JP2007003945A - Inkjet ink for color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet ink for color filter, capable of forming a coating film for a pixel or the like having reduced surface roughness even if P/V ratio is high, to provide a color filter manufactured by using the inkjet ink, and to provide a liquid crystal display device provided with the color filter. <P>SOLUTION: The inkjet ink for color filter comprises pigments, a binder and a fluorine surface active agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an inkjet ink for a color filter used to form a cured layer having a predetermined pattern such as a pixel portion (colored layer), a color filter using the inkjet ink, and a liquid crystal display device using the color filter About.

  Examples of the color filter include a color filter used for an image output device such as a liquid crystal display device, a color filter used for an image input device such as a solid-state imaging device, and the like. As an example, a typical example of a color filter structure used in a liquid crystal display device will be described with reference to FIG.

  In general, as shown in FIG. 1A, a color liquid crystal display device (101) is provided with a gap portion 3 of about 1 to 10 μm with a color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other. 3 is filled with a liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), blue (B) three primary colors) arranged in a predetermined order, a protective film 8 and a transparent electrode film 9 are laminated in this order from the side close to the transparent substrate. Have taken. An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, pearls 11 having a fixed particle diameter are dispersed, or columnar spacers 12 having a height corresponding to the cell gap as shown in FIG. It forms in the area | region which overlaps with the position in which the layer 6 is formed. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

  As a conventional method for forming pixels of a color filter or the like with a predetermined pattern shape, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G, and B color filter layers are formed. Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers. Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset.

However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem of high cost, and the yield decreases because the same process is repeated. There is a problem of doing.
As a method for manufacturing a color filter that solves these problems, Patent Document 1 describes that a pixel portion is formed by spraying a colored ink containing a thermosetting resin onto a substrate by an inkjet method and heating. Has been.

Japanese Patent Laid-Open No. 9-21910

  Ink used in the ink jet method needs to increase the weight ratio (hereinafter referred to as P / V ratio) between the pigment (P) and the solid content (V) other than the pigment in order to prevent the ink from breaking from the formation area during patterning. is there. However, in this case, the surface may be roughened. When such surface roughness occurs in the pixel, display unevenness occurs, light incident on the pixel is scattered, and the light transmitted to the pixel is lost, resulting in a problem of a decrease in contrast. Further, due to such surface roughness, there is a problem that current leaks easily after the ITO film is formed.

The present invention has been accomplished in view of the above circumstances, and a first object thereof is an inkjet for a color filter capable of forming a coating film such as a pixel with reduced surface roughness even when the P / V ratio is high. To provide ink.
The second object of the present invention is to provide a color filter having pixels with reduced surface roughness.
A third object of the present invention is to provide a liquid crystal display device provided with a color filter that achieves the above object.

The inkjet ink for a color filter according to the present invention contains a pigment, a binder, and a fluorosurfactant.
According to the inkjet ink for a color filter according to the present invention, it is possible to reduce the surface roughness of the formed coating film even when the P / V ratio is high by adding a fluorine-based surfactant. . Since the surface of the formed pixel or the like is smooth, display unevenness is reduced, and further, the incident light to the pixel can be transmitted without being scattered or refracted. As a result, the contrast is improved. Pixels can be obtained.

  In the inkjet ink for a color filter according to the present invention, the fluorosurfactant includes a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, and a monomer containing a silicone chain and an ethylenic double bond ( A fluorine-based copolymer polymerized by using at least B) is preferable from the viewpoint of preventing surface roughness of the formed coating film even if the P / V ratio is high.

  Moreover, in the inkjet ink for color filters which concerns on this invention, it is that P / V ratio is high that content of the said fluorosurfactant is 0.0005 to 5 weight% with respect to the whole solid content. Is also preferable from the viewpoint of preventing surface roughness of the formed coating film.

  The inkjet ink for a color filter according to the present invention further contains a solvent, and the solvent contains a solvent component having a boiling point of 180 ° C. to 260 ° C. as a main solvent and a vapor pressure at room temperature of 0.5 mmHg or less. It is contained in a ratio of 80% by weight or more with respect to the above, and since it has appropriate drying and evaporating properties, it is excellent in straightness and stability when discharged from the head, and can be dried more efficiently. It is preferable from the point which can be performed.

  In addition, the inkjet ink for a color filter according to the present invention uses a standard solution shown in the wettability test specified in JIS K6768, measures the contact angle (θ) after 30 seconds from contact with a droplet, It is preferable that the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined from the Manplot graph is 10 ° or less from the viewpoint of good ink wetting and spreading and easy prevention of color loss of pixels. .

The color filter according to the present invention is a color filter including at least a transparent substrate and pixels provided on the transparent substrate, and the pixels include a fluorine-based surfactant and / or a chemical change body thereof. It is characterized by that.
The color filter according to the present invention is a color filter in which display unevenness is reduced and contrast is further improved because the pixel surface includes a fluorosurfactant and / or a chemical change body thereof to increase the smoothness of the pixel surface. It is.

  In the color filter according to the present invention, the fluorosurfactant includes a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, and a monomer (B) containing a silicone chain and an ethylenic double bond. A fluorine-based copolymer polymerized by using at least is preferable from the viewpoint of further improving the smoothness of the pixel surface.

  Moreover, in the color filter which concerns on this invention, it is from the point which the smoothness of the pixel surface improves more that content of the said fluorosurfactant is 0.0005 to 5 weight% with respect to the whole pixel. preferable.

  In the color filter according to the present invention, the surface roughness (Ra) of the pixel is preferably 10 nm or less from the viewpoint of further improving the contrast.

  Furthermore, the liquid crystal display device according to the present invention is a liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed therebetween, and the display side substrate is included in the present invention. It is the color filter which concerns.

The inkjet ink for a color filter according to the present invention can form a coating film such as a pixel with reduced surface roughness even if the P / V ratio is high.
The color filter according to the present invention is a color filter having pixels with reduced surface roughness.
Further, according to the present invention, since a color filter having pixels with reduced surface roughness is used, a high-quality liquid crystal display device can be obtained.

The present invention is described in detail below.
In the present invention, (meth) acrylate means either acrylate or methacrylate, (meth) acryloyl means either acryloyl or methacryloyl, and (meth) acrylic means acrylic. Or it means either methacryl.

1. Ink-jet ink for color filter The ink-jet ink for color filter according to the present invention contains a pigment, a binder, and a fluorosurfactant.
According to the inkjet ink for a color filter according to the present invention, it is possible to reduce the surface roughness of the formed coating film even when the P / V ratio is high by adding a fluorine-based surfactant. . Since the surface of the formed pixel or the like is smooth, display unevenness is reduced, and further, the incident light to the pixel can be transmitted without being scattered or refracted. As a result, the contrast is improved. Pixels can be obtained.
Hereinafter, components used in the inkjet ink according to the present invention will be described in order from the fluorine-based surfactant that is characteristic in the present invention.

(Fluorosurfactant)
The present invention is characterized by containing a fluorosurfactant as an essential component as a leveling agent. Here, the fluorosurfactant refers to a surfactant containing fluorine. The fluorinated surfactant is usually one obtained by substituting all or part of the hydrogen atoms of the hydrophobic group of the hydrocarbon surfactant with fluorine atoms.

  Among the fluorosurfactants used in the present invention, at least a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond and a monomer (B) containing a silicone chain and an ethylenic double bond are at least A fluorine-based copolymer polymerized by use is preferable from the viewpoint of preventing surface roughness of the formed coating film even if the P / V ratio of the ink is high.

  As the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, known ones can be used. Specifically, a compound represented by the following general formula (a1), or Examples include compounds having a plurality of perfluoroalkyl groups in one molecule such as the compound represented by the general formula (a2).

（式中、Ｒ^f は炭素原子数１〜２０のパ−フロロアルキル基又は部分フッ素化アルキル基を表し、これらのアルキル基は直鎖状又は分岐状であっても良く、また、主鎖中に酸素原子が介入したもの（例えば、−（ＯＣＦＣＦ₂）₂ＣＦ（ＣＦ_３）₂ 等）であっても良く、Ｒ^１ はＨ、ＣＨ₃、Ｃｌ又はＦを表し、Ｘは２価の連結基を表し、ａは０又は１を表す。）

(In the formula, R ^f represents a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, and these alkyl groups may be linear or branched, and in the main chain. It may be an oxygen atom intervening (for example, — (OCFCF ₂ ) ₂ CF (CF ₃ ) ₂ etc.), R ¹ represents H, CH ₃ , Cl or F, and X is a divalent linkage. Represents a group, and a represents 0 or 1.)

（式中、ｊは１〜１４の整数を表す。）
一般式（ａ１）におけるＸは、具体的には、下記式で表される連結鎖が挙げられる。

(Wherein j represents an integer of 1 to 14)
Specific examples of X in the general formula (a1) include a connecting chain represented by the following formula.

（式中、ｎは１〜１０の整数を表し、Ｒ² はＨ又は炭素原子数１〜６のアルキル基を表す。）

(In the formula, n represents an integer of 1 to 10, and R ² represents H or an alkyl group having 1 to 6 carbon atoms.)

フッ素化アルキル基とエチレン性二重結合を含有するモノマー（Ａ）中のパ−フロロアルキル基又は部分フッ素化アルキル基の炭素原子数は、３以上が好ましく、６以上が特に好ましい。フッ素化アルキル基とエチレン性二重結合を含有するモノマー（Ａ）の具体例としては、以下の式（ａ−１）〜（ａ−５６）で表される化合物が挙げられる。

The number of carbon atoms of the perfluoroalkyl group or partially fluorinated alkyl group in the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond is preferably 3 or more, and particularly preferably 6 or more. Specific examples of the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond include compounds represented by the following formulas (a-1) to (a-56).

  As the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, a single compound may be used, or two or more kinds of compounds may be used in combination.

  On the other hand, the monomer (B) containing a silicone chain and an ethylenic double bond can also be a known one, and a polysiloxane chain has one or both ends via a divalent linking group, A group in which a functional group having an ethylenic double bond such as a vinyl group, an acryloyl group, or a methacryloyl group is linked is preferable. The monomer (B) containing a silicone chain and an ethylenic double bond preferably has a (meth) acryloyl group from the viewpoint of polymerization reactivity.

  Specific examples of the monomer (B) containing a silicone chain and an ethylenic double bond include, for example, a compound represented by the general formula (b-1) or a compound represented by the general formula (b-2). Can be mentioned.

［式中、Ｒ³及びＲ⁴は、各々独立的に、炭素原子数１〜２０のアルキル基又はフェニル基を表し、また、シロキシ単位毎に同一でも異なっていてもよい。ｐは３〜５２０の整数を表し、ｑは０又は１を表し、Ｘ² は２価の連結基であって、具体的には、一般式 −ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ＯＣＯ−、−（ＣＨ₂）_ｎ１ＮＨＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ＯＣＯ−、−（ＣＨ₂）_ｎ１ＯＣＯ−、−（ＣＨ₂）_ｎ１−Ｏ−（ＣＨ₂）_ｍ１ＯＣＯ− 又は −ＯＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ ＯＣＯ−（式中、ｎ¹及びｍ¹は、それぞれ独立的に、２〜６の整数を表す。）で表される連結鎖を表す。Ｒ¹ は前記一般式（ａ１）において定義したものと同じものを表し、Ｚ¹はメチル基、フェニル基又は一般式 ＣＨ₂＝Ｃ（Ｒ¹）−（Ｘ²）_q−で表される基を表す。］

[Wherein, R ³ and R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and may be the same or different for each siloxy unit. p represents an integer of 3 to 520, q represents 0 or 1, X ² represents a divalent linking group, specifically, a general formula —CH ₂ CH (OH) CH ₂ OCO—, — _{(CH 2) n1 NHCH 2 CH} (OH) CH 2 OCO -, - (CH 2) n1 OCO -, - (CH 2) n1 -O- (CH 2) m1 OCO- or -OCH ₂ CH (OH) CH ₂ represents a connecting chain represented by OCO- (wherein n ¹ and m ¹ each independently represents an integer of 2 to 6). R ¹ represents the same as defined in the general formula (a1), Z ¹ represents a methyl group, a phenyl group, or a group represented by the general formula CH ₂ ═C (R ¹ ) — (X ² ) _q —. Represents. ]

（式中、Ｒ⁵、Ｒ⁵'、Ｒ⁵"、Ｒ⁶、Ｒ⁶'、Ｒ⁶"、Ｒ⁷、Ｒ⁷'及びＲ⁷"は、 各々独立的に、炭素原子数１〜２０のアルキル基又はフェニル基を表す。ｒ、ｓ及びｔは、各々独立的に、０又は１〜２００の整数を表す。Ｘ²、ｑ及びＲ¹は、一般式（ｂ−１）において定義したものと同じものを表す。）

(Wherein R ⁵ , R ⁵ ′, R ⁵ ″, R ⁶ , R ⁶ ′, R ⁶ ″, R ⁷ , R ⁷ ′ and R ⁷ ″ are each independently a group having 1 to 20 carbon atoms. Represents an alkyl group or a phenyl group, r, s and t each independently represent 0 or an integer of 1 to 200. X ² , q and R ¹ are as defined in formula (b-1) Represents the same thing as

  The molecular weight of the silicone chain portion of the monomer (B) containing a silicone chain and an ethylenic double bond is preferably 5,000 or less, and particularly preferably 1,000 or less. Further, the structure of the silicon chain portion is preferably a branched type as represented by the general formula (b-2), and among them, in the general formula (b-2), r, s and Those having t = 0 are particularly preferred.

  Specific examples of the monomer (B) containing a silicone chain and an ethylenic double bond include compounds represented by the following formulas (b-1-1) to (b-3-7).

  As the monomer (B) containing a silicone chain and an ethylenic double bond, a single compound may be used, or two or more kinds of compounds may be used in combination.

  As the fluorosurfactant used in the present invention, in particular, a monomer represented by (a-1) as a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, a silicone chain and an ethylenic dimer The fluorine-containing copolymer polymerized using at least the monomer represented by (b-3-1) as the monomer (B) containing a heavy bond, or contains a fluorinated alkyl group and an ethylenic double bond Polymerized using at least the monomer represented by (a-56) as the monomer (A) and the monomer represented by (b-2-1) as the monomer (B) containing a silicone chain and an ethylenic double bond. A fluorine-based copolymer is preferable from the viewpoint of preventing surface roughness of the formed coating film even if the P / V ratio of the ink is high.

  Moreover, the fluorine-type surfactant used for this invention is a monomer (A) containing the said fluorinated alkyl group and an ethylenic double bond as a constituent monomer, and a monomer containing a silicone chain and an ethylenic double bond ( In addition to B), a monomer containing a non-fluorine and non-silicone ethylenic double bond may be used in combination.

  Non-fluorine and non-silicone ethylenic double bond monomers include, for example, styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, acetic acid Fatty acid vinyl such as vinyl; α, β-ethylenically unsaturated carboxylic acid such as mono- or divalent carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid; (meth) acrylic acid (Hereinafter, this expression is a generic term for both acrylic acid and methacrylic acid.) Carbon atoms of alkyl groups such as methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, decyl, dodecyl, stearyl ester (Meth) acrylic acid alkyl ester having a number of 1 to 18; 2-hydroxyethyl ester C1-C18 hydroxyalkyl esters of (meth) acrylic acid such as stealth, hydroxypropyl ester, hydroxybutyl ester; (meth) acrylic acid such as dimethylaminoethyl ester, diethylaminoethyl ester, diethylaminopropyl ester Aminoalkyl esters having 1 to 18 carbon atoms; (meth) acrylic acid having 3 to 18 carbon atoms such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methylcarbyl ester, ethylcarbyl ester, butylcarbyl ester Ether oxygen-containing alkyl esters;

  Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Mono (meth) acrylic ester of polyalkylene glycol such as cyclopentenyl (meth) acrylate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide, or the like Di (meth) acrylic acid esters, or polyethylene glycols having a degree of polymerization of 1 to 100, capped with alkyl groups having 1 to 6 carbon atoms, polypropylene glycol, and ethylene oxide and propylene. Polyalkylene glycol having a copolymer of N'okishido - Le mono (meth) acrylic acid ester,

  Alkyl vinyl ethers having 1 to 18 alkyl carbon atoms such as methyl vinyl ether, propyl vinyl ether, dodecyl vinyl ether; glycidyl ester of (meth) acrylic acid such as glycidyl methacrylate and glycidyl acrylate; styrene macromonomer 4500 manufactured by Sartomer, new Macromonomer such as NK ester M-230G manufactured by Nakamura Chemical Co., Ltd .; 2- (meth) acryloyloxyethyl succinic acid, 2-acrylamido-2-methylpropanesulfonic acid, partially sulfonated styrene, mono (acryloyloxy) And ethyl) acid phosphate and mono (methacryloxyethyl) acid phosphate.

  Among these non-fluorine and non-silicone ethylenic double bond monomers, polyalkylenes such as polyethylene glycol, polypropylene glycol and copolymers of ethylene oxide and propylene oxide in the side chain Poly (ethylene glycol) or polypropylene glycol having a degree of polymerization of 1 to 100, which is capped with a mono (meth) acrylate or di (meth) acrylate of glycol or an alkyl group having 1 to 6 carbon atoms at the end And a (meth) acrylate monomer having a polyoxyalkylene group in the side chain, such as a mono (meth) acrylate ester of polyalkylene glycol such as a copolymer of ethylene oxide and propylene oxide; carbon atom (Meth) acrylic acid having an alkyl group of at least 6 In a side chain an alkyl group having 6 or more carbon atoms as ether (meth) acrylate monomers are preferred.

  A monomer (A) containing a fluorinated alkyl group and an ethylenic double bond and a monomer (B) containing a silicone chain and an ethylenic double bond, and if necessary, non-fluorine and non-silicone There is no limitation on the production method of the fluorine-based polymer that is copolymerized with a monomer containing an ethylenic double bond, and a known method, that is, a polymerization mechanism such as a radical polymerization method, a cation polymerization method, or an anion polymerization method is used. Based on this, it can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or the like, but a radical polymerization method is particularly convenient and industrially preferable.

In this case, known polymerization initiators can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azo compounds such as azobisisobutyronitrile and phenylazotriphenylmethane, Examples include metal chelate compounds such as triacetylacetonate manganese. In the polymerization reaction, if necessary, a coupling group such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, γ-mercaptopropyltrimethoxysilane, etc. A chain transfer agent such as a thiol compound having a polymerization initiator can be used in combination with the polymerization initiator.
The fluorine-based random or block copolymer according to the present invention can also be obtained by photopolymerization in the presence of a photosensitizer or photoinitiator or by polymerization using radiation or heat as an energy source.

  The polymerization can be carried out in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent from the viewpoint of workability. Examples of the solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones; Esters such as methyl acetate, ethyl acetate and butyl acetate; Polar solvents such as dimethylformamide and dimethyl sulfoxide; Halogen solvents such as 1,1,1-trichloroethane and chloroform; Tetrahydrofuran and Dioxane And ethers; aromatics such as benzene, toluene and xylene; and fluorinated inner-trikids such as perfluorooctane and perfluorotri-n-butylamine.

  The copolymerization ratio of the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond to the monomer (B) containing a silicone chain and an ethylenic double bond is 100: 1 to 1: A range of 100 is preferred, and a range of 40: 1 to 1:40 is particularly preferred. Further, a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond, and a monomer (B) containing a silicone chain and an ethylenic double bond are combined with a non-fluorine and non-silicone ethylenic double bond. When introducing a monomer containing a bond, relative to the total weight of the monomer (A) containing a fluorinated alkyl group and an ethylenic double bond and the monomer (B) containing a silicone chain and an ethylenic double bond, 1,000 times or less are preferable, and 100 times or less are particularly preferable.

  The molecular weight of the fluoropolymer used in the present invention is a number average molecular weight (Mn), preferably in the range of 1,000 to 2,000,000, particularly preferably in the range of 1,000 to 500,000.

  Among the commercially available products of fluorosurfactants, Megafac R-08MH, Megafac F445, Megafac F470, Megafac F471, and Megafac F472SF manufactured by Dainippon Ink and Chemicals, Inc. are preferably used.

  Further, the content of the fluorosurfactant is 0.0005 to 5% by weight with respect to the whole solid content, further 0.005 to 0.5% by weight with respect to the whole solid content, and particularly with respect to the whole solid content. 0.005 to 0.2% by weight is preferable from the viewpoint that it is easy to prevent surface roughness of the formed coating film even if the P / V ratio of the ink is high. Here, the solid content of the inkjet ink for specifying the blending ratio includes all components except for the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

  In the present invention, a fluorosurfactant is included as an essential component as a leveling agent, but other leveling agents may be added as long as the effects of the present invention are not impaired. Examples of other leveling agents include silicon surfactants, polyoxyalkylene surfactants, fatty acid ester surfactants, special acrylic polymers, and the like.

(Pigment)
The pigment as the colorant may be selected from any organic colorant and inorganic colorant according to the color required by the pixel (pixel part) R, G, B, etc. and the black matrix layer. it can. As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, an extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. As organic pigments, for example, compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers are attached. Can be mentioned.
CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment CI Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175;

  CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Buy Olet 32, C.I. pigment violet 36, C.I. pigment violet 38;

  CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;

  CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25 CI pigment black 1, pigment black 7.

  Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  When forming the pattern of the black matrix layer on the substrate of the color filter using the inkjet ink of the present invention, a black pigment having a high light shielding property is blended in the inkjet ink. As the black pigment having a high light shielding property, for example, an inorganic colorant such as carbon black or iron trioxide, or an organic colorant such as cyanine black can be used.

  Ink layers formed from inkjet inks containing pigments with high light-shielding properties make it difficult for light to reach the inside. Therefore, when forming a black matrix layer pattern using the inkjet ink of the present invention, a binder described later is used. It is preferable to use a thermosetting binder rather than a photocurable binder. However, it can be cured by light by adjusting the curing method such as increasing the thickness of the ink layer and the exposure time.

  In the case of forming pixels, the pigment is usually blended in a proportion of 1 to 60% by weight, preferably 15 to 40% by weight, based on the total solid content of the inkjet ink. When there are too few pigments, there exists a possibility that the permeation | transmission density | concentration at the time of apply | coating an inkjet ink to predetermined | prescribed film thickness (usually 0.1-2.0 micrometers) may not be enough. Moreover, when there are too many pigments, there exists a possibility that the characteristics as films, such as adhesion to the substrate when the ink-jet ink is applied onto the substrate and cured, surface roughness of the cured film, and coating film hardness may be insufficient. is there.

(binder)
The ink-jet ink according to the present invention contains a binder in order to impart film formability and adhesion to the surface to be coated. As the binder, a non-curable thermoplastic resin composition may be used. However, it is preferable to use a binder containing a curable resin because it imparts sufficient hardness to the coating film by curing.
Examples of the curable binder include a thermosetting binder including a thermosetting resin that can be polymerized and cured by heating, and light including a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, an electron beam, and the like. A curable binder, and further, one containing both a thermosetting binder and a photocurable binder can be used.

(1) Thermosetting binder As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of accelerating the thermosetting reaction is added. You may do it. An epoxy group is preferably used as the thermosetting functional group. Moreover, you may use further the polymer which has no polymerization reactivity in itself.

As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.
As an epoxy compound, in order to impart solvent resistance and heat resistance to the cured film, to increase the crosslink density of the polymer with a relatively high molecular weight and the cured film, or to improve the inkjet ejection performance by lowering the viscosity In addition, it is preferable to use a compound having a relatively low molecular weight in combination.

i) Compound having two or more thermosetting functional groups in one molecule As an epoxy compound (hereinafter sometimes referred to as “binder epoxy compound”) which is a polymer having a relatively high molecular weight, which is usually used as a binder component. Further, a polymer having at least two structural units represented by the following formula (1) and structural units represented by the following formula (2) and having two or more glycidyl groups can be used.

（Ｒ¹¹は水素原子または炭素数１〜３のアルキル基であり、Ｒ¹²は炭素数１〜１２の炭化水素基である。）

(R ¹¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² is a hydrocarbon group having 1 to 12 carbon atoms.)

（Ｒ¹³は水素原子又は炭素数１〜１０のアルキル基である。）
式（１）で表される構成単位は、下記式（３）で表されるモノマーから誘導される。

(R ¹³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The structural unit represented by the formula (1) is derived from a monomer represented by the following formula (3).

（Ｒ¹¹およびＲ¹²は式（１）と同じである。）

(R ¹¹ and R ¹² are the same as in formula (1).)

By using the monomer represented by the formula (3) as a constituent unit of the binder epoxy compound, sufficient hardness and transparency can be imparted to the cured coating film formed from the inkjet ink of the present invention. In the formula (3), R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, and may be any of a linear aliphatic, alicyclic, and aromatic hydrocarbon group, and an additional structure, For example, it may contain a double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intra-ring bridged hydrocarbon group, or the like.

Specific examples of the monomer represented by the formula (3) include methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, and i-butyl (meth). Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, Examples thereof include para-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenyl (meth) acrylate.
In formula (3), R ¹¹ is preferably hydrogen or a methyl group, and R ¹² is preferably an alkyl group having 1 to 12 carbon atoms. Among them, a methyl group and a cyclohexyl group are particularly preferable. Preferable examples of the monomer represented by the above formula (3) include methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA).

  The structural unit represented by the formula (2) in the polymer is derived from a monomer represented by the following formula (4).

（Ｒ¹³は式（２）と同じである。）

(R ¹³ is the same as in formula (2).)

The monomer represented by the formula (4) is used for introducing an epoxy group (epoxy reaction point) into the polymer. The ink-jet ink containing the polymer is excellent in storage stability and hardly increases in viscosity during storage and discharge operations. One of the reasons is the epoxy group in formula (2) or formula (4). Is presumed to be because of glycidyl group. When an alicyclic epoxy acrylate is used instead of the monomer represented by the formula (4), the viscosity of the inkjet ink is likely to increase.
In the formula (4), R ¹³ is preferably hydrogen or a methyl group. Specific examples of the monomer represented by the formula (4) include glycidyl (meth) acrylate, and glycidyl methacrylate (GMA) is particularly preferable.

  The polymer may be a random copolymer or a block copolymer. Further, the polymer may contain main chain constituent units other than those of formula (1) or formula (2) as long as performance required for each detail of the color filter, such as hardness and transparency, can be ensured. Good. Specific examples of such a monomer include acrylonitrile and styrene.

The content of the structural unit of formula (1) and the structural unit of formula (2) in the binder epoxy compound is derived from the monomer that derives the structural unit of formula (1) and the structural unit of formula (2). The weight ratio with the monomer to be charged (monomer that derives formula (1): monomer that derives formula (2)) is in the range of 10:90 to 90:10. preferable.
When the amount of the structural unit of the formula (1) is more than the above ratio of 10:90, there is a possibility that the reaction point of curing decreases and the crosslinking density is lowered, whereas the structural unit of the formula (2) If the amount is more than the above ratio 90:10, the bulky skeleton may be reduced and curing shrinkage may be increased.

  The weight average molecular weight of the binder epoxy compound is preferably 3,000 or more, particularly 4,000 or more, when expressed in terms of polystyrene-converted weight average molecular weight. This is because if the molecular weight of the binder epoxy compound is less than 3,000, physical properties such as strength and solvent resistance required for the cured resin layer as details of the color filter are likely to be insufficient. In addition, since the ink according to the present invention is used in an ink jet system, the binder epoxy compound preferably has a weight average molecular weight of 20,000 or less, more preferably 15,000 or less when expressed in terms of polystyrene equivalent weight average molecular weight. It is particularly preferred that If the molecular weight is more than 20,000, the viscosity is likely to increase, the stability of the ejection amount when ejected from the ejection head and the straightness in the ejection direction may be degraded, and the stability of long-term storage is degraded. Because there is a fear.

  As the binder epoxy compound, it is particularly preferable to use a glycidyl methacrylate (GMA) / methyl methacrylate (MMA) copolymer having a polystyrene-reduced weight average molecular weight (Mw) in the above range. The GMA / MMA copolymer may contain other monomer components as long as the object of the present invention can be achieved.

  As a synthesis example of the binder epoxy compound, for example, a solvent containing no hydroxyl group is charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and the temperature is raised to 120 ° C. while stirring. . The reason for using a solvent that does not contain a hydroxyl group is to avoid the decomposition of the epoxy group during the synthesis reaction. Next, a mixture of the monomer represented by the above formula (3), the monomer represented by the above formula (4), and a composition obtained by combining other monomers as necessary with a polymerization initiator (dropping component) is 2 Drop at a constant rate from the dropping funnel over time. After completion of the dropping, the temperature is lowered to 120 ° C., a catalyst is added, the reaction is performed for 3 hours, and the reaction is terminated when the temperature is raised to 130 ° C. and kept for 2 hours, whereby the binder epoxy compound is obtained.

  The thermosetting binder used in the present invention is an epoxy compound having two or more epoxy groups in one molecule, and has a molecular weight smaller than that of the binder epoxy compound (hereinafter referred to as “polyfunctional epoxy compound”). May also be used. Especially, it is preferable to use the said binder epoxy compound and the said polyfunctional epoxy compound together. In this case, the polystyrene equivalent weight average molecular weight of the polyfunctional epoxy compound is preferably 4,000 or less, and particularly preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith.

  In addition, the polystyrene conversion weight average molecular weight of an epoxy compound can be calculated | required by GPC (gel permeation chromatography), As a measurement condition, tetrahydrofuran is used as a developing solution, for example, HLC-8029 (made by Tosoh Corporation) is used. Can be measured.

  Since the epoxy group (glycidyl group) is introduced into the binder epoxy compound by the structural unit represented by the formula (2), there is a limit to the amount of epoxy that can be introduced into the molecule of the copolymer. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the ink-jet ink, the epoxy group is replenished in the ink-jet ink, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased.

  Among polyfunctional epoxy compounds, it is preferable to use an epoxy compound having four or more epoxy groups in one molecule in order to increase the crosslink density of the acid-epoxy reaction. In particular, when the ink-jet ink of the present invention is used in an ink-jet method, and the weight average molecular weight of the binder epoxy compound is 10,000 or less in order to improve the discharge performance from the ink-jet discharge head. Since the strength and hardness of the cured resin layer are likely to decrease, it is preferable to sufficiently increase the crosslink density by blending such a tetrafunctional or higher polyfunctional epoxy compound into the ink jet ink.

  The polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, Bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy Resin, trifunctional epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A included Polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

More specifically, bisphenol A type epoxy resins such as trade name Epicoat 828 (manufactured by Yuka Shell Epoxy), bisphenol F type epoxy resins such as trade name YDF-175S (manufactured by Tohto Kasei Co., Ltd.), trade name YDB-715 Brominated bisphenol A type epoxy resin (made by Toto Kasei Co., Ltd.), bisphenol S type epoxy resin such as trade name EPICLON EXA1514 (Dainippon Ink Chemical Co., Ltd.), trade name YDC-1312 (made by Toto Kasei Co., Ltd.) Hydroquinone type epoxy resins such as Naphthalene type epoxy resins such as EPICLON EXA4032 (manufactured by Dainippon Ink & Chemicals, Inc.), biphenyl type epoxy resins such as Epicoat YX4000H (manufactured by Yuka Shell Epoxy), Product name Epicote 157S70 Bisphenol A type novolak epoxy resin such as Epoxy Co., Ltd., product name Epicoat 154 (manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin such as product name YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), product name YDCN- Cresol novolac type epoxy resin such as 701 (manufactured by Toto Kasei Co., Ltd.), dicyclopentadiene phenol type epoxy resin such as EPICLON HP-7200 (manufactured by Dainippon Ink & Chemicals, Inc.), and brand name Epicoat 1032H60 (oilification) Trishydroxyphenylmethane type epoxy resin such as Shell Epoxy), trifunctional type epoxy resin such as trade name VG3101M80 (Mitsui Chemicals), tetraphenylolethane such as Epicoat 1031S (made by Yuka Shell Epoxy) Type epoxy tree Tetrafunctional epoxy resins such as trade name Denacol EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.), hydrogenated bisphenol A type epoxy resins such as trade name ST-3000 (manufactured by Toto Kasei Co., Ltd.), trade name Epicoat 190P (Oilized) Glycidyl ester type epoxy resin such as Shell Epoxy), glycidyl amine type epoxy resin such as trade name YH-434 (manufactured by Tohto Kasei Co., Ltd.), glyoxal type epoxy resin such as trade name YDG-414 (manufactured by Tohto Kasei Co.), Examples include alicyclic polyfunctional epoxy compounds such as trade name Epolide GT-401 (manufactured by Daicel Chemical Industries), and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC). Further, if necessary, a trade name Neotote E (manufactured by Toto Kasei Co., Ltd.) can be mixed as an epoxy reactive diluent.

  Among these polyfunctional epoxy compounds, bisphenol A type novolac epoxy resins such as trade name Epicoat 157S70 (manufactured by Yuka Shell Epoxy) and cresol novolak type epoxy such as trade name YDCN-701 (manufactured by Tohto Kasei) Resins are particularly preferred.

ii) Curing agent The thermosetting binder used in the present invention is usually combined with a curing agent. As the curing agent, for example, a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid is used.
Specific examples of the polyvalent carboxylic acid anhydride include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tristrimitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

  Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.

  These curing agents can be used singly or in combination of two or more. The amount of the curing agent used in the present invention is usually in the range of 1 to 100 parts by weight, preferably 5 to 100 parts by weight per 100 parts by weight of the epoxy group-containing component (binder epoxy compound and polyfunctional epoxy compound). 50 parts by weight. When the blending amount of the curing agent is less than 1 part by weight, curing becomes insufficient and a tough coating film cannot be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, while the adhesiveness with respect to the board | substrate of a coating film is inferior, a uniform and smooth coating film cannot be formed.

iii) Catalyst In order to improve the hardness and heat resistance of the cured resin layer, a catalyst capable of promoting an acid-epoxy thermosetting reaction may be added to the thermosetting binder of the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.

The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds and the like, and various compounds described in JP-A-4-218561 can be used. Specifically, (i) compounds obtained by neutralizing halogenocarboxylic acids, sulfonic acids, phosphoric acid mono- and diesters with various amines such as ammonia, monomethylamine, triethylamine, pyridine, ethanolamine, or trialkylphosphine (B) compounds obtained by neutralizing Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the aforementioned Lewis base, (c) methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, etc. Examples include primary alcohols, ester compounds with secondary alcohols, (d) primary alcohols, secondary monoalcohol phosphate monoester compounds, and phosphate diester compounds. Examples of the onium compound include an ammonium compound [R ₃ NR ′] ⁺ X ⁻ , a sulfonium compound [R ₃ SR ′] ⁺ X ⁻ , and an oxonium compound [R ₃ OR ′] ⁺ X ⁻ . Here, R and R ′ are alkyl, alkenyl, aryl, alkoxy and the like.

  The thermal latent catalyst is usually blended at a ratio of about 0.01 to 10.0 parts by weight with respect to a total of 100 parts by weight of the compound having two or more thermosetting functional groups in one molecule and the curing agent. .

(2) Photo-curable binder i) Polymer In a binder containing a photo-curable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, it is necessary to provide film formability and adhesion to the coated surface. For the purpose, it is preferable to include a polymer having a relatively high molecular weight. Here, the relatively high molecular weight means that the molecular weight is higher than that of so-called monomers and oligomers, and the weight average molecular weight can be 5,000 or more. As a polymer having a relatively high molecular weight, any of a polymer having no polymerization reactivity per se and a polymer having a polymerization reactivity per se may be used, and a combination of two or more types may be used. May be. It is mainly composed of a polymer having a relatively high molecular weight, and if necessary, a polyfunctional monomer or oligomer, a monofunctional monomer or oligomer, a photopolymerization initiator activated by light, and a sensitizer. Thus, a photocurable binder is constituted.

  When a polymer having no polymerization reactivity is used as a polymer having a relatively high molecular weight, a polyfunctional polymerizable component such as a bifunctional or higher polyfunctional monomer or oligomer is added to the binder. In this case, in the binder, the polyfunctional polymerizable component itself is spontaneously polymerized by light irradiation or polymerized by the action of other components such as a photopolymerization initiator activated by light irradiation. A network structure is formed in the film, and components such as resins and pigments having no polymerization reactivity are wrapped in the network structure and cured.

As such a polymer having no polymerization reactivity, for example, a copolymer comprising two or more of the following monomers can be used: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate. 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate macromonomer.
More specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, benzyl methacrylate / styrene macromonomer A copolymer etc. can be illustrated.

  The polymer itself having polymerization reactivity is an oligomer obtained by introducing a polymerizable functional group into a non-polymerizable binder molecule or a polymer having a higher molecular weight than an oligomer, and is itself exposed to light irradiation. May cause a polymerization reaction, or may induce a polymerization reaction by the action of other components such as a photopolymerization initiator activated by light irradiation.

Various ethylenic double bond-containing compounds themselves have polymerization reactivity and can be used as photocurable resins. Conventionally, prepolymers blended in UV inkjet inks used in various fields such as inks, paints and adhesives can be used as a polymer having a relatively high molecular weight in the present invention. Conventionally known prepolymers include radical polymerization type prepolymers, cationic polymerization type prepolymers, thiol / ene addition type prepolymers, and any of them may be used.
Among these, radical polymerization type prepolymers are most easily available on the market, such as ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, acrylic resin acrylates, unsaturated polyesters. Examples can be given.

Especially, the following graft polymers are mentioned as a comparatively high molecular weight polymer which can be used suitably in this invention.
The graft polymer suitably used in the present invention has a weight average molecular weight of 5,000 or more, and one of the main chain and the graft portion is composed of a styrenic polymer chain containing a styrenic monomer unit, and the other Is a graft polymer composed of methacrylate polymer chains containing methacrylate monomer units.

  The graft polymer may have a structure in which a main chain (trunk) is constituted by a styrene polymer chain and a graft part is constituted by a methacrylate polymer chain, and conversely, the main chain is constituted by a methacrylate polymer chain. And a structure in which a graft portion is constituted by a styrenic polymer chain. Among the above, those having a structure in which a main chain is constituted by a styrene polymer chain and a graft part is constituted by a methacrylate polymer chain are preferred.

The styrenic polymer chain is a polymer chain mainly composed of a styrenic monomer, and may be a homopolymer of only one kind of styrenic monomer or a copolymer of two or more kinds of styrenic monomers. It may be a copolymer of a styrene monomer and another monomer.
In addition to styrene, the styrenic monomer includes styrene monomers with substituents such as alkyl-substituted styrene (methyl styrene, ethyl styrene, trimethyl styrene, octyl styrene, etc.), methoxy styrene, and α-methyl styrene.

Examples of the monomer that can be copolymerized with the styrene monomer include various (meth) acrylate monomers, acrylonitrile, amide monomers, and the like.
When the inkjet ink according to the present invention contains a pigment, the styrenic polymer chain preferably contains a styrene monomer unit in a proportion of 50% by weight or more from the viewpoint of pigment dispersibility, and more preferably 60% by weight or more. It is particularly preferable to contain at a ratio of

The methacrylate polymer chain is a polymer chain mainly composed of methacrylate and may be a homopolymer of only one type of methacrylate or a copolymer of two or more types of methacrylate, or methacrylate. And a copolymer of other monomers.
As methacrylate monomers, alkyl methacrylate (methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc.), benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrophthalimide Examples include ethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, methoxypolyethylene glycol methacrylate, and butoxyethyl methacrylate. It is preferable to select and use a methacrylate monomer so that a graft polymer having a Tg of 30 ° C. or higher can be obtained. A graft polymer having a Tg of less than 30 ° C. is not preferable because the film hardness after curing decreases.

  Moreover, as a monomer to be copolymerized with methacrylate, alkyl acrylate, hydroxyalkyl acrylate, amide monomer, imide group-containing monomer, alkylene glycol (meth) acrylate, Daicel Chemical's brand name Plexel FM series, or the like can be used.

  The methacrylate polymer has a relatively high Tg and is excellent in hardness and dispersibility because it causes microphase separation from styrene. From this point of view, the methacrylate polymer chain preferably contains a methacrylate monomer unit in a proportion of 50% by weight or more, more preferably 70% by weight or more.

  The graft polymer may have a photopolymerizable group such as an ethylenically unsaturated bond or an epoxy group. Reaction curability can be imparted by introducing a photopolymerizable group into the graft polymer. The graft polymer into which the photopolymerizable group has been introduced can be suitably used as a photocurable resin having a relatively high molecular weight in the present invention, since the crosslinking point is improved and the surface hardness is improved. When the polymerizable group of the graft polymer is an ethylenically unsaturated bond, it can be cured by a photoradical polymerization reaction, and when the polymerizable group is an epoxy group, photocationic polymerization is possible. In particular, when the graft polymer having an ethylenically unsaturated bond is used in combination with an ethylenically unsaturated bond-containing monomer such as a (meth) acrylic monomer and / or an oligomer, an inkjet ink having excellent reaction curability can be obtained. it can. The photopolymerizable group may be introduced into one or both of the styrenic polymer chain and the methacrylate polymer chain, or may be introduced into one or both of the main chain and the graft portion.

  Among them, the graft polymer has an ethylenically unsaturated bond in an ethylenically unsaturated bond equivalent of 1200 g / eq or less, and one of the main chain and the graft portion contains a styrene monomer unit. A preferred graft polymer is a graft polymer composed of a styrene methacrylate polymer chain and the other composed of a benzyl methacrylate polymer chain containing a monomer unit derived from benzyl methacrylate. This is because, among the methacrylate monomers, benzyl methacrylate is particularly excellent in pigment dispersibility, and is therefore preferably used in an inkjet ink for a color filter for forming a pixel or a black matrix layer.

The graft polymer may have a structure in which a main chain (trunk) is constituted by a styrene polymer chain and a graft part is constituted by a benzyl methacrylate polymer chain, and conversely, by a benzyl methacrylate polymer chain. It may have a structure in which the main chain is constituted and the graft portion is constituted by a styrene polymer chain. Among the above, those having a structure in which a main chain is constituted by a styrene polymer chain and a graft part is constituted by a benzyl methacrylate polymer chain are preferred.
The benzyl methacrylate polymer chain of the graft polymer is a polymer chain mainly composed of benzyl methacrylate, and may be a homopolymer of benzyl methacrylate, or a copolymer of benzyl methacrylate and other monomers as described above. It may be a coalescence.
The benzyl methacrylate-based polymer chain preferably contains benzyl methacrylate monomer units in a proportion of 30% by weight or more, particularly preferably 50% by weight or more.

  The graft polymer has at least one of the main chain or graft portion having an ethylenically unsaturated bond, and can be cured by light or thermal radical polymerization reaction. The ethylenically unsaturated bond equivalent of the graft polymer needs to be 1200 g / eq or less, and preferably 700 g / eq or less. Here, the ethylenically unsaturated bond equivalent is a value obtained by dividing the weight of 1 gram molecule of the graft polymer by the number of ethylenically unsaturated bonds contained in one molecule. This is because when the ethylenically unsaturated bond equivalent of the graft polymer exceeds 1200 g / eq, the film hardness after curing and the solvent resistance may be insufficient. On the other hand, a graft polymer having an ethylenically unsaturated bond equivalent of 1200 g / eq or less is excellent in various physical properties such as solvent resistance, hardness, strength, and adhesion because there are many ethylenically unsaturated bonds contained in one molecule. is there. Even in the case where a graft polymer having a relatively low molecular weight is used in order to improve the ejection property, it can be sufficiently cured if the ethylenically unsaturated bond equivalent is 1200 g / eq or less, so that the ink has excellent ejection properties. This is because a cured film having excellent physical properties can be formed.

The weight ratio of the graft (branch) portion / main chain (trunk) portion of the graft polymer is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30. If the weight ratio of the graft portion is less than 20%, the solubility, viscosity, fluidity, dischargeability and the like are deteriorated. On the other hand, when the weight ratio of the main chain portion is less than 20%, the pigment dispersibility is deteriorated.
Furthermore, by changing the acid value and amine value of the above graft polymer, various physical properties such as ink solvent solubility, film solvent resistance, pigment dispersion stability, dyeability, film hardness, and film strength can be adjusted. it can.

  The method for producing the graft polymer includes (1) a method in which a monomer is polymerized in the presence of a polymer and a peroxide catalyst, followed by grafting by hydrogen abstraction, and (2) a polymer having a functional group at one end and other functional groups. Although a method of addition reaction of a polymer with a mark and (3) a method of copolymerizing a polymerizable polymer (macromonomer) and a monomer can be used, the macromonomer method is preferred from the viewpoint of high product purity. As a procedure for synthesizing the graft polymer, reference can be made to specific examples of paragraph numbers 0094 to 0105 of JP-A-2002-201387.

In addition, since the ink according to the present invention is an ink used in an ink jet system, the molecular weight of a polymer having a relatively high molecular weight is set so that the viscosity of the ink is not too high to adversely affect the discharge performance from the discharge head. The weight average molecular weight is preferably 25,000 or less.
The polymer having a relatively high molecular weight is preferably blended at a ratio of 1 to 50% by weight with respect to the total solid content of the inkjet ink.

ii) Polyfunctional polymerizable component In order to improve the strength of the coating film and the adhesion to the substrate even in the case of using a polymer having a relatively high molecular weight that can be polymerized and cured, a polyfunctional monomer It is preferable to blend a polyfunctional polymerizable component such as olefin or oligomer. Polymer molecules with relatively high molecular weight that are polymerizable not only polymerize with polymers with relatively high molecular weight, but also polymerize with other polymerizable components such as polyfunctional monomers to form a network and cure. To do.

As the polyfunctional polymerizable component forming the network structure of the coating film, a bifunctional or higher functional monomer or oligomer can be used. In order to impart sufficient film strength and adhesion to the photocurable resin, a tetrafunctional or higher functional monomer or oligomer is usually used.
However, in particular, since the ink according to the present invention is used as an ink jet ink, a polymerizable component other than a polymer having a relatively high molecular weight is a bifunctional to trifunctional monomer or oligomer or monomer having a relatively small number of functional groups. Is preferably used as a main component, and it is particularly preferable to use a bi- or trifunctional monomer having a viscosity of 100 cps or less. During ink jet spraying, it is difficult for the viscosity to increase at the tip of the head, clogging of the head does not occur, and ink ejection during operation is stable, so the amount and direction of ink ejection is stable. This is because the ink can be accurately and uniformly deposited on the substrate in a predetermined pattern.

Examples of the bifunctional to trifunctional monomers include 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diester. Examples thereof include acrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, and 3-butylene glycol dimethacrylate.
In the ink-jet ink according to the present invention, the blending ratio of the bi- to tri-functional monomer is preferably 20 to 70% by weight based on the total solid content of the ink-jet ink.
If the blending ratio of the bi- or trifunctional monomer is less than 20% by weight of the total solid content, the ink-jet ink is not sufficiently diluted with the monomer, and the viscosity of the ink is high from the beginning or becomes high after volatilization of the solvent. There is a risk of clogging the nozzles of the inkjet head. In addition, when the blending ratio of the bi- or trifunctional monomer exceeds 70% by weight of the total solid content, the cross-linking density of the coating film becomes low, and the solvent resistance, adhesion, and hardness of the coating film are inferior and sufficient. This is because the characteristics may not be obtained.

However, when all the polyfunctional monomers blended in the ink-jet ink are di- or tri-functional monomers, the viscosity increase due to drying of the ink is unlikely to occur, so that the ejection performance of the ink-jet head is stable. The cured layer obtained by curing the ink layer may have insufficient film strength, adhesion to the substrate, solvent resistance, and the like. Therefore, by adding an appropriate amount of a tetrafunctional or higher polyfunctional monomer or oligomer together with the above bifunctional to trifunctional monomers, the crosslinking density can be increased, and sufficient film strength and adhesion can be imparted to the pattern of the cured layer. .
Examples of tetrafunctional or higher polyfunctional monomers and oligomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

The polyfunctional component having 4 or more functional groups is usually preferably blended at a ratio of 1 to 30% by weight with respect to the total solid content of the inkjet ink. The ink jet ink according to the present invention is 100 parts by weight of 2 to 3 functional monomers in order to balance discharge stability with 2 to 3 functional monomers and strength and adhesion improvement with 4 or more functional components. On the other hand, the blending ratio of the tetrafunctional or higher polyfunctional component is usually 1 to 50 parts by weight, preferably the lower limit of the blending ratio is 2 parts by weight and / or the upper limit of the blending ratio is 35. It is preferable to be not more than parts by weight.
When the blending ratio of the tetrafunctional or higher polyfunctional component is less than 1 part by weight with respect to 100 parts by weight of the bi- to tri-functional monomer, characteristics such as hardness and solvent resistance after the ink is cured May not be sufficiently obtained. Moreover, when the said mixture ratio of the polyfunctional component more than tetrafunctional exceeds 50 weight part, there exists a possibility that the cure rate of an ink may become slow and process speed may become slow.

iii) Monofunctional polymerizable component The photocurable binder may be mixed with a monofunctional monomer or oligomer, if necessary.
Examples of monofunctional monomers and oligomers include vinyl monomers such as styrene and vinyl acetate, and monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate.

iv) Photopolymerization initiator The photocurable binder is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the binder and the polyfunctional monomer (for example, radical polymerization and cationic polymerization) and the type of each material. For example, 1-hydroxycyclohexyl-phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bisacylphospho Fin oxide, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone -9-one mesochloride, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl), p- Dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 1,3,5-triacroylhexahydro-s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl]- 4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methylbenzoylformate, 2,4,6-trimethylbenzoyldiphenyl A photopolymerization initiator such as phosphine oxide can be used.
Also, in order to give sufficient adhesion, strength, and hardness to the cured ink layer, the total proportion of thermosetting and / or photocurable binder components in the total solid content of the ink including pigments and other components Is preferably 50% by weight or more.

(solvent)
In order to prepare the ink for a color filter of the present invention so that the ink can be discharged from a high-concentration liquid or immediately from the head, a solvent is blended as necessary.
In order to prepare the inkjet ink for a color filter of the present invention as a high-concentration ink for storage or an ink that can be applied immediately, there is no particular limitation as long as it is a solvent that suitably dissolves and disperses solid components.

  The inkjet ink of the present invention has a boiling point of 180 ° C. to 260 ° C., particularly 210 ° C. to 260 ° C., and a vapor pressure at room temperature (especially in the range of 18 ° C. to 25 ° C.) of 0.5 mmHg or less, particularly 0.1 mmHg or less. It is preferable to use a solvent component as the main solvent, and blend such a main solvent in a proportion of 80% by mass or more, particularly 85% by mass or more, based on the total amount of the solvent. When such a solvent is used, since it has appropriate drying and evaporation properties, it has excellent straightness and stability when ejected from the head, and can be dried more efficiently. This is because the pixel portion and the like can be accurately and uniformly formed by discharging in accordance with a predetermined pattern. The surface tension of the main solvent is preferably 29 mN / m or more at room temperature.

  A solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less has an appropriate drying property and evaporation property. For this reason, if a single solvent or mixed solvent containing such a solvent component in a high blending ratio is used, the inkjet ink does not dry rapidly at the nozzle tip of the discharge head, causing a sudden increase in viscosity or clogging of the ink. Without adversely affecting the straightness and stability of the discharge. At the same time, since the drying proceeds at an appropriate speed after spraying on the surface to be ejected, the ink becomes familiar with the surface to be coated and the surface of the coating film becomes horizontal and smooth, followed by natural drying or a general heating process. The ink can be dried quickly and completely. Compared to the case of using a wetting agent or a solvent having a very high boiling point, there is less possibility that the solvent remains in the coating film after the drying step.

If necessary, the organic solvent may contain a small amount of a solvent component other than the main solvent. However, even in that case, it is preferable to use the main solvent having the above boiling point and vapor pressure at a ratio of 80% by mass or more based on the total amount of the solvent. When the ratio of the main solvent is less than 80% by mass of the total amount of the solvent, there are cases where it is not possible to reliably obtain the drying property and the evaporation property suitable for the ink jet method.
The main solvent is desirably used at the highest possible blending ratio, specifically, at least 80% by mass or more, preferably 85% by mass or more, and desirably 100% by mass as much as possible.

  By forming a wettability variable layer on the surface of the substrate and exposing it, an ink-philic region is formed on a portion of the substrate where the ink layer is to be formed, and the inkjet ink of the present invention is selectively applied to the ink-philic region by the inkjet method. When adhering to the liquid, the standard solution shown in the wettability test specified in JIS K6768 is used as the main solvent, and the contact angle (θ) after 30 seconds is measured after contact with the liquid droplets. A test in which the contact angle with respect to the surface of a test piece having a critical surface tension of 30 mN / m determined by the graph of 25 ° or more, preferably 30 ° or more, and the critical surface tension determined by the same measurement method is 70 mN / m. You may select and use what the contact angle with respect to the surface of a piece shows 10 degrees or less.

  When an ink is prepared using a solvent that exhibits the above behavior with respect to wettability, the ink exhibits a large repellent property with respect to the surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After changing the wettability of the wettability variable layer to increase the hydrophilicity, the wettability variable layer shows a great affinity for the surface of the wettability variable layer. Therefore, the difference between the wettability of the ink with respect to the ink-philic region formed by selectively exposing a part of the surface of the wettability variable layer and the wettability of the ink repellent region with respect to the surrounding region can be increased. As a result, the ink sprayed onto the ink-philic area by the ink jet method spreads evenly to every corner of the ink-philic area. As a result, a fine and precise ink layer pattern can be formed by the inkjet method.

  Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. Examples of test pieces having a critical surface tension of 30 mN / m include, for example, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate having a smooth surface, and the polymer or surface modifier applied on a smooth glass surface. The above test can be actually performed from among those, and the corresponding one can be selected. Moreover, as a test piece which shows critical surface tension 70mN / m, the said test is actually performed from what apply | coated nylon, the glass surface which hydrophilized, etc., and the applicable thing can be selected.

  The main solvent can be selected from the following solvents: ethylene glycol monoethyl ether, glycol ethers such as diethylene glycol diethyl ether; glycol ether esters such as ethylene glycol monomethyl ether acetate; diethylene glycol Glycol oligomer ethers such as monomethyl ether; glycol oligomer ether esters such as diethylene glycol monomethyl ether acetate; aliphatic or aromatic esters such as ethyl acetate, propyl benzoate; dicarboxylic acid diesters such as diethyl carbonate; Alkoxycarboxylates such as methyl 3-methoxypropionate; ketocarboxylates such as ethyl acetoacetate; ethanol Alcohols or phenols such as isopropanol and phenol; aliphatic or aromatic ethers such as diethyl ether and anisole; alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol; diethylene glycol and tripropylene Glycol oligomers such as glycol; alkoxy alcohol esters such as 2-ethoxyethyl acetate; ketones such as acetone and methyl isobutyl ketone.

  In addition, since the ink for a color filter according to the present invention contains a pigment, the main solvent that occupies most of the solvent is one that does not contain a hydroxyl group from the viewpoint of the dispersibility and dispersion stability of the pigment. It is preferable.

  Preferred solvents include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dimethyl malonate, diethyl malonate, succinate Examples thereof include dimethyl acid and diethyl succinate. These solvents are preferable not only because they satisfy the requirements of a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less, but also have no hydroxyl group in the molecule. Furthermore, these solvents are mixed with or without mixing with highly dispersible solvents conventionally used for preparing pigment dispersions such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate (PGMEA). It can be used as a solvent to prepare a pigment dispersion.

  The above-mentioned solvent exemplified as a preferable example uses a standard solution shown in the wettability test specified in JIS K6768, measures the contact angle (θ) 30 seconds after contacting a droplet, The contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m determined by the above is 25 ° or more, and the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 10 Also meets the requirement to show below. Therefore, these solvents are mainly used when a wettability variable layer is provided on the surface of a substrate for exposure, and ink jet ink is selectively attached using a difference in wettability between an exposed portion and an unexposed portion. It can be suitably used as a solvent.

  Further, when water is mixed in the solvent, the hydroxyl group of the water molecule is present in the solvent, so that the same problem as in the case of using the solvent having a hydroxyl group may be caused. Therefore, in order to substantially exclude water from the acid-epoxy crosslinking reaction system, it is preferable to prepare an inkjet ink using an organic solvent having low miscibility with water. From this viewpoint, the solubility of the solvent for preparing the ink-jet ink in water is preferably 20 parts by weight or less with respect to 100 parts by weight of water having a liquid temperature of 20 ° C.

  Among the main solvents mentioned as specific examples, diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and the solubility in 100 parts by weight of water at a liquid temperature of 20 ° C. is low at 6.5 parts by weight. It is particularly preferable since it exhibits the property.

  The solvent is usually used at a ratio of 40 to 95% by mass with respect to the total amount of the ink-jet ink containing the solvent to prepare the ink-jet ink. When the amount of the solvent is too small, the viscosity of the inkjet ink is high, and in the case of the inkjet ink, it becomes difficult to discharge from the inkjet head. If there is too much solvent, the ink film deposited on the wettability change site will be broken before the ink deposit amount (ink deposition amount) for the predetermined wettability change site (ink layer formation site) is not sufficient, It protrudes to the surrounding unexposed area and further spreads to the adjacent wettability change site (ink layer forming site). In other words, the amount of ink that can be deposited without protruding from the wettability change site (ink layer forming site) to which the ink is to be deposited becomes insufficient, the film thickness after drying is too thin, The transmission density cannot be obtained.

(Pigment dispersant)
The pigment dispersant is blended in the inkjet ink as necessary in order to disperse the pigment satisfactorily. As the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone-based surfactants, special acrylic polymers, and the like can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.
That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Polymeric surfactants such as polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes are preferably used.
The content of the pigment dispersant is preferably 1 to 60% by weight based on the entire solid content, and more preferably 15 to 40% by weight based on the entire solid content.

(Other ingredients)
Furthermore, the ink for ink for color filters of this invention can mix | blend 1 type (s) or 2 or more types of other additives as needed. The following can be illustrated as such an additive.
a) Filler: For example, glass, alumina and the like.
b) Adhesion promoter: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
c) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
d) Anti-aggregation agent: for example, sodium polyacrylate.
In the inkjet ink for a color filter of the present invention, the weight ratio (P / V) of the pigment (P) and the solid content (V) other than the pigment is preferably 0.3 to 1.5, and more preferably 0. .3 to 0.7 from the viewpoint of preventing ink from breaking from the formation area during patterning while ensuring sufficient transmission density when applied to a predetermined film thickness (usually 0.1 to 2.0 μm). preferable.

(Ink physical properties)
The inkjet ink for a color filter according to the present invention uses the standard solution shown in the wettability test specified in JIS K6768, measures the contact angle (θ) after 30 seconds by contacting a droplet, It is preferable that the contact angle with respect to the surface of the test piece having a critical surface tension of 70 mN / m determined from the graph of 10 is 10 ° or less from the viewpoint of improving the wettability of ink and preventing the color loss of the pixels. Note that the color loss of the pixel means that a portion that appears white without a colored layer is generated in a part of the pixel formation region. This is because, when the contact angle of the ink for inkjet is too large, the wettability of the ink deteriorates, and the ink does not spread to every corner during pixel formation, and pixel color loss may occur.

(Ink production method)
The inkjet ink for a color filter of the present invention may be produced by introducing each component into a single solvent or a solvent that is a mixed solvent and mixing them, and dissolving or dispersing the solid components.
However, if the pigment is directly put into the entire solvent together with other components such as a binder and mixed with stirring, the pigment is often not sufficiently dispersed in the solvent. Therefore, usually, a solvent having good dispersibility and dispersion stability of the pigment is prepared, and the pigment is added thereto together with the pigment dispersant and sufficiently stirred by a dissolver or the like to prepare a pigment dispersion. Then, the obtained pigment dispersion, together with the components other than the pigment, is put into a solvent consisting essentially of the main solvent or only of the main solvent, and sufficiently stirred and mixed by a dissolver or the like, whereby the ink jet according to the present invention Ink can be used.

  As the remaining solvent into which the pigment dispersion is charged, an inkjet ink having a composition obtained by subtracting the amount of the solvent used for preparing the pigment dispersion from the final composition of the entire solvent is diluted to the final concentration. May be completed. Alternatively, a high-concentration inkjet ink may be prepared by introducing the pigment dispersion into a relatively small amount of the main solvent. The high-concentration ink-jet ink can be stored as it is and diluted to the final concentration just before use and used in the ink-jet method.

  In the present invention, in particular, when a blending ratio of a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less as a main solvent is used by 90% by weight or more of the whole solvent, pigment dispersion In preparing the liquid, there may be a case where a sufficient amount of a conventionally used dispersion solvent such as 3-methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA) cannot be used. In that case, select a solvent with relatively good dispersibility and dispersion stability from among the solvents that can be used as the main solvent, and use a solvent mixed with the conventionally used dispersion solvent as the dispersion solvent. Alternatively, the main solvent is used as a dispersion solvent as it is.

(Use)
The inkjet ink for a color filter according to the present invention is particularly preferably used for forming a film having a predetermined pattern such as a pixel or a black matrix in a color filter. As the color filter, any of a color filter used for an image output device such as a liquid crystal display device or a color filter used for an image input device such as a solid-state imaging device can be suitably used.

2. Color filter The color filter according to the present invention is a color filter including at least a transparent substrate and pixels provided on the transparent substrate, and the pixels include a fluorosurfactant and / or a chemical change body thereof. It is characterized by that.

In the color filter according to the present invention, when the pixel contains a fluorine-based surfactant and / or a chemical change body thereof, surface roughness is suppressed and the surface smoothness is excellent. As a result, the incident light to the pixel is reduced from being scattered or refracted, and the incident light to the pixel can be transmitted as it is without loss, and the fluorosurfactant and / or its chemical change body can be reduced. It is possible to obtain a color filter in which display unevenness is reduced and contrast is improved as compared with the case where the color filter is not included.
In particular, in the color filter according to the present invention, when the pixel is formed using the inkjet ink according to the present invention, the cost can be reduced and the surface roughness of the pixel is reduced as described above. A color filter can be obtained.

  FIG. 2 is a longitudinal sectional view showing an example (color filter 103) of the color filter according to the present invention. The color filter 103 covers a black matrix 6 formed in a predetermined pattern on the transparent substrate 5, pixels 7 (7R, 7G, 7B) formed in a predetermined pattern on the black matrix, and covers the pixels. The formed protective film 8 is provided. A transparent electrode film 9 for driving liquid crystal is formed on the protective film 8. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.

  The columnar spacer 12 is a shape of a convex spacer, and is formed at a plurality of predetermined locations (five locations in FIG. 2) on the transparent electrode 9 in accordance with the region (non-display region) where the black matrix layer 6 is formed. ing. The columnar spacer 12 is formed on the transparent electrode 9, the pixel 7, or the protective film 8. In the color filter 102, columnar spacers are formed in a sea-island shape on the protective film 8 via the transparent electrode film 9, but the protective film 8 and the columnar spacer 12 are integrally formed and covered thereover. A transparent electrode film 9 may be formed. When the color filter does not include a black matrix layer, columnar spacers can be formed in regions where pixels are not formed.

(Transparent substrate)
The transparent substrate 5 is not particularly limited as long as it is conventionally used for a color filter. For example, the transparent substrate 5 is not transparent, such as quartz glass, Pyrex glass (registered trademark), or synthetic quartz plate. A transparent material having flexibility such as a rigid material, a transparent resin film, an optical resin plate, or the like can be used. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices. In the present invention, a transparent substrate is usually used, but a reflective substrate or a white colored substrate can also be used. Moreover, you may use the board | substrate which surface-treated for the purpose of alkali elution prevention, gas-barrier provision, and other purposes as needed.

(Pixel)
The pixel of the color filter according to the present invention is characterized by containing a fluorosurfactant and / or a chemical change body thereof.
Here, since the fluorosurfactant is the same as that described in the ink-jet ink according to the present invention, description thereof is omitted here.
Moreover, the chemical change body of a fluorine-type surfactant means what changed the fluorine-type surfactant caused the chemical reaction by the heat | fever, light, etc. at the time of color filter formation or use.

  In the color filter according to the present invention, the content of the fluorosurfactant is 0.0005 to 5% by weight, more preferably 0.005 to 0.5% by weight, particularly 0.005 to 5% by weight based on the entire pixel. The content of 0.2% by weight is preferable from the viewpoint of increasing the smoothness of the pixel surface. Here, with respect to the whole pixel means a value with respect to the whole solid content forming the pixel, that is, the colored layer.

  Furthermore, in the color filter according to the present invention, the P / V ratio in the pixel is preferably 0.3 to 1.5, and more preferably 0.3 to 0.7. Usually, it is preferable from the viewpoint of preventing ink breakage from the formation region during patterning while ensuring a sufficient transmission density when applied to 0.1 to 2.0 μm.

  A pixel is usually formed of three colors of red (R), green (G), and blue (B). The coloring pattern shape in the pixel can be a known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type, and the coloring area can be arbitrarily set.

  In the color filter of the present invention, the method for forming the pixel is not particularly limited, but it is preferably formed by an inkjet method using the inkjet ink according to the present invention as described later. This is because a pixel can be formed with high definition, and a color filter having pixels with reduced surface roughness that can realize cost reduction and yield improvement can be obtained.

  The thickness of the pixel is usually about 0.5 to 2.5 μm. Alternatively, the thickness of each color pixel may be changed so that the red pixel 7R is the thinnest, and the green pixel 7G and the blue pixel 7B become thicker in this order, and the optimal liquid crystal layer thickness may be set for each color.

  In the color filter according to the present invention, the surface roughness (Ra) of the pixel is preferably 10 nm or less, more preferably 7.5 nm or less, and particularly preferably 5 nm or less from the viewpoint of improving the contrast. . Here, the surface roughness (Ra) refers to the arithmetic average roughness obtained by the following formula.

式中、Ｎは測定の際の基準長さに対する分割数であり、Ｒｎは、表面に対する厚み方向を高さとした時の、分割した区画ｎの平均高さからの偏差である。表面粗度（Ｒａ）は、ＡＦＭ（atomic force microscope；原子間力顕微鏡）により測定することができる。

In the formula, N is the number of divisions with respect to the reference length at the time of measurement, and Rn is a deviation from the average height of the divided sections n when the thickness direction with respect to the surface is height. The surface roughness (Ra) can be measured by an AFM (atomic force microscope).

(Black matrix layer)
The black matrix layer 6 is provided so as to surround the pixels 7R, 7G, and 7B and the outside of the pixel formation region in order to improve the contrast of the display image. The black matrix layer 6 may be a metal thin film such as chromium by sputtering, vacuum deposition, or the like. Alternatively, the black matrix layer 6 may be a resin layer in which light shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist and a method of patterning using an inkjet ink containing light-shielding particles. The black matrix layer 6 may be formed using the inkjet ink according to the present invention containing light-shielding particles.
The thickness of the black matrix layer is about 0.1 to 0.2 μm in the case of a metal thin film, and about 0.5 to 2.5 μm in the case of a light shielding resin layer.

(Protective film)
The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the pixels 7 from eluting into the liquid crystal layer. The protective film 8 covers the black matrix layer 6 and the pixels 7 by a known negative photocurable transparent resin composition or thermosetting transparent resin composition by a method such as spin coater, roll coater, spray, printing, etc. And can be formed by curing with light or heat.
The thickness of the protective film 8 can be set in consideration of the light transmittance of the material used, the surface state of the color filter, and the like, and can be set in the range of 0.1 to 2.0 μm, for example.

(spacer)
A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can set suitably from thickness etc. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar spacers, for example, red, green and blue Necessary and sufficient spacer function is expressed at a ratio of one for each pixel. The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer is, for example, applied by applying a coating solution of the curable resin composition directly on the transparent substrate by a method such as spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode. And dried to form a curable resin layer. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. Usually, a photocurable ink-jet ink is preferably used as the ink-jet ink for forming the spacer. Next, the resin layer is exposed through a photomask for a convex spacer, and then a developer such as an alkaline liquid is used. Development is performed to form a predetermined convex pattern, and this convex pattern is heat-treated (post-baked) in a clean oven or the like as necessary to form a convex spacer.

  The convex spacer can be provided directly on the color filter or indirectly through another layer. For example, a transparent electrode such as ITO or a protective film may be formed on the color filter, and a convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed on the color filter in this order, and the transparent electrode A convex spacer may be formed on the top.

(Transparent electrode)
The transparent electrode 9 can be formed using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

(Other layers)
Other members usually formed on the color filter may be further included. For example, when a color filter is formed using an inkjet method, there may be a partition between pixels. The partition for the inkjet method will be described in the manufacturing method by the inkjet method described later. In addition, the alignment film and other members can be formed by a usual method using those usually used for a color filter.

(Color filter manufacturing method)
Next, as an example of a method for producing a color filter, a method for producing an ink jet method using the color filter ink-jet ink according to the present invention will be described.
First, a transparent substrate for a color filter is prepared as shown in FIG.

Next, as shown in FIG. 3B, a black matrix layer 6 is formed in a region serving as a boundary between pixel portions on one surface side of the transparent substrate 5. When a metal thin film is formed as the black matrix layer 6, it can be formed by patterning the thin film. As the patterning method, a normal patterning method such as a sputtering method or a vacuum deposition method can be used.
Moreover, when forming a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder as the black matrix layer 6, a patterning method is a photolithography method. A generally used method such as a printing method can be used. Or you may form using an inkjet system similarly to the pixel 7 mentioned later.

  Next, as shown in FIG. 3C, an ink-repellent partition wall 20 having a width smaller than that of the black matrix layer is formed in the center in the width direction of the pattern of the black matrix layer as necessary. The composition of such an ink repellent partition is not particularly limited as long as it is a resin composition having ink repellent properties. Moreover, it does not need to be transparent in particular and may be colored. For example, a material that is used for the black matrix layer and does not include a black material can be used. Specifically, a composition in which one or more aqueous resins such as polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose are mixed, or an O / W emulsion type resin composition, for example, an emulsion of reactive silicon And the like. For reasons such as easy handling and curing, a photocurable resin is preferably used. Further, since the ink repellency partition wall is more preferable as the ink repellency is stronger, the surface thereof may be treated with an ink repellent treatment agent such as a silicon compound or a fluorine-containing compound.

  The patterning of the ink repellent partition wall can be performed by printing using a coating liquid of the ink repellent resin composition or photolithography using a photocurable coating liquid. The height of the ink repellent partition is preferably set to a certain degree because it is provided to prevent ink from being mixed when colored by the ink jet method as described above. Considering the overall flatness of the pixel, the thickness is preferably close to the thickness of the pixel. Specifically, although it varies depending on the amount of ink deposited, it is usually preferably in the range of 0.1 to 2.0 μm.

  Next, an ink-jet ink for a color filter according to the present invention in which an R, G, or B pigment is blended is prepared. Then, as shown in FIG. 3D, the pixel forming ink jets corresponding to the color pixel forming regions 21R, 21G, and 21B defined by the pattern of the black matrix layer 6 on the surface of the transparent substrate 5. Ink is sprayed by an ink jet method to form an ink layer. The ink layer is formed so that a red pattern, a green pattern, and a blue pattern are arranged in a desired form such as a mosaic type, a stripe type, a triangle type, or a four-pixel arrangement type. In this ink spraying process, it is difficult for the ink-jet ink to increase in viscosity at the tip of the head 22 and to maintain good ejection properties. In this case, the ink of the corresponding color can be adhered accurately and uniformly in the predetermined pixel formation region, and a pixel portion without color unevenness or color loss can be formed with an accurate pattern. In addition, since the inkjet ink for pixel formation of each color can be simultaneously sprayed onto the substrate using a plurality of heads, the working efficiency is improved as compared with the case where the pixel portion is formed for each color by a method such as printing. Can do.

  Next, as shown in FIG. 3E, the ink layers 23R, 23G, and 23B of the respective colors are dried and pre-baked as necessary, and then cured by being appropriately exposed and / or heated. When the ink layer is appropriately exposed and / or heated, the crosslinking element of the curable resin contained in the inkjet ink causes a crosslinking reaction, and the ink layer is cured.

  Next, as shown in FIG. 3F, the protective film 8 is formed on the side of the transparent substrate on which the pixels 24R, 24G, and 24B are formed. The protective film can be formed by a method such as spin coater, roll coater, spray, printing, etc. using a transparent resin composition. For example, it is preferably formed by applying a spin coater within a range of 500 to 1500 revolutions / minute and then curing by exposure and / or heating.

The transparent electrode on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and can be formed into a predetermined pattern by etching using a photoresist or using a jig as necessary.
In others, it can manufacture using the method similar to the method of forming a normal color filter.

3. Furthermore, the liquid crystal display device according to the present invention is a liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed between the two, and the display side substrate is It is a color filter according to the present invention.
Since the liquid crystal display device according to the present invention uses the color filter with reduced display defects as described above, it can be a high-quality liquid crystal display device.

  When the color filter 103 (display side substrate) obtained as described above and the TFT array substrate (liquid crystal drive side substrate) are opposed to each other and the inner peripheral side peripheral portions of both the substrates are joined with a sealant, the both substrates are separated by a predetermined distance. Bonding is performed with the cell gap maintained. An active matrix color liquid crystal display device belonging to the liquid crystal display device according to the present invention can be obtained by filling the gap between the substrates with liquid crystal and sealing it.

Since other configurations and manufacturing methods in the liquid crystal display device can use commonly used configurations and methods, description thereof is omitted here.
The liquid crystal display device of the present invention is not particularly limited as long as it has the above-described color filter, and may be a known liquid crystal display device. Specifically, IPS (In-Plane Switching) type, STN (Super Twisted Nematic) type, TN (Twisted Nematic) type, ferroelectric type, antiferroelectric type, MVA mode type and the like can be mentioned.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

(Production Example 1: Synthesis of binder epoxy compound)
In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, diethylene glycol monobutyl ether acetate (also referred to as butyl carbitol acetate, hereinafter may be referred to as BCA) according to the mixing ratio shown in Table 1. 40.7 parts by weight were charged and heated with stirring to 140 ° C. Next, 54.7 parts by weight of a mixture (dropping component) of a monomer having a composition described in Table 1 and a polymerization initiator at 140 ° C. was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropwise addition, the temperature was lowered to 110 ° C., 4.6 parts by weight of a mixture of polymerization initiator and solvent-free diethylene glycol monobutyl ether acetate (BCA) (additional catalyst component) was added, and the temperature at 110 ° C. was maintained for 2 hours. By the way, by terminating the reaction, a binder epoxy compound having the characteristics shown in Table 1 was obtained.

＊１）表中の略号は以下の通りである。
ＧＭＡ：グリシジルメタクリレート
ＭＭＡ：メチルメタクリレート
パーブチルＯ：ｔ−ブチルパーオキシ２−エチルヘキサノエート（日本油脂（株）製商品名）
＊２）重量平均分子量：ゲル浸透クロマトグラフィーによるポリスチレン換算の値である。

* 1) Abbreviations in the table are as follows.
GMA: Glycidyl methacrylate MMA: Methyl methacrylate Perbutyl O: t-Butylperoxy 2-ethylhexanoate (trade name, manufactured by NOF Corporation)
* 2) Weight average molecular weight: A value in terms of polystyrene by gel permeation chromatography.

(Production Example 2: Synthesis of fluorosurfactant)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 18 parts by weight of a fluorinated alkyl group-containing (meth) acrylate monomer (a-1) and a silicone chain-containing ethylenically unsaturated monomer (b-3- 1) 12 parts by weight, 57 parts by weight of a monoacrylate compound having a side chain of a copolymer of ethylene oxide and propylene oxide having a molecular weight of 4000, 4 parts by weight of a compound in which both ends of tetraethylene glycol are methacrylated, 9 parts by weight of methyl methacrylate 1 part by weight of azobisisobutyronitrile as a polymerization initiator under reflux in a nitrogen gas stream, and then refluxed at 100 ° C. for 15 hours to complete the polymerization. I let you.

  The molecular weight of this polymer in terms of polystyrene according to the gel permeation graph was Mn = 47000. This copolymer was designated as fluorosurfactant 1.

(Examples 1-3, Comparative Examples 1-4: Preparation of green inkjet ink for color filter)
(1) Preparation of pigment dispersion Each pigment, pigment dispersant, and organic solvent are mixed at the following ratio, and 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. PG36 (CI Pigment Green 36) pigment dispersion, PG7 (CI Pigment Green 7) pigment dispersion, PY138 (CI Pigment Yellow 138) pigment dispersion and PY150 (C I. Pigment Yellow 150) A pigment dispersion was prepared.

[Composition of pigment dispersion]
-Each pigment: 10 parts by weight-Pigment dispersant (Disperbyk161 (manufactured by Big Chemie Japan) (solid content 30% by weight in solvent BCA)): 10 parts by weight-Pigment dispersion aid (N-phenylmaleimide / benzyl methacrylate copolymer) Combined (solid content 30% by weight in solvent BCA): 10 parts by weight BCA (diethylene glycol monobutyl ether acetate): 70 parts by weight

(2) Preparation of binder A rotor coated with Teflon (registered trademark) was placed in a sample bottle and placed on a magnetic stirrer. In this sample bottle, add the binder-type epoxy compound, polyfunctional epoxy resin, etc. described in Preparation Example 1 according to the following proportions, dissolve with sufficient stirring at room temperature, and then add a diluent solvent to adjust the viscosity. After stirring and dissolving, this was filtered to obtain a binder composition.

[Binder composition]
-Binder epoxy compound of Production Example 1 (solid content 30% by weight in solvent BCA): 11 parts by weight-Multifunctional epoxy resin (trade name Epicoat 154, manufactured by Yuka Shell Epoxy): 2.2 parts by weight-Neopentyl Glycol glycidyl ether: 1.1 parts by weight Trimellitic acid: 2.2 parts by weight BCA (diethylene glycol monobutyl ether acetate): 13.5 parts by weight

  19.25 parts by weight of the PG36 pigment dispersion prepared above, 13.65 parts by weight of PG7 pigment dispersion, 24.64 parts by weight of PY138 pigment dispersion, 12.46 parts by weight of PY150 pigment dispersion, and 30 parts by weight of binder. The ink jet ink of Comparative Example 4 was prepared by thoroughly mixing. Then, each surfactant etc. were added to the inkjet ink of the comparative example 4 with the mixture ratio shown by Table 2, and the green inkjet ink for color filters of Examples 1-3 and Comparative Examples 1-3 was obtained.

表中の略号は以下の通りである。
＊３）製造例２で合成したフッ素系界面活性剤１（フッ素化アルキル基とエチレン性二重結合を含有するモノマー（Ａ）及びシリコーン鎖とエチレン性二重結合を含有するモノマー（Ｂ）を少なくとも用いて重合されたフッ素系共重合体）
＊４）Ｒ−０８ＭＨ：フッ素系界面活性剤（商品名メガファックＲ−０８ＭＨ：大日本インキ化学工業（株））
＊５）Ｆ−４４５：フッ素系界面活性剤（商品名メガファックＦ４４５：大日本インキ化学工業（株））
＊６）Ｌ−１９８５−５０：アクリル系界面活性剤（商品名Ｌ−１９８５−５０、楠本化成（株））
＊７）ＥＦＫＡ３７７７：フルオロカーボン変性ポリマー（商品名ＥＦＫＡ３７７７、ＥＦＫＡ社）
＊８）ＴＳＬ８２５７：フルオロアルキルシラン（商品名ＴＳＬ８２５７、ＧＥ東芝シリコーン（株））
＊９）顔料分散液やバインダー成分等は固形分のみの重量部を表示し、インク中に含まれる溶剤は全て最下段に計上した。

Abbreviations in the table are as follows.
* 3) Fluorosurfactant 1 synthesized in Production Example 2 (a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond) and a monomer (B) containing a silicone chain and an ethylenic double bond Fluorine copolymer polymerized using at least)
* 4) R-08MH: Fluorosurfactant (Brand name Megafac R-08MH: Dainippon Ink & Chemicals, Inc.)
* 5) F-445: Fluorosurfactant (trade name MegaFuck F445: Dainippon Ink & Chemicals, Inc.)
* 6) L-1985-50: Acrylic surfactant (trade name L-1985-50, Enomoto Kasei Co., Ltd.)
* 7) EFKA3777: fluorocarbon modified polymer (trade name EFKA3777, EFKA)
* 8) TSL8257: Fluoroalkylsilane (trade name TSL8257, GE Toshiba Silicone Co., Ltd.)
* 9) For pigment dispersions and binder components, only parts by weight of solid content are displayed, and all solvents contained in the ink are counted at the bottom.

[Evaluation]
1. village
Each of the ink jet inks was used to accurately and uniformly adhere to the coating film forming portion on the substrate by the ink jet method.
Then, it dried under reduced pressure at 10 Torr for 120 seconds, and also pre-baked for 10 minutes on an 80 degreeC hotplate. Then, in a clean oven, post-baking is performed by heating at 200 ° C. for 30 minutes, and further post-baking is performed by heating at 230 ° C. for 30 minutes. The average film thickness after drying and curing is 1.8 μm on the substrate. A coating film was formed.
As a result, the presence or absence of unevenness was evaluated by visually confirming unevenness of reflection and unevenness of transmission by the Na light source lamp. A case where there was no unevenness was indicated by ○, and a case where there was unevenness was indicated by ×.
Moreover, the external appearance photograph of each coating film permeate | transmitted with the table light is shown in FIG.

2. Chromaticity coordinates (x, y, luminance Y)
Measurement was performed using a microspectrophotometer (Olympus Co., Ltd., OSP200).

3. Measurement of surface roughness Ra The surface roughness Ra of the coating film used for the evaluation of unevenness was measured by AFM. The AFM used was NanoScope IIIa manufactured by Biko Japan.

(Example 4, Comparative Example 5: Preparation of red inkjet ink for color filter)
(1) Preparation of pigment dispersion Each pigment, pigment dispersant, and organic solvent are mixed at the following ratio, and 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. After dispersion for 4 hours, PR254 (CI Pigment Red 254) pigment dispersion and PR177 (CI Pigment Red 177) pigment dispersion were prepared.

[Composition of pigment dispersion]
-Each pigment: 10 parts by weight-Pigment dispersant (Disperbyk161 (manufactured by Big Chemie Japan) (solid content 30% by weight in solvent BCA)): 10 parts by weight-Pigment dispersion aid (N-phenylmaleimide / benzyl methacrylate copolymer) Combined (solid content 30% by weight in solvent BCA): 10 parts by weight BCA (diethylene glycol monobutyl ether acetate): 70 parts by weight

(2) Preparation of binder According to the following ratio, it prepared similarly to the binder used for Example 1.
[Binder composition]
-Binder epoxy compound of Production Example 1 (solid content 30% by weight in solvent BCA): 10 parts by weight-Polyfunctional epoxy resin (trade name Epicoat 154, manufactured by Yuka Shell Epoxy): 2 parts by weight-Neopentyl glycol glycidyl Ether: 1 part by weight-Trimellitic acid: 2 parts by weight-BCA (diethylene glycol monobutyl ether acetate): 10 parts by weight

  68.85 parts by weight of the PR254 pigment dispersion prepared above, 6.15 parts by weight of PR177 pigment dispersion, and 25 parts by weight of a binder were sufficiently mixed to prepare a red inkjet ink of Comparative Example 5. Thereafter, a surfactant was added to the inkjet ink of Comparative Example 5 at a blending ratio shown in Table 3 to obtain a red inkjet ink for a color filter of Example 4.

(Example 5, Comparative Example 6: Preparation of blue inkjet ink for color filter)
(1) Preparation of pigment dispersion Each pigment, pigment dispersant, and organic solvent are mixed at the following ratio, and 500 parts by weight of zirconia beads having a diameter of 0.3 mm are added, and a paint shaker (manufactured by Asada Steel Corporation) is used. After dispersion for 4 hours, PB15: 6 (CI Pigment Blue 15: 6) pigment dispersion and PV23 (CI Pigment Violet 23) pigment dispersion were prepared.

[Composition of pigment dispersion]
-Each pigment: 10 parts by weight-Pigment dispersant (Disperbyk161 (manufactured by Big Chemie Japan) (solid content 30% by weight in solvent BCA)): 10 parts by weight-Pigment dispersion aid (N-phenylmaleimide / benzyl methacrylate copolymer) Combined (solid content 30% by weight in solvent BCA): 10 parts by weight BCA (diethylene glycol monobutyl ether acetate): 70 parts by weight

(2) Preparation of binder According to the following ratio, it prepared similarly to the binder used for Example 1.
[Binder composition]
-Binder epoxy compound of Production Example 1 (solid content 30% by weight in solvent BCA): 15 parts by weight-Polyfunctional epoxy resin (trade name Epicoat 154, manufactured by Yuka Shell Epoxy): 3 parts by weight-Neopentyl glycol glycidyl Ether: 1.5 parts by weight Trimellitic acid: 3 parts by weight BCA (diethylene glycol monobutyl ether acetate): 27.5 parts by weight

    The PB15: 6 pigment dispersion prepared above (46.8 parts by weight), PV23 pigment dispersion (3.2 parts by weight), and binder (50 parts by weight) were sufficiently mixed to prepare a blue inkjet ink of Comparative Example 6. Thereafter, a surfactant was added to the inkjet ink of Comparative Example 6 at the blending ratio shown in Table 4 to obtain a blue inkjet ink for a color filter of Example 5.

(Example 6: Production of color filter)
A black matrix pattern having a line width of 20 μm and a film thickness of 1.2 μm is formed on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm by a photolithographic method using a curable resin composition for black matrix. Formed.
The red inkjet ink of Example 4 was accurately and uniformly attached to the red pixel forming portion partitioned by the black matrix of the substrate by the inkjet method. Next, the green inkjet ink of Example 2 was adhered to the green pixel forming portion of the same substrate accurately and uniformly by the inkjet method. Next, the blue inkjet ink of Example 5 was adhered accurately and uniformly to the blue pixel formation portion of the same substrate by the inkjet method.

Then, it dried under reduced pressure at 10 Torr for 120 seconds, and also pre-baked for 10 minutes on an 80 degreeC hotplate. Then, in a clean oven, post-baking is performed by heating at 200 ° C. for 30 minutes, and further post-baking is performed by heating at 230 ° C. for 30 minutes, and the average film thickness after drying and curing is 1.8 μm on the substrate. An RGB three-color pixel pattern was formed.
The substrate on which the RGB pixel pattern was formed was immersed in IPA for 5 minutes, then dried by IPA vapor, washed, and then ITO (indium oxide) at a substrate setting temperature of 200 ° C. under a vacuum of 6 × 10 ⁻³ Torr. A tin) electrode was deposited to a thickness of 120 nm. The substrate on which this ITO film was formed was further immersed in IPA for 5 minutes, steam-washed with IPA, spin-coated with polyimide, and baked at 180 ° C. for 60 minutes to form an alignment film. Got.
In the same manner as in Example 1, chromaticity coordinates x, y, luminance Y, and surface roughness Ra were evaluated. The results are shown in Table 5.

(Comparative Example 7: Production of color filter)
The same procedure as in Example 6 was used except that the blue inkjet ink of Comparative Example 1 was used as the blue inkjet ink, the green inkjet ink of Comparative Example 6 was used as the green inkjet ink, and the red inkjet ink of Comparative Example 5 was used as the red inkjet ink. An RGB three-color pixel pattern having an average film thickness after drying and curing of 1.8 μm was formed on the substrate, and a color filter was produced in the same manner.
In the same manner as in Example 1, chromaticity coordinates x, y, luminance Y, and surface roughness Ra were evaluated. The results are shown in Table 5.

  It is clear that the surface roughness of the color filter of the example prepared with the ink containing the fluorine-based surfactant is smaller than that of the color filter of the comparative example prepared with the ink containing no fluorine-based surfactant. Became.

It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is a typical longitudinal section showing an example of a color filter concerning the present invention. It is a figure explaining an example of the method of manufacturing a color filter using the inkjet ink of this invention. It is an external appearance photograph of each coating film formed using Examples 1-3 and the inkjet ink of Comparative Examples 1-4.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Electrode board 3 ... Gap part 4 ... Sealing material 5 ... Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Pixel 8 ... Protective film 9 ... Transparent electrode film 10 ... Orientation film 11 ... Pearl 12 ... Columnar spacer 20 ... Ink-repellent partition wall 21 ... Pixel formation region 22 ... Inkjet head 23 ... Ink layer 24 ... Pixel portion 101, 102 ... Color liquid crystal display device 103, 104 ... Color filter

Claims (10)

  An ink-jet ink for a color filter containing a pigment, a binder, and a fluorine-based surfactant.   Fluorine-based surfactant polymerized using at least a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond and a monomer (B) containing a silicone chain and an ethylenic double bond The inkjet ink for a color filter according to claim 1, which is a copolymer.   The inkjet ink for color filters according to claim 1 or 2, wherein the content of the fluorosurfactant is 0.0005 to 5 wt% with respect to the entire solid content.   Further, a solvent is contained, and the solvent contains, as a main solvent, a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 0.5 mmHg or less at room temperature in a proportion of 80% by weight or more based on the total amount of the solvent. The inkjet ink for a color filter according to any one of claims 1 to 3, wherein the inkjet ink is used.   Using the standard solution shown in the wettability test stipulated in JIS K6768, the contact angle (θ) after 30 seconds was measured by bringing the droplet into contact with each other, and the critical surface tension obtained from the graph of Zisman plot was 70 mN / The inkjet ink for a color filter according to claim 1, wherein a contact angle of m to the surface of the test piece is 10 ° or less.   A color filter comprising at least a transparent substrate and a pixel provided on the transparent substrate, wherein the pixel contains a fluorosurfactant and / or a chemical change body thereof.   Fluorine-based surfactant polymerized using at least a monomer (A) containing a fluorinated alkyl group and an ethylenic double bond and a monomer (B) containing a silicone chain and an ethylenic double bond The color filter according to claim 6, wherein the color filter is a copolymer.   8. The color filter according to claim 6, wherein the content of the fluorosurfactant is 0.0005 to 5 wt% with respect to the entire pixel.   The color filter according to claim 6, wherein a surface roughness (Ra) of the pixel is 10 nm or less. A liquid crystal display device in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and liquid crystal is sealed between the two, wherein the display side substrate is the color filter according to any one of claims 6 to 9. A liquid crystal display device comprising:

Images