolymerization initiators that carry out polymerization reactions are roughly classified into two types. As the photocrosslinking agent, a diazo resin or an azide compound is preferable. The diazo resin is a condensate of an aromatic diazonium compound and formaldehyde. A typical aromatic diazonium compound is 4-diazo-3-methoxydiphenylamine. Further, as the azide compound, it is desirable to use a polyfunctional azide compound containing two or more azide groups.
Diazidostilbene-2,2 'sodium disulfonate. Such a photopolymerization initiator is preferably used at a ratio of 0.5 to 20% by weight, and more preferably at a ratio of 1 to 10% by weight, based on all the polymers and monomers present in the aqueous solution. Is preferred. As the photopolymerization initiator, sodium benzophenone-4-carboxylate, sodium anthraquinone-2-sulfonate, 2-hydroxy-3-
It is preferable to use (4-benzoylphenoxy) N, N, N-trimethyl-1-propanaminium chloride monohydrate or the like.

For example, when an aqueous solution obtained by adding the polymer (B) and the photocrosslinking agent to an aqueous solution of the pigment-containing polymer (A) is irradiated with ultraviolet rays, active hydrogen is extracted from the polymer (B). Then, an addition reaction occurs, and the polymer (B) functions as a crosslinking agent for the polymer (A), where the resin is cured to generate a cured resin. Thus, a colored resin film is formed.

[0026]

According to the present invention, the pigment powder is dispersed in an aqueous solution of the monomer (A) containing a polymerizable unsaturated group and a polyoxyolefin group. Both non-charged pigments and charged pigments act as nonionic surfactants, so that pigments can be easily dispersed regardless of the sign of the charges, and the pigments can be uniformly dispersed. In this way, after the pigment powder is dispersed, a polymerization initiator is added to the aqueous solution to polymerize the monomer (A), so that the polymerization reaction is carried out on the surface of the pigment powder as a nucleus. The polymer (A) produced by the polymerization of (A) is closely linked to the pigment powder, and the pigment is uniformly and stably dispersed. Thereafter, a polymer (B) containing a polymerizable unsaturated group and active hydrogen is added, and a photoreactivity imparting agent is added to form a composition. Therefore, the composition is subjected to a photocrosslinking reaction or a photopolymerization reaction. Light curing is performed. Since the cured resin thus obtained is colored by the pigment, it forms a uniform colored portion, and is therefore suitable for producing a color filter. The present invention provides such advantages.

[0027]

The present invention will now be described by way of examples and comparative examples to clarify the advantages of the method of the present invention. Hereinafter, the term “parts” means parts by weight.

[0028]

Example 1 In this example, a water-containing cake containing 38% by weight of phthalocyanine bleed was used as a pigment, and polyoxyethylene- (2-allyl-4) was used as the monomer (A).
-Nonylphenyl) ether and 2-hydroxyethyl methacrylate as the monomer (B).

First, the following composition was prepared in order to prepare an aqueous solution of the polymer (A) containing the pigment powder. Phthalocyanine blue pigment cake 100 parts polyoxyethylene- (2-allyl-4-nonylphenyl) ether 7.6 parts water 209 parts

The mixture was stirred with a rolling mixer for 30 minutes, then transferred to a bead mill filled with zirconia beads, and stirred for 1 hour. 100 parts of this dispersion liquid was placed in a flask, and the liquid temperature was raised to 80 ° C. while stirring in a nitrogen stream.
Was raised. Next, 2,2′-azobis (2-amidinopropane) hydrochloride was used as a polymerization initiator.
One part of a 5% by weight aqueous solution was added, and stirring was continued for 7 hours to carry out polymerization.

The reaction product was transferred to a ball mill, pulverized for 1 hour, centrifuged, and filtered to obtain an aqueous solution of the polymer (A) containing the pigment.

On the other hand, the following composition was prepared for preparing the polymer (B). 2-hydroxyethyl methacrylate 75 parts Dimethylacrylamide 15 parts Methacrylamide 10 parts Water 150 parts 2,2'-azobis (2-amidinopropane) hydrochloride 1 part This composition was mixed with 150 parts of water at 80 ° C in a nitrogen atmosphere. The mixture was added dropwise over 4 hours, and then stirred at 80 ° C. for 4 hours to produce a polymer (B). Water was added to the aqueous solution of the polymer (B) to adjust the solid content to 17% by weight.

As the photopolymerization initiator, an aqueous solution (solid content: 10% by weight) of a formaldehyde condensate of 4-diazo-3-methoxydiphenylamine was used to prepare the following composition, which was used as a photopolymerization initiator according to the present invention. A curable colored resin composition was obtained. Pigment-containing polymer (A) aqueous solution 100 parts Polymer (B) aqueous solution 110 parts Polymerization initiator 20 parts

The above composition was spin-coated on a glass plate at 1500 rpm to obtain a transparent blue film having a thickness of 0.95 μm. A photomask was superimposed on this film, exposed at 80 mJ / cm ² using an ultra-high pressure mercury lamp, washed with water at room temperature, and an image with a width of 10 μm appeared, and the transparency was good. there were.

[0035]

Example 2 In this example, the pigment was changed to use a phthalocyanine green (solid content of 40% by weight) water-containing cake in the same manner as in Example 1, and when the monomer (A) was polymerized, In the middle, 2.5 parts of 2-hydroxyethyl methacrylate was added to convert the polymer (A) to polyoxyethylene- (2-allyl-4-nonylphenyl).
The procedure was carried out in exactly the same manner as in Example 1 except that a copolymer of ether and 2-hydroxyethyl methacrylate was used.

The production of the pigment-containing polymer (A) was carried out as follows. First, the following composition was prepared. Phthalocyanine green water-containing cake 100 parts Polyoxyethylene- (2-allyl-4-nonylphenyl) ether 7.6 parts Water 209 parts

After the mixture was stirred for 30 minutes by a rolling mixer, it was transferred to a bead mill filled with zirconia beads and stirred for 1 hour. 100 parts of this dispersion liquid was placed in a flask, and the liquid temperature was raised to 80 ° C. while stirring in a nitrogen stream.
Was raised. Next, the same amount of the polymerization initiator as in Example 1 was added, and the mixture was stirred at 80 ° C. for 4 hours to carry out a polymerization reaction. Thereafter, 2.5 parts of 2-hydroxyethyl methacrylate was added, and the mixture was further stirred at 80 ° C. for 4 hours. Was continued to carry out copolymerization, thus obtaining a polymer (A).

Thereafter, exactly as in Example 1,
A photocurable colored resin composition was obtained. Further, an image test was performed in exactly the same manner as in Example 1 except that the exposure amount was set to 20 mJ / cm ² using this resin composition, and a good green image was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/038 G03F 7/004 G03F 7/027

Claims (1)

(57) [Claims] 1. A pigment powder is dispersed in an aqueous solution of a polymerizable monomer (A) containing a polymerizable unsaturated group and a polyoxyolefin group, and then a polymerization initiator is added thereto. The polymer (A) is polymerized, and thus a pigment-containing polymer aqueous solution is first prepared, and a polymer of a polymerizable monomer (B) containing a polymerizable unsaturated group and active hydrogen is added to the aqueous solution. A method for producing a photocurable colored resin composition, comprising adding a property imparting agent.