JP2015068962A - Colored curable composition, color filter, method for manufacturing color filter, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable composition that gives a pattern with high optical density and has excellent pattern forming property and resolution, and a color filter and a method for manufacturing the color filter using the colored curable composition, and a display device including the color filter.SOLUTION: The colored curable composition comprises (A) a dye, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent. Under the conditions that the content of the (A) dye with respect to the whole solid content is 25 mass% or more and that the content of the (D) solvent with respect to the total mass is 25 mass% or less, the colored curable composition shows a melt viscosity of 1.0×10Pa s or more in a temperature range of 80°C or higher and 250°C or lower.

Description

  The present invention relates to a colored curable composition, a color filter, a method for producing a color filter, and a display device.

In recent years, the enlargement of liquid crystal display devices (hereinafter referred to as LCDs) and organic EL display devices has progressed in applications such as display monitors for personal computers and televisions, and color reproducibility is emphasized in these display devices. Therefore, a color filter colorant is required to have higher image quality, that is, improvement in color purity, luminance, and contrast.
In response to the above requirements, an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and other components are further added to the pigment composition having a finer particle diameter of the pigment to obtain a photocurable colored curable composition. A color filter in which a colored pattern of red, green, blue, etc. is formed on a transparent substrate such as glass by using a photolithographic method has been developed and put into practical use.
On the other hand, in order to obtain higher luminance, a method of using a dye as a coloring material instead of a pigment has been proposed. Since the dye is present in the color filter film in a molecular state, a color filter having high color purity, light contrast, and high brightness can be obtained. As dyes, various structures such as dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, triarylmethane dyes, and the like have been proposed (for example, see Patent Documents 1 to 4). .

In order to prepare a color filter from a colored curable composition, a colored photo-resist film is usually formed on a substrate, and then the colored curable composition film is exposed to light using a photomask to form a photomask pattern. A corresponding latent image is formed. After the latent image is formed, a method (photolithographic method) is generally used in which only a pattern corresponding to a photomask is developed and left on a substrate, and this is post-baked to form a color filter.
The photoresist used can form a pattern with either a positive action or a negative action, but since a fine pattern is easily formed, a colored curable composition having a negative action is often used. In the colored curable composition used for the production of the color filter, since a part of the light of pattern exposure is absorbed, the film surface farthest from the substrate surface is usually the strongest when cured by exposure. Attenuates as it approaches the surface. Therefore, a pattern obtained by pattern exposure through a mask and development develops a large area on the surface farthest from the substrate surface, and the area tends to gradually become smaller as it approaches the substrate surface.

1 to 3 show cross-sectional shapes of three types of patterns that can be formed on a substrate. The cross section is a cross section in a plane perpendicular to the substrate surface.
FIG. 1 shows a pattern obtained by pattern-exposing and developing a colored curable composition film on a substrate, and has a reverse trapezoidal structure (reverse tapered shape) pattern 21 on the substrate 11.
When this pattern 21 is post-baked, the pattern 21 is softened and deformed by heat, and as shown in FIG. 2, a pattern 22 having a trapezoidal structure (forward taper shape) with the lower portion expanded is obtained. Such a forward-tapered pattern 22 is very important for preventing breakage (disconnection) of a transparent electrode (circuit) formed using ITO (indium oxide doped with Sn) after forming a color filter. This is one of the important performance requirements for the curable composition.
On the other hand, with regard to the adhesive composition used for the adhesive layer of the adhesive sheet for dicing and die bonding, the viscosity of the adhesive composition is increased, particularly for the purpose of suppressing thermoplasticity at high temperatures (for example, Patent Document 5). See also), a photosensitive resin layer formed on a temporary support, or thermoplastic for the purpose of improving the transferability of the transfer material (for example, the ability to follow the uneven shape of the transfer surface) and the characteristics after transfer. It is also known to increase the viscosity of a resin layer (see, for example, Patent Documents 6 to 8).

JP 2008-292970 A JP 2007-39478 A Japanese Patent Laid-Open No. 06-230210 JP 2010-256598 A JP 2012-167174 A JP 2005-17521 A JP 2007-187772 A JP 2010-72589 A

In a colored curable composition containing a dye as a coloring material, pattern deformation due to post-baking is too large, and a semicircular pattern 23 may be formed as shown in FIG.
Such a semicircular pattern 23 has a pattern width much wider than the width of the mask pattern, resulting in a decrease in resolution, and the pattern itself is semicircular, resulting in uneven color.
Such a phenomenon is more likely to occur as the concentration of the dye contained in the colored curable composition is higher in order to obtain a color filter having a high optical density. Since such a phenomenon hardly occurs in a colored curable composition containing a pigment as a color material, it is considered to be a problem peculiar to a colored curable composition containing a dye as a color material.
Increasing the dye concentration or the dye ratio in the colorant is preferable from the viewpoint of improving the luminance, but it becomes a semicircular pattern as described above, that is, the pattern forming property is limited. In some cases, the content of the dye contained in the colored curable composition must be lowered.

  Accordingly, an object of the present invention is to provide a colored curable composition having a high optical density pattern and having a pattern forming property with excellent resolution. Furthermore, the subject of this invention is providing the color filter which has a high brightness | luminance and has a coloring pattern whose cross-sectional shape perpendicular | vertical to the base-material surface is a desired forward taper shape, and its manufacturing method. Furthermore, this invention is providing the display apparatus provided with the said color filter.

Means for solving the above problems are as follows.
<1> (A) a dye, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, wherein the content of (A) dye relative to the total solid content is 25% by mass or more, In addition, when the content of the solvent (D) with respect to the total mass is in the range of 25% by mass or less, the melt viscosity at a temperature of 80 ° C. or more and 250 ° C. or less is 1.0 × 10 ³ Pa · s or more. Curable composition.
<2> The colored curable composition according to <1>, wherein the polymerizable compound (B) includes a compound having a molecular weight of 1,000 or more and 50,000 or less.
<3> The colored curable composition according to <1> or <2>, wherein the polymerizable compound (B) is a multi-branched compound having at least one polymerizable group selected from an acryloyl group and a methacryloyl group at the terminal. object.
<4> The colored curable composition according to <3>, wherein the multibranched compound includes a multibranched structure derived from an aliphatic polyhydric alcohol selected from glycerol, trimethylolpropane, and pentaerythritol.
<5> The multi-branched polymerizable compound is a compound having a multi-branched structure including an ether bond or an ester bond and having at least four polymerizable groups selected from an acryloyl group and a methacryloyl group at the terminal. > Or <4> The colored curable composition according to <4>.
<6> The colored curable composition according to <5>, wherein the multibranched polymerizable compound is a dendrimer or a hyperbranched polymer.

<7> The colored curable composition according to any one of <1> to <6>, further including a curing agent <8> and further including a resin compound having a molecular weight of 100,000 or more <1> to <1 The colored curable composition according to any one of 7>.
<9> A colored curable layer forming step in which the colored curable composition according to any one of <1> to <8> is provided on a substrate and dried to form a colored curable layer; A pattern exposure process for exposing the curable layer in a pattern, a development process for developing the colored curable layer exposed in the pattern to form a pattern image on the substrate, and heating the pattern image And a post-baking step for producing a color filter.
<10> A color filter produced by the method for producing a color filter according to <9>.
<11> A display device comprising the color filter according to <10>.

  According to the present invention, a colored curable composition having a high optical density pattern and having a pattern forming property excellent in resolution is provided. Furthermore, according to the present invention, a color filter having a high luminance and a colored pattern having a desired forward taper cross section perpendicular to the surface of the substrate and a method for producing the same are provided. Furthermore, according to this invention, a display apparatus provided with the said color filter is provided.

It is sectional drawing in the surface perpendicular | vertical to the base-material surface which shows the shape which concerns on the one aspect | mode of the pattern formed on a base material. It is sectional drawing in a surface perpendicular | vertical to the base-material surface which shows the shape which concerns on another aspect of the pattern formed on a base material. It is sectional drawing in the surface perpendicular | vertical to the base-material surface which shows the shape which concerns on another aspect of the pattern formed on a base material.

The colored curable composition according to the present invention contains (A) a dye, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent. In the temperature range of 80 ° C. or higher and 250 ° C. or lower (hereinafter referred to as “specific melting”). Also referred to as “viscosity”) is 1.0 × 10 ³ Pa · s or more.

The reason why a high optical density pattern can be obtained and a colored curable composition having excellent pattern forming properties and resolution can be obtained by the present invention is presumed as follows.
Since the content of the (A) dye with respect to the total solid content is 25% by mass or more in the colored curable composition according to the present invention, a pattern having a high optical density is obtained. Furthermore, the colored curable composition according to the present invention has a melt viscosity in a temperature range of 80 ° C. or higher and 250 ° C. or lower when the content of the solvent (D) relative to the total mass is in the range of 25% by mass or less. Since it is 1.0 × 10 ³ Pa · s or more, the cross-sectional shape of the colored pattern after post baking is a forward tapered shape. That is, a colored curable composition having excellent pattern forming properties and resolution can be obtained. Further, the color filter formed by forming a colored pattern by the photolithographic method using the colored curable composition according to the present invention and further performing post-baking has a high brightness and a cross section perpendicular to the substrate surface. The shape has a colored pattern with a forward taper shape.

In measuring the melt viscosity, it is necessary to remove the solvent (D) in order to make the content of the solvent (D) contained in the colored curable composition not more than 25% by mass. The removal of the solvent may be naturally dried as long as the thermal polymerization reaction does not occur, or may be actively dried. In order not to cause an error in the viscosity measurement, it is preferable that the solvent is removed by any one of the following methods 1) to 3) to adjust the content of the solvent (D).
1) The solvent is volatilized at normal temperature and pressure (so-called natural drying).
2) Put under reduced pressure at room temperature to evaporate the solvent.
3) Heat drying at 100 ° C. or lower (preferably 80 ° C. or lower).
The melt viscosity can be measured using a known apparatus and method. As the rheometer, AR-2000 manufactured by TA Instruments, Borin Gemini manufactured by Malvern, MCR manufactured by Anton Paar, etc. are preferably used.

In the process of producing a color filter using the colored curable composition according to the present invention, the colored curable composition is applied on a substrate by a known coating method to form a coating film, and then applied. As the film is dried and the content of the solvent (D) contained in the coating film decreases, the viscosity increases and finally becomes a solid colored curable layer. The content of the solvent (D) in this colored curable layer is in the range of 25% by mass or less. Therefore, the definition that the content of the solvent (D) with respect to the total mass is in the range of 25% by mass or less is equal to the content of the solvent (D) in the colored curable layer.
The colored curable layer on the substrate is patterned by a photolithographic method. That is, when the colored curable layer is subjected to pattern exposure and developed, the colored curable layer in the region exposed at the time of pattern exposure remains on the substrate, and a pattern image is formed.
The pattern image is then post-baked. The post-baking causes the pattern image to simultaneously decrease in viscosity due to temperature increase and increase in viscosity due to thermal polymerization. In a general photoresist, the temperature at which thermal polymerization starts is higher than the temperature at which temperature decrease starts. That is, the phenomenon that the pattern with reduced viscosity is deformed as the temperature rises occurs first, and after deformation into a shape determined by the viscosity and the resist / substrate / atmosphere interface tension, it is fixed in that shape by thermal polymerization later The Therefore, in order to regulate the pattern shape, process control for reducing the viscosity is important. It is possible to use a material that cures at a low temperature. However, in this case, the use is limited to a range that does not adversely affect the aging stability at room temperature, and the effect is limited.
In the colored curable composition according to the present invention, when the specific melt viscosity is 1.0 × 10 ³ Pa · s or more, the pattern image after post-baking suppresses the viscosity decrease due to temperature rise to a certain level or less. As a result, in the post-baked pattern, the cross-sectional shape perpendicular to the substrate surface becomes a forward taper shape, and good pattern formability is realized.
As mentioned above, post-baking causes the pattern image to increase in viscosity due to thermal polymerization, but it has the intrinsic property that there is a limit to the increase in viscosity due to thermal polymerization. It is not practical to do.

In addition, the cross section perpendicular | vertical to the base-material surface by the melt viscosity (namely, specific melt viscosity) in the temperature range of 80 to 250 degreeC of the colored curable layer formed with the colored curable composition which concerns on this invention The reason for determining whether or not the shape has a forward-tapered coloring pattern is that, as described above, before the deformation becomes excessive so that the pattern becomes semicircular due to the reduced viscosity. Further, it is considered that further deformation is suppressed by thermal polymerization.
Hereinafter, each component which comprises the colored curable composition of this invention is demonstrated in detail.
In the following, the colored curable composition of the present invention may be simply referred to as “colored composition of the present invention” or “colored composition”.
In addition, in this specification, the numerical range represented using "to" means the range which includes the numerical value described before and behind "to" as a lower limit and an upper limit.
In the present specification, the “alkyl group” is a general term for “linear, branched and cyclic” alkyl groups. Moreover, the substituent (atomic group) in this specification is used by the meaning including the thing which has an unsubstituted thing and a substituent further. That is, in the present specification, the “alkyl group” is used in a meaning including an unsubstituted alkyl group and a substituted alkyl group, and the same applies to other substituents.

(A) Dye There is no restriction | limiting in the structure of a dye, and a hue, A suitable thing can be selected from a commercially available dye and the dye described in well-known literature.
The structure of the dye includes pyrazole azo, anilino azo, anthraquinone, anthrapyridone, benzylidene, oxonol, triarylmethane, phthalocyanine, pyrrolotriazole, pyrazolotriazole azo, pyridone azo, cyanine, Preferable examples include phenothiazine dyes, pyrrolopyrazole azomethine dyes, squarylium dyes, quinophthalone dyes, benzopyran dyes, and indigo dyes.

Examples of commercially available dyes include the following.
C. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190 and 191;

  C. I. Solvent orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112 and 113;

  C. I. Solvent Red 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236, 38,239,240,241,242,243,244,245,247 and 248;

C. I. Solvent violet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60 and 61;
C. I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139 and 143;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35;
C. I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62 and 63;
C. I. Solvent Black 3, 5, 5: 2, 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49 and 50;

C. I. Acid Red 6, 11, 26, 52, 60, 80, 88, 111, 186, 215 and 289;
C. I. Acid Green 3, 25 and 27;
C. I. Acid Blue 22, 25, 40, 78, 92, 112, 113, 129, 167, 182, 230 and 249;
C. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72 and 78;
C. I. Acid Violet 34 and 43;

C. I. Basic Red 1, 2, 12, 13, 14, 16, 18: 1, 21, 22, 26, 27, 28, 29, 36, 39, 46, 54, 56, 58 and 78;
C. I. Basic green 1, 3, 4, 5, 8 and 10;
C. I. Basic Blue 1, 3, 4, 7, 8, 9, 11, 12, 15, 17, 18: 1, 22, 41, 42, 45, 53, 54, 54: 1, 55, 57, 60, 62, 66, 71, 75, 77, 92, 105, 113, 141, 147, 148 and 162;
C. I. Basic violet 1, 3, 18, 39 and 66;
C. I. Basic yellow 1, 11, 12, 13, 14, 15, 23, 24, 25, 28, 29, 30, 37, 40, 41, 45, 46, 51, 57, 62 and 67;

C. I. Direct Red 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149 and 224;
C. I. Direct green 26 and 28;
C. I. Direct blue 71, 78, 86, 87, 98, 106, 108, 192 and 201;
C. I. Direct violet 51;
C. I. Direct yellow 26, 27, 28, 33, 44, 50, 86 and 142;
C. I. Direct orange 26, 29, 34, 37 and 72;

C. I. Reactive Red 8, 22, 46 and 120;
C. I. Reactive Blue 1, 2, 7, and 19;
C. I. Reactive violet 2 and 4;
C. I. Reactive Yellow 1, 2, 4, 14, and 16;
C. I. Reactive Orange 1, 4, 7, 13, 16, and 20,

C. I. Disperse thread 4, 11, 50, 54, 55, 58, 65, 73, 90, 117, 118, 122, 126, 127, 128, 129, 141, 145, 146, 157, 177, 196, 210, 229, 354 and 356;
C. I. Disperse Blue 3, 7, 9, 10, 20, 24, 35, 55, 56, 58, 62, 63, 65, 79, 82, 85, 86, 87, 89, 91, 95, 102, 104, 106 118, 124, 125, 142, 143, 148, 162, 165, 166, 179, 181 and 183;
C. I. Disperse violet 1, 6, 12, 26, 27 and 28;
C. I. Disperse Yellow 3, 4, 5, 7, 8, 22, 23, 27, 33, 42, 50, 56, 60, 64, 74, 84, 88, 114, 119, 160, 164, 182, 184, 187 , 203, 227 and 221;
C. I. Disperse Orange 13, 29 and 30;
C. I. Disperse Green 7;
And so on.

  Specific examples of the dyes described in the publicly known literature include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10-123316, JP-A-11 -302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-29771 JP-A-8-146215, JP-A-11-343437, JP-A-8-62416, JP2002-14220, JP2002-14221, JP2002-14222, JP2002-2002. No. 14223, JP-A-8-302224, JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, JP-A-6-230210, JP-A-2008-292970. No. 3,324,279, No. 3279035, No. 11-256057, No. 2005-77953, No. 11-352686, No. 2000-19729, and No. 11 of Hei. -352686 and the like.

The dyes may be used alone or in combination of two or more. The content of the dye (the total amount when two or more types are combined) is 25% by mass or more based on the total solid content. When the content of the dye is less than 25% by mass, the film thickness when adjusted to the required hue is increased, which may affect the panel thickness when used as a display device.
The upper limit is not particularly limited, but if there are too many dyes, the content of the other (B) polymerizable compound and (D) photopolymerization initiator decreases, and the pattern formability by the lithography method decreases. Therefore, it is practical that it is 70 mass% or less.

The colored curable composition can contain a pigment for the purpose of color adjustment. Examples of preferable pigments include the following pigments.
C. I. Pigment red 177, 224, 242, 254, 255 and 264;
C. I. Pigment yellow 138, 139, 150, 180 and 185;
C. I. Pigment oranges 36, 38 and 71;
C. I. Pigment green 7, 36 and 58;
C. I. Pigment blue 15: 6;
C. I. Pigment Violet 23.
When using a pigment, the amount of pigment contained as a colorant is not particularly limited as long as the amount of dye is not less than the lower limit, but from the same viewpoint as the upper limit of the amount of dye, the sum of the dye and the pigment is colored. It is practical that it is 70 mass% or less with respect to the total solid of a curable composition.

(B) Polymerizable compound The polymerizable compound has at least one unsaturated double bond in the molecule, and (C) the composition combined with the photopolymerization initiator is imparted with curability and cured. The resulting composition forms a cured film that is insoluble in the developer described below.
In order to maintain the viscosity of the colored curable composition at a high temperature, the polymerizable compound is preferably a compound having a molecular weight of 1,000 to 50,000. A colored curable composition containing such a compound as a polymerizable compound is easy to handle at room temperature, and it is easy to adjust the specific melt viscosity to 1.0 × 10 ³ Pa · s or more. This is preferable.

The polymerizable compound is a multi-branched polymerizable compound having a number of branched structures in the molecule and having a polymerizable group at at least one of its ends, and has a specific melt viscosity of 1.0 × 10 ³ Pa · s. Since it is easy to adjust above, it is preferable.
The compound containing a large number of branched structures in the molecule is preferably a compound selected from the group consisting of dendrimers, hyperbranched monomers and hyperbranched polymers, and the multibranched polymerizable compound is at least one of its ends. For example, it is a compound having a polymerizable group such as an acryloyl group or a methacryloyl group or having a polymerizable group introduced therein. The colored curable composition containing such a multi-branched polymerizable compound is more easily adjusted to a specific melt viscosity of 1.0 × 10 ³ Pa · s or more, and can maintain a high melt viscosity even at a high temperature. Further, by post-baking, an image in which a close three-dimensional structure is formed in the coating film is formed.

A dendrimer has a chemical structure in which a chemical structure (hereinafter also referred to as a “core part”) constituting a core is regularly branched to the outside thereof, and has a spherical highly controlled chemical structure and Has a molecular weight. Hyperbranched monomers and hyperbranched polymers have a chemical structure similar to that of dendrimers, but not as highly regular branching structures or high molecular weight controls as in dendrimers, and the branches are formed according to a probability distribution, It has a broad molecular weight distribution.
Dendrimers, hyperbranched monomers and hyperbranched polymers have excellent solubility, low viscosity when in solution, and have a large number of functional groups (for example, carboxyl group, amino group, epoxy group, acryloyl group, methacryloyl group, etc.). doing.

Dendrimers, hyperbranched monomers and hyperbranched polymers are described in, for example, JP2012-173549A, WO2008-047620A, JP2012-83594A, and the like. These compounds have a core portion, a branched chain portion bonded to the core portion, and an end group bonded to the branched chain portion. The branched chain portion includes a highly branched structure in which a two-dimensional or three-dimensional branched partial structure is repeated two or more steps, and the terminal group has a large number of functional groups (for example, a hydroxy group, a carboxyl group, an amino group). , Epoxy group, acryloyl group, methacryloyl group, etc.).
The compound constituting the core is preferably synthesized using a branched polyhydric alcohol having three or more chain groups having a methylol group at the end, and further having a chain shape having a methylol group at the end. Those synthesized using a branched polyhydric alcohol having 4 or more groups are particularly preferred.
Specific preferred examples of the polyhydric alcohol include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. A structure in which branching is repeated by connecting a linking group having a branched structure (hereinafter also referred to as a branched chain portion) to the hydroxy group of the polyhydric alcohol in two or more stages. That is, a highly branched dendritic compound is obtained by binding a branched chain portion to each branched chain end of the branched structure closest to the hydroxy group of the polyhydric alcohol. Since glycerol, trimethylol, and pentaerythritol contain a hydroxyl group, it is easy to connect them with an ether bond using this. In this case, the hydroxyl group of glycerol, trimethylol, or pentaerythritol may be directly dehydrated and condensed, or a polyether may be formed by dehydration condensation with dialcohol. Direct dehydration condensation is preferred. In addition, an ester bond may be formed using a dicarboxylic acid. Many terminals of the compound having such a highly branched dendritic structure have the above-described functional group. When groups other than the above functional groups are included at the terminal, these groups include alkyl groups such as methyl groups.

The multi-branched polymerizable compound may be a compound in which a plurality of terminal functional groups of the multi-branched compound as described above, in particular, some or all of the terminal hydroxyl groups are substituted with hydrogen atoms with acryloyl groups and / or methacryloyl groups. preferable.
Preferred structures of the multibranched polymerizable compound include the following structures (1) to (3).

In structures (1) to (3), n = 1 to 10, R _a is hydrogen, an acryloyl group, or a methacryloyl group, and R _b is hydrogen or a methyl group. (1), (2), and (3) are linear dendrimers composed of a glycerol derivative, a trimethylolpropane derivative, and a pentaerythritol derivative, respectively.

  Specific examples of the hyperbranched polymerizable compound having a hyperbranched monomer and a hyperbranched polymer structure include, for example, a compound in which pentaerythritol is multimerized in a branched manner via a linking group, as represented by the following structure (4). Is included.

In said structure (4), l is 1-10 and m is 0-10. R _a has the same meaning as R _a in the structure (1), and R _c is either the structure (5) or the structure represented by the structure (6).

Structure (5), and in the structure (6), ^{n 1} is 1 to 10, l is 1 to 10, m is 0-10. R _a has the same meaning as R _a in the structure (1), and R _d represents a structure represented by the structure (5).

As a commercially available compound having the structure of structure (4), Star-501 (Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.
Further, as another preferred form of the multi-branched polymerizable compound used in the present invention, it has a multi-branched structure containing an ether bond or an ester bond, and at least four selected from an acryloyl group and a methacryloyl group at the terminal. It is a compound having a polymerizable group. Specific examples include compounds having the following structure.

In the structure (7), n is synonymous with n in the structure (1), _{R d} represents a hydrogen atom or a methyl group.

  V # 802 (Osaka Organic Chemical Co., Ltd.) etc. are mentioned as a commercial compound which has a structure of a structure (7).

Further, a multibranched polymerizable compound having an ethylenically unsaturated bond at a plurality of terminals of a dendrimer or hyperbranched polymer having a structure in which the core part has a plurality of repeating terminals and the terminals are branched in a dendritic manner is preferable.
The structure of the core part is preferably one represented by the following structure (8a) to structure (8d).

  In the structure (8a), the * part represents a binding site with the branched chain part. ]

  In the structure (8b), n represents an integer of 0 to 2, and the * part has the same meaning as described above. ]

  In the structure (8c), the * part has the same meaning as described above. ]

  In the structure (8d), the * part has the same meaning as described above. ]

  The branched chain portion is preferably a structural unit having three or more branched structures, and examples thereof include polyamide, polyester, polyether, polyurethane, and polyurea. Of these, polyester units and polyurethane units are preferred. The branched chain portion is preferably a polyhydroxycarboxylic acid unit, and more preferably a unit represented by the following structure (9) or structure (10).

  In the structure (5), the * part represents a binding site with the core part or branched chain unit.

In the structure (6), the * part represents a binding site with the core part or the branched chain unit.
The core portion and the branched chain portion may be bonded by a single bond, or may be bonded via a bonding site derived from an alkylene oxide such as ethylene oxide or propylene oxide. In the case of bonding through a bonding site derived from alkylene oxide, it is preferable that the oxygen terminal side of alkylene oxide is bonded to the * part of the branched chain.

The group bonded to the terminal of the multi-branched compound is preferably a group having an ethylenically unsaturated bond, and examples of such a group include a (meth) acryloyl group and a vinyloxy group. Of these, a (meth) acryloyl group is preferable.
Further, the alkali-developable multi-branched polymer described in International Publication No. 2008-047620 is more advantageous for pattern formation by alkali development because of its increased solubility before curing by radiation.
These compounds can be produced, for example, by a method described in International Publication No. 2008/047620 pamphlet or Japanese Patent Application Laid-Open No. 2008-174518.
The molecular weight or weight average molecular weight of these compounds is 1,300 or more and 50,000 or less, more preferably 1,300 or more and 30,000 or less, more preferably 1,300 or more and 15,000 or less. .
Specific examples include compounds represented by the following structural formulas (B-1) to (B-5).

  Also, under the trade names, Biscote # 1000 (Osaka Organic Chemical Co., Ltd., weight average molecular weight: 4000), STAR-501 (Osaka Organic Chemical Co., Ltd., weight average molecular weight: 11000), A-HBR-5 (Shin Nakamura Chemical) Manufactured by Co., Ltd., weight average molecular weight: 8000), New Frontier R-1150 (made by Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight: 11500), SN-2301 (manufactured by Sartomer, weight average molecular weight: 7500), Nissan Chemical Industries Products sold under the name of “Hypertech” manufactured by Co., Ltd., UR-101 (weight average molecular weight: 8000), Dendron product number 686581 (manufactured by SIGMA-ALDRICH, weight average molecular weight: 3803, etc.) may be used. it can.

  In addition to the above compounds, the polymerizable compound of the present invention may contain other monomers from the viewpoint of adjusting developability and the like. The polymerizable compound of such a monomer is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention.

  In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984) can also be used.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix Preferable examples include M-402, TO-1382, TO-2349 (above, Toagosei Co., Ltd.), KAYARAD D-330, D-320, D-310, DPHA (above, Nippon Kayaku Co., Ltd.). be able to.

  Moreover, as a polymeric compound, the component as described in Paragraph No. [0031]-[0061] of Unexamined-Japanese-Patent No. 2009-265630 can be mentioned from a viewpoint of low temperature curability. Especially, as said (C) polymeric compound, (11)-(25) and (M-1)-(M-8) shown below are preferable. In particular, a colored film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is excellent from the viewpoint of low-temperature curability.

  When the polymerizable compound is used for the colored curable composition, the content of the polymerizable compound in the total solid content of the polymerizable compound (the total content in the case of two or more types) is 10% by mass to 80% by mass. Preferably, 15 mass%-75 mass% is more preferable, and 20 mass%-60 mass% is especially preferable.

(C) Photopolymerization initiator The colored curable composition of the present invention contains at least one photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, JP-A No. 2001-233842, and the like. These oxime compounds are mentioned.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenylthio) -1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone and the like. However, it is not limited to these.
Moreover, in this invention, the compound represented by the following general formula (A) or general formula (B) is more preferable as an oxime compound from a viewpoint of a sensitivity, temporal stability, and the coloring at the time of post-heating.

In the general formula (A), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ is —R, —OR, —COR, —SR, —CONRR. 'Or -CN, R ² and R ³ are each independently. -R, -OR, -COR, -SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. To form a ring)

In general formula (A), when X ¹ , X ² , and X ³ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are alkyl. Examples of the alkyl group in the case of representing a group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, Examples thereof include trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > all represent a hydrogen atom.

In general formula (A), examples of the alkyl group represented by R and R ′ include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl , Perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R2 and R3 including R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—Br. This is a particularly preferred mode.
Among the photopolymerization initiators represented by the general formula (A), X ¹ , X ² and X ^{3 in} the general formula (A) are all hydrogen atoms, R ¹ is an alkyl group, particularly methyl. Those having a group, those in which R ² is an alkyl group, particularly a methyl group, and those in which R ³ is an alkyl group, particularly an ethyl group, are particularly suitable as a photopolymerization initiator.

In general formula (B), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl. Represents a group, a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group or -CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

R ¹⁰² represents an alkyl group, an aryl group, or a heterocyclic group, which may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.
R ^{105 to} R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R105 to R111 are electron-withdrawing substituents, i.e., a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group, or an arylcarbonyl group. Since an ionic composition is obtained, it is preferable.

    Specific examples of the compound represented by the general formula (B) are given below. However, it is not limited to these compounds.

The compound represented by the general formula (B) can be synthesized, for example, according to the synthesis method described in JP-A-2008-292970.

  The biimidazole compound is not limited in its structure as long as it is a dimer of an imidazole ring substituted with three aryl groups, and is particularly represented by the following general formula (C) or general formula (D). A compound having a structure is preferred.

In the general formula (C), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A represents each having 1 to 12 carbon atoms, A substituted or unsubstituted alkoxy group, or —COO—R ⁹ (wherein R ⁹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms), and n represents 1 to 3 And m is an integer of 1 to 3.

In the general formula (D), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, two or more of X ¹ , X ² and X ³ do not take a hydrogen atom at the same time.
Biimidazole represented by general formula (C) or general formula (D) can also be obtained as a commercial product.
As a particularly preferred biimidazole compound, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (commercially available products include B-CIM, (Hodogaya Chemical Co., Ltd.) ))), 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (HABI1311, DKSH Japan Ltd.) 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (Kurokin Kasei Co., Ltd.).

In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used for the colored curable composition.
A photoinitiator can be contained individually by 1 type or in combination of 2 or more types. The content (total content in the case of two or more) of the photopolymerization initiator in the total solid content of the colored curable composition is 1% by mass to 20% by mass from the viewpoint of obtaining the effect of the present invention more effectively. % Is preferable, 2% by mass to 19% by mass is more preferable, and 2% by mass to 15% by mass is particularly preferable.

(D) Solvent The solvent is basically not particularly limited as long as it satisfies the applicability in the case of a colored curable composition. Is preferably selected.

  Examples of esters as organic solvents include ethyl acetate, N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, cyclohexyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, pyruvin Ethyl acid, pill Phosphate propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

  Examples of ethers as organic solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl Examples include methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.

Examples of the ketones as the organic solvent include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons as the organic solvent include toluene and xylene.

It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethyl acetate, butyl acetate, cyclohexyl acetate, 3-methoxypropionic acid It is a mixed solution composed of two or more selected from methyl, 2-heptanone, cyclohexanone, methyl ethyl ketone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate.
The content of the organic solvent in the colored curable composition is preferably such that the total solid content concentration in the colored curable composition is 10% by mass to 80% by mass, and is 15% by mass to 60% by mass. Is more preferable.

(Curing agent)
By adding a curing agent to the colored curable composition, the specific melt viscosity can be easily adjusted to 1.0 × 10 ³ Pa · s or more.
The curing agent is a compound that can take a crosslinked structure, for example, (a) an epoxy resin, (b) an oxetane compound, (c) at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A substituted melamine compound, guanamine compound, glycoluril compound and urea compound, and (d) a phenol compound and a naphthol compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group And hydroxyanthracene compounds. Of these, epoxy resins (particularly polyfunctional epoxy resins) and oxetane compounds are preferred.

Here, as the epoxy resin, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic type epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylates, triglycidyl An isocyanurate etc. are mentioned.
Examples of commercially available epoxy compounds include EHPE3150, CEL2021P (Daicel Corporation), JER1031S, JER157S65, JER1007, JER152, JER154, JERYX6810 (Mitsubishi Chemical Corporation), Denacol EX411, Denacol EX810, 8 Denacol E82, Denacor EX841 (Nagase ChemteX Corporation), EPICLON EXA1514, EPICLON HP-7200, EPICLON HP7200L, EPICLON HP7200H, EPICLON N670, EPICLON N680 and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored curable composition contains an epoxy compound, an oxetane compound, or the like as a curing agent, the colored curable composition may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of such compounds include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. Of these, the polyvalent carboxylic acid may be contained in a binder, a monomer or a polymerizable compound used in the tourism composition.

  If the content of the curing agent is too large, the preservability and developability of the colored curable composition at room temperature may deteriorate, and depending on the type of the curing agent, the colored curable composition may be colored. The range of 2% by mass to 30% by mass is preferable with respect to the total solid content, and more preferably 5% by mass to 20% by mass.

(Resin compound having a molecular weight of 200,000 or more)
The colored curable composition has advantages such as easy adjustment of the specific melt viscosity and the ability to improve the hardness of the image after post-baking. , Also referred to as “polymer resin”). Here, the high molecular weight means that the weight average molecular weight is 200,000 or more. Furthermore, depending on the type of the polymer resin, various properties such as alkali developability and photocurability can be imparted to improve the properties of the colored curable composition.

  As the polymer resin, various known resins can be used. For example, Celum superpolymers A1000 and AU1000 (Advanced Soft Materials, Inc., molecular weight 600,000) and the like can be mentioned. Since many high molecular weight resins are solid at room temperature, the content is preferably about 5 to 20% of the total solids so as not to impair the resist performance.

(Other ingredients)
The colored curable composition contains an alkali-soluble binder, a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, a surfactant, an adhesion improver, a crosslinking agent, a development accelerator, and the like as necessary. May be. Below, these compounds are demonstrated.

(Alkali-soluble binder)
In the colored curable composition, a binder resin may be used for improving the film-forming property. As the binder resin, an alkali-soluble binder is preferably used from the viewpoint of pattern formation.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to those described above, the alkali-soluble binder includes, for example, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  Further, the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency and improve the melt viscosity, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. Also useful are polymers containing in the side chain. Examples of the polymer containing the above-mentioned polymerizable group include a dial NR series (Mitsubishi Rayon Co., Ltd.), PHOTOMER 6173 (COOH-containing POLYURETANE ACRYLIC OLIGOMER. DIAMOND SHAMROCK CO. LTD.), Biscote R-264, KS Resist 106 (all are Osaka Organic Chemical Industries, Ltd.), Cyclomer P series, Plaxel CF200 series (all are Daicel Chemical Industries, Ltd.), EBECRYL3800 (Daicel UC Corporation), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist. 106, cyclomer P series and the like are preferable.

  The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferably, the polymer of 5,000-50,000 is especially preferable.

  The alkali-soluble binder can be used alone or in combination of two or more. When the alkali-soluble binder is used, the content of the alkali-soluble binder in the total solid content of the colored curable composition (the total content in the case of two or more) is preferably 5% by mass to 60% by mass, and 8 More preferably, 50% by mass to 50% by mass is preferable, and 10% by mass to 45% by mass is particularly preferable.

(Polyfunctional thiol compound)
The colored curable composition may contain a polyfunctional thiol compound. By including a polyfunctional thiol compound, the exposure sensitivity of the colored curable composition can be increased and the crosslinking density can be improved.
“Polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6, and particularly preferably 2 to 4. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass relative to the total solid content of the composition, or less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.

  Specific examples of the polyfunctional thiol compound include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. As a suitable polyfunctional thiol compound And the like. A compound containing secondary SH is particularly preferable, and it is preferable to have a triazine skeleton from the viewpoint of liquid stability. Specific examples include Karenz MT series (Showa Denko Co., Ltd.).

  It is preferable that content of a polyfunctional thiol compound is 0.01 mass%-20 mass% with respect to the total solid in a colored curable composition, and it is 0.1 mass%-10 mass%. Further preferred. When the content of the polyfunctional thiol compound is within this range, the sensitivity of the colored curable composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. A colored curable composition can be provided.

(Sensitizer)
A sensitizer can also be added to the colored curable composition. Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

(Chain transfer agent)
A chain transfer agent can also be added to the colored curable composition. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. And mercapto compounds having a heterocyclic ring such as benzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together. The addition amount of the chain transfer agent is preferably in the range of 0.01% by mass to 15% by mass with respect to the total solid content of the colored curable composition, from the viewpoint of reducing sensitivity variation, More preferably, 10% by mass to 10% by mass is preferable, and 0.5% by mass to 5% by mass is particularly preferable.

(Polymerization inhibitor)
The colored curable composition may contain a polymerization inhibitor. The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored curable composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used. Among these, P-methoxyphenol is preferably mentioned as a polymerization inhibitor.
The content of the polymerization inhibitor in the colored curable composition is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass with respect to the total mass of the polymerizable compound, and 0 0.001% by mass to 1% by mass is particularly preferable.

(Surfactant)
The colored curable composition may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, NOVEC FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105,7000,950,7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.

  Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula (W), and has a polystyrene-equivalent weight average molecular weight (MW) measured by gel permeation chromatography using tetrahydrofuran as a solvent. A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

In formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to ⁴ carbon atoms, and R ⁴ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% by mass to 80% by mass. Q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less. )
L is preferably a branched alkylene group represented by the following formula (W-2).

R ⁵ in formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass. The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used alone or in combination of two or more.

  0.01-2.0 mass% is preferable in the total solid of a colored curable composition, and, as for the addition amount of surfactant in a colored curable composition, 0.02-1.0 mass% is especially preferable. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The colored curable composition may contain an adhesion improving agent.
The adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.

As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, Γ-glycidoxypropyltrialkoxysilane and Γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored curable composition is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored curable composition. preferable.

(Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored curable composition layer is exposed and to further improve the developability of the colored curable composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the colored curable composition may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.

  The colored curable composition may contain a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph [0081] of the publication.

(Method for preparing colored curable composition)
The colored curable composition is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a colored curable composition.
The colored curable composition prepared as described above can be subjected to use preferably after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.

Since the colored curable composition of the present invention can form a colored cured film having excellent brightness and contrast, it can be used for forming colored pixels such as color filters used in liquid crystal display devices, as well as printing inks and inkjet inks. And can be suitably used as a production application for paints and the like.

(Color filter and manufacturing method thereof)
The color filter of the present invention includes a substrate and a colored pixel formed of a colored cured film formed on the substrate by the colored curable composition of the present invention. The colored region on the substrate is composed of colored hardened layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.
The method for producing a color filter of the present invention includes a colored curable layer forming step (a) for forming a layer of the above-described colored curable composition on a support, and the coloring formed in the step (a). A pattern exposure step (b) for exposing the curable layer in a pattern and curing the colored curable layer in a pattern, and a colored curable layer cured in a pattern in the step (b) A development step (c) for developing and removing the uncured portion to form a colored cured pattern, and a heating step (d) for heating the colored cured pattern are included.

It is also possible to provide a step (post-exposure) for irradiating the colored pattern with ultraviolet rays between the developing step (c) and the heating step (d).
As a light source used for the said pattern exposure process (b), g line | wire, h line | wire, i line | wire, and various laser beams are preferable, and i line | wire is especially preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .
In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable.
There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. In addition, devices other than those described above are also preferably used.

The developer used in the development step (c) is a combination of various organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion of the colored curable composition layer and does not dissolve the cured portion. Can do. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like. Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

The colored curable composition of the present invention is not only a color filter that forms a colored layer on a conventionally used support, but also a color-filter on array (COA) that is effective from the viewpoint of improving luminance and yield. ) Method color filter.
The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in luminance and contrast because the colored curable composition of the present invention is used.

The display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.
When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device or the like, it is possible to display an image with high luminance and excellent spectral characteristics and contrast.

A liquid crystal display device using the color filter of the present invention will be described. For the definition of organic EL display devices and liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA system.
When the color filter of the present invention is used in a liquid crystal display device, it has a good display performance not only when combined with a conventionally known three-wavelength tube of a cold cathode tube, but also in a liquid crystal display device using an LED light source as a backlight. A liquid crystal display device is obtained.

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

Example 1
-Preparation of colored curable composition 1-
The following components were mixed and dissolved to prepare a colored curable composition 1.
Organic solvent 1: Propylene glycol monomethyl ether acetate 184 parts Alkali-soluble binder 1: benzyl methacrylate / methacrylic acid (60/40 [molar ratio]) copolymer (weight average molecular weight: 15,000, 50% propylene glycol monomethyl ether Solution) 72 parts Polymerizable compound: Osaka Organic Chemical Industry Co., Ltd. SIRIUS-501 (50% ethyl acetate solution of Star-501 [molecular weight: 11,000]) 60 parts Photopolymerization initiator: 1- (O— Acetyloxime) -1- [9-Ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone 4 parts Fluorosurfactant: DIC Corporation Megafac F-554 (2% propylene glycol monomethyl ether) Acetate solution) 5 parts, Dye solution A: Acid 300 (10% propylene glycol monomethyl ether solution)

-Formation of colored curable composition layer (colored curable layer) 1-
The colored curable composition 1 prepared above was applied onto a 10 cm square glass (# 1737; Corning Japan Co., Ltd.) substrate by spin coating, and then pre-baked on a hot plate at 80 ° C. for 2 minutes to volatilize. The components were volatilized to form a colored curable layer 1.
Using a proxy exposure photomask having a line pattern with a pattern width of 50 μm, the colored curable layer 1 was irradiated with i-line (wavelength 365 nm) to form a latent image. An ultra high pressure mercury lamp was used as the i-line light source with a proxy gap of 200 μm at the time of exposure, and the parallel light was irradiated before irradiation. The amount of irradiation light was 40 mJ / cm ² .
Next, the colored curable layer 1 on which this latent image was formed was developed at 26 ° C. using an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%), and 90% of the coating area was developed. Was defined as the development time of the colored curable composition.
After the development time is determined, the colored layer 1 having the latent image formed as described above is developed (development time + 20 seconds), then rinsed with running water for 20 seconds, and then dried with an air gun. A fine line pattern image 1 was obtained. The obtained fine line pattern image 1 was post-baked at 230 ° C. for 20 minutes to obtain a colored cured film 1 having a thickness of 2 μm.

(Evaluation)
<Measurement of melt viscosity of colored curable layer>
The melt viscosity of the colored curable layer 1 was measured as follows.
The colored curable composition was spread thinly, and the solvent was evaporated and dried at room temperature. Thereafter, AR-2000 manufactured by TA Instruments was used, the dry sample was sandwiched between 25φ parallel plates, the sample gap was adjusted to 1500 μm, and the melt viscosity was measured. The temperature was adjusted in an electric furnace chamber and in an air atmosphere.
The measurement frequency was 1 Hz (oscillation control), and the distortion was 0.5%.
<Measurement of line width change>
Fine line pattern width (hereinafter also referred to as “line width 1”) of fine line pattern image 1 obtained by developing, rinsing and drying with an air gun as described above, and developing as described above, Rinse, dry with an air gun, and measure the fine line pattern width (hereinafter also referred to as “line width 2”) of the colored cured film 1 obtained by post-baking. A difference amount was calculated, and this difference amount was defined as a line width change amount.
It is considered that as the line width change amount is small, excessive deformation of the pattern accompanying post-baking is small, and is preferably +1 μm or less.
<Pattern formability>
The shape observed when the fine line after post-baking was cut on a glass substrate with a plane perpendicular to the surface and perpendicular to the longitudinal direction of the fine line was displayed as “forward taper” or “semicircular”.

(Example 2)
In Example 1, the colored curable composition 2 was prepared by changing the organic solvent 1 and the amount thereof, and the polymerizable compound and the amount thereof to the following compounds and amounts. About this colored curable composition 2, it carried out similarly to Example 1, and measured the melt viscosity and line | wire width change amount of the colored curable layer.
Organic solvent 1: 214 parts of propylene glycol monomethyl ether acetate Polymerizable compound: Dendrimer having terminal acryloyl group (Osaka Organic Chemical Co., Ltd. V # 1000) 30 parts

(Example 3)
In Example 1, the colored curable composition 3 was prepared by changing the organic solvent 1 and the amount thereof, and the polymerizable compound and the amount thereof to the following compounds and amounts. About this colored curable composition 3, it carried out similarly to Example 1, and measured the melt viscosity and line | wire width change amount of the colored curable layer.
Organic solvent 1: 214 parts of propylene glycol monomethyl ether acetate Polymerizable compound: Dendrimer having a terminal acryloyl group (Shin Nakamura Chemical Co., Ltd. A-HBR-5, molecular weight: 8,000) 30 parts

Example 4
In Example 1, the colored curable composition 4 was prepared by changing the organic solvent 1 and the amount thereof, and the polymerizable compound and the amount thereof to the following compounds and amounts. About this colored curable composition 4, it carried out similarly to Example 1, and measured the melt viscosity and the line | wire width change amount of the colored curable layer.
Organic solvent 1: Propylene glycol monomethyl ether acetate 214 parts Polymerizable compound: Daiichi Kogyo Seiyaku Co., Ltd. New Frontier R-1150, molecular weight: 11,500 30 parts

(Example 5)
-Preparation of colored curable composition 5-
The following components were mixed and dissolved to prepare a colored curable composition 5.
Organic solvent 1: Propylene glycol monomethyl ether acetate 190 parts Alkali-soluble binder 2: Adduct of cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid (30/30/40 [molar ratio] (45% propylene glycol monomethyl ether solution) 60 parts Polymerizable compound: Osaka Organic Chemical Industry Co., Ltd. SIRIUS-501 60 parts Photopolymerization initiator: 1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H- Carbazol-3-yl] propanone 4 parts Fluorosurfactant: DIC Corporation MegaFuck F-554 (2% propylene glycol monomethyl ether acetate solution) 5 parts Curing agent: Daicel Corporation EHPE-3150 6 parts Dye solution A: Acid For de 289 (10% of propylene glycol monomethyl ether solution) 300 parts colored curable composition was prepared 5, in the same manner as in Example 1, the melt viscosity was measured in the colored curable layer and the line width variation.

(Example 6)
-Preparation of colored curable composition 6-
The following components were mixed and dissolved to prepare a colored curable composition 6.
Organic solvent 1: propylene glycol monomethyl ether acetate 194 parts Alkali soluble binder 1: benzyl methacrylate / methacrylic acid (60/40 [molar ratio]) copolymer (weight average molecular weight: 15,000, 50% propylene glycol monomethyl ether Solution) 52 parts High molecular weight compound: Advanced Soft Materials Co., Ltd. A1000 (weight average molecular weight 600,000) 10 parts Polymerizable compound: Osaka Organic Chemical Industry Co., Ltd. SIRIUS-501 60 parts Photopolymerization initiator : 1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone Fluorosurfactant: Megafac F-554 (manufactured by DIC) 2% propylene glycol monomethyl ether acetate Solution) 5 parts / dye solution A: Acid Red 289 (10% propylene glycol monomethyl ether solution) 300 parts For the prepared colored curable composition 5, as in Example 1, the melt viscosity of the colored curable layer And the amount of change in line width was measured.

(Examples 7 to 12)
In each colored curable composition of Examples 1-6, dye solution A was changed to the following dye solution B, and colored curable compositions 7-12 were prepared. About the prepared colored curable compositions 7-12, it carried out similarly to Example 1, and measured the melt viscosity and the line | wire width change amount of the colored curable layer.
-Dye solution B: Basic blue 7 (10% propylene glycol monomethyl ether solution) 300 parts

(Examples 13 to 18)
In each colored curable composition of Examples 1 to 6, the dye solution A was changed to the following dye solution C to prepare colored curable compositions 13 to 18. About the prepared colored curable compositions 13-18, it carried out similarly to Example 1, and measured the melt viscosity and the line | wire width change amount of the colored curable layer.
Dye solution C: Basic green 1 (10% propylene glycol monomethyl ether solution) 300 parts

(Comparative Example 1)
-Preparation of colored curable composition 19-
The following components were mixed and dissolved to prepare a colored curable composition 19.
Organic solvent 1: Propylene glycol monomethyl ether acetate 214 parts Alkali soluble binder 1: benzyl methacrylate / methacrylic acid (60/40 [molar ratio]) copolymer (weight average molecular weight: 65,000, 50% propylene glycol monomethyl ether Solution) 72 parts Polymerizable compound: Nippon Kayaku Co., Ltd., KAYARAD DPHA 30 parts Photopolymerization initiator: 1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H- Carbazol-3-yl] propanone 4 parts Fluorosurfactant: DIC's MegaFuck F-554 (2% propylene glycol monomethyl ether acetate solution) 5 parts Dye solution A: Acid Red 289 (10% propylene glycol monomethyl 300 parts ether solution) About the prepared colored curable composition 19, it carried out similarly to Example 1, and measured the melt viscosity and the line | wire width change amount of the colored curable layer.

(Evaluation results)
Table 1 shows the measurement results of the melt viscosity and the line width change amount of each of the colored curable layers of the above colored curable compositions 1 to 19.

In Table 1 above, “AR” is an abbreviation for Acid Red, “BB” is Basic Blue, and “BG” is Basic Green.
From the results in Table 1, the colored curable compositions 1 to 18 according to the present invention have a small amount of change in line width due to post-baking even at a high dye concentration, and have excellent suitability for the production of color filters with high resolution. You can see that
On the other hand, it can be seen that the colored curable composition 19 according to the comparative example has a large amount of change in line width and does not have the suitability for producing a color filter with high resolution.

(Example 19)
A color filter and a liquid crystal display device provided with this color filter were produced and evaluated as follows.
-Production of black colored photosensitive resin composition K-
A pigment dispersion composition having the following composition was prepared, and a black pigment dispersion was prepared by performing a dispersion treatment in the same manner as in the preparation of the red pigment dispersion.
(Black pigment dispersion composition)
Carbon black (trade name: Nippon 35, manufactured by Degussa Japan Co., Ltd.) 13.1 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000) 7 parts ・ 79.1 parts of propylene glycol monomethyl ether acetate ・ Dispersant (the following compound) 0.65 parts

Using the obtained black pigment dispersion composition, a black photosensitive resin composition K having the following composition was prepared.
(Black photosensitive resin composition K composition)
-Black pigment dispersion 25 parts-Propylene glycol monomethyl ether acetate 8.5 parts-Methyl ethyl ketone 53 parts-Binder (Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio, molecular weight 38,000) 27 parts and a mixture of propylene glycol monomethyl ether acetate 73 parts) 9.1 parts hydroquinone monomethyl ether 0.002 parts polymerizable compound (Nippon Kayaku Co., Ltd. KAYARAD DPHA) 12 parts photopolymerization initiator (2, 4-bis (trichloroethyl) -6- [4 '-(N, Nbisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine) 0.16 parts. Methyl ethyl ketone as a surfactant (the following compound) 0.042 parts of 30% solution

-Fabrication of color filter-
-Production of black matrix-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. Next, the substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.
On the non-alkali glass substrate treated as described above, the above-described black colored photosensitivity was obtained with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Resin composition K was applied.
Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm black photosensitive resin layer was obtained.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and the above The distance between the black photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .

  Next, after spraying pure water with a shower nozzle and uniformly moistening the surface of the black photosensitive resin layer, the developer (containing KOH, nonionic surfactant, trade name: CDK-1, Fuji Film Electronics Material) The product was shower-developed with a flat nozzle pressure of 0.04 MPa at 23 ° C. for 80 seconds to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Finally, heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix on the alkali-free glass substrate.

-RGB pixel formation-
Prepared on the alkali-free glass substrate on which the black matrix was formed, the red colored curable composition 1 prepared in Example 1, the green colored curable composition 13 prepared in Example 13, and the Example 7. Apply the blue colored curable composition 7 in this order in the same procedure as in the case of black matrix formation, drying, pattern exposure (however, the exposure mask is changed for each color pixel), shower of pure water, shower development, Residue removal by jetting ultrapure water and heat treatment were performed to form RGB three-color pixels to obtain a color filter. The color portion film thickness of each color of RGB of this color filter was 1.6 μm.

-Formation of ITO electrode-
The obtained color filter was put in a sputtering apparatus, and 1300 mm thick ITO was vacuum-deposited at 100 ° C. on the surface having the black matrix and RGB three-color pixels, and then annealed at 240 ° C. for 90 minutes. ITO was crystallized to form an ITO transparent electrode.
-Spacer formation-
A spacer was formed on the ITO transparent electrode prepared above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

-Formation of liquid crystal alignment control protrusions-
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution. However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, the 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying the substrate at 33 ° C. for 30 seconds with a shower type developing device. In this way, the insoluble part (exposed part) of the photosensitive resin layer is developed and removed, thereby obtaining a liquid crystal display device substrate in which a liquid crystal alignment control protrusion having a pattern of a desired shape is formed on the color filter side substrate. It was.

Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display device substrate.

(Coating liquid formulation for positive photosensitive resin layer)
・ Positive resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.0 parts ・ Methyl ethyl ketone 46.5 parts ・ Surfactant (Megafac F-780F manufactured by DIC Corporation) 0.05 Part

-Production of liquid crystal display device-
An alignment film made of polyimide was further provided on the liquid crystal display device substrate obtained above. After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, an LED light source (a liquid crystal television manufactured by SONY, a backlight light source of KDL-40ZX1) was disposed as a light source on the side of the liquid crystal cell provided with the polarizing plate, thereby obtaining a liquid crystal display (LCD).
The liquid crystal display device produced as described above has high contrast and brightness, and is suitable as a display device.

  In this example, the MVA mode liquid crystal display device was evaluated. However, even when the color effect composition of the present invention is used for a liquid crystal display device of another mode or a color filter of an organic EL display, the same applies. Good image quality can be obtained.

11 substrate 21, 22, 23 pattern

Claims (11)

It contains (A) a dye, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, and the content of (A) the dye based on the total solid content is 25% by mass or more and the total mass ( D) A colored curable composition having a melt viscosity of 1.0 × 10 ³ Pa · s or more at a temperature of 80 ° C. or more and 250 ° C. or less when the content of the solvent is in the range of 25% by mass or less.   The colored curable composition according to claim 1, wherein the polymerizable compound (B) includes a compound having an average molecular weight of 1,000 or more and 50,000 or less.   The colored curable composition according to claim 1 or 2, wherein the polymerizable compound (B) is a multi-branched polymerizable compound having at least one polymerizable group selected from an acryloyl group and a methacryloyl group at a terminal. object.   The colored curable composition according to claim 3, wherein the hyperbranched polymerizable compound includes a hyperbranched structure derived from an aliphatic polyhydric alcohol selected from glycerol, trimethylolpropane, and pentaerythritol.   The multi-branched polymerizable compound is a compound having a multi-branched structure including an ether bond or an ester bond and having at least four polymerizable groups selected from an acryloyl group and a methacryloyl group at the terminal. The colored curable composition according to claim 4.   The colored curable composition according to claim 5, wherein the multibranched polymerizable compound is a dendrimer or a hyperbranched polymer.   Furthermore, the colored curable composition as described in any one of Claims 1-6 containing a hardening | curing agent.   The colored curable composition according to any one of claims 1 to 7, further comprising a resin compound having a molecular weight of 100,000 or more. A colored curable layer forming step of providing the colored curable composition according to any one of claims 1 to 8 on a substrate and drying to form a colored curable layer;
A pattern exposure step of exposing the colored curable layer in a pattern; and
Developing the colored curable layer exposed in a pattern, and forming a pattern image on the substrate; and
A post-baking step of heating the patterned image;
A method for producing a color filter comprising:   A color filter produced by the method for producing a color filter according to claim 9. A display device comprising the color filter according to claim 10.