TWI547724B - Color filter, liquid crystal display device, and method for fabricating color filter - Google Patents

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 includes a liquid crystal panel in which liquid crystal is sandwiched between a pair of substrates such as a glass substrate. An alignment film may be provided on the surface of the substrate sandwiching the liquid crystal. The aligning film liquid crystal alignment control ability is imparted from the prior art by using an organic film which is chemically stable and has high heat resistance such as polyimide, and is rubbed in one direction by a cloth such as nylon or polyester. Friction treatment.

A spherical or rod-shaped spacer including glass, alumina, or resin is disposed between a pair of substrates of the liquid crystal display device by dispersion or the like, and the thickness of the liquid crystal is maintained at a predetermined value of about 1 μm to 20 μm. In the liquid crystal display device, the alignment change of the liquid crystal occurs, and the light emitted from the light source such as the backlight or the external light functions as a fine shutter. Further, the light is partially transmitted or blocked to display. The liquid crystal display element is characterized by being thin, lightweight, and the like.

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.

In addition, the liquid crystal display device overcomes the problems of high definition, colorization, and viewing angle expansion, and further expands its use to display of PCs (personal computers). In use. Recently, a wider viewing angle, a high-speed response of a liquid crystal, an improvement in display quality, and the like 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, technology using color filters has been developed, and liquid crystal display elements have become color-displayable.

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. Further, when a color filter is used, a charge coupled device (CCD) image sensor, a complementary metal oxide semiconductor (CMOS) image sensor, or the like can be used. Color photography of solid-state imaging elements.

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. Development treatment. 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). For example, a transparent electrode is formed on the colored pattern, and the above alignment film is formed thereon.

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, there is a problem in the coloring pattern formed using the previous coloring composition containing the dye that the reliability is poor as compared with the coloring pattern using the coloring composition containing the pigment. Such a problem is caused by the fact that the dye used in the colorant is inferior in heat resistance and light resistance, and is easily deteriorated by heating or ultraviolet irradiation. Therefore, in the step of forming the colored pattern of the color filter in the hardening step at a high temperature, the heat resistance of the dye and the colored pattern using the same also becomes a problem.

Further, in the color filter, the alignment film provided on the coloring pattern has also been improved, and in recent years, attention has been paid to the optical alignment technique. As described above, the alignment film of the conventional liquid crystal display element uses an organic film which is chemically stable such as polyimide and has high heat resistance, and is subjected to alignment treatment by rubbing the surface with rubbing. However, since the beginning of the development, in addition to In addition to dust or foreign matter generated by the rubbing treatment, there is also a problem that a flaw on the alignment film which lowers the display quality of the liquid crystal display element is caused. In addition, with the recent refinement of the liquid crystal display device, the components such as the switching active device or the electrode on the substrate are also miniaturized, and the unevenness on the substrate is also fined, and the alignment is performed on the entire surface of the substrate. The uniform rubbing treatment of the film becomes difficult. Therefore, there has been a strong demand for a frictionless alignment treatment technique.

The photoalignment technique is a frictionless alignment treatment technique using light, such as polarized light that illuminates the alignment film from the ultraviolet region from a prescribed direction. Further, it is a technique in which a photoreaction is generated in the alignment film, and anisotropy is introduced to the surface of the alignment film to impart alignment control ability to the liquid crystal. Further, an alignment film obtained by a photo-alignment technique is sometimes referred to as a photo-alignment film.

A photo-alignment type or a photo-decomposition type photo-alignment technique is known as a method of photo-alignment processing (see, for example, Non-Patent Document 1). The photocrosslinking type is, for example, a polarizing ultraviolet ray is applied to an alignment film containing a polyvinyl cinnamate derivative, and a cross-linking reaction is generated by photodimerization to introduce anisotropy into the alignment film.

Further, the photodecomposition type is, for example, by irradiating a polarizing ultraviolet ray to an alignment film containing polyimine, and anisotropically generating a photodecomposition reaction in the alignment film to introduce anisotropy into the alignment film. This photo-decomposable photo-alignment technique is a more preferable photo-alignment technique because it can use a polyimide-alignment film which is chemically stable and has high heat resistance and has been used since the prior art.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-99584

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-219466

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-316179

[Non-patent literature]

[Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992)

As described above, although it is a liquid crystal display element developed by the advancement technology, further improvement in image quality and display quality is required. Therefore, the liquid crystal display element has become necessary to surely adopt the new technology developed. In particular, as a color filter which is an important constituent element, it is required to apply a novel high image quality technique or a technique for improving display quality, for example, a coloring pattern forming technique using the above dye in a colorant or a light alignment of an alignment film. Technology, etc.

The current situation is that the above technologies have their own problems, and it is not possible to directly adopt each technology or to combine these technologies only.

For example, as described above, the heat resistance of the dye is poor, and deterioration due to decomposition or the like is likely to occur due to heating. Therefore, in the color filter of the colored pattern formed by the previous coloring composition containing the dye, there is a problem that heat resistance is poor, and it cannot be directly applied to the prior liquid crystal display element.

Further, in the color filter using a dye in the colorant, when the alignment film formed on the colored pattern is subjected to an alignment treatment using a photo-alignment technique, the light resistance of the dye is poor, and there is a possibility that it is subjected to an alignment film. Irradiation of the irradiated ultraviolet rays causes deterioration of dye decomposition or the like. In particular, in the photo-dissociation type optical alignment technique described above, it is necessary to decompose the organic film constituting the alignment film. Therefore, the use of ultraviolet rays as the irradiation light increases the influence on the dye having poor light resistance.

When the dye in the colored pattern is decomposed or the like to cause deterioration, the liquid crystal display element using the color filter is likely to cause the following problems.

First, fading of the color filter is caused, so that there is a phenomenon that the color characteristics of the color filter including the coloring pattern using the dye are excellent.

Second, when decomposition occurs in the dye in the colored pattern, there is a phenomenon in which impurities of high polarity are generated, and the impurities are eluted into the liquid crystal in the liquid crystal panel to lower the display quality of the liquid crystal display element. The liquid crystal of the liquid crystal display element is sandwiched by the alignment film provided on each of the pair of substrates as described above, and is subjected to alignment control. The alignment film is, for example, an organic film containing a polyimide having a highly polar structure. Therefore, if the highly polar impurities eluted in the liquid crystal increase, a part of the impurities may be adsorbed on the surface of the alignment film. Such adsorption of highly polar impurities on the surface of the alignment film may cause display failure, for example, a so-called afterimage phenomenon in which the display quality of the liquid crystal display element is lowered.

For the above problems, technical development is required to improve them. For example, in order to suppress the thermal deterioration of the coloring pattern of the dye as a coloring agent and to improve the problem of fading, it is effective to achieve lower temperature heating in the curing step of the colored pattern.

In this case, using the previous coloring composition and being hardened by low temperature In the color filter of the previous coloring pattern obtained by the chemical conversion step, sufficient performance cannot be achieved in reliability such as development resistance or voltage holding ratio when applied to a liquid crystal display element. The reason for this is that the curing reactivity of the coloring pattern of the previous coloring composition is not sufficient.

Therefore, it is required to use a colored composition which can be cured at a low temperature and which can contain a dye, and realize a colored pattern which can be produced by a low-temperature hardening step.

Further, in order to suppress the photodegradation of the colored pattern of the dye as a coloring agent and to improve the problem of fading, it is effective to provide a layer for protecting the colored pattern from ultraviolet rays on the colored pattern of the color filter.

In the production of the color filter, after the coloring 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. The protective film is formed in such a manner that the unevenness of the substrate is flattened and an ITO electrode having excellent characteristics is realized. If the protective film can also be used as a layer for protecting the colored pattern, it becomes possible to protect the dye contained in the colored pattern from ultraviolet rays at the time of photoalignment treatment.

In addition, as the arrangement of such a protective film, decomposition of the dye in the colored pattern occurs, and when highly polar impurities are generated, the effect of suppressing elution of impurities into the liquid crystal can be achieved.

Here, in order to form a protective film, a hardening step is usually required. As for the heating in the hardening step, when there is a colored pattern formed by using the colored composition containing the dye in the lower layer, there is a fear that the colored pattern is deteriorated. Therefore, it is desirable that the protective film is a protective film which can be formed in a hardening step at a low temperature.

Moreover, in order to suppress adsorption of highly polar impurities on the surface of the alignment film, In order to suppress the display failure phenomenon which deteriorates the display quality of the liquid crystal display element, it is necessary to optimize the structure of the organic film constituting the alignment film. In other words, it is effective to optimize the structure while suppressing adsorption of highly polar impurities on the surface of the alignment film while maintaining necessary characteristics such as thermal stability and chemical stability of the alignment film. In this case, as described above, a polyimide film which is chemically stable and excellent in heat resistance is preferably used as the alignment film, and it is effective to select an alignment film of a polyimide having a low polarity structure. Further, as the alignment treatment method, it is effective to select a photo-dissociation type optical alignment technique which can be applied to a polyimide film.

According to the above, it is desirable to realize a color filter including a dye-containing coloring pattern formed of a low-temperature-curable coloring composition, and a low polarity which can be applied to a photo-alignment processing technique such as a photodecomposition type. Structural alignment film. The color filter preferably contains a protective film which can be formed by low temperature hardening. Further, it is strongly desired that the color filter is excellent in development resistance, heat resistance, solvent resistance, voltage holding ratio, and the like, and the liquid crystal display element using the color filter can achieve high image quality and high display quality.

The present invention has been made in view of the above problems. That is, it is an object of the present invention to provide a color filter comprising a colorant-containing coloring composition and a dye-containing coloring agent, and a method of producing the color filter. A coloring pattern, an alignment film of a low polarity structure capable of photoalignment treatment. Further, a liquid crystal display element constructed using the color filter is provided.

Moreover, another object of the present invention is to provide a color filter and In the method of producing a color filter, the color filter includes a colored pattern which can be formed by using a coloring composition which can be cured at a low temperature, a coloring pattern containing a dye in a coloring agent, a protective film formed by low-temperature curing, and light-receiving. An alignment film of a low polarity structure that is oriented to the treatment. Further, a liquid crystal display element constructed using the color filter is provided.

A first aspect of the invention relates to a color filter comprising a coloring pattern and an alignment film: the coloring pattern contains a pigment selected from the group consisting of diketopyrrolopyrroles, zinc halide phthalocyanine pigments, and triarylmethane. At least one coloring agent of a group consisting of a dye-like dye and an azo dye; the alignment film is an alignment film formed by irradiating polarized ultraviolet rays to a polyimine containing a structural unit represented by the general formula [a] ;

(In the general formula [a], P ¹ represents a tetravalent organic group having an alicyclic structure, and P ² represents a divalent organic group).

In the first aspect of the present invention, P ¹ of the general formula [a] which is a structural unit of the polyimine is preferably at least one selected from the group consisting of the following structures;

(In the formula, P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent hydrogen or an organic group having 1 to 4 carbon atoms).

In the first aspect of the invention, the colored pattern is preferably formed of a coloring composition containing a compound: [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 group consisting of the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, and an amine salt. At least one compound of the group consisting of a phosphonium salt, a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring; [Chemical 3]

(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; 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 by a hydrocarbon group having 1 to 6 carbon atoms; 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 an alkylene group are hydrogen All or a portion of an atom may also be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

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 colored pattern is a colored pattern formed at a curing temperature of 200 ° C or lower.

In a first aspect of the invention, it is preferable that a protective film is formed on the colored pattern, and the protective film is formed of a radiation-sensitive resin composition containing a compound: [A] a compound having an epoxy group, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, and [D] selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2) At least one compound of the group.

In the first aspect of the invention, it is preferred that the compound having an epoxy group contained in the radiation-sensitive resin composition of [A] is a polymer.

In the first aspect of the invention, it is preferable that the compound having an epoxy group contained in the radiation-sensitive resin composition of [A] further has a carboxyl group.

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 preferable that the colored pattern is a colored pattern formed at a curing temperature lower than a curing temperature of the protective film.

A second aspect of the invention relates to a liquid crystal display element characterized in A color filter comprising 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 pyryrrolopyrrole pigment, a zinc halide phthalocyanine pigment, a triarylmethane dye, and an azo dye; [2] formed on the coating film of the coloring composition a step of coloring the pattern; [3] a step of hardening the coating film on which the colored pattern is formed at 200 ° C or lower; [4] forming a pass on the substrate having the cured coating film of the step [3] a step of forming a polyimine film of the structural unit represented by the formula [a]; and [5] a step of irradiating the polyimide film with polarized ultraviolet rays to form an alignment film;

(In the general formula [a], P ¹ represents a tetravalent organic group having an alicyclic structure, and P ² represents a divalent organic group).

In the third aspect of the present invention, P ¹ of the general formula [a] which is a structural unit of the polyimine is preferably at least one selected from the group consisting of the following structures;

(In the formula, P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent hydrogen or an organic group having 1 to 4 carbon atoms).

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 present invention, the coloring composition preferably contains a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, and a phosphonium salt. At least one compound of the group consisting of a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring; [Chem. 7]

(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; 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 by a hydrocarbon group having 1 to 6 carbon atoms; 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 an alkylene group are hydrogen All or a portion of an atom may also be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

In a third aspect of the invention, preferably, the step of [3] and the step [4] includes the step of: [x] forming a coating film of the radiation-sensitive resin composition on the substrate, the radiation. The resin composition contains: [A] a compound having an epoxy group, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, and [D] selected from the above formula ( 1) at least one compound of the group consisting of the compound represented by the above formula (2); [xi] a step of irradiating at least a part of the coating film of the radiation sensitive resin composition; [xii a step of developing a coating film irradiated with radiation in the step [xi]; and [xiii] a step of hardening the coating film developed in the step [xii] at 200 ° C or lower.

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 [xiii].

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.

Further, according to the present invention, a liquid crystal display element comprising a color filter having high reliability which is produced by low-temperature curing and having excellent display quality is provided.

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 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 by a liquid crystal layer. In addition, the liquid crystal display element may be formed by forming a coloring pattern or a protective film 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, doping). The substrate of the tin-doped indium oxide electrode, which 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 an ITO electrode 4 provided on the colored pattern 6 are disposed on a transparent substrate 5 The alignment film 12 on the ITO electrode 4. In addition, the color of the colored pattern 6 is not limited to the above RGB 3 colors, and other colors may be selected or yellow may be further added. (Y) is made into a four-color coloring 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 color former (including a dye or the like) is applied onto a substrate, patterned, and then cured. The colored composition can be formed into a resin composition containing a radiation sensitive resin as described later, and has a feature that a colored pattern can be formed by low temperature curing at 200 ° C or lower. Therefore, even in the case where the dye is contained in the coloring agent, the phenomenon that the dye is exposed to a high temperature when the colored pattern 6 is formed can be avoided.

The alignment film 12 of the color filter 10 of the present embodiment is an alignment film of polyimide which is chemically stable and excellent in heat resistance. Further, the alignment film 12 is formed by performing an alignment process using a photodegradable photoalignment technique. In the photodegradation type optical alignment technique, the alignment film 12 containing the polyimide is irradiated with polarized ultraviolet rays, and an optical decomposition reaction is anisotropically generated in the alignment film 12, and anisotropy is introduced into the film. This photoalignment technique can be applied to a polyimide film used from the past, and thus is a more preferable photoalignment technique. Further, in the color filter 10 of the present embodiment, the polyimine of the low-polar structure is selected as described later. Therefore, even if impurities of high polarity are diffused from the coloring pattern 6 containing the dye, adsorption of the impurities onto the alignment film 12 can be suppressed.

The color filter of the liquid crystal display element of this embodiment can provide a protective film on the coloring pattern 6.

Fig. 2 is a schematic cross-sectional view showing another example of the color filter of the embodiment.

The color filter 20 shown in FIG. 2 is another example of the color filter of the present embodiment, and the color filter 10 of the present embodiment has a protective film in addition to the ITO electrode. Have the same structure. Therefore, the constituent elements that are common to the color filter 10 will be described using the same reference numerals, and the description thereof will not be repeated.

The color filter 20 has a structure in which a red (R), green (G), and blue (B) colored pattern 6 , a black matrix 7 , and a protective film provided on the colored pattern 6 are disposed on the transparent substrate 5 . 8. An ITO electrode 4 provided on the protective film 8, and an alignment film 12 provided on the ITO electrode 4. Further, as described above, 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.

In the color filter 20 of the present embodiment, the colored pattern 6 is composed of a suitable coloring agent (including a dye or the like). Specifically, a colored composition containing a coloring agent such as a dye is applied onto the substrate 5 to be patterned, and then cured at a low temperature of 200° C. or lower.

The protective film 8 of the color filter 20 of the present embodiment is disposed on the colored pattern 6 in order to realize the ITO electrode 4 excellent in electrical characteristics and reliability. The protective film 8 covers the colored pattern 6. Therefore, the protective film 8 functions to protect the dye contained in the colored pattern 6 from ultraviolet rays during the photoalignment treatment of the alignment film 12 to be described later. Further, when the dye in the colored pattern is decomposed to generate a highly polar impurity, the function of suppressing the diffusion of the impurity from the colored pattern 6 into the inside of the liquid crystal display element is exhibited.

At this time, the protective film 8 is formed by applying a radiation-sensitive resin composition in the same manner as the coloring pattern 6 and patterning it, followed by curing. In addition, the radiation-sensitive resin composition for forming a protective film 8 (hereinafter, abbreviated as a radiation-sensitive resin composition) can be a resin composition using a similar material similar to the coloring composition as will be described later. Each of these compositions has a feature that the colored pattern 6 and the protective film 8 can be formed by low-temperature curing at 200 ° C or lower.

Therefore, in the color filter 20 of the present embodiment, the colored pattern 6 and the protective film 8 can be formed by low-temperature curing at 200 ° C or lower. The color filter 20 of the present embodiment can be produced by low-temperature curing.

Further, in the color filter 20, the protective film 8 can be formed by low-temperature curing at 200 ° C or lower, so that the previously formed colored pattern 6 becomes not exposed to the high-temperature heating for forming the protective film 8 . Therefore, in the color filter 20, when the colored pattern 6 is formed, even if a dye having a problem in heat resistance is used as a coloring agent, the step deterioration can be reduced. In other words, in the color filter 20, the dye can be selected as a 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 and the radiation sensitive resin composition may each be a radiation sensitive resin composition using a similar material of the same type. Moreover, they are used to manufacture the color filter 20, respectively. Therefore, when manufacturing the color filter 20, 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, on the substrate 5, compared with the most suitable hardening temperature when the colored pattern 6 is separately formed. The colored pattern 6 is formed at a lower hardening temperature. Thereafter, the colored pattern 6 can be heated by hardening and heating the protective film 8 formed on the colored pattern 6.

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, the colored pattern 6 can be formed on the substrate 5 in advance with a curing temperature of 150 ° C. Next, a coating film of a radiation-sensitive resin composition is formed on the colored pattern 6, and is cured at an optimum temperature of 180 ° C to form a protective film 8. In this case, and it becomes possible to perform heating of the coloring pattern 6 in the lower layer thereof, the coloring pattern 6 of the desired state is obtained. As a result, a 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 20 excellent in color characteristics.

Further, in the color filter 20 of the present embodiment, after the ITO electrode 4 is formed on the protective film 8, the alignment film 12 for liquid crystal alignment control is formed on the ITO electrode 4. The alignment film 12 is an alignment film containing polyimide which is chemically stable and excellent in heat resistance, and is formed by performing the above-described alignment treatment by a photodegradable photoalignment treatment method. Further, in the color filter 20 of the present embodiment, the polyimide may be selected from a polyimide having a low polarity structure which satisfies heat resistance or electrical properties. Therefore, even if there is a phenomenon in which the coloring pattern 6 containing the dye diffuses highly polar impurities, the impurities can be suppressed from being adsorbed on the alignment film 12. Further, it is possible to suppress deterioration in display quality of the liquid crystal display element.

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

Fig. 3 is a schematic cross-sectional view showing a liquid crystal display element including the color filter of the embodiment.

The liquid crystal display element 1 shown in FIG. 3 is an example of a liquid crystal display element of the present embodiment, and is a TFT-driven twisted nematic (TN) liquid crystal mode liquid crystal display element. The liquid crystal display element 1 has a structure in which a driving substrate and a substrate constituting the color filter 20 of the present embodiment shown in FIG. 2 are opposed to each other by a liquid crystal 13 containing TN liquid crystal. Further, in the present embodiment, a substrate constituting the color filter 10 shown in FIG. 1 may be used, and other configurations may be the same as those of the liquid crystal display element 1 to constitute another example of the liquid crystal display element of the present embodiment.

As shown in FIG. 3, on the side of the transparent substrate 2 of the liquid crystal display element 1 that is in contact with the liquid crystal 13, the transparent pixel electrode 3 including ITO and the 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 or the like which is produced by low-temperature curing is disposed to constitute the color filter 20. Specifically, the color filter 20 is formed on the substrate 5 by the following elements: a red, green, and blue coloring pattern 6 provided at a position facing the pixel electrode 3, and a black matrix 7 in the coloring pattern 6 The protective film 8 provided above, the ITO electrode 4 provided on the protective film 8, and the alignment film 12 provided on the ITO electrode 4. The ITO electrode 4 constitutes a common electrode in the liquid crystal display element 1.

In the liquid crystal display element 1, the alignment film 12 similar to the substrate 5 is provided on the substrate 2. Each of the alignment films 12 contains a polyimine having a low polarity structure satisfying heat resistance or electrical properties. Further, the light alignment treatment of the polarized ultraviolet light is performed to realize the liquid crystal sandwiched between the substrate 2 and the substrate 5. 13 uniform orientation. The alignment film 12 contains a polyimine having a low polarity structure, and even if a phenomenon of diffusing highly polar impurities from the colored pattern 6 exists, adsorption of the impurities on the alignment film 12 can be suppressed. Moreover, the deterioration of the display quality of the liquid crystal display element 1 can be suppressed.

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. 3, 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 white light by color mixing, and combines a blue LED, a red luminescent phosphor, and a green luminescent phosphor to obtain a white white by color mixing. The LED obtains a white LED of white light by color mixing of a blue LED and a YAG-based phosphor, and combines a blue LED, an orange-emitting phosphor, and a green-emitting phosphor to obtain a white LED of white light by color mixing. A white LED or the like which combines an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor to obtain white light by color mixing.

In addition to the TN type, the 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). Liquid crystal mode such as Alignment, VA) or Optically Compensated Birefringence (OCB) type. In this case, the alignment film for liquid crystal alignment selects an alignment film which exhibits optimum alignment characteristics in each liquid crystal mode, and for example, in the case of the VA type, a vertical alignment type alignment film is used.

The liquid crystal display element of the present embodiment has the above configuration, and the color filter of the present embodiment which is the main constituent element will be described in more detail. In particular, each constituent member constituting the color filter of the present embodiment will be described in detail.

As described above, the color filter of the present embodiment includes a colored pattern and an alignment film disposed on the ITO electrode on the colored pattern. A protective film may be disposed on the colored pattern. Further, the color filter of the present embodiment is a color filter which is excellent in color characteristics and can be produced by low-temperature curing.

As the colored pattern, a colored composition can be used to form a suitable substrate. As the alignment film, a polyimide film having a low polarity structure is formed on a substrate by using a liquid crystal alignment agent, and a photoalignment treatment is performed. The protective film can be formed on the colored pattern using a radiation sensitive resin composition. Therefore, the color filter of the present embodiment can be configured by using the coloring composition, the radiation sensitive resin composition, and the liquid crystal alignment agent of the present embodiment.

Hereinafter, first, the coloring pattern of the color filter of the present embodiment, in particular, the coloring composition of the embodiment in which the coloring pattern is formed will be described. Bright.

<Coloring composition>

The coloring pattern of the color filter of the present embodiment can be formed using the coloring composition of the present embodiment.

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] an alkali-soluble resin can be imparted to a compound (I-1) which imparts a structural unit containing a carboxyl group in the presence of a polymerization initiator in a solvent, for example. The compound of the formula (I-2) containing an epoxy group-containing structural unit is copolymerized and produced. 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 the solvent resistance and the solvent resistance of the coloring pattern and the like, 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 ring Oxypropane, 3-(2-methylpropenyloxyethyl)-2-phenyl propylene oxide, 3-(2-methylpropenyloxyethyl)-2,2-difluoropropylene oxide Ethyl methacrylate and the like.

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. Wait.

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, sec-butyl methacrylate, tert-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, sec-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and acrylic lauric acid. A base ester, a tridecyl acrylate, a n-stearyl acrylate or 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 Yttrium Butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) ) Maleidin 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 and methacrylonitrile. Vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 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, or a diethylene glycol. Monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol 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, tert-dodecyl mercaptan, and mercaptoacetic acid; Xanthogenates such as dimethyl xanthate sulfide and diisopropyl xanthate disulfide; tertylene olefin, α-methyl styrene 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 (made by Showa Denko)

Column: Combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

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

Reference 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 Stir for a specified 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 (I-1) compound 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 coloring composition of the present embodiment 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(meth) acrylate, polypropylene glycol di(a) Acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, 2-hydroxy-3-(methyl) methacrylate醯oxypropyl 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 methoxyethyl) phosphate, epoxy Ethyl modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, etc., and other examples thereof include a linear alkyl group and an alicyclic structure and having two or more isocyanides. An ester group with a compound having at least one hydroxyl group in the molecule and having three to five (meth) Bing Xixi group of polyurethane obtained by reacting (meth) acrylate compound.

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 as a polyurethane acrylate compound (First Industrial Pharmaceutical Co., Ltd.) Company), KAYARAD (registered trademark) DPHA, KAYARAD (registered trademark) DPHA-40H, UX-5000 (Nippon Chemical Co., Ltd.), UN-9000H (Guanshang Industrial Co., Ltd.), ARONIX (registered trademark) M-5300, ARONIX M- 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, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100 , MU-4001 (above manufactured 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 (manufactured by the above root Industry Co.), Viscoat 260, Viscoat 312, Viscoat 335HP (manufactured by Osaka Organic Chemical Industry above, Inc.).

[II] The polymerizable compound may be used singly or in combination of two or more. use. 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 coloring composition of the present embodiment 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 colored pattern and the color filter having the colored pattern. Therefore, as the [IV] coloring agent contained in the coloring composition of the present embodiment 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. As the colorant, for example, any of a pigment, a dye, and a natural pigment can be used. Further, in consideration of high color purity, brightness, and the like required for the colored pattern and the color filter, it is preferred to select a pigment and a dye, and among them, a dye is particularly preferably selected.

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, CI Solvent Yellow 4 (hereinafter, the description of "CI Solvent Yellow" is omitted, and only the number is described. 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, etc.

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, and the like.

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 and so on.

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 Yan 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, etc.

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.

A triarylmethane-based colorant which is an example of a preferred [IV] colorant is a blue, violet color former.

Blue and purple coloring agents are pigments such as CI Pigment Blue, CI Pigment Violet, 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.

Triaryl methane colorants can use the following five forms of dyes and pigments material.

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 a color filter of the present embodiment which can be produced at a low temperature. 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 modified by a resin or a rosin ester having an acid group such as a carboxyl group, and a rosin-modified horse. The acid resin (rosin-modified fumarate resin is also synonymous) is mixed to improve the 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- Naphthylamine sulfonic acid (lauranic acid), 1,6-naphthylamine sulfonic acid (6-cliphoric acid), 1,7-naphthylamine sulfonic acid (7-cliphoric acid), 1,8-naphthylamine sulfonic acid (peripheral acid), 2,1-naphthylamine sulfonic acid (Tobias 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. .

Disulfonates of naphthalenes, disulfides of naphthols and triarylmethane When the basic dye is reacted to form the [IV] coloring agent of the colored composition of the present embodiment, 1 mol of the disulfonate is reacted with the triarylmethane dye 2 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, C.I. 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 C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 14, C.I. Blue 62, C.I. Pigment Violet 3, C.I. Pigment Violet 27, C.I. Pigment Violet 39 and the like.

Specifically, a more preferable triarylmethane-based pigment is: 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 any of a linear chain, a branched chain or a cyclic group. 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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, ethylhexyl (2- Ethylhexyl or the like), cyclopentyl, cyclohexyl and cyclohexylalkyl groups.

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 any of a linear chain, a branched chain or a cyclic group. 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 sec-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 any of a linear chain, a branched chain or a cyclic group. 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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methyl. 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 any of a linear or branched form. 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 any of a linear chain, a branched chain or a cyclic group. The carbon number of the aliphatic hydrocarbon group includes the carbon number of all the substituents, and the number thereof is usually from 1 to 12, 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, sec-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 any of a linear chain, a branched chain or a cyclic group, 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 any of a linear chain, a branched chain or a cyclic group. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is usually from 1 to 16, preferably from 6 to 10. Examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methylbutyl (1,1,3,3- Tetramethylbutyl or the like), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, methylcyclohexyl (2-A) Alkylcyclohexyl or the like) and a 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 usually 6 to 20, 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 any of a linear or branched form. The aralkyl group has a carbon number of usually 7 to 20, preferably 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 phenylethylene group (2-phenylethylene 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 usually 2 to 15, 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 sec-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 has a carbon number of usually 6 to 30, preferably 6 to 20, and more preferably 6 to 16. 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 any of a linear or branched form, 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 alkoxycarbonyl group has a carbon number of usually 2 to 20, preferably 2 to 16, 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 carbon number is usually from 7 to 30, preferably from 7 to 20, 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 any of saturated or unsaturated, may be cyclic, or may further have a substituent. The carbon number is usually 2 to 20, preferably 2 to 15, 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 usually from 1 to 30, preferably from 1 to 20, and 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 carbon number is usually from 6 to 30, preferably from 6 to 20, more preferably from 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 One to twelve, particularly preferably one to six carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an isopropyl group, a sec-butyl group, a tert-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 a pure heterocyclic ring type, and may also contain one heterocyclic ring and one or more condensed benzene rings, and specific examples thereof include a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, and a furyl group. , pyrrolyl, thienyl, quinolyl, coumarinyl, benzofuranyl, benzimidazolyl or benzoxazolyl 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>

The colored composition of the present embodiment used in the production of the color filter of the present embodiment may contain a [V] compound. [V] compound is a masterpiece 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 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~ The alkyl group of 6 may be substituted with all or a part of the hydrogen atom of the above amine group by an alkyl group having 1 to 6 carbon atoms.

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.

In the above formula (1) and formula (2), examples of the electron withdrawing group represented by R ¹ to R ¹⁶ include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, a decyl group, and an alkylsulfonyl group. , alkoxysulfonyl, dicyanovinyl, tricyanovinyl, sulfonyl and the like. Preferred among these groups are a nitro group, an alkoxysulfonyl group, and a trifluoromethyl 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 4,4'-diaminodiphenylanthracene, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 3-amino group 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 or secondary amine compound having high reactivity is obtained In the case of coexistence with the epoxy compound, in the storage of the composition solution, the hardening reaction proceeds due to the nucleophilic attack of the epoxy group on the amine, 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.

In the above formula (5), the alkyl group having 1 to 20 carbon atoms represented by R ²⁴ to R ²⁶ may, for example, be a linear or branched methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group. Hexyl, heptyl, octyl, decyl, decyl, lauryl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecane Base, nonadecyl, eicosyl and the like.

In the above formula (5), examples of the aryl group having 6 to 18 carbon atoms represented by R ²⁴ to R ²⁶ include a phenyl group and a naphthyl group.

In the above formula (5), examples of the aralkyl group having 7 to 30 carbon atoms represented by 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, 2-dimethylaminomethylphenol, N,N-diethylaniline 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.

[化18]

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.

In the above formula (6), the alkyl group having 1 to 20 carbon atoms represented by R ²⁷ to R ³⁰ may, for example, be a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. , heptyl, octyl, decyl, decyl, 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.

In the above formula (6), examples of the aralkyl group having 7 to 30 carbon atoms represented by R ²⁷ to R ³⁰ include a benzyl group and a phenethyl group.

In the above formula (6), the monovalent anion represented by Q ^- may, for example, be a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a nitrate ion, a nitrite ion, a hypochlorite ion, or a chlorous acid. Acid ion, 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 a guanamine group represented by the following formulas (8) to (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 group, a naphthene, or an ethylene support. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthene group 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 a carbon number of 2 to 12, a phenylene group, a naphthene, or an ethylene support. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthene group 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, p-xylyleneamine, malonamide, succinimide, N,N'-diethylindenyl-p-phenylenediamine. , N,N'-diethylene-hexamethylenediamine, N,N'- Diethyl decyl-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 a chemical bond, respectively.

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, 1,4-butanediol, and pentaerythritol.

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, norbornene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, Xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5- Trimethylcyclohexyl diisocyanate or the like.

As a commercial item, for example, Duranate (registered trademark) TPA-B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF- can be cited by blocking the isocyanate group with hydrazine of methyl ethyl ketone. B80M (the above is 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.); isocyanate having a (meth) acrylonitrile group. Examples of the block of the 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 an alcohol compound, a phenol compound, an active methylene compound, a thiol compound, a guanamine compound, a quinone compound, an imidazole compound, a pyrazole compound, a urea compound, and the like. An anthracene 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 ethylene urea; and examples of the oxime compound include formaldehyde oxime and acetaldehyde oxime. Examples of the amine compound include diphenylamine, aniline, and carbazole; and the imine compound includes, for example, ethyleneimine or polyethyleneimine; and pyridine. Examples of the compound include 2-hydroxypyridine and 2-hydroxyquinoline.

The block polyisocyanate compounds may be used singly or in combination of two or more kinds. Used together. 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 in} the above formula (16) include methyl group, ethyl group and n-propyl group. Base, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecane Base, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, An alkyl group having a carbon number of 1 to 20 such as n-icosyl group; a cycloalkyl group having a carbon number of 3 to 20 such as a cyclopentyl group, a cyclobutyl group or a cyclohexyl group; a phenyl group, a tolylmethyl group, a benzyl group, and a methyl group; An aryl group having a carbon number of 6 to 20, such as a benzyl group, a xylyl group, a mesityl group, a naphthyl group or a fluorenyl group; a norbornyl group, a tricyclic fluorenyl group, a tetracyclododecyl group, an adamantyl group, a group A crosslinked alicyclic hydrocarbon group having a carbon number of 6 to 20, such as a hydroxyalkyl group, an ethyladamantyl group or a butyl hydroxyalkylene group.

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; methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, and third butoxy group An alkoxycarbonylalkoxy group having 3 to 6 carbon atoms such as a carbonylmethoxy group; a halogen atom such as fluorine or chlorine; or a fluoroalkyl group such as a fluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group.

The ring formed by linking A ⁶ and A ⁷ in the above formula (16) 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. through When the content ratio of the compound containing an imidazole ring is within the above specific range, the storage stability of the colored composition and the low-temperature curing can be achieved 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.

A commercially available product of an anthrone-based surfactant can be exemplified by 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 manufactured by Dow Corning Toray Silicone Co., Ltd.) and the like.

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. The auxiliary agent is preferably a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxiranyl group, and examples thereof include trimethoxynonylbenzene. Formic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidyl oxygen Propyltrimethoxydecane, 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, C Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (poly) alkanediol single Alkyl ethers; 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, 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 (poly)alkylene glycol monoalkyl ether acetates such as monoethyl ether acetate, acetic acid-3-methoxybutyl ester, acetic acid-3-methyl-3-methoxybutyl ester; diethylene glycol II Other ethers such as methyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; butanone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4- Ketones such as methylpentan-2-one) and 4-hydroxy-4-methylhexane-2-one; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6- Diacetate such as hexanediol diacetate; lactate such as methyl lactate or ethyl lactate Base esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, 3-methoxybutyl acetate, acetic acid - 3-methyl-3-methoxybutyl ester, 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, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2- Other esters such as ethyl hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-A Amidoxime such as pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

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. It is 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 or a desired film thickness or the like (for example, 5) Mass%~50% by 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 can be provided with a protective film on the colored pattern. The protective film is formed on the colored pattern using a radiation sensitive resin composition. Further, the protective film has a function of protecting the coloring agent such as a dye contained therein by covering the colored pattern, and achieving excellent characteristics of the transparent electrode formed thereon. Hereinafter, the 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.

<Inductive Radiation Resin Composition>

The radiation sensitive resin composition of the present embodiment used for forming the protective film of the color filter of the present embodiment contains the [A] compound, the [B] polymerizable compound, the [C] polymerization initiator, and [D]. The compound may further contain an optional component. Radiation-sensitive resin composition can be utilized by using Radiation exposure and development easily form a fine and delicate pattern to achieve low temperature hardening. Moreover, it has storage stability and has sufficient resolution and radiation sensitivity. The components are detailed below.

<[A] compound>

The compound [A] contained in the radiation sensitive resin composition of the present embodiment is a compound having an epoxy group. The compound [A] may, for example, be a compound having two or more 3,4-epoxycyclohexyl groups 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, ethylene bis(3,4-epoxycyclohexanecarboxylic acid) ester, lactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane formate, and the like.

Examples of the other [A] compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether. a diglycidyl ether of a bisphenol compound such as hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether or brominated bisphenol S diglycidyl ether; , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene a polyglycidyl ether of a polyhydric alcohol such as an alcohol diglycidyl ether or a polypropylene glycol diglycidyl ether; or a method of adding one or more alkylene oxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; Polyglycidyl ether of the obtained polyether polyol; phenol novolak type epoxy resin; cresol novolac type epoxy resin; polyphenol type epoxy resin; cyclic aliphatic epoxy resin; aliphatic long chain dibasic acid Glycidyl ester; 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 201, EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), etc.; cresol novolac type epoxy resin can be listed as EOCN (registered trademark) 102, EOCN 103S, EOCN 104S, EOCN 1020 EOCN 1025, EOCN 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Nippon Epoxy Co., Ltd.), etc.; and polyphenol type epoxy resin, such as Epikote 1032H60 and Epikote XY-4000 (above, manufactured by Nippon Epoxy Co., Ltd.); Examples of the cyclic aliphatic epoxy resin include CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), and ERL-4234. , ERL-4299, ERL-4221, ERL-4206 (above manufactured by UCC), Shodyne 509 (Showa Denko), Epiclon 200, Epiclon 400 (above manufactured by Dainippon Ink Co., Ltd.), Epikote 871, Epikote 872 (above) Manufactured by Japan Epoxy Resin Co., Ltd., ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), etc.; aliphatic polyglycidyl ethers include Epolight 100MF (Kyoeisha Chemical Co., Ltd.) and EPIOL TMP (Japan Oil & Fats Co., Ltd.) )Wait.

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

When the compound [A] exemplified above is contained in the radiation sensitive composition together with the compound [A] which is a copolymer having a carboxyl group to be described later, the amount of the compound [A] exemplified above is relative to 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group, which is described later, is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 2 parts by mass to 15 parts by mass.

The compound [A] is preferably a polymer, and more preferably the polymer further has a carboxyl group. Further, the compound [A] is more preferably a copolymer having a carboxyl group. [A] The compound has a structure having a carboxyl group, and thus the radiation sensitive resin composition can be A cured film having more excellent heat resistance, light resistance, chemical resistance, transmittance, flatness, and the like is formed.

The [A] compound may be a structural unit formed of at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and structural units formed of an epoxy group-containing unsaturated compound. Copolymer. In this case, as the [A] compound, the same copolymer as the [I] alkali-soluble resin contained in the coloring composition of the above-described embodiment can be used. For example, (I-1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides ((I-1) compound) and (I-2) epoxy group-containing unsaturated group can be used. An alkali-soluble resin obtained by copolymerizing a compound ((I-2) compound).

<[B] polymerizable compound>

[B] The polymerizable compound is a polymerizable compound having an ethylenically unsaturated bond. [B] The polymerizable compound can be the same compound as the [II] polymerizable compound contained in the coloring composition of the above-described embodiment.

[B] The polymerizable compound may be used singly or in combination of two or more. The content ratio of the [B] polymerizable compound in the radiation sensitive resin composition is preferably 20 parts by mass to 200 parts by mass, more preferably 100 parts by mass to 200 parts by mass of the [A] compound which is a copolymer having a carboxyl group. 40 parts by mass to 160 parts by mass. When the content ratio of the [B] 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 protective film.

<[C] Polymerization initiator>

[C] The polymerization initiator is a radiation-sensitive polymerization initiator, which can be inductively placed. The ray produces a component of the active species capable of initiating a polymerization reaction. The same compound as the [III] polymerization initiator contained in the coloring composition of the present embodiment described above can be used.

[C] The polymerization initiator may be used singly or in combination of two or more. The content ratio of the [C] polymerization initiator in the radiation-sensitive resin composition is preferably 1 part by mass to 40 parts by mass, based on 100 parts by mass of the [A] compound which is a copolymer having a carboxyl group. It is preferably 5 parts by mass to 30 parts by mass. When the content ratio of the [C] polymerization initiator is from 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition can form a cured film having high hardness and adhesion even at a low exposure amount. Provides an excellent protective film.

<[D] compound>

The radiation-sensitive resin composition used for forming the protective film of the color filter of the present embodiment can achieve low-temperature hardening of the radiation-sensitive resin composition by containing the [D] compound having an amine group and an electron-withdrawing group. The hardening of the hardened film 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 cured film) can be maintained at a high level.

The compound [D] 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. Therefore, in the formula (2), 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 by a hydrocarbon group having 1 to 6 carbon atoms, which is radiation sensitive. In the case of the [D] compound used in the resin composition, 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 [D] 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-diamine 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, ethyl 3-aminobenzenesulfonate, 3,5 - bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline, more preferably 4,4'-diaminodi Phenylhydrazine, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, ethyl 3-aminobenzenesulfonate, 3,5- Bis-trifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N,N-dimethyl-4-nitroaniline.

The content ratio of the [D] compound in the radiation-sensitive resin composition is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2% by mass based on 100 parts by mass of the [A] compound which is a copolymer having a carboxyl group. Parts by mass to 10 parts by mass. When the content ratio of the [D] compound is from 0.1 part by mass to 10 parts by mass, the curing of the protective film formed of the radiation sensitive resin composition can be promoted. In short, the storage stability of the radiation sensitive resin composition is improved, and the liquid crystal display element including the color filter (the color filter having the obtained protective film) can be held at a high level. Voltage retention rate.

<Other optional ingredients>

In addition to the above [A] compound, [B] polymerizable compound, [C] polymerization initiator, and [D] compound, the radiation sensitive resin composition of the present embodiment may not impair the desired effect. Any components such as [J-1] adhesion aid, [J-2] surfactant, [J-3] storage stabilizer, and [J-4] heat resistance promoter are contained in the range as needed. These optional components may be used singly or in combination of two or more. Hereinafter, it will be described in detail.

[[J-1] Adhesives]

[J-1] Next, an auxiliary agent can be used to further improve the adhesion of the obtained protective film to the substrate. Such a [J-1] adjunct additive may be the same compound as the adjunct agent in the other optional component of the coloring composition described above.

The amount of use of the [J-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 compound [A] which is a copolymer having a carboxyl group. When the amount of the auxiliary agent used in [J-1] exceeds 20 parts by mass, the development tends to be likely to occur.

[[J-2] surfactant]

[J-2] The surfactant can be used to further improve the coating film formability of the radiation sensitive resin composition. [J-2] The surfactant may, for example, be a fluorine-based surfactant, an anthrone-based surfactant, or another surfactant, and a compound similar to the surfactant in any other component of the coloring composition described above may be used.

The amount of the surfactant used as the [J-2] is preferably 1.0 part by mass based on 100 parts by mass of the compound [A] which is a copolymer having a carboxyl group. Next, it is more preferably 0.8 parts by mass or less. When the amount of the [J-2] surfactant is more than 1.0 part by mass, film unevenness is likely to occur.

[[J-3] Preservation Stabilizer]

[J-3] The storage stabilizer may be the same compound as the storage stabilizer in the other optional components of the above colored composition, and examples thereof include sulfur, anthraquinone, hydroquinone, polyoxyl compound, amine, and nitro group. Specific examples of the nitroso compound and the like include 4-methoxyphenol and N-nitroso-N-phenylhydroxylamine aluminum.

The amount of use of the [J-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 compound [A] which is a copolymer having a carboxyl group. When the amount of the [J-3] storage stabilizer is more than 3.0 parts by mass, the sensitivity of the radiation-sensitive resin composition may be lowered to deteriorate the pattern shape.

[[J-4] Heat resistance promoter]

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

The amount of use of the heat resistance promoter of [J-4] 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 compound [A] which is a copolymer having a carboxyl group. When the amount of the heat-resistant accelerator of [J-4] exceeds 50 parts by mass, the sensitivity of the radiation-sensitive resin composition may be lowered to deteriorate the pattern shape.

<Modulation of Radiation-Linear Resin Composition>

The radiation sensitive resin composition of the present embodiment can be prepared by polymerizing the [A] compound, the [B] polymerizable compound, and [C]. The starting agent and the [D] compound are mixed as needed in a predetermined ratio within a range that does not impair the desired effect. The 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 radiation sensitive resin composition can be used to uniformly dissolve or disperse the [A] compound, the [B] polymerizable compound, the [C] polymerization initiator, the [D] compound, and the optional component, and A solvent that reacts with each component. The solvent is exemplified as the solvent used in the preparation of the coloring composition of the present embodiment. The solvent may be used singly or in combination of two or more.

When the solvent of the radiation-sensitive linear 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% by mass based on the total amount of the solvent. the following. 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 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 to any concentration depending on the purpose of use, the value of the desired film thickness, or the like. (for example, 5 mass% to 50 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 filtered by using a micropore filter having a pore diameter of about 0.5 μm, and then used.

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

Next, the ITO electrode of the color filter of the present embodiment will be described. 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, the transparent electrode on the colored pattern may be formed of a transparent material having high transmittance and conductivity for visible light, in addition to ITO. For example, indium zinc oxide (IZO), ZnO (zinc oxide), or the like can be used.

Further, the color filter of the present embodiment may have a liquid crystal alignment control alignment film on the liquid crystal layer side surface when the liquid crystal display element is formed as described above. That is, an alignment film is provided on the ITO electrode on the protective film of the color filter. The alignment film of the color filter of the present embodiment is an alignment film containing a polyimide which is chemically stable and excellent in heat resistance. Further, the alignment treatment of the photodegradable photoalignment technique is carried out to impart liquid crystal alignment control capability. The photodegradable photoalignment technique is an ultraviolet ray that irradiates a polarizing film to a aligning film, and anisotropically generates a photodecomposition reaction in the alignment film, and introduces anisotropy into the alignment film. Further, in the alignment film of the color filter of the present embodiment, the polyimine is selected to have a low polarity structure. The alignment film is formed on the color filter using a liquid crystal alignment agent. Next, the alignment film of the color filter of the present embodiment and the liquid crystal alignment agent of this embodiment which forms the alignment film will be described.

<Alignment film and liquid crystal alignment agent>

The alignment film of the color filter of the present embodiment contains a general formula [a] The polyimine film of the structural unit shown is formed by irradiating polarized ultraviolet rays.

In the above formula [a], P ¹ represents a tetravalent organic group having an alicyclic structure, and P ² represents a divalent organic group.

The alignment film of the color filter of the present embodiment has a low-polar structure because P ^{1 of the} general formula [a] has an alicyclic structure.

The polyimine film containing the structural unit represented by the above formula [a] can be obtained by polyphosphonic acid (the polyamino acid is an alicyclic tetracarboxylic dianhydride and the following formula [b] The obtained diamine reaction is obtained by performing a dehydration ring closure.

[Formula 31] H ^₂ NP ₂ -NH ₂ [b]

The alicyclic tetracarboxylic dianhydride which can be used in the formation of the film of the polythenimine containing the structural unit represented by the general formula [a] is exemplified by 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2, 3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dimethyl Anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane- 2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, and the like. In addition, when a film of a polyimine containing a structural unit represented by the general formula [a] is formed, one or two or more kinds of these tetracarboxylic acids and derivatives thereof may be used in combination. Further, if the obtained polyimine is subjected to ultraviolet irradiation to achieve a liquid crystal alignment control ability, other tetracarboxylic dianhydrides other than the alicyclic group may be used in combination.

The alignment film of the color filter of the present embodiment has a low polarity structure, and is required to have heat resistance and chemical stability as an alignment film of a liquid crystal display element. In order to achieve such a performance, it is preferable that P ¹ of the general formula [a] is at least one structure selected from the group consisting of the following structures.

Here, in the above formula, P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent hydrogen or an organic group having 1 to 4 carbon atoms.

The diamine represented by the above formula [b] which can be used for forming a film of the polyimine which is a structural unit represented by the above-mentioned general formula [a], for example, an aliphatic diamine or an alicyclic diamine , an aromatic diamine, a diamine organic decane, and the like.

Specific examples of the aliphatic diamine include 1,3-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, and the like; alicyclic diamines. Examples thereof include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, and the like; and aromatic diamines such as Examples thereof include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminopurine, 4,4'- Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-double [4-(4-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene Diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-amine Phenyloxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-di Amino oxazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diamino Oxazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)- N,N'-dimethylbenzidine, dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4 -diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecane Oxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2, 5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteryl-2,4- Diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoic acid Acid ester, lanolin alkyl 3,5-diaminobenzoic acid ester, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 1,4-bis-(4-amino group Phenyl)-pyridazine or the like; and examples of the diamine-based organodecane may, for example, be 1,3-bis(3-aminopropyl)-tetramethyldioxane, and other Japanese patents may be used. The diamine described in Japanese Laid-Open Patent Publication No. 2010-97188.

The synthesis reaction of the polyaminic acid used in the formation of the polyimine containing the structural unit represented by the general formula [a] is preferably 1 equivalent of the amine group of the diamine represented by the above formula [b]. The acid anhydride group of the alicyclic tetracarboxylic dianhydride is in a ratio of 0.2 equivalent to 2 equivalents, more preferably in a ratio of 0.3 equivalent to 1.2 equivalents.

The synthesis reaction of polylysine is preferably carried out in an organic solvent at a polymerization temperature of preferably -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, preferably 0.1 to 24 hours, more preferably It is carried out at a polymerization time of 0.5 to 12 hours.

Here, examples of the organic solvent include an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, and the like.

Specific examples of the organic solvent include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and the like. Methyl hydrazine, γ-butyrolactone, tetramethylurea, hexa Examples of the phenol derivative include m-cresol, xylenol, and halogenated phenol; and examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, and propylene glycol. Examples of the ketone include 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether; and examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and the above esters include, for example, lactic acid B. Ester, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, etc.; Examples thereof include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate And tetrahydrofuran or the like; examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like; Include hydrocarbons such as hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether and the like.

Among the organic solvents, it is preferred to use one or more selected from the group consisting of an aprotic polar solvent and a phenol and a derivative thereof (the first group of organic solvents), or an organic solvent selected from the first group. One or more kinds of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, The use ratio of the organic solvent as the second group is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total of the organic solvent of the first group and the organic solvent of the second group, and further It is preferably 30 wt% or less.

The amount (a) of the organic solvent to be used is preferably an amount in which the total amount (t) of the alicyclic tetracarboxylic dianhydride and the diamine becomes 0.1 wt% with respect to the total amount (s+t) of the reaction solution. ~50 wt% amount.

A reaction solution obtained by dissolving polylysine was obtained as described above.

The reaction solution may be directly supplied to the liquid crystal alignment agent, or may be prepared by isolating the polylysine contained in the reaction solution to the liquid crystal alignment agent, or purifying the isolated polyamic acid to the liquid crystal. Modulation of the alignment agent.

When polylysine is subjected to dehydration ring closure to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or the polylysine contained in the reaction solution may be isolated and dehydrated. The ring closure reaction, or the isolated polylysine is purified and supplied to the dehydration ring closure reaction. The isolation and purification of polylysine can be carried out in accordance with a known method.

The polyimine containing the structural unit represented by the above formula [a] can be obtained by subjecting the polylysine synthesized as described above to dehydration ring closure to ruthenium.

The polyimine of the alignment film constituting the color filter of the present embodiment may be a fully ruthenium imide formed by dehydration ring closure of a proline structure of polyglycine as a precursor thereof, or may be Only a part of the structure of the proline is dehydrated and closed, and the part of the proline structure and the quinone ring structure coexist. Yttrium imide. The polyimine which constitutes the alignment film of the color filter of the present embodiment preferably has a ruthenium iodide ratio of 30% or more, more preferably 50% to 100%, and still more preferably 65% to 100%. 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 also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, as needed The method of heating. Among them, the latter method is preferably used.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the above polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 mol to 20 mol with respect to the proline structure of polylysine. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of use as the dehydration ring-closure catalyst is preferably 0.01 mol to 10 mol per mol of the dehydrating agent used. The organic solvent used for the dehydration ring-closure reaction is exemplified as an organic solvent exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

This was carried out to obtain a reaction solution containing polyimine. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or can be removed from the reaction solution. After dehydrating agent and dehydration ring-closing catalyst are supplied to the liquid crystal alignment agent, the polyimine may be isolated and supplied to the liquid crystal alignment agent, or the isolated polyimine may be purified and then supplied. Modulation of liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method.

In the liquid crystal alignment agent of the present embodiment, the above-mentioned polyaminic acid or a polyimine containing the structural unit represented by the above formula [a] obtained by using the polyamic acid, and optionally arbitrarily formulated The other components are preferably dissolved in an organic solvent. The other component is, for example, a polymer other than the polyaminic acid and the polyimine containing the structural unit represented by the above formula [a], a curing agent, a curing catalyst, and a curing accelerator. Agents, epoxy compounds, functional decane compounds, surfactants, photosensitizers, and the like.

Examples of the organic solvent used in the liquid crystal alignment agent of the present embodiment include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylide, N,N-dimethylformamide, and N. , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethoxylate Ethyl propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, and the like. These organic solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1 wt% to 10 wt%. In other words, the liquid crystal alignment agent of the present invention can be applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film, but the solid concentration is less than 1 wt. In the case of %, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film; on the other hand, when the solid content exceeds 10 wt%, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment. Further, the film and the viscosity of the liquid crystal alignment agent are increased to cause deterioration in coating properties.

A particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of using the rotator method (rotary coating method), the solid content concentration is particularly preferably in the range of 1.5 wt% to 4.5 wt%. In the case of using the printing method, it is particularly preferable to make the solid content concentration in the range of 3 wt% to 9 wt%, thereby making the solution viscosity 12 mPa. s~50 mPa. The scope of s. In the case of using the ink jet method, it is particularly preferable to make the solid content concentration in the range of 1 wt% to 5 wt%, thereby making the solution viscosity 3 mPa. s~15 mPa. The scope of s.

The polyimine or polylysine solution of the present embodiment obtained as described above is applied onto a substrate by a method such as a spinner method, a transfer printing method, or an inkjet method, and is heated and cured to form a poly醯 imine film. The curing temperature at this time is preferably selected to suppress the fading of the colored pattern, and is preferably 150° C. or higher and 200° C. or lower, and more preferably 150° C. or higher and 180° C. or lower. The thickness of the polyimide film is not particularly limited, and it is considered as a liquid crystal alignment film. The use is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, still more preferably 0.01 μm to 0.3 μm.

Next, by irradiating a linearly polarized light or a partially polarized radiation or a non-polarized radiation on the surface of the formed polyimide film, anisotropy is introduced into the film of the polyimide, and the liquid crystal alignment ability is imparted. 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 containing light having a wavelength of 100 nm to 400 nm can be used. Further, it is preferred to perform irradiation by selecting an appropriate wavelength via a filter or the like depending on the type of the polyimide. 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 time of the ultraviolet rays is preferably in the range of several seconds to several hours, and it is preferred to select an appropriate time depending on the type of the polyimide used.

The respective constituent members constituting the color filter of the present embodiment have been described in detail. Next, a method of manufacturing the color filter of the present embodiment will be described.

<Coloring Pattern, Protective Film, Alignment Film, Color Filter, and Manufacturing Method Thereof>

In the production of the color filter of the present embodiment, a step of forming a colored pattern from the colored composition and a step of forming an alignment film using the liquid crystal alignment agent are included as main manufacturing steps. Further, a protective film may be formed on the colored pattern. In this case, become included A step of forming a protective film from the above-described radiation sensitive resin composition. Hereinafter, a color filter and a method of manufacturing the same will be described.

The method for producing a color filter of the present embodiment includes the following steps [1] to [5] in the following order: [1] a step of forming a coating film for a colored composition 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 The step of hardening the film (hereinafter sometimes referred to as "[3] step"), [4] the step of forming a polyimide film on the substrate after the step [3] (hereinafter sometimes referred to as "[4] step) "), [5] A step of forming a alignment film by irradiating a polarized ultraviolet ray to a polyimide film (hereinafter sometimes referred to as "[5] step").

Further, the color filter of the present embodiment can have a protective film on the colored pattern. In this case, the following steps [x] to [xiii] may be included between the above [3] step and the above [4] step in the following order: [x] on the substrate after the [3] step a step of forming a radiation-sensitive resin composition coating film (hereinafter sometimes referred to as "[x] step"), [xi] a step of irradiating at least a part of the radiation-sensitive resin composition coating film on the substrate (hereinafter, The step of developing the coating film irradiated with radiation (hereinafter sometimes referred to as "[xii] step") and [xiii] may be performed at 200 ° C or lower, sometimes referred to as "[xi] step"), [xii]. Developing film hardening step (The following is sometimes referred to as "[xiii] step").

According to the method for producing a color filter of the present embodiment, the colored composition of the present embodiment can be used to form a colored pattern on the substrate, and the alignment film of the photoalignment technique can be formed by using the liquid crystal alignment agent of the present embodiment. . Further, the radiation-sensitive resin composition of the present embodiment described above can be used to form a protective film. 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, and in the above step [3], the coloring pattern can be cured at a temperature of 200 ° C or lower. Even in the case where a protective film is formed on the colored pattern, in the hardening step of the above [xiii], the curing of the protective film 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, according to the method for producing a color filter of the present embodiment, a color filter excellent in color characteristics can be produced.

In addition, as a color filter manufactured by the method for producing a color filter of the present embodiment, when a heating step is desired to be lowered from the viewpoint of energy saving, it is also a suitable color filter.

Hereinafter, each step in the method of manufacturing the color filter of the present embodiment will be described in detail.

[[1] Steps]

In this step, a coating film of the coloring composition of the above-described embodiment 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, coating on the substrate, for example A colored composition containing a red [IV] colorant is then prebaked to evaporate the solvent to form a coating film. In addition, a method of obtaining a color pattern by using 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 therefore has a thicker film thickness than the black matrix.

Examples of the material of the substrate include glass such as soda lime glass or alkali-free glass, bismuth, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and aromatic polyamine. Polyamidomine, polyimine, 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.

Examples of the method of applying the colored composition to the substrate include a spray method, a roll coating method, a spin coating method (also sometimes referred to as a spin coating method or a spinner method), a slit die coating method, a bar coating method, and the like. Among these methods, a spin coating method or a slit die coating method is preferred.

Prebaking is usually carried out by combining reduced pressure drying with heat drying. Drying under reduced pressure is usually carried out in such a manner as to reach 50 Pa to 200 Pa. Moreover, the conditions of heat drying are usually from 1 minute to 10 minutes at 70 ° C to 110 ° C. right.

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 The coloring pattern before hardening of the red pixel pattern is arranged in a predetermined arrangement.

Next, using the green or blue colored composition, the above steps [1] and [2] are repeatedly performed to sequentially form a green colored pattern and a blue colored pattern on the same substrate. Thereby, a color filter in which the coloring patterns before curing of the three primary colors 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 of chromium or the like formed by sputtering or vapor deposition into a desired pattern by photolithography, and forming a coloring composition containing a black colorant with the above-described pixel. The situation is similarly 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 alkaline developing solution is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1, 5-diazabicyclo-[4.3.0]-5-decene.

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, water washing is usually carried out after alkali development. As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. 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 performing hardening (also referred to as post-baking), whereby the formation of the colored pattern can be completed. The heating condition for post-baking is 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 pixel is usually from 0.5 μm to 5.0 μm, preferably from 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, a hardening step at a temperature exceeding 120 ° C is usually required. Moreover, in the range of 180 ° C or lower, hardening at a higher temperature is preferred.

Further, in the production of the color filter of the present embodiment, after the coloring pattern is formed, there is a step of forming an ITO electrode. The method of forming the ITO electrode can be performed by forming a transparent conductive layer containing ITO on the colored pattern by a sputtering method or the like. Further, when a protective film is placed on the colored pattern, After the protective film forming step described later, a transparent conductive layer is formed on the formed protective film. Next, when the ITO electrode is required to be patterned, the transparent conductive layer is etched by photolithography to form a patterned transparent ITO electrode on the colored pattern or the protective film.

[[4] Steps]

The liquid crystal alignment agent of the above embodiment is used in the step [4]. Further, the ITO electrode on which the colored pattern is formed by the steps [1] to [3] described above is applied by a suitable coating method such as a roll coating method, a spinner method, a printing method, or an inkjet method. Liquid crystal alignment agent. Next, the substrate coated with the liquid crystal alignment agent is prebaked, and then post-baked to form a coating film of the polyimine containing the structural unit represented by the above formula [a]. The prebaking conditions are, for example, from 40 ° C to 120 ° C for 0.1 minutes to 5 minutes. The post-baking conditions are carried out at 120 ° C to 230 ° C, preferably 150 ° C to 200 ° C, more preferably 150 ° C to 180 ° C for 5 minutes to 200 minutes, preferably 10 minutes to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm, still more preferably 0.01 μm to 0.3 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 from the viewpoint of volatility and the like, and is preferably in the range of 1 wt% to 10 wt%, and is preferably selected in accordance with a method of applying a liquid crystal alignment agent.

[[5] Steps]

Secondly, by irradiating the coating film formed in the step [4] with linear polarization or Partially polarized radiation, or non-polarized radiation, imparts liquid crystal alignment capability. Such a treatment corresponds to a method of the previous alignment treatment such as rubbing treatment, and problems such as generation of dust or damage can be avoided, and the processing can be performed more easily. Here, as the radiation, for example, ultraviolet rays containing light having a wavelength of 100 nm to 400 nm can be used. 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 . The irradiation time of the radiation is preferably in the range of several seconds to several hours. It is preferred to select a suitable amount of radiation and an irradiation time depending on the type of the polyimide used.

Further, when the color filter of the present embodiment has a protective film on the colored pattern, the following steps [x] to [xiii] are performed after the step [3] and before the formation of the ITO electrode. Protective film.

[[x]step]

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

When a coating film is formed by a coating method, after coating a solution of a radiation sensitive resin composition on a substrate on which a colored pattern is formed, it is preferred to 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 amount%. The coating method of the radiation sensitive resin composition solution can be, for example, a spray method, a roll coating method, a spin coating method (also referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method), or a rod. A suitable method such as a coating method or an inkjet coating method. Among these coating 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, preferably from 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.

[[xi]Steps]

Next, at least a part of the formed coating film is irradiated with radiation. At this time, when only a part of the coating film is irradiated, for example, a method of irradiating with a photomask having a predetermined pattern can 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 radiation sensitive resin composition used in the formation of the protective film 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 protective film. 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 a high hardness protective film can be obtained.

[[xii]step]

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

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. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be added to the aqueous solution of the basic compound. 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 of a liquid coating method, a dipping method, a shower method, and the like, and the development time is preferably about 10 seconds to 180 seconds at normal temperature. After the development treatment, for example, a running water rinse is performed for 30 seconds to 90 seconds, and then air-dried with compressed air or compressed nitrogen gas, thereby obtaining a desired pattern.

[[xiii]step]

Next, the obtained pattern-like coating film is cured (also referred to as post-baking) by a suitable heating means such as a hot plate or an oven to obtain a cured film to obtain a protective film. The hardening temperature 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 150° C. to 180° C. As the hardening time, for example, it is preferably 5 minutes to 30 minutes on a hot plate, and preferably 30 in an oven. Minutes ~ 180 minutes. The radiation sensitive resin composition contains the [D] compound as described above, and thus such low low temperature hardening can be achieved. Moreover, storage stability can be achieved with sufficient resolution and radiation sensitivity.

Therefore, in the case where the radiation-sensitive resin composition is formed, it is suitably used as a material for forming a protective film (the protective film is used in combination with a colored pattern of a dye which is preferably used for low-temperature curing).

According to the above manufacturing method, a colored pattern, a protective film, and an alignment film 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. The protective film is similarly coated with a radiation sensitive resin composition, patterned, and then cured. Further, the colored composition and the radiation-sensitive resin composition can be formed into a colored pattern and a protective film by low-temperature curing at 200 ° C or lower as described above.

Therefore, in the color filter of the present embodiment, the colored pattern can be formed by low-temperature curing at 200 ° C or lower, and even when the protective film is provided, the protective film can be formed by low-temperature curing at 200 ° C or lower. Manufacturing of low temperature hardening.

Further, in the color filter of the present embodiment, since the protective film can be formed by low-temperature curing at 200 ° C or lower, the colored pattern is not exposed to the high-temperature heating for forming the protective film after the 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.

In addition, as described above, the coloring composition is composed of a radiation-sensitive resin The material can be set to a radiation-sensitive resin composition using a similar material. Therefore, 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 subsequent protective film. That is, the colored pattern is formed using a lower curing temperature than the curing temperature most suitable for separately forming a colored pattern on the substrate. Thereafter, the colored pattern may be heated by hardening and heating of the protective film formed on the colored pattern.

Therefore, when the optimum curing temperature of the colored pattern and the protective film is, for example, 200 ° C or lower, specifically 180 ° C, the colored pattern can be formed in advance at a curing temperature of 150 ° C. Next, a coating film of a 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, in the color filter of the present embodiment, when the protective film is provided, the protective film can realize an ITO electrode excellent in electrical characteristics, reliability, and the like. Further, the protective film covers the colored pattern, and the dye which is a coloring agent of the colored pattern can be protected from ultraviolet rays or the like which are irradiated during the photoalignment treatment of 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 a compound (I-4). 10 parts by mass of styrene, 32 parts by mass of benzyl methacrylate, and 35 parts by mass of methyl methacrylate, further charged with 2.7 parts by mass of α-methylstyrene dimer, and slowly stirred while stirring The temperature 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 a 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 is added to the obtained solution containing the copolymer, 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor, and after stirring at 90 ° C for 30 minutes in an air atmosphere, 16 parts by mass of glycidyl methacrylate as a compound (I-2) was placed and kept at 90%. The reaction was carried out for 10 hours at ° C, whereby an alkali-soluble resin (IB) as a copolymer was obtained. 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, cyclohexanone was used as a solvent, and a solvent was added so that the solid content concentration of the coloring composition became 30% by mass, and then filtered using a micropore filter having a pore diameter of 0.5 μm to prepare a red colored composition.

In addition to using green colorant (IV-2) containing green dye as [IV] Other than the colorant, the green coloring composition was prepared in the same manner as described above. 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 (a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C) was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter of 1 mm) to thereby perform shower development on the substrate. A colored pattern of 200 μm × 200 μm was formed thereon. 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 Compounds]

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 slowly, and the temperature was maintained for 4 hours to carry out polymerization, thereby obtaining a copolymer (A-1). (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 7 [Modulation of Radiation-Linear Resin Composition]

100 parts by mass of dipentaerythritol hexaacrylate (B-1) as a [B] polymerizable compound was mixed with 100 parts by mass of the copolymer (A-1) obtained in Example 6 as the compound [A] as [C] Ethylketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine) of the polymerization initiator Irgacure OXE02, Ciba Specialty Chemicals Co., Ltd.) (C-1) 5 parts by mass, and 4,4'-diaminodiphenyl hydrazine (D-1) as a compound of [D], further mixed as [J- 1] 5 parts by mass of γ-glycidoxypropyltrimethoxydecane followed by auxiliary agent, 0.5 parts by mass of [J-2] surfactant (FTX-218, Neos), and stable as [J-3] 0.5 parts by mass of the 4-methoxyphenol of the agent, and propylene glycol monomethyl ether acetate was added thereto so that the solid content concentration was 30% by mass, and then filtered by a micropore filter having a pore diameter of 0.5 μm, thereby preparing A radiation sensitive resin composition.

Example 8 [Formation of Protective Film]

The radiation-sensitive resin composition solution 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 700 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

A protective film was formed by the formation method of Example 8 from the radiation-sensitive resin composition solution of Example 7 immediately after preparation, and the film thickness (referred to as "film thickness immediately after preparation" in the following formula) was measured. Further, after the preparation was carried out by the formation method of Example 7, the radiation sensitive resin composition solution 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 (referred to as the following formula). "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 is 2% or less, so that the light resistance is judged to be 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, and the heating was measured by a stylus type film thickness measuring machine (Alpha Step IQ, KLA-TENCOR Co., Ltd.). Film thickness before and after. 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.

<Modulation of liquid crystal alignment agent> Example 10

N-methylpyrrolidone (hereinafter abbreviated as NMP) as a solvent was placed in a reaction vessel, and 100 parts by mass of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was charged and 1 47 parts by mass of 2,3,4,-cyclobutanetetracarboxylic dianhydride was reacted in NMP at room temperature for 10 hours to prepare a polyaminic acid solution as a polyimide precursor. Further using NMP to carry out the solution Dilute and adjust the solid concentration to obtain a liquid crystal alignment agent.

<Manufacture of color filters> Example 11

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 colored pattern (pattern width of 100 μm) having a film thickness of 2.0 μm was formed.

Next, the operation was carried out in the same manner, and a green coloring pattern was formed using a green coloring composition. Further, a blue coloring composition was used to form a blue coloring pattern, and three color filters of red, green, and blue 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 three-color coloring pattern can be formed.

Next, on the obtained three-color coloring pattern, the radiation-sensitive resin composition prepared in Example 7 was applied by a slit die coater. Next, prebaking was performed on a hot plate at 90 ° C for 5 minutes to form a coating film. Then, the obtained coating film is irradiated with radiation by using a high-pressure mercury lamp to have an exposure amount of 700 J/m ^{2 ,} and the coating film after the radiation irradiation is developed to remove unnecessary portions, thereby forming a coating film having a predetermined shape. . Further, heat treatment was carried out in an oven at 180 ° C for 60 minutes to form a protective film having a film thickness of 2.0 μm from the upper surface of the three-color colored 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 color pattern in the red, green, and blue directions, and the long axis direction of the color pattern 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 220 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, an ITO film was formed on the protective film by a sputtering method using a substrate on which a protective film was formed on the colored pattern to form an ITO electrode.

Next, using the liquid crystal alignment agent prepared in Example 10, it was applied by a spinner onto an ITO electrode on a substrate on which a protective film was formed on a colored pattern. 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. Secondly, since it is perpendicular to the base The surface of the coating film was irradiated with polarized ultraviolet rays in a direction inclined by 40 degrees in the direction of the surface of the sheet to produce a color filter having a photoalignment film.

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.

<Application of color filter in liquid crystal display element> Example 12 [Manufacture of color liquid crystal display elements]

A color liquid crystal display element was produced using the color filter having the alignment film subjected to the photoalignment treatment obtained in Example 11. The liquid crystal display element manufactured has the same structure as the liquid crystal display element shown in FIG. 3 described above. In the liquid crystal display element of the present example, defect-free liquid crystal alignment is realized, and excellent display characteristics and reliability performance are exhibited.

[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 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

10, 20‧‧‧ 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 another example of the color filter of the embodiment.

Fig. 3 is a schematic cross-sectional view showing a 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

12‧‧‧Alignment film

13‧‧‧LCD

14‧‧‧Polar plate

16‧‧‧ Sealing material

17‧‧‧Backlight light

20‧‧‧Color filters

Claims (14)

A color filter comprising a coloring pattern and an alignment film formed of a coloring composition containing a compound: [I] an alkali-soluble resin, [II] a polymerizable property having an ethylenically unsaturated bond; a compound, [III] a radiation-sensitive polymerization initiator, [IV] 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 and [V] are selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, a phosphonium salt, a phosphonium salt, a guanamine compound, and At least one compound selected from the group consisting of a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring; 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 at least one of R ¹ to R ⁶ One of them 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 a hydrogen atom and are attracted. An electron 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 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 a hydrogen atom of an alkylene group All or a part thereof may be substituted by a cyano group, a halogen atom or a fluoroalkyl group; the alignment film is formed by irradiating a polarized ultraviolet ray of a polyimine containing a structural unit represented by the general formula [a]; ] (In the general formula [a], P ¹ represents a tetravalent organic group having an alicyclic structure, and P ² represents a divalent organic group). The color filter according to claim 1, wherein P ¹ of the general formula [a] indicating the structural unit is at least one selected from the group consisting of the following structures; (In the formula, P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent hydrogen or an organic group having 1 to 4 carbon atoms). The color filter according to claim 1, wherein the [I] alkali-soluble resin contained in the colored 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 the 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 any one of claims 1 to 3, wherein the coloring pattern is formed at a curing temperature of 200 ° C or lower. A color filter comprising: a coloring pattern formed of a coloring composition containing a compound: [I] an alkali-soluble resin, [II] a polymerization having an ethylenically unsaturated bond, and a protective film comprising: a compound, [III] a radiation-sensitive polymerization initiator, [IV] 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 and [V] are selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, a phosphonium salt, a phosphonium salt, and a guanamine compound. At least one compound selected from the group consisting of a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring; 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 at least one of R ¹ to R ⁶ One of them 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 a hydrogen atom and are attracted. An electron 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 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 a hydrogen atom of an alkylene group All or a part thereof may be substituted by a cyano group, a halogen atom or a fluoroalkyl group; a protective film is formed on the coloring pattern, and the protective film is formed of a radiation-sensitive resin composition containing a compound: [A] has a compound of an epoxy group, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation-sensitive polymerization initiator, and [D] are selected from the above formula (1) At least one compound of the group consisting of the compound and the compound represented by the above formula (2). The color filter according to claim 5, wherein the compound having an epoxy group contained in the radiation sensitive resin composition is a polymer. The color filter according to claim 5, wherein the [A] epoxy group-containing compound contained in the radiation sensitive resin composition further has a carboxyl group. The color filter according to claim 5, wherein the protective film is formed at a hardening temperature of 200 ° C or lower. The color filter according to any one of claims 5 to 8, wherein the coloring pattern is formed at a hardening temperature lower than a curing temperature of the protective film. A liquid crystal display element comprising the color filter according to any one of claims 1 to 9. A method of producing a color filter, comprising the steps of: [1] forming a coating film of a colored composition on a substrate, the colored composition containing [I] an alkali-soluble resin, [II] having ethylene a polymerizable compound having an unsaturated bond, [III] a radiation-sensitive polymerization initiator, [IV] selected from the group consisting of diketopyrrolopyrrole pigments, zinc halide phthalocyanine pigments, triarylmethane dyes, and azos At least one coloring agent and [V] in the group consisting of the dyes are selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, and a phosphonium salt. At least one compound selected from the group consisting of a phosphonium salt, a guanamine compound, a thiol compound, a blocked isocyanate compound, and a compound containing an imidazole ring; 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 at least one of R ¹ to R ⁶ One of them 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 a hydrogen atom and are attracted. An electron 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 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 a hydrogen atom of an alkylene group All or a part thereof may be substituted by a cyano group, a halogen atom or a fluoroalkyl group; [2] a step of forming a colored pattern on the coating film of the colored composition; [3] forming the coloring at 200 ° C or lower a step of hardening the coating film of the pattern; [4] a step of forming a polyimide film containing the structural unit represented by the general formula [a] on the substrate having the hardened coating film of the step [3]; [5] a step of irradiating the polyimine film with polarized ultraviolet rays to form an alignment film; (In the general formula [a], P ¹ represents a tetravalent organic group having an alicyclic structure, and P ² represents a divalent organic group). The method of producing a color filter according to claim 11, wherein P ¹ of the general formula [a] indicating the structural unit is at least one selected from the group consisting of the following structures. Structure; [6] (In the formula, P ³ , P ⁴ , P ⁵ and P ⁶ each independently represent hydrogen or an organic group having 1 to 4 carbon atoms). The method of manufacturing a color filter according to Item 11 or 12, wherein the step (3) and the step [4] include the following steps: [x] forming a radiation on the substrate The step of coating a film of a resin composition comprising: [A] a compound having an epoxy group, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] a radiation sensitive The polymerization initiator and [D] are at least one compound selected from the group consisting of the compound represented by the above formula (1) and the compound represented by the above formula (2); [xi] the radiation a step of irradiating at least a part of the coating film of the resin composition with radiation; [xii] a step of developing the coating film irradiated with radiation in the step [xi]; and [xiii] making the step [xii] at 200 ° C or lower The step of hardening the coating film developed is carried out. The method for producing a color filter according to claim 13, wherein the hardening temperature of the step [3] is a hardening temperature higher than the step [xiii] Lower temperature.