TW201841951A - Photosensitive color resin composition, cured product thereof, color filter, and display device - Google Patents

Abstract

Provided is a photosensitive color resin composition that can provide high luminance after high temperature heating and form a pattern with a desired line width. Disclosed is a photosensitive color resin composition comprising a color material containing a phthalocyanine pigment and a color material represented by the following general formula (1), wherein a content of the color material represented by the following general formula (1) is 20% by mass or more and 85% by mass or less, with respect to a total content of the phthalocyanine pigment and the color material represented by the following general formula (1): (the symbols in the general formula (1) are as described in the specification.).

Description

 Photosensitive colored resin composition and cured product thereof, color filter and display device  

The present invention relates to a photosensitive colored resin composition and a cured product thereof, a color filter and a display device.

In recent years, with the development of personal computers, especially the development of portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, and tablets) has also increased, showing an ever-expanding market for liquid crystal displays. Further, recently, an organic light-emitting display device such as an organic EL display which uses self-luminous light and has high visibility has also been attracting attention as a new-generation image display device. The performance of these image display devices is expected to be further improved in image quality and contrast.

Color filters can be used in such liquid crystal display devices or organic light emitting display devices. For example, the color image formation of the liquid crystal display device is directly colored by the light passing through the color filter to form the color of each pixel constituting the color filter, and then combined with the color light to form a color image. In the light source at this time, in addition to the conventional cold cathode tube, there are cases where an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is used. Further, the organic light-emitting display device uses a color filter for color adjustment or the like.

In recent years, there has been a demand for power saving of an image display device, and in order to improve the utilization efficiency of a backlight, a color filter is required to have high luminance. In particular, it is a big issue for mobile displays (mobile phones, smart phones, tablets).

Here, the color filter generally includes a substrate, a coloring layer formed on the substrate and containing red, green, and blue primary coloring patterns, and a light blocking portion formed on the substrate so as to distinguish the respective colored patterns.

One of the methods for forming such a coloring layer is a method in which a photosensitive colored resin composition containing a color material and a photopolymerizable compound is applied onto a substrate, and the film is cured by irradiation with ultraviolet rays or the like.

The color material of the photosensitive colored resin composition is a pigment or a dye. The pigment is generally superior in heat resistance and light resistance to dyes, but has a problem that the transmittance is low and the luminance is not sufficiently improved. Therefore, in recent years, from the viewpoint of further increasing the luminance of the color filter, the photosensitive resin composition for a color filter using a generally high transmittance dye is reviewed, and in order to improve the heat resistance or light resistance of the dye, Review for the use of dye-insoluble lake color materials.

Patent Document 1 discloses a color filter using a divalent or higher cation containing a complex dye skeleton by crosslinking with a crosslinking group, and a specific color material having an anion of two or more. It is described that the color material is excellent in heat resistance, and the color filter using the color material has high contrast, and is excellent in solvent resistance and electrical reliability.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: International Publication No. 2012/144521

However, even if Patent Document 1 uses a specific color material, heat resistance or light resistance is inferior to that under the pigment, and thus chromaticity is likely to occur after high-temperature heating (post-baking) in the color filter manufacturing step. The change, and finally the brightness of the colored layer obtained is still insufficient, and it is expected to be further improved.

Furthermore, the colored layer for a general color filter is patterned on the substrate. When a coloring layer is formed using a photosensitive colored resin composition, for example, after a coating film of a photosensitive colored resin composition is formed on a substrate, exposure is performed through a predetermined mask pattern, and then development processing is performed to obtain a patterned pattern. Colored layer.

In recent years, in order to improve the production efficiency and desire to perform patterning with a smaller amount of exposure, the inventors of the present invention have found that if a blue colored layer is to be formed using a phthalocyanine pigment, there is a case where a color layer as designed cannot be formed.

The present invention has been made in view of the above findings, and an object thereof is to provide a photosensitive colored resin capable of forming a pattern according to a desired line width while improving the luminance after a high-temperature heating step (post-baking) in the color filter manufacturing step. a composition; a color filter that enhances the luminance formed by using the photosensitive colored resin composition; and a display device excellent in display characteristics using the color filter.

The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a photosensitive colored resin composition of a solvent; wherein the color material contains a phthalocyanine pigment, And the color material of the following general formula (1); the content of the color material shown by the following general formula (1) with respect to the total content of the phthalocyanine pigment and the color material shown by the following general formula (1). 20% by mass or more and 85% by mass or less.

[Chemical 1]

(In the general formula (1), each symbol is as described later.)

The present invention provides a cured product of the above-mentioned photosensitive colored resin composition of the present invention.

The color filter provided by the present invention is provided with at least a substrate and a color filter provided on the substrate; wherein at least one of the colored layers is the photosensitive coloring resin of the present invention. A hardened substance of the composition.

The display device provided by the present invention includes the color filter of the present invention described above.

According to the present invention, it is possible to provide a photosensitive colored resin composition capable of forming a pattern according to a desired line width while improving the luminance after the high-temperature heating step (post-baking) in the color filter manufacturing step; A color filter having a luminance formed by the coloring resin composition; and a display device excellent in display characteristics using the color filter.

1‧‧‧Substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧Anti-substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Fig. 1 is a schematic view showing an example of a color filter of the present invention.

Fig. 2 is a schematic view showing an example of a display device of the present invention.

Fig. 3 is a schematic view showing another example of the display device of the present invention.

Hereinafter, the photosensitive colored resin composition, the color filter, and the display device of the present invention will be described in detail in order.

Further, in the present invention, the light system covers electromagnetic waves of wavelengths of visible and non-visible regions, and radiation, and the radiation system covers, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

In the present invention, the "(meth)acryl group" means each of a propylene group and a methacryl group; and the "(meth)acrylate" means each of an acrylate and a methacrylate.

Further, C.I. Pigment Blue is appropriately referred to as "PB", and C.I. Pigment Violet is appropriately referred to as "PV".

 I. Photosensitive colored resin composition  

The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent-based photosensitive colored resin composition; wherein the color material contains a phthalocyanine pigment And the color material of the general formula (1) below; the total content of the color material shown by the following general formula (1) with respect to the phthalocyanine pigment and the following general formula (1), and the content of the color material shown by the following general formula (1) It is 20% by mass or more and 85% by mass or less.

[Chemical 2]

(In the general formula (1), A represents an a-valent organic group having a carbon atom directly bonded to N and having no π bond, and the organic group is an aliphatic group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may further contain O, S, and N. The B ^c- system represents a c-valent anion. R ⁱ to R ^v each independently represent a hydrogen atom, and may also a substituted alkyl group or an aryl group which may have a substituent, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may also be bonded to each other to form a ring structure. R ^vi and R ^vii each independently represent or have a substitution. The alkyl group, the alkoxy group which may have a substituent, a halogen atom or a cyano group. Ar ¹ represents a divalent aromatic group which may have a substituent, and the plural R ⁱ ~ R ^vii and Ar ¹ may be the same respectively. It can also be different.

a and c represent an integer of 2 or more, and b and d represent an integer of 1 or more. The e system indicates 0 or 1, and when e is 0, there is no bond. f and g are integers of 0 or more and 4 or less, and f+e and g+e are 0 or more and 4 or less. The plural e, f, and g systems may be the same or different. )

The photosensitive colored resin composition of the present invention has an effect of forming a pattern according to a desired line width while improving the luminance after high-temperature heating (post-baking) in the color filter manufacturing step.

In the color filter manufacturing step, the post-baking step is performed at a high temperature of 230 ° C or 240 ° C, and thus it is conventional to use a pigment from the viewpoint of heating at such a high temperature and not easily fading. In recent years, in order to improve the production efficiency, it is required to perform patterning with a smaller amount of exposure, and the inventors of the present invention found that if a blue colored layer is to be formed using a phthalocyanine pigment, a color layer as designed may not be formed. The reason is presumed that since the blue phthalocyanine pigment absorbs 300 nm before and after the absorption wavelength (radical generation wavelength) of the photoinitiator, the photopolymerization reaction does not sufficiently proceed, and the hardening of the inside of the colored layer occurs during exposure.

On the other hand, in the present invention, by using the color material shown in the above specific general formula (1) in combination with a specific ratio in the phthalocyanine pigment, the color material shown by the above specific general formula (1) is not easily absorbed by the wavelength before and after 300 nm. Even if the negative photosensitive adhesive component is combined to form a photosensitive colored resin composition for a blue colored layer, insufficient hardening occurs inside the colored layer during exposure, and the pattern can be easily formed according to the desired line width.

Further, by using the color material shown in the above specific general formula (1) in combination with a specific ratio in the phthalocyanine pigment, the fading caused by the color material shown by the above specific general formula (1) can be suppressed, and the penetration can be improved. The rate is presumed to increase the luminance of the finally obtained colored layer after high-temperature heating (post-baking) in the color filter manufacturing step.

The photosensitive colored resin composition of the present invention contains at least a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. .

Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail in order.

 [color material]  

In the present invention, the color material contains a phthalocyanine pigment and a color material represented by the above general formula (1), and is characterized by a total content of the phthalocyanine pigment and a color material represented by the following general formula (1). The content of the color material represented by the following general formula (1) is 20% by mass or more and 85% by mass or less.

 <phthalocyanine pigment>  

Since the phthalocyanine pigment is used in combination with the coloring material represented by the above general formula (1), it is preferably a blue phthalocyanine pigment, and is preferably a copper phthalocyanine pigment from the viewpoint of excellent luminance. For example: C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and the like. In particular, the phthalocyanine pigment is preferably one or more selected from the group consisting of C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3, and C.I. Pigment Blue 15:4 from the viewpoint of excellent brightness.

 <Color material shown in general formula (1)>  

On the other hand, the color material represented by the above general formula (1) contains an anion of two or more valences and a cation of two or more valences. Therefore, the aggregate of the color material is not anion and a cation, and the ionic bond is simply one molecule to one molecule. The junction, but the ionic bond can form a molecular association of complex molecules, and thus the apparent molecular weight is particularly increased compared to the molecular weight of the conventional lake pigment. By forming such a molecular association, the cohesive force in the solid state is further improved, the thermal motion is reduced, and the dissociation of the ion pair or the decomposition of the cation portion can be suppressed, and it is estimated that the conventional lake pigment is less likely to fade.

In the above general formula (1), A is directly bonded to a carbon atom of N (nitrogen atom) and has no a-valent organic group having a π bond, and the organic group means at least a terminally bonded N has a saturated aliphatic group. The aliphatic hydrocarbon group of the hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may further contain O (oxygen atom), S (sulfur atom), or N (nitrogen atom) in the carbon chain. Since the carbon atoms directly bonded to N do not have a π bond, the color characteristics such as hue or transmittance of the cationic color-developing portion are not affected by the linker A or other color-developing portions, and can be maintained. The same color as the monomer.

In A, an aliphatic hydrocarbon group having at least a terminal having a saturated aliphatic hydrocarbon group at the end of N is taken up before the terminal carbon atom directly bonded to N does not have a π bond, and may be arbitrarily linear, branched or cyclic. The carbon atom other than the terminal may have an unsaturated bond or a substituent, and the carbon chain may further contain O, S, and N. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, a guanamine group or the like may be contained, and the hydrogen atom may be further substituted with a halogen atom or the like.

Further, in the above, the aromatic group having an aliphatic hydrocarbon group may, for example, be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group bonded at least at the terminal of N; It may have a substituent or may be a hetero ring containing O, S or N.

Among them, from the viewpoint of skeleton fastness, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.

The cyclic aliphatic hydrocarbon group is preferably a bridged alicyclic hydrocarbon group from the viewpoint of skeleton fastness. The "bridged alicyclic hydrocarbon group" refers to a polycyclic aliphatic hydrocarbon group having a bridge structure in an aliphatic ring and having a polycyclic structure, and for example, Alkane, bicyclo[2,2,2]octane, adamantane, and the like. Among the bridged alicyclic hydrocarbon groups, it is preferred to lower alkyl. Further, the aromatic group may, for example, be a group containing a benzene ring or a naphthalene ring, and among them, a group containing a benzene ring is preferred. For example, when A is a divalent organic group, for example, a straight chain, a branched or a cyclic alkyl group having a carbon number of 1 to 20, or a benzoyl group may be substituted with two carbon atoms of 1 to 20 Aromatic alkyl group

The valence number a of A is the number of chromogenic cation sites constituting a cation, and a is an integer of 2 or more. In the lake color material, since the valence a of the cation is 2 or more, heat resistance is excellent, and among them, the valence a of the cation is preferably 3 or more. The upper limit of a is not particularly limited, and from the viewpoint of easiness of production, a is preferably 4 or less, more preferably 3 or less.

The alkyl group in R ⁱ to R ^v is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms may be used. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred, and a carbon number of 1 is preferred from the viewpoint of luminance and heat resistance. a linear or branched alkyl group of ~5. Wherein the alkyl group particularly preferably ethyl or methyl lines R ⁱ ~ R ^v in. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group. The alkyl group which has been substituted may, for example, be an aralkyl group such as a benzyl group.

The aryl group in R ⁱ to R ^v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. The substituent which the aryl group may have may, for example, be an alkyl group, a halogen atom or an alkoxy group.

Among them, from the viewpoint of chemical stability, R ⁱ to R ^{v are} preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a combination of R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v . Forming a pyrrolidine ring, a piperidine ring, A porphyrin ring.

R ⁱ ~ R ^v each independently may be formed in the above-described system configuration, which, from the viewpoint of color purity, preferably based R ⁱ is a hydrogen atom, and further material from the manufacturing point of view of ease of scheduling, more preferably based R ⁱⁱ ~ R ^v All the same.

R ^vi and R ^vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R ^vi and R ^vii is not particularly limited, and is preferably a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, more preferably an alkyl group having 1 or more and 4 or less carbon atoms. . The alkyl group having 1 or more and 4 or less carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group, and may have a linear chain or may have a branch. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.

Further, the alkoxy group in R ^vi and R ^vii is not particularly limited, and preferably has a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms, more preferably 1 or more carbon atoms. 4 or less alkoxy groups. The alkoxy group having 1 or more and 4 or less carbon atoms may, for example, be a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and may have a linear chain or may have a branch. The substituent which the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and an alkoxy group.

Examples of the halogen atom in R ^vi and R ^vii include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of substitutions of R ^vi and R ^vii , that is, f and g are each independently represented by an integer of 0 or more and 4 or less, and more preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. The plural f and g systems may be the same or different.

Furthermore, R ^vi and R ^vii may be substituted for the triarylmethane skeleton, or Any portion of the aromatic ring having a resonance structure in the skeleton, wherein the position of the amine group represented by -NR ⁱⁱ R ⁱⁱⁱ or -NR ^iv R ^{v is} preferably substituted for the meta position.

The divalent aromatic group in Ar ¹ is not particularly limited. The aromatic group in Ar ¹ can be the same as those listed in the aromatic group in A.

Ar ^{1 is} preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms. Among them, from the viewpoints of simple structure and low raw materials, it is more preferred to extend a phenyl group or a naphthyl group.

The complex numbers R ⁱ to R ^vii and the Ar ¹ system in one molecule may be the same or different. By the combination of R ⁱ ~R ^vii and Ar ¹ , it is possible to adjust to the desired color.

In the color material of the general formula (1), the anion moiety (B ^c- ) is a c-valent anion or a divalent or higher anion, and is not particularly limited, and may be an organic anion or an inorganic anion. The term "organic anion" as used herein means an anion having at least one carbon atom. Moreover, the "inorganic anion" means an anion which does not contain a carbon atom. Specific examples of the organic anion and the inorganic anion include those described in, for example, International Publication No. 2012/144520.

In the present invention, the general formula (1) color material, wherein the high brightness viewpoint of excellent heat resistance, preferred is an inorganic anion B ^c- based.

Examples of the inorganic anion include an anion of an oxo acid (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), or a plurality of An inorganic anion such as a polybasic anion obtained by oxidizing an oxyacid or a mixture thereof. Among them, a polybasic acid anion is preferred from the viewpoint of heat resistance.

The polybasic acid may be an allopolyacid anion (M _m O _n ) ^c- or an anisotropic polyacid anion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of a poly atom, and n represents a composition ratio of an oxygen atom. Examples of the polyatomic M system include Mo, W, V, Ti, Nb, and the like. Further, examples of the hetero atom X include Si, P, As, S, Fe, Co, and the like.

Among them, from the viewpoint of heat resistance, a polybasic acid anion containing at least one of molybdenum (Mo) and tungsten (W) is preferable, and a c-valent polybasic anion having at least tungsten is more preferable.

In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular association, and b and d represent an integer of 1 or more. When b is 2 or more, the plural cations in the molecular association may be used alone or in combination of two or more. In addition, when d is 2 or more, the plural anion in the molecular association may be used alone or in combination of two or more, and an organic anion and an inorganic anion may be used in combination.

In the general formula (1), e is an integer of 0 or 1. e=0 represents a triarylmethane skeleton, and e=1 represents skeleton. The plural e-systems may be the same or different. In the lake color material of the general formula (1) used in the present invention, those containing at least a triarylmethane skeleton are suitably used.

Further, the lake color material of the general formula (1) can be produced by referring to, for example, International Publication No. 2012/144520.

 <Other color materials>  

The color material in the photosensitive colored resin composition of the present invention contains the above-mentioned phthalocyanine pigment as an essential component and the color material shown in the above general formula (1), but is adjusted within the range that does not impair the effects of the present invention. Tones, you can use other color materials in combination.

Other color materials may be used alone or in combination of two or more kinds of known pigments, dyes, lake color materials, and the like.

Among other color materials, other blue color materials, purple color materials, and red color materials are preferably used, but are not limited thereto.

Other blue color materials are: a known organic blue pigment different from the phthalocyanine pigment, a triarylmethane-based lake material different from the color material shown in the above general formula (1), and the like.

The purple color material is a well-known organic purple pigment such as C.I. Pigment Violet 1, 14, 15, 19, 23, 29, 32, 33, 36, 37, 38.

Red and reddish purple color materials: Dyes and A dye-based lake color material or the like.

 <Content ratio of color material>  

In the photosensitive colored resin composition of the present invention, the content of the coloring material represented by the above general formula (1) is 20% by mass or more based on the total content of the phthalocyanine pigment and the coloring material represented by the above general formula (1). In addition, from the viewpoint of the luminance and the easiness of patterning according to the desired line width, it is preferably 30% by mass or more, more preferably 40% by mass or more, and on the other hand, from the viewpoint of heat resistance. It is preferably 80% by mass or less, more preferably 75% by mass or less.

Further, in the photosensitive colored resin composition of the present invention, the color material may further contain a phthalocyanine pigment and other colors than the color material shown in the above general formula (1) within a range that does not impair the effects of the present invention. The total content of the phthalocyanine pigment and the coloring matter represented by the above general formula (1) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% based on the total amount of the coloring material. The mass% or less is particularly preferably 90% by mass or more and 100% by mass or less.

The average primary particle diameter of the color material used in the present invention is not particularly limited as long as it can be used as the coloring layer of the color filter, and is different depending on the type of the color material to be used. It is preferably in the range of 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm or less. When the average primary particle diameter of the color material is within the above range, a display device using the color filter produced by using the color material dispersion of the present invention can provide high contrast and high quality.

In addition, the average dispersed particle diameter of the color material in the photosensitive colored resin composition varies depending on the type of the color material to be used, and is preferably in the range of 10 nm or more and 100 nm or less, more preferably 15 nm or more and 60 nm. Within the scope below.

The average dispersed particle diameter of the color material in the photosensitive colored resin composition is a dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. The particle size measurement by the laser light scattering particle size distribution analyzer uses a solvent used for the color material dispersion liquid to appropriately dilute the color material dispersion liquid (for example, 1000 times or the like) as a concentration which can be measured by a laser light scattering particle size distribution meter. The measurement was carried out at 23 ° C by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.). The "average distribution particle diameter" herein is a volume average particle diameter.

The total content of the color materials is preferably 3% by mass or more and 65% by mass or less, more preferably 4% by mass or more and 60% by mass or less, based on the total amount of the solid content of the photosensitive colored resin composition. . When the photosensitive colored resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm), the colored layer has a sufficient color density. Moreover, when it is below the above-mentioned upper limit, the coloring layer which is excellent in storage stability, has sufficient hardness, or has adhesiveness with a board|substrate is acquired. In particular, when a coloring layer having a high color material concentration is formed, the total content of the color material is preferably 15% by mass or more and 65% by mass or less, more preferably, based on the total amount of the solid content of the photosensitive colored resin composition. The mixture is mixed at a ratio of 25% by mass or more and 60% by mass or less.

 [alkali soluble resin]  

The alkali-soluble resin in the present invention has an acidic group and can be appropriately selected and used under the premise that it can function as a binder resin and is soluble in the alkali developer used for pattern formation.

In the present invention, the "alkali-soluble resin" is an index having an acid value of 40 mgKOH/g or more.

The alkali-soluble resin which is preferable in the present invention is a resin having an acidic group and usually having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group. Acrylic resin, etc.; epoxy (meth) acrylate resin having a carboxyl group.

Among these, those having a carboxyl group and a side chain having a photopolymerizable functional group such as an ethylenically unsaturated group are preferred. In the case where the photopolymerizable functional group is contained, in the resin composition hardening step in the production of the color filter, the alkali-soluble resin or the photo-polymerizable compound such as the alkali-soluble resin and the polyfunctional monomer can be crosslinked. key. The film strength of the cured film is further improved, the development resistance is improved, the heat shrinkage of the cured film is suppressed, and the adhesion to the substrate is excellent.

The method of introducing an ethylenic double bond into the alkali-soluble resin can be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and an ethylenic double bond, such as glycidyl (meth)acrylate, may be added to the carboxyl group of the alkali-soluble resin, and ethylenic acid may be introduced into the side chain. A method of introducing a double bond; or a method of introducing a structural unit having a hydroxyl group into a copolymer, and adding a compound having an isocyanate group and an ethylenic double bond in the component, and introducing an ethylenic double bond to the side chain.

Further, the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. When the alkali-soluble resin has a bulky hydrocarbon ring, shrinkage during curing, relaxation of the peeling from the substrate, and improvement in substrate adhesion can be suppressed.

The hydrocarbon ring system may, for example, be an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, or a combination thereof, and the hydrocarbon ring may have an alkyl group, a carbonyl group or a carboxyl group. a substituent such as an oxycarbonyl group, a decylamino group, a hydroxyl group, a nitro group, an amine group or a halogen atom.

The hydrocarbon ring system may be contained in the form of a monovalent group or may be contained in the form of a divalent or higher group.

Specific examples of the hydrocarbon ring include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. Alkane, different An aliphatic hydrocarbon ring such as alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane) or adamantane; aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene or anthracene; biphenyl, hydrazine A chain polycyclic ring such as triphenyl, diphenylmethane, triphenylmethane or anthracene; or a cardo structure (9,9-diarylfluorene); a group in which a part of the group is substituted by a substituent.

The substituent may, for example, be an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amine group or a halogen atom.

The hydrocarbon ring preferably contains an aliphatic hydrocarbon ring from the viewpoint of improving heat resistance or adhesion of the colored layer and improving the brightness of the obtained colored layer.

In addition, from the viewpoint of improving the coloring layer hardenability, suppressing fading of the color material, and improving solvent resistance (NMP swelling inhibition), it is particularly preferable to contain the above-described card structure.

An acrylic resin containing an acrylic copolymer having a carboxyl group-constituting unit and a styrene-acrylic copolymer having a carboxyl group, for example, a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, other copolymerizable copolymers A monomer (co)polymer obtained by (co)polymerization by a known method.

The carboxyl group-containing ethylenically unsaturated single system may, for example, be (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid. , crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reaction of a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate with a cyclic acid anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride can also be used. And ω-carboxy-polycaprolactone mono(meth)acrylate and the like. Further, an acid anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the precursor of the carboxyl group. Among them, from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like, it is particularly preferred (meth)acrylic acid.

The alkali-soluble resin in the present invention preferably has a carboxyl group-constituting unit, an acrylic copolymer having a hydrocarbon ring-constituting unit, and a carboxyl group-containing copolymer such as a styrene-acrylic copolymer, and more preferably A carboxyl group-containing copolymer having a carboxyl group-constituting unit, a hydrocarbon ring-constituting unit, and an acrylic double-bonding unit; and a carboxyl group-containing copolymer such as a styrene-acrylic copolymer.

Examples of the ethylenically unsaturated single system having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, and (meth)acrylic acid. The ester, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene, etc. are preferably used from the viewpoint of maintaining a large cross-sectional shape of the colored layer after development in the heat treatment. At least one selected from the group consisting of cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene.

The carboxyl group-containing copolymer may further contain other constituent units such as an ester group structural unit such as methyl (meth)acrylate or ethyl (meth)acrylate. The constituent unit having an ester group functions not only as a component which suppresses alkali solubility of the photosensitive colored resin composition, but also as a component which improves solubility in a solvent and solvent resolubility.

The carboxyl group-containing copolymer can be an alkali-soluble resin having desired properties by appropriately adjusting the loading amount of each constituent unit.

The loading amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more based on the total amount of the monomers, from the viewpoint of obtaining a good pattern. On the other hand, the loading amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 50% by mass or less, and more preferably 40% by mass or less based on the total amount of the monomers, from the viewpoint of suppressing film roughness on the surface of the pattern after development. .

Further, it is more preferable to use an acryl-based copolymer having an ethylenic double bond as a base-soluble resin and a carboxyl group-containing copolymer such as a styrene-acrylic copolymer, and to have an epoxy group. The amount of the compound having a vinyl group and the ethylenic double bond is preferably 10% by mass or more and 95% by mass or less, more preferably 15% by mass or more and 90% by mass or less based on the loading amount of the carboxyl group-containing ethylenically unsaturated monomer.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the function of the binder after curing is improved, and when it is 50,000 or less, the pattern formation is good when developing with an alkali developer.

Further, the above weight average molecular weight (Mw) of the carboxyl group-containing copolymer is determined by using Shodex GPC System-21H using styrene as a standard and polystyrene as a standard.

The epoxy (meth) acrylate resin having a carboxyl group is not particularly limited, but an epoxy (meth) acrylate obtained by reacting an epoxy compound with a reaction product of an unsaturated group-containing monocarboxylic acid with an acid anhydride Ester compounds are preferred.

The epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride can be appropriately selected from known ones.

The epoxy (meth) acrylate resin having a carboxyl group preferably has the above hydrocarbon ring in the molecule, and is preferably contained from the viewpoint of improving the curability of the colored layer, suppressing fading of the color material, and high residual film ratio of the colored layer. Cardo structure.

Each of the epoxy (meth) acrylate resins having a carboxyl group may be used alone or in combination of two or more.

The alkali-soluble resin preferably has an acid value of 50 mgKOH/g or more from the viewpoint of developability (solubility) of the aqueous alkali solution used for the developer. The alkali-soluble resin is preferably 70 mgKOH/g or more and 300 mgKOH/g or less, more preferably 80 mgKOH/g from the viewpoint of developability (solubility) of the aqueous alkali solution used for the developer and adhesion to the substrate. g or more and 280 mgKOH/g or less.

Further, in the present invention, the acid value can be measured in accordance with JIS K 0070:1992.

When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is superior to the effect of obtaining the film strength of the cured film, improving the development resistance, and excellent adhesion to the substrate. The range of the best system is 100~2000, and the range of the best is 140~1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, the development resistance and the adhesion are excellent. In addition, when the ratio is 100 or more, the ratio of the other constituent unit such as the carboxyl group-constituting unit or the hydrocarbon ring-constituting unit can be relatively increased, so that the developability and heat resistance are excellent.

Here, the "ethylenically unsaturated bond equivalent" means the weight average molecular weight per 1 mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1): Formula (1) Ethylene Unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(In the formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent can be calculated, for example, by measuring the number of ethylenic double bonds per 1 g of the alkali-soluble resin according to the iodine value test method described in JIS K 0070:1992.

The alkali-soluble resin to be used for the photosensitive colored resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and the total amount of the solid content of the photosensitive colored resin composition is The alkali-soluble resin is preferably in a range of 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the alkali-soluble resin is at least the above lower limit value, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is at most the above upper limit value, film roughness or pattern defect during development can be suppressed. situation.

 [Photopolymerizable compound]  

The photopolymerizable compound used in the photosensitive colored resin composition is removed before being polymerized by a photoinitiator, and the rest thereof is not particularly limited, and usually two or more ethylenically unsaturated double bonds are preferably used. The compound is particularly preferably a polyfunctional (meth) acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups.

Such a polyfunctional (meth) acrylate can be appropriately selected from those known in the art. Specific examples include those described in Japanese Laid-Open Patent Publication No. 2013-029832.

These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Further, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the photopolymerizable compound preferably has three (trifunctional) or more polymerizable double bonds, preferably a trivalent value. The poly(meth)acrylates of the above polyols or the dicarboxylic acid modifiers are specifically preferably: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate a succinic acid modification of pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (methyl) An acrylate succinic acid modification, dipentaerythritol hexa(meth) acrylate, tris(2-(meth) propylene methoxyethyl) phosphate, or the like. If a polyfunctional (meth) acrylate containing a phosphorus atom such as tris(2-(meth) propylene methoxyethyl) phosphate is used, it is easy to suppress the fading of the lake coloring material, and it is easy to improve post-baking. The brightness is preferred from the standpoint of brightness.

The content of the photopolymerizable compound to be used in the photosensitive coloring resin composition is not particularly limited, and the photopolymerizable compound is preferably 5% by mass or more based on the total amount of the solid content of the photosensitive colored resin composition. It is 60% by mass or less, more preferably 10% by mass or more and 40% by mass or less. When the content of the photopolymerizable compound is at least the above-mentioned lower limit value, the photocuring is sufficiently performed, and it is possible to suppress the elution of the exposed portion during development, and the alkali developability when the content of the photopolymerizable compound is at most the above upper limit value sufficient.

 [light initiator]  

The photoinitiator used in the photosensitive coloring resin composition of the present invention is not particularly limited, and may be used alone or in combination of two or more kinds thereof in various conventionally known initiators.

The photoinitiator may, for example, be an aromatic ketone, a benzoin ether or a halomethyl group. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, 9-oxosulfur Wait. Specific examples of the photoinitiator include, for example, diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl ketone, and the like. Aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; biimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer ; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halogen methyl group Diazole compound; 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Isohalomethyl-S-three Compound; 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Polinylacetone, 1,2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-benzophenone, benzyl, benzhydrylbenzoic acid, methyl benzylidenebenzoate, 4-benzylidene-4'- Methyl diphenyl sulfide, benzyl methyl ketal, dimethylamino benzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzene Formate, 2-chloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur , 4-benzylidene-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-benzophenone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2- is preferably used. Lolinylpropan-1-one (for example, IRGACURE 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, IRGACURE 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, HICURE ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), diethyl 9 - Oxygen sulfur . From the viewpoints of sensitivity adjustment, water stain suppression, and development resistance, it is more preferable to use, for example, 2-methyl-1-[4-(methylthio)phenyl]-2- Alkyl propan-1-one-like α-aminoacetophenone photoinitiator, and, for example, diethyl 9-oxosulfur 9-oxosulfur A photoinitiator.

In the present invention, the photoinitiator is preferably an oxime ester photoinitiator from the viewpoint of enhancing sensitivity. By using an oxime ester photoinitiator, it is easy to suppress the variation in the line width in the plane when the fine line pattern is formed. Moreover, by using an oxime ester-based photoinitiator, the development resistance is improved, and the effect of suppressing the occurrence of water staining tends to be improved. In addition, the term "water stain" means that if a component having high alkali developability is used, after washing with pure water after alkali development, a trace such as water infiltration occurs. Although such water stains will disappear after post-baking, there is no problem in the product. However, when the appearance of the patterned surface is checked after development, it is regarded as an abnormal spot and is detected, resulting in an inability to distinguish between normal and abnormal products. problem. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the result is that the yield of the final color filter product is lowered to cause a problem.

From the viewpoint of reducing the contamination of the photosensitive colored resin composition or the contamination of the device caused by the decomposition product, it is preferred that the oxime ester-based photoinitiator has an aromatic ring, and more preferably has a condensed ring containing an aromatic ring. More preferably, it has a condensed ring containing a benzene ring and a hetero ring.

The oxime ester photoinitiator can be derived from 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzhydrylhydrazine), ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(o-ethylidene), Japanese Patent Laid-Open No. 2000-80068, JP-A-2001- The oxime ester-based photoinitiator described in, for example, JP-A-2010-527339, JP-A-2010- 527 338, and JP-A-2013-041153, is appropriately selected. Commercially available products such as IRGACURE OXE-01 (manufactured by BASF) having a carbazole skeleton, ADEKA ARKLS NCI-831 (manufactured by Adeka), and TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.); ADEKA ARKLS NCI-930 (made by ADEKA), TR-PBG-345, and TR-PBG-3057 (all of which are manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) of phenyl sulfide skeleton; TR-PBG-365 with 茀 skeleton Changzhou Power Electronic New Material Co., Ltd.), SPI-04 (Sanyang System), etc. From the viewpoint of enhancing the luminance, it is particularly preferable to use an oxime ester photoinitiator having a diphenyl sulfide skeleton or an anthracene skeleton. Further, from the viewpoint of high sensitivity, an oxime ester photoinitiator having a carbazole skeleton is preferably used.

In addition, when two or more kinds of oxime ester-based photoinitiators are used in combination, by appropriately selecting two or more kinds of oxime ester compounds having different sensitivities, the line width at the time of pattern formation can be adjusted while maintaining good sensitivity. It is easy to improve the development resistance or the brightness, and the effect of suppressing the occurrence of water stains is high, and in this case, it is preferable. In particular, two kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton or an oxime ester photoinitiator having a diphenyl sulfide skeleton and an oxime ester photoinitiator having an anthracene skeleton are used in combination. It is preferred that the heat resistance and the brightness can be easily improved.

Further, since the patterning is performed with a small amount of exposure, when a high-sensitivity photoinitiator is used, the radicals move to the unexposed portion after the radicals are generated. Therefore, when the colored layer is patterned, and at the same time, the desired minute holes are formed on the colored layer, it is difficult to form the unexposed portion peripheral portion without tremor in a state in which the shape of the unexposed portion inside the exposed portion is maintained. . On the other hand, in the color material combination of the present invention, when an oxime ester-based photoinitiator having an anthracene skeleton is used, when the colored layer is patterned, there is an advantage that the desired minute pores can be easily formed on the colored layer at the same time. . Among them, from the viewpoint of not greatly reducing the luminance and sensitivity and easily increasing the shape of the micropore, it is preferred to use an oxime ester photoinitiator of the fluorene skeleton and an oxime ester photoinitiator having a phenyl sulfide skeleton. When the desired minute pores are easily formed on the colored layer, since the photosensitive colored resin composition of the present invention forms, for example, a reflective color filter, a colored layer is formed on the TFT substrate, and is also suitable for the colored layer. The use of a common through hole is formed. In addition, "trembling" means that the straight line or the curved line at the end of the pattern is uneven, resulting in a deterioration in dimensional accuracy.

Further, from the viewpoint of suppressing water stains and improving sensitivity, the above-mentioned α-aminoacetophenone photoinitiator is preferably used in combination with the oxime ester photoinitiator. The reason is a photoinitiator having a tertiary amine structure like α-aminoacetophenone. Since the molecule has a tertiary amine structure belonging to an oxygen quencher, the radical generated from the initiator is not easily oxygenated. And to activate, you can improve the sensitivity.

Further, from the viewpoints of sensitivity adjustment, suppression of water stains, and improvement of developability, it is preferred to use 9-oxosulfuric acid in combination with a phthalic ester-based photoinitiator. It is preferred to use two or more kinds of oxime ester photoinitiators and 9 from the viewpoints of improving the brightness and the development resistance, easily adjusting the sensitivity, suppressing the occurrence of water stains, and improving the development resistance. - Oxygen sulfur A combination of photoinitiators.

The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited until the effect of the present invention is impaired, and the solid content of the photosensitive colored resin composition is not particularly limited. The total amount is preferably in the range of 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. When the content is at least the above lower limit value, photocuring is sufficiently performed, and it is possible to suppress elution of the exposed portion during development. On the other hand, when the content is at most the above upper limit, yellowing of the obtained colored layer can be suppressed. The brightness is reduced.

In addition, the "solid content" means all components other than a solvent, and also includes a liquid photopolymerizable compound.

 [solvent]  

The solvent to be used in the present invention is not affected by the reaction with each component in the photosensitive colored resin composition, but it is not particularly limited as long as it can dissolve or disperse the organic solvent. The solvent may be used singly or in combination of two or more.

Specific examples of the solvent include an alcohol solvent such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol or ethoxylated alcohol; methoxyethoxyethanol and ethoxyethoxy group; a carbitol solvent such as ethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, Ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate, etc.; acetone, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, acetic acid-3-methoxy-3-methyl-1-butyl ester, acetic acid-3 a glycol ether acetate solvent such as methoxybutyl ester or ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate ( BCA), carbitol acetate solvent such as carbitol acetate; diacetate such as propylene glycol diacetate or 1,3-butanediol diacetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ethylene glycol a glycol ether solvent such as ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether or dipropylene glycol dimethyl ether; N,N-dimethylformamidine Aprotic guanamine solvent such as amine, N,N-dimethylacetamide or N-methylpyrrolidone; lactone solvent such as γ-butyrolactone; cyclic ether solvent such as tetrahydrofuran; benzene and toluene An unsaturated hydrocarbon solvent such as xylene or naphthalene; a saturated hydrocarbon solvent such as N-heptane, N-hexane or N-octane; or an organic solvent such as an aromatic hydrocarbon such as toluene or xylene. Among these solvents, a glycol ether acetate solvent, a carbitol acetate solvent, a glycol ether solvent, or an ester solvent is preferably used from the viewpoint of solubility of other components. Among them, the solvent used in the present invention is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), or card from the viewpoints of solubility or coating suitability of other components. a group consisting of benzal acetate, 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate Choose one or more.

In the photosensitive colored resin composition of the present invention, the solvent content may be appropriately set within a range in which the coloring layer can be formed with high precision. The total amount of the photosensitive colored resin composition containing the solvent is usually preferably in the range of 55% by mass or more and 95% by mass or less, more preferably in the range of 65% by mass or more and 88% by mass or less. . When the solvent content is within the above range, the coating property is excellent.

 [Dispersant]  

In the photosensitive colored resin composition of the present invention, the color material is preferably used by being dispersed in a solvent using a dispersing agent. In the present invention, the dispersing agent can be appropriately selected from the conventionally known dispersing agents. As the dispersant, for example, a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric surfactant, a polyfluorinated system or a fluorine-based surfactant can be used. Among the surfactants, a polymer dispersant is preferred from the viewpoint of obtaining uniform and fine dispersion.

Examples of the polymer dispersant include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid, and (partial) ammonium a salt or a (partial) alkylamine salt; a (co)polymer of a hydroxyl group-containing unsaturated carboxylic acid ester such as a hydroxyl group-containing polyacrylate; or a modified product thereof; a polyurethane; an unsaturated polyamine; Oxyalkanes; long-chain polyamine phthalamide phosphates; polyethylenimine derivatives (by the reaction of poly(lower alkylenimine) with a polyester containing a free carboxyl group, the obtained guanamine or the like (alkali); polyallylamine derivative (select one or more of polyallylamine, three kinds of compounds such as a polyester having a free carboxyl group, a polycondensate or a copolycondensate of a polyamine or a decylamine (polyester decylamine) The compound, the reaction product obtained by the reaction, and the like.

In the polymer dispersant, from the viewpoint that the color material can be appropriately dispersed and the dispersion stability is good, a polymer dispersant having a nitrogen atom and an amine value in the main chain or the side chain is preferable, and the coating film is excellent in dispersibility. A polymer dispersant containing a polymer having a tertiary amine constituent unit is more preferable because it does not precipitate foreign matter during formation and can improve luminance and contrast.

A moiety having a tertiary amine constituent unit having affinity with the above color material. A polymer containing a tertiary amine constituent unit usually contains a constituent unit which is a moiety having affinity with a solvent. In the polymer containing a tertiary amine structural unit, it is particularly preferable to contain a block having a tertiary amine structural unit from the viewpoint of being excellent in heat resistance and capable of forming a high-luminance coating film (hereinafter also referred to as "A". Block ") and a block copolymer having a solvent affinity block portion (hereinafter also referred to as "B block").

The tertiary amine constituent unit may have a tertiary amine, and the tertiary amine may be included in the side chain of the block polymer or may constitute the main chain.

In particular, a structural unit having a tertiary amine is preferable, and a structural unit represented by the following general formula (I) is more preferable from the viewpoint that the main chain skeleton is not easily thermally decomposed and has high heat resistance: [Chemical 3] General formula (I)

(In general formula (I), R ¹ is a hydrogen atom or a methyl group; Q is a divalent linking group; R ² is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ ) -O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group; each of R ³ and R ⁴ The independent representation may be substituted with a chain or cyclic hydrocarbon group, or R ³ and R ^{4 may} be bonded to each other to form a cyclic structure. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

The x system represents an integer from 1 to 18; the y system represents an integer from 1 to 5; and the z system represents an integer from 1 to 18. )

The divalent linking group Q of the above general formula (I) may, for example, be an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group or an ether group having 1 to 10 carbon atoms ( -R'-OR"-: R' and R" are each independently an alkyl group) and combinations thereof. Among them, Q is preferably a -COO- group or a -CONH- from the viewpoint of heat resistance of the obtained polymer, or solubility of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and a relatively inexpensive material. base.

The above-mentioned divalent organic group R ² of the general formula (I) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ )-O] _x -CH(R ⁵ )-CH ( R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y -. The above-mentioned alkylene group having 1 to 8 carbon atoms may be linear or branched.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

The above R ^{2 is} preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility, and R ^{2 is more} preferably a methylene group, an ethyl group, a propyl group, a butyl group, and a butyl group. Methyl and ethyl.

In the above general formula (I), the cyclic structure in which R ³ and R ⁴ are bonded to each other may, for example, be a nitrogen-containing heterocyclic monocyclic ring having a five to seven-membered ring or a condensation obtained by condensing the two ring. The nitrogen-containing heterocyclic ring is preferably not aromatic, and more preferably a saturated ring.

The constituent unit represented by the above general formula (I) may, for example, be dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate or diethylaminoethyl (meth)acrylate. (meth)acrylate containing an alkyl-substituted amino group such as diethylaminopropyl (meth)acrylate; dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (A) (meth) acrylamide containing an alkyl-substituted amine group such as acrylamide. Among them, from the viewpoint of improving dispersibility and dispersion stability, it is preferred to use dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (A) Base) acrylamide.

Further, as described later, at least a part of the amine group having the tertiary amine constituent unit may be formed into a salt by a salt-forming agent.

The constituent unit contained in the solvent affinity block portion can be appropriately selected from the constituent units known to be copolymerizable with the above general formula (I).

Further, for example, the above-mentioned B block may be the same as the B block of International Publication No. 2016/104493.

In addition, the dispersing agent of the present invention preferably has a structure represented by the above general formula (I) and an amine value from the viewpoint of good dispersibility, no precipitation of foreign matter during formation of a coating film, and improvement in luminance and contrast. It is a polymer of 40 mgKOH/g or more and 120 mgKOH/g or less.

When the amine value is within the above range, the viscosity is excellent in stability over time or heat resistance, and alkali developability or solvent resolubility is also excellent. The amine value is the number of mg of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237:1995. When measured by this method, even if it is an amine group which forms a salt with an organic acid compound in a dispersing agent, since the organic acid compound dissociates normally, the amine value of the block copolymer itself used as a dispersing agent can be measured.

The acid value of the dispersant used in the present invention is preferably 0 mgKOH/g from the viewpoint of further improving solvent resolubility and development adhesion, and substrate adhesion and dispersion stability. The smaller the acid value, the less likely it is to be attacked by the alkaline developing solution, and thus the development adhesiveness is considered to be better. On the other hand, from the viewpoint of suppressing the effect of developing residue, it is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. Moreover, the acid value of the dispersing agent used in the present invention is preferably 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. In particular, the acid value of the dispersant is preferably 12 mgKOH/g or less, and particularly preferably 8 mgKOH/g or less from the viewpoint of good development adhesion and solvent resolubility.

The dispersant used in the present invention preferably has a block copolymer acid value of 0 mgKOH/g from the viewpoint of further improving solvent resolubility and development adhesion, and substrate adhesion and dispersion stability. the above. On the other hand, from the viewpoint of suppressing the effect of developing residue, it is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more. Moreover, the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less, and particularly preferably 8 mgKOH/g or less from the viewpoint of good development adhesiveness and solvent resolubility.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or higher from the viewpoint of improving the development adhesion. That is, the glass transition temperature is preferably 30 ° C or more regardless of the block copolymer before the formation of the dispersant salt or the salt block copolymer. If the glass transition temperature of the dispersant is low, particularly close to the developer temperature (usually about 23 ° C), there is a possibility that the development adhesiveness is lowered. The reason is that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, it is estimated that the development adhesiveness is deteriorated. When the glass transition temperature is 30° C. or higher, the molecular motion of the dispersant during development is suppressed, and it is estimated that the development adhesiveness is suppressed from being lowered.

The glass transition temperature of the dispersant is preferably 32 ° C or higher, more preferably 35 ° C or higher, from the viewpoint of development adhesion. On the other hand, from the viewpoint of operability when the fine scale is easy to be used, etc., it is preferably 200 ° C or lower.

The glass transition temperature of the dispersant of the present invention can be determined by measurement by differential scanning calorimetry (DSC) according to JIS K7121.

Furthermore, the glass transition temperature (Tg) of the block portion and the block copolymer can be calculated according to the following formula: 1/Tg = Σ (Xi / Tgi)

Here, the block portion is made to be copolymerized by n monomer components of i=1 to n. The weight fraction of the i-th monomer of Xi system (ΣXi=1), and the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer of Tgi. However, the Σ is set to the sum of i=1 to n. Additionally, each monomer having a homopolymer glass transition temperature (Tgi) can be based ^{Polymer Handbook (3 rd Edition) (} J.Brandrup, EHImmergut the (Wiley-Interscience, 1989)) value.

In addition, the glass transition temperature of the dispersant used in the present invention is set to a specific value or more, and from the viewpoint of improving the development adhesion, the monomer having a homopolymer glass transition temperature (Tgi) of 10 ° C or higher is used. In general, the B block is preferably 75% by mass or more, and more preferably 85% by mass or more.

In the block copolymer, the ratio m/n of the number of units m of the A block constituent unit to the number of units n of the B block constituent unit is preferably from the viewpoints of dispersibility of color material and dispersion stability. It is in the range of 0.05 to 1.5, more preferably in the range of 0.1 to 1.0.

The weight average molecular weight Mw of the block copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and more preferably from 3,000 to 12,000, from the viewpoints of good dispersibility of color material and dispersion stability. .

Here, the weight average molecular weight (Mw) is determined by a gel permeation chromatography (GPC) based on a standard polystyrene conversion value. Further, the macromonomer, the salt block copolymer, and the graft copolymer which are related to the block copolymer raw material are also subjected to the above conditions.

In the present invention, from the viewpoint of dispersibility of color material and dispersion stability, it is also preferred to form at least a part of the amine group including the polymer having a tertiary amine structural unit, and an organic acid compound or a halogenated hydrocarbon. The agent is formed into a salt and used as a dispersing agent (hereinafter, such a polymer is referred to as a "salt type polymer").

Among them, from the viewpoint of excellent dispersibility of color material and dispersion stability, it is preferred to contain a polymer block copolymer having a tertiary amine constituent unit, and the above organic acid compound is phenylphosphonic acid or phenylphosphinic acid. An acidic organic phosphorus compound such as an acid. Specific examples of the organic acid compound to be used in such a dispersing agent include, for example, an organic acid compound described in JP-A-2012-236882.

In addition, the halogenated hydrocarbon is preferably at least one of a halogenated allyl group such as allyl bromide or chlorotoluene and a halogenated aralkyl group from the viewpoint of excellent dispersibility of color material and dispersion stability. .

When a dispersing agent is used, the content is not particularly limited as long as the coloring material can be uniformly dispersed. For example, 1% by mass or more and 40% by mass can be used based on the total amount of the solid content of the photosensitive colored resin composition. the following. In addition, the total amount of the solid content of the photosensitive colored resin composition is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less. When it is more than the above lower limit value, the dispersibility of the color material and the dispersion stability are excellent, and the storage stability of the photosensitive colored resin composition is more excellent. Moreover, when it is below the said upper limit, the developability is favorable.

 [Antioxidants]  

The photosensitive colored resin composition of the present invention preferably further contains an antioxidant from the viewpoint of improving heat resistance, suppressing discoloration of the color material, and improving brightness. When the photosensitive colored resin composition of the present invention is combined with an oxime ester-based photoinitiator and contains an antioxidant, when microscopic pores are formed in the cured film, the hardenability is not impaired, and excessive micropores can be controlled. The free radical chain reaction makes it easier to form tiny pores of the desired shape.

The antioxidant used in the present invention is not particularly limited, and can be appropriately selected from known ones. Specific examples of the antioxidant include a hindered phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and a lanthanide-based antioxidant, and the viewpoint of heat resistance and good micropore shape are preferable. Preferably, a hindered phenol-based antioxidant is used. It may also be a latent antioxidant as described in International Publication No. 2014/021023.

The hindered phenol-based antioxidant is, for example, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1, 3 , 5-paraxyl (3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate (trade name: IRGANOX 3114, manufactured by BASF), 2,4,6-gin (4-hydroxy-3) , 5-di-tert-butylbenzyl) mesitylene (trade name: IRGANOX 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-cresol) (trade name) :SUMIRAIZA MDP-S, Sumitomo Chemical Co., Ltd., 6,6'-thiobis(2-tert-butyl-4-cresol) (trade name: IRGANOX 1081, manufactured by BASF), 3,5-two third Diethyl butyl-4-hydroxybenzylphosphonate (trade name: IRGAMOD 195, manufactured by BASF). Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation) is preferred. .

The antioxidant is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the total solid content in the colored resin composition. When it is at least the above lower limit value, both heat resistance and light resistance are excellent. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

When the antioxidant is used in combination with the above-described oxime ester-based photoinitiator, the antioxidant content is preferably 1 part by mass or more based on 100 parts by mass of the total of the oxime ester-based photoinitiator. It is 250 parts by mass or less, more preferably 3 parts by mass or more and 80 parts by mass or less, and particularly preferably 5 parts by mass or more and 65 parts by mass or less. If it is in the above range, the effect of the above combination is excellent.

 [optional addition]  

The photosensitive colored resin composition of the present invention may contain various additives as needed. The additive may, for example, be a mercapto compound, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a adhesion promoter or the like.

Specific examples of the surfactant and the plasticizer are described in, for example, Japanese Laid-Open Patent Publication No. 2013-029832.

In the photosensitive colored resin composition of the present invention, the P/V ratio ((the mass of the color component in the composition) / (the mass of the solid component other than the color component in the composition)) is set to be blue colored In the case of the resin composition, P/V is preferably 0.20 or more, more preferably 0.28 or more, and particularly preferably 0.35 or more from the viewpoint of desired color development. On the other hand, from the viewpoints of excellent solvent resolubility, development residue, development adhesion, development resistance, suppression of occurrence of development damage or unevenness, contrast, and suppression of occurrence of chattering of minute pores, it is preferably 0.65 or less. More preferably, it is 0.50 or less, and it is more preferably 0.45 or less.

 [Method for Producing Photosensitive Colored Resin Composition]  

The method for producing a photosensitive colored resin composition of the present invention contains a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, a preferred dispersant, an antioxidant, and various kinds of materials to be used as needed. The component to be added is preferably prepared by uniformly mixing a color material in a solvent by a dispersing agent from the viewpoint of enhancing the contrast, and mixing by using a known mixing means.

The method for producing the resin composition is, for example, (1) first adding a color material and a dispersant to a solvent to prepare a color material dispersion, and then mixing the alkali-soluble resin, the photopolymerizable compound, and the light into the dispersion. a starter, and a method of adding various components as required; (2) simultaneously inputting a color material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and, if necessary, a solvent a method of adding various components and mixing; (3) adding, in a solvent, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and various additives to be used as needed, after mixing, a method of adding a color material and dispersing; (4) adding a color material, a dispersing agent, and an alkali-soluble resin in a solvent to prepare a color material dispersion, and further adding an alkali-soluble resin, a solvent, and photopolymerization to the dispersion A compound, a photoinitiator, a method of mixing various additives as needed, and a method of mixing.

Among these methods, the methods (1) and (4) above are preferred from the viewpoint of effectively preventing the color material from agglomerating and uniformly dispersing.

The method of preparing the color material dispersion can be appropriately selected from the conventionally known dispersion methods. For example, (1) premixing a dispersing agent in a solvent and stirring to prepare a dispersing agent solution, and then mixing an organic acid compound as needed to form a salt of an amine group of the dispersing agent with an organic acid compound, and then combining the coloring material with the coloring material. And mixing other components as needed, using a known mixer or disperser to perform dispersion; (2) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, followed by coloring materials, optionally organic acid compounds, and Mixing other components as needed, dispersing using a known mixer or disperser; (3) mixing the dispersant in a solvent and stirring to prepare a dispersant solution, and then mixing the color material and other components as needed, using well-known A method in which an organic acid compound is added as needed after a dispersion or a disperser forms a dispersion.

Examples of the dispersing machine for performing the dispersion treatment include a roll mill such as a twin roll or a triple roll; a ball mill such as a ball mill or a vibrating ball mill; a bead such as a paint regulator, a continuous disc bead mill, and a continuous annular bead mill; Mill. The preferred dispersion conditions of the bead mill are preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

The photosensitive colored resin composition of the present invention can be used for color filter applications because it can enhance the luminance after repeated high-temperature heating steps and can form a pattern according to a desired line width.

 II. Hardened material  

The cured product of the present invention is a cured product of the above-mentioned photosensitive colored resin composition of the present invention.

The cured product of the present invention can be obtained, for example, by forming a coating film of the photosensitive colored resin composition of the present invention described above, drying the coating film, performing exposure, and developing as necessary. The method of forming, exposing, and developing the coating film is, for example, the same method as the method of forming the coloring layer provided in the color filter of the present invention to be described later.

Further, the cured product of the present invention can increase the luminance even after the high-temperature heating step, and can form a pattern according to the required line width, and it is suitable to use a coloring layer as a color filter.

 III. Color filter  

The color filter of the present invention includes at least a substrate and a coloring layer provided on the substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present invention.

The color filter of the present invention is described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention includes a substrate 1, a light blocking portion 2, and a coloring layer 3.

 [Coloring layer]  

The coloring layer used in the color filter of the present invention is a cured product of at least one layer of the photosensitive coloring resin composition of the present invention, that is, a colored layer formed by curing the colored resin composition.

The colored layer is usually formed in an opening of a light-shielding portion on a substrate to be described later, and is usually composed of a three-color or more colored pattern.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration or the viscosity of the photosensitive colored resin composition, and the like, and is usually preferably in the range of 1 μm or more and 5 μm or less.

This colored layer can be formed, for example, by the following method.

First, the photosensitive colored resin composition of the present invention is applied onto a substrate to be described later by a coating means such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed. Among them, a spin coating method or a die coating method is preferably used.

Next, the wet coating film is dried by a heating plate, an oven, or the like, and then exposed to a mask having a predetermined pattern to photopolymerize the alkali-soluble resin with a photopolymerizable compound such as a polyfunctional monomer. A hardened coating film is formed. Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted in accordance with the light source used or the thickness of the coating film.

Further, after the exposure, in order to promote the polymerization reaction, heat treatment may be performed. The heating conditions are appropriately selected in accordance with the mixing ratio of each component in the photosensitive colored resin composition to be used, or the thickness of the coating film.

Next, development processing is carried out using a developing solution, and by dissolving and removing the unexposed portion, a coating film is formed in a desired pattern. The developer is usually a solution in which an alkali is dissolved in water or a water-soluble solvent. An appropriate amount of a surfactant or the like may be added to the alkali solution. Further, the development method can be carried out by a general method.

After the development treatment, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. Further, after the development treatment, heat treatment may be applied to sufficiently cure the coating film. The heating conditions are not particularly limited, and may be appropriately selected in accordance with the use of the coating film.

 [shading section]  

The light-shielding portion of the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be used in the same manner as a light-shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and may be, for example, a stripe shape or a matrix shape. The light-shielding portion can form a metal thin film such as chromium by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing a light-shielding particle such as carbon fine particles, a metal oxide, an inorganic pigment, or an organic pigment in the resin binder. When the resin layer containing the light-shielding particles is used, a method of patterning by development using a photosensitive photoresist, a method of patterning using an inkjet ink containing light-shielding particles, and heat transfer of the photosensitive photoresist can be employed. Printing method, etc.

The film thickness of the light-shielding portion is set to be 0.2 μm or more and 0.4 μm or less in the case of the metal thin film, and is set to be 0.5 μm or more and 2 μm or less when the black pigment is dispersed or dissolved in the binder resin.

 [substrate]  

For the substrate, a transparent substrate or a germanium substrate, which will be described later, and an aluminum, silver, silver/copper/palladium alloy thin film or the like are formed on the substrate. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on the substrates.

The transparent substrate of the color filter of the present invention is not particularly limited as long as it is a transparent substrate for visible light, and a transparent substrate used for a general color filter can be used. Specifically, for example, a transparent transparent material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a transparent transparent resin such as a transparent resin film, an optical resin plate, or a flexible glass can be used. Sexual material.

The thickness of the transparent substrate is not particularly limited, and for the use of the color filter of the present invention, for example, a thickness of 100 μm or more and 1 mm or less can be used.

Further, in the color filter of the present invention, in addition to the substrate, the light shielding portion, and the coloring layer, for example, a protective layer or a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, or the like may be formed.

 IV. Display device  

The display device of the present invention is characterized by having the above-described color filter of the present invention. The configuration of the display device of the present invention is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device.

 [Liquid Crystal Display Device]  

A liquid crystal display device of the present invention includes the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

A liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic view showing an example of a display device of the present invention, and is a schematic view showing an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, and the like, and a surface between the color filter 10 and the counter substrate 20. Liquid crystal layer 30.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may be a known configuration of a liquid crystal display device used in a general color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Such a driving method may be, for example, a TN method, an IPS method, an OCB method, or an MVA method. The invention is suitable for use in any of these ways.

Further, the counter substrate can be appropriately selected and used in accordance with the driving method of the liquid crystal display device of the present invention.

The method for forming the liquid crystal layer may be a method used in a general liquid crystal cell production method, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

 [Organic light-emitting display device]  

The organic light-emitting display device of the present invention is characterized by comprising the color filter of the present invention and an organic light-emitting body.

The organic light-emitting display device of the present invention will be described with reference to the drawings. Fig. 3 is a schematic view showing another example of the display device of the present invention, and is a schematic view showing an example of an organic light-emitting display device. As illustrated in FIG. 3, the organic light-emitting display device 100 of the present invention is provided with a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

The method of laminating the organic light-emitting body 80 is, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80 can be appropriately used. The organic light-emitting display device 100 thus fabricated is applicable to, for example, a passively driven organic EL display, and an actively driven organic EL display.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration of an organic light-emitting display device used in a general color filter.

 [Examples]  

Hereinafter, an exemplary embodiment of the present invention will be specifically described. However, the invention is not limited by the description.

Further, the acid value of the block copolymer before salt formation was determined by the method described in JIS K 0070:1992.

The block copolymer amine value before salt formation was determined according to the method described in JIS K 7237:1995.

The weight average molecular weight (Mw) of the block copolymer before salt formation is determined by a GPC (gel permeation chromatography) according to a standard polystyrene conversion value according to the measurement method of the present invention.

The glass transition temperature (Tg) of the block copolymer before salt formation and after salt formation was measured by differential scanning calorimetry (DSC) (EXSTAR DSC 7020, manufactured by SII NanoTechnology Co., Ltd.) according to the method described in JIS K7121.

 (Synthesis Example 1: Synthesis of alkali-soluble resin A)  

150 parts by mass of PGMEA was charged in the polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), and PERBUTYL® were continuously dropped over 1.5 hours. 6 parts by mass of O (manufactured by Nippon Oil Co., Ltd.) and 2 parts by mass of a chain transfer agent (n-dodecylmercaptan). Then, the reaction was continued while maintaining the temperature at 100 ° C. After the completion of the dropwise addition of the mixture for forming the main chain, after 2 hours, 0.1 part by mass of p-methoxyphenol as a polymerization terminator was added to terminate the polymerization.

Next, while blowing air, 14 parts by mass of glycidyl methacrylate (GMA) containing an epoxy compound was added, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto, and the mixture was added at 110 ° C for 15 hours. In the reaction, an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value: 90 mgKOH/g, solid content: 40% by mass) was obtained.

 (Synthesis Example 2: Synthesis of Block Copolymer 1)  

PTFE: 250 parts by mass and 0.6 parts by mass of lithium chloride were added to a 500 mL round bottom four-port separable flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet tube, a mechanical stirrer, and a digital thermometer. Fully perform nitrogen replacement. After the reaction flask was cooled to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel for 60 minutes, dropwise: 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of a monomer for B block, 2-(trimethyldecyloxy)ethyl methacrylate ( TMSMA) 29.1 parts by mass, 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and methyl group Methyl acrylate (MMA) was 17.5 parts by mass. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) which is a monomer for the A block was dropped over 20 minutes. After the reaction for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration, vacuum drying, and diluted with PGMEA to obtain a 30% by mass solid solution. 32.5 parts by mass of water was added, and the temperature was raised to 100 ° C for 7 hours, and the structural unit derived from EEMA was deprotected to form a constituent unit derived from methacrylic acid (MAA), and the constituent unit derived from TMSMA was deprotected. A constituent unit derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer 1 (amine value: 95 mgKOH/g, which contains the structural unit represented by the above general formula (I), The acid value was 8 mgKOH/g, Tg 38 ° C). The weight average molecular weight Mw is 7730.

 (Synthesis Example 3: Synthesis of Salt Block Copolymer 2)  

THF: 250 parts by mass and 0.75 parts by mass of lithium chloride were added to a 500 mL round bottom four separable flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet tube, a mechanical stirrer, and a digital thermometer. Fully perform nitrogen replacement. After the reaction flask was cooled to -60 ° C, 6.1 parts by mass of butyllithium (15 mass% hexane solution), 1.4 parts by mass of diisopropylamine, and 1.2 parts by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel for 60 minutes, it was dropped: 9 parts by mass of 2-ethylhexyl methacrylate (EHMA) of a monomer for B block, 13.4 parts by mass of n-butyl methacrylate (BMA), benzyl methacrylate (BzMA) 7.5 parts by mass, and methyl methacrylate (MMA) 47.5 parts by mass. After 30 minutes, 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA) which is a monomer for the A block was dropped over 20 minutes. After the reaction for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. It was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer 2 (amine value: 95 mgKOH/g, acid value: 0 mgKOH/g) containing the structural unit represented by the above general formula (I). The weight average molecular weight Mw is 7600.

2:50 parts by mass of the obtained block copolymer was dissolved in PGMEA: 213 parts by mass. 3.2 parts by mass of chlorotoluene was added thereto, and the reaction was carried out at 90 ° C for 12 hours to obtain a PGMEA solution (solid content of 20%) of the salt type block copolymer 2.

 (Synthesis Example 4: Synthesis of Blue Color Material 1)    (1) Synthesis of Intermediate 1  

According to the production method of the intermediate 3 and the intermediate 4 described in International Publication No. 2012/144521, 1:15.9 g (yield 70%) of the intermediate represented by the following chemical formula (a) is obtained.

The obtained compound was confirmed to be a target compound by the following analysis.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

 (2) Synthesis of blue color material 1  

Intermediate 1: 5.00 g (4.58 mmol) was added to 300 ml of water and dissolved in an intermediate 2 solution at 90 °C. Next, 10.4 g (3.05 mmol) of phosphotungstic acid ‧n hydrate H ₃ [PW ₁₂ O ₄₀ ]‧nH ₂ O (n=30) manufactured by Nippon Inorganic Chemical Industry was thrown into 100 mL of water, and stirred at 90 ° C to prepare An aqueous solution of phosphotungstic acid is obtained. In the solution of the intermediate 2 immediately, an aqueous solution of phosphotungstic acid was mixed at 90 ° C, and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 1:13.25 g (yield 98%) of the blue color material represented by the following chemical formula (b).

The obtained compound was confirmed to be a target compound by the following analysis. (Morby W/Mo=100/0)

‧MS(ESI)(m/z): 510(+), 2 price

‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)

Further, the polybasic acid structure of the phosphotungstic acid was maintained after the blue color material 1 was obtained, and it was confirmed by ³¹ P-NMR.

[Chemical 5]

 (Synthesis Example 5: Synthesis of Blue Color Material 2)   (1) Preparation of K ₆ (P ₂ MoW ₁₇ O ₆₂ )

44.0 g of NaWO ₄ ‧2H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.90 g of Na ₂ MoO ₄ ‧2H ₂ O (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 230 g of purified water. In the solution, 64.9 g of 85% phosphoric acid was added using a dropping funnel with stirring. The obtained solution was heated and refluxed for 8 hours. The reaction solution was cooled to room temperature, and 1 drop of bromine water was added thereto, and 45 g of potassium chloride was added thereto while stirring. After further stirring for 1 hour, the precipitate was filtered. The solid obtained was dried at 90 ° C to obtain 29.4 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ).

 (2) Synthesis of blue color material 2  

5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in 350 ml of purified water, and dissolved by stirring at 40 ° C to prepare a BB7 solution. In addition, 10.0 g of K ₆ (P ₂ MoW ₁₇ O ₆₂ ) prepared in the above (1) was dissolved in 40 ml of purified water. A K ₆ (P ₂ MoW ₁₇ O ₆₂ ) solution was placed in the BB7 solution, and the mixture was directly stirred at 40 ° C for 1 hour in this state. Next, the internal temperature was raised to 80 ° C, and further stirred for 1 hour to carry out lake formation. After cooling, filtration was carried out, and washing was performed three times with 300 ml of purified water. The obtained solid was dried at 90 ° C to obtain a blue color material 2: 10.4 g of a triaryl methane laked color material having a dark blue solid and an average primary particle diameter of 40 nm.

 (Production Example 1: Preparation of Color Material Dispersion A)  

In a 225 mL milk bottle, PGMEA: 57.8 parts by mass, the alkali-soluble resin A solution of Synthesis Example 1 (solid content: 40% by mass), 16.3 parts by mass, and the salt-type block copolymer 2 of Synthesis Example 3 were charged. The solution (solid content: 20% by mass) was 13.0 parts by mass and stirred.

13.0 parts by mass of CI Pigment Blue 15:6 (PB15:6, trade name FASTOGEN BLUE A510 DIC), and 100 parts by mass of 2.0 mm zirconia balls were placed therein, using a paint mixer (Asada) Pre-crushing by shaking for 1 hour, and then changing to 200 parts of zirconia balls having a particle diameter of 0.1 mm, and performing formal disintegration by dispersing for 4 hours using a paint shaker, the color material dispersion A was obtained.

 (Production Example 2: Preparation of Color Material Dispersion B)  

In the production example 1, except for the substitution of CI Pigment Blue 15:6, the use of CI Pigment Blue 15:3 (PB15:3, trade name: Chromofine blue A-220JC Dairi Seiki Co., Ltd.) was used instead. The color material dispersion liquid B was obtained in the same manner as in Production Example 1.

 (Production Example 3: Preparation of Color Material Dispersion C)  

In a 225 mL milk bottle, PGMEA: 63.3 parts by mass, the alkali-soluble resin A solution of Synthesis Example 1 (solid content: 40% by mass), 13.0 parts by mass, and the PGMEA of the block copolymer 1 of Synthesis Example 2 were charged. A solution (amine value: 95 mgKOH/g, solid content: 45 mass%) of 10.0 parts by mass was stirred. 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 mol equivalent with respect to the tertiary amine group of the block copolymer) was added thereto, and the mixture was stirred at room temperature for 30 minutes.

1:13.0 parts by mass of the blue color material obtained in Synthesis Example 4 and 100 parts by mass of the zirconium oxide balls having a particle diameter of 2.0 mm were placed therein, and pre-crushing was performed by using a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour. Then, 200 parts of zirconia balls having a particle diameter of 0.1 mm were changed, and the main material was dispersed by a paint shaker for 4 hours to obtain a color material dispersion C.

 (Production Example 4: Preparation of Color Material Dispersion D)  

In the production example 3, the color material dispersion liquid D was obtained in the same manner as in the production example 3 except that the blue color material 1 obtained in the synthesis example 4 was used instead of the blue color material 2 obtained in the synthesis example 5.

 (Production Example 5: Preparation of Color Material Dispersion E)  

In Production Example 1, except that CI Pigment Blue 15:6 was used instead of CI Pigment Violet 23 (PV23, trade name: Hostaperm Violet RL-NF Clariant Co., Ltd.), the color material was obtained in the same manner as in Production Example 1. Dispersion E.

 (Preparation Example 1: Preparation of Photosensitive Adhesive Component CR-1)  

36.9 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Synthesis Example 1 was added: dipentaerythritol hexaacrylate (DPHA) (Aronix M402 (manufactured by Toagosei Co., Ltd.)) as a photopolymerizable compound, 21.9 mass IRGACURE 907 (manufactured by BASF, α-Aminoacetophenone photoinitiator) 1.1 parts by mass, SPI-04 (three-nutrient, oxime ester photoinitiator with ruthenium skeleton) 1.3 parts by mass, KAYACURE DETX-S (Nippon Chemical, 9-oxosulfur 0.3 parts by mass of the photoinitiator), 0.8 parts by mass of the antioxidant IRGANOX 1010 (manufactured by BASF), and 38.1 parts by mass of PGMEA, the photosensitive binder component CR-1 was obtained.

 (Preparation Example 2: Preparation of Photosensitive Adhesive Component CR-2)  

26.1 parts by mass relative to an alkali-soluble resin solution (propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy acrylate having an anthracene skeleton, trade name V259ME, manufactured by Nippon Steel Chemical Co., Ltd., 55.8% solid content) , addition: 18.2 parts by mass of dipentaerythritol hexaacrylate (DPHA) (Aronix M403, manufactured by Toagosei Co., Ltd.) as a photopolymerizable compound, and tris(2-(methyl)propenyloxyethyl phosphate) (Biscoat 3PA, Osaka) 3.7 parts by mass of IRGACURE 907 (manufactured by BASF, α-aminoacetophenone photoinitiator) 1.1 parts by mass, SPI-04 (three-culture, 茀 skeleton) Ester-based photoinitiator) 0.5 parts by mass, TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., an oxime ester photoinitiator having a diphenyl sulfide skeleton) 0.8 parts by mass, KAYACURE DETX-S (Japan Chemical system, 9-oxygen sulfur 0.3 parts by mass of the photoinitiator), 0.8 parts by mass of the antioxidant IRGANOX 1010 (manufactured by BASF), and PGMEA: 48.5 parts by mass, the photosensitive binder component CR-2 was obtained.

 (Preparation Example 3: Preparation of Photosensitive Adhesive Component CR-3)  

In Preparation Example 1, in place of SPI-04 (three-nutrient, oxime-based photoinitiator with an anthracene skeleton), OXE-02 (manufactured by BASF, an oxime-based photoinitiator-based photoinitiator) was used instead. The photosensitive adhesive component CR-3 was obtained in the same manner as in Production Example 1 except for the above.

 (Preparation Example 4: Preparation of Photosensitive Adhesive Component CR-4)  

In the preparation example 1, in place of SPI-04 (three-nutrient, oxime-based photoinitiator having an anthracene skeleton), 1.3 parts by mass was changed to SPI-04 (three-nutrient, oxime-based light having an anthracene skeleton) 0.5 parts by mass of TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., an oxime ester photoinitiator having a diphenyl sulfide skeleton) of 0.8 parts by mass, the same as in Preparation Example 1 The photosensitive adhesive component CR-4 was obtained.

 (Example 1: Preparation of photosensitive colored resin composition)  

The color material dispersion A: 4.0 parts by mass, the color material dispersion C: 22.6 parts by mass, the photosensitive adhesive component CR-1 of Preparation Example 1: 24.6 parts by mass, and the surfactant MEGAFAC® R08MH (made by DIC) 0.02 mass The mixture and PGMEA: 48.8 parts by mass were mixed to obtain the photosensitive colored resin composition of Example 1.

 (Examples 2 to 5, Comparative Examples 1 to 10: Preparation of Photosensitive Colored Resin Composition)  

Examples 2 to 5 were obtained in the same manner as in Example 1 except that the color material ratio (mass ratio) shown in Tables 1-1 to 1-3 was changed, and the color material dispersion liquid used was changed. The photosensitive colored resin compositions of Comparative Examples 1 to 10.

 (Example 6: Preparation of photosensitive colored resin composition)  

The photosensitive colored resin composition of Example 6 was obtained in the same manner as in Example 1 except that the photosensitive adhesive component CR-1 of Example 1 was changed to the photosensitive adhesive component CR-2 of Preparation Example 2. Things.

 (Examples 7 to 10, Comparative Examples 11 to 20: Preparation of photosensitive colored resin composition)  

Examples 7 to 10 were obtained in the same manner as in Example 6 except that the color material ratio (mass ratio) shown in Tables 2-1 to 2-3 was changed, and the color material dispersion liquid used was changed. Comparative Examples 11 to 20 of the photosensitive colored resin composition.

 (Example 11: Preparation of photosensitive colored resin composition)  

The photosensitive colored resin composition of Example 11 was obtained in the same manner as in Example 1 except that the photosensitive adhesive component CR-1 of Example 1 was changed to the photosensitive adhesive component CR-3 of Preparation Example 3. Things.

 (Example 12: Preparation of photosensitive colored resin composition)  

The photosensitive colored resin composition of Example 12 was obtained in the same manner as in Example 1 except that the photosensitive adhesive component CR-1 of Example 1 was changed to the photosensitive adhesive component CR-4 of Preparation Example 4. Things.

 [Evaluation method]    <Highness evaluation, heat resistance evaluation>  

The photosensitive colored resin compositions of the examples and the comparative examples were subjected to post-baking chromaticity on a glass substrate (manufactured by NH Techno Glass, "NA35") having a thickness of 0.7 mm using a spin coater. Coating was carried out in such a manner as to be y=0.093. Then, it was dried by heating on a hot plate at 80 ° C for 3 minutes. The cured film (blue colored film) was obtained by irradiating ultraviolet rays of 60 mJ/cm ² with an ultrahigh pressure mercury lamp without being interposed with a photomask. The obtained film was baked in a clean oven at 230 ° C for 25 minutes, and the luminance was measured using a "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd. Then, the obtained film was further baked by a 240 ° C clean oven for 25 minutes, and the chromaticity (L ₀ , a ₀ , b ₀ ) of the colored film was measured, and then further performed by a 240 ° C clean oven. After baking in minutes, the chromaticity (L ₁ , a ₁ , b ₁ ) of the obtained colored film was measured again, and the luminance was also measured.

The table shows the luminance after baking at 230 ° C for 25 minutes, and the luminance after the heat resistance test (after baking at 230 ° C for 25 minutes + 240 ° C for 25 minutes + 240 ° C for 25 minutes).

Further, the change in the chromaticity of the colored film after 50 minutes from 25 minutes at 240 ° C was evaluated by the following formula. The results are shown in the table.

△Eab={(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2

Those who have △Eab 3 or less are rated as "A", those whose △Eab is more than 3 and 5 or less are rated as "B", those whose △Eab is more than 5 and 10 or less are rated as "C", and those whose △Eab is more than 10 are evaluated as "C" It is "D". The smaller the ΔEab value, the more excellent the heat resistance.

 (Evaluation of line width displacement, evaluation of micro holes)  

The colored resin compositions of the examples and the comparative examples were applied to a glass substrate (manufactured by NH Techno Glass, "NA35") having a thickness of 0.7 mm by a spin coater so as to have a film thickness of 3 μm. Then, it was heated and dried on a hot plate at 80 ° C for 3 minutes, and then a fine line pattern (pattern for evaluation of line width displacement) having an opening width of 90 μm and a center of 20 μm at the center of the independent thin line having an opening size of 90 μm × 300 μm were interposed. The mask pattern of the pattern of the 20 μm chrome mask (pattern for micro hole evaluation) was irradiated with ultraviolet rays of 60 mJ/cm ₂ using an ultrahigh pressure mercury lamp. Then, the glass plate on which the colored layer was formed was spray-developed using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution, and baked in a 230 ° C clean oven for 30 minutes. The independent thin line width (line width) actually measured when the mask opening width was 90 μm and the design line width was 95 μm was measured in the individual thin lines of the colored layer fine line pattern formed on the glass substrate. Moreover, the shape of the micropore and the tremor of the peripheral portion of the micropore were evaluated in accordance with the following criteria.

 [Line width displacement]  

The line width displacement value (μm) deviating from the design line width is calculated by the following formula.

Line width displacement value (μm) = measured line width (μm) - 95 (μm)

A: The line width displacement value is -2 μm or more and 2 μm or less.

B: Line width displacement value is -4 μm or more and less than -2 μm

C: line width displacement value is less than -4μm or more than 2μm

The smaller the deviation from the design line width, the better the pattern can be formed according to the required line width.

 [micro hole shape]  

A: The size deviation of the micro holes formed on the colored layer relative to the size of the chrome mask disposed in the individual fine line pattern is less than 2% in absolute value

B: The size deviation of the micropores formed on the colored layer with respect to the size of the chrome mask disposed in the individual thin line pattern is 2% or more and 6% or less in absolute value

C: the size deviation of the micropores formed on the colored layer relative to the size of the chrome mask disposed in the individual fine line pattern is greater than 6% and less than 8% in absolute value

D: the size deviation of the micro holes formed on the colored layer relative to the size of the chrome mask disposed in the independent thin line pattern is greater than 8% in absolute value

In addition, the dimensional shift is calculated as the average of the offsets of the respective sides.

 [shake]  

A: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is less than 0.1

B: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is 0.1 or more and less than 0.4.

C: The ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is 0.4 or more and less than 0.6.

D: the ten-point average roughness of the peripheral portion of the minute hole formed on the colored layer is 0.6 or more

In addition, the ten point average roughness was measured in accordance with JIS B0601.

 <Result finishing>  

As is apparent from the results of the table, the color material is a photosensitive colored resin composition of Examples 1 to 12 which is a combination of the phthalocyanine pigment and the color material shown in the above general formula (1) in a specific ratio, and is subjected to 230 ° C. After the minute, the brightness after baking and the heat resistance test (after 230 ° C 25 minutes + 240 ° C 25 minutes + 240 ° C 25 minutes post-baking) are improved, can be raised in the high temperature heating step (post-bake In the state of the luminance after baking, a pattern is formed according to the required line width.

On the other hand, in the comparative examples of the phthalocyanine pigments which are different from the coloring materials of the coloring materials represented by the above general formula (1), the heat resistance is poor, and even if the same ratio as in the examples is used, the high-temperature heating step (post-baking) The brightness after baking is still low. Further, in the comparative example in which the violet pigment is combined with the phthalocyanine pigment, although the heat resistance itself is not problematic, the luminance after the high-temperature heating step (post-baking) is low, and the displacement value deviating from the design line width is large, which is difficult to follow. The desired line width is obtained.

In the examples, examples 1, 6, 11 and 12; examples 2 and 7; examples 3 and 8; examples 4 and 9; and examples 5 and 10 are compared, and it is found that if used, it is classified as aliphatic. The alkali-soluble resin having a hydrocarbon ring structure and the polyfunctional (meth) acrylate having a phosphorus atom can improve heat resistance, and the luminance after the heat resistance test is finally obtained. Further, by comparing Examples 1, 6, 11, and 12, it was found that an oxime ester-based photoinitiator is an oxime ester photoinitiator having an anthracene skeleton or an oxime ester having a diphenyl sulfide skeleton. When the photoinitiator is used, the luminance after the heat resistance test is finally obtained is improved. Further, when two kinds of oxime ester photoinitiators are contained, and an oxime ester photoinitiator having an anthracene skeleton and an oxime ester photoinitiator having a diphenyl sulfide skeleton are used in combination, the micropores can be raised. shape.

Claims (8)

A photosensitive colored resin composition comprising: a color material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent-based photosensitive colored resin composition; wherein the color material contains a phthalocyanine pigment, and The color material shown in the following general formula (1); the total content of the color material shown in the following general formula (1) with respect to the total content of the phthalocyanine pigment and the color material represented by the following general formula (1) is 20% by mass or more and 85% by mass or less; (In the general formula (1), A represents an a-valent organic group having a carbon atom directly bonded to N and having no π bond, and the organic group is an aliphatic group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain may further contain O, S, and N; B ^c- represents a c-valent anion; and R ⁱ to R ^v each independently represent a hydrogen atom; a substituted alkyl group or an aryl group which may have a substituent, R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may also be bonded to form a ring structure; R ^vi and R ^vii each independently represent or may have a substitution The alkyl group, the alkoxy group which may have a substituent, a halogen atom or a cyano group; Ar ¹ represents a divalent aromatic group which may have a substituent; the plural R ⁱ ~ R ^vii and Ar ¹ may be the same respectively It may be different; a and c are integers of 2 or more, b and d are integers of 1 or more; e is 0 or 1, and when e is 0, there is no bond; f and g are 0. In the above and 4 or more integers, f+e and g+e are 0 or more and 4 or less; and the plural e, f, and g may be the same or different.  The photosensitive colored resin composition of claim 1, wherein the phthalocyanine pigment is one or more selected from the group consisting of CI Pigment Blue 15:6, CI Pigment Blue 15:3, and CI Pigment Blue 15:4. .    The photosensitive colored resin composition of claim 1 or 2, wherein the photoinitiator comprises an oxime ester photoinitiator.    The photosensitive colored resin composition of claim 1 or 2, wherein the photoinitiator contains at least two oxime ester photoinitiators.    The photosensitive colored resin composition of claim 3, which further contains an antioxidant.    A cured product which is a cured product of the photosensitive colored resin composition according to any one of claims 1 to 5.    A color filter comprising at least a substrate, and a color filter provided on the substrate; wherein at least one of the colored layers is photosensitive according to any one of claims 1 to 5. A cured product of a colored resin composition.    A display device characterized by the color filter of claim 7.