JP2001249215A - Color filter and composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain high transmittance and excellent color separation of a color filter especially from a viewpoint of pigments. SOLUTION: The color filter contains C.I. pigment green 7, C.I. pigment green 36 and C.I. pigment yellow 150. Additionally the color filter has <=20% transmittance in 400-470 nm, <=20% transmittance in 610-650 nm, a wavelength of 40% transmittance on the short wavelength side of the transmission spectrum in 470-490 nm range, a wavelength of 40% transmittance on the long wavelength side of the transmission spectrum in 570-600 nm range and >=80% peak value of transmittance in the visible ray region.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent colored image using a photosensitive resin, and more particularly, to a color liquid crystal display, a color facsimile, a digital camera, a three-tube and single-tube color video camera, and a solid color image. The present invention relates to a color filter mounted on a video camera or the like and a composition for a color filter.

[0002]

2. Description of the Related Art A color filter used for a liquid crystal display device or a solid-state image pickup device is provided by providing an extremely fine region colored in two or three or more different colors on a transparent substrate or a solid-state image pickup device. Is formed. As a method for producing the color filter, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known. The pigment dispersion method is a method of producing a color filter by a photolithographic method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions.

This method is stable to light and heat due to the use of pigments, and is patterned with a photolithographic method. Therefore, the position accuracy is sufficient, and a color filter for a digital camera having a large number of pixels and a large size. This method is suitable for producing a color filter for a screen and a high-definition color display.

In recent years, however, color filters, especially for digital cameras and solid color video cameras, have been required to have higher definition, higher brightness, and higher color reproducibility. There is a demand for higher transmittance and excellent color separation.

Conventionally, in order to further increase the transmittance of a color filter, the pigment is finely divided or finely dispersed, or a yellow pigment whose transmittance rises on a shorter wavelength side, such as a yellow pigment, C. I. Pigment Yellow 1
By using 50 or 138, the wavelength of the transmittance of 40% on the long wavelength side of the transmission spectrum is shifted to the longer wavelength side, or the wavelength of the transmittance of 40% on the long wavelength side of the transmission spectrum is shifted to the shorter wavelength side. The method of shifting to is adopted. Further, in order to realize excellent color separation properties, a method of increasing the pigment content in a color filter has been adopted.

However, according to the above-mentioned method, the color separation property is deteriorated as the transmittance is increased, and the transmittance is reduced as the color separation property is improved. That is, there has been a problem that high transmittance and excellent color separation cannot be simultaneously satisfied.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and aims to solve the problem of further increasing the transmittance and excellent color separation of a color filter, particularly from the viewpoint of pigments. It is an issue.

[0008]

SUMMARY OF THE INVENTION The above-mentioned problems are related to R, G,
Focusing on the spectral characteristics of the transmittance of B, the spectral characteristics of G having an overlapping portion on both sides with R on the long wave side and B on the short wave side,
The problem is solved by the following color filter consisting of the following composition having specific pigment selection and specific properties. (1) C.I. I. Pigment Green 7 and C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150
A color filter comprising: (2) Transmittance at 400 to 470 nm of 20% or less, 61
The transmittance at 0 to 650 mm is 20% or less, the wavelength at the transmittance of 40% on the short wavelength side of the transmission spectrum (short wave 40% transmittance wavelength) is in the range of 470 to 490 nm, and the transmittance at the long wavelength side of the transmission spectrum. The color filter according to (1), wherein a wavelength of 40% (a long-wavelength 40% transmittance wavelength) is in a range of 570 to 600 nm, and a transmittance peak value in a visible region is 80% or more.

(3) a pigment and (a) a photopolymerizable ethylenically unsaturated compound having at least two terminal ethylene groups,
(B) a photopolymerization initiator that is activated by ultraviolet irradiation,
In a photopolymerizable composition comprising at least (c) an organic high molecular polymer having a water-soluble atomic group in a part of a side chain and (d) an organic solvent, the pigment is C.I. I. Pigment Green 7
And C. I. Pigment Green 36 and C.I. I. Pigment Yellow 150. A composition for a color filter, comprising: Pigment Yellow 150.

(4) The dry film thickness after exposure and development is 0.5 to
The spectral characteristic of the coating film in any of the ranges of 2.0 μm is such that the transmittance at 400 to 470 nm is 20% or less,
The transmittance at 20 to 650 nm is 20% or less, the wavelength at the transmittance 40% on the short wavelength side of the transmission spectrum (short wave 40% transmittance wavelength) is in the range of 470 to 490 mm, and the transmittance 40 at the long wavelength side of the transmission spectrum. % (Wavelength 40% transmittance wavelength) is in the range of 570 to 600 nm, and the peak value of transmittance in the visible region is 80% or more, wherein the composition for a color filter according to the above (3), .

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing a color filter of the present invention is not particularly limited, and a printing method, an electrodeposition method, a photolithography method for forming a pattern in combination with a resist, and the like can be applied. As an example, a case where a pigment and a photopolymerizable composition are used will be specifically described.

The pigment used in the color filter of the present invention is C.I. I. Pigment Green 7 and C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150
It is.

The mixing ratio (% by mass) of these pigments is generally C.I. I. Pigment Green 7
90, C.I. I. Pigment Green 36 is 1-90,
C. I. Pigment Yellow 150 is 5 to 50,
C. I. Pigment Green 7 is 3 to 80, and C.I. I. Pigment Green 36 is 3 to 80, and C.I. I. Pigment Yellow 150 is preferably from 10 to 45, and C.I. I. Pigment Green 7 is 5 to 70, and C.I. I. Pigment Green 36 is 5 to 70, and C.I. I. Pigment Yellow 15
0 is more preferably 15 to 40.

Further, as long as the above-mentioned definition of the present invention is satisfied, pigments other than those described above may be used in combination depending on the purpose.
The amount of addition is suitably 5% by mass or less based on the total amount of pigments added. Specifically, barium sulfate, zinc white, lead sulfate, titanium oxide, yellow lead, red bengal, ultramarine, navy blue, chromium oxide,
Inorganic pigments such as carbon black, benzidine yellow G, benzidine yellow GR, lithol first orange 3GL, vulcan first orange GG, pigment scarlet 3B, thioindigo maroon, phthalocyanine blue, phthalocyanine green, indanthrene blue, green gold, malachite green lake And the like. The color index (C.I.
I. ) More specifically by number. C. I. Yellow pigment 20, 24, 83, 86, 93, 1
09, 110, 117, 125, 137, 138, 14
7, 148, 150, 153, 154, 166, 168 C.I. I. Orange pigment 36, 43, 51, 55, 5
9, 61 C.I. I. Red pigment 9,97,122,123,14
9,168,177,180,192,215,216
Or 217,220,223,224,226,22
7, 228, 240, 242, 244, 254 C.I. I. Violet pigments 19,23,29,30,
37, 40, 50 C.I. I. Blue pigment 15,15: 3,15: 6,22,
60, 64 C.I. I. Green pigment 36 C.I. I. Brown pigment 23, 25, 26 C.I. I. Black pigment 7

The photopolymerizable composition of the present invention comprises an organic high molecular polymer having a water-soluble atomic group in a part of a side chain and a photopolymerizable ethylenically unsaturated compound having at least two terminal ethylene groups. And at least one of the above, a photopolymerization initiator activated by irradiation with ultraviolet light, and an organic solvent.

Examples of the photopolymerizable ethylenically unsaturated compound having at least two terminal ethylene groups (hereinafter sometimes simply referred to as a monomer) include, for example, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate , Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate;

Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) A) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane (Meth) acrylate after adding ethylene oxide or propylene oxide to

Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-
Urethane acrylates described in JP-A-6034 and JP-A-51-37193;
64183, JP-B-49-43191, JP-B-52
Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid described in JP-A-30490.

Further, the Journal of the Adhesion Society of Japan, Vol. 20, N
o. The compounds introduced as photocurable monomers and oligomers on pages 300 to 308 can also be used. The above monomers or oligomers may be used alone or in combination of two or more. The use amount of these compounds is 5 to 50% by mass, and preferably 10 to 40% by mass, based on the solid content of the photopolymerizable composition.

The organic polymer having a water-soluble atomic group in a part of the side chain (hereinafter, may be simply referred to as a binder) includes a linear organic polymer having a compatibility with a monomer. Those which are united, soluble in an organic solvent, and developable with a weak alkaline aqueous solution are preferred. Such polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957,
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer described in JP-A-59-53836 and JP-A-59-71048. There are polymers, partially esterified maleic acid copolymers, and the like, and similarly, there are acidic cellulose derivatives having a carboxylic acid in the side chain.

In addition, a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group is useful. Among them, benzyl (meth) acrylate / (meth) acrylic acid copolymers and benzyl (meth) acrylate / (meth) acrylic acid / multi-component copolymers with other monomers are particularly preferable. These polymers can be mixed in an arbitrary amount, but if the amount exceeds 90% by mass based on the solid content of the photopolymerizable composition, a preferable result is not obtained in view of the strength of the formed image and the like. Preferably it is 30 to 85% by mass.

As the photopolymerization initiator activated by irradiation with ultraviolet rays, at least one kind of trihalomethyl compound can be used. In addition, the following materials can be used in combination.
A picinal polyketo aldonyl compound disclosed in U.S. Pat. No. 2,367,660;
Α-carbonyl compounds disclosed in 367,661 and 2,367,670, acyloin ether disclosed in U.S. Pat. No. 2,448,828, U.S. Pat. No. 2,722,512 No. 3,046,127 and 2,951,758, polynuclear quinone compounds disclosed in U.S. Pat. Nos. 3,046,127 and 2,951,758. Combination of triallylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 4,212,9.
No. 76, oxadiazole compounds and the like. The use amount of the trihalomethyl compound is suitably about 0.2 to 20% by mass, more preferably 0.5 to 15% by mass in terms of the solid content ratio to the monomer.

The ratio of the compound used in combination with the trihalomethyl compound is 1 to the trihalomethyl compound.
0 to 800% by mass, more preferably 20 to 300% by mass
It is.

Examples of the organic solvent used in preparing the composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyric acid. Isopropyl, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate 3, such as methyl 3-oxypropionate and ethyl 3-oxypropionate;
-Oxypropionic acid alkyl esters;

Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate;
Propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-
Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2
-Ethyl methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;
Diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;
Aromatic hydrocarbons, for example, toluene, xylesi and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexane Xanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. These solvents may be used alone or in combination of two or more.

A dispersant may be added to the composition of the present invention in order to improve the dispersibility of the pigment. As these dispersants, many kinds of dispersants such as cationic surfactants, fluorine surfactants, and polymer dispersants are used.

Further, the graft copolymer described in JP-A-10-254133 and having a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain thereof is excellent in dispersing the pigment finely. Having an action, by using this, it is possible to finely disperse the pigment without taking much energy or time, and the dispersed pigment does not aggregate or settle even after a lapse of time. A composition having good dispersion stability over a long period of time can be obtained, which is preferable as a dispersant, and can be blended with the composition of the present invention. These dispersants may be used alone or in combination of two or more. Such a dispersant is usually used in an amount of 0, 1 to 5 based on 100 parts by mass of the pigment.
It is used in an amount of 0 parts by weight.

The composition of the present invention may contain, if necessary, other various additives such as a filler, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent. it can.

In order to improve the storage stability of the composition of the present invention, a thermal polymerization inhibitor is generally added.

Further, in order to promote the alkali solubility of the non-irradiated portion of the ultraviolet ray to further improve the developability of the composition of the present invention, the composition of the present invention may contain an organic carboxylic acid, preferably having a molecular weight of 1,000 or less. Of low molecular weight organic carboxylic acids can be added.

The composition of the present invention can be prepared by mixing and dispersing the pigment and the above-mentioned materials using various mixers and dispersers. Conventionally known mixers and dispersers can be used. For example, a homogenizer, a kneader, a ball mill, a two or three roll mill, a paint shaker, a sand grinder,
A sand mill such as a dyno mill can be used.

As a preferable preparation method, first, a solvent is added to the pigment and the binder, and the mixture is uniformly mixed. Then, using two or two rolls, kneading is performed while heating as necessary, so that the pigment and the binder are sufficiently mixed. To obtain a uniform colored body. Next, a solvent, a monomer, and a photopolymerization initiator are added to the obtained colored body, a dispersant and various additives are added as necessary, and various types of sand mills using a ball mill or glass beads as a dispersion media, such as a Dyno mill, are used. Perform dispersion. At this time, a smaller dispersion can be obtained as the diameter of the glass beads is smaller. At this time, a dispersion result with good reproducibility can be obtained by controlling the temperature of the dispersion liquid to be constant. The dispersion obtained here can remove coarse particles by centrifugation, filtration, or decantation, if necessary.

The composition of the present invention thus obtained is
The substrate was coated by a spin coating, casting coating, roll coating, or other coating method to form an ultraviolet-sensitive composition layer, exposed through a predetermined mask pattern, and developed with a developer to be colored. Form a pattern. As the radiation used at this time, ultraviolet rays such as g-rays and i-rays are particularly preferably used.

In the case of a solid-state imaging device,
A photoelectric conversion element substrate, for example, a silicon substrate is used. In the case of a liquid crystal display element, soda glass, Pyrex (registered trademark) glass, quartz glass, or a material obtained by attaching a transparent conductive film to these may be used. In general, a black stripe separating each pixel may be formed on these substrates.

As the developer, any developer may be used as long as it dissolves the unirradiated ultraviolet-sensitive composition and does not dissolve the ultraviolet-irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.

Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Alkaline compounds such as choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5.4.0] -7-undecene at concentrations of 0.001 to 0.001.
An alkaline aqueous solution dissolved to be 10% by mass, preferably 0.01 to 1% by mass is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

[0040]

EXAMPLES (Example 1) 12 parts of benzyl methacrylate / methacrylic acid copolymer C.I. I. Pigment Green 7 3.5 parts C.I. I. Pigment Green 36 14.0 parts C.I. I. Pigment Yellow 150 5.3 parts ・ Propyrene glycol monomethyl ether acetate 20 parts were mixed and kneaded with a three-roll mill.

To the obtained kneaded product, 50 parts of propylene glycol monomethyl ether acetate and 50 parts of ethyl 3-ethoxypropionate were added and dispersed by a bead mill using beads having a diameter of 0.2 mm. In the resulting dispersion:-40 parts of dipenquethritol pentaacrylate-4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 3 parts 7 [{4-chloro-6- (diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin 2 parts Hydroquinone monomethyl ether 0.01 parts Propylene glycol monomethyl ether acetate 200 parts And stirred, and then centrifuged at 10,000 rpm.
Filtration through a μm filter gave the composition of the present invention.

The obtained composition was applied to a glass substrate using a spin coater, dried, exposed to light, developed and dried to obtain a color filter film of the present invention having a thickness of 1.5 μm. When the transmittance of the obtained color filter was measured with an MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) spectrometer, the transmittance was 400 nm.
In the range from 650 to 650 nm, the wavelengths having a transmittance of 20% or less are 473 nm or less on the short wave side and 603 nm or more on the long wave side, and the 40% transmission wavelength on the short wave side is 481 nm and the long wave side 4
The 0% transmission wavelength was 588 nm, and the transmittance peak value was 86%.

Examples 2 and 3 A color filter composition and a color filter were prepared in the same manner as in Example 1 except that the amount of the pigment was changed to the value shown in Table 1. Further, the transmittance of the color filter was measured in the same manner as in Example 1. 20% or less short wavelength transmission wavelength of each color filter,
Longwave 20% or less transmission wavelength, shortwave 40% transmission wavelength, longwave 4
Table 2 shows the 0% transmission wavelength and the transmittance peak value.

(Comparative Example 1) The pigment of Example 1 was replaced with C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 1
The composition for a color filter and the color filter were prepared in the same manner except that the addition amount was changed to 39 and the addition amount was changed to the value shown in Table 1. Thereafter, the transmittance of the color filter was measured in the same manner as in Example 1. Short wave side 2 of each color filter
0% or less transmission wavelength, long wave side 20% or less transmission wavelength, short wave 4
Table 2 shows the 0% transmission wavelength, the long wave 40% transmission wavelength, and the transmittance peak value.

Further, the pigment is C.I. I. Pigment Red 224 and C, I. Pigment Yellow 139
Was changed to 4 g, a red filter was produced in the same manner as in Example 1, and the transmittance thereof was measured. The pigment is C.I. I. Pigment Blue 15: 6 and 14 g of C.I.
I. Pigment Violet 23 was changed to 10 g, a blue filter was prepared in the same manner as in Example 1, and the transmittance was measured.

The integrated value (A) of the transmittance of the portion where the transmittance of 550 nm to 650 nm of the color filter obtained in each of Examples 1 to 3 and Comparative Example 1 overlaps the transmittance of the red filter, and Examples 1 to 3 and Table 3 shows the integrated value (B) of the portion where the transmittance of the color filter obtained in Comparative Example 1 from 400 nm to 550 nm overlaps the transmittance of the blue filter and the total value (A + B).

As is clear from Table 3, the portion where the transmittance of the color filter obtained in the example of the present invention overlaps with the transmittance of the red filter and the blue filter is greatly reduced. It can be seen that the color filter has a good spectral transmittance.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

According to the present invention, high transmittance, R,
It is possible to provide a color filter having excellent color separation of the three colors G and B. The color filter of the present invention is also suitable for transparent colored images such as stained glass.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating spectral characteristics of Example 1, Comparative Example 1, a red filter, and a blue filter.

Claims (4)

[Claims] Claims: 1. I. Pigment Green 7 and C.I.
I. Pigment Green 36 and C.I. I. A color filter comprising Pigment Yellow 150. 2. The transmittance at 400 to 470 nm is 20% or less, the transmittance at 610 to 650 mm is 20% or less, and the wavelength at a transmittance of 40% on the short wavelength side of the transmission spectrum is 470 to 4%.
A wavelength of 90%, and a wavelength of 40% transmittance on the long wavelength side of the transmission spectrum is in a range of 570 to 600 nm;
The color filter according to claim 1, wherein a peak transmittance value in a visible region is 80% or more. 3. A pigment and (a) a photopolymerizable ethylenically unsaturated compound having at least two terminal ethylene groups,
(B) a photopolymerization initiator that is activated by ultraviolet irradiation,
In a photopolymerizable composition comprising at least (c) an organic high molecular polymer having a water-soluble atomic group in a part of a side chain and (d) an organic solvent, the pigment is C.I. I. Pigment Green 7
And C. I. Pigment Green 36 and C.I. I. Pigment Yellow 150. A composition for a color filter, comprising: Pigment Yellow 150. 4. The dry film thickness after exposure and development is 0.5-2.
The spectral characteristic of the coating film in any of the ranges of 0 μm is 4
The transmittance at 00 to 470 nm is 20% or less,
The transmittance of 0 nm is 20% or less, the wavelength of the transmittance 40% on the short wavelength side of the transmission spectrum is in the range of 470 to 490 mm, and the wavelength of the transmittance 40% on the long wavelength side of the transmission spectrum is the range of 570 to 600 nm. Wherein the transmittance peak value in the visible region is 80% or more.
The composition for a color filter as described in the above.