TW201310170A - Color filter, liquid crystal display device, and method for producing color filter - Google Patents

Abstract

A color filter having high reliability and cured at a lower temperature is provided, and a liquid crystal display device using the color filter is provided. The color filter 10 is produced using a coloring pattern 6, a protective film 8 and a spacer 9. The coloring pattern 6 contains any of diketopyrrolopyrrole pigments, halogenated zinc phthalocyanine pigments, triarylmethane dyes and azoic dyes. The protective film 8 is formed from a first radiation sensitive resin composition containing siloxane polymer. The spacer 9 is formed from a second radiation sensitive resin composition containing an alkali soluble resin and at least one compound represented by formula (1) or (2). The liquid crystal display device 1 is constructed by using the color filter 10.

Description

Color filter, liquid crystal display element, and method of manufacturing color filter

The present invention relates to a color filter, a liquid crystal display element, and a method of manufacturing a color filter.

The liquid crystal display element is configured by sandwiching a liquid crystal, for example, on a pair of substrates such as a glass substrate.

The liquid crystal display element may have a liquid crystal alignment alignment film on the surface of the substrate sandwiching the liquid crystal. In the prior art, a spherical or rod-shaped spacer formed of glass, alumina, or resin is placed between the substrates of the liquid crystal display element by dispersion or the like, and the thickness of the liquid crystal is maintained at a predetermined value of about 1 μm to 10 μm. The liquid crystal display element functions as a fine shutter for light emitted from a light source such as a backlight or external light. Further, the liquid crystal display element transmits light by partially transmitting or blocking light, and is excellent in characteristics such as thinness and lightness.

The liquid crystal display element was originally developed as a display element of a calculator or a clock centered on a character display or the like. Thereafter, since dot matrix display in a large screen can be performed, the use is expanded to a display element of a notebook computer or the like.

Further, the liquid crystal display element overcomes the problems of high definition, colorization, and viewing angle expansion, and further expands the use to display applications of PCs (Personal Computers). Recently, a wide viewing angle, high-speed response of liquid crystals, and improvement in display quality have been realized, and it has been used as a display element for a large-sized thin television.

One of the techniques for realizing the development of such a liquid crystal display element is the colorization technique which realizes color display as described above.

Liquid crystal display elements generally cannot develop color by themselves, making it difficult to perform color display. Therefore, a technique using a color filter has been developed, and color display can be realized.

Further, the coloring technique using a color filter can also be used for color display of an organic electroluminescence (EL) element or an electronic paper using a white light-emitting layer. In addition, when a color filter is used, a solid-state imaging device such as a charge coupled device (CCD) image sensor or a complementary metal oxide semiconductor (CMOS) image sensor can be used. Color photography.

The color filter includes a transparent substrate such as glass and a minute colored pattern of red, green, and blue. The coloring patterns are arranged on a transparent substrate in a regular shape such as a lattice shape.

As a method of manufacturing a color filter, for example, the method described below is known. A colored composition of an appropriate inductive illumination line is applied to a transparent substrate or a transparent substrate on which a light-shielding layer having a desired pattern is formed. As the coloring composition, a pigment dispersion type coloring radiation-sensitive linear composition containing a pigment such as red, green, or blue in the coloring agent can be used. Next, after drying the coating film, the dried coating film is irradiated with radiation (hereinafter referred to as "exposure") through a mask, and development processing is performed. Then, the curing at a high temperature of, for example, 230 ° C or higher is performed at a high temperature, and a fixed color pattern is obtained by these operations (for example, refer to Patent Document 1 or Patent Document 2).

In recent years, there has been an increasing demand for high image quality and high luminance of display elements, and there is a strong demand for color filters to contribute to such performance improvement. In order to achieve high contrast of the display element or high definition of the solid-state imaging element, it is effective to use a dye as a coloring agent (for example, refer to Patent Document 3 to Patent Document 5). Among color filters, a technique using a dye as a colorant has also been attracting attention. In the prior coloring composition containing a dye, a hardening method in which a polyfunctional acrylate, an alkoxymethyl melamine resin, or the like is combined with a polymerization initiator is mainly used.

However, in the colored pattern formed using the colored composition containing the dye, there is a problem that reliability, particularly heat resistance, is inferior to the coloring pattern using the colored composition containing the pigment. Therefore, in the hardening step for forming the colored pattern, heating at a lower temperature is required.

Further, in the production of the color filter, after the colored pattern is formed, a protective film can be formed on the colored pattern before the formation of ITO (Indium Tin Oxide) which is an electrode. This protective film is formed to protect the colored pattern and to realize ITO having excellent characteristics. Here, in order to form a protective film, a hardening step is usually necessary. The heating in the hardening step becomes a deterioration of the colored pattern formed by using the colored composition containing the dye in the lower layer of the protective film. Therefore, the low temperature of the hardening step for forming the protective film is required.

In addition, in the color filter, a technique of providing a columnar spacer has recently been developed (for example, refer to Patent Document 6). The columnar spacer which is erected on the color filter can be formed, for example, by using a photosensitive resin or the like which can maintain a predetermined interval between the pair of substrates sandwiching the liquid crystal. Columnar room The spacer can control the thickness of the liquid crystal sandwiched between the substrates with high precision. Therefore, in order to replace the spherical or rod-shaped spacer disposed between the substrates in the prior art, the uniformity of the characteristics in the plane of the liquid crystal display element can be improved.

When a columnar spacer is provided on the color filter, the spacer is formed on the ITO as a transparent electrode of the color filter. That is, after a colored pattern is formed on the substrate, an ITO film is formed thereon, and a columnar spacer is formed on the ITO by, for example, photolithography. At this time, in order to form the spacer, a hardening step is usually necessary. The heating in the hardening step of the spacer causes the colored pattern of the color filter in the lower layer to deteriorate. In particular, when a colored pattern is formed from a colored composition containing a dye, the deterioration becomes a big problem. Therefore, for the hardening step of the column spacer, low temperature is strongly required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2007-316179 (Patent Document 5) Japanese Patent Laid-Open No. Hei 11-344700

As described above, there is a problem that heat resistance is poor in a color filter formed using a previous coloring composition containing a dye.

Therefore, it is required to manufacture a color filter including a colored pattern, a protective film, and a columnar spacer by a low temperature hardening step. under these circumstances, In the conventional color filter, there is a problem that sufficient performance cannot be achieved in terms of reliability such as development resistance or voltage holding ratio when applied to a liquid crystal display element, which poses a problem. The cause of such a problem is that the coloring composition of the low-temperature curing or the protective film or the spacer has insufficient curing reactivity. Therefore, development of a highly reliable color filter which can be formed by low temperature hardening using a colored composition which can contain a dye is required.

In the production of the conventional color filter, the formation of the colored pattern, the formation of the protective film, and the formation of the columnar spacer (hereinafter, simply referred to as a spacer unless otherwise specified) are performed by a high-temperature heating step exceeding 200 °C. . The film formation of the alignment film for liquid crystal alignment is also carried out by a high-temperature heating step exceeding 200 °C. However, recently, from the viewpoint of energy saving, the temperature reduction of the heating step in such a manufacturing step is gradually pursued. That is, it is gradually sought to achieve energy saving by lowering the manufacturing steps including the hardening step.

In view of the above circumstances, there is a strong demand for a color filter having a colored composition which can form a colored pattern by low-temperature curing, a protective film which can be formed by low-temperature curing, and a spacer which can be formed by low-temperature hardening, and which is resistant. It is excellent in developability, heat resistance, solvent resistance, voltage holding ratio, and the like, and can realize a color filter having high image quality and high luminance of a liquid crystal display element.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a color filter comprising: a colored pattern formed by low temperature hardening using a colored composition which can contain a dye, and formed by low temperature hardening. Protective film, and through A spacer formed by low temperature hardening.

Further, another object of the present invention is to provide a liquid crystal display element comprising a color filter comprising: a colored pattern formed by low temperature hardening using a coloring composition which can contain a dye, and hardening by low temperature. The protective film is formed, and a spacer formed by low temperature hardening.

A first aspect of the invention relates to a color filter comprising a colored pattern and a protective film.

The coloring pattern contains at least one coloring agent selected from the group consisting of diketopyrrolopyrrole pigments, zinc halide phthalocyanine pigments, triarylmethane dyes, and azo dyes;

The protective film is formed of a first radiation sensitive resin composition containing the following components: [A] a siloxane polymer, [B] a radical polymerization initiator, and [C] an organic solvent.

In a first aspect of the invention, it is preferable that the spacer further comprises a spacer which is formed of a second radiation-sensitive resin composition containing the following components: [α] alkali-soluble resin, [β] having ethylenic unsaturation The polymerizable compound of the bond, the [γ] radiation-sensitive polymerization initiator, and [δ] are selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). At least one compound;

(In the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ¹ to R ⁶ is an electron withdrawing group, and R ¹ to R ⁶ are At least one of the amine groups is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted by an alkyl group having 1 to 6 carbon atoms; in the formula (2), R ⁷ to R ¹⁶ are each independently hydrogen. An atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; wherein the above methylene group and alkylene group All or a part of the hydrogen atom may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

In the first aspect of the invention, it is preferable that the colored pattern is formed of a coloring composition containing the following components: [I] an alkali-soluble resin, [II] a polymerizable compound having an ethylenically unsaturated bond, and [III] radiation-sensitive. a polymerization initiator, and the colorant described in [IV].

In the first aspect of the invention, the coloring composition further contains [V] a compound selected from the above formula (1), a compound represented by the above formula (2), a tertiary amine compound, an amine salt, and an anthracene. At least one compound of the group consisting of a salt, a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring.

In the first aspect of the invention, it is preferred that the [I] alkali-soluble resin contained in the coloring composition is a copolymer comprising the following structural unit: (I-1) is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. At least one structural unit formed in the group formed, and (I-2) a structural unit formed of an epoxy group-containing unsaturated compound.

In the first aspect of the invention, it is preferable that the [A] siloxane polymer contained in the first radiation sensitive resin composition is a hydrolysis condensate of a hydrolyzable decane compound, and the hydrolyzable decane compound comprises: (a1) a hydrolyzable decane compound represented by the following formula (A-1) and (a2) a hydrolyzable decane compound represented by the following formula (A-2);

(In the formula (A-1), R ¹ is an alkyl group having 1 to 6 carbon atoms; R ² is an organic group containing a radical reactive functional group; p is an integer of 1 to 3; wherein, when R ¹ When R ^{2 is} plural, a plurality of R ¹ and R ² are each independently; in the formula (A-2), R ³ is an alkyl group having 1 to 6 carbon atoms; and R ⁴ is a hydrogen atom or a carbon number. Is an alkyl group of 1 to 20, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group; n is an integer of 0 to 20; q is 0 to 3 An integer; wherein, when R ³ and R ^{4 are} plural, a plurality of R ³ and R ⁴ are each independently).

In the first aspect of the invention, it is preferable that the first radiation sensitive resin composition further contains [D] an ethylenically unsaturated compound other than the [A] alkane polymer.

In the first aspect of the invention, it is preferable that the first radiation sensitive resin composition further contains an [E] radiation sensitive acid generator or a radiation sensitive alkali generator.

In the first aspect of the invention, it is preferable that the [α] alkali-soluble resin contained in the second radiation-sensitive resin composition is a copolymer comprising the following structural unit: (α-1) is selected from the group consisting of unsaturated carboxylic acids And a structural unit formed of at least one of the group consisting of unsaturated carboxylic anhydrides and (α-2) a structural unit formed of an epoxy group-containing unsaturated compound.

In the first aspect of the invention, it is preferable that the colored pattern is a colored pattern formed at a curing temperature of 200 ° C or lower.

In the first aspect of the invention, it is preferable that the protective film is a protective film formed at a curing temperature of 200 ° C or lower.

In the first aspect of the invention, it is preferred that the spacer be a spacer formed at a curing temperature of 200 ° C or lower.

In the first aspect of the invention, it is preferable that the colored pattern is a colored pattern formed at a curing temperature lower than a curing temperature of the protective film.

In the first aspect of the invention, it is preferable that the colored pattern is a colored pattern formed at a curing temperature lower than a curing temperature of the spacer.

In the first aspect of the invention, it is preferable that the protective film is a protective film formed at a curing temperature lower than a curing temperature of the spacer.

In a first aspect of the invention, it is preferable to include an alignment film which is a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group and a polyimine containing no photo-alignment group. An alignment film obtained from any of the liquid crystal alignment agents.

In the first aspect of the invention, it is preferred that the alignment film is an alignment film obtained by using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group.

A second aspect of the invention relates to a liquid crystal display element comprising the color filter of the first aspect of the invention.

A third aspect of the invention relates to a method of producing a color filter, comprising the steps of: [1] forming a coating film of a color composition on a substrate, the coloring composition containing a diketone selected from the group consisting of At least one coloring agent of a group consisting of a pyridylpyrrole pigment, a zinc halide phthalocyanine pigment, a triarylmethane dye, and an azo dye; [2] forming a colored pattern on the coating film of the coloring composition [3] a step of curing a coating film on which a colored pattern is formed at 200 ° C or lower; [4] a step of forming a coating film of a first radiation sensitive resin composition on a substrate, the first radiation The resin composition contains the following components: [A] a siloxane polymer, [B] a radical polymerization initiator, and [C] an organic solvent; [5] a coating film for the first radiation-sensitive resin composition. a step of irradiating at least a part of the radiation; [6] a step of developing the coating film irradiated with radiation in the step [5]; [7] a step of hardening the coating film developed in the step [6] at 200 ° C or lower [8] Forming the second on the substrate having the hardened coating film of the step [7] In the step of coating the film of the radiation-sensitive resin composition, the second radiation-sensitive resin composition contains the following components: [α] an alkali-soluble resin, [β] a polymerizable compound having an ethylenically unsaturated bond, and [γ] radiation. The polymerization initiator and [δ] are at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); [9] for the second compound a step of irradiating at least a part of the coating film of the radiation sensitive resin composition with radiation; [10] a step of developing the coating film irradiated with radiation in the step [9]; and [11] performing the step [10] at 200 ° C or lower. a step of hardening the developed coating film to form a spacer;

[Chemical 6]

(In the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ¹ to R ⁶ is an electron withdrawing group, and R ¹ to R ⁶ are At least one of the amine groups is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted by an alkyl group having 1 to 6 carbon atoms; in the formula (2), R ⁷ to R ¹⁶ are each independently hydrogen. An atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; wherein the above methylene group and alkylene group All or a part of the hydrogen atom may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

In the third aspect of the invention, it is preferable that the coloring composition further contains [I] an alkali-soluble resin, [II] a polymerizable compound having an ethylenically unsaturated bond, and [III] a radiation-sensitive polymerization initiator.

In the third aspect of the invention, it is preferred that the hardening temperature of the step [3] is a temperature lower than the hardening temperature of the step [7].

In the third aspect of the invention, it is preferred that the hardening temperature of the step [3] is a temperature lower than the hardening temperature of the step [11].

In the third aspect of the invention, it is preferred that the hardening temperature of the step [7] is a temperature lower than the hardening temperature of the step [11].

In the third aspect of the invention, it is preferred to include the step of forming an alignment film at 200 ° C or lower after [11] after the step [11].

In a third aspect of the present invention, preferably, the step [12] is a liquid crystal alignment agent comprising a radiation-sensitive polymer having a photo-alignment group and a liquid crystal alignment agent comprising a polyimine having no photo-alignment group. Any one of them forms an alignment film.

According to the present invention, a color filter which can be manufactured by low-temperature hardening and which has high reliability and a method of manufacturing the same are provided.

Moreover, according to the present invention, there is provided a liquid crystal display element comprising a color filter which can be manufactured by low temperature hardening and which has high reliability and which can perform color display.

Embodiments of the present invention will be described below.

Further, in the present invention, the "radiation" irradiated at the time of exposure is a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

<Liquid crystal display element>

The liquid crystal display element of the present embodiment is a color liquid crystal display element including the color filter of the present embodiment.

Hereinafter, the configuration of the liquid crystal display element of the present embodiment will be described.

The liquid crystal display device of the present embodiment may be configured such that a driving substrate on which a thin film transistor (TFT) is disposed and a other substrate constituting the color filter of the present embodiment are opposed to each other via a liquid crystal layer. Alternatively, the liquid crystal display element may be a substrate formed by forming a coloring pattern or a protective film or a spacer of the present embodiment to be described later on a driving substrate on which a thin film transistor (TFT) is disposed, and forming ITO (Indium Tin Oxide). The structure in which the substrate of the tin-doped indium oxide electrode is opposed to the liquid crystal layer. The latter structure has the advantage that the numerical aperture can be significantly improved, and a bright high-definition liquid crystal display element can be obtained.

Fig. 1 is a schematic cross-sectional view showing a color filter of the embodiment.

The color filter 10 shown in Fig. 1 is an example of the color filter of the present embodiment. A configuration in which a red (R), green (G), and blue (B) colored pattern 6 , a black matrix 7 , and a protective film 8 provided on the colored pattern 6 are disposed on the transparent substrate 5 The ITO electrode 4 on the protective film 8 and the spacer 9 which is provided upright on the ITO electrode 4.

Further, the color of the colored pattern 6 is not limited to the above-described RGB three colors, and other colors may be selected or yellow (Y) may be further added to form a four-color colored pattern.

As will be described later, in the color filter 10 of the present embodiment, the colored pattern 6 is formed by containing a suitable coloring agent. Specifically, a colored composition containing a preferred coloring agent is applied onto a substrate, patterned, and then cured. Similarly, the protective film 8 is formed by applying a radiation-sensitive resin composition and patterning it, followed by curing. The spacer 9 is similarly patterned by applying a radiation sensitive resin composition. Thereafter, it is formed by hardening. In the following description, for the sake of convenience, the radiation sensitive resin composition for forming the protective film 8 is referred to as a first radiation sensitive resin composition, and the radiation sensitive resin for forming the spacer 9 is used. The composition is referred to as a second sensitizing radiation resin composition. In addition, the coloring composition, the first radiation sensitive resin composition, and the second radiation sensitive resin composition are characterized in that they can be made into a radiation sensitive resin composition and can pass through 200 ° C or less as will be described later. The colored pattern 6 and the protective film 8 and the spacer 9 are respectively formed by low temperature hardening.

Therefore, in the color filter 10 of the present embodiment, the colored pattern 6 and the protective film 8 and the spacer 9 can be formed by low-temperature curing at 200 ° C or lower, and can be produced by low-temperature curing.

Further, in the color filter 10, the protective film 8 is formed after the coloring pattern 6 is formed. The protective film 8 can be formed by low-temperature hardening of 200 ° C or less, and thus it becomes unnecessary to expose the colored pattern 6 to a state of high-temperature heating for forming a protective film after formation. Similarly, in the color filter 10, the spacer 9 is formed after the coloring pattern 6 is formed and the protective film 8 is formed. The spacer 9 can be formed by low-temperature hardening of 200 ° C or less, and thus it becomes unnecessary to expose the colored pattern 6 to a state of high-temperature heating for forming the spacer 9 after formation. Therefore, in the color filter 10, even if a dye having excellent color characteristics in the formation of the colored pattern 6 but having a problem in heat resistance is used as a coloring agent, step deterioration can be reduced. That is, a dye can be selected as the coloring agent of the coloring composition, and the coloring pattern 6 excellent in color characteristics can be formed by using the coloring composition of the dye.

Further, as described above, the coloring composition, the first radiation sensitive resin Both the composition and the second radiation-sensitive resin composition are radiation-sensitive resin compositions for producing the color filter 10, respectively. Therefore, when manufacturing the color filter 10, it is conceivable to form the protective film 8 on the colored pattern 6 to adjust the hardening temperature at the time of forming the colored pattern 6. That is, the colored pattern 6 is formed on the substrate 5 by a lower curing temperature than the optimum curing temperature when the colored pattern 6 is separately formed. Thereafter, the colored pattern 6 can be heated by hardening and heating the protective film 8 formed on the colored pattern 6. Similarly, when manufacturing the color filter 10, it is conceivable to form the spacer 9 after forming the colored pattern 6, and to adjust the hardening temperature when forming the colored pattern 6. That is, the colored pattern 6 is formed on the substrate 5 by a lower curing temperature than the optimum curing temperature when only the colored pattern 6 is formed. Further, after the ITO electrode 4 is formed, the colored pattern 6 can also be heated by hardening heating of the spacer 9 provided on the ITO electrode 4 standing upright.

For example, in the case where the optimum curing temperature of the colored pattern 6 and the protective film 8 is 200 ° C or lower, specifically 180 ° C, a colored pattern can be formed on the substrate 5 in advance with a curing temperature lower than 180 ° C. 6. For example, the colored pattern 6 can be formed in advance by a hardening temperature of 150 °C. Next, a coating film of the first radiation sensitive resin composition is formed on the colored pattern 6, and is cured at an optimum temperature of 180 ° C to form the protective film 8. Further, the colored pattern 6 in the lower layer is heated to obtain the colored pattern 6 in a desired state. Further, on the substrate 5, the colored pattern 6 is formed in advance at a curing temperature of, for example, 150 ° C, and thereafter formed of a second radiation-sensitive resin composition at an optimum curing temperature of 180 ° C. Spacer 9. As a result, the colored pattern 6 in the lower layer of the spacer 9 is heated, and the colored pattern 6 in a desired state can be obtained. In the above case, the dye can be selected as the coloring agent of the coloring composition, and the coloring pattern 6 formed by using the coloring composition of the dye can provide the color filter 10 excellent in color characteristics.

Further, in the case of manufacturing the color filter 10, it is conceivable to form the spacer 9 after forming the colored pattern 6 and the protective film 8, and to adjust the curing temperature when forming the colored pattern 6 and the curing temperature when the protective film 8 is formed. That is, the colored pattern 6 is formed on the substrate 5 by a lower curing temperature than the optimum curing temperature when only the colored pattern 6 is formed. Next, the protective film 8 is formed by a lower curing temperature than the optimum hardening temperature when only the protective film 8 is formed. Further, after the ITO electrode 4 is formed, the colored pattern 6 and the protective film 8 can also be heated by the hardening heating of the spacer 9 provided on the ITO electrode 4 standing upright.

For example, in the case where the optimum curing temperature of the colored pattern 6 and the protective film 8 and the spacer 9 is 200 ° C or lower, specifically 180 ° C, the substrate 5 can be previously used with a curing temperature lower than 180 ° C. A colored pattern 6 is formed thereon. For example, the colored pattern 6 can be formed in advance by a hardening temperature of 150 °C. Next, a coating film on which the first radiation-sensitive resin composition is formed on the colored pattern 6 can be formed in advance by, for example, a curing temperature of 150 °C. Next, after the ITO electrode 4 is formed on the protective film 8, a coating film of the second radiation-sensitive resin composition is formed on the ITO electrode 4. Next, the coating film is patterned and cured at an optimum temperature of 180 ° C to form a spacer 9. As a result, the coloring pattern 6 and the lower layer are formed. The protective film 8 is heated to obtain the colored pattern 6 and the protective film 8 in a desired state. In this case, the dye can be selected as the coloring agent of the coloring composition, and the coloring pattern 6 formed by using the coloring composition of the dye can provide the color filter 10 excellent in color characteristics.

Further, in the color filter 10 of the present embodiment, after the spacer 9 is formed, a liquid crystal alignment alignment film (not shown in FIG. 1) can be provided as will be described later. The alignment film can be obtained by using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group or a liquid crystal alignment agent containing a polyimide having no photo-alignment group. In this case, it becomes possible to form an alignment film at a heating temperature of 200 ° C or lower.

Next, a liquid crystal display element of this embodiment to which the color filter of the present embodiment is applied will be described.

Fig. 2 is a schematic cross-sectional view showing a color liquid crystal display element including the color filter of the embodiment.

The liquid crystal display element 1 shown in FIG. 2 is an example of a liquid crystal display element of the present embodiment, and is a TFT-driven twisted nematic (TN) liquid crystal mode display element. This color liquid crystal display device has a structure in which the above-described driving substrate and a substrate constituting the color filter of the above-described embodiment are opposed to each other with a TN liquid crystal layer interposed therebetween.

As shown in FIG. 2, on the side of the transparent substrate 2 that is in contact with the liquid crystal 13, a transparent pixel electrode 3 including ITO and a TFT (not shown) are arranged in a lattice shape to constitute a driving substrate.

Further, on the side of the transparent substrate 5 that is in contact with the liquid crystal 13, the above-described colored pattern 6 and the like which are produced by low-temperature curing are disposed to form a color. Filter 10. More specifically, the color filter 10 is disposed, and the color filter 10 includes, on the substrate 5, a red, green, and blue coloring pattern 6 disposed at a position facing the pixel electrode 3, black. The matrix 7, the protective film 8 provided on the colored pattern 6, the ITO electrode 4 provided on the protective film 8, the spacer 9 provided upright on the ITO electrode 4, and the alignment film 12. The ITO electrode 4 constitutes a common electrode in the liquid crystal display element 1.

The alignment film 12 similar to the substrate 5 is provided on the substrate 2. By performing an alignment treatment such as rubbing treatment on each of the alignment films 12 as necessary, uniform alignment of the liquid crystals 13 sandwiched between the substrate 2 and the substrate 5 can be realized.

In the substrate 2 and the substrate 5, a polarizing plate 14 is disposed on the side opposite to the side in contact with the liquid crystal 13, respectively. The distance between the substrate 2 and the substrate 5 is usually 2 μm to 10 μm, and these elements are fixed to each other by the sealing material 16 provided at the peripheral portion.

In FIG. 2, reference numeral 17 denotes backlight light that is irradiated to the liquid crystal 13 from a backlight unit (not shown). As the backlight unit, for example, a backlight unit having a structure in which a fluorescent tube such as a Cold Cathode Fluorescent Lamp (CCFL) and a diffusion plate are combined can be used. Moreover, a backlight unit using a white LED as a light source can also be used. Examples of the white LED include a white LED that obtains white light using a red LED having an independent spectrum, a green LED, and a blue LED, and a white LED that combines a red LED, a green LED, and a blue LED to obtain white light by color mixing. A white LED that combines a blue LED, a red LED, and a green phosphor to obtain a white light by mixing colors, and a blue LED, a red luminescent phosphor, and a green hair A white LED that combines light phosphors to obtain white light by color mixing, and a white LED that obtains white light by color mixing of blue LEDs and YAG-based phosphors, and blue LEDs, orange-emitting phosphors, and green-emitting phosphors A white LED which combines light bodies to obtain white light by color mixing, and combines an ultraviolet LED, a red light-emitting phosphor, a green light-emitting phosphor, and a blue light-emitting phosphor to obtain a white light white LED or the like by color mixing.

In addition to the TN type, the color liquid crystal display device of the present embodiment may be a Super Twisted Nematic (STN) type, an In-Planes Switching (IPS) type, or a vertical alignment ( Vertical Alignment, VA) or optically compensated birefringence (OCB) type liquid crystal mode. In this case, the alignment film for liquid crystal alignment selects an optimum alignment film in each liquid crystal mode, and for example, in the case of the VA type, a vertical alignment type alignment film is used.

Next, the color filter of this embodiment which is a main component of the liquid crystal display element of the present embodiment will be described in more detail.

As described above, the color filter of the present embodiment includes a colored pattern and a protective film provided on the colored pattern. The ITO electrode on the protective film may include a spacer disposed upright, and is a color filter excellent in color characteristics and curable by low temperature hardening.

The colored pattern can be formed on a suitable substrate using a coloring composition, and the protective film is formed on the colored pattern using a first radiation-sensitive resin composition. The spacer can be formed on the ITO electrode on the protective film using the second radiation-sensitive resin composition. That is, the color of this embodiment The filter can be produced by using a coloring composition, a first radiation sensitive resin composition, and a second radiation sensitive resin composition.

In the following, the coloring pattern of the color filter of the present embodiment will be described first, and in particular, the coloring composition of the present embodiment used for forming the colored pattern will be described.

<Coloring composition>

The colored composition used in the production of the color filter of the present embodiment contains [I] an alkali-soluble resin, a [II] polymerizable compound, a [III] polymerization initiator, and a [IV] colorant. Further, a compound of [V] may be further contained. Further, other optional components may be contained as long as the effects of the present invention are not impaired. Hereinafter, each component contained in the coloring composition will be described.

<[I] alkali soluble resin>

[I] The alkali-soluble resin is not particularly limited as long as it has a carboxyl group and has alkali developability. Further, a copolymer comprising at least one structural unit selected from the group consisting of a structural unit having a (meth)acryloxy group and a structural unit having an epoxy group is preferable. [I] The alkali-soluble resin has the specific structural unit described above, and thus a cured film having excellent surface hardenability and deep-curing property can be formed.

[I] an alkali-soluble resin can be synthesized by copolymerizing a structural unit to obtain a copolymer comprising the structural unit: (I-1) is selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. At least one structural unit (hereinafter also referred to as "(I-1) compound")), (I-2) is an unsaturated compound containing an epoxy group (hereinafter also referred to as "(I-2) compound) ") The structural unit formed.

[I] the alkali-soluble resin can be, for example, a compound (I-1) which imparts a structural unit containing a carboxyl group to a compound of the formula (I-2) which imparts an epoxy group-containing structural unit in the presence of a polymerization initiator in a solvent. Manufactured by copolymerization. Further, (I-3) a hydroxyl group-containing unsaturated compound (hereinafter also referred to as "(I-3) compound")) to which a structural unit containing a hydroxyl group is added may be further added to form a copolymer. Further, in the production of the [I] alkali-soluble resin, the compound (I-4) may be further added together with the compound (I-1), the compound (I-2) and the compound (I-3). The (I-1) compound, the (I-2) compound, and the unsaturated compound of the structural unit other than the structural unit of the (I-3) compound are used to form a copolymer. Hereinafter, each compound will be described in detail.

[(I-1) compound]

Examples of the compound (I-1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an acid anhydride of an unsaturated dicarboxylic acid, and a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid at both ends. A mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group, an unsaturated polycyclic compound having a carboxyl group, an acid anhydride thereof, and the like.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid; and examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like; Examples of the acid anhydride of the dicarboxylic acid include an acid anhydride of a compound exemplified as the above dicarboxylic acid; and a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid, for example, succinic acid mono [2-(A) Alkenyloxyethyl]ester, mono[2-(methyl)propenyloxyethyl] phthalate, etc.; mono(meth)acrylic acid having a polymer having a carboxyl group and a hydroxyl group at both ends Examples of the ester include ω-carboxypolycaprolactone mono(meth)acrylate; Examples of the unsaturated polycyclic compound having a carboxyl group and an acid anhydride thereof include 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, and 5 -carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2 .1] hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like.

Among the compounds (I-1), monocarboxylic acid, dicarboxylic anhydride, acrylic acid, methacrylic acid, and maleic anhydride are preferred, and self-copolymerization reactivity, solubility in an aqueous alkaline solution, and ease of availability are more preferable. Acrylic acid, methacrylic acid, maleic anhydride. These (I-1) compounds may be used singly or in combination of two or more.

The ratio of use of the compound (I-1) is based on the total of the (I-1) compound and the (I-2) compound (optionally any of the (I-3) compound and the (I-4) compound). It is preferably 5 mass% to 30 mass%, and more preferably 10 mass% to 25% by mass. When the use ratio of the compound (I-1) is from 5% by mass to 30% by mass, the solubility of the [I] alkali-soluble resin in an aqueous alkaline solution can be optimized, and a coloring composition excellent in radiation sensitivity can be obtained. .

[(I-2) compound]

The compound (I-2) is an epoxy group-containing unsaturated compound having a radical polymerizable property. The epoxy group may, for example, be an oxiranyl group (1,2-epoxy structure) or an propylene oxide group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, and -2-methyl methacrylate. Glycidyl ester, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3 , 4-epoxybutyl ester, acrylate-6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid-3,4-epoxycyclohexylmethyl ester, and the like. From the viewpoint of improving solvent resistance such as copolymerization reactivity and coloring pattern, among these compounds, glycidyl methacrylate, -2-methylglycidyl methacrylate, and methacrylic acid-6,7- are preferable. Epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate.

Examples of the unsaturated compound having an oxypropylene group include 3-(acryloxymethyl) propylene oxide, 3-(acryloxymethyl)-2-methyl propylene oxide, and 3-(propylene).醯oxymethyl)-3-ethyl propylene oxide, 3-(acryloxymethyl)-2-phenyl propylene oxide, 3-(2-propenyl methoxyethyl) propylene oxide, 3-(2-propenyloxyethyl)-2-ethyl propylene oxide, 3-(2-propenyloxyethyl)-3-ethyl propylene oxide, 3-(2-propylene oxime Acrylate such as ethyl ethyl)-2-phenyl propylene oxide; 3-(methacryloxymethyl) propylene oxide, 3-(methacryloxymethyl)-2-methyl ring Oxypropane, 3-(methacryloxymethyl)-3-ethyl propylene oxide, 3-(methacryloxymethyl)-2-phenyl propylene oxide, 3-(2- Methyl propylene methoxyethyl) propylene oxide, 3-(2-methylpropenyloxyethyl)-2-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl) 3-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2-phenyl ring A methacrylate such as oxypropane or 3-(2-methylpropenyloxyethyl)-2,2-difluoroepoxypropane.

Among these (I-2) compounds, glycidyl (meth)acrylate is preferred. These (I-2) compounds may be used alone or in combination of two or more.

The ratio of use of the compound (I-2) is based on the total of the (I-1) compound and the (I-2) compound (optionally any of the (I-3) compound and the (I-4) compound). It is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass. When the use ratio of the compound (I-2) is from 5% by mass to 60% by mass, a cured film having excellent curability or the like can be formed.

[(I-3) compound]

The (I-3) compound may first be a (meth) acrylate having a hydroxyl group, a (meth) acrylate having a phenolic hydroxyl group, or a hydroxystyrene.

Examples of the acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

Further, examples of the methacrylate having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 5-hydroxyl methacrylate. Ester, -6-hydroxyhexyl methacrylate, and the like.

Examples of the acrylate having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylate having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

The hydroxystyrene is preferably o-hydroxystyrene, p-hydroxystyrene, or α-methyl-p-hydroxystyrene. These (I-3) compounds may be used alone or in combination of two or more.

The ratio of use of the compound (I-3) is based on the total of the (I-1) compound, the (I-2) compound, and the (I-3) compound (optionally any (I-4) compound). It is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 25% by mass.

[(I-4) compound]

The compound (I-4) is not particularly limited as long as it is an unsaturated compound other than the compound (I-1), the compound (I-2) and the compound (I-3). Examples of the compound (I-4) include a chain alkyl methacrylate, a cyclic alkyl methacrylate, a chain alkyl acrylate, a cyclic alkyl acrylate, an aryl methacrylate, and an aryl acrylate. Base ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleic imine compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton Equal unsaturated compounds and other unsaturated compounds.

Examples of the chain alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, t-butyl methacrylate, and methacrylic acid. 2-ethylhexyl ester, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate. Tricyclo[meth] methacrylate [5.2.1.0 ^2,6 ]decane-8-yloxyethyl ester, isobornyl methacrylate, and the like.

Examples of the chain alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, second butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and acrylic acid. Cinnamyl ester, tridecyl acrylate, n-stearyl acrylate, and the like.

Examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, and tricyclohexyl acrylate [5.2.1.0]. ^2,6 ]decane-8-yloxyethyl ester, isobornyl acrylate, and the like.

Examples of the aryl methacrylate include phenyl methacrylate and benzyl methacrylate.

Examples of the aryl acrylate include phenyl acrylate and benzyl acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

Examples of the bicyclic unsaturated compound include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene. 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, and the like.

Examples of the maleic imine compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-(4-hydroxyphenyl)male. Yttrium, N-(4-hydroxybenzyl)maleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-ma醯iminobutyrate, N-succinimide-6-maleimide caproate, N-amber Imino-3-maleimide propionate, N-(9-acridinyl)maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

Examples of the conjugated diene include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofuran methyl (meth)acrylate, 2-methylpropenyloxy-propionic acid tetrahydrofuran methyl ester, and 3-(methyl)acryloxytetrahydrofuran-2- Ketones, etc.

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5-(3-furyl)-1-penten-3-one, decyl (meth)acrylate, and 1-furan-2-butyl. 3-en-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexene 3-ketone, 6-furan-2-yl-hex-1-en-3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furanyl) -6-Methyl-1-hepten-3-one and the like.

Examples of the unsaturated compound containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl)methyl methacrylate and 2,6-dimethyl-8-(tetrahydropyran-2-yloxy). )-oct-1-en-3-one, 2-hydropyran-2-yl methacrylate, 1-(tetrahydropyran-2-yloxy)-butyl-3-ene-2- Ketones, etc.

Examples of the unsaturated compound containing a pyran skeleton include 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyran, 4-(1,5). -Dioxa-6-oxo-7-octenyl)-6-methyl-2-pyran and the like.

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and ethyl acetate. Ester esters and the like.

Among these (I-4) compounds, a linear alkyl methacrylate, a cyclic alkyl methacrylate, an aryl methacrylate, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, and four are preferable. Hydropyran skeleton, pyran skeleton, unsaturated aromatic compound, cyclic alkyl acrylate. Among these compounds, styrene, methyl methacrylate, butyl methacrylate, n-lauryl methacrylate, methacrylic acid are more preferable from the viewpoints of copolymerization reactivity and solubility in an aqueous alkaline solution. Benzyl ester, tricyclo [5.0.1.02 ^2,6 ]decane-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenyl malayan Amine, N-cyclohexylmaleimide, tetrahydrofuranmethyl (meth)acrylate, polyethylene glycol (n=2~10) mono(meth)acrylate, 3-(methyl)propene oxide Tetrahydrofuran-2-one. These (I-4) compounds may be used singly or in combination of two or more.

The ratio of use of the compound (I-4) is preferably based on the total of the (I-1) compound, the (I-2) compound, and the (I-4) compound (and any (I-3) compound). 10% by mass to 80% by mass.

<[I] Method for synthesizing alkali-soluble resin 1>

[I] an alkali-soluble resin can be, for example, a compound of the above (I-1) and a compound of (I-2) (any compound of (I-3) and (I-4) in the presence of a polymerization initiator in a solvent. The compound) is produced by copolymerization. By this synthesis method, a copolymer containing at least a structural unit containing an epoxy group can be synthesized.

The solvent used in the polymerization reaction for producing the [I] alkali-soluble resin may, for example, be an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol monoalkyl ether or a diethylene glycol. Alkyl ether, dipropylene glycol dialkyl ether, propane Alcohol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester, and the like.

As the polymerization initiator used in the polymerization for producing the [I] alkali-soluble resin, a compound known as a radical polymerization initiator can be usually used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'- An azo compound such as azobis-(4-methoxy-2,4-dimethylvaleronitrile).

In the polymerization reaction for producing the [I] alkali-soluble resin, a molecular weight modifier may be used in order to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tridodecanethiol, and mercaptoacetic acid; and sulfurization; Xanthogenates such as dimethylxanthate and diisopropylxanthate disulfide; terpinene, α-methylstyrene dimer, and the like.

The weight average molecular weight (Mw) of the [I] alkali-soluble resin is preferably from 1,000 to 30,000, more preferably from 5,000 to 20,000. When the Mw of the [I] alkali-soluble resin is in the above range, the sensitivity and developability of the colored composition can be improved. Further, the Mw and the number average molecular weight (Mn) of the polymer in the present specification can be measured by gel permeation chromatography (GPC) using the following conditions.

Device: GPC-101 (manufactured by Showa Denko) Pipe column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were combined with mobile phase: tetrahydrofuran column temperature: 40 °C Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection amount: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[I] Method for synthesizing alkali-soluble resin 2>

In addition, the [I] alkali-soluble resin can be reacted with the above-mentioned (I-2) compound by using a copolymer (hereinafter also referred to as "specific copolymer") which can be synthesized using one or more of the above compounds (I-1). And synthesis. By this synthesis method, a copolymer containing at least a structural unit having a (meth) acryloxy group can be synthesized.

[I] The structural unit having a (meth) acryloxy group contained in the alkali-soluble resin is represented by the following formula (3). This structural unit is obtained by reacting a carboxyl group in a specific copolymer derived from the compound (I-1) with an epoxy group of the compound (I-2) to form an ester bond.

In the above formula (3), R ²⁰ and R ²¹ each independently represent a hydrogen atom or a methyl group. c is an integer from 1 to 6. R ²² is a divalent group represented by the following formula (4-1) or formula (4-2).

In the above formula (4-1), R ²³ is a hydrogen atom or a methyl group. In the above formula (4-1) and formula (4-2), ^* represents a site bonded to an oxygen atom.

With respect to the structural unit represented by the above formula (3), for example, a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate as a compound (I-2) is reacted with a copolymer having a carboxyl group. In the case, R ²² in the formula (3) becomes the formula (4-1). On the other hand, when a compound such as -3,4-epoxycyclohexylmethyl methacrylate as the compound (I-2) is reacted with a copolymer having a carboxyl group, R ²² in the formula (3) becomes Formula (4-2).

In the synthesis of the specific copolymer, a compound other than the compound (I-1), for example, the above compound (I-3), the compound (I-4), or the like may be used as a copolymerization component. From the viewpoint of copolymerization reactivity, the compounds are preferably methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, trimethyl methacrylate [5.2. 1.0 ^2,6 ]decane-8-yl ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene.

The copolymerization method of the specific copolymer is, for example, a method in which a (I-1) compound and, if necessary, a compound (I-3) are polymerized, using a radical polymerization initiator in a solvent. The radical polymerization initiator is the same as the radical polymerization initiator exemplified in the item of the above [I] alkali-soluble resin. The amount of the radical polymerization initiator to be used is usually 0.1% by mass to 50% by mass, and preferably 0.1% by mass to 20% by mass based on 100% by mass of the polymerizable unsaturated compound. The specific copolymer may be directly supplied to the [I] alkali-soluble resin in the polymerization reaction solution, or may be supplied to the [I] alkali-soluble resin after the copolymer is temporarily separated from the solution.

The Mw of the specific copolymer is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000. When Mw is 2,000 or more, sufficient development latitude of the colored composition can be obtained, and the residual film ratio of the formed coating film (ratio of the pattern film remaining properly) can be prevented from being lowered, and the obtained product can be further favorably maintained. The shape of the pattern or heat resistance. On the other hand, by setting Mw to 100,000 or less, a high degree of sensitivity can be maintained, and a good pattern shape can be obtained. Further, the molecular weight distribution (Mw/Mn) of the specific copolymer is preferably 5.0 or less, and more preferably 3.0 or less. By setting Mw/Mn to 5.0 or less, the shape of the obtained spacer pattern can be favorably maintained. Further, the coloring composition containing the specific copolymer having the above-specified range of Mw/Mn has high developability, and in the developing step, a predetermined pattern shape can be easily formed without causing development residue.

The content of the structural unit derived from the (I-1) compound of the [I] alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, and particularly preferably 8% by mass to 40% by mass. quality%.

The content of the structural unit of the compound (I-3) or the compound (I-4) other than the compound (I-1), which is an alkali-soluble resin, is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass.

In the reaction of the specific copolymer with the compound (I-2), if necessary, an unsaturated compound having an epoxy group is introduced in the presence of a suitable catalyst, preferably in a copolymer solution containing a polymerization inhibitor, under heating Stirring is carried out for a predetermined period of time. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably from 70 ° C to 100 ° C. The reaction time is preferably from 8 hours to 12 hours.

The use ratio of the compound (I-2) is preferably 5% by mass to 99% by mass, and more preferably 10% by mass to 97% by mass based on the carboxyl group derived from the compound (I-2) in the copolymer. . When the ratio of use of the compound (I-2) is in the above range, the reactivity with the copolymer, the curability of the cured film, and the like can be further improved. (I-2) The compounds may be used singly or in combination of two or more.

<[II] Polymerizable Compound>

The [II] polymerizable compound contained in the colored composition used in the production of the color filter of the present embodiment will be described.

[II] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond.

Examples of the compound which can be used as the [II] polymerizable compound include ω-carboxypolycaprolactone mono(meth)acrylate, ethylene glycol (meth)acrylate, and 1,6-hexanediol II ( Methyl) acrylate, 1,9-nonanediol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, methacrylate 2-hydroxyl 3-(meth)acryloxypropyl propyl ester, 2-(2'-vinyloxyethoxy)ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris(2-(methyl) propylene oxychloride a base ethyl ester, an ethylene oxide-modified dipentaerythritol hexaacrylate, a succinic acid-modified pentaerythritol triacrylate, etc., and other than a linear alkyl group and an alicyclic structure, and having two or more A polyamine ester (meth) acrylate compound obtained by reacting a compound having an isocyanate group with a compound having one or more hydroxyl groups in the molecule and having three to five (meth) acryloxy groups.

Commercial products of the [II] polymerizable compound which can be used include, for example, ARONIX (registered trademark) M-400, ARONIX M-402, ARONIX M-405, ARONIX M-450, ARONIX M-1310, ARONIX M-1600. , ARONIX M-1960, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, ARONIX M-8100, ARONIX M-8530, ARONIX M-8560, ARONIX M-9050, ARONIX (registered trademark) TO-756, ARONIX TO-1450, ARONIX TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 ( The above is manufactured by Nippon Kayaku Co., Ltd., Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier (registered trademark) R-1150 (first industrial pharmaceutical company), KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) DPHA-40H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), UN-9000H (Kyosei Industrial Co., Ltd.), ARONIX (registered trademark) M-5300, ARONIXM-5600, ARONIX M-5700, ARONIX M-210, ARONIX M-220, ARONIX M-240, ARONIX M-270, ARONIX M-6200, ARONIX M-305, ARONIX M-309, ARONIX M-310, ARONIX M-315 (above manufactured by Toagosei Co., Ltd.), KAYARAD ( Registered trademark) HDDA, KAYARAD (registered trademark) HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, KAYARAD UX-2201, KAYARAD UX-2301, KAYARAD UX-3204, KAYARAD UX-3301, KAYARAD UX-4101, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8101, KAYARAD UX-0937, KAYARAD MU-2100, KAYARAD MU-4001 (above made by Nippon Kayaku Co., Ltd.), Artresin UN-9000PEP, Artresin UN-9200A, Artresin UN-7600 Artresin UN-333, Artresin UN-1003, Artresin UN-1255, Artresin UN-6060PTM, Artresin UN-6060P, Artresin SH-500B (above manufactured by Gensei Industrial Co., Ltd.), Viscoat 260, Viscoat 312, Viscoat 335HP (above by Osaka) Organic Chemical Industry Co., Ltd.) and so on.

[II] The polymerizable compound may be used singly or in combination of two or more. The use ratio of the [II] polymerizable compound in the coloring composition is preferably 10 parts by mass to 700 parts by mass, and more preferably 20 parts by mass to 600 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. When the use ratio of the [II] polymerizable compound is in the above range, the colored composition can form a colored pattern having sufficient heat resistance, solvent resistance, and voltage holding ratio even at a low exposure amount.

<[III] Polymerization initiator>

The [III] polymerization initiator contained in the colored composition used in the production of the color filter of the present embodiment will be described.

[III] The polymerization initiator is a radiation-sensitive polymerization initiator which is a component which induces radiation to form an active species which can initiate polymerization of the [II] polymerizable compound. Examples of such a [III] polymerization initiator include an O-indenyl hydrazine compound, an acetophenone compound, a biimidazole compound, and the like. These compounds may be used singly or in combination of two or more.

Examples of the O-indenyl hydrazine compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)], and ethyl ketone-1-[9-ethyl -6-(2-methylbenzimidyl)-9H-carbazol-3-yl]-1-(O-acetamidine), 1-[9-ethyl-6-benzylidene-9H -oxazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole-3 -yl]-ethane-1-ketooxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidene)-9H-indazol-3-yl] -ethane-1-ketooxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9H-carbazole- 3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9H-oxime Zin-3-yl]-1-(O-acetonitrile 肟), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine) Ethylketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzimidazole }}-9H-carbazol-3-yl]-1-(O-acetamidine) and the like.

Among these compounds, preferred is 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)], and ethyl ketone-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl- 4-tetrahydrofuranylmethoxybenzylidene)-9H-carbazol-3-yl]-1-(O-acetamidine) or ethyl ketone-1-[9-ethyl-6-{2- 4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidene}-9H-indazol-3-yl]-1-(O-B醯肟).

Examples of the acetophenone compound include an α-amino ketone compound and an α-hydroxy ketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethylamino-2. -(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthienyl)-2 - Morpholinopropan-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1. a ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone or the like.

Among these compounds, an α-amino ketone compound is preferred, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethyl dimethyl ester is more preferred. Amino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methyl Thienyl)-2-morpholinopropan-1-one.

The biimidazole compound is, for example, preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)-4 , 4',5,5'-tetraphenyl-1,2'-biimidazole, of which 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5' is more preferred. -Tetraphenyl-1,2'-biimidazole.

The use ratio of the [III] polymerization initiator is preferably from 1 part by mass to 40 parts by mass, more preferably from 5 parts by mass to 30 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. When the use ratio of the [III] polymerization initiator is from 1 part by mass to 40 parts by mass, the colored composition can form a color pattern and a color filter having high solvent resistance and the like even at a low exposure amount. .

<[IV] colorant>

As described above, high color purity, brightness, contrast, and the like are strongly required for the coloring pattern and the color filter. Therefore, as the [IV] coloring agent contained in the colored composition used in the production of the color filter of the present embodiment, it is necessary to select a coloring agent suitable for realizing such characteristics. [IV] The coloring agent may be, for example, any of a pigment, a dye, and a natural coloring matter. However, in consideration of a high color purity, brightness, and the like required for the coloring pattern and the color filter, it is preferred to select a pigment and a dye. It is also particularly preferred to select a dye.

Examples of the dye which can be used as the [IV] coloring agent include oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, and vehicle dyes. As the dye, a known dye can be used as long as it is soluble in an organic solvent.

C.I. Oil-soluble dyes, for example, C.I. Solvent Yellow 4 (hereinafter, the description of "C.I. Solvent Yellow" is omitted and only Number. Other dyes are also described in the same manner), 14, 15, 23, 24, 38, 62, 63, 68, 82, 88, 94, 98, 99, 162, 179; CI solvent red 45, 49, 125, 130; CI Solvent Orange 2, 7, 11, 15, 26, 56; CI Solvent Blue 35, 37, 59, 67; CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 Wait.

Examples of the CI acid dyes include: CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; Valifast yellow 1101, 1109, 1151, 3108, 3120, 3130, 3150, 3170, 4120; CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35 , 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145 , 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277 , 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75 , 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 108, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 249, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324, 335, 340; CI Acid Violet 6B, 7, 9, 17, 19, 49; CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109; CI acid black 24 and other dyes.

Examples of CI direct dyes include: CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177 ,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95 , 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84 , 89, 90, 93, 95, 96, 103, 104; CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. .

For CI medium dyes, for example, CI medium yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI medium red 1, 2, 3 , 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48 , 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI medium orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22 , 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI medium purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI medium green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 Wait.

As the pigment which can be used as the [IV] coloring agent, any of an organic pigment and an inorganic pigment can be used. The organic pigment may, for example, be a compound classified as a pigment in a dye index (C.I.; issued by The Society of Dyers and Colourists). Specifically, a pigment having a dye index (C.I.) name as described below can be cited.

Can be cited as: CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211; CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60 , CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7, and the like.

Next, the chemical structure of the [IV] colorant as a dye or a pigment will be described. Examples of the chemical structure include azo, triarylmethane, anthracene, benzylidene, oxaphthalocyanine, cyanine, phenothiazine, pyrrolopyrazole azomethine, and oxygen. Heteroquinones, phthalocyanines, benzopyrans, indigo, diketopyrrolopyrroles, and the like. Among these colorants, triarylmethane, barbituric azo, pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, phthalocyanine are preferably selected. A coloring agent for quinones, anthraquinones and diketopyrrolopyrroles.

Triarylmethane colorant as an example of a preferred [IV] colorant It is a blue, purple coloring agent.

Blue and purple coloring agents are pigments such as CI Pigment Blue, CI Pigment Violet, etc., CI Basic Blue, CI Basic Violet and other basic dyes, CI Solvent Blue, CI Solvent Violet and other oil-soluble dyes, CI Acid Blue, Acid dyes such as CI acid purple, disperse dyes such as CI disperse blue and CI disperse violet, and colorants such as CI food blue, CI edible violet, and other food coloring agents.

In addition, it is a salt-forming dye which is modified by using a counter ion to modify some of the acid dyes (including direct dyes) and basic dyes.

The triphenylmethane-based colorant which is an example of a triarylmethane-based coloring agent is a color-developing coloring because the NH ₂ or OH group located at a position opposite to the center carbon is oxidized to form a fluorene structure. Agent. Further, it is mainly a basic dye, but a dye into which a sulfonic acid group is introduced becomes an acid dye.

The following three types are classified according to the number of NH ₂ and OH groups, and the form of the triaminotriphenylmethane dye is a preferable form in terms of exhibiting a good blue color.

a) Diaminotriphenylmethane dyes

b) Triaminotriphenylmethane dyes

c) Rose sulphur dyes with OH groups

The triaminotriphenylmethane dye is preferably used because it has a clear color tone and is excellent in light resistance. Further, among them, a diphenylnaphthylmethane dye which is a basic dye is particularly preferable.

As the triarylmethane coloring agent, the following five forms of dyes and pigments can be used.

1) Basic dyes of triaryl methane dyes (triarylmethane basic dyes)

2) salt-forming compounds of triarylmethane-based basic dyes and organic sulfonic acids, salt-forming compounds of triarylmethane-based basic dyes and aromatic hydroxycarboxylic acids

3) Acid dyes of triaryl methane dyes

4) Salt formation compounds of triarylmethane acid dyes and quaternary ammonium

5) Lake pigments of triarylmethane dyes (especially metal lake pigments of triarylmethane dyes)

As such a form, a basic dye using a triarylmethane dye, a salt forming compound of a triarylmethane-based basic dye and an organic sulfonic acid, a salt of a triarylmethane-based basic dye and an aromatic hydroxycarboxylic acid are preferably used. A metal lake pigment of a compound, a triarylmethane dye.

The triarylmethane dye has the following spectral characteristics: high transmittance in the range of 400 nm to 430 nm. However, even if it has a good spectral characteristic, it is extremely inferior in heat resistance like a general dye. When used in a color liquid crystal display element requiring high reliability, the characteristics are not sufficient in the past. Therefore, it is preferably used in the color filter of the present embodiment. Further, the dye may be alkalized, salified, oil-soluble, or modified with a resin as in the prior problem of improving the triarylmethane dye. Alternatively, the dye can be laked to form a pigment.

The basic dye and the oil-soluble dye of the triarylmethane dye are preferably improved by mixing with a resin having a acid group such as a carboxyl group or a rosin ester, and a rosin-modified maleic acid resin (synonym for rosin-modified fumaric acid resin). Tolerance. The acid value of the resin having an acid group, the rosin ester, and the rosin-modified maleic acid resin is preferably 20 to 200. Here, the acid value is a value measured by the method of JIS K-0070.

Examples of the triarylmethane-based basic dyes include C.I. Basic Blue 1, 5, 7, 26, C.I. Basic Violet 1, 3, and the like. Among them, C.I. Basic Blue 7 is preferably used.

Next, a salt-forming compound of a triarylmethane-based basic dye and an organic sulfonic acid will be described. The triarylmethane-based basic dye and the organic sulfonic acid can be reacted to obtain a salt-forming compound by dissolving both in an aqueous solution or an alcohol solution.

As the organic sulfonic acid, a naphthalene sulfonate or a naphthol sulfonate can be used.

The naphthalene sulfonate is a general term for a compound having a sulfonic acid group bonded to a carbon atom of naphthalene, and the naphthol sulfonate is a general term for a compound having a sulfonic acid group bonded to a carbon atom of naphthol.

Among the naphthalene sulfonates, there are naphthalene monosulfonic acid having one sulfonic acid group bonded thereto, naphthalene disulfonic acid having two sulfonic acid groups bonded thereto, and naphthalene trisulfonic acid having three sulfonic acid groups bonded thereto. Specifically, it is 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,3-naphthalenedisulfonic acid, 1,5-naphthalene disulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalene disulfide Acid, 2,6-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 1,3,5-naphthalenetrisulfonic acid, 1,3,6-naphthalenetrisulfonic acid, 1,3,7-naphthalene Sulfonic acid, etc.

Further, the naphthalene sulfonate contains naphthylamine sulfonic acid in addition to the above naphthalenesulfonic acid. Further, there are naphthylamine monosulfonic acid having one sulfonic acid group bonded thereto, naphthylamine disulfonic acid having two sulfonic acid groups bonded thereto, and naphthylamine trisulfonic acid having three sulfonic acid groups bonded thereto. Specifically, 1,4-naphthylaminesulfonic acid (p-aminonaphthalenesulfonic acid), 1,5-naphthylaminesulfonic acid (lauranic acid), 1,6-naphthylaminesulfonic acid (6-cliphoric acid) 1,7- Naphthylamine sulfonic acid (7-cliphoric acid), 1,8-naphthylamine sulfonic acid (peripheric acid), 2,1-naphthylamine sulfonic acid (tobes acid), 2,5-naphthylamine sulfonic acid , 2,6-naphthylamine sulfonic acid (bromonic acid), 1,3,6-naphthylamine disulfonic acid (Froud acid), 1,3,7-naphthylamine disulfonic acid, 2,3, 6-naphthylamine disulfonic acid (amino R acid), 2,4,6-naphthylamine disulfonic acid (C acid), 2,5,7-naphthylamine disulfonic acid (amino J acid), 2, 6,8-naphthylamine disulfonic acid (amino G acid), 1,3,6,8-naphthylamine trisulfonic acid (kohic acid), and the like.

Among the naphthol sulfonates, there are also naphthol monosulfonic acid bonded with one sulfonic acid group, naphthol disulfonic acid bonded with two sulfonic acid groups, and naphthalene bonded with three sulfonic acid groups. Phenol trisulfonic acid. Specifically, 1-naphthol-2-sulfonic acid, 1-naphthol-4-sulfonic acid (NW acid), 1-naphthol-5-sulfonic acid (L acid), 1-naphthol-8-sulfonate Acid, 2-naphthol-1-sulfonic acid, 2-naphthol-6-sulfonic acid (Schiff's acid), 2-naphthol-8-sulfonic acid (saffronic acid), 1-naphthol-2,4 -disulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 2-naphthol-3,6-disulfonic acid (R acid ), 2-naphthol-3,8-disulfonic acid, 2-naphthol-6,8-disulfonic acid (G acid), 1-naphthol-2,4,7-trisulphonic acid, 1-naphthalene Phenol-3,6,8-trisulphonic acid (oxocochic acid), 2-naphthol-3,6,8-trisulphonic acid, and the like.

Among them, naphthalenedisulfonic acid and naphthol disulfonic acid having two sulfonic acid groups bonded thereto are preferred. Among them, preferred are 1,5-naphthalenedisulfonic acid, 2,7-naphthalene disulfonic acid, 2-naphthol-3,6-disulfonic acid, and 2-naphthol-3,8-disulfonic acid.

In addition, a salt-forming compound comprising Victoria Pure Blue BO (CI Basic Blue 7) and naphthalenedisulfonic acid, a salt-forming compound comprising Victoria Pure Blue BO (CI Basic Blue 7) and naphthol disulfonic acid is a preferred dye. .

A case where a disulfonate of a naphthalene or a disulfonate of a naphthol is reacted with a triarylmethane-based basic dye to prepare a [IV] colorant of the present embodiment. At the time, 1 mole of the disulfonate reacted with the triarylmethane dye 2 mole to form a salt. Since the charge is contained and the colorant component is twice as large as the molar ratio of the counter ion component, it is a preferable component which does not impair the color development of the dye as a colorant. That is, it is preferred to use an organic sulfonic acid having at least 2 sulfonic acid groups.

Further, a salt-forming compound of a triarylmethane-based basic dye and an organic sulfonic acid or (aromatic hydroxycarboxylic acid) can be synthesized by a previously known method. A specific method is disclosed in Japanese Laid-Open Patent Publication No. 2003-215850.

Further, an aromatic hydroxycarboxylic acid can be used in the same manner as the above organic sulfonic acid to obtain a salt-forming compound. As a preferred aromatic hydroxycarboxylic acid, 3,5-di-t-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, and 3-phenylsalicylic acid are preferably used. In the case of using an aromatic hydroxycarboxylic acid, a salt formed by bonding an amine group (-NHC ₂ H ₅ ) moiety of a triarylmethane dye to a carboxylic acid (-COOH) moiety of an aromatic hydroxycarboxylic acid is obtained. Compound. Moreover, the hydroxyl group (-OH) remains unrelated to the salt formation reaction.

Further, a salt-forming compound comprising Victoria Pure Blue BO (C.I. Basic Blue 7) and 3,5-di-t-butylsalicylic acid is a preferred dye.

The acid dye of the triarylmethane dye is preferably Edible Blue No. 101 (CI Acid Blue 1), Acid Pure Blue (CI Acid Blue 3), Lake Blue I (CI Acid Blue 5), Lake Blue II (CI Acid Blue) 7), Edible Blue No. 1 (CI Acid Blue 9), CI Acid Blue 22, CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 93, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104, CI Acid blue 109.

A salt forming compound of a triarylmethane acid dye and a quaternary ammonium compound can be synthesized by a previously known method.

As an example, after the triarylmethane acid dye is dissolved in water, the quaternary ammonium compound may be added and the salt formation treatment may be carried out while stirring. Here, a salt-forming compound obtained by bonding a sulfonic acid group (-SO ₃ H) moiety in a triarylmethane-based acid dye to an ammonium group (NH ₄ ⁺ ) moiety of a quaternary ammonium compound is obtained. As the quaternary ammonium compound, triethylbenzylammonium chloride or the like is preferably used.

In the present embodiment, a triarylmethane lake pigment can be used as the triarylmethane colorant.

The lake formation carried out in the pigmentation is a state in which a preservative salt is obtained from a soluble dye using a precipitating agent, and a chemical reaction is carried out, and the dye component is adsorbed on the precipitant particles.

The triaminotriphenylmethane dye is improved in weather resistance and heat resistance by performing lake formation, and is a stable and excellent color former.

Examples of the precipitating agent used for the lamination of the triarylmethane dye include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, katatan (Katanol), and A complex heteropoly acid (phosphoric acid, phosphomolybdic acid, phosphotungstic acid, samarium tungsten molybdate, samarium tungstic acid, samarium molybdate) called a complex acid. Among them, a lake pigment using a composite heteropoly acid is a preferred pigment because of its sharpness, large coloring power, and markedly improved light resistance.

Specific examples of the triarylmethane pigments include CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 9, CI Pigment Blue 10, CI Pigment Blue 14, CI Pigment Blue 62, CI Pigment Violet 3, CI Pigment Violet 27, CI Pigment. Purple 39 and so on.

More preferred triarylmethane-based pigments are specifically indicated below.

C.I. Pigment Blue 1.

The C.I. Basic Blue 26, C.I. Basic Blue 7 was subjected to lake formation with phosphotungstic acid.

C.I. Pigment Violet 3.

The C.I. Basic Violet 1 was subjected to lake formation with phosphotungstic acid.

C.I. Pigment Violet 39.

The C.I. Basic Violet 3 (crystal violet) was subjected to lake formation with phosphotungstic acid.

Among them, C.I. Pigment Blue 1 is preferably used.

Next, as an example of a preferred [IV] coloring agent, a barbituric azo dye and a pyridone azo have the following structures, for example. However, the barbituric azo dye and the pyridone azo used in the present embodiment are not limited to these structures.

In the formula (101), T ¹ and T ² each independently represent an oxygen atom or a sulfur atom.

R ¹⁰¹ to R ¹⁰⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having a carbon number of 7 to 20 or a fluorenyl group having a carbon number of 2 to 10 which may have a substituent.

R ¹⁰⁵ to R ¹¹² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, an aminesulfonyl group or an N-substituted aminesulfonate.醯基. The hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted by a halogen atom.

More specifically, in the formula (101), the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁰¹ to R ¹⁰⁴ may be linear, branched or cyclic. The number of carbon atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferably 2 to 8, more preferably 3 to 6. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and ethylhexyl group (2). -ethylhexyl or the like), cyclopentyl, cyclohexyl and cyclohexylalkyl.

Further, the hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 10 carbon atoms may be a hydroxyl group or an alkoxy group having a carbon number of 1 to 8 (preferably having a carbon number of 1 to 4) or a carbon number of 1 to 8. (preferably having a carbon number of 1 to 4) substituted by a thioalkoxy group. Examples of the substituted aliphatic hydrocarbon group include a hydroxyethyl group (2-hydroxyethyl group, etc.), an ethoxyethyl group (2-ethoxyethyl group, etc.), and an ethylhexyloxypropyl group (3-(2-). Ethylhexyloxypropyl, etc.) and methylthiopropyl (3-methylthiopropyl, etc.) and the like.

The aryl group having 6 to 20 carbon atoms in R ¹⁰¹ to R ¹⁰⁴ may be unsubstituted, and may have a substituent such as an aliphatic hydrocarbon group, an alkoxy group, a carboxyl group, a sulfo group or a group containing an ester bond. The carbon number of the aryl group is counted by the carbon number of the substituent, and is preferably 6 to 10. Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxy group. A phenyl group, a 2-sulfophenyl group, a 3-sulfophenyl group, a 4-sulfophenyl group, and an ethoxycarbonylphenyl group (4-(COOC ₂ H ₅ )Ph group (Ph group represents a phenyl group), etc.).

The alkyl moiety of the aralkyl group having 7 to 20 carbon atoms in R ¹⁰¹ to R ¹⁰⁴ may be linear, branched or cyclic. The carbon number of the aralkyl group is counted by the carbon number of the substituent, and is preferably 7 to 10. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

The fluorenyl group having 2 to 10 carbon atoms in R ¹⁰¹ to R ¹⁰⁴ may be unsubstituted or may be bonded to a substituent such as an aliphatic hydrocarbon group or an alkoxy group. The carbon number of the mercapto group is counted by the carbon number of the substituent, and the number thereof is preferably 2 to 10. Examples of the mercapto group include an ethenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁰⁵ to R ¹¹² may be the same as those in the case of R ¹⁰¹ to R ¹⁰⁴ . The hydrogen atom contained in the aliphatic hydrocarbon group of R ¹⁰⁵ to R ¹¹² may be substituted by a halogen atom, and the halogen atom is preferably a fluorine atom. Specific examples of the aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group and the like.

The number of carbon atoms of the alkoxy group having 1 to 8 carbon atoms in R ¹⁰⁵ to R ¹¹² is preferably 1 to 4. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a n-propoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group.

The N-substituted sulfonyl group in R ¹⁰⁵ to R ¹¹² is, for example, preferably an N-substituted monosulfonylsulfonyl group, which is represented by -SO ₂ NHR ¹⁴⁰ .

R ¹⁴⁰ contained in -SO ₂ NHR ¹⁴⁰ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having a carbon number of 7 to 20 or a fluorenyl group having a carbon number of 2 to 10 which may have a substituent.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁴⁰ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably 6 to 10.

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁴⁰ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, and third butyl group. Butyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1-methylhexyl, 1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl) Etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹⁴⁰ contained in -SO ₂ NHR ¹⁴⁰ may be substituted by an alkoxy group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms), for example, Examples thereof include a propoxypropyl group (3-(isopropoxy)propyl group, etc.).

The aryl group having 6 to 20 carbon atoms in R ¹⁴⁰ may be unsubstituted, and may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted by the carbon number of the substituent, and is preferably 6 to 10. Examples of the aryl group include a phenyl group, a hydroxyphenyl group (such as a 4-hydroxyphenyl group), a trifluoromethylphenyl group (such as a 4-trifluoromethylphenyl group), and the like.

The alkyl moiety of the aralkyl group having 7 to 20 carbon atoms in R ¹⁴⁰ may be either linear or branched. The aralkyl group has a carbon number of usually 7 to 20, preferably 7 to 10. Examples of the aralkyl group include a phenyl group such as a benzyl group, a phenylpropyl group (1-methyl-3-phenylpropyl group), or a phenyl group such as a phenylbutyl group (3-amino-1-phenylbutyl group). Base.

The fluorenyl group having 2 to 10 carbon atoms in R ¹⁴⁰ may be unsubstituted, and the hydrogen atom contained in the fluorenyl group may be substituted by an aliphatic hydrocarbon group or an alkoxy group. The carbon number of the mercapto group is counted by the carbon number of the substituent, and the number thereof is preferably 6 to 10. Examples of the mercapto group include an ethyl fluorenyl group, a benzamidine group, an o-tolylmethyl fluorenyl group, a m-tolylmethyl fluorenyl group, a p-tolyl fluorenyl group, and a methoxybenzyl fluorenyl group (p-methoxybenzyl fluorenyl group). Wait.

The pyridone azo which is an example of a preferable [IV] coloring agent has the following structures, for example.

In the formula (102), Z represents a halogen atom, may have a substituent having an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and having 1 or 2 selected from a hydroxyl group. a phenyl group having at least one substituent of a group consisting of a carboxyl group, an amine methyl sulfonyl group, a sulfo group, an amine sulfonyl group, and an N-substituted amine sulfonyl group, or having one to three selected from a halogen atom, An aliphatic hydrocarbon group having a carbon number of 1 to 12, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, an aminomethyl sulfonyl group, a sulfo group, an amine sulfonyl group, and an N-substituted amine. A naphthyl group having at least one substituent of the group consisting of sulfonyl groups.

R ¹²¹ represents a hydrogen atom, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.

R ¹²² represents a hydrogen atom, a cyano group, an amine carbenyl group, an N-substituted amine carbenyl group, an amine sulfonyl group or a sulfo group.

R ¹²³ represents a hydrogen atom, and may have a linear, branched or cyclic aliphatic hydrocarbon group having a carbon number of 1 to 10, or a aryl group having a carbon number of 6 to 30, which may have a substituent. An aralkyl group having 7 to 20 carbon atoms which may have a substituent, a heterocyclic group having 3 to 20 carbon atoms which may have a substituent, an amine carbenyl group, an N-substituted amine carbenyl group, or The alkoxycarbonyl group having 2 to 20 carbon atoms of the substituent may have an aryloxycarbonyl group having 7 to 30 carbon atoms as a substituent, or a fluorenyl group having 2 to 20 carbon atoms having a substituent. An aliphatic sulfonyl group having 1 to 30 carbon atoms which may have a substituent or an arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent.

More specifically, in the formula (102), the aliphatic hydrocarbon group having 1 to 12 carbon atoms in Z may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group includes the carbon number of all the substituents, and the number thereof is preferably from 1 to 12, more preferably from 2 to 11. Examples of the aliphatic hydrocarbon group include n-octyl group, methylhexyl group (1,5-dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl group, etc.), cyclooctyl group, and methylcyclohexyl group (2,2- Dimethylcyclohexyl or the like) and cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include an alkoxypropyl group (3-(2'-ethylhexyloxy)propyl group) and an 8-(carboxy)octyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms in Z include methoxy group and ethoxy group. Base, isopropoxy, n-propoxy, n-butoxy, isobutoxy, second butoxy and tert-butoxy.

Examples of the halogen atom in Z include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

The N-substituted sulfonyl group in Z is represented by -SO ₂ N(R ¹⁴¹ )R ¹⁴² . R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a substituent. The aralkyl group having a carbon number of 7 to 20 or a fluorenyl group having a carbon number of 2 to 15 which may have a substituent (wherein R ¹⁴¹ and R ¹⁴² are not simultaneously a hydrogen atom).

The aliphatic hydrocarbon group having 1 to 16 carbon atoms may be linear, branched or cyclic, and the aliphatic hydrocarbon group preferably has 6 to 16 carbon atoms.

The aliphatic hydrocarbon group having 1 to 16 carbon atoms in R ¹⁴¹ and R ¹⁴² may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably from 1 to 16, more preferably from 6 to 10. Examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, methylbutyl (1, 1, 3, 3). -tetramethylbutyl or the like), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2- Methylcyclohexyl or the like) and cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include a propoxypropyl group (3-(isopropoxy)propyl group, etc.), a 2-(carboxy)ethyl group, a 3-(carboxy)ethyl group, a 4-carboxyethyl group, and the like. .

The aryl group having 6 to 20 carbon atoms in R ¹⁴¹ and R ¹⁴² may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted by the carbon number of the substituent, and is preferably 6 to 20, and more preferably 6 to 10. Examples of the aryl group include a phenyl group, a carboxyphenyl group (2-carboxyphenyl group, a 2,4-dicarboxyphenyl group, etc.), a hydroxyphenyl group (4-hydroxyphenyl group, etc.), and a trifluoromethylphenyl group (4-three). Fluoromethylphenyl or the like) and methoxyphenyl (4-methoxyphenyl) and the like.

The alkyl moiety of the aralkyl group having 7 to 20 carbon atoms in R ¹⁴¹ and R ¹⁴² may be either linear or branched. The carbon number of the aralkyl group is preferably from 7 to 20, and more preferably from 7 to 10. Examples of the aralkyl group include a benzyl group, a phenylethyl group (2-phenylethyl group, a 2-(4-hydroxyphenyl)ethyl group, etc.), a phenylethyl group (2-phenylethyl group, etc.), and a phenyl group. A phenylalkyl group such as a propyl group (1-methyl-3-phenylpropyl group or the like) or a phenylbutyl group (3-amino-1-phenylbutyl group or the like).

The fluorenyl group having 2 to 15 carbon atoms in R ¹⁴¹ and R ¹⁴² may be unsubstituted, and may have a substituent such as an aliphatic hydrocarbon group, an alkoxy group or a carboxyl group. The carbon number of the mercapto group is counted by the carbon number of the substituent, and the number thereof is preferably 2 to 15, more preferably 6 to 10. Examples of the mercapto group include an ethyl fluorenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.), a carboxyethyl group, a 2-carboxypropyl group, and a 3-carboxypropene group. A group, a 2-carboxybutanyl group, a 3-carboxybutanyl group, a 4-carboxybutanyl group, and the like.

R ¹²¹ represents a hydrogen atom, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.

The carbon number of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹²¹ does not include the carbon number of the substituent. The carbon number is preferably 2 to 8, more preferably 3 to 6. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group.

R ¹²² represents a hydrogen atom, a cyano group, an amine carbenyl group or an N-substituted amine carbenyl group, an amine sulfonyl group or a sulfo group.

The N-substituted aminemethanyl group in R ¹²² may be -CON(R ¹⁴³ )R ¹⁴⁴ . R ¹⁴³ and R ¹⁴⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a substituent. An aralkyl group having 7 to 20 carbon atoms or a fluorenyl group having 2 to 10 carbon atoms which may have a substituent.

The description and specific examples of the aliphatic hydrocarbon group, the aryl group, the aralkyl group and the fluorenyl group of R ¹⁴³ and R ¹⁴⁴ are the same as those of the above R ¹⁴¹ and R ¹⁴² . Among them, the fluorenyl group may have a halogen atom. Examples of the thiol group which may have a halogen atom include a bromobenzylidene group (p-bromobenzylidene group, etc.).

R ¹²³ represents a hydrogen atom, and may have a linear, branched or cyclic aliphatic hydrocarbon group having a carbon number of 1 to 10, or a aryl group having a carbon number of 6 to 30, which may have a substituent. An aralkyl group having 7 to 20 carbon atoms which may have a substituent, a heterocyclic group having 3 to 20 carbon atoms which may have a substituent, an amine carbenyl group, an N-substituted amine carbenyl group, or The alkoxycarbonyl group having 2 to 20 carbon atoms of the substituent may have an aryloxycarbonyl group having 7 to 30 carbon atoms as a substituent, or a fluorenyl group having 2 to 20 carbon atoms having a substituent. An aliphatic sulfonyl group having 1 to 30 carbon atoms which may have a substituent or an arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent.

The aliphatic hydrocarbon group in R ¹²³ may be the same one as the aliphatic hydrocarbon group in the above R ¹²¹ .

The aryl group in R ¹²³ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 16 carbon atoms. Specific examples of the aryl group include a phenyl group, a 4-nitrophenyl group, a 2-nitrophenyl group, a 2-chlorophenyl group, a 2,4-dichlorophenyl group, a 2,4-dimethylphenyl group, and 2 -methylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 2-methoxycarbonyl-4-nitrophenyl, and the like.

The aralkyl group in R ¹²³ may be either linear or branched, and the number of carbon atoms is preferably 7 to 10. Specific examples of the aralkyl group include benzyl, phenylpropyl (1-methyl-3-phenylpropyl, etc.), and phenylbutyl (3-amino-1-phenylbutyl) and the like. Alkyl group.

The heterocyclic group having 3 to 20 carbon atoms in R ¹²³ may be saturated or unsaturated, and the carbon number is preferably 3 to 20, and more preferably 5 to 15. Specific examples of the heterocyclic group include pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazolyl, thiazolyl, benzothiazolyl, oxazolyl, and 1,2,4-. Thiadiazolyl and the like. Further, it may further have a substituent.

The N-substituted amine indenyl group in R ^{123 is the same} as the N-substituted amine indenyl group described for R ¹²² .

The alkoxycarbonyl group in R ¹²³ may be unsubstituted or may have a substituent or may be cyclic. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 16, and still more preferably 2 to 10. The alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group or a butoxycarbonyl group.

The aryloxycarbonyl group in R ¹²³ may be unsubstituted or have a substituent, and the number of carbon atoms is preferably from 7 to 30, more preferably from 7 to 20, still more preferably from 7 to 16. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.

The mercapto group in R ¹²³ may be an aliphatic carbonyl group or an arylcarbonyl group, and may be either saturated or unsaturated, may be cyclic, or may further have a substituent. The carbon number is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10. Examples of the fluorenyl group include an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isopentenyl group, a pentamidine group, a benzamidine group and the like.

The aliphatic sulfonyl group in R ¹²³ may be saturated or unsaturated, or may be cyclic. The carbon number is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 16. Examples of the aliphatic sulfonyl group include a methylsulfonyl group, a butyl sulfonyl group, a methoxymethylsulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.

The arylsulfonyl group in R ¹²³ may have a substituent, and the number of carbon atoms is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 18. Examples of the arylsulfonyl group include a benzenesulfonyl group and a toluenesulfonyl group.

Next, the diketopyrrolopyrroles and phthalocyanines which are examples of preferred [IV] colorants have the following structures, for example. However, the diketopyrrolopyrrole and phthalocyanine coloring agents used in the present embodiment are not limited thereto.

In the formula (103), Y represents an oxygen atom or a sulfur atom. R ¹³¹ and R ¹³² may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an amine carbaryl group, an alkylamine carbaryl group, an arylamine. Mercapto, or alkoxycarbonyl. R ¹³³ and R ¹³⁴ may be the same or different and each represents an alkyl group, a cycloalkyl group, an aralkyl group, or a carbocyclic or heterocyclic aromatic residue.

More specifically, in the formula (103), the alkyl groups in R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ may or may not be branched, and preferably have from 1 to 18, more preferably 1 From 12 to 12, more preferably from 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an isopropyl group, a second butyl group, a third butyl group, a third pentyl group, an octyl group, a decyl group, a dodecyl group or an octadecyl group.

The cycloalkyl group in R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ preferably has 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. . The alkenyl group in R ¹³¹ and R ¹³² preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and specific examples thereof include a vinyl group and an allyl group. The alkynyl group in R ¹³¹ and R ¹³² preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and specific examples thereof include an ethynyl group. The aryl group in R ¹³¹ and R ¹³² preferably has 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The alkyl group of the alkylaminecarbamyl group in R ¹³¹ and R ¹³² may be the same alkyl group as the above alkyl group. The aryl group of the arylaminecarbamyl group in R ¹³¹ and R ¹³² may be the same aryl group as the above aryl group. Examples of the alkoxy group of the alkoxycarbonyl group in R ¹³¹ and R ¹³² include alkoxy groups having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group.

In the formula (103), when R ¹³¹ , R ¹³² , R ¹³³ and R ¹³⁴ represent an aralkyl group, it is particularly preferred to contain a monocyclic to tricyclic formula, more preferably a monocyclic or bicyclic aryl residue. base. Specific examples thereof include a benzyl group and a phenylethyl group. In the formula (103), when R ¹³³ and R ¹³⁴ represent a carbocyclic aromatic residue, a monocyclic to tetracyclic ring, particularly a monocyclic or bicyclic residue, that is, Phenyl, biphenyl or naphthyl.

In the formula (103), when R ¹³³ and R ¹³⁴ represent a heterocyclic aromatic residue, a monocyclic to tricyclic residue is suitable. These groups may be pure heterocyclic rings, and may also contain one heterocyclic ring and one or more condensed benzene rings. Specific examples thereof include a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, a coumarin group, a benzofuranyl group, a benzimidazolyl group or a benzo group. Oxazolyl and the like.

In the formula (103), R ¹³¹ and R ^{132 are} preferably a hydrogen atom. Further, R ¹³³ and R ¹³⁴ are each preferably an alkyl group having 1 to 4 carbon atoms, a dialkylamino group, a haloalkyl group or a phenyl group which may have a halogen atom as a substituent. Next, a phthalocyanine coloring agent which is an example of a preferred [IV] coloring agent is preferably a zinc halide phthalocyanine coloring agent, and has the following structure, for example.

In the formula (104), X ¹ to X ¹⁶ each independently represent a hydrogen atom, a chlorine atom or a bromine atom.

More specifically, in the formula (104), the number of the substituents represented by X ¹ to X ¹⁶ is preferably from 0 to 6 in the chlorine atom, from 10 to 16 in the bromine atom, and the chlorine atom and the bromine. The sum of atoms is 10 to 16; more preferably 0 to 3 chlorine atoms, 13 to 16 bromine atoms, and 13 to 16 chlorine atoms and bromine atoms; further more preferably The chlorine atom is 1 to 3, the bromine atom is 13 to 15, and the sum of the chlorine atom and the bromine atom is 14 to 16.

Next, examples of the inorganic pigment which can be used in the [IV] coloring agent include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, chrome yellow, zinc yellow, and iron oxide (red iron oxide (III)). , cadmium red, ultramarine blue, Prussian blue, chrome oxide green, cobalt green, brown soil, titanium black, synthetic iron black, carbon black and so on.

Next, the content of the [IV] coloring agent contained in the colored composition will be described.

The content of the [IV] coloring agent is preferably 1 part by mass to 400 parts by mass, more preferably 5 parts by mass to 350 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. When the content of the [IV] coloring agent is in the above range, the alkali developability of the coloring composition, the heat resistance of the pixel, the solvent resistance, and the coloring pattern and the color filter can be achieved with good balance at a high level. High brightness or high contrast.

<[V] compound>

Coloring group used in the manufacture of the color filter of the present embodiment The product may contain a [V] compound. The [V] compound is a compound that functions as a hardener. Therefore, it is sometimes referred to as a [V] hardener.

The compound [V] is a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, a phosphonium salt, a guanamine compound, a thiol compound. At least one compound of the group consisting of a blocked isocyanate compound and a compound containing an imidazole ring. The colored composition can achieve low temperature hardening of the colored pattern by containing a compound of [V] selected from the group of the specific compounds. Moreover, the storage stability of the colored composition can also be improved. Hereinafter, each compound will be described in detail.

[Compounds represented by formula (1) and formula (2)]

The compound [V] is preferably at least one compound selected from the group consisting of the compounds represented by the above formulas (1) and (2). As the [V] compound, low-temperature hardening of the colored pattern can be achieved by selecting the above specific compound having an amine group and an electron-deficient group. Moreover, the storage stability of the colored composition can also be improved. The voltage holding ratio of the liquid crystal display element using the obtained color filter can be further improved.

In the above formula (1), R ¹ to R ⁶ each independently represent a hydrogen atom, an electron withdrawing group or an amine group. Wherein at least one of R ¹ to R ⁶ is an electron withdrawing group, and at least one of R ¹ to R ⁶ is an amine group, and all or a part of the hydrogen atom of the amine group may be a carbon number of 1~ 6 alkyl substitution.

In the above formula (2), R ⁷ to R ¹⁶ each independently represent a hydrogen atom, an electron withdrawing group or an amine group. Among them, at least one of R ⁷ to R ¹⁶ is an amine group. Further, all or a part of the hydrogen atom of the amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. Further, in the case of the [V] compound used in the coloring composition, the amine group may be substituted with an alkyl group having 1 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. Here, all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

Examples of the electron withdrawing group represented by the above R ¹ to R ¹⁶ include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, a decyl group, an alkylsulfonyl group, an alkoxysulfonyl group, and a dicyano group. Vinyl, tricyanovinyl, sulfonyl, and the like. Preferred among these groups are a nitro group, a trifluoromethyl group, and an alkoxysulfonyl group. The group represented by A is preferably a sulfonyl group or a methylene group which may be substituted by a fluoroalkyl group.

The compound represented by the above formula (1) and formula (2) is preferably 2,2-bis(4-aminophenyl)hexafluoropropane or 2,3-bis(4-aminophenyl)butane. Nitrile, 4,4'-diaminobenzophenone, phenyl 4,4'-diaminobenzoate, 4,4'-diaminodiphenylanthracene, 1,4-diamino-2 -Chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1,4-diamine Benzyl-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2'-dichlorobenzidine , 2,2'-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis(trifluoromethyl)benzidine, 3-amine Ethyl benzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline, more preferably Is 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylanthracene, 2,2'-bis(trifluoromethyl)benzidine, 3-amino Ethyl benzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline.

The compounds represented by the above formulas (1) and (2) may be used singly or in combination of two or more. The content ratio of the compound represented by the above formula (1) and the formula (2) is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass per 100 parts by mass of the [I] alkali-soluble resin. Parts by mass. By setting the content ratio of the compound represented by the above formulas (1) and (2) to the above range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[Tribasic amine compound]

If a general primary amine compound or a secondary amine compound having high reactivity is allowed to coexist with the epoxy compound, in the preservation of the composition solution, The nucleophilic attack of the amine on the epoxy group undergoes a hardening reaction, which may impair the quality of the product. However, in the case of using a tertiary amine, storage stability is improved because the reactivity is relatively low or coexistence with the epoxy compound in the composition portion.

As the tertiary amine compound, at least one selected from the group consisting of compounds represented by the following formula (5) can be used.

In the above formula (5), R ²⁴ to R ²⁶ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. Wherein R ²⁴ and R ²⁵ may be bonded to each other to form a cyclic structure together with the nitrogen atoms bonded thereto. Some or all of the hydrogen atoms of the above alkyl group, aryl group and aralkyl group may be substituted.

Examples of the alkyl group having 1 to 20 carbon atoms represented by the above R ²⁴ to R ²⁶ include a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and a octyl group. Base, fluorenyl, fluorenyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl , eicosyl and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by the above R ²⁴ to R ²⁶ include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by the above R ²⁴ to R ²⁶ include a benzyl group and a phenethyl group.

Examples of the tertiary amine compound include N,N-dimethylbenzylamine, triphenylamine, tributylamine, trioctylamine, tris(dodecyl)amine, dibutylbenzylamine, and trisole. Naphthylamine, N-ethyl-N-methylaniline, N,N-diethylaniline, N-phenyl-N-methylaniline, N,N-dimethyl-p-toluidine, N,N - dimethyl-4-bromoaniline, N,N-dimethyl-4-methoxyaniline, N-phenyl acridine, N-(4-methoxyphenyl)acridine, N-phenyl -1,2,3,4-tetrahydroisoquinoline, 6-benzyloxy-N-phenyl-7-methoxy-1,2,3,4-tetrahydroisoquinoline, N,N '-Dimethylpyridazine, N,N-dimethylcyclohexylamine, 2-dimethylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, and the like.

Among these tertiary amine compounds, trioctylamine, N,N-diethylaniline, 2-dimethylaminomethylphenol and the like are preferable. The tertiary amine compound may be used singly or in combination of two or more. The content ratio of the tertiary amine compound in the coloring composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the tertiary amine compound to the above specific range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[amine salt and strontium salt]

As the amine salt and the phosphonium salt, at least one selected from the group consisting of compounds represented by the following formula (6) can be used.

[Chemistry 16]

In the above formula (6), A ¹ is a nitrogen atom or a phosphorus atom. R ²⁷ to R ³⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. Among them, some or all of the hydrogen atoms of the groups may be substituted. Q ^- is a monovalent anion.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ²⁷ to R ³⁰ include a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , mercapto, fluorenyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, Eicosyl and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by the above R ²⁷ to R ³⁰ include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by the above R ²⁷ to R ³⁰ include a benzyl group and a phenethyl group.

Examples of the monovalent anion represented by Q ^- above include a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a nitrate ion, a nitrite ion, a hypochlorite ion, a chlorite ion, and a chlorate ion. Perchlorate ion, permanganate ion, hydrogencarbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carboxylate ion, sulfonate ion, phenoxy ion, tetrafluoroborate ion , tetraaryl borate ion, hexafluoroantimonate ion, and the like.

When A ¹ is a nitrogen atom, that is, the ammonium salt may, for example, be tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride or octyltrimethyl chloride. Ammonium, mercaptotrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethyl Ammonium chloride, cetyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, benzalkonium bromide, dimercaptodimethyl chloride Ammonium, distearyl dimethyl ammonium chloride.

When A ¹ is a phosphorus atom, that is, a phosphonium salt is exemplified by tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Tetrakis(p-tolyl)borate, tetraphenylphosphonium. Tetrakis(p-ethylphenyl)borate, tetraphenylphosphonium. Tetrakis(p-methoxyphenyl)borate, tetraphenylphosphonium. Tetrakis(p-ethoxyphenyl)borate, tetraphenylphosphonium. Tetrakis(p-tert-butoxyphenyl)borate, tetraphenylphosphonium. Tetra(m-tolyl)borate, tetraphenylphosphonium. Tetra(m-methoxyphenyl)borate, tris(p-tolyl)phenylhydrazine. Tetrakis(p-tolyl)borate, tetra (p-tolyl) oxime. Tetrakis(p-tolyl)borate, tris(p-methoxyphenyl)phenylhydrazine. Tetra(p-tolyl)borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltriphenylphosphonium thiocyanate, p-tolyltriphenylsulfonium thiocyanate Salt and so on.

Among these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferred. The amine salt and the phosphonium salt may be used singly or in combination of two or more. The content ratio of the amine salt and the cerium salt in the coloring composition is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the amine salt and the onium salt to the above specific range, it is possible to achieve a higher level The storage stability of the colored composition is low temperature hardening.

[脒盐]

As the onium salt, at least one selected from the group consisting of salts of the compounds represented by the following formula (7) can be used.

In the above formula (7), m is an integer of 2-6. Among them, a part or all of the hydrogen atoms of the alkylene group may be substituted by an organic group. Further, the above alkylene group means both an alkylene group in the tetrahydropyrimidine ring and an alkylene group represented by (CH ₂ ) _m in the formula (7).

Examples of the organic group which may be a substituent of the alkylene group include a methyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a n-butyl group, a t-butyl group and a n-hexyl group. ; hydroxymethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 3-hydroxy-tert-butyl, 6-hydroxyhexyl, etc. a hydroxyalkyl group having 1 to 6 carbon atoms; dimethylamino group, methyl ethylamino group, diethylamino group, diisopropyl group A dialkylamino group having 2 to 12 carbon atoms such as an amine group, a dibutylamino group, a tert-butylmethylamino group or a di-n-hexylamino group.

Examples of the compound represented by the above formula (7) include 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN) and 1,5-diazabicyclo[4,4,0]. -decene-5,1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo[5,4 , 0]-undecene-7,5-dibutylamino-1,8-diazabicyclo[5,4,0]-undecene-7 and the like. Among these compounds, DBN and DBU are preferred.

Examples of the acid represented by the above formula (7) for forming a salt include an organic acid and an inorganic acid.

Examples of the organic acid include a carboxylic acid, a monoalkyl carbonate, an aromatic hydroxy compound, and a sulfonic acid.

Among these acids, a carboxylic acid, an aromatic hydroxy compound, a sulfonic acid is preferred, a saturated fatty acid, an aromatic hydroxy compound, a sulfonic acid is more preferred, a sulfonic acid as a strong acid is particularly preferred, and toluenesulfonic acid, methanesulfonic acid, and octylbenzene are most preferred. Sulfonic acid. The onium salt is preferably a salt of DBU with toluenesulfonic acid, a salt of DBU with octylbenzenesulfonic acid, a salt of DBN with toluenesulfonic acid, or a salt of DBN with octylbenzenesulfonic acid.

The onium salts may be used singly or in combination of two or more. The content ratio of the cerium salt in the coloring composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the onium salt to the above specific range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[guanamine compound]

As the guanamine compound, at least one selected from the group consisting of compounds having the guanamine group represented by the following formula (8) to the following formula (10) can be used.

In the above formula (8), R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group or a 2-pyridyl group. Here, the alkyl group having 1 to 12 carbon atoms, a phenyl group and a naphthyl group may be substituted by an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group or an ethyl fluorenyl group.

In the above formula (9), R ³³ and R ³⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group. A ² is a methylene group, an alkylene group having a carbon number of 2 to 12, a phenylene, a naphthene, or an ethylene support. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthene support may be substituted by an alkyl group having 1 to 6 carbon atoms or a halogen atom.

In the above formula (10), R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a cyclohexyl group. A ³ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene, a naphthene, or an ethylene support. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthene support may be substituted by an alkyl group having 1 to 6 carbon atoms or a halogen atom.

The guanamine compound represented by the above formula (8) is a compound having one guanamine bond in the molecule. Specific examples thereof include acetamide, N-methylacetamide, N-ethylacetamide, o-amine methyl benzoic acid, acrylamide, benzamide, naphthylamine, and nicotinamide. , isoniazid, etc.

Among these compounds, acetamide, N-methylacetamide, and orthoamine A are preferable from the viewpoints of improvement in storage stability at room temperature, heat resistance of the obtained coloring pattern, and the like. Benzoic acid.

The compound represented by the above formula (9) and formula (10) is a compound having two indoleamine bonds in the molecule. Specific examples thereof include o-xylyleneamine, m-xylyleneamine, hexamethyleneamine, p-xylyleneamine, malonamide, succinimide, and N,N'-diethylhydrazine. -p-phenylenediamine, N,N'-diethylhydrazine- Hexamethylenediamine, N,N'-diethylindenyl-dodecylmethylenediamine, and the like.

Among these compounds, m-xylyleneamine, hexamethylenediamine, N,N'-diethylhydrazine-p-phenylenediamine, N are preferable from the viewpoint of achieving high stability in both storage stability and low-temperature hardening. , N'-diethenyl-hexanediamine.

The guanamine compound may be used singly or in combination of two or more. The content ratio of the guanamine compound in the coloring composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the guanamine compound to the above specific range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[thiol compound]

The thiol compound is a compound having two or more mercapto groups in one molecule. The thiol compound is not particularly limited as long as it has two or more thiol groups in one molecule, and at least one selected from the group consisting of compounds represented by the following formula (11) can be used.

In the formula (11), R ³⁷ is a methylene group and an alkylene group having 2 to 10 carbon atoms. Among them, some or all of the hydrogen atoms of the groups may be substituted with an alkyl group. Y ¹ is a single bond, -CO- or O-CO- ^* . Among them, the key with ^* is connected with the R ³⁷ key. n is an integer from 2 to 10. A ⁴ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether linkages, or a group represented by the following formula (12) when n is 3.

In the above formula (12), R ³⁸ to R ⁴⁰ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms. " ^* " indicates the key.

As the compound represented by the above formula (11), an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol can be typically used. Examples of the mercaptocarboxylic acid constituting the ester compound include mercaptoacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercaptovaleric acid, and the like. Further, examples of the polyhydric alcohol constituting the ester compound include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, tetraethylene glycol, dipentaerythritol, and 1,4-butanediol.

The compound represented by the above formula (11) is preferably trimethylolpropane tris(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, tetraethylene glycol bis(3-mercaptopropionate) ester. Dipentaerythritol hexa(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(mercaptoacetic acid) ester, 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol Tetrakis(3-mercaptovalerate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- Triketone.

As the compound having two or more mercapto groups in one molecule of the thiol compound, a compound represented by the following formulas (13) to (15) can also be used.

In the above formula (13), R ⁴¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms. R ⁴² is a methylene group or a linear or branched alkyl group having 2 to 6 carbon atoms. k is an integer from 1 to 20.

In the above formula (14), R ⁴³ to R ⁴⁶ each independently represent a hydrogen atom, a hydroxyl group or a group represented by the following formula (15). However, at least one of R ⁴³ to R ⁴⁶ is a group represented by the following formula (15).

In the above formula (15), R ⁴⁷ is a methylene group or a linear or branched alkyl group having 2 to 6 carbon atoms.

The thiol compound may be used singly or in combination of two or more. The content ratio of the thiol compound in the coloring composition is preferably 1 part by mass to 20 parts by mass, more preferably 5 parts by mass to 15 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the thiol compound to the above specific range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[Block isocyanate compound]

The block polyisocyanate compound is a compound which reacts with an active hydrogen group-containing compound (blocking agent) and is inert at normal temperature, and has a property that if it is heated, the blocking agent dissociates and regenerates the isocyanate. base. The colored composition contains a block polyisocyanate, and the isocyanate-hydroxyl crosslinking reaction is carried out as an effective crosslinking agent, so that the storage stability and the low-temperature curing of the colored composition can be achieved at a high level. The blocked polyisocyanate compound can be obtained by a known reaction of a polyisocyanate derived from an aliphatic or alicyclic diisocyanate with a compound (blocker) having an active hydrogen.

Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, and 2 , 4,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatemethyl)cyclohexane Alkane, 4,4-dicyclohexylmethane diisocyanate, lower Borneene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene isocyanate, 1,4-tetramethylene Isocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl diisocyanate, and the like.

For example, Duranate (registered trademark) TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, and the isocyanate group are blocked by hydrazine of methyl ethyl ketone. MF-B80M (above, manufactured by Asahi Kasei Industrial Co., Ltd.); those which are blocked by an active methylene group to beocyanate groups include Duranate (registered trademark) MF-K60X (Asahi Kasei Kogyo Co., Ltd.); Examples of the block of the isocyanate compound include Karenz (registered trademark) MOI-BP and Karenz (registered trademark) MOI-BM (all manufactured by Showa Denko Co., Ltd.). Among these commercial products, when using Duranat (registered trademark) E402-B80T or MF-K60X, high flexibility is exhibited, and by using a mixture with other compounds, the hardness can be freely controlled. It is therefore preferably used.

Examples of the polyisocyanate derived from the diisocyanate include a hetero-cyanate type polyisocyanate, a biuret type polyisocyanate, a urethane type polyisocyanate, and an allophanate type polyisocyanate. From the viewpoint of hardenability, a isocyanurate type polyisocyanate is preferred.

Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, thiol compounds, guanamine compounds, and sulfimines. a compound, an imidazole compound, a pyrazole compound, a urea compound, an anthraquinone compound, an amine compound, an imine compound, a pyridine compound, or the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol, and the like; phenolic compounds; Examples thereof include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester; and examples of the active methylene-based compound include malonic acid Methyl ester, diethyl malonate, ethyl acetonitrile acetate, ethyl acetate, ethyl acetate, etc.; examples of the mercaptan compound include butyl mercaptan, dodecyl mercaptan, etc.; Examples of the compound include acetanilide, acetamide, ε-caprolactam, δ-valeroinamide, γ-butylidene, and the like; and the quinone imine compound may, for example, be a succinimide or malazone. Examples of the imidazole compound include imidazole and 2-methylimidazole; and pyrazole compounds include, for example, 3-methylpyrazole, 3,5-dimethylpyrazole, and 3,5-ethylpyrazole. Examples of the urea compound include urea, thiourea, and ethyl urea; and examples of the hydrazine compound include formaldehyde hydrazine and acetaldehyde. , Acetone oxime, butanone oxime, cyclohexanone oxime and the like; amines include compounds such as diphenylamine, aniline, and carbazole; imine compounds include, for example, extending ethyl, polyethyleneimine Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

The block polyisocyanate compounds may be used singly or in combination of two or more.

The content ratio of the block polyisocyanate compound in the coloring composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. When the content ratio of the block polyisocyanate compound is in the above range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

[Compound containing imidazole ring]

As the compound containing an imidazole ring, at least one selected from the group consisting of compounds represented by the following formula (16) can be used.

In the above formula (16), each of A ⁵ , A ⁶ , A ⁷ and R ^{48 is} independently a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Further, A ⁶ and A ⁷ may be bonded to each other to form a ring.

Examples of the linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms represented by A ⁵ , A ⁶ , A ⁷ and R ⁴⁸ include methyl group, ethyl group, n-propyl group and isopropyl group. n-Butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-xyl Alkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl An alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms such as cyclobutyl, cyclopentyl or cyclohexyl; phenyl, tolylmethyl, benzyl, methylbenzyl, and An aryl group having 6 to 20 carbon atoms such as tolyl, mesityl, naphthyl or anthracenyl; norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, A cross-linked alicyclic hydrocarbon group having a carbon number of 6 to 20 such as ethyladamantyl or butanylalkyl.

The above hydrocarbon group may also be substituted, and specific examples of the substituent include a hydroxyl group; a carboxyl group; a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and 3- Hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. hydroxyalkyl group having a carbon number of 1 to 4; methoxy, ethoxy, n-propoxy Alkoxy group having a carbon number of 1 to 4, such as a group, an isopropoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a third butoxy group; a cyano group; a cyano group; a cyano group having a carbon number of 2 to 5 such as a methyl group, a 2-cyanoethyl group, a 3-cyanopropyl group or a 4-cyanobutyl group; a methoxycarbonyl group, an ethoxycarbonyl group, and a third butoxy group Alkoxycarbonyl group having a carbon number of 2 to 5 such as a carbonyl group; alkoxy group having a carbon number of 3 to 6 such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group or a third butoxycarbonylmethoxy group; a carbonyl alkoxy group; a halogen atom such as fluorine or chlorine; a fluoroalkyl group such as a fluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group; and the like.

The ring formed by linking A ⁶ and A ^{7 to} each other is preferably an aromatic ring or a saturated or unsaturated nitrogen-containing hetero ring having 2 to 20 carbon atoms. A compound represented by the following formula (17) is exemplified as the imidazole ring-containing compound in the case where the ring formed by the combination of A ⁶ and A ⁷ is a benzene ring.

In the above formula (17), R ⁴⁸ and A ^{5 are} synonymous with the above formula (16). R ⁴⁹ to R ⁵² are each independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Further, examples of the hydrocarbon group represented by R ⁴⁹ to R ⁵² include the same groups as those of the hydrocarbon group in the above formula (16).

The imidazole ring-containing compound is preferably 2-phenylbenzimidazole, 2-methylimidazole or 2-methylbenzimidazole. The compound containing an imidazole ring may be used singly or in combination of two or more. The content ratio of the imidazole ring-containing compound is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [I] alkali-soluble resin. By setting the content ratio of the imidazole ring-containing compound to the above specific range, it is possible to achieve both the storage stability of the colored composition and the low-temperature curing at a higher level.

<Other optional ingredients>

In addition to the above [I] alkali-soluble resin, [II] polymerizable compound, [III] polymerization initiator, [IV] colorant, and [V], the coloring composition used in the production of the color filter of the present embodiment. In addition to the compound (hardener), other optional components such as a surfactant, a storage stabilizer, a bonding aid, and a heat resistance promoter may be contained as needed within a range that does not impair the effects of the present invention. These optional components may be used singly or in combination of two or more. The components are detailed below.

[Surfactant]

The surfactant can be used to further improve the coating film formability of the colored composition. Examples of the surfactant include a fluorine-based surfactant, an anthrone-based surfactant, and other surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine alkyl group at at least any part of the terminal, the main chain and the side chain.

Commercial products of the fluorine-based surfactant include, for example, Ftergent (registered trademark) FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, and Ftergent FT-300. Ftergent FT-310, Ftergent FT-400S, Ftergent (registered trademark) FTX-218, Ftergent FTX-251 (above manufactured by Neos), and the like.

Commercial products of an anthrone-based surfactant include, for example, Toray Silicone DC3PA, Toray Silicone DC7PA, Toray Silicone SH11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH-190, Toray Silicone SH-193, Toray Silicone SZ-6032, Toray Silicone SF-8428, Toray Silicone DC-57, Toray Silicone DC-190 (above by Dow Corning Toray Silicone Co., Ltd.) Manufacturing).

The amount of the surfactant to be used is preferably 1.0 part by mass or less, and more preferably 0.7 part by mass or less based on 100 parts by mass of the [I] alkali-soluble resin. When the amount of the surfactant used exceeds 1.0 part by mass, film unevenness is likely to occur.

[storage stabilizer]

Examples of the storage stabilizer include sulfur, hydrazines, hydroquinones, polyoxygen compounds, amines, nitronitroso compounds, and the like, and more specifically, 4-methoxyphenol and N-nitroso- N-phenylhydroxylamine aluminum and the like.

The amount of use as the storage stabilizer is preferably 3.0 parts by mass or less, and more preferably 1.0 parts by mass or less, based on 100 parts by mass of the [I] alkali-soluble resin. When the amount of the stabilizer to be added exceeds 3.0 parts by mass, the sensitivity may be lowered to deteriorate the pattern shape.

[Next auxiliaries]

The additive can then be used to further improve the adhesion of the resulting colored pattern and color filter to the substrate. Next, the auxiliary agent is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl fluorenyl group, a vinyl group, an isocyanate group or an oxiranyl group, and examples thereof include trimethoxydecyl benzoic acid and γ- Methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxy propyl trimethyl Oxydecane, β-(3,4- Epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The amount of the auxiliary agent to be used is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, based on 100 parts by mass of the [I] alkali-soluble resin. When the amount of the auxiliary agent used exceeds 20 parts by mass, the development residue tends to be likely to occur.

<Modulation method of coloring composition>

The coloring composition used in the production of the color filter of the present embodiment can be obtained by using [I] an alkali-soluble resin, [II] a polymerizable compound, [III] a polymerization initiator, [IV] a colorant, [V]. The compound (hardener) and other optional components added as needed are uniformly mixed and prepared. The coloring composition is preferably dissolved in a suitable solvent and used in the form of a solution.

As a solvent used for preparation of a coloring composition, a solvent which can uniformly dissolve an essential component and an arbitrary component and does not react with each component is used. Examples of such a solvent include the same solvents as those exemplified above as the solvent which can be used for producing the [I] alkali-soluble resin.

Among these solvents, from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, and the like, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol single positive are exemplified. Propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate Ester, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc.; diethylene glycol dimethyl ether, diethyl Other ethers such as glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; butanone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentane- Ketones such as 2-keto) and 4-hydroxy-4-methylhexan-2-one; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diethyl Diacetate such as acid ester; alkyl lactate such as methyl lactate or ethyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate , isoamyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, acid Amyl ester, isoamyl acetate, n-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxyl Methyl propionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-hydroxy-2-methyl Other esters such as ethyl propyl propionate, methyl 2-hydroxy-3-methylbutyrate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N,N-dimethyl B Amidoxime, such as guanamine.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are preferable from the viewpoints of solubility, pigment dispersibility, and coating properties. Ethyl acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butane Alcohol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, Isopropyl butyrate, n-butyl butyrate, ethyl pyruvate. The solvent may be used singly or in combination of two or more.

In addition, together with the above solvent, benzyl ethyl ether, di-n-hexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, benzene may also be used together. A high boiling point solvent such as ethyl formate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate. These high boiling point solvents may be used singly or in combination of two or more.

The content of the solvent is not limited, and the total concentration of each component of the solvent in which the coloring composition is removed is preferably from 5% by mass to 50% by mass, more preferably from the viewpoint of the coating property and stability of the obtained colored composition. An amount of 10% by mass to 40% by mass. When the coloring composition is prepared in a solution state, the solid content concentration (component other than the solvent in the composition solution) can be set to an arbitrary concentration depending on the purpose of use, the value of the desired film thickness, and the like. The solid concentration can be set, for example, to 5 mass% to 50 mass. %. A more preferable solid content concentration differs depending on a method of forming a coating film on a substrate, which will be described later. The composition solution prepared in this manner can be filtered using a micropore filter having a pore diameter of about 0.5 μm, and then used.

The coloring composition of the above components and the preparation method can be cured by low temperature to form a colored pattern. Specifically, even at a curing temperature of 200 ° C or lower and further at a curing temperature of 180 ° C or lower, a colored pattern having good reliability such as solvent resistance can be obtained. Further, the color filter of the present embodiment can be provided by low-temperature curing.

Next, the color filter of this embodiment includes a colored pattern and a protective film provided on the colored pattern. This protective film is formed on the colored pattern using the first radiation-sensitive resin composition.

In the following, the first radiation sensitive resin composition of the present embodiment used for forming the protective film of the color filter of the present embodiment will be described.

<1st sense radiation linear resin composition>

The first radiation sensitive resin composition used for forming the protective film of the color filter of the present embodiment contains the following compounds: [A] a siloxane polymer, [B] a radical polymerization initiator, and [C] Organic solvent. Further, a [D] ethylenically unsaturated compound may be contained as a suitable component. Further, an [E] acid generator or a base generator may be contained as a suitable component. Further, other optional components such as a surfactant may be contained within a range that does not impair the effects of the present invention. Hereinafter, each component will be described in detail. In the case of containing a surfactant, it can be used as the coloring group which can be used in the present embodiment. Among the surfactants exemplified as the surfactant in the product, an appropriate compound is selected and used.

<[A] oxirane polymer>

The first radiation sensitive resin composition of the present embodiment contains [A] a siloxane polymer. Further, the [A] decane polymer contained in the first radiation sensitive resin composition of the present embodiment is preferably a siloxane polymer having a radical reactive functional group. In the case where the [A] methoxyalkane polymer is a siloxane polymer having a radically reactive functional group, if it is a polymer having a oxime bond, the polymer has a radical reactivity in a main chain or a side chain. The compound of a functional group is not specifically limited. In this case, the [A]methoxyl polymer can be hardened by radical polymerization, and the hardening shrinkage can be suppressed to a minimum. Examples of the radical reactive functional group include an unsaturated organic group such as a vinyl group, an α-methylvinyl group, an acrylonitrile group, a methacryl fluorenyl group, or a styryl group. Among these bases, a group having an acrylonitrile group or a methacryl group is preferred from the viewpoint that the hardening reaction proceeds smoothly.

The [A]methoxyl polymer is preferably a hydrolysis condensate of a hydrolyzable decane compound. The hydrolyzable decane compound constituting the [A] siloxane polymer is preferably a hydrolyzable decane compound containing the following compound: (a1) a hydrolyzable decane compound represented by the following formula (A-1) (hereinafter also referred to as (a1) (a) a hydrolyzable decane compound (hereinafter also referred to as a compound (a2)) represented by the following formula (A-2).

In the above formula (A-1), R ¹ is an alkyl group having 1 to 6 carbon atoms. R ² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, when R ¹ and R ² are plural, a plurality of R ¹ and R ² are each independently.

In the above formula (A-2), R ³ is an alkyl group having 1 to 6 carbon atoms. R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. However, when R ³ and R ⁴ are plural, a plurality of R ³ and R ⁴ are each independently.

In the present invention, the "hydrolyzable decane compound" means a compound having a group which is usually heated at a temperature ranging from room temperature (about 25 ° C) to about 100 ° C in the absence of a catalyst and excess water. Thus, it can be hydrolyzed to form a thiol group or a group which can form a decane condensate. In the hydrolysis reaction of the hydrolyzable decane compound represented by the above formula (A-1) and the above formula (A-2), a part of the hydrolyzable group remains in the unhydrolyzed state in the produced siloxane polymer. Here, the "hydrolyzable group" means a group which can carry out the above hydrolysis to form a sterol group or a group which can form a siloxane condensate. Further, in the first radiation sensitive resin composition, a part of the hydrolysis The decane compound may be in a state in which a part or all of the hydrolyzable group in the molecule is not hydrolyzed, and is not condensed with another hydrolyzable decane compound to remain in a monomer state. Further, the "hydrolysis condensate" is a hydrolysis condensate obtained by condensing a part of sterol groups of the hydrolyzed decane compound with each other. Hereinafter, the compound (a1) and the compound (a2) will be described in detail.

[(a1) compound]

In the above formula (A-1), R ¹ is an alkyl group having 1 to 6 carbon atoms. R ² is an organic group containing a radical reactive functional group. p is an integer from 1 to 3. However, when R ¹ and R ² are plural, a plurality of R ¹ and R ² are each independently.

Examples of the alkyl group having 1 to 6 carbon atoms in the above R ¹ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. Among these groups, a methyl group or an ethyl group is preferred from the viewpoint of easiness of hydrolysis. The above p is preferably 1 or 2, and more preferably 1 from the viewpoint of carrying out the hydrolysis condensation reaction.

The organic group having a radical reactive functional group may be a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a carbon substituted by one or more hydrogen atoms of the above-mentioned radical reactive functional group. The number is 6 to 12 aryl groups, and the carbon number is 7 to 12 aralkyl groups. When there are a plurality of R ² in the same molecule, the R ² are independent. Further, the organic group represented by R ² may have a hetero atom. Examples of such an organic group include an ether group, an ester group, a sulfide group and the like.

Examples of the (a1) compound in the case of p=1 include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltripropoxydecane, o-styryltrimethoxydecane, and o-styryl. Triethoxy decane, between Styryl trimethoxy decane, m-styryl triethoxy decane, p-styryl trimethoxy decane, p-styryl triethoxy decane, allyl trimethoxy decane, allyl triethyl Oxydecane, methacryloxytrimethoxydecane, methacryloxytriethoxydecane, methacryloxytripropoxydecane, propylene decyloxytrimethoxydecane, propylene oxime Oxytriethoxydecane, propylene decyloxytripropoxydecane, 2-methylpropenyloxyethyltrimethoxydecane, 2-methylpropenyloxyethyltriethoxydecane, 2 -Methacryloxymethoxyethyltripropoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methyl Propylene methoxypropyltripropoxydecane, 2-propenyloxyethyltrimethoxydecane, 2-propenyloxyethyltriethoxydecane, 2-propenyloxyethyltripropoxyl Baseline, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyltripropoxydecane, 3 -Methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropenyloxypropyltripropoxydecane,trifluoropropyl A trialkoxydecane compound such as trimethoxydecane, trifluoropropyltriethoxydecane, trifluorobutyltrimethoxydecane or 3-(trimethoxydecyl)propyl succinic anhydride.

Examples of the (a1) compound in the case of p = 2 include vinyl methyl dimethoxy decane, vinyl methyl diethoxy decane, vinyl phenyl dimethoxy decane, and vinyl phenyl di A dialkoxy decane compound such as oxydecane, allylmethyldimethoxydecane, allylmethyldiethoxydecane or phenyltrifluoropropyldimethoxydecane.

The compound (a1) in the case of p=3 is, for example, allyl dimethyl Methoxy decane, allyl dimethyl ethoxy decane, divinyl methyl methoxy decane, divinyl methyl ethoxy decane, 3-methyl propylene methoxy propyl dimethyl Methoxydecane, 3-propenyloxypropyl dimethyl methoxy decane, 3-methyl propylene methoxy propyl diphenyl methoxy decane, 3-propenyl methoxy propyl diphenyl Methoxydecane, 3,3'-dimethylpropenyloxypropyl dimethoxydecane, 3,3'-dipropenyloxypropyl dimethoxydecane, 3,3',3" - monoalkoxy such as trimethyl propylene methoxypropyl methoxy decane, 3,3', 3"-tripropylene methoxy methoxy methoxy decane, dimethyl trifluoropropyl methoxy decane A quinone compound.

Among these (a1) compounds, vinyltrimethoxydecane, p-styryltriethoxydecane, and 3-methylpropene oxime are preferable from the viewpoint of achieving scratch resistance and the like at a high level and performing condensation. Oxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltriethoxylate Decane, 3-(trimethoxydecyl)propyl succinic anhydride.

[(a2) compound]

In the above formula (A-2), R ³ is an alkyl group having 1 to 6 carbon atoms. R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a naphthyl group, an epoxy group, an amine group or an isocyanate group. n is an integer from 0 to 20. q is an integer from 0 to 3. In the case where each of R ³ and R ⁴ is plural, a plurality of R ³ and R ⁴ are each independently.

Examples of the alkyl group having 1 to 6 carbon atoms in the above R ³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a butyl group. Among these groups, a methyl group or an ethyl group is preferred from the viewpoint of easiness of hydrolysis. The above q is preferably 1 or 2, and more preferably 1 from the viewpoint of performing the hydrolysis condensation reaction.

In the case where the above R ⁴ is an alkyl group having 1 to 20 carbon atoms, the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group or a third group. Butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3- Methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2 ,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl , 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethyl Pentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethyl Pentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, positive Octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl , 壬基基,正正Base, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, N-nonadecyl and the like. It is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the (a2) compound in the case of q = 0, for example, a tetradecyl compound substituted with four hydrolyzable groups, tetramethoxy decane, tetraethoxy decane, tetrabutoxy decane, tetra-n-propoxy decane , tetraisopropoxy decane, and the like.

Examples of the (a2) compound in the case of q=1, a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, for example, methyltrimethyl Oxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tributoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy Base decane, ethyl tributoxy decane, butyl trimethoxy decane, phenyl trimethoxy decane, naphthyl trimethoxy decane, phenyl triethoxy decane, naphthyl triethoxy decane, amine group Trimethoxydecane, Amino Triethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy, γ-glycidoxypropyltrimethoxydecane, 3-isocyanopropane Trimethoxy decane, 3-isocyanopropyltriethoxy decane, o-tolyltrimethoxy decane, m-tolyltrimethoxydecane, p-tolyltrimethoxydecane, and the like.

Examples of the (a2) compound in the case of q=2, a decane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups may, for example, be dimethyldimethoxydecane or diphenyldimethoxydecane. , dibutyl dimethoxy decane, and the like.

Examples of the (a2) compound in the case of q=3, a decane compound substituted with three non-hydrolyzable groups and one hydrolyzable group may, for example, be trimethylmethoxydecane, triphenylmethoxydecane or the like. Butyl methoxy decane, and the like.

Among these (a2) compounds, a decane compound substituted with four hydrolyzable groups, a decane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, and more preferably one non-hydrolyzable group and three Hydrolyzable group-substituted decane compound. Particularly preferred hydrolyzable decane compounds include tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tributoxy decane, and phenyl. Trimethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl triisopropoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, γ-condensation Glycidoxypropyltrimethoxydecane, naphthyltrimethoxynonane, γ-aminopropyltrimethoxydecane, and γ-isocyanatepropyltrimethoxydecane. These hydrolyzable decane compounds may be used singly or in combination of two or more.

Regarding the mixing ratio of the above compound (a1) and the compound (a2), it is preferred that the compound (a1) exceeds 5 mol%. When the amount of the compound (a1) is 5 mol% or less, there is a tendency that the exposure sensitivity at the time of forming the cured film is low, and the scratch resistance of the obtained cured film or the like is further lowered.

[(a1) Hydrolysis and Condensation of Compound and (a2) Compound]

When the compound (a1) and the compound (a2) are hydrolyzed and condensed, the hydrolysis reaction group is converted into a sterol group to cause a condensation reaction. There is no particular limitation, and as one example, it can be carried out as follows.

The water to be subjected to the hydrolysis condensation reaction is preferably water which has been purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably from 0.1 mol to 3 mol, more preferably from 0.3 mol to 2 mol, based on the total amount of the hydrolyzable group of the compound (a1) and the compound (a2). The ear is particularly preferably from 0.5 mol to 1.5 mol. By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

Examples of the solvent to be subjected to hydrolysis condensation include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol monoalkyl ether acetates. Ester, propylene glycol monoalkyl ether propionate, Aromatic hydrocarbons, ketones, other esters, and the like. These solvents may be used singly or in combination of two or more.

Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethanol, and 3-phenyl-1-propanol.

Examples of the ethers include tetrahydrofuran and the like.

Examples of the glycol ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate.

Examples of the aromatic hydrocarbons include toluene and xylene.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

Examples of other esters include methyl acetate, ethyl acetate, and ethyl acetate. Ester, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl ester, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, Methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2- Butyl ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2 - propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3 - butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3 Methyl propoxy propionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3 - ethyl butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, butyl methoxy acetate, and particularly preferably diethyl ether are preferable. Diol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl methoxy acetate.

The hydrolysis condensation reaction is preferably carried out in the presence of a catalyst such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, and the like. a base catalyst (for example, an amine, a primary amine, a secondary amine, a tertiary amine, a nitrogen-containing compound such as pyridine; a basic ion exchange resin; a hydroxide such as sodium hydroxide; a carbonate such as potassium carbonate; sodium acetate, etc. a carboxylate; various Lewis bases or the like) or an alkoxide (for example, azoxide zirconium, alkoxide titanium, alkoxide aluminum, etc.). For example, aluminum alkoxide can be used for the aluminum alkoxide. The amount of the catalyst to be used is preferably 0.2 mol or less, and more preferably 0.00001 mol to 0.1 mol, based on the monomer 1 mol of the hydrolyzable decane compound, from the viewpoint of promoting the hydrolysis condensation reaction.

The reaction temperature and the reaction time in the hydrolysis condensation can be appropriately set. For example, the reaction temperature is preferably 40 to 200 ° C, and more preferably 50 to 150 ° C. The reaction time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 12 hours. By setting such a reaction temperature and reaction time, a hydrolysis condensation reaction can be performed efficiently. In the hydrolytic condensation, the hydrolyzable decane compound, water, and a catalyst may be added in one reaction to the reaction system in one step, or the hydrolyzable decane compound, water, and catalyst may be added to the reaction system in several stages. The hydrolysis and condensation reactions are carried out in multiple stages. Further, after the hydrolysis condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then evaporating. The dehydrating agent used in this stage generally adsorbs or contains excess water and completely consumes the dehydrating ability or is removed by evaporation.

Gel permeation chromatography of the above hydrolysis condensate (Gel The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") obtained by Permeation Chromatograph (GPC) is preferably 500 to 10,000, and more preferably 1,000 to 5,000. By setting Mw to 500 or more, the film formability of the first radiation sensitive resin composition of the present embodiment can be improved. On the other hand, when Mw is 10,000 or less, the developability of the first radiation sensitive resin composition can be prevented from being lowered.

The polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") obtained by GPC of the hydrolysis-condensation product is preferably 300 to 5,000, and more preferably 500 to 3,000. When the Mn of the [A]methoxyl polymer is in the above range, the curing reactivity at the time of curing of the coating film of the first radiation sensitive resin composition can be improved.

The molecular weight distribution "Mw/Mn" of the hydrolysis-condensation product is preferably 3.0 or less, and more preferably 2.6 or less. When the Mw/Mn of the hydrolysis-condensation product of the compound (a1) and the compound (a2) is 3.0 or less, the developability of the obtained cured film can be improved.

The first radiation-sensitive resin composition containing the [A]methoxyl polymer has less development residue during development and is likely to form a desired pattern shape.

<[B] Radical polymerization initiator]

Since the first radiation-sensitive resin composition of the present embodiment contains the [B] radical polymerization initiator, it can be cured by radical polymerization of [A] a siloxane polymer, and can be formed even at a low exposure amount. A sufficiently scratch-resistant cured film can provide a protective film of the present embodiment having sufficient scratch resistance at a low exposure amount. Further, [B] a radical polymerization initiator is preferred A radiation-sensitive polymerization initiator (radiometric polymerization initiator).

The [B] radical polymerization initiator may, for example, be an O-indenyl hydrazine compound, an acetophenone compound, a biimidazole compound or the like. These [B] radical polymerization initiators may be used singly or in combination of two or more.

Examples of the O-indenyl hydrazine compound include ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetonitrile).肟), 1-[9-ethyl-6-benzylidene-9H-carbazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl- 6-(2-Methylbenzylidene)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-( 2-ethylbenzhydryl)-9H-indazol-3-yl]-ethane-1-one oxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2 -methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2- Methyl-4-tetrahydropyranylbenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-( 2-methyl-5-tetrahydrofuranylbenzylidene)-9H-carbazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2 -methyl-4-(2,2-dimethyl-1,3-dioxolyl)methoxybenzylidene}-9H-indazol-3-yl]-1-(O -acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-1- (O-Ethene) and so on.

Among these compounds, preferred O-mercaptopurine compounds include ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1 -(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl] -1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxole) Alkyl) methoxybenzimidyl}-9H-indazol-3-yl]-1-(O-acetamidine).

The acetophenone compound may, for example, be an α-amino ketone compound or an α-hydroxy ketone compound.

Examples of the α-amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethylamino-2. -(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthienyl)-2 - Morpholinopropan-1-one and the like.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1. a ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone or the like.

Among these compounds, a more preferred acetophenone compound is an α-amino ketone compound. Ethyl 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1 -(4-Methylthienyl)-2-morpholinopropan-1-one.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole. 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole.

Among these compounds, preferred biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2. 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6- Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, more preferably 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-Tetraphenyl-1,2'-biimidazole.

When a biimidazole compound is used as the [B] radical polymerization initiator, an aliphatic or aromatic compound having a dialkylamine group may be added for sensitization (hereinafter referred to as "amine-based sensitization" Agent").

Examples of the amine-based sensitizer include 4,4′-bis(dimethylamino)benzophenone and 4,4′-bis(diethylamino)benzophenone. Among these amine-based sensitizers, 4,4'-bis(diethylamino)benzophenone is preferred. These amine-based sensitizers may be used singly or in combination of two or more.

Further, when a biimidazole compound and an amine-based sensitizer are used in combination in the first radiation sensitive resin composition, a thiol compound may be added as a hydrogen radical supply agent. The biimidazole compound is sensitized by the amine-based sensitizer to be cracked to generate an imidazole radical, but there is also a case where the high polymerization initiation ability is not directly exhibited. However, by adding a thiol compound to a system in which a biimidazole compound and an amine-based sensitizer coexist, a hydrogen radical derived from a thiol compound can be supplied to the imidazole radical. As a result, the imidazole radical is converted into a neutral imidazole, and a component having a sulfur radical having a high polymerization initiation ability is produced, whereby a cured film having a high scratch resistance or the like can be formed even with a low radiation irradiation amount.

Examples of the above thiol compound include aromatic mercaptan compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole; An aliphatic monothiol compound such as mercaptopropionic acid or methyl 3-mercaptopropionate; a bifunctional or higher aliphatic thiol compound such as pentaerythritol tetrakis(mercaptoacetic acid) ester or pentaerythritol tetrakis(3-mercaptopropionic acid) ester. Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferred.

In the case of using a biimidazole compound together with an amine-based sensitizer, an amine group The amount of the sensitizer to be used is preferably 0.1 parts by mass to 50 parts by mass, more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of the biimidazole compound. When the amount of the amine-based sensitizer used is from 0.1 part by mass to 50 parts by mass, the curing reactivity of the first radiation-sensitive resin composition at the time of exposure can be improved, and the scratch resistance of the obtained cured film can be improved. Wait.

In the case where a biimidazole compound, an amine-based sensitizer, and a thiol compound are used in combination, the amount of the thiol compound used is preferably 0.1 part by mass to 50 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the biimidazole compound. It is 1 part by mass to 20 parts by mass. By using the thiol compound in an amount of from 0.1 part by mass to 50 parts by mass, the scratch resistance of the obtained cured film can be improved.

The amount of the [B] radical polymerization initiator to be used in the first radiation-sensitive resin composition is preferably 0.05 parts by mass to 30 parts by mass based on 100 parts by mass of the [A] siloxane polymer. It is preferably 0.1 parts by mass to 15 parts by mass. By using the amount of the [B] radical polymerization initiator in the above range, the first radiation-sensitive resin composition can form a cured film which exhibits high radiation sensitivity and further has high scratch resistance and the like. A protective film of the present embodiment excellent in scratch resistance and the like can be provided.

<[C]organic solvent>

The first radiation sensitive resin composition of the present embodiment contains a [C] organic solvent.

The organic solvent [C] preferably contains (C1) an organic solvent having a vapor pressure at 20 ° C of 0.1 mmHg or more and less than 1 mmHg. Further, it is preferable to contain (C2) an organic solvent having a vapor pressure at 20 ° C of 1 mmHg or more and 20 mmHg or less. [C] organic solvent by using a specific range of vapor pressure Even if the nozzle coating method is employed, coating unevenness can be prevented and coating can be performed at a high speed. Further, a known method can be used for the measurement of the vapor pressure, and in the present invention, a value measured by an evapotranspiration method (gas flow method).

In the organic solvent, an organic solvent which uniformly dissolves or disperses the above-described respective components contained in the first radiation-sensitive resin composition and does not react with each component can be suitably used. Examples of such an [C] organic solvent include alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, and diethyl ether. Glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol esters, guanamines, lactones, ketones, and the like. These organic solvents may be used alone or in combination of two or more.

<[D]ethylenically unsaturated compound>

The first radiation sensitive resin composition of the present embodiment preferably further contains a [D] ethylenically unsaturated compound. The [D] ethylenically unsaturated compound is an ethylenically unsaturated compound other than the above [A] nonoxyl polymer. By further containing the [D] ethylenically unsaturated compound in the first radiation sensitive resin composition, the radiation sensitivity can be improved and the sublimation property can be lowered. Therefore, the cured film formed of the first radiation-sensitive resin composition is further improved in scratch resistance and transparency, and the protective film of the present embodiment excellent in scratch resistance and transparency can be provided.

The [D] ethylenically unsaturated compound is preferably a monofunctional, bifunctional or trifunctional or higher (meth) acrylate from the viewpoint of having good self-polymerization properties and improving the strength of the obtained cured film. By including these compounds in the first radiation-sensitive resin composition, transparency, scratch resistance, and the like can be formed. A highly balanced hardened film.

Examples of the monofunctional (meth) acrylate as the [D] ethylenically unsaturated compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, and diethyl ether. Glycol monoethyl ether methacrylate, (2-propenyloxyethyl) (2-hydroxypropyl) phthalate, (2-methylpropenyloxyethyl) (2-hydroxypropane) Phthalate, ω-carboxypolycaprolactone monoacrylate, and the like. For example, ARONIX (registered trademark) M-101, ARONIX M-111, ARONIX M-114, ARONIX M-5300 (above manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) TC-110S, KAYARAD TC- 120S (above manufactured by Nippon Kayaku Co., Ltd.); Viscoat 158, Viscoat 2311 (above manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

Examples of the bifunctional (meth) acrylate as the [D] ethylenically unsaturated compound include ethylene glycol di(meth)acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, and ethylene glycol dimethyl. Acrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, and the like. Commercial products include, for example, ARONIX (registered trademark) M-210, ARONIX M-240, ARONIX M-6200 (manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) HDDA, KAYARAD HX-220, KAYARAD R-604 ( The above is manufactured by Nippon Kayaku Co., Ltd.); Viscoat 260, Viscoat 312, Viscoat 335HP (above manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate 1,9-NDA (Kyoeisha Chemical Co., Ltd.).

Examples of the trifunctional or higher (meth) acrylate of the [D] ethylenically unsaturated compound include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol. Mixture of methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate , dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tris(2-propenyloxyethyl) phosphate, tris(2-methylpropenyloxyethyl) phosphate , isocyanuric acid modified triacrylate, isocyanuric acid EO modified triacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, in addition to linear alkane a compound having an alicyclic structure and having two or more isocyanate groups and having one or more hydroxyl groups in the molecule and having three, four or five (A) A polyfunctional polyurethane acrylate compound obtained by reacting a compound of a propylene methoxy group. Commercial products include, for example, ARONIX (registered trademark) M-309, ARONIX M-313, ARONIX M-315, ARONIX M-400, ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060, ARONIX TO-1450 (manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD DPEA -12 (above manufactured by Nippon Kayaku Co., Ltd.); Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); New Frontier (registered trademark) R-1150 as a commercial product containing a polyfunctional polyurethane acrylate compound (First Industrial Pharmaceutical Company), KAYARAD (registered trademark) DPHA-40H (Nippon Chemical Co., Ltd.), and the like.

Among the [D] ethylenically unsaturated compounds, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol III Acrylate, succinic acid-modified dipentaerythritol pentaacrylate, and a commercially available product containing a polyfunctional polyurethane acrylate compound.

The above [D] ethylenically unsaturated compound may be used singly or in combination of two or more kinds. The use ratio of the [D] ethylenically unsaturated compound in the first radiation-sensitive resin composition is preferably 5 parts by mass to 80 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the [A] siloxane polymer. It is 10 parts by mass to 30 parts by mass. By using the amount of the [D] ethylenically unsaturated compound in the above range, the radiation sensitivity of the first radiation sensitive resin composition and the scratch resistance of the obtained cured film can be further improved.

<[E]acid generator or base generator>

The first radiation sensitive resin composition of the present embodiment may contain an [E] acid generator or a base generator. The [E] acid generator or base generator can be defined as a compound capable of releasing an acidic active substance or a basic active substance. Moreover, [E] The acid generator or base generator is preferably an [E] sensitizing radioactive acid generator or a sensitizing radioactive base generator. In this case, the [E] sensitizing radioactive acid generator or the sensitizing radioactive base generator may be defined as a compound capable of releasing an acidic active material or a basic active material by irradiation with radiation. The [A] siloxane polymer is hardened by the action of a catalyst of the [E] acid generator or the alkali generator, so that the polymerizability is further increased. As a result, the first radiation-sensitive resin composition can form a cured film excellent in scratch resistance and the like, and can provide a protective film having excellent scratch resistance and the like.

Examples of the radiation to be irradiated by a cation or an anion which decomposes the [E] acid generator or the alkali generator to generate an acidic active material or a basic active material include visible light, ultraviolet light, infrared light, X-ray, α-ray, and β. Rays, gamma rays, etc. Among these radiations, ultraviolet rays are preferably used because they have a fixed energy level and can achieve a high curing speed in the cured film, and the irradiation device is relatively inexpensive and small.

The radiation sensitive acid generator is preferably a diphenyliodonium salt, a triphenylsulfonium salt or a tetrahydrothiophene salt, and more preferably a triphenylsulfonium salt or a tetrahydrothiophene salt.

Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, and diphenyliodonium trifluoromethanesulfonate. Acid salt, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, diphenyliodonium butyl tris(2,6-difluorophenyl)borate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, bis(4-t-butylphenyl)iodonium tetrafluoroborate, bis(4-t-butylphenyl)iodonium hexafluoroarsenate, double 4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodine 鎓Trifluoroacetate, bis(4-t-butylphenyl)iodonium p-toluenesulfonate, bis(4-t-butylphenyl)iodonium sulfonate, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenyl camphorsulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium. P-toluenesulfonate, triphenylphosphonium butyl tris(2,6-difluorophenyl)borate, and the like.

Examples of the tetrahydrothiophene sulfonium salt include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate and 1-(4-n-butoxynaphthalen-1-yl)tetra. Hydrothiophene quinone nonafluorobutane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-1,1,2,2-tetrafluoro-2-(norbornane-2 -yl)ethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(5-t-butoxycarbonyloxybicyclo[2.2.1]heptane- 2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-2-(6-tributoxy) Carbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(4,7-dibutoxy-1-naphthalenyl)tetra Hydrothiophene trifluoromethanesulfonate and the like.

Among these radiation-sensitive acid generators, triphenylsulfonium trifluoromethanesulfonate and triphenyl camphorsulfonate are particularly preferable from the viewpoint of improving the radiation sensitivity of the first radiation sensitive resin composition. 1-(4,7-Dibutoxy-1-naphthalenyl)tetrahydrothiophene trifluoromethanesulfonate.

Examples of the above-mentioned radiation-sensitive base generator include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, and N-( 2-nitrobenzyloxycarbonyl)pyrrolidine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, O-amine formazanylhydroxyl Indoleamine, O-amine-mercaptopurine, 4-(methylthiobenzimidyl)-1-methyl-1-morpholinoethane, (4- Morpholinobenzylidene)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone , hexaamine cobalt (III) tris(triphenylmethylborate), and the like.

Among these sensitizing radioactive alkali generators, 2-nitrobenzylcyclohexyl carbazate and O-amine formazan are more preferable from the viewpoint of improving the radiation sensitivity of the first radiation sensitive resin composition. Hydroxy guanamine.

The [E] acid generator or the alkali generator may be used singly or in combination of two or more. The amount of use of the [E] acid generator or the alkali generator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass per 100 parts by mass of the [A] decane polymer. The following. When the amount of the [E] acid generator or the alkali generator is from 0.01 parts by mass to 20 parts by mass, the balance of radiation sensitivity, scratch resistance, transparency, and the like can be achieved as the first radiation-sensitive resin composition. A favorable cured film is formed favorably, and the protective film of this embodiment which is excellent in such characteristics can be provided.

The first radiation sensitive resin composition containing the above components can be cured by low temperature to form a protective film. Specifically, even at a curing temperature of 200 ° C or lower, and further at a curing temperature of 180 ° C or lower, a protective film having good reliability can be obtained. Further, the color filter of the present embodiment can be provided by low-temperature curing.

Next, the color filter of this embodiment has an ITO electrode on the protective film. The ITO electrode is formed by forming an ITO film on a protective film by a known method such as sputtering. Further, in the color filter of the present embodiment, another transparent electrode may be used instead of the ITO electrode on the protective film. The transparent electrode can be formed using a transparent material having high transmittance and conductivity for visible light. For example, a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), indium zinc oxide (Indium Zinc Oxide, IZO), zinc oxide (ZnO), or the like can be used. In this case, a tin oxide electrode, an IZO electrode, or the like may be disposed on the protective film instead of the ITO electrode.

Next, the color filter of this embodiment may include a spacer which is erected on the ITO electrode on the protective film. The spacer can be formed using a second radiation-sensitive resin composition. In the following, the second radiation-sensitive resin composition of the present embodiment used for forming the spacer of the color filter of the present embodiment will be described.

<Second-sensing radiation resin composition>

The second radiation sensitive resin composition used for forming the spacer of the color filter of the present embodiment contains [α] compound, [β] polymerizable compound, [γ] polymerization initiator, and [δ] The compound may further contain an optional component. The second radiation-sensitive resin composition can be easily formed into a fine and delicate pattern by radiation-sensitive exposure and development, thereby achieving low-temperature curing. Moreover, it has storage stability and has sufficient resolution and radiation sensitivity. The components are detailed below.

<[α] compound>

The [α] compound contained in the second radiation-sensitive resin composition is preferably an alkali-soluble resin in consideration of patterning of the spacer of the color filter of the present embodiment. The alkali-soluble resin is not particularly limited as long as it has a base developability resin having a carboxyl group. Further, a compound having an epoxy group may be contained in the alkali-soluble resin.

The compound having an epoxy group may, for example, be a compound having two or more ethylene oxide groups, an oxypropylene group, a glycidyl group or a 3,4-epoxycyclohexyl group in one molecule.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane formate, 2-( 3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, double (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methyl Cyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl) Ether, ethyl bis(3,4-epoxycyclohexanecarboxylic acid) ester, lactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane formate, etc. .

Examples of the compound having two or more propylene oxide groups (1,3-epoxy structure) in one molecule include 1,4-bis[(3-ethyl-3-epoxypropenylmethoxy)methyl group. Benzene, bis{[1-ethyl(3-epoxypropenyl)]methyl}ether, bis(3-ethyl-3-epoxypropanemethyl)ether, and the like.

Examples of the epoxy compound which may be contained in the [α] compound, and examples of the compound having a glycidyl group include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenation. Bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol a diglycidyl ether of a bisphenol compound such as S diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, a polyglycidyl ether of a polyhydric alcohol such as trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; by aliphatic pluralism such as ethylene glycol, propylene glycol or glycerin a polyglycidyl ether of a polyether polyol obtained by adding one or more kinds of alkylene oxides to an alcohol; a phenol novolak type epoxy resin; a cresol novolac type epoxy resin; a polyphenol type epoxy resin; Aliphatic epoxy resin; diglycidyl ester of aliphatic long-chain dibasic acid; glycidyl ester of higher fatty acid; epoxidized soybean oil, epoxidized linseed oil, and the like.

As such commercially available products, for example, bisphenol A type epoxy resin includes Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, and Epikote 828 (above by Japanese epoxy resin company) (manufactured by Japan Epoxy Resins Co., Ltd.); bisphenol F-type epoxy resin: Epikote 807 (Nippon Epoxy Co., Ltd.); and phenol novolac type epoxy resin; Epikote 152, Epikote 154, Epikote 157S65 ( The above is manufactured by Japan Epoxy Resin Co., Ltd., EPPN (registered trademark) 201, EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), and the like; cresol novolac type epoxy resin is exemplified by EOCN (registered trademark) 102. EOCN 103S, EOCN 104S, EOCN 1020, EOCN 1025, EOCN 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Co., Ltd.), etc.; polyphenol type epoxy resin can be cited as Epikote 1032H60, Epikote XY-4000 (The above is manufactured by Japan Epoxy Resin Co., Ltd.), etc.; cyclic aliphatic epoxy resins include CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above Ciba Specialty Chemicals Co., Ltd.), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above manufactured by UCC), Shodyne 509 (Showa Denko), Epiclon 200, Epiclon 400 (above from Greater Japan) Ink Company), Epikote 871, Epikote 872 (above manufactured by Japan Epoxy Co., Ltd.), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), etc.; aliphatic polyglycidyl ether can be listed as Epolight 100MF (total) Rongshe Chemical Co., Ltd., EPIOL (registered trademark) TMP (Japanese Oil Company).

Among these, a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferable.

As the alkali-soluble resin as the [α] compound contained in the second radiation-sensitive resin composition, an alkali-soluble resin containing a copolymer of the following structural unit: (α-1) selected from the group consisting of unsaturated carboxylic acid and unsaturated can be used. a structural unit formed of at least one group ((α-1) compound) composed of a carboxylic anhydride, and (α-2) formed of an epoxy group-containing unsaturated compound ((α-2) compound) Structural units. Further, the [I] base contained in the colored composition used in the production of the color filter of the present embodiment described above can be used. The same copolymer of soluble resin. For example, (I-1) at least one compound ((I-1)) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides can be used as the (α-1) compound, and (I- 2) An epoxy group-containing unsaturated compound ((I-2) compound) is used as the (?-2) compound. Further, as the alkali-soluble resin of the [α] compound, an alkali-soluble resin containing a copolymer of the following structural unit: a structural unit formed of the compound (I-1), and a structural unit formed of the compound (I-2) can be used. .

<[β] polymerizable compound>

The [β] polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. Further, as the [β] polymerizable compound, the same compound as the [II] polymerizable compound contained in the colored composition used in the production of the color filter of the above-described embodiment can be used.

The [β] polymerizable compound may be used singly or in combination of two or more. The content ratio of the [β] polymerizable compound in the radiation sensitive resin composition is preferably 20 parts by mass to 200 parts by mass, more preferably 40 parts by mass to 160 parts by mass, per 100 parts by mass of the [α] compound. . When the content ratio of the [β] polymerizable compound is in the above range, the radiation-sensitive resin composition can form a cured film which is excellent in adhesion and has sufficient hardness even at a low exposure amount, and can provide an excellent spacer. .

<[γ] polymerization initiator>

The [γ] polymerization initiator is a radiation-sensitive polymerization initiator. As the [γ] polymerization initiator, the same compound as the [III] polymerization initiator contained in the coloring composition used in the production of the color filter of the present embodiment described above can be used.

The [γ] polymerization initiator may be used singly or in combination of two or more. The content ratio of the [γ] polymerization initiator in the second radiation-sensitive resin composition is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass, per 100 parts by mass of the [α] compound. 30 parts by mass. When the content ratio of the [γ] polymerization initiator is from 1 part by mass to 40 parts by mass, the second radiation-sensitive resin composition can form a hardening having high hardness and adhesion even at a low exposure amount. Membrane and excellent spacers can be formed.

<[δ] compound>

The second radiation-sensitive resin composition used for forming the spacer of the color filter of the present embodiment contains a [δ] compound having an amine group and an electron-withdrawing group, whereby the second radiation-sensitive resin composition can be realized. The hardening of the cured film at the time of low temperature hardening of the object is promoted. Further, storage stability can be achieved, and the voltage holding ratio of the liquid crystal display element including the color filter (the color filter having the obtained spacer) can be maintained at a high level.

The [δ] compound is at least one compound selected from the group consisting of the compounds represented by the above formulas (1) and (2). The details of the structures of the compounds represented by the above formulas (1) and (2) have been described in the description of the [V] compound contained in the above colored composition. In particular, at least one of R ⁷ to R ¹⁶ is an amine group, and all or a part of the hydrogen atom of the amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms, and is a second radiation-sensitive resin composition. In the case of the [δ] compound used, all or a part of the hydrogen atom of the amine group may be substituted with an alkylene group having 2 to 6 carbon atoms.

As the [δ] compound, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,3-bis(4-aminophenyl)succinonitrile, 4,4'-diamino group are preferable. Benzophenone, phenyl 4,4'-diaminobenzoate, 4,4'-diaminodiphenylanthracene, 1,4-diamino-2- Chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1,4-diamino -2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2'-dichlorobenzidine, 2,2'-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis(trifluoromethyl)benzidine, 3-amino Ethyl benzenesulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline, more preferably 4,4'-Diaminodiphenylphosphonium, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 3-aminobenzene Ethyl sulfonate, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline.

The content ratio of the [δ] compound in the second radiation-sensitive resin composition is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass based on 100 parts by mass of the [α] compound. Share. By setting the content ratio of the [δ] compound to 0.1 part by mass to 10 parts by mass, the curing of the spacer formed of the second radiation sensitive resin composition can be promoted. Further, the storage stability of the second radiation-sensitive resin composition is improved, and the voltage holding of the liquid crystal display element including the color filter (the color filter having the obtained spacer) can be maintained at a high level. rate.

<Other optional ingredients>

In addition to the above [α] compound, [β] polymerizable compound, [γ] polymerization initiator, and [δ], the second radiation sensitive resin composition used for forming the spacer of the color filter of the present embodiment In addition to the compound, it may contain [ω-1] an auxiliary agent, [ω-2] as needed within a range that does not impair the desired effect. Any component such as a surfactant, [ω-3] storage stabilizer, and [ω-4] heat resistance promoter. These optional components may be used singly or in combination of two or more. Hereinafter, it will be described in detail.

[[ω-1] Adhesives]

[ω-1] Next, an auxiliary agent can be used to further improve the adhesion of the resulting spacer to the substrate. As the [ω-1]-adhesive auxiliary, the same compound as the above-mentioned auxiliary agent in the other optional component of the above colored composition can be used.

The amount of use of the [ω-1]-based auxiliary agent is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less based on 100 parts by mass of the [α] compound. When the amount of the [ω-1]-based auxiliary agent used exceeds 20 parts by mass, the development tends to be likely to occur.

[[ω-2] surfactant]

The [ω-2] surfactant can be used to further improve the coating film formability of the second radiation-sensitive resin composition. Examples of the [ω-2] surfactant include a fluorine-based surfactant, an anthrone-based surfactant, and other surfactants, and a compound similar to the surfactant in any other component of the coloring composition described above can be used.

The amount of the [ω-2] surfactant to be used is preferably 1.0 part by mass or less, and more preferably 0.8 part by mass or less based on 100 parts by mass of the [α] compound. When the amount of the [ω-2] surfactant is more than 1.0 part by mass, film unevenness is likely to occur.

[[ω-3] preservation stabilizer]

As the storage stabilizer, the same compound as the storage stabilizer in the other optional components of the above colored composition can be used. For example, sulfur, bismuth can be cited Examples thereof include hydroquinones, polyoxygen compounds, amines, and nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like.

The amount of use of the [ω-3] storage stabilizer is preferably 3.0 parts by mass or less, and more preferably 1.0 part by mass or less based on 100 parts by mass of the [α] compound. When the amount of the [ω-3] storage stabilizer is more than 3.0 parts by mass, the sensitivity of the second radiation-sensitive resin composition may be lowered to deteriorate the pattern shape.

[[ω-4] heat resistance promoter]

[ω-4] The heat resistance promoter may be the same compound as the heat resistant stabilizer in the other optional components of the coloring composition described above.

The amount of use of the [ω-4] heat resistance promoter is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the [α] compound. When the blending amount of the [ω-4] heat-resistant accelerator exceeds 50 parts by mass, the sensitivity of the second radiation-sensitive resin composition may be lowered to deteriorate the pattern shape.

<Preparation of the second radiation-sensitive resin composition>

The second radiation-sensitive resin composition forming the separator of the color filter of the present embodiment can be prepared by polymerizing an [α] compound, a [β] polymerizable compound, and [γ]. The agent and the [δ] compound, and any optional components as needed within a range not impairing the desired effect, are mixed in a predetermined ratio. The second radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state.

The solvent used in the preparation of the second radiation-sensitive linear resin composition may be A solvent capable of uniformly dissolving or dispersing the [α] compound, the [β] polymerizable compound, the [γ] polymerization initiator, the [δ] compound, and an optional component without reacting with each component is used. The solvent exemplified as the solvent used for preparation of the coloring composition of the color filter of the present embodiment is exemplified. The solvent may be used singly or in combination of two or more.

When the solvent of the second radiation-sensitive resin composition is used in combination with a high-boiling solvent, the amount thereof is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% based on the total amount of the solvent. Below mass%. When the amount of the high boiling point solvent used is 50% by mass or less, the film thickness uniformity, the sensitivity, and the residual film ratio of the coating film become good.

When the second radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (component other than the solvent in the composition solution) can be set according to the purpose of use, the value of the desired film thickness, or the like. Any concentration. The solid content concentration can be set, for example, from 5% by mass to 50% by mass. The more preferable solid content concentration differs depending on the method of forming the coating film on the substrate, which will be described later. The composition solution prepared in this manner can be used by filtration using a micropore filter having a pore diameter of about 0.5 μm or the like.

The second radiation-sensitive resin composition of the above components and the preparation method can be formed by forming a separator by low-temperature curing. Specifically, a spacer having good reliability can be obtained even at a curing temperature of 200 ° C or lower and further at a curing temperature of 180 ° C or lower. Further, the color filter of the present embodiment can be provided by low-temperature curing.

The color filter of this embodiment can be constructed as described above. A liquid crystal alignment alignment film is provided on the liquid crystal side surface of the liquid crystal display element. The alignment film can be obtained by using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group or a liquid crystal alignment agent containing a polyimide having no photo-alignment group. In this case, it becomes possible to form an alignment film at a heating temperature of 200 ° C or lower. Next, the liquid crystal alignment agent which forms an alignment film, especially the main component is demonstrated.

<Liquid alignment agent>

The liquid crystal alignment agent which forms the alignment film of the color filter of the present embodiment contains a [L] radiation sensitive polymer having a photoalignment group or a [M] polyfluorene having no photoalignment group as described above. The imine serves as a main component. In particular, the liquid crystal alignment agent which forms the alignment film of the color filter of the present embodiment preferably contains a [L] radiation sensitive polymer having a photoalignment group. Each of these components can form an alignment film at a low temperature heating temperature of, for example, 200 ° C or lower. Further, the liquid crystal alignment agent may contain [N] other components as long as the effects of the present invention are not impaired. The ingredients are described below.

[[L] Sense Radiation Polymer]

The [L] radiation sensitive polymer contained in the liquid crystal alignment agent forming the alignment film of the color filter of the present embodiment is a polymer having a photoalignment group. The photoalignment group of the [L] radiation sensitive polymer is a functional group that imparts anisotropy to the film by light irradiation. In the present embodiment, in particular, photoisomerization reaction and photodimerization are produced. At least one of the reactions imparts an anisotropic substrate to the film.

a photo-alignment group, specifically having a source selected from the group consisting of azo Benzene, hydrazine, α-imino-β-ketoester, spiropyran, spirooxazine, cinnamic acid, chalcone, carbazole, benzylidene phthalimide, coumarin, two A group having a structure of at least one compound of the group consisting of phenylacetylene and hydrazine. As the above photo-alignment group, those having a structure derived from cinnamic acid are particularly preferable among these.

The [L] radiation-sensitive polymer having a photo-alignment group is preferably a polymer in which the above-mentioned photo-alignment group is bonded directly or via a linking group. Examples of such a polymer include a polymer obtained by bonding the above photo-alignment group to at least any polymer of polyacrylic acid and polyimine; in contrast to polyglycine and polyimine A polymer obtained by bonding the above photo-alignment group to the polymer. In the latter case, examples of the basic skeleton of the polymer having a photo-alignment group include poly(meth)acrylate, poly(meth)acrylamide, polyvinyl ether, polyolefin, polyorganosiloxane, and the like. .

As the radiation sensitive polymer, a radiation sensitive polymer having polyacetamide, polyamidimide or polyorganosiloxane as a basic skeleton is preferable. Further, among these, a polyorganosiloxane is particularly preferable, and it can be obtained, for example, by the method described in the specification of International Publication (WO) No. 2009/025386.

[[M]polyimine]

The [M] polyimine contained in the liquid crystal alignment agent which forms the alignment film of the color filter of this embodiment is a polyimine which does not have a photo-alignment group.

Such a [M] polyimine which does not have a photo-alignment group can be obtained by hydrazine imidization by dehydration of a poly-proline which does not have a photo-alignment group. Such a polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. It can be obtained as described in Japanese Laid-Open Patent Publication No. 2010-97188.

[M] Polyimine may be a complete quinone imide formed by dehydration ring closure of the proline structure of polyglycine as a precursor thereof, or may be only a part of the dehydration ring closure of the proline structure. A partial ruthenium imide of a proline structure and a quinone ring structure. The [M] polyimine has a quinone imidization ratio of preferably 30% or more, more preferably 50% to 99%, still more preferably 65% to 99%. The ruthenium imidization ratio is a ratio of the number of quinone ring structures to the total number of guanidine structures and the number of quinone ring structures of the polyimine. Here, a part of the quinone ring may be an isoindole ring, and is obtained, for example, as described in JP-A-2010-97188.

[[N]Other ingredients]

The liquid crystal alignment agent which forms the alignment film of the color filter of the present embodiment may contain a radiation sensitive polymer having a photoalignment group and [N] other components other than the polyimide having no photoalignment group. Examples of the [N] other component include a [L] radiation-sensitive polymer having a photo-alignment group and a polymer other than the [M] poly-imine having no photo-alignment group, a curing agent, a curing catalyst, and a curing accelerator. An epoxy compound, a functional decane compound, a surfactant, a photosensitizer, and the like.

<Coloring Pattern, Protective Film, Spacer, Color Filter, and Manufacturing Method of These>

In the production of the color filter of the present embodiment, the following steps are included as a main manufacturing step for forming a color by the coloring composition described above. a step of patterning, a step of forming a protective film from the first radiation-sensitive resin composition, and a step of forming a spacer from the second radiation-sensitive resin composition. Hereinafter, a colored pattern, a protective film, a spacer, a color filter, and a manufacturing method of these will be described.

The method for producing a color filter of the present embodiment preferably includes the following steps [1] to [11] in the following order: [1] a step of forming a coloring composition coating film on a substrate (hereinafter sometimes referred to as " [1] Steps "), [2] A step of forming a colored pattern on a colored composition coating film (hereinafter sometimes referred to as "[2] step"), [3] coating a colored pattern at 200 ° C or lower a step of hardening the film (hereinafter sometimes referred to as "[3] step)), [4] a step of forming a coating film of the first radiation sensitive resin composition on the substrate after the step [3] (hereinafter sometimes referred to as a coating film) "[4] Step"), [5] A step of irradiating at least a part of the first radiation-sensitive resin composition coating film on the substrate (hereinafter referred to as "[5] step"), [6] a step of developing a coating film irradiated with radiation (hereinafter sometimes referred to as "[6] step"), [7] a step of curing a developed coating film at 200 ° C or lower (hereinafter sometimes referred to as " [7] Steps "), [8] A step of forming a coating film of the second radiation-sensitive resin composition on the substrate having the coating film which has been hardened in the step [7] (hereinafter sometimes referred to as "[8 [Step 2], [9] The second radiation-sensitive resin composition formed in the [8] step The step of irradiating at least a part of the coating film with radiation (hereinafter sometimes referred to as "[9] step)), and [10] the step of developing the coating film irradiated with radiation (hereinafter sometimes referred to as "[10] step") [11] A step of forming a spacer by curing the developed coating film at 200 ° C or lower (hereinafter sometimes referred to as "[11] step").

In the case where the color filter of the present embodiment has a liquid crystal alignment alignment film, the step of forming an alignment film [12] may be provided after the [11] step (hereinafter sometimes referred to as "[12] step"). ).

According to the method for producing a color filter of the present embodiment, the colored composition can be used to form a colored pattern on the substrate, and the first radiation-sensitive resin composition can be used to form a protective film, and the second radiation can be used. The resin composition forms a spacer. Further, when the color filter of the present embodiment has an alignment film, the alignment film can be formed using the liquid crystal alignment agent. As a result, a color filter excellent in heat resistance, chemical resistance, voltage holding ratio, and the like can be formed. In this case, low temperature hardening can be achieved. In the above [3] step, the above [7] step, and the above [11] step, the curing can be performed at a temperature of 200 ° C or lower. Therefore, as the coloring agent, a dye having a problem in heat resistance can be used as the coloring composition. Therefore, a color filter excellent in color characteristics can be manufactured. Further, in the above step [12], the formation of the alignment film may be carried out at a heating temperature of 200 ° C or lower. Further, from the viewpoint of energy saving, the color filter manufactured as described above also becomes a suitable color filter in the case where low temperature hardening is desired. Hereinafter, each step will be described in detail.

[[1] Steps]

In this step, a coating film of the above colored composition is formed on a substrate.

On the surface of the substrate, a light shielding layer (black matrix) is formed in a manner to divide a portion where the pixels are formed as needed. Next, a colored composition containing, for example, a red [IV] coloring agent is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. In another method of forming a colored pattern on a substrate, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. This method first forms a separator having a light-shielding function on the surface of the substrate. Next, a coloring composition containing, for example, a red coloring agent is ejected into the formed separator by an ink jet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed to form a red pixel pattern. Further, the separator not only functions as a light-shielding function, but also functions to prevent the coloring composition of each color discharged into the scribe region from being mixed, and has a thicker film than the black matrix.

Examples of the material of the substrate include glass such as soda lime glass or alkali-free glass, quartz, ruthenium, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and aromatic polyfluorene. An amine, a polyamidimide, a polyamidiamine, a ring-opening polymer of a cyclic olefin, a hydride thereof, and the like. Further, an appropriate pretreatment such as a chemical treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition may be previously performed on the substrates.

As a method of applying a coloring composition onto a substrate, in addition to the above-described inkjet method, a spray method, a roll coating method, or a spin coating method may be mentioned. Coating method, slit die coating method, bar coating method, and the like. Among these methods, a spin coating method or a slit die coating method is preferred. Prebaking is preferably carried out by combining reduced pressure drying with heat drying. In the case of performing drying under reduced pressure, it is usually carried out so as to reach 50 Pa to 200 Pa. Further, the conditions for heat drying are usually from about 1 minute to about 10 minutes at 70 ° C to 110 ° C.

The film thickness after drying is usually from 0.6 μm to 8.0 μm, preferably from 1.2 μm to 5.0 μm.

[[2] Steps]

In the step [2], the coating film formed in the step [1] is exposed through a photomask, developed using an alkaline developing solution, and the unexposed portion of the coating film is dissolved and removed, whereby A red coloring pattern of a red pixel pattern is arranged in a predetermined arrangement.

Next, using the green or blue colored composition, the above steps [1] and [2] are repeated to sequentially form a green colored pattern and a blue colored pattern on the same substrate. Thus, a color filter in which three primary color patterns of red, green, and blue are disposed on the substrate is obtained. However, in the present embodiment, the order in which the pixels of the respective colors are formed and the number of colors are not limited to the above order and the number of colors.

Further, the black matrix can be formed by forming a metal film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, using a colored composition containing a black colorant and the above colored pattern. The formation of the same is formed.

Examples of the radiation source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or the like, or an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen gas. Laser light source such as a laser. Radiation having a wavelength in the range of 190 nm to 450 nm is preferred. The exposure amount of the radiation is preferably from 10 J/m ² to 10,000 J/m ² .

The basic compound contained in the alkaline developing solution is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7. - undecene, 1,5-diazabicyclo-[4.3.0]-5-decene, and the like. A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. Further, after development using an alkaline developer, water washing is carried out under normal conditions. The method of developing treatment can be applied by a shower (developing) method, a jet (developing) method, a dipping (developing) method, a liquid coating (developing) method, or the like. The developing conditions are preferably from 5 seconds to 300 seconds at normal temperature.

[[3] Steps]

After the coloring pattern is formed in the step [2], the colored pattern can be hardened by hardening (also referred to as post-baking), whereby the formation of the colored pattern can be completed. The heating condition for post-baking can be set to 200 ° C or lower. The post-baking heating time is 10 minutes to 60 minutes. In the present embodiment, even if the post-baking temperature is low, a good coloring pattern such as solvent resistance can be obtained. Specifically, even if the post-baking temperature is 200° C. or lower and further 180° C. or lower, a color filter having sufficient solvent resistance or the like can be obtained. The film thickness of the colored pattern is preferably 0.5 μm to 5.0 μm, and more preferably 1.0 μm to 3.0 μm. Further, in order to increase the hardness and the like to a level which is practically required in the art, it is usually necessary to carry out a hardening step at a temperature exceeding 120 °C. Moreover, at 180 ° C Within the lower range, hardening at higher temperatures is preferred. Therefore, the curing temperature is preferably, for example, 150 ° C to 180 ° C.

[[4] Steps]

After the colored pattern is formed by the step [3], a coating film of the first radiation-sensitive resin composition is formed on the colored pattern on the substrate on which the colored pattern is formed.

When the coating film is formed by the coating method, after the first radiation sensitive resin composition solution is applied onto the substrate on which the colored pattern is formed, it is preferred to heat (pre-bake) the coated surface to form a coating film. The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass. The coating method of the first radiation-sensitive resin composition solution can be, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, or a spray method. A suitable method such as an ink coating method. Among these methods, a spin coating method or a slit coating method is preferred.

In addition, the first radiation-sensitive resin composition of the present embodiment is composed of the above-described components, and can be applied at a high speed without uneven coating. Therefore, a nozzle coating method can be employed. In the step [4] in the case of using the nozzle coating method, the first radiation sensitive resin composition is applied to the substrate on which the colored pattern is formed while the nozzle is moved relative to the substrate, and the coated surface is preferably applied to the coated surface. Prebaking, thereby forming a coating film. By the nozzle coating method, the first radiation sensitive resin composition can be uniformly applied to the substrate without waste.

The pre-baking conditions in the [4] step are due to the type of each component, the ratio of blending, and the like. The difference is preferably from 70 ° C to 120 ° C for about 1 minute to 15 minutes. The film thickness after prebaking of the coating film is preferably from 0.5 μm to 10 μm, and more preferably from about 1.0 μm to 7.0 μm.

[[5] Steps]

Next, at least a part of the coating film formed in the step [4] is irradiated with radiation. At this time, when patterning of the coating film is required, and only a part of the coating film is irradiated, for example, a method of irradiating with a photomask having a predetermined pattern may be used.

Examples of the radiation used in the irradiation include visible light rays, ultraviolet rays, far ultraviolet rays, and the like. Among them, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The radiation exposure amount (exposure amount) is a value obtained by measuring the intensity at a wavelength of 365 nm of the irradiated radiation by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), preferably 500 J/m ² to 10,000 J/m ^{2 .} More preferably, it is 1,500 J/m ² - 7,000 J/m ² .

[[6] Steps]

Next, the coating film after the radiation irradiation is developed to remove unnecessary portions (unirradiated portions of the radiation) to form a predetermined pattern. This step is carried out in the case where patterning of the coating film is necessary.

The developer used in the development is preferably an alkaline aqueous solution. Examples of the basic compound which can be used in the developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and amine; tetramethylammonium hydroxide and tetraethylammonium hydroxide. a quaternary ammonium salt such as ammonium.

Moreover, an appropriate amount of methanol, B may be added to the alkaline aqueous solution. It is used as a water-soluble organic solvent such as an alcohol or a surfactant. The alkali concentration in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. The developing method can be, for example, a suitable method such as a liquid coating method, a dipping method, a (shaking) dipping method, or a shower method. The development time varies depending on the composition of the first radiation-sensitive resin composition, and is preferably about 10 seconds to 180 seconds. After such development treatment, for example, after running water cleaning for 30 seconds to 90 seconds, a desired pattern can be formed, for example, by air drying with compressed air or compressed nitrogen.

[[7] Steps]

Then, the obtained coating film is heated by a heating device such as a hot plate or an oven to promote the curing reaction of the first radiation sensitive resin composition, thereby forming a protective film as a cured film. The hardening temperature in the step of [7] is preferably 200 ° C or lower. Further, a protective film having sufficient characteristics can be obtained even at 180 ° C or lower. Specifically, it is preferably 100° C. to 200° C., and when it is desired to achieve both low-temperature curing and reliability at a high level, it is more preferably 120° C. to 180° C. The heat curing time varies depending on the type of the heating device. For example, when the heating step is performed on the hot plate, the heating step can be 5 minutes to 30 minutes, and when the heating step is performed in the oven, the temperature can be set to 30 minutes to 90 minutes. Further, a step-by-step baking method or the like which performs a heating step twice or more may be used.

The first radiation-sensitive resin composition is composed of the above components, and can be cured at a low temperature. Moreover, it has sufficient resolution and radiation sensitivity. Therefore, when a protective film is formed in combination with a coloring pattern which is preferably used for low-temperature curing in order to use a dye, the first feeling is placed. A radiation resin composition can be suitably used as a material for forming the protective film.

In the production of the color filter of the present embodiment, after the step [7] of forming the protective film, a step of forming a transparent electrode on the protective film is included. The transparent electrode can be selected from an ITO electrode. The method of forming an ITO electrode can be performed by forming an ITO film by a sputtering method. As the patterned ITO electrode, if necessary, the formed ITO film can be patterned by photolithography.

[[8] Steps]

A protective film is formed by the step [7], and then an ITO electrode is formed on the protective film, and then a coating film of the second radiation-sensitive resin composition is formed on the ITO electrode on the substrate on which the protective film is formed.

When the coating film is formed by the coating method, after applying the second radiation-sensitive resin composition solution to the substrate on which the colored pattern or the like is formed, it is preferred to heat (pre-bake) the coated surface to form a coating film. . The solid content concentration of the composition solution used in the coating method is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and particularly preferably 15% by mass to 35% by mass. The coating method of the second radiation-sensitive resin composition solution can be, for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit coating method (slit die coating method), a bar coating method, or a spray method. A suitable method such as an ink coating method. Among these methods, a spin coating method or a slit coating method is preferred.

The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, and are preferably from 70 ° C to 120 ° C for about 1 minute to 15 minutes. The film thickness after prebaking of the coating film is preferably from 0.5 μm to 10 μm, and more preferably from about 1.0 μm to 7.0 μm.

[[9] Steps]

Next, at least a part of the coating film formed in the step [8] is irradiated with radiation. At this time, in order to form a spacer at a desired position, a part of the coating film is irradiated with radiation, and for example, a method of irradiating with a photomask having a predetermined pattern may be used. Examples of the radiation used in the irradiation include visible light rays, ultraviolet rays, far ultraviolet rays, and the like. Among them, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation containing ultraviolet rays of 365 nm is more preferable.

The radiation exposure amount (exposure amount) is a value obtained by measuring the intensity at the wavelength of 365 nm of the irradiated radiation by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), and preferably 100 J/m ² to 5,000 J/m ^{2 .} More preferably, it is 200 J/m ² - 3,000 J/m ² .

The second radiation sensitive resin composition used for forming the spacer of the color filter of the present embodiment has an advantage that the radiation sensitivity is higher than that of the composition formed by the previously known spacer. Therefore, even when the radiation irradiation amount is 700 J/m ² or less and further 600 J/m ² or less, a desired film thickness, a good shape, excellent adhesion, and high hardness of the cured film can be obtained. And get the spacer.

[[10] Steps]

Next, the coating film after the irradiation of the radiation is developed to remove unnecessary portions, thereby forming a pattern of a predetermined spacer.

For the developer to be used for development, for example, an inorganic base such as sodium hydroxide, potassium hydroxide or sodium carbonate, or an aqueous solution of a basic compound such as a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. Water soluble of the above basic compound An appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added to the liquid for use. Further, it may be used by merely adding an appropriate amount of a surfactant, or by adding an appropriate amount of a surfactant together with the above-described water-soluble organic solvent.

The development method may be any one of a liquid coating method, a dipping method, and a shower method, and the development time is preferably about 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, a running water cleaning is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen gas, thereby obtaining a pattern of a desired spacer.

[[11] Steps]

Next, the obtained pattern-like coating film is cured by a suitable heating means such as a hot plate or an oven to obtain a cured film to obtain a separator. The hardening temperature is preferably 200 ° C or lower. Moreover, a spacer having sufficient characteristics can be obtained even at 180 ° C or lower. Specifically, it is preferably 100° C. to 200° C., and when it is desired to achieve both low-temperature curing and reliability at a high level, it is more preferably 150° C. to 180° C. The curing time is, for example, preferably 5 minutes to 30 minutes on a hot plate, and preferably 30 minutes to 180 minutes in an oven.

Since the second radiation-sensitive resin composition contains the [δ] compound as described above, it can be cured at a low temperature as described above. Moreover, storage stability can be achieved, and sufficient resolution and radiation sensitivity can be achieved. Therefore, when a spacer is used in combination with a coloring pattern which is preferably used for low-temperature curing in order to use a dye, the second radiation-sensitive resin composition can be suitably used as a material for forming the spacer.

According to the above manufacturing method, a colored pattern, a protective film, and a spacer can be produced, and the color filter of this embodiment can be manufactured. As described above, the coloring pattern of the color filter of the present embodiment is formed by applying a colored composition onto a suitable substrate, patterning, and then curing. Similarly, the protective film is formed by applying a first radiation-sensitive resin composition and patterning it, followed by curing. Similarly, the spacer is formed by applying a second radiation-sensitive resin composition and patterning it, followed by curing. Further, the colored composition, the first radiation sensitive resin composition, and the second radiation sensitive resin composition can be formed by a low temperature curing at 200 ° C or lower to form a colored pattern, a protective film, or a spacer.

Therefore, in the color filter of the present embodiment, it can be produced by low-temperature curing.

Further, in the color filter of the present embodiment, a protective film is formed after the coloring pattern is formed. The protective film can be formed by low-temperature curing at 200 ° C or lower, so that the colored pattern is not exposed to a high-temperature heating state for forming a protective film after formation. Similarly, in the color filter of the present embodiment, a spacer is formed after the coloring pattern is formed. The spacer can be formed by low-temperature hardening of 200 ° C or less, so that the colored pattern is not exposed to a state of high-temperature heating for forming the spacer after formation. Therefore, even if a dye having excellent color properties but having problems in heat resistance is used as a colorant, step deterioration can be reduced.

Further, when the colored pattern is formed in the production of the color filter of the present embodiment, the curing temperature can be adjusted in consideration of the formation of the protective film or the formation of the spacer. That is, the use and the most suitable for forming a colored pattern on the substrate alone The hardening temperature forms a colored pattern compared to a lower hardening temperature. Thereafter, the colored pattern can also be heated by hardening heating of the protective film formed on the colored pattern or hardening heating of the spacer.

For example, in the case where the optimum curing temperature of the colored pattern and the protective film and the spacer is 200 ° C or lower, specifically 180 ° C, the colored pattern can be formed with a curing temperature lower than 180 ° C. In this case, the colored pattern can be formed in advance by, for example, a hardening temperature of 150 °C. Next, a coating film of the first radiation sensitive resin composition is formed on the colored pattern, and is cured at an optimum temperature of 180 ° C to form a protective film. As a result, the colored pattern formed in the lower layer is also heated, and the color filter of the present embodiment including the colored pattern and the protective film in a desired state can be obtained. Further, for example, a colored pattern and a protective film are formed in advance at a curing temperature of 150 ° C, and thereafter, a spacer can be formed using the second radiation-sensitive resin composition at an optimum curing temperature of 180 ° C. As a result, the color pattern and the protective film formed previously are also heated, and the color filter of the present embodiment including the colored pattern and the protective film and the spacer in a desired state can be obtained.

[[12]Steps]

Next, in the method of producing a color filter of the present embodiment, the step of forming an alignment film [12] may be provided after the step [11] as described above. Further, in the color filter of the present embodiment, an alignment film having a liquid crystal alignment ability and capable of controlling the alignment of the liquid crystal can be provided.

The above liquid crystal alignment agent was used in the step [12]. Further, a colored pattern and a protective film and space are formed by the above steps [1] to [11]. The liquid crystal alignment agent is applied onto the substrate by a suitable coating method such as a roll coating method, a spinner method, a printing method, or an inkjet method. Next, the substrate coated with the liquid crystal alignment agent is prebaked, and then post-baked to form a coating film. The prebaking conditions are preferably from 0.1 minute to 5 minutes at 40 ° C to 120 ° C. The post-baking conditions are, for example, 120 ° C to 230 ° C, preferably 150 ° C to 200 ° C, more preferably 150 ° C to 180 ° C, and the time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

The solid content concentration of the liquid crystal alignment agent used when the liquid crystal alignment agent is applied to the substrate (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) may be considered to be viscous, It is suitably selected as a volatile matter, and is preferably in the range of 1% by weight to 10% by weight.

In the case of using a liquid crystal alignment agent containing a [L] radiation sensitive polymer having a photoalignment group, the coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation to impart liquid crystal alignment ability. . Such a process corresponds to the method of the previous alignment process, such as a rubbing process, and can be performed more easily. Here, as the radiation, for example, ultraviolet rays and visible rays including wavelengths of light of 150 nm to 800 nm can be used. It is particularly preferable to use ultraviolet rays containing light having a wavelength of 300 nm to 400 nm as radiation.

When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction to impart a pretilt angle, or may be performed by combining the methods. In the case of irradiating non-polarized radiation, the irradiation direction must be an oblique direction.

The irradiation amount of the radiation is preferably 1 J/m ² or more and less than 10,000 J/m ² , and more preferably 10 J/m ² to 3,000 J/m ² .

In the case of using a liquid crystal alignment agent containing [M] polyimine which does not have a photo-alignment group, the post-baking coating film can also be used as an alignment film as it is. Further, the post-baking coating film may be subjected to a rubbing treatment (friction treatment) in a fixing direction by, for example, a roll wound with a cloth comprising fibers such as nylon, rayon, or cotton, to impart liquid crystal alignment ability.

As described above, in the color filter manufacturing method of the present embodiment, the alignment film can be formed at a heating temperature of 200 ° C or lower and a heating temperature of 180 ° C or lower, using the liquid crystal alignment agent. Therefore, the coloring pattern of the color filter formed in the above steps [1] to [3] can be prevented from being exposed to a high temperature in the step [12] of forming the alignment film.

[Example]

Hereinafter, the embodiments of the present invention will be described in detail based on examples, but the present invention is not limited by the examples.

<Formation and Evaluation of Colored Patterns>

Example 1

[[I] Synthesis of alkali soluble resin (IA)]

In a flask equipped with a condenser and a stirrer, 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were placed. Next, 18 parts by mass of methacrylic acid as a compound (I-1), 14 parts by mass of 2-methylglycidyl methacrylate as a compound of (I-2), and 20 mg of glycidyl methacrylate. And 10 parts by mass of styrene as the compound (I-4), 23 parts by mass of tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate, and 15 parts by mass of methyl methacrylate. After the nitrogen gas was replaced, the temperature of the solution was gradually raised to 70 ° C while stirring, and the temperature was maintained for 5 hours to carry out polymerization, whereby a solution containing an alkali-soluble resin (IA) as a copolymer was obtained. The solid solution concentration of the obtained polymer solution was 31.5%, and the Mw of the alkali-soluble resin (IA) as a copolymer was 10,100.

Example 2

[[I] Synthesis of alkali soluble resin (IB)]

4 parts by mass of AIBN and 300 parts by mass of diethylene glycol methyl ethyl ether were placed in a flask equipped with a condenser and a stirrer, and 23 parts by mass of methacrylic acid as a compound (I-1) was added thereto as (I-4). 10 parts by mass of styrene, 32 parts by mass of benzyl methacrylate, and 35 parts by mass of methyl methacrylate, and further charged with 2.7 parts by mass of α-methylstyrene dimer, while stirring slowly The temperature of the solution was raised to 80 ° C, and after maintaining the temperature for 4 hours, the temperature was raised to 100 ° C, and the temperature was maintained for 1 hour to carry out polymerization, whereby a solution containing the copolymer was obtained. The resulting polymer solution had a solids concentration of 24.9% and a Mw of 12,500. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the obtained solution containing the copolymer, and the mixture was stirred at 90 ° C for 30 minutes in an air atmosphere. 16 parts by mass of glycidyl methacrylate as the compound (I-2) was placed and kept at 90 ° C for 10 hours to obtain an alkali-soluble resin (IB) as a copolymer. The obtained polymer solution had a solid concentration of 29.0% and a Mw of 14,200.

Example 3

[Modulation of coloring composition]

Ethylene oxide-modified dipentaerythritol hexaacrylate (II-1) and polyfunctional acrylic acid as a [II] polymerizable compound were mixed with 90 parts by mass of the alkali-soluble resin (IA) as a copolymer obtained in Example 1. a mixture of a mixture of ester compounds (KAYARAD (registered trademark) DPHA-40H, Nippon Kayaku Co., Ltd.) (II-2) (mixing ratio ((II-1) / (II-2)) = 4) 100 parts by mass, as [III] 2-methyl-1-(4-methylthienyl)-2-morpholinopropan-1-one (Irgacure 907, Ciba Specialty Chemicals Co., Ltd.) (III-1) as a polymerization initiator 25 parts by mass, 100 parts by mass of a red coloring agent (IV-1) containing a red dye as a [IV] coloring agent, pentaerythritol tetrakis(3-mercaptopropionate) (V-1) as a compound of [V] and 3 parts by weight a mixture of ethylaminobenzenesulfonate (V-2) (mixing ratio ((V-1) / (V-2) = 5)) 6 parts by mass, the base obtained in Example 2 as another alkali-soluble resin The soluble resin (IB) was 10 parts by mass. Next, using cyclohexanone as a solvent, a solvent was added so that the solid content concentration of the coloring composition became 30 wt%, and then filtration was carried out using a micropore filter having a pore diameter of 0.5 μm to prepare a red colored composition.

A green coloring composition was prepared in the same manner as above except that a green coloring agent (IV-2) containing a green dye was used as the [IV] coloring agent. Further, a blue coloring composition was prepared in the same manner as above except that a blue coloring agent (IV-3) containing a blue dye was used as the [IV] coloring agent.

Example 4

[Formation of coloring pattern]

On the soda glass substrate on which the SiO ₂ film for preventing elution of sodium ions was formed on the surface, the red colored composition obtained in Example 3 was applied using a spin coater. Next, prebaking was performed on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. After the substrates were cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to the coating film at a exposure amount of 1,000 (J/m ² ) using a high-pressure mercury lamp through a photomask. Thereafter, a developing solution (0.04 wt% aqueous potassium hydroxide solution at 23 ° C) was sprayed onto the substrates at a developing pressure of 1 (kgf/cm ² ) (nozzle diameter of 1 mm), thereby performing shower development. A colored pattern of 200 μm × 200 μm was formed on the substrate. Further, post-baking was performed at 180 ° C for 30 minutes to form a red colored pattern.

A green coloring pattern was formed in the same manner as described above except that the green coloring composition obtained in Example 3 was used as the coloring composition. Further, a blue coloring pattern was formed in the same manner as described above except that the blue coloring composition obtained in Example 3 was used as the coloring composition.

Example 5

[Evaluation of coloring patterns]

The following coloring patterns were evaluated.

Evaluation of development resistance

In the formation of the color pattern of each of the above colors, the value of the following formula was calculated: the film thickness ratio before and after development = (film thickness after development / film thickness before development) × 100.

The coloring pattern of each of the above colors was 95% or more in thickness before and after development, and it was found that the coloring resistance was excellent.

Evaluation of heat resistance

The coloring pattern of each of the above colors was further heated at 180 ° C for additional 30 minutes. Further, the color change ΔEab ^* before and after the additional heating is obtained. The coloring patterns of the respective colors described above were all ΔEab ^* less than 3, and it was found to have good heat resistance.

Solvent resistance evaluation

The colored pattern was immersed in N-methylpyrrolidone at 60 ° C for 30 minutes together with the substrate. Thereafter, the coloring patterns of the respective colors on the substrate were observed, and as a result, it was confirmed that the coloring pattern was maintained after the immersion, and the immersed N-methylpyrrolidone was not colored at all. It is understood that any of the above colored patterns has good solvent resistance.

<Formation and evaluation of protective film>

Example 6

[[A] Synthesis of alkoxylate polymer]

24 parts by mass of propylene glycol monomethyl ether was placed in a container equipped with a stirrer, followed by 54 parts by mass of methyltrimethoxydecane, 30 parts by mass of tetraethoxydecane, and 3-propenylmethoxypropyltrimethoxy group. 16 parts by mass of decane was heated until the solution temperature became 60 °C. After the solution temperature reached 60 ° C, 0.1 part by mass of formic acid and 19 parts by mass of ion-exchanged water were charged, and after heating to 75 ° C, the mixture was kept for 2 hours. After cooling to 45 ° C, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Further, the temperature of the solution was changed to 40 ° C, and evaporation was carried out while maintaining the temperature, thereby removing water and methanol and ethanol due to hydrolysis condensation. Obtained by the above operation Hydrolyzed condensate (A-I) (solid content = 35 mass%, Mw = 1,800, Mw / Mn = 2.2).

Example 7

[Modulation of the first sense radiation linear resin composition]

Mixed as a solution containing the hydrolysis condensate (AI) obtained in Example 6 of [A] a methoxyalkane polymer (corresponding to an amount of 100 parts by mass (solid matter) of the hydrolysis condensate (AI)) as [B] 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane (Irgacure 907, BASF Corporation) of a radical polymerization initiator 5 parts by mass, 2-benzyl-2 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (Irgacure 369, BASF Corporation) 2 parts by mass of dipentaerythritol hexaacrylic acid as [D] ethylenically unsaturated compound Mixture of ester and dipentaerythritol pentaacrylate (Morby 50/50) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5 parts by mass, isocyanuric acid EO modified triacrylate (trade name: ARONIX (registered trademark) 15 parts by mass of M-313, manufactured by Toagosei Co., Ltd., and propylene glycol monomethyl ether as a [C] organic solvent was added and dissolved in a solid content of 25% by mass to prepare a first radiation-sensitive resin composition. .

Example 8

[Formation of Protective Film]

The first radiation sensitive resin composition prepared in Example 7 was applied onto an alkali-free glass substrate by a spinner, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a coating film having a film thickness of 4.0 μm. . Next, the obtained coating film was irradiated with radiation by using a high pressure mercury lamp so that the exposure amount was 2,000 J/m ² . Next, post-baking was carried out in an oven at a curing temperature of 180 ° C and a hardening time of 30 minutes to form a protective film.

Example 9

[Evaluation of Protective Film]

Evaluation of preservation stability

The protective film was formed by the formation method of Example 8 from the first radiation-sensitive resin composition of Example 7 immediately after preparation, and the film thickness (referred to as "film thickness immediately after preparation" in the following formula) was measured. Furthermore, after preparing by the formation method of Example 7, the first radiation sensitive resin composition was stored at 25 ° C for 5 days, and the film thickness of the formed protective film was measured in the same manner after 5 days (in the following formula) It is "film thickness after 5 days"). The film thickness increase rate (%) was calculated from the following formula.

Film thickness increase rate (%) = (film thickness after 5 days - film thickness immediately after preparation) / (film thickness immediately after preparation) × 100

The film thickness increase rate was 3% or less, and it was judged that the storage stability was good.

Light resistance evaluation

The protective film obtained by the method of the formation of Example 8 was further irradiated with 800,000 J/m ² at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.) to examine the amount of film reduction. The film reduction amount was 2% or less, and it was judged that the light resistance was good.

Evaluation of heat resistance

The protective film obtained by the formation method of Example 8 was further heated in an oven at 230 ° C for 20 minutes using a stylus type film thickness measuring machine (Alpha Step IQ, KLA-TENCOR, measured the film thickness before and after heating. Further, the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated, and the residual film ratio was taken as heat resistance. The residual film ratio was 99%, and it was judged that the heat resistance was good.

Chemical resistance evaluation

The protective film obtained by the formation method of Example 8 was immersed in an aligning film stripping solution CHEMICLEAN (registered trademark) TS-204 (Sanyo Chemical Industry Co., Ltd.) heated to 60 ° C for 15 minutes, washed with water, and further in an oven. Dry at 120 ° C for 15 minutes. The film thickness before and after the treatment was measured by a stylus type film thickness measuring machine (Alpha Step IQ, Meike), and the residual film ratio (film thickness after treatment/film thickness before treatment × 100) was calculated, and the residual film was obtained. Rate as chemical resistance. The residual film ratio was 99%, and it was judged that the chemical resistance was good.

<Formation and evaluation of spacers>

Example 10

[[α] compound synthesis]

In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were charged. Next, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate, 38 parts by mass of methyl methacrylate, and 10 parts by mass of styrene, A were charged. 20 parts by mass of glycidyl acrylate, after nitrogen substitution, the temperature of the solution was gradually increased to 70 ° C while stirring, and the temperature was maintained for 4 hours to carry out polymerization, thereby obtaining a copolymer (α-I). (Solid concentration = 34.4% by mass, Mw = 8,000, Mw / Mn = 2.3). Further, the solid concentration is a ratio indicating the mass of the copolymer in the total mass of the copolymer solution.

Example 11

[Modulation of the second radiation-sensitive resin composition]

100 parts by mass of dipentaerythritol hexaacrylate (β-I) as a [β] polymerizable compound was mixed with 100 parts by mass of the copolymer (α-I) obtained in Example 10 as the [α] compound, as [γ] Ethylketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine) of the polymerization initiator Irgacure (registered trademark) OXE02, Ciba Specialty Chemicals Co., Ltd.) (γ-I) 5 parts by mass, and 4,4'-diaminodiphenyl hydrazine (δ-I) as a [δ] compound, further mixed 5 parts by mass of γ-glycidoxypropyltrimethoxydecane as a [ω-1]-adjuvant auxiliary agent, and 0.5 parts by mass of a surfactant (FTX-218, Neos) as a [ω-2] surfactant 0.5 parts by mass of 4-methoxyphenol as a [ω-3] storage stabilizer, and after adding propylene glycol monomethyl ether acetate so that the solid content concentration was 30% by mass, it was filtered using a micropore having a pore diameter of 0.5 μm. The device was filtered and the second radiation-sensitive resin composition was prepared.

Example 12

[Formation of spacers]

As an example of forming a spacer, an example in which only a spacer is formed on a substrate will be described.

The second radiation sensitive resin composition prepared in Example 11 was applied onto an alkali-free glass substrate using a spin coater. Next, prebaking was performed on a hot plate at 100 ° C for 2 minutes to form a coating film having a film thickness of 6.0 μm. Next, the obtained coating film was irradiated with radiation by using a high pressure mercury lamp so that the exposure amount was 700 J/m ² . Thereafter, a developing solution (0.04% by mass aqueous solution of potassium hydroxide at 23° C.) was sprayed onto the substrate at a developing pressure of 1 (kgf/cm ² ) (nozzle diameter of 1 mm), thereby performing shower development. A pattern of spacers is formed on the substrate. Next, post-baking was performed in an oven at a hardening temperature of 180 ° C and a hardening time of 30 minutes, thereby forming a spacer on the substrate. Further, it was confirmed that a spacer was formed on the substrate at a desired position and shape (resolution).

Example 13

[Evaluation of spacers]

With respect to the spacer obtained in Example 12, the cross-sectional shape was observed with a scanning electron microscope.

The spacers were formed with the pattern edges being wedge-shaped and all good.

Next, on a spacer formed on the substrate in Example 12, AL3046 (manufactured by JSR Corporation) was applied by a printer for coating a liquid crystal alignment film, and dried at 180 ° C for 1 hour to form a dry film thickness of 0.05. The coating film of the alignment film of μm is used as a liquid crystal alignment film. The coating film was subjected to a rubbing treatment under the conditions of a rotation speed of the roll of 500 rpm and a moving speed of the stage of 1 cm/sec using a friction device having a roll wound with a nylon cloth. At this time, no cut or peeling occurred in the spacer.

<Manufacture of color filters>

Example 14

A color filter was produced using the coloring compositions of the respective colors (the red coloring composition, the green coloring composition, and the blue coloring composition) described in Example 3. First, a red colored composition was applied onto a glass substrate on which a black matrix pattern was formed by a slit die coater, and pre-baked on a hot plate at 90 ° C for 2 minutes to form a coating film. Thereafter, a ghi line (wavelength of 436 nm, 405 nm, and an exposure amount of 1,000 J/m ² in terms of i-line conversion was irradiated with an exposure machine Canon PLA501F (Canon Inc.) in accordance with a predetermined pattern mask. Intensity ratio at 365 nm = 2.7:2.5:4.8), development was carried out using a 0.05% aqueous potassium hydroxide solution, rinsing in ultrapure water for 60 seconds, and further heat treatment in an oven at 180 ° C for 30 minutes. A red stripe pattern having a film thickness of 2.0 μm (pattern width of 100 μm) was formed.

Next, the operation was carried out in the same manner, and a green colored composition was used to form a green striped pattern. Further, a blue colored composition was used to form a blue striped pattern, and red, green, and blue three-color striped color filters (strip width of 100 μm) were formed.

The red, green, and blue three-color coloring patterns formed under the conditions of the post-baking temperature of 180 ° C and 30 minutes formed as described above do not cause problems such as pattern defects caused by insufficient curing, peeling off from the substrate, and the like. A stripe pattern of three colors can be formed.

Next, the first radiation-sensitive resin composition described in Example 7 was applied to the obtained three-color striped pattern by a slit die coater. Next, pre-baking was performed on a hot plate at 90 ° C for 5 minutes to form a coating film. The obtained pre-baked coating film was irradiated with radiation at a exposure amount of 2,000 J/m ² using a high-pressure mercury lamp, developed with an alkaline aqueous solution, and further heated in an oven at 180 ° C for 60 minutes to form a self-heating process. A protective film having a film thickness of 2.0 μm from the upper surface of the three-color striped pattern. The substrate on which the protective film was formed on the colored pattern was produced as described above.

The substrate having the protective film formed on the colored pattern was measured for the unevenness (flatness) of the surface of the protective film using a contact-type film thickness measuring device α-Step (Keide Japan Co., Ltd.) (measurement length was 2,000 μm, measurement range) It is 2,000 μm square, and the number of measurement points is n=5). In other words, the measurement direction is the short-axis direction of the stripe line in the red, green, and blue directions, and the long-axis direction of the stripe line of the same color of red-red, green-green, and blue-blue, and the direction is n for each direction. The measurement was carried out at =5 (the total number of n was 10). The average of 10 times of the height difference (nm) of the highest part and the lowest part of each measurement was calculated. The average value at this time is 200 nm. Even after the formation of the protective film, the colored pattern does not shrink or swell, and the surface of the protective film has no unevenness, and exhibits good flatness.

Next, regarding the obtained substrate on which the protective film was formed on the colored pattern, an ITO film was formed on the protective film by a sputtering method to form an ITO electrode.

Next, the second radiation-sensitive resin composition prepared in Example 11 was applied onto the ITO electrode by a slit die coater. Next, prebaking was performed on a hot plate at 100 ° C for 2 minutes to form a coating film having a film thickness of 6.0 μm. Next, the obtained coating film was irradiated with radiation using a high pressure mercury lamp and an exposure amount of 700 J/m ² . Thereafter, a developing solution (0.04% by mass aqueous solution of potassium hydroxide at 23° C.) was sprayed onto the substrate at a developing pressure of 1 (kgf/cm ² ) (nozzle diameter of 1 mm), thereby performing shower development. A pattern of spacers is formed on the substrate. Next, post-baking was carried out in an oven at a hardening temperature of 180 ° C and a hardening time of 30 minutes. Thereby a spacer is formed on the ITO electrode. The spacer is formed in a region on the ITO electrode corresponding to the black matrix forming region.

The color filter of the present example was fabricated in the above manner. The color filter of the present example produced has excellent color characteristics.

Example 15

[Manufacture of color filter with photo-alignment film]

In the present example, using the color filter obtained in Example 14, a photo-alignment film was formed using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group.

First, in the color filter of Example 14, an international publication (WO) 2009 as a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group was coated on a substrate on which a spacer was formed by a spinner. Liquid crystal alignment agent A-1 described in Example 6 of No. 025386. Next, after prebaking for 1 minute on a hot plate at 80 ° C, it was heated in an oven which was internally purged with nitrogen at 180 ° C for 1 hour to form a coating film having a film thickness of 80 nm. Next, using Hg-Xe lamp and a Glan - Taylor prism, autocorrelation vertical direction is inclined 40 ° in terms of the direction of the surface of the substrate, / m ² comprising a bright line of 313 nm of the polarized light irradiating the surface of the coating film 200 J Ultraviolet rays are used to produce a color filter having a photo-alignment film.

Example 16

[Manufacture of color filter with vertical alignment film]

In this example, the color filter obtained in Example 14 was used to make A vertical alignment film is formed using a liquid crystal alignment agent containing a polyimine having no photo-alignment group.

First, in the color filter of Example 14, an AL60101 for vertical alignment film formation as a liquid crystal alignment agent containing a polyimide having no photo-alignment group was coated on a substrate on which a spacer was formed by using a spinner. Manufactured by JSR Corporation). Next, after prebaking for 1 minute on a hot plate at 80 ° C, the film was heated at 180 ° C for 1 hour in an oven purged with nitrogen to form a coating film having a film thickness of 80 nm, and was produced. Color filter for vertical alignment film.

<Application of color filter in liquid crystal display element>

Example 17

[Manufacture of color liquid crystal display elements]

In the manufacture of a liquid crystal display element, a color filter having a photo-alignment film of Example 15 was used as the color filter. As the driving substrate, a driving substrate on which a photo-alignment film was formed on a substrate prepared in accordance with a known method was used in the same manner as in Example 15. These are combined to produce a color liquid crystal display element. The manufactured color liquid crystal display element is provided with a polarizing plate or the like, and has the same structure as the color liquid crystal display element shown in FIG. 2 described above. The liquid crystal display element of this example shows the uniformity of the height of the gap between the substrates sandwiching the liquid crystal. Moreover, a color display that achieves excellent color characteristics.

[Industrial availability]

The color filter of the present invention can be produced by low-temperature curing, and has high reliability and excellent color characteristics. Therefore, the color filter of the present invention can be It is suitably used as a color filter for a flexible liquid crystal display using a resin substrate or a color filter for a large liquid crystal television requiring high image quality.

1‧‧‧Liquid display components

2, 5‧‧‧ substrate

3‧‧‧pixel electrode

4‧‧‧ITO electrodes

6‧‧‧Coloring pattern

7‧‧‧Black matrix

8‧‧‧Protective film

9‧‧‧ spacers

10‧‧‧Color filters

12‧‧‧Alignment film

13‧‧‧LCD

14‧‧‧Polar plate

16‧‧‧ Sealing material

17‧‧‧Backlight light

Fig. 1 is a schematic cross-sectional view showing a color filter of the embodiment.

Fig. 2 is a schematic cross-sectional view showing a color liquid crystal display element including the color filter of the embodiment.

1‧‧‧Liquid display components

2, 5‧‧‧ substrate

3‧‧‧pixel electrode

4‧‧‧ITO electrodes

6‧‧‧Coloring pattern

7‧‧‧Black matrix

8‧‧‧Protective film

9‧‧‧ spacers

10‧‧‧Color filters

12‧‧‧Alignment film

13‧‧‧LCD

14‧‧‧Polar plate

16‧‧‧ Sealing material

17‧‧‧Backlight light

Claims (25)

A color filter comprising a colored pattern and a protective film, the colored pattern comprising a pigment selected from the group consisting of a diketopyrrolopyrrole pigment, a zinc halide phthalocyanine pigment, a triarylmethane dye, and an azo dye At least one coloring agent of the group formed; the protective film is formed of a first radiation sensitive resin composition containing the following components: [A] a siloxane polymer, [B] a radical polymerization initiator, And [C] organic solvents. The color filter according to claim 1, wherein the spacer further comprises a spacer formed of a second radiation-sensitive resin composition containing the following components: [α] alkali-soluble resin, [β a polymerizable compound having an ethylenically unsaturated bond, a [γ] radiation-sensitive polymerization initiator, and [δ] are selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) At least one compound of the group formed; [Chemical 1] In the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ¹ to R ⁶ is an electron withdrawing group, and in R ¹ to R ⁶ At least one of them is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with an alkyl group having 1 to 6 carbon atoms; in the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom. And an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms; Is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having a carbon number of 2 to 6; wherein the above methylene group and alkylene group are present All or a part of the hydrogen atom may be substituted by a cyano group, a halogen atom or a fluoroalkyl group. The color filter according to claim 1, wherein the coloring pattern is formed of a coloring composition containing the following components: [I] an alkali-soluble resin, [II] a polymerizable property having an ethylenically unsaturated bond. a compound, a [III] radiation-sensitive polymerization initiator, and a colorant according to [IV]. The color filter according to claim 3, wherein the coloring composition further contains [V] a compound selected from the formula (1), a compound represented by the above formula (2), and three At least one compound of the group consisting of a primary amine compound, an amine salt, a phosphonium salt, a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring. The color filter according to claim 3, wherein the [I] alkali-soluble resin contained in the coloring composition is a copolymer comprising the following structural unit: (I-1) is selected from the group consisting of A structural unit formed of at least one of a group consisting of a saturated carboxylic acid and an unsaturated carboxylic anhydride, and (I-2) a structural unit formed of an epoxy group-containing unsaturated compound. The color filter according to the first aspect of the invention, wherein the [A] siloxane polymer contained in the first radiation sensitive resin composition is a hydrolysis condensate of a hydrolyzable decane compound, The hydrolyzable decane compound includes: (a1) a hydrolyzable decane compound represented by the following formula (A-1); and (a2) a hydrolyzable decane compound represented by the following formula (A-2); In the formula (A-1), R ¹ is an alkyl group having 1 to 6 carbon atoms; R ² is an organic group containing a radical reactive functional group; and p is an integer of 1 to 3; wherein, when R ¹ and When R ^{2 is} plural, a plurality of R ¹ and R ² are each independently; in the formula (A-2), R ³ is an alkyl group having 1 to 6 carbon atoms; R ⁴ is a hydrogen atom and the carbon number is 1 to 20 alkyl groups, 1 to 20 carbon atoms, phenyl, naphthyl, epoxy, amino or isocyanate groups; n is an integer from 0 to 20; Wherein, when R ³ and R ^{4 are} plural, a plurality of R ³ and R ⁴ are each independently. The color filter according to claim 1, wherein the first radiation sensitive resin composition further contains [D] an ethylenically unsaturated compound other than the [A] alkane polymer. The color filter according to claim 1, wherein the first radiation sensitive resin composition further contains an [E] radiation sensitive acid generator or a radiation sensitive alkali generator. For example, the color filter described in claim 2, wherein: The [α] alkali-soluble resin contained in the second radiation-sensitive resin composition is a copolymer containing a structural unit: (α-1) is selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. At least one structural unit formed in the group, and (α-2) a structural unit formed of an epoxy group-containing unsaturated compound. The color filter according to claim 1, wherein the coloring pattern is a colored pattern formed at a curing temperature of 200 ° C or lower. The color filter according to claim 1, wherein the protective film is a protective film formed at a curing temperature of 200 ° C or lower. The color filter of claim 2, wherein the spacer is a spacer formed at a hardening temperature of 200 ° C or lower. The color filter according to claim 1, wherein the coloring pattern is a colored pattern formed at a hardening temperature lower than a curing temperature of the protective film. The color filter of claim 2, wherein the colored pattern is a colored pattern formed at a hardening temperature lower than a hardening temperature of the spacer. The color filter according to claim 2, wherein the protective film is a protective film formed at a hardening temperature lower than a hardening temperature of the spacer. As described in any one of claims 1 to 15, a color filter comprising: an alignment film which is a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group; and a liquid crystal alignment agent containing a polyimide having no photo-alignment group Any of the resulting alignment films. The color filter according to claim 16, wherein the alignment film is an alignment film obtained by using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group. A liquid crystal display element comprising the color filter according to any one of claims 1 to 17. A method of producing a color filter, comprising the steps of: [1] forming a coating film of a coloring composition on a substrate, the coloring composition containing a halogenated pyridylpyrrole pigment selected from the group consisting of halogenated At least one coloring agent of a group consisting of a zinc phthalocyanine pigment, a triarylmethane dye, and an azo dye; [2] a step of forming a colored pattern on a coating film of the coloring composition; [3] a step of curing the coating film on which the colored pattern is formed at 200 ° C or lower; [4] a step of forming a coating film of the first radiation-sensitive resin composition on the substrate, the first radiation-sensitive resin composition The composition contains the following components: [A] a siloxane polymer, [B] a radical polymerization initiator, and [C] an organic solvent; [5] at least a coating film of the first radiation-sensitive resin composition a step of irradiating a part of the radiation; [6] a step of developing the coating film irradiated with radiation in the step [5]; [7] hardening the coating film developed in the step [6] at 200 ° C or lower; a step; [8] on the substrate having the hardened coating film of the step [7] In the step of forming the second radiation-sensitive resin composition coating film, the second radiation-sensitive resin composition contains the following components: [α] alkali-soluble resin, [β] a polymerizable compound having an ethylenically unsaturated bond, and [ γ] sensitizing radiation polymerization initiator; and [δ] at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2); a step of irradiating at least a part of the coating film of the second radiation-sensitive resin composition; [10] a step of developing the coating film irradiated with radiation in the step [9]; and [11] a step of hardening the coating film developed in the step [10] to form a spacer at 200 ° C or lower; [Chemical 5] In the formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ¹ to R ⁶ is an electron withdrawing group, and in R ¹ to R ⁶ At least one of them is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with an alkyl group having 1 to 6 carbon atoms; in the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom. And an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and all or a part of the hydrogen atom of the above amine group may be substituted with a hydrocarbon group having 1 to 6 carbon atoms; Is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having a carbon number of 2 to 6; wherein the above methylene group and alkylene group are present All or a part of the hydrogen atom may be substituted by a cyano group, a halogen atom or a fluoroalkyl group. The method for producing a color filter according to claim 19, wherein the coloring composition further contains [I] an alkali-soluble resin, [II] a polymerizable compound having an ethylenically unsaturated bond, [III] A radiation sensitive linear polymerization initiator. The method of producing a color filter according to claim 19, wherein the hardening temperature of the step [3] is a temperature lower than a hardening temperature of the step [7]. The method of producing a color filter according to claim 19, wherein the hardening temperature of the step [3] is a temperature lower than a hardening temperature of the step [11]. The method of producing a color filter according to claim 19, wherein the hardening temperature of the step [7] is a temperature lower than a curing temperature of the step [11]. The method for producing a color filter according to claim 19, wherein the step of forming an alignment film at 200 ° C or lower after [11] is included in the step [11]. The method of manufacturing a color filter according to claim 24, wherein the step [12] is to use a radiation containing a photoalignment group. The alignment film is formed of any one of a liquid crystal alignment agent of a polymer and a liquid crystal alignment agent containing a polyimide having no photo-alignment group.