JP2009210689A - Ink composition for printing, method for manufacturing color filter, color filter, and image display - Google Patents

Abstract

[PROBLEMS] To improve the releasability of ink filled in a concave portion of an intaglio in the gravure offset printing method, improve the adhesion to the substrate, improve the transferability to the substrate, and achieve high productivity. A color filter manufacturing method and a high-quality color display device are provided.
A printing ink composition comprising: (a) a colorant; and (b) a compound having a fluorene ring and an epoxy ring.
[Selection figure] None

Description

  The present invention relates to a printing ink composition, particularly a printing ink composition suitable for producing a color filter, a method for producing a color filter using the same, and a color filter and an image display device obtained.

  In recent years, liquid crystal display devices are used from televisions to information terminal interfaces, from industrial device interfaces to portable information devices, and are at the center of thin display devices. In particular, as the display area of liquid crystal display devices has increased in size and definition, the mother glass substrate area of color filters has been steadily expanding in order to increase productivity and reduce manufacturing costs. On the other hand, color filters that are indispensable for colorization of liquid crystal display devices are required to improve quality, and high optical characteristics such as high contrast and high saturation are required.

  In the production of color filters, a number of production methods have been proposed, including dyeing methods, photolithography methods using photocurable resin compositions in which pigments are dispersed, inkjet methods, screen printing methods, electrodeposition methods, and gravure printing methods. However, from the viewpoint of quality, a photolithography method using a photocurable resin composition in which a pigment is dispersed has become mainstream.

  However, since the photolithography method is manufactured by repeating coating, drying, exposure, development, and post-baking, it requires many steps and a large number of facilities. Coupled with the increase in the size of the mother glass substrate, it has led to an increase in the size of the line and the resulting increase in the price of production equipment, and it is difficult to meet the demand for cost reduction.

  When forming a multicolor pattern, apply a photopolymerizable composition of another color on the pattern once formed and repeat the pattern formation process again. May remain as scum, causing color mixing and causing a decrease in color purity. In order to suppress this phenomenon, it is necessary to further cure the pattern once formed at a high temperature. On the other hand, the pigment used is miniaturized for high contrast. In the photolithography method, many heating steps are repeated, so that the miniaturized pigment is deteriorated by heat, easily changes in hue, and it is difficult to maintain high optical characteristics.

On the other hand, the production of color filters by printing, which is considered to be difficult in terms of quality with high productivity, especially the gravure printing method and the production method by the gravure offset method, improve the accuracy of the printing apparatus, plate making technology (e.g., cited document) 1)) suggests the possibility of producing a high quality color filter at low cost. When a color filter is manufactured by a printing method, it is important that the ink is completely transferred from the intaglio to the transfer target (substrate) and the ink is in close contact with the transfer target. As a device for complete transfer, a release layer is applied to the surface of the intaglio and a device for improving the adhesion of ink to the transfer target (for example, Patent Document 2) has been made, but in gravure printing and gravure offset printing As for suitable ink compositions, proposals have not been sufficient.
In addition, it has been proposed to introduce extender pigments for the adjustment of the viscosity of gravure ink, but there is a concern that optical properties may be deteriorated by containing components unnecessary for color development and curing. It is also possible to use a polymer vehicle component to adjust the viscosity, but the thixotropic property increases and the viscosity changes in the ink supply system of the printing press as a large number of sheets are printed. It becomes difficult to obtain a color filter with stable quality. (See Patent Document 3)
JP 2007-118593 A JP-A-8-072384 Japanese Patent Laid-Open No. 10-10309

  The present invention improves the peelability of the ink filled in the concave portions of the intaglio in the gravure printing and gravure offset printing methods, improves the adhesion to the substrate, and improves the transferability to the substrate. This provides a method for manufacturing a color filter by gravure printing and gravure offset printing, which has high productivity and continuous productivity even with a large substrate for a display device, and provides a color for a high-quality display device. It is an object to provide a filter.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by the following method.
<1> A printing ink composition comprising (a) a colorant and (b) a compound having a fluorene ring and an epoxy ring.

<2> The printing ink composition according to <1>, wherein the compound having a fluorene ring and an epoxy ring is represented by the following general formula (I).

In general formula (I), R is ethylene or propylene, and n and m each independently represent an integer having a relationship in which m + n is 0 to 12.
<3> The printing ink composition according to <1> or <2>, further comprising (c) a polymerizable compound and (d) a polymerization initiator.
<4> A color filter, wherein a pattern is provided on a transparent substrate by a gravure printing method or a gravure offset printing method using the ink composition according to any one of <1> to <3>. Production method.

<5> A color filter manufactured by the manufacturing method according to <4>.
<6> An image display device that performs color display using the color filter according to <5>.

<7> A method for producing a color filter, wherein the ink composition filled in the concave portion is irradiated with light before being transferred from the intaglio by the production method according to <4>.

  In the present invention, by using a compound having both a fluorene ring and an epoxy ring, the ink composition is moderately flexible and has a film-forming property. The image is transferred to a blanket or the like at a high transfer rate with almost no untransferred ink remaining in the recesses, and the transferred pixels are also retransferred to the substrate in a state and capacity where the desired shape is maintained. It is thought that. In a preferred embodiment of the present invention, since the curable component is further contained in the ink composition, the transferability is further improved. This is presumably because the film forming property of the ink composition was strengthened, and the effect of improving the shape retention and transferability of the image in the recesses became more prominent. In addition, by using a low molecular weight specific fluorene compound, thixotropic properties do not become high, precise measurement can be performed with an intaglio, and even when repeated printing is performed, a change in transfer rate is small and a stable color filter is obtained. It is thought that it was possible.

  INDUSTRIAL APPLICABILITY The present invention can improve the releasability of the ink filled in the recesses of the intaglio in the gravure printing and gravure offset printing methods, and can provide an ink composition having a high transferability to the substrate. It is possible to provide a color filter manufacturing method and a gravure printing method and a gravure offset printing method which have high productivity and continuous productivity even for a large substrate for an apparatus, and further, it is possible to provide a color filter for a display device with high image quality.

Hereinafter, the best mode for carrying out the invention will be described in detail.
The present invention comprises a printing ink composition comprising (a) a colorant and (b) a compound having a fluorene ring and an epoxy ring (hereinafter sometimes referred to as a specific epoxy compound). Is done.

(A) As the colorant, organic and inorganic pigments, dyes, or mixtures thereof can be used. As the pigment, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used. As the particle size of the pigment, considering that the color filter in which the pigment dispersion composition of the present invention is suitably used preferably has a high transmittance, an organic pigment is preferable, and a pigment having a particle size as small as possible. Is preferably used. Considering the handling properties of the pigment dispersion composition and the photocurable composition containing the same, the average primary particle diameter of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 to 25 nm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast. The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. The above range is preferable from the viewpoints of light transmittance, color purity, and coloring power. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. The above range is preferable from the viewpoints of light transmittance, color purity, and NTSC target hue. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

  Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable. The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. The above range is preferable from the viewpoint of dispersion stability.

  The pigment of the present invention can be used finely for improving color purity, increasing transmittance, improving contrast, and the like. Such fine pigments are produced by mixing i) a pigment, ii) a water-soluble inorganic salt, iii) a small amount of a water-soluble organic solvent that does not substantially dissolve ii), and, if necessary, iv) a dispersion resin. A step of mechanically kneading with a kneader or the like (this pigment refining step is called salt milling), a step of putting this mixture into water and stirring it with a high-speed mixer or the like to form a slurry, and this slurry Is filtered, washed with water, and dried if necessary. By such a production method, a finely processed pigment can be obtained which is fine and has little aggregation of the pigment when dried.

  The salt milling described above will be described more specifically. First, a small amount of iii) a water-soluble organic solvent is added as a wetting agent to a mixture of i) an organic pigment and ii) a water-soluble inorganic salt, and iv) if necessary, after kneading the dispersion resin with a kneader, etc. This mixture is put into water and stirred with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary to obtain a finer pigment. In addition, when using it disperse | distributing to an oil-based varnish, it is also possible to disperse | distribute the process pigment (it is called a filter cake) before drying to an oil-based varnish, removing water by the method generally called flushing. When dispersed in an aqueous varnish, the treated pigment does not need to be dried, and the filter cake can be dispersed in the varnish as it is.

By using iv) a dispersion resin in combination with the above iii) organic solvent at the time of salt milling, a finer processed pigment with a finer surface and coated with the dispersion resin iv) and less agglomeration of the pigment upon drying can be obtained. .
Note that iv) the timing of adding the dispersed resin may be added all at the beginning of the salt milling step, or may be added in divided portions.

ii) Water-soluble inorganic salt The water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used. Sodium chloride or sodium sulfate is preferably used.
The amount of the inorganic salt used for salt milling is preferably 1 to 30 times, particularly 5 to 25 times, that of the organic pigment from the viewpoint of both processing efficiency and production efficiency. The larger the ratio of the inorganic salt to the organic pigment is, the higher the refinement efficiency is.

iii) A small amount of a water-soluble organic solvent that does not substantially dissolve ii) A water-soluble organic solvent serves to wet organic pigments and inorganic salts, and is an inorganic salt that is dissolved (mixed) in water and used. If it does not melt | dissolve substantially, it will not specifically limit. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.

The addition amount of the water-soluble organic solvent is preferably 5% by mass to 50% by mass with respect to the inorganic salt. More preferably, it is 10 mass%-40 mass% with respect to an inorganic salt, and optimally it is 15 mass%-35 mass% with respect to an inorganic salt. The above range is preferable from the viewpoint of physical properties suitable for kneading.
iii) The water-soluble organic solvent may be added in the initial stage of salt milling, or may be added separately. A water-soluble organic solvent may be used independently and can also use 2 or more types together.

  If necessary, iv) a dispersion resin can be used in the above-described refinement step, but as the dispersion resin, a natural resin, a synthetic resin, or a polymer compound having a specific structure can be used. The polymer compound has a strong adsorptivity to the pigment and can coat the pigment. This is effective for ensuring the dispersion stability of the pigment dispersion and the ink composition by dispersing the fine pigment coated with a resin having a specific structure as primary particles.

  The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.

  The above-mentioned covering state can be confirmed by measuring the free amount (release rate) of the polymer compound by washing with an organic solvent shown below. That is, most of the polymer compound simply adsorbed is washed and washed with an organic solvent, specifically, 65% or more is liberated and removed. In the case of a surface-coated pigment as in the present invention, the liberation rate Is very small, 30% or less.

  The pigment after the coating treatment of the present invention is washed with 1-methoxy-2-propanol, and the free amount is calculated. In this method, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was allowed to settle for 8 hours at 80,000 rpm in a centrifuge, and the solid content of the supernatant was determined from the drying method. The mass of the polymer compound released from the pigment was determined, and the liberation rate (%) was calculated from the ratio to the mass of the polymer compound used in the initial treatment.

The liberation rate of commercially available pigments can be measured by the following method. That is, after dissolving the entire pigment with a solvent that dissolves the pigment (for example, dimethyl sulfoxide, dimethylformamide, formic acid, sulfuric acid, etc.), the polymer compound and the pigment are separated by an organic solvent using the difference in solubility. And calculated as “mass of the polymer compound used in the initial treatment”. Separately, the pigment is washed with 1-methoxy-2-propanol, and the obtained liberation amount is divided by the “mass of the polymer compound used in the initial treatment” to obtain the liberation rate (%). .
The smaller the liberation rate, the higher the coverage of the pigment, and the better the dispersibility and dispersion stability. The preferable range of the liberation rate is 30% or less, more preferably 20% or less, and most preferably 15% or less. Ideally 0%.

  The polymer compound having a specific structure used for coating the pigment is a polymer containing a polymerization unit derived from a monomer represented by the following general formula (1) or a monomer comprising a maleimide or a maleimide derivative. It is particularly preferable that the polymer contains a polymer unit derived from the monomer represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
As the alkyl group for R ¹ , an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group can be mentioned.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
The alkylene group represented by R ² may be one in which two or more are connected via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the above alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

  In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

  Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

  In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring C in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  Specific examples of these compounds include [0029] to [0030] of Japanese Patent Application No. 2006-259673, [0044] to [0047] of Japanese Patent Application No. 2007-85382, and [0045] to [0047] of Japanese Patent Application No. 2007-231695. And those disclosed in [0075] to [0076] can be used.

  The ink composition of the present invention is preferably made into an ink composition after a pigment is previously dispersed with the polymer compound having the specific structure described above to prepare a pigment dispersion. In preparing the pigment dispersion, it is more preferable to disperse the pigment using a dispersant and a pigment derivative, in addition to the polymer compound having a specific structure, and use it as a pigment dispersion composition. By containing this dispersant, the dispersibility and dispersion stability of the pigment can be further improved.

  Dispersion is mainly carried out using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., and finely dispersed with beads made of glass having a particle diameter of 0.01 to 1 mm, zirconia, etc., and pigment dispersion A composition is obtained. Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.
Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The solvent in the pigment dispersion composition is not particularly limited as long as it is an organic solvent, and can be appropriately selected from known ones such as 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, (Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and their acetates; ethyl acetate Acetates such as n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; methyl ethyl keto , Acetone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, alcohols such as glycerin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, alkylene glycol monoalkyl ethers and their acetates, acetates, methyl ethyl ketone, and the like are preferable.

  The content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition. When the pigment dispersion composition is used for the preparation of a photocurable composition to be described later, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass from the viewpoint of handleability. Can do.

In the present invention, when a dye is used as the colorant, a photocurable composition that is uniformly dissolved is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

  The content of the colorant in the ink composition of the present invention is 5 to 70% by mass, and more preferably 10 to 60% by mass with respect to the total solid content (mass) of the composition. When the content of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.

(B) Compound having a fluorene ring and an epoxy ring In the present invention, a compound (specific epoxy compound) having at least one fluorene ring and one epoxy ring in the molecule is used. Particularly preferred are compounds having one or more fluorene rings and two or more epoxy rings in the molecule. By having two or more epoxy rings, a crosslinked product is formed after curing, so that toughness is improved and a strong pixel can be obtained, which is preferable.

  The specific epoxy compound is more preferably a compound having a structure represented by the following general formula (I).

  In the general formula (I), R represents ethylene or propylene, and n and m each independently represent an integer having a relationship in which m + n is 0 to 12.

  The specific epoxy compound is a low molecular compound having a molecular weight of 2000 or less, but from the viewpoint of thermal polymerization at the time of post-baking (epoxy equivalent), the molecular weight is preferably 1500 or less, and preferably 1000 or less. It is more preferable.

The specific epoxy compound may have an alkyleneoxy group. In the general formula (I), R represents ethylene or propylene. The alkyleneoxy group is an ethyleneoxy group or a propyleneoxy group. It is preferable from the viewpoint of thermal polymerizability during post-baking that the alkyleneoxy group selected from these is repeatedly in the range of 0 to 12. The alkyleneoxy group may further have a substituent.
As said substituent, hydrophilic groups, such as a hydroxy group, an amino group, and a carboxy group, can be mentioned. Further, the alkyleneoxy group may have both an ethyleneoxy group and a propyleneoxy group in one molecule.

  Examples of the specific epoxy compound include Ogsol EG-210 and PG-100 manufactured by Osaka Gas Chemical Co., Ltd., ESF-300 manufactured by Nippon Steel Chemical Co., Ltd., and in particular, Ogsol EG-210 manufactured by Osaka Gas Chemical Co., Ltd. is a glass substrate. This is preferable because the transfer rate can be improved.

  In the ink composition of the present invention, (c) a polymerizable compound and (d) a polymerization initiator can be used as necessary. In particular, after the ink composition is filled in the intaglio and before being transferred to the printing body (substrate), the ink composition is appropriately cured by light irradiation to reduce the remaining ink in the concave portion and the printed material ( Since it becomes easy to transfer to a substrate), it is preferable.

(C) Polymerizable compound As the polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable. Is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, 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 di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

  Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

A polymeric compound can be used in combination of 2 or more types, in addition to being used alone.
The content of the polymerizable compound in the ink composition is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

(D) Polymerization initiator Examples of the polymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428, and the like. Active halogen compounds such as halomethyl-s-triazine, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050 , Aromatic ketone compounds such as benzophenones described in US Pat. No. 4,199,420, (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, described in JP-A-10-62986 Of coumarin or biimidazole compounds, JP-A-8-015521, etc. And the like, and the like.

  Examples of the polymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series), acridine series, biimidazole series. An oxime ester type is preferable.

  Examples of the acetophenone polymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4 '-Isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2 Preferred examples include -tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. Can do.

  Preferred examples of the ketal polymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone polymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. it can.

  Preferred examples of the benzoin-based or benzoyl-based polymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl bezoate.

  Preferable examples of the xanthone-based polymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen polymerization initiator (triazine-based, oxadiazole-based, coumarin-based) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis ( Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4 -Bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di ( Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxys Ryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- ( Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) ) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloro Methyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl- 5 Amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl- Preferable examples include 5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferred examples of the acridine polymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole polymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2 Preferred examples include-(2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In the present invention, the polymerization initiator is not limited to the above, and other known initiators can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these polymerization initiators can also be used in combination.

  The content of the polymerization initiator in the ink composition is preferably 0.5 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, based on the total solid content of the composition. is there. When the content of the polymerization initiator is within the above range, the polymerization reaction can be favorably progressed to form a film with good strength.

  In the present invention, it is preferable to add a sensitizing dye as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a polymerization initiator.

  Spectral sensitizing dyes or dyes preferred as the sensitizing dye used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  As content in the ink composition of a sensitizing dye, 0.1-10 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-7 mass%. When the content of the sensitizing dye is within the above range, the polymerization reaction can proceed well to form a film with good strength.

  In the ink composition of the present invention, a polymer compound can be used as necessary. The addition of the polymer compound is preferable because the peelability of the ink composition from the intaglio is improved and the adhesion to the substrate and the like is improved. Further, it is desirable that the polymer compound has an appropriate polar group such as a carboxyl group or a hydroxyl group, and this improves the dispersion stability when a pigment is used as the colorant.

  The polymer compound that can be used in the ink composition of the present invention is a linear organic polymer, and in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Can be appropriately selected from those having at least one polar group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferable are those soluble in an organic solvent.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the polymer compound that can be used in the ink composition of the present invention, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and CH _2. = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. At least one.

  As content in the ink composition of the high molecular compound which can be used for the ink composition of this invention, 1-60 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-50 mass. %, Particularly preferably 5 to 40% by mass. When the content is in the range of 5 to 40% by mass, high transferability is obtained, the thixotropic property is low, and the change in the viscosity of the ink on the printing press (ink supply system) is small, which is preferable.

  The ink composition of the present invention may further include a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and an epoxy compound having the above specific structure as necessary. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor.

Examples of chain transfer agents that can be added to the ink composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercapto. Examples include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the ink composition can be improved, and the uniformity of the ink film thickness on the intaglio can be improved.
3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within the above range, the printed film thickness uniformity is effective, and the solubility in the composition is also good.
In addition, the addition of a fluorine-based organic compound to the black matrix ink causes the black matrix to repel other color filter inks, and if the printing position accuracy is shifted due to a change in printing pressure, the target opening is also opened. An ink film can be formed uniformly.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 8 2 (manufactured by JEMCO (Ltd.)), and the like.

  The addition amount of the fluorinated organic compound is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total mass of the ink composition.

  It is also effective to further contain a thermal polymerization initiator in the ink composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

  In order to increase the strength of the film, it is also effective to further contain an epoxy compound having another structure in the ink composition of the present invention. The epoxy compound that may be added is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Tohto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

  In the ink composition of the present invention, it is preferable to use various surfactants from the viewpoint of improving adhesion to an intaglio, etc. In addition to the above-mentioned fluorosurfactants, nonionic and cationic systems are used. Various anionic surfactants can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the ink composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And phenoxy resin formed from alcohol-soluble nylon, bisphenol A and epichlorohydrin.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the ink composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- Butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful. is there.

  Using the ink composition obtained as described above, printing is performed on a substrate (substrate) by a gravure printing method and a gravure offset printing method, and a colored layer having a pattern is added to form a color filter or the like. As the method, a conventionally known gravure printing method or gravure offset printing method can be used.

  The gravure offset printing method used in the present invention will be described below with reference to the drawings, but the present invention is not limited to this. [FIG. 1] and [FIG. 2] are sectional views showing an embodiment of the method of the present invention.

In FIG. 1, the intaglio (1) forms a desired pattern in advance by an ordinary method such as a combination of a photolithography method and an etching method, an engraving method, or a laser ablation method. The width of the recess (2) formed on the intaglio (1) is 10 to 300 μm, and the depth of the recess is about 1 to 50 μm, more preferably about 2 to 40 μm. Intaglio materials include, for example, metals, glass, ceramics, engineering plastics, and the like, and those with less wear and deformation due to printing pressure and doctor blade are preferable. For example, in order to prevent damage due to a doctor blade, it is also preferable to cover the plate-making surface (the surface of the shoulder portion and the concave portion) of the intaglio plate (1) made of these materials with a hard metal such as chromium or nickel. Examples of the coating method include a wet plating method, a sputtering method, and a vacuum deposition method.
The material of the intaglio (1) may be a rigid material. For example, a flexible material such as stainless steel, low bronze iron alloy such as phosphor bronze and Inver-42 alloy is also preferably used. Even when a press is used in the curing process and the transfer process, it is preferable to select a material having such a property that the intaglio does not remain deformed and is restored to its original shape when pressed.

  Moreover, as a board | substrate of a to-be-transferred body (7), for example, a non-alkali glass used for a liquid crystal display element, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto And photoelectric conversion element substrates used for solid-state imaging elements and the like, for example, silicon substrates and plastic substrates. On these substrates, usually, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.

The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. Examples of the material of the plastic substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
In addition to this, a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device, a driving substrate on which a wiring of a transparent conductive film is arranged, and the like can also be used as a printing medium.

  The intaglio and the substrate to be printed preferably have substantially the same thermal expansion coefficient, and it is preferable to use a low-expansion iron alloy or glass as the intaglio (1). A low-expansion iron alloy has the advantage of being highly flexible and capable of following even if there is some thickness unevenness on the surface of the transfer object. Is preferred. The thickness of the intaglio (1) is appropriately selected in consideration of mechanical strength according to the material.

  After the intaglio is filled with ink, irradiation is performed using an ultraviolet light source or the like (5), and the ink before transfer is partially cured, which is preferable because transferability is improved. [Fig. 1 (b)]

When using the blanket (6), the ink quantitatively filled in the intaglio is transferred to the blanket. At this time, the blanket is transferred while being rotated while being pressed.
The blanket is not particularly limited as long as it is durable to ink and has a flat surface. In particular, a blanket made of silicone rubber (see JP-A-5-19116), NBR rubber, urethane rubber, or the like is preferable. In particular, a blanket of silicone rubber is preferable when the transferred ink is retransferred to a transfer target. Next, the ink (4) transferred to the blanket in FIG. 1 (d) is retransferred to the transfer target (7).

In order to improve the retransferability to the printing medium (substrate), a transparent adhesive layer may be provided on the printing medium. Examples of the pressure-sensitive adhesive layer include an adhesive or pressure-sensitive adhesive whose pressure-sensitive adhesive process is a solvent activation type, a heat activation type, a pressure activation type, a chemical reaction type, or the like. Among these various pressure-sensitive adhesives, preferred are pressure-sensitive pressure-sensitive adhesives and hot-melt pressure-sensitive adhesives. Usable rubber or acrylic thermoplastics can be used as the adhesive, but it is thermosetting when heat resistance is required or in order to avoid the outflow of a small amount of adhesive in the subsequent process. Or a photocurable adhesive is preferable. After the ink filled in the recesses of the intaglio plate in FIG. 1B is semi-cured, an adhesive may be applied and then directly transferred to the substrate (substrate). In FIG. 1 (b), the ink layer is divided into a surface layer and an inner layer, and is schematically shown by changing the degree of curing.
When providing an adhesive layer, it is preferable to preliminarily coat the substrate with a film thickness of about 2.0 to 0.4 μm.

  As shown in FIG. 2, it is also possible to use an intaglio plate that is a rotating body. This is particularly suitable when the substrate of the printing medium is enlarged. Curing with ultraviolet rays or the like can be performed between the end of the doctor blade (14) and the transfer to the blanket (12). In addition, the transferred body (13) is suitable for a plastic substrate and a thin glass substrate (for example, 0.5 mm or less) from the viewpoint of flexibility. In this case, a flat plate for fixing the substrate of FIG. It is also possible to provide a backup roll instead of applying printing pressure.

As described above, a printed image having a precise fine pattern can be obtained. In the case of a color filter of a liquid crystal display device, a similar pattern is repeated four times, whereby a fine pattern of red, green, blue, and black can be obtained and can be used as a color filter.
Further, the black matrix can be formed by sputtering using chromium or chromium oxide, or can be patterned by photolithography to form a pattern of only red, green and blue by the method of the present invention. .

  In the printing method, other colors do not appear on the pattern once formed, and ink is transferred to a necessary place, so that there is no problem of color mixing. Therefore, since curing by heat is not performed more than necessary, even when the pigment used in the ink is miniaturized, deterioration of the pigment due to heat can be minimized.

  According to the present invention, even if the screen is large, mass productivity can be secured, the color resist used in the color filter that has been manufactured by the conventional photolithography method can be saved, and it is inexpensive and is applied to each color. Since the post-baking process that has been performed can be reduced, it is possible to provide a color filter and an image display device having good image quality such as color characteristics and contrast.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

<Synthesis example of polymer compound having heterocycle in side chain>
(Synthesis of polymer 1)
M-11 (27.0 g), methyl methacrylate (126.0 g), methacrylic acid (27.0 g), and 1-methoxy-2-propanol (420.0 g) were introduced into a nitrogen-substituted three-necked flask and a stirrer (Shinto Kagaku Co., Ltd.). ): Three-one motor), and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. Moreover, the acid value per solid content was 98 mgKOH / g from the titration using sodium hydroxide.

(Synthesis of polymer 2)
M-6 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: The mixture is stirred with a three-one motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 99 mgKOH / g.

(Preparation of Red Pigment 1)
50 g of pigment (CI Pigment Red254), 500 g of sodium chloride, 25 g of the above-described polymer 1 solution, and 100 g of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare Red pigment 1.

(Preparation of Green Pigment 2)
In the adjustment of Red pigment 1, instead of Pigment Red254, C.I. I. Green Pigment 36 was prepared in the same manner as Red Pigment 1 except that Pigment Green 36 was used, and Polymer 2 was used instead of Polymer 1.

(Preparation of Blue Pigment 3)
In the adjustment of Green Pigment 2, instead of Pigment Green 36, C.I. I. Blue Pigment 3 was prepared in the same manner as Green Pigment 2 except that Pigment Blue 15: 6 was used.

(Preparation of Black pigment 4)
In the adjustment of Green Pigment 2, instead of Pigment Green 36, C.I. I. Black Pigment 4 was prepared in the same manner as Green Pigment 2 except that Pigment Black 7 was used.

(Preparation of Red Dispersion 1)
120 parts of Red Pigment 1, 80 parts of a dispersant (Disperbyk 166, manufactured by Big Chemie Co., Ltd.) and 800 parts of a solvent, propylene glycol monomethyl ether acetate, are stirred and mixed at a rotational speed of 3,000 rpm for 3 hours using a homogenizer. Then, a mixed solution was prepared, and further a dispersion process was performed for 6 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries) using 0.1 mmφ zirconia beads to obtain Red dispersion 1.

(Preparation of Green dispersion 2)
In preparation of Red dispersion 1, instead of 150 parts of Green pigment 2, 90 parts of a dispersant (Disperbyk 161 manufactured by Big Chemie Co., Ltd.) and 760 parts of solvent propylene glycol monomethyl ether acetate, the composition was dispersed in the same manner as in Red dispersion 1. Green dispersion 2 was obtained.

(Preparation of Blue dispersion 3)
In the preparation of Red dispersion 1, instead of 120 parts of Blue pigment 3, 60 parts of a dispersant (Disperbyk 166 manufactured by Big Chemie Co., Ltd.) and 820 parts of solvent propylene glycol monomethyl ether acetate, the composition was dispersed in the same manner as in Red dispersion 1. Blue dispersion 3 was obtained.

(Preparation of Black dispersion 4)
In the preparation of Red dispersion liquid 1, the composition was replaced with Black pigment 427 parts, dispersant (Disperbyk 130 manufactured by Big Chemie Co., Ltd.) 8 parts, cyclohexanone 20 parts as a solvent, and propylene glycol monomethyl ether acetate 45 parts Red dispersion liquid 1 Then, Black dispersion liquid 4 was obtained.

(Adjustment of Red ink composition 1)
Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 5 parts Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 30 parts / solvent 17 parts propylene glycol monomethyl ether acetate / solvent ethyl, 3-ethoxypropionate 148 parts / polymerization initiator 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-Tetraphenylbiimidazole (B-CIM manufactured by Hodogaya Chemical Co., Ltd.) 13 parts ・ Surfactant (Solsperse 20000 manufactured by Avicia) 8 parts ・ Specific epoxy compound (Ogsol manufactured by Osaka Gas Chemical Co., Ltd.) EG-210)
In the general formula (I), R is C ₂ H ₄ , m = 1, n = 1, molecular weight 550 25 parts are added and sufficiently stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor),
-724 parts of Red dispersion 1 was added and further sufficiently stirred to obtain 1000 parts of a polymerizable composition.

(Adjustment of Green Ink Composition 2)
-Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 26 parts-Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)-Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 40 parts / solvent Propylene glycol monomethyl ether acetate 98 parts / solvent ethyl, 3-ethoxypropionate 137 parts / polymerization initiator 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (B-CIM, manufactured by Hodogaya Chemical Co., Ltd.) 12 parts, sensitizing dye, diethylaminobenzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.)
2 parts-Surfactant (Solsperse 20000) 9 parts-Specific epoxy compound (Ogsol EG-210 manufactured by Osaka Gas Chemical Co., Ltd.)
Add 30 parts of the structure described above and stir well with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor)
-606 parts of Green dispersion liquid 2 was added, and further sufficiently stirred to obtain 1000 parts of a polymerizable composition.

(Preparation of Blue ink composition 3)
-Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 65 parts-Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 47 parts-Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 47 parts Solvent Propylene glycol monomethyl ether acetate 120 parts Solvent Ethyl 3-ethoxypropionate 140 parts Polymerization initiator 1-Phenyl-1,2-propanedione-2- (o -Ethoxycarbonyl) oxime (OXE01 manufactured by Ciba Specialty Chemicals) 8 parts Surfactant 2000 parts of Solsperse 20000 Specific epoxy compound (Ogsol EG-210 manufactured by Osaka Gas Chemical Co., Ltd.)
Add 30 parts of the structure described above and stir well with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor)
-534 parts of Blue dispersion liquid 3 was added and further sufficiently stirred to obtain 1000 parts of a polymerizable composition.

(Preparation of Black ink composition 4)
-Polymer compound: benzyl methacrylate / acrylic acid (7/3 mol ratio) copolymer weight average molecular weight 5000 24 parts-Polymerizable compound (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 38 parts- Polymerizable compound (Shin Nakamura Chemical Co., Ltd.) Company A-BPE-20) 36 parts Solvent Propylene glycol monomethyl ether acetate 140 parts Solvent Ethyl 3-ethoxypropionate 65 parts Polymerization initiator Etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (OXE02 manufactured by Ciba Specialty Chemicals) 8 parts Surfactant 9 parts of Solsperse 20000 Specific epoxy compound (Osaka Gas Chemical) Ogsol Co., Ltd. EG-210)
Add 42 parts of the structure described above and stir well with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor)
-Black dispersion 4 638 parts was added and it fully stirred and 1000 parts of polymeric compositions were obtained.

(Example 1: Creation of color filter 1)
Using the Red ink composition 1, the Green ink composition 2, the Blue ink composition 3, and the Black ink composition 4, a color filter was prepared as follows.
The printing speed was 32 mm / sec using the apparatus shown in FIG.
First, a black matrix was printed by a gravure printing method using the black ink composition 4 with a repetitive pattern having a shape as shown in FIG. 3 made at a cell depth (recess depth) of 4.8 μm.

The printed pattern was heated with a pot plate at 100 ° C. for 80 seconds, exposed from both the printed surface and the back surface with a high-pressure mercury lamp (100 mJ / cm 2 each), and then post-baked for 10 minutes in an oven at 200 ° C. Further, a black matrix was obtained by fluorine plasma treatment.
The film thickness of the black matrix was 1.2 μm, and the OD value was measured using an optical densitometer 310TR (manufactured by X-Rite) to obtain a value of 4.3.

Next, using a strip pattern plate having a line width of 70 μm and a cell depth of 11.2 μm on the basis of the black matrix, a Green pattern is formed on the substrate on which the black matrix is formed by a gravure offset method (see FIG. 4). After heating for 80 seconds with a pot plate at 100 ° C., exposure (100 mJ / cm ² each) was performed from both the printed surface and the back surface.
The finished Green line width was 92 μm, the film thickness of the opening of the black matrix (corresponding to Green pixels) was 2.2 μm, and the pattern ends overlapped on the black matrix.

Next, as in the case of Green, using a stripe pattern plate having a line width of 70 μm and a cell depth of 11.2 μm with a black matrix as a reference, a gravure offset method is applied to a substrate on which a black matrix and a green pattern are formed. After printing a blue pattern as shown in FIG. 5, after heating for 80 seconds with a pot plate at 100 ° C., using a high-pressure mercury lamp from the printed surface and the back surface, exposure from both the printed surface and the back surface (100 mJ / each respectively). cm ² ).
The finished line width at this time was 93 μm, the film thickness of the opening of the black matrix was 2.2 μm, and the pattern ends overlapped on the black matrix.

Next, a red pattern is applied to the substrate on which the black matrix, green, and blue patterns are formed using a gravure offset method using a stripe pattern plate having a line width of 65 μm and a depth of 15.8 μm with reference to the black matrix pattern. After printing as shown in [FIG. 6], after heating for 80 seconds in a pot plate at 100 ° C., exposure (100 mJ / cm ² each) from both the printed surface and the back surface with a high-pressure mercury lamp from the printed surface and the back surface, and curing did.

At this time, the finished line width was 95 μm, the film thickness of the opening of the black matrix was 2.3 μm, and the pattern ends overlapped on the black matrix.
The substrate on which printing was completed was heat-treated (post-baked) in an oven at 220 ° C. for 30 minutes to obtain a color filter substrate. When the cross section of this substrate was observed, it was as shown in FIG.
The film thicknesses of Red, Green, and Blue were all 2.0 μm, and a flat color filter was obtained.

(Comparative Example 1: Creation of color filter 2)
In the preparation of all ink compositions of the Red ink composition 1, the Green ink composition 2, the Blue ink composition 3, and the Black ink composition 4 in the production of the color filter 1, a specific epoxy compound is added with a cresol novolac type epoxy resin ( A red ink composition 5, a green ink composition 6, and a blue ink composition 7 were obtained in the same manner except that EPICLON N-695 manufactured by Dainippon Ink and Chemicals, Inc. was used.
Using the Red ink composition 5, the Green ink composition 6, the Blue ink composition 7, and the Black ink composition 4, a color filter 2 was produced in the same manner as the production of the color filter 1.

  Compared to the case of the color filter 1 using the specific epoxy compound, in the production of the color filter 3 using the cresol novolac epoxy compound, it is difficult to fill the concave portion of the intaglio plate with the ink composition, and the ink composition is accurately measured by the intaglio plate. As a result, chipping occurred in some parts of the pattern, resulting in poor linearity. This was noticeable with Red, which has a large cell depth. This did not change even when the printing speed was reduced to 16 mm / sec.

(Comparative Example 2: Creation of color filter 3)
For this purpose, an ink composition is prepared by diluting the solid contents of the Red ink composition 5, the Green ink composition 6, and the Blue ink composition 7 with a solvent (propylene glycol monomethyl ether acetate) by 5 mass%, A color filter 3 was prepared. The ink compositions obtained here are referred to as a Red ink composition 8, a Green ink composition 9, and a Blue ink composition 10, respectively.

(Example 2: Creation of color filter 4)
In the production of the color filter 1 using the Red ink composition 1, the Green ink composition 2, the Blue ink composition 3, and the Black ink composition 4, the printing surface and the back surface are printed using a high-pressure mercury lamp from the printing surface and the back surface. Instead of exposing from both (100 mJ / cm ² each), a color filter 4 was prepared in the same manner as the color filter 1 except that after printing, heat treatment was performed in an oven at 200 ° C. for 10 minutes.

(Example 3: Creation of color filter 5)
In each of the red ink composition 1, the green ink composition 2, the blue ink composition 3, and the black ink composition 4, Osaka Gas Chemical Co., Ltd. is used as a specific epoxy compound in place of Ogsol EG-210 manufactured by Osaka Gas Chemical Co., Ltd. Red Ink Composition 1, Green Ink Composition 2, Blue Ink Composition 3, and Black Ink, except that Ogsol PG-100 (general formula (I), m = 0, n = 0 molecular weight 462) is used. Red ink composition 11, Green ink composition 12, Blue ink composition 13, and Black ink composition 14 were obtained in the same manner as in the preparation of composition 4. Using this ink composition, a color filter 5 was produced in the same manner as the production of the color filter 1 at a printing speed of 16 mm / sec.

Each color pattern of the obtained color filter was observed with an optical microscope to evaluate linearity. The evaluation results are summarized in Table 1.
Evaluation criteria for linearity ○: No defect such as a chip was found in the pattern. Δ: A chip was found in the pattern, but the black matrix opening was not exposed.
X: Exposure of the black matrix opening where a chip was observed in the pattern was observed.
XX: Ink entered the adjacent cell and color mixing occurred.

  From Table 1, the color filter using the specific epoxy compound of the present invention has good linearity in any of Red, Green, and Blue. On the other hand, the color filters 2 and 3 using a cresol novolac epoxy compound instead of the specific epoxy compound have poor linearity and are diluted with a solvent to easily fill the recess with the ink composition. The linearity of both the green ink composition 9 and the blue ink composition 10 was poor. The cause of poor linearity in the color filter 2 is presumed to be due to the film quality of the ink composition, not only due to the filling properties into the recesses.

(Evaluation of optical properties)
The obtained ink composition was spin-coated on a 100 mm square, 0.7 mm thick glass substrate so that the film thickness after heat treatment (post-bake) for 30 minutes in an oven at 220 ° C. was 2.0 μm. did. After the application, heat treatment was performed in an oven at 220 ° C. for 30 minutes to prepare a test substrate for optical property evaluation.

The obtained substrate was sandwiched between two polarizing plates used in a liquid crystal display device, placed in front of the light source, and the brightness of the transmitted light was measured. The brightness was measured using BM-5A (Topcon Co., Ltd.). At this time, the value of the polarization direction of the polarizing plate in the parallel state was set as the luminance in the parallel state, the value in the orthogonal state was set as the luminance in the crossed Nicol, and the contrast was evaluated by the following formula. The color filter 3 was not evaluated for contrast because good printing could not be performed even when the viscosity was lowered.
Contrast = brightness in parallel / brightness in crossed Nicols

  The color filters 1, 4, and 5 using the specific epoxy compound of the present invention all showed high contrast, but the color filter 4 that was thermally cured instead of photocured was slightly inferior. It can be seen that the color filter 2 not using the specific epoxy compound of the present invention is inferior to the color filter 1 in any color. In particular, the color filters 1, 4, and 5 are considered that the specific epoxy compound has some influence on the optical characteristics because the luminance value at the time of crossed Nicols is lowered.

FIG. 1 is a schematic view of a gravure offset lithographic printing method. FIG. 2 is a schematic diagram of the gravure offset rotational printing method. FIG. 3 is a plan view after the black matrix is formed. FIG. 4 is a plan view after the first colored layer (green) is formed. FIG. 5 is a plan view after the second colored layer (red) is formed. FIG. 6 is a plan view after the third colored layer (blue) is formed. FIG. 7 is a cross-sectional view of the color filter. (The cutting position is displayed in FIG. 6)

Explanation of symbols

1: Intaglio plate 2: Concave portion 3: Doctor blade 4: Ink (4a: Surface layer after irradiation, 4b: Inner layer)
5: Exposure light source 6: Blanket 7: Substrate to be transferred 8: 8a: Ink IN, 8b: Ink OUT
9: Ink 10: Anilox roller 11: Intaglio 12: Blanket roller 13: Substrate to be transferred 14: Doctor blade

Claims (6)

  A printing ink composition comprising: (a) a colorant; and (b) a compound having a fluorene ring and an epoxy ring. The printing ink composition according to claim 1, wherein the compound having a fluorene ring and an epoxy ring is a compound represented by the following general formula (I).

In general formula (I), R represents ethylene or propylene, and n and m each independently represent an integer having a relationship in which m + n is 0 to 12.   The printing ink composition according to claim 1 or 2, further comprising (c) a polymerizable compound and (d) a polymerization initiator.   A method for producing a color filter, wherein a pattern is provided on a transparent substrate using the ink composition according to any one of claims 1 to 3 by a gravure printing method or a gravure offset printing method.   A color filter manufactured by the manufacturing method according to claim 4.   An image display apparatus that performs color display using the color filter according to claim 5.

Images