JP3120416B2 - Photosensitive 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 liquid crystal display, a color video camera,
The present invention relates to an acrylic photosensitive coloring composition useful as a coating liquid for producing a color filter used in an image scanner or the like, and a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, as a color filter for a color liquid crystal display, a color video camera, an image scanner, etc., a color filter produced using an acrylic photosensitive coloring composition containing an acrylic resin has been widely used. ing.

[0003] Such an acrylic photosensitive coloring composition is prepared by diluting an acrylic resin with a good solvent for the acrylic resin, for example, ethylcellosolve, and adding the diluted resin to the diluted resin.
A pigment such as CI No. 9 and a dispersant such as a nonionic surfactant are added and kneaded well, and the pigment particles are coated with an acrylic resin so that the pigment is uniformly dispersed. It is prepared by further adding a photopolymerizable monomer such as an acrylate and a photopolymerization initiator and mixing them uniformly. In this case, when benzyldimethyl ketal or the like is used as the photopolymerization initiator, the polymerization reaction is inhibited by the presence of oxygen, and thus it is necessary to perform the polymerization in an oxygen-blocking atmosphere.

[0004]

However, when the conventional acrylic photosensitive coloring composition is stored at room temperature, the acrylic resin coating the pigment particles gradually dissolves in the solvent in the composition. However, as a result, there is a problem that the pigment particles are chelated and aggregated, and the viscosity of the composition is increased, and the composition is unstable with time. This lowers the uniform coatability of the thickened acrylic photosensitive coloring composition, and causes a problem that a color filter having intended performance cannot be obtained. In particular, this problem has been raised in recent years because a highly reactive triazine-based compound (Japanese Patent Application Laid-Open No. Hei 6 (1994) -19764) has recently been proposed as a photopolymerization initiator so that the polymerization reaction of a photopolymerizable monomer can be initiated even in the presence of oxygen.
No. 201913) was remarkable.

An object of the present invention is to solve the above-mentioned problems of the prior art, and an object of the present invention is to impart high temporal stability to an acrylic photosensitive coloring composition at ordinary temperature.

[0006]

Means for Solving the Problems The present inventors have found that the above object can be solved by adding a predetermined amount of a poor solvent for an acrylic resin to an acrylic photosensitive coloring composition, and completed the present invention. It led to.

That is, the present invention provides an acrylic resin, a pigment,
In a photosensitive coloring composition comprising a dispersant, a photopolymerizable monomer, a photopolymerization initiator and a good solvent for the acrylic resin , 1% by weight of the acrylic resin is further added at room temperature.
A poor solvent for the acrylic resin , which cannot be completely dissolved, is 100 to 3 parts by weight based on 100 parts by weight of the acrylic resin.
The present invention provides a photosensitive coloring composition characterized by containing 50 parts by weight.

The present invention also relates to a method for producing a photosensitive coloring composition as described above, wherein a mixture of an acrylic resin, a pigment, a dispersant and a good solvent for the acrylic resin is added to a photopolymerizable monomer, And 1% by weight of the accelerator at room temperature.
There is also provided a production method characterized by mixing a poor solvent for an acrylic resin which cannot dissolve all of the rill resin .

Hereinafter, the present invention will be described in detail.

[0010] The photosensitive coloring composition of the present invention contains a poor solvent for the acrylic resin. The presence of the poor solvent can prevent the acrylic resin coating the pigment particles from being dissolved in a good solvent for the acrylic resin. Therefore, aggregation of the pigments is prevented, and the temporal stability of the photosensitive coloring composition can be improved.

In the present invention, the poor solvent for the acrylic resin refers to a solvent that cannot completely dissolve 1% by weight of the acrylic resin at room temperature. Therefore, a specific solvent may be positioned as a poor solvent or a good solvent depending on the type of acrylic resin used. As the poor solvent for the acrylic resin used in the present invention, aromatic hydrocarbons, for example, benzene, toluene,
Examples thereof include xylene and ethylbenzene, and acetates such as n-amyl acetate and i-pentyl acetate.

The amount of the poor solvent used relative to the acrylic resin is 100 to 35 parts per 100 parts by weight of the acrylic resin.
0 parts by weight, preferably 150 to 200 parts by weight. 1
If the amount is less than 00 parts by weight, the stability over time of the photosensitive coloring composition cannot be sufficiently improved, and if it exceeds 350 parts by weight, the acrylic resin cannot be sufficiently dispersed.

On the other hand, the good solvent for the acrylic resin used in the present invention is a solvent other than the poor solvent, but the type of the acrylic resin, the type of the photopolymerizable monomer, the type of the photopolymerization initiator and the like described later. Is appropriately selected according to the conditions.
Such good solvents are generally ketones, methyl ethyl ketone, acetone, methyl isobutyl ketone,
Ketones such as cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, cellsolves such as diethylene glycol, ethanol, propanol, butanol, hexanol, cyclohexanol,
Alcohols such as ethylene glycol, diethylene glycol, and glycerin can be used.

If the amount of the good solvent used for the acrylic resin is too small, the acrylic resin and the photopolymerizable monomer cannot be uniformly dissolved, and if the amount is too large, the effect of the present invention tends not to be obtained. The appropriate amount can be appropriately determined according to the type and amount of the acrylic resin or pigment to be used.

In the present invention, the acrylic resin is used as a pigment dispersing resin which coats pigment particles and prevents aggregation of the pigment. As such an acrylic resin, for example, acrylic acid, methacrylic acid, alkyl acrylate or alkyl methacrylate such as methyl acrylate or methyl methacrylate, cyclic acrylate or methacrylate, a monomer selected from hydroxyethyl acrylate or hydroxyethyl methacrylate, Usually, about 3 to 5 kinds are used, and the molecular weight is 5000 to 10
Resins polymerized to about 0000 can be used.

When an acrylic resin is copolymerized from such a monomer, benzyl acrylate, phenyl acrylate, benzyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate and the like may be further added. Good.

In the present invention, pigments generally include
As a red pigment, C.I. I. No. 9, 97, 122, 12
3, 149, 168, 177, 180, 192, 215
And the like, and as a green pigment, C.I. I. N
o. 7, 36 and the like can be used, and C.I. I. No. 15, 22, 60, 64 and the like, and C.I. I. No. 20, 24,
86, 93, 109, 110, 117, 125, 13
7, 138, 147, 148, 153, 154, 16
6, 168, etc., and C.I. I. No. 36, 43, 51, 55, 59, 61
And the like, and C.I.
I. No. 19, 23, 29, 30, 37, 40, 50
Etc. can be used. Of these, only one type may be used or a plurality of types may be used together. Usually, two or three kinds of pigments are used together for spectral adjustment of the color filter.

The amount of the pigment used is not particularly limited, but is usually 5 to 100 parts by weight of the acrylic resin.
It is about 0 to 150 parts by weight, and can be appropriately determined depending on the purpose of use of the photosensitive coloring composition and the like.

In the present invention, the dispersant can be appropriately selected from a wide range and can be used, for example, natural products such as linseed oil, carnauba wax, hydrogenated rosin ester, petroleum resin or partially processed products thereof, modified products Synthetic resins such as alkyd resin, polystyrene, synthetic rubber and acrylic oligomer can be exemplified. In addition, an organic pigment or a derivative thereof having the same parent skeleton as a dye can be exemplified as the dispersant. The use amount of the dispersant is not particularly limited, but usually,
It is about 1 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin, and can be appropriately determined depending on the degree of dispersion of the pigment.

In the present invention, the photopolymerizable monomer is used for imparting a film forming property to the photosensitive coloring composition. Such photopolymerizable monomers include bifunctional monomers, 3
Functional or polyfunctional monomers can be used. Here, as the bifunctional monomer, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate,
Triethylene glycol diacrylate and the like can be used. As the trifunctional monomer, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate and the like can be used. For example, ditrimethylolpropane tetraacrylate, dipentaerythritol penta, hexaacrylate and the like can be used. Commercial products of such photopolymerizable monomers include, for example, products of Showa High Polymer Co., Ltd., Toa Gosei Co., Ltd., Nippon Kayaku Co., Ltd.

In the present invention, the amount of the photopolymerizable monomer is not particularly limited, but is usually about 20 to 150 parts by weight per 100 parts by weight of the acrylic resin.
Preferably, it is about 50 to 150 parts by weight.

In the present invention, the photopolymerization initiator includes
For example, Irgacure 907, 65 manufactured by Ciba Geigy
One or more known photopolymerization initiators such as 1,184 (benzyldimethyl ketal), 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.), and benzophenone can be used, but photosensitive coloring can be used. In order to enable polymerization under an oxygen atmosphere of the composition, as a main component of a photopolymerization initiator,
Triazine-based compound photopolymerization initiator, for example, piperonyl-s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like can be used. Such a triazine compound may be used alone,
Multiple types may be used. Particularly preferred triazine compounds include 2- (p-methoxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine or 2-
(4'-Methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine.

As the photopolymerization initiator, an imidazole compound may be used in combination with the triazine compound.
Thereby, the sensitivity of the photosensitive coloring composition can be improved and a good pattern can be obtained. Such imidazole compounds include 2- (2,3-dichlorophenyl) -4,5-diphenyl-imidazole dimer,
(2,3-dichlorophenyl) -4,5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3
-Dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-chlorophenyl)-
Imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-di (2-furyl) -imidazole, 2,
2'-bis (2-chlorophenyl) -4,5,4 ', 5
'-Tetraphenyl-1,2'-biimidazole, 2,
2'-bis- (2-chlorophenyl) -4,5,4 ',
5'-tetra (3,4-methylenedioxyphenyl)-
It is preferable to use 1,1'-bi-1H-imidazole and the like. Particularly preferred imidazole compounds are 2,2'-bis- (2-chlorophenyl) -4,
5,4 ', 5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis- (2-chlorophenyl)-
4,5,4 ', 5'-Tetra (3,4-methylenedioxyphenyl) -1,1'-bi-1H-imidazole.

The amount of the photopolymerization initiator used is not particularly limited, but when only one or more triazine compounds are used, the triazine compound is usually used in an amount of 100 parts by weight of the photopolymerizable monomer. Is 5 to 50 parts by weight, preferably about 10 to 30 parts by weight. When the triazine compound and the imidazole compound are used in combination, the triazine compound is usually used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the photopolymerizable monomer.
And about 1 to 40 parts by weight, preferably about 5 to 20 parts by weight of the imidazole compound.

The photosensitive coloring composition of the present invention can be produced by uniformly mixing the above-mentioned components.
Care must be taken when mixing the poor solvent. That is, when the acrylic resin and the pigment are uniformly dispersed, it becomes difficult to disperse when the poor solvent coexists, so that a mixture of the acrylic resin, the pigment, the dispersant, and the good solvent for the acrylic resin is used as a photopolymerizable monomer. It is necessary to mix the photopolymerization initiator and the poor solvent for the acrylic resin later. Specifically, an acrylic resin and a pigment are kneaded well using two rolls or the like to form a chip, and then a dispersant and a good solvent for the acrylic resin are mixed to form a paste, and the photopolymerizable monomer is added to the paste. And a photopolymerizable initiator and a poor solvent for the acrylic resin. Alternatively, the acrylic resin is diluted with a good solvent for the acrylic resin, a pigment and a dispersant are added thereto, and the mixture is kneaded, and then a photopolymerizable monomer, a photopolymerizable initiator, and a poor solvent for the acrylic resin are added. It can be manufactured by mixing.

The photosensitive coloring composition of the present invention thus obtained is useful for producing a color filter, particularly for producing a color filter used for a color liquid crystal display, a color video camera, an image scanner and the like. It will be useful. Further, the present invention is not limited to this, and the photosensitive coloring composition of the present invention can be used widely as a UV ink, a photosensitive paint, or the like.

[0027]

The photosensitive coloring composition of the present invention contains a poor solvent for an acrylic resin which is a resin for dispersing a pigment. Therefore, it is possible to prevent the acrylic resin coating the pigment particles from being dissolved in a good solvent for the acrylic resin. This makes it possible to prevent the pigments from aggregating with each other and to improve the temporal stability of the photosensitive coloring composition.

[0028]

Embodiments of the present invention will be described below in detail with reference to the drawings. In each of the drawings, the same numbers indicate the same or equivalent components.

Example 1 First, 20 parts by weight of methacrylic acid, 10 parts by weight of methyl methacrylate, 55 parts by weight of butyl methacrylate and 15 parts by weight of hydroxyethyl methacrylate were dissolved in 300 parts by weight of ethyl cellosolve, and the mixture was dissolved in a nitrogen atmosphere under azobisisopropane. Add 0.75 parts by weight of butyronitrile, and add
After reacting for an hour, an acrylic resin was obtained.

The obtained acrylic resin was diluted with ethyl cellosolve so as to have a resin concentration of 8%.

Next, 70.2 g of the diluted acrylic resin was added to a pigment [Riotogen Red GD (CI Pigment Red 168) manufactured by Toyo Ink Mfg. Co., Ltd .; Paliotor Yellow D1819 (CI Pigment Yellow 139);
As pigments for green coloring compositions, Lionol Green 2YS (CI Pigment Green 36) manufactured by Toyo Ink Mfg. Co., Ltd. and Palio Tol Yellow D18 manufactured by BASF are used.
19 (CI Pigment Yellow 139); or as a pigment for a blue colored composition, Lionol Blue ES (CI Pigment Blue 15: manufactured by Toyo Ink Mfg. Co., Ltd.)
6), Lionogen Violet HR (CI Pigment Violet 32) and B manufactured by Toyo Ink Manufacturing Co., Ltd.
Paliotor Yellow D1819 (CI.
Pigment Yellow 139)] and 0.5 g of an organic dye derivative suitable for dispersing each pigment as a dispersing agent were added, and the mixture was sufficiently kneaded with three rolls to obtain a resin mixture of each color of red, green, and blue. .

Further, with respect to 85.2 g of the resin mixture of each color, 4 g of trimethylolpropane triacrylate as a photopolymerizable monomer, 0.8 g of piperonyl-s-triazine as a photopolymerization initiator, and a poor solvent for an acrylic resin. Ethylbenzene (10 g) was added and mixed uniformly to obtain a photosensitive coloring composition of each color of red, green and blue.

Example 2 A photosensitive colored composition of each color of red, green and blue was obtained in the same manner as in Example 1 except that 10 g of isopentyl acetate was used instead of ethylbenzene as a poor solvent for the acrylic resin.

Comparative Example 1 Photosensitive coloring of each color of red, green and blue was carried out in the same manner as in Example 1, except that 10 g of ethylcellosolve as a good solvent was used in place of ethylbenzene as a poor solvent for acrylic resin. A composition was obtained.

COMPARATIVE EXAMPLE 2 In place of ethylbenzene, which is a poor solvent for an acrylic resin, 10 g of ethyl acetate, which is a good solvent, was used.
In the same manner as in Example 1, red, green, and blue photosensitive coloring compositions were obtained.

(Evaluation) (1) Stability over time The photosensitive coloring compositions of each color obtained in the Examples and Comparative Examples were stored in a brown glass light-shielding container at room temperature, and stored at room temperature. The viscosities (cp / 25 ° C.) of the compositions after 2 months, 2 months and 3 months were measured to determine the difference in viscosity from before storage. Table 1 shows the results.

[0037]

[Table 1] As can be seen from Table 1, the photosensitive coloring composition of the example was 3
Even after storage for a month, the viscosity difference was within +3 cp, indicating a temporal stability with no practical problem. On the other hand, since the photosensitive coloring composition of the comparative example did not contain a poor solvent for the acrylic resin, the viscosity increased to a practically problematic level (10 cp or more) after 2 months.

(2) Coating Properties Using the photosensitive coloring compositions obtained in Examples and Comparative Examples immediately after preparation and after storage for 3 months, spin coating the photosensitive coloring compositions on a glass substrate ( 1300 rpm, 5 seconds)
And dried. The in-plane film thickness uniformity (3σ) of the obtained thin film was measured with a contact-type film thickness meter, and further, the coating unevenness of the external appearance was examined visually. Table 2 shows the results.

[0039]

[Table 2] In-plane film thickness uniformity (3σ (μm)) Immediately after the appearance unevenness Three months after preparation Example 1 ≤0.05 ≤0.05 None 2 ≤0.05 ≤0.05 None Comparative Example 1 ≤0.05 ≥0.1 Color unevenness 2 ≤0.05 ≥0.1 color as it can be seen from unevenness Yes table 2, the photosensitive coloring composition of the embodiment,
Uniform coating was possible without uneven appearance. On the other hand, in the photosensitive coloring composition of the comparative example, the in-plane film thickness uniformity was insufficient, and color unevenness was observed.

(B) Color Filter Characteristics According to the process chart shown in FIG. 1 and the cross-sectional explanatory view of each process shown in FIG. 2, the photosensitive coloring composition prepared in the examples is stored immediately after preparation and for 2 months. A color filter was produced using the latter one.

That is, first, a red photosensitive coloring composition 2 was spin-coated (1300 rpm, 5300 rpm) on a transparent glass substrate 1 (FIG. 2A) on which a color separation band 1a was previously provided.
sec) and dried, and prebaked at 70 ° C. for 20 minutes (FIG. 2B).

Next, as shown in FIG. 2C, a photomask 3 having a light-shielding pattern 3a was overlaid and exposed to light L (200 mJ / cm ² ). Then, the film was developed with a 2.5% aqueous solution of sodium carbonate and sufficiently washed with water. Thereafter, the pigment adhering to the glass substrate 1 was removed by rubbing with a soft sponge, further washed with water, dried, and baked at 230 ° C. for 1 hour. Thus, as shown in FIG.
On the glass substrate 1, a red colored layer pattern 2R made of a cured product of the red photosensitive colored composition was formed.

Similarly, a blue colored layer pattern 2B and a green colored layer pattern 2
G was produced (FIG. 2E). The exposure amount for the green photosensitive coloring composition was 300 mJ / cm ^2, and the exposure amount for the red photosensitive coloring composition was 150 mJ / c.
It was m ^2.

The color filter thus produced was subjected to a chemical resistance test. That is, 5% NaOH, 5%
% H ₂ SO ₄ , N-methylpyrrolidone (NMP), γ-
Each was immersed in butyl lactone and isopropanol (IPA) at room temperature for 30 minutes, and the appearance of the color filter after immersion and the adhesion of the pattern of the colored layer to the glass substrate were visually observed. Further, a treatment with vapor of isopropanol (IPA) was also performed, and the appearance after the treatment and the adhesion of the pattern of the colored layer to the glass substrate were similarly visually observed.
As a result, the color filters prepared from the photosensitive coloring compositions of Examples immediately after preparation and after storage for 2 months did not change in appearance and adhesion, and both exhibited excellent chemical resistance.
This indicates that the photosensitive coloring composition of the present invention can produce an excellent color filter even after long-term storage.

[0045]

According to the present invention, high temporal stability can be imparted to the photosensitive coloring composition.

[Brief description of the drawings]

FIG. 1 is a process chart for producing a color filter using the photosensitive coloring composition of the present invention.

FIG. 2 is a sectional view illustrating each step of a color filter using the photosensitive coloring composition of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Photosensitive coloring composition 2R, 2B, 2G coloring layer 3 Photomask

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/027 502 G03F 7/027 502 7/028 7/028 7/033 7/033 (56) References 289601 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004 C09D 4/02 C09D 11/00 G02B 5/20 101 G03F 7/027 G03F 7/028 G03F 7 / 033

Claims (6)

(57) [Claims] 1. A photosensitive coloring composition comprising an acrylic resin, a pigment, a dispersant, a photopolymerizable monomer, a photopolymerization initiator and a good solvent for the acrylic resin,
Unable to dissolve all 1% by weight of acrylic resin at room temperature
There, a poor solvent for the acrylic resin, photosensitive coloring composition characterized in that it is contained 100-350 parts by weight per 100 parts by weight of the acrylic resin. 2. The photosensitive coloring composition according to claim 1, wherein the poor solvent for the acrylic resin is contained in an amount of 150 to 200 parts by weight based on 100 parts by weight of the acrylic resin. 3. The photosensitive coloring composition according to claim 1, wherein the poor solvent for the acrylic resin is an aromatic hydrocarbon or an acetic ester. 4. The photosensitive coloring composition according to claim 1, which comprises at least one triazine compound as a main component of the photopolymerization initiator. 5. The photosensitive coloring composition according to claim 4, further comprising at least one imidazole compound as a main component of the photopolymerization initiator. 6. A mixture of an acrylic resin, a pigment, a dispersant and a good solvent for the acrylic resin, a photopolymerizable monomer, a photopolymerization initiator and 1% by weight of the acrylic resin at room temperature.
The method for producing a photosensitive coloring composition according to any one of claims 1 to 5 , wherein a poor solvent for the acrylic resin , which cannot dissolve all the resins, is mixed.