JP2010015063A - Colored photosensitive resin composition, color filter and method for manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having high exposure sensitivity and giving a colored film free of a crease and unevenness when subjected to heat treatment after exposure. <P>SOLUTION: The colored photosensitive resin composition comprises a solvent, pigments including one selected from the following group (B-1) and one selected from the following group (B-2), a binder resin, a photopolymerizable compound, and photopolymerization initiators including one selected from the following group (E-1) and one selected from the following group (E-2) in a range of (E-1):(E-2)=80:20 to 40:60 (mass ratio). (B-1): a group consisting of diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, etc.; (B-2): a group consisting of anthraquinone-based pigments, disazo-based pigments, isoindoline-based pigments, etc.; (E-1): a group consisting of triazine-based photopolymerization initiators and oxime-based photopolymerization initiators; (E-2): a group consisting of hexaarylbiimidazole-based photopolymerization initiators and acetophenone-based photopolymerization initiators. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition, and specifically relates to a colored photosensitive resin composition that can be suitably used for producing a color filter, a color filter using the same, and a method for producing the same.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where the screen is large and high image quality is required.

In color filter applications for liquid crystal displays (LCDs), the substrate size is increasing due to the increase in panel size, and curing with low energy is desired for improving productivity when using a large substrate. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity.
In order to improve contrast, with respect to the colored photosensitive resin composition used for the production of the color filter, a finer particle size is required as the particle size of the colorant (organic pigment or the like) used. When the pigment is made finer, the surface area of the pigment increases, so that the amount of the dispersant added for dispersing the pigment tends to increase. Furthermore, in order to improve color purity, a higher content of the colorant (organic pigment) in the solid content of the colored photosensitive resin composition is required. For these reasons, while curability at low energy is desired, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content of the colored photosensitive resin composition tends to decrease.

As a colored photosensitive resin composition for forming a colored film having excellent curing sensitivity and a high film hardening degree, one containing hexaarylbiimidazole has been proposed (for example, see Patent Document 1).
In addition, a colored photosensitive resin composition containing at least three kinds of pigments has been proposed in order to improve brightness and contrast (see, for example, Patent Document 2).

On the other hand, the manufacturing process of the color filter by the photolithographic method usually includes coating, exposure, development, and high-temperature heating (post-baking) of the colored photosensitive resin composition on the glass substrate or the chromium substrate as the support.
In order for the colored film obtained by this method to have good optical properties, the colored film needs to be uniform. However, the colored photosensitive resin composition can be exposed to low energy or colored photosensitive resin composition. When the colored film is not sufficiently cured due to insufficient curable components in the curable resin composition, there is a problem that wrinkles and unevenness occur in the colored film due to heating in the post-baking process.

As described above, various techniques have been proposed for the colored photosensitive resin composition that can be suitably used for the production of a color filter. However, even after being subjected to exposure with low energy, heating is performed thereafter. At present, it has not yet been provided that a colored film without wrinkles or unevenness can be obtained when the treatment is performed.
JP-A-6-148417 JP 2007-133131 A

Then, this invention makes it a subject to achieve the following objectives.
An object of the present invention is to provide a colored photosensitive resin composition having a high exposure sensitivity and capable of obtaining a colored film free from wrinkles and unevenness when subjected to heat treatment after exposure.
Another object of the present invention is to provide a color filter having a coloring pattern free from wrinkles and unevenness and having good optical characteristics free from display unevenness when formed into a panel, and a method for producing the same.

That is, the object of the present invention is achieved by the following means.
<1> a pigment containing (A) a solvent, (B) one selected from the following (B-1) group and one selected from the following (B-2) group, (C) a binder resin , (D) a photopolymerizable compound, and (E) one selected from the following group (E-1) and one selected from the following group (E-2): ) Group: (E-2) group = colored photosensitive resin composition containing a photopolymerization initiator contained in the range of 80:20 to 40:60 (mass ratio) (however, selected from group (B-1)) And one type selected from the group (B-2) are not the same pigment).
Group (B-1): Group consisting of diketopyrrolopyrrole pigment, anthraquinone pigment, and perylene pigment (B-2) group: From anthraquinone pigment, disazo pigment, isoindoline pigment, and quinophthalone pigment Group (E-1) group: Triazine photopolymerization initiator and group (E-2) group consisting of oxime photopolymerization initiator: hexaarylbiimidazole photopolymerization initiator and acetophenone photopolymerization initiator Group of

<2> Further, (F) a fluorine-based surfactant or a silicone-based surfactant is contained in a range of 0.1% by mass to 1.5% by mass with respect to the total solid content in the colored photosensitive resin composition. The colored photosensitive resin composition according to <1>.

<3> The pigment (B) includes one type selected from the group (B-1) and one type selected from the group (B-2), and is composed of three or more types. The colored photosensitive resin composition according to <1> or <2>.

<4> A color filter having a colored pattern formed using the colored photosensitive resin composition according to any one of <1> to <3> on a substrate.

<5> A step of applying the colored photosensitive resin composition according to any one of <1> to <3> on the substrate to form a colored photosensitive resin composition layer;
Exposing the colored photosensitive resin composition layer through a mask;
Developing the colored photosensitive resin composition layer after exposure to form a colored pattern; and
A method for producing a color filter, comprising:

According to the present invention, it is possible to provide a colored photosensitive resin composition having high exposure sensitivity and capable of obtaining a colored film without wrinkles and unevenness when subjected to heat treatment after exposure.
Moreover, according to the present invention, it is possible to provide a color filter having a coloring pattern free from wrinkles and unevenness and having good optical characteristics free from display unevenness when formed into a panel, and a method for producing the same.

Hereinafter, the best mode for carrying out the invention will be described in detail.
<Colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention comprises (A) a solvent, (B) one type selected from the following group (B-1), and one type selected from the following group (B-2). Pigment to be included, (C) binder resin, (D) photopolymerizable compound, and (E) one type selected from group (E-1) described later and one type selected from group (E-2) described later And (E-1) group: (E-2) group = 80: 20 to 40:60 (mass ratio) is included, (B) -1) One type selected from the group and one type selected from the group (B-2) are not the same pigment.
Hereafter, each component of (A)-(E) which comprises the colored photosensitive resin composition of this invention is demonstrated.

[(A) Solvent]
The colored photosensitive resin composition of the present invention contains (A) a solvent.
Examples of the solvent used in the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxy 3-oxypropionic acid alkyl esters such as ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, -Ethyl oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Methyl oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;
Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, etc. Is preferred.
You may use a solvent in combination of 2 or more types besides using independently.

[(B) Pigment]
The colored photosensitive resin composition of the present invention contains (B) a pigment.
In the present invention, the pigment includes one type selected from the following group (B-1) and one type selected from the following group (B-2). However, one type selected from the (B-1) group and one type selected from the (B-2) group are not the same pigment.
Group (B-1): Group consisting of diketopyrrolopyrrole pigment, anthraquinone pigment, and perylene pigment (B-2) Group: From anthraquinone pigment, disazo pigment, isoindoline pigment, and quinophthalone pigment Group

As the diketopyrrolopyrrole pigment in the group (B-1), conventionally known pigments can be used. Specifically, for example, C.I. I. Pigment red 254, C.I. I. Pigment red 255 and the like.
As the anthraquinone pigments in the groups (B-1) and (B-2), conventionally known pigments can be used. Specifically, for example, C.I. I. And CI Pigment Red 177.
As the perylene pigment in the group (B-1), a conventionally known pigment can be used. Specifically, for example, C.I. I. Pigment red 224, C.I. I. Pigment red 155, and the like.

As the disazo pigment in the group (B-2), conventionally known pigments can be used. Specifically, for example, C.I. I. Pigment red 242, C.I. I. And CI Pigment Yellow 150, Yellow Pigment E4GN-GT (manufactured by LANXESS), and the like.
As the isoindoline pigment in the group (B-2), conventionally known pigments can be used. Specifically, for example, C.I. I. Pigment yellow 139, C.I. I. And CI Pigment Yellow 185.
As the quinophthalone pigment in the group (B-2), a conventionally known pigment can be used. Specifically, for example, C.I. I. Pigment yellow 138, and the like.

In the present invention, among the groups (B-1), diketopyrrolopyrrole pigments and anthraquinone pigments are preferable. I. Pigment red 254, and C.I. I. Pigment Red 177 is preferred.
Among the groups (B-2), anthraquinone pigments, disazo pigments, and isoindoline pigments are preferable. I. Pigment red 177, C.I. I. Pigment Yellow 150, Yellow Pigment E4GN-GT (manufactured by LANXESS), and C.I. I. Pigment Yellow 139 is preferable.

In the present invention, the (B) pigment includes one type selected from the group (B-1) and one type selected from the group (B-2), and is composed of three or more types. Is a preferred embodiment.
Thus, when using together 3 or more types of pigments, you may include pigments other than what is selected from the said (B-1) group and the said (B-2) group, but all are the said (B- It is preferable to be selected from the group 1) and the group (B-2).

  In the present invention, the mixing ratio of the total amount of the pigment of the (B-1) group and the total amount of the pigment of the (B-2) group is (B-1) group: (B-2) group = 100. : 1 to 100: 50 (mass ratio) is preferable, more preferably 100: 1 to 100: 40, and still more preferably 100: 1 to 100: 30.

  In the present invention, as a preferable combination of pigments, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150 or Yellow Pigment E4GN-GT, C.I. I. Pigment red 177 and C.I. I. Three combinations of Pigment Red 254 are preferred.

Here, in the present invention, within the range not impairing the effects of the present invention, as described above, pigments other than those selected from the group (B-1) and the group (B-2) (hereinafter, “ May be referred to as "other groups of pigments").
As another group of pigments used in the present invention, inorganic pigments or organic pigments can be used.
Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

Examples of organic pigments that are other groups of pigments include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 166, 168, 169, 170, 171, 172, 175, 176, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 226, 246, 279,

  C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 147, 148, 151, 152, 153, 154, 155, 156, 161, 162, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 17 7, 179, 180, 181, 182, 187, 188, 193, 194, 199, 213, 214,

  C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, etc. Can do.

Among these, examples of pigments that can be preferably used in combination include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 151, 154, 167, 180,
C. I. Pigment Orange 36,
C. I. Pigment Red 122, 150, 171, 175, 209

The total content of the pigment (B) in the colored photosensitive resin composition of the present invention is preferably 15% by mass to 55% by mass, and 20% by mass to the total solid content of the composition. 50 mass% is more preferable.
In addition, the total amount of the pigment of the (B-1) group and the pigment of the (B-2) group is preferably 40% by mass or more, and more preferably 55% by mass or more in the total pigment.
When the total content of the pigment is within the above range, the color density is sufficient, and it is effective to ensure excellent color characteristics in the formed colored film.

  Regardless of whether the pigment is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, considering the handling property, considering that it is preferable to have a high transmittance. The average primary particle diameter is preferably 0.01 μm to 0.3 μm, and more preferably 0.01 μm to 0.15 μm. When the particle size of the pigment is within the above range, it is effective for forming a color filter having high transmittance, good color characteristics, and high contrast.

  In the present invention, a fine and sized organic pigment can be used as necessary. In order to refine the pigment, it is preferable to use a method in which the pigment is mixed with a water-soluble organic solvent and a water-soluble inorganic salt to prepare a highly viscous liquid composition, and then the pigment in the liquid composition is ground. .

Examples of the water-soluble organic solvent used for refining the pigment include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Examples include propylene glycol and propylene glycolic monomethyl ether acetate.
In addition, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate can be used if the amount is small enough not to be absorbed into the wastewater. , Hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Moreover, you may mix and use 2 or more types of solvents as needed.
The usage-amount of the water-soluble organic solvent is the range of 50 mass%-300 mass% with respect to a pigment, Preferably it is the range of 100 mass%-200 mass%.

Examples of the water-soluble inorganic salt used for refining the pigment include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times the mass in terms of productivity. It is.

In order to refine the pigment, a wet grinding apparatus is used to grind the pigment in the liquid composition.
There are no particular restrictions on the operating conditions of the wet pulverizer in the present invention, but the operating conditions in the case where the wet pulverizer is a kneader are used in order to effectively advance grinding with a pulverizing medium (water-soluble inorganic salt). The rotation speed of the blade is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time of the wet pulverizer is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the device is preferably 50 ° C to 150 ° C.
Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape. The water content of the water-soluble inorganic salt is preferably 1% or less.

  In the present invention, it is preferable to use a coated pigment obtained by coating the pigment surface with a polymer compound in the pigment miniaturization step or the dispersion step. By coating the pigment with the polymer compound, the formation of secondary aggregates is suppressed even when the pigment is made finer, and can be dispersed in the form of primary particles. That is, in the coated pigment, the dispersed primary particles are stably maintained, and the coated pigment has excellent dispersion stability.

  The coating treatment for obtaining the coated pigment is preferably performed at the same time in the step of refining the pigment. More specifically, the coated pigment is prepared by adding i) a pigment, ii) a water-soluble inorganic salt, iii) a water-soluble organic solvent, and iv) a polymer compound, and mechanically kneading with a kneader (a salt milling step). The mixture is poured into water and stirred with a high speed mixer or the like to form a slurry, and the slurry is filtered, washed with water, and dried if necessary. .

Hereinafter, this coating method will be described more specifically.
First, a mixture of i) a pigment and ii) a water-soluble inorganic salt with a small amount of iii) a water-soluble organic solvent as a wetting agent, and iii) a polymer compound that is at least partially soluble in the water-soluble organic solvent. In addition, knead strongly with a kneader (salt milling process). Thereafter, this mixture is put into water and stirred with a high speed mixer or the like to form a slurry. Next, the slurry is filtered, washed with water, and dried as necessary to obtain a finer pigment. Here, at the time of the salt milling step, iii) by using a polymer compound that is at least partially soluble in a water-soluble organic solvent, and further finer and the surface is coated with the polymer compound iv) at the time of drying A coated pigment with less aggregation of the pigment is obtained.

Here, when the obtained coated pigment is dispersed in an oily varnish, the oily varnish is removed by removing the water-removed finely coated pigment (referred to as filter cake) before drying by a method generally called flushing. It is also possible to disperse in Moreover, when disperse | distributing to an aqueous varnish, it is not necessary to dry a coating pigment, and a filter cake can be disperse | distributed to a varnish as it is.
Note that iv) the polymer compound may be added at the initial stage of the salt milling process, or may be added separately. Also, iv) the polymer compound can be added in the dispersion step as described above.

Hereinafter, iv) the polymer compound used for coating the pigment will be described.
As the iv) polymer compound, any compound having an adsorbing group (pigment adsorbing group) to the pigment can be used. In particular, it is preferable to use a polymer compound having a heterocyclic group in the side chain as a pigment adsorbing group.
Specifically, the polymer compound having a pigment-adsorptive group in the side chain is a single monomer selected from the group consisting of a monomer represented by the following general formula (1), a maleimide, and a maleimide derivative The polymer preferably contains a polymer unit derived from the body (hereinafter referred to as “specific polymer”). Especially, as a specific polymer, it is especially preferable that it is a polymer containing the polymer unit derived from the monomer represented by following General formula (1).

In the general formula (1), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a heterocyclic group.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ has a substituent, the substituent is preferably, for example, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group. As this alkoxy group, a C1-C5 thing is preferable and a C1-C3 thing is preferable.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, Examples include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group.
Among them, R ¹ is most preferably a hydrogen atom or a methyl group.

The divalent linking group represented by R ² in the general formula (1) is preferably an alkylene group or a divalent group containing an alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
When this alkylene group has a substituent, examples of the substituent include a hydroxy group.
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

The divalent group containing an alkylene group represented by R ² may be a group in which two or more of the above alkylene groups are linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
The divalent group containing an alkylene group represented by R ^2, the end towards which binds to Z in the alkylene group, -O -, - S -, - C (= O) O -, - CONH-, -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- A hetero atom selected from or a partial structure containing a hetero atom may be bonded.

Specific examples of the heterocyclic structure constituting the heterocyclic group represented by Z in the general formula (1) include, for example, phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone-based, dioxazine-based, diketo Pyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, Pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoi Dorin, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic Examples include heterocyclic structures such as amides, cyclic ureas, and cyclic imides.
These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, and an alkoxycarbonyl group. It is done.

The heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. It is particularly preferred.
Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea A structure and a cyclic imide structure are preferable, and a structure represented by the following general formula (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (2), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In General Formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Preferred examples of the combination of Y and Z include a combination (imidazolyl group) in which one of Y and Z is —N═ and the other is —NH—.

  In general formula (2), (3), or (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring A and the ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

  Among the structures represented by the general formula (2), (3) or (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

  In addition, the maleimide derivative in the present invention means a maleimide in which the N position is substituted with a substituent such as an alkyl group or an aryl group.

Hereinafter, although the preferable specific example of the monomer represented by General formula (1), a maleimide, and a maleimide derivative is given below, this invention is not restrict | limited to these.
In addition to the following, for example, [0029] to [0030] of Japanese Patent Application Laid-Open No. 2008-83089, [0044] to [0047] of Japanese Patent Application No. 2007-85382, and [0045] of Japanese Patent Application No. 2007-231695. ] To [0047] and monomers disclosed in [0075] to [0076] can also be used.

In the present invention, the pigment is preferably used as a pigment dispersion composition by dispersing the pigment using at least one dispersant. The same applies to the case where the above-described coated pigment is used. By using this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 62,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-CHEMIE Co., Ltd.).
In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content in the pigment dispersion composition of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the mass of the above-mentioned pigment, and 3 mass%-70 mass% are more preferable.

Moreover, a pigment derivative is added to a pigment dispersion composition as needed.
The pigment is dispersed in the pigment dispersion composition in the form of fine particles by adsorbing the pigment derivative having a part having affinity with the dispersant or a polar group-introduced pigment to the pigment surface and using it as the adsorption point of the dispersant. Can be made. Since the colored photosensitive resin composition containing such a pigment dispersion composition can prevent reaggregation of the pigment, it is effective in forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into the base skeleton as a substituent.
Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic acids. Examples include imidazolone pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not called pigments can also be used as the base skeleton.
Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be performed satisfactorily while keeping the viscosity low, and the dispersion stability after dispersion can be improved. As a result, a colored photosensitive resin composition containing such a pigment dispersion composition, high transmittance, excellent color characteristics can be obtained, and suitable for producing a high-contrast color filter having good color characteristics It is.

  The method for dispersing the pigment is, for example, by mixing the pigment and the dispersant in advance and finely dispersing the material previously dispersed with a homogenizer using a bead disperser using zirconia beads or the like. Done.

〔dye〕
The colored photosensitive resin composition of the present invention may use a dye as a colorant in addition to the pigment (B) as long as the effects of the present invention are not impaired.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

[(C) Binder resin]
The colored photosensitive resin composition of the present invention contains (C) a binder resin.
The binder resin used in the present invention is a linear organic high molecular polymer having at least one alkali in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group that promotes solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with an aqueous alkaline solution.

  For example, a known radical polymerization method can be applied to the production of the binder resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

As the linear organic polymer used as the binder resin, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain And acid cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group to which an acid anhydride is added.
Furthermore, a high molecular polymer having a (meth) acryloyl group in the side chain is also preferable as the binder resin.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable as the binder resin. .
In addition, examples of useful binder resins include those obtained by copolymerizing 2-hydroxyethyl methacrylate.
These binder resins can be mixed and used in an arbitrary amount.

  Further, as the binder resin, in addition to the above-described ones, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy- 3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Examples thereof include benzyl methacrylate / methacrylic acid copolymer.

  As mentioned above, preferred binder resins include copolymers of (meth) acrylic acid and other monomers copolymerizable therewith. Here, (meth) acrylic acid is a generic term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a generic term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group in the alkyl (meth) acrylate and the aryl group in the aryl (meth) acrylate may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. ═CR ⁶ R ⁷ , CH ₂ ═C (R ⁶ ) (COOR ⁷ ) [wherein R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁷ is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ⁸ represents an alkyl group having 1 to ⁸ carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more.
Preferred other copolymerizable monomers are selected from CH ₂ ═CR ⁶ R ⁷ , CH ₂ ═C (R ⁶ ) (COOR ⁸ ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one selected from the group consisting of CH ₂ ═CR ⁶ R ⁷ and CH ₂ ═C (R ⁶ ) (COOR ⁸ ).

  As content in the coloring photosensitive resin composition of binder resin, 1 mass%-30 mass% are preferable with respect to the total solid of this composition, More preferably, they are 2 mass%-25 mass%. Especially preferably, it is 3 mass%-20 mass%.

[(D) Photopolymerizable compound]
The colored photosensitive resin composition of the present invention contains (D) a photopolymerizable compound.
The photopolymerizable compound used in the present invention is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure. Compounds are more preferred.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylol ethane, added with ethylene oxide and propylene oxide and then (meth) acrylated, poly (pentaerythritol or dipentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, as the photopolymerizable compound, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and those having a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues Is preferred. These oligomer types can also be used.
In addition to these, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58-49860 Urethane compounds having an ethylene oxide skeleton described in JP-B Nos. 56-17654, 62-39417 and 62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, A photosensitive resin composition having an excellent photosensitive speed can be obtained. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T. UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable as the photopolymerizable compound. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and carboxyl. And TO-1382 which is a group-containing pentafunctional acrylate.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
As content in the coloring photosensitive resin composition of a photopolymerizable compound, 3 mass%-55 mass% are preferable with respect to the total solid of this composition, More preferably, it is 10 mass%-50 mass%. is there. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

[(E) Photopolymerization initiator]
The colored photosensitive resin composition of the present invention comprises (E) one selected from the following (E-1) group and one selected from the following (E-2) group: (E-1 ) Group: (E-2) Group = A photopolymerization initiator included in a range of 80:20 to 40:60 (mass ratio) is contained.
Group (E-1): Group consisting of triazine photopolymerization initiator and oxime photopolymerization initiator (E-2) Group: From hexaarylbiimidazole photopolymerization initiator and acetophenone photopolymerization initiator Group

  Examples of the triazine photopolymerization initiator in the group (E-1) include s-triazine derivatives in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specifically, for example, 2,4,6-tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6- Su (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-tria 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (Tribromomethyl) -s-triazine, 4- (o-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine, etc. It is done.

  Among these, a preferable triazine photopolymerization initiator is 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-. Triazine (manufactured by Wako Pure Chemical Industries, Ltd.), 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

As the oxime photopolymerization initiator in the group (E-1), known compounds can be used.
Specific examples of the oxime photopolymerization initiator include at least one compound selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (6). .

In the general formulas (5) and (6), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group.
R ¹² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms. Represents a click group (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the substituent when the phenyl group is substituted is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms , A phenyl group, or a halogen atom. Here, the number of these substituents may be 1 to 5.
R ⁴ represents an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
Q represents an integer of 1 to 5, p represents an integer of 0 to 5, r represents an integer of 0 to 6, and p and q satisfy p + q ≦ 5.

In the general formulas (5) and (6), the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ is preferably a linear or branched alkyl group. , Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl Group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R ¹¹ include a cyclopentyl group and a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

Among these, as R ¹¹ , for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-hexyl group and the like are preferable.

As a C1-C20 alkyl group represented by R < ¹² >, R < ³ >, it is preferable that it is linear or branched, As a specific example, a methyl group, an ethyl group, n-propyl group is mentioned, for example. I-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , N-undecyl group and n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

The cycloalkyl group of R ^12, carbon atoms represented by R ³ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

Examples of the “alkyl group having 1 to 6 carbon atoms” which is a substituent of the substituted phenyl group represented by R ¹² and R ³ include linear, branched, or cyclic alkyl groups, and specific examples thereof are as follows. Are methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc. Can be mentioned. Especially, a C1-C6 alkyl group is preferable and a C1-C5 alkyl group is especially preferable.

In addition, examples of the “C1-C6 alkoxy group” which is a substituent of the substituted phenyl group represented by R ¹² and R ³ include linear, branched, or cyclic alkoxy groups. Examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group and the like. Among these, an alkoxy group having 1 to 3 carbon atoms is preferable.

Examples of the halogen atom that is a substituent of the substituted phenyl group represented by R ¹² and R ³ include a fluorine atom and a chlorine atom.

Examples of the alicyclic group having 7 to 20 carbon atoms represented by R ¹² and R ³ (excluding a cycloalkyl group having 7 to 8 carbon atoms) include, for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, Examples thereof include a ter-cycloalkyl group, a terpene skeleton-containing group, and an adamantyl skeleton-containing group. Among these, alicyclic groups having 9 to 18 carbon atoms are preferable, and 9 to 12 carbon atoms are particularly preferable.

Among these, R ¹² is preferably a bicycloalkyl group, a tricycloalkyl group, an adamantyl skeleton-containing group or the like, and R ³ is preferably a tricycloalkyl group, an adamantyl skeleton-containing group or the like.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms represented by R ⁴ include a thiolanyl group, Azepinyl group, dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group , Thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindoryl group, benzofuranyl group , Benzothiophenyl group, indolizini Group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, thioxanthenyl group, phenazinyl group, phenothiazinyl group, phenoxy group Examples include a satinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.
Of these, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms is preferable, and a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ include a linear, branched, or cyclic alkyl group, and specific examples thereof include, for example, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like. Especially, a C1-C12 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

Further, the alkoxy group having 1 to 12 carbon atoms represented by R ^5, straight chain, can be an alkoxy group branched or cyclic, and examples thereof include a methoxy group, an ethoxy group, n- A propoxy group, i-propoxy group, n-butoxy group, t-butoxy, n-pentyloxy group, etc. can be mentioned. Among these, an alkoxy group having 1 to 2 carbon atoms is preferable.

Among these, as R ⁵ , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, and an ethoxy group are particularly preferable.

  In the general formulas (5) and (6), q is preferably 1. Further, p is preferably 1 or 2, particularly preferably 1, and r is preferably 0, 1, or 2, and particularly preferably 1.

Among the structures represented by the general formula (5) or (6), while obtaining high sensitivity and polymerization reactivity (curing), liquid storage stability after preparation and stability over time in a dry film state after film formation R ¹¹ is an ethyl group from the viewpoint of maintaining the property, and further improving the controllability of the shape of the colored pattern to be formed and the film thickness necessary for it, and improving the adhesion to the solid surface to be applied. R ¹² is a methyl group, R ³ is a methyl group, R ⁴ is a tetrahydrofuranyl group, R ⁵ is a methyl group, q is 1, and p is 1. Thus, it is particularly preferred that r is 1. Furthermore, the structure represented by the general formula (6) is more preferable.

Specific examples of the compound represented by the general formula (5) or (6) include those shown below.
That is, ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);

  Of these, in particular, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) is preferred.

Further, by using at least one selected from the group of compounds represented by the following general formula (5 ′) as the oxime photopolymerization initiator, the sensitivity is enhanced, the progress of the polymerization reaction is improved, and the coloring pattern is improved. The controllability of the shape and the required film thickness can be further improved. That is, by using such an oxime-based photopolymerization initiator, good sensitivity can be obtained even with a low exposure amount of 150 mJ / cm ² or less, and the colored film has excellent adhesion to a solid surface. Can be formed.

In the general formula (5 ′), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group.
R ¹² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms. Represents a click group (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the substituent when the phenyl group is substituted is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms , A phenyl group, or a halogen atom. Here, the number of these substituents may be 1-5.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
Moreover, p represents the integer of 0-5.

In the general formula (5 ′), the alkyl group having 1 to 20 carbon atoms represented by R ¹¹ is preferably a linear or branched alkyl group, and specific examples thereof include, for example, methyl Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Examples thereof include an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

Examples of the cycloalkyl group having 3 to 8 carbon atoms represented by R ¹¹ include a cyclopentyl group and a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
Among these, as R ¹¹ , for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-hexyl group and the like are preferable.

As a C1-C20 alkyl group represented by R < ¹² >, R < ³ >, it is preferable that it is linear or branched, As a specific example, a methyl group, an ethyl group, n-propyl group is mentioned, for example. I-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , N-undecyl group and n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

The cycloalkyl group of R ^12, carbon atoms represented by R ³ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

Examples of the alkyl group having 1 to 6 carbon atoms that is a substituent of the substituted phenyl group represented by R ¹² and R ³ include linear, branched, or cyclic alkyl groups. List methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can do. Especially, a C1-C6 alkyl group is preferable and a C1-C5 alkyl group is especially preferable.

Moreover, as a C1-C6 alkoxy group which is a substituent of the substituted phenyl group represented by R <^12> , R < ³ >, a linear, branched, or cyclic alkoxy group is mentioned, As the specific example, Can include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy and the like. Among these, an alkoxy group having 1 to 3 carbon atoms is preferable.

Examples of the halogen atom that is a substituent of the substituted phenyl group represented by R ¹² and R ³ include a fluorine atom and a chlorine atom.

Examples of the alicyclic group having 7 to 20 carbon atoms represented by R ¹² and R ³ (excluding a cycloalkyl group having 7 to 8 carbon atoms) include, for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, Examples thereof include a ter-cycloalkyl group, a terpene skeleton-containing group, and an adamantyl skeleton-containing group. Among these, alicyclic groups having 9 to 18 carbon atoms are preferable, and 9 to 12 carbon atoms are particularly preferable.

Among these, R ¹² is preferably a bicycloalkyl group, a tricycloalkyl group, an adamantyl skeleton-containing group or the like, and R ³ is preferably a tricycloalkyl group, an adamantyl skeleton-containing group or the like.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ include a linear, branched, or cyclic alkyl group, and specific examples thereof include, for example, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like. Especially, a C1-C12 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ⁵ include a linear, branched, or cyclic alkoxy group. Specific examples thereof include a methoxy group, an ethoxy group, and n-propoxy. Group, i-propoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group and the like. Among these, an alkoxy group having 1 to 2 carbon atoms is preferable.
Among these, as R ⁵ , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, and an ethoxy group are particularly preferable.

  In the general formula (5 ′), p is preferably 0, 1, or 2, and particularly preferably 0 or 1.

Of the structure represented by the general formula (5 ′), while maintaining high sensitivity and polymerization reactivity (curing), maintaining liquid storage stability after preparation and stability over time in a dry film state after film formation Furthermore, from the viewpoint of enhancing the controllability of the shape of the colored pattern to be formed and the film thickness necessary for it, and improving the adhesion to the solid surface to be applied, R ¹¹ is an ethyl group, and R ¹² Is particularly preferred when is a methyl group, R ³ is a methyl group, R ⁵ is a methyl group and p is 1.

  Specific examples of the compound represented by the general formula (5 ′) include the following compounds.

  The hexaarylbiimidazole photopolymerization initiator in the group (E-2) is not particularly limited as long as it is a dimer of an imidazole ring substituted with three aryl groups. In particular, the following general formula (I) Or a polymerization initiator represented by formula (II) is preferred.

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

In the general formula (II), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms. Show. However, two or more of X ¹ , X ² , and X ³ are not simultaneously hydrogen atoms.

  Specific examples of the hexaarylbiimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis ( 4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,4) -Trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5 5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2, 2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4 Ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2- Ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-pheny Ruphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4 -Biimidazole compounds such as phenoxycarbonylphenyl) biimidazole;

2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (m-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) bisimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5′-tetra- (3-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) bis Imidazole, 2, 2 -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6- Tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dimethylphenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (2,4-diphenylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triphenylphenyl) -4,4 ′, 5 5'-tetraphenylbiimidazole, 2,2'-bis (2-fluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o-fluorophenyl) -4 , 4 ', 5,5'-Tetraphenylbisui And biimidazole compounds such as midazole.

  Among these, particularly preferable compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B-CIM, Hodogaya Chemical Industries), 2,2 ′. -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra- (3,4-dimethoxyphenyl) biimidazole (HABI 1311, Nippon Sebel Hegner), 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (Kurokin Kasei) is mentioned.

  Examples of the acetophenone photopolymerization initiator in the group (E-2) include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one. , P-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone -1 etc. can be mentioned suitably.

In this invention, the preferable combination of the photoinitiator of (E-1) group and the photoinitiator of (E-2) group is shown below.
That is, 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine and 2-tolyl-2-dimethylamino-1- A combination with (4-morpholinophenyl) -butanone-1;
A combination of 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1;
4- [o-Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine and 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole;
2- (p-Tolyl) -4,6-bis (trichloromethyl) -s-triazine and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4 A combination with -ethoxycarbonylphenyl) biimidazole;
A combination of OXE-01 manufactured by Ciba Specialty Chemicals and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1;
A combination of OXE-01 manufactured by Ciba Specialty Chemicals and 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole;
A combination of OXE-02 manufactured by Ciba Specialty Chemicals and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1;
Combination of Ciba Specialty Chemicals OXE-02 and 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole

  Among the above combinations, 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine and 2-tolyl-2-dimethyl Combination with amino-1- (4-morpholinophenyl) -butanone-1; 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine in combination with 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole; OXE-01 from Ciba Specialty Chemicals, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 in combination; OXE-01 manufactured by Ciba Specialty Chemicals; Combination with 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole; OXE-02 manufactured by Ciba Specialty Chemicals and 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole is preferable, and in particular, OXE-01 manufactured by Ciba Specialty Chemicals and 2,2'-bis (2-chlorophenyl)- Combination with 4,4 ′, 5,5′-tetraphenylbiimidazole; 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) The combination of -s-triazine and 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole is particularly preferred. Yes.

In the present invention, one type selected from the group (E-1) and one type selected from the group (E-2) are the group (E-1): the group (E-2). It needs to be included in the range of = 80: 20 to 40:60 (mass ratio). A more preferable range is (E-1) :( E-2) = 80: 20 to 50:50 (mass ratio), particularly preferably 80:20 to 60:40 (mass ratio).
Within this range, wrinkles and unevenness of the colored film that occurs when subjected to heat treatment even under conditions where curing of the colored photosensitive resin composition is insufficient, such as low-energy exposure conditions. It can suppress, and the uniformity of a cured film can be improved.

[Other photopolymerization initiators]
The colored photosensitive resin composition of the present invention is a triazine photopolymerization initiator, an oxime photopolymerization initiator, a hexaarylbiimidazole photopolymerization initiator, and an acetophenone system as long as the effects of the present invention are not impaired. Photopolymerization initiators other than the photopolymerization initiator can be used in combination.
As other photopolymerization initiators, the following can be used.
For example, halomethyl oxadiazole described in JP-A-57-6096, ketal, acetal, or benzoin alkyl described in each specification such as US Pat. No. 4,318,791 and European Patent Application No. 88050. Aromatic carbonyl compounds such as ethers, aromatic ketone compounds such as benzophenones described in US Pat. No. 4,199,420, (thio) xanthone-based or acridine-based compounds described in French Patent No. 2456741, A coumarin-based compound described in Kaihei 10-62986, and a sulfonium organic boron complex disclosed in JP-A-8-015521.

  Among these photopolymerization initiators, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (halomethyloxadiazole, coumarin), and acridine photopolymerization initiators are preferred. .

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, and methyl-o-benzoyl bezoate.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen photopolymerization initiator (oxadiazole series, coumarin series) include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl). ) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl -1,3,4-oxodiazole, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazine 2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin Rukoto can.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  In addition to the above, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like can be mentioned as other photopolymerization initiators.

  In the present invention, in addition to the above-mentioned photopolymerization initiator, for example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2 Α-carbonyl compounds described in US Pat. No. 2,367,670, acyloin ethers described in US Pat. No. 2,448,828, α-carbonization described in US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with hydrogen, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, and benzothiazole compounds described in Japanese Patent Publication No. 51-48516 Etc. can also be used.

The content of the photopolymerization initiator in the colored photosensitive resin composition is preferably 5% by mass to 30% by mass, more preferably 8% by mass to 20% by mass with respect to the total solid content of the composition. is there.
Further, the total amount of the photopolymerization initiator in the group (E-1) and the photopolymerization initiator in the group (E-2) is preferably 50% by mass to 100% by mass in the total photopolymerization initiator, and more preferably. Is 70% by mass to 100% by mass.
Within the above range, the uniformity of the colored film is obtained, and it is preferable in that a tapered colored film can be easily formed.

  The colored photosensitive resin composition of the present invention may contain an optional component as described below, if necessary, in addition to the components (A) to (E) described above.

[Sensitizing dye]
It is preferable to add a sensitizing dye to the colored photosensitive resin composition of the present invention as necessary. The sensitizing dye promotes the radical generation reaction of the above-mentioned photopolymerization initiator component and the polymerization reaction of the photopolymerizable compound by exposure with a wavelength that can be absorbed by the sensitizing dye.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Spectral sensitizing dyes or dyes preferred as the sensitizing dye used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A 64-56767; benzoxanthene dyes described in JP-A-2-17714; acridines described in JP-A-2-226148 and JP-A-2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes; dyes described in JP-A-57-1605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  The content of these sensitizing dyes is preferably 0.1% by mass to 5.0% by mass, more preferably 0.1% by mass to 3.% by mass with respect to the total solid content in the colored photosensitive resin composition. 0% by mass.

[(F) Fluorine-based surfactant or silicone-based surfactant]
The colored photosensitive resin composition of the present invention preferably contains (F) a fluorine-based surfactant or a silicone-based surfactant.
As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specifically, for example, Mega Fuck F142D, F172, F173, F173, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R-61 , R-90 (manufactured by DIC Corporation), FLORARD FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (JEMCO (Commercially available) and the like.

  Examples of silicone surfactants include surfactants having a siloxane bond. Specifically, FZ-2122, FZ-2191, SH-28PA (manufactured by Toray Dow Corning Co., Ltd.), Tore Silicone DC3PA, Tore Silicone SH7PA, Tole Silicone DC11PA, Tore Silicone SH21PA, Tole Silicone SH28PA, Tole Silicone 29SHPA, Torre Silicone SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone Co., Ltd.), KF-6001, KF-6002, KF-6003, X-22-170BX, X-22-170DX, KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, SF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicones Co.), and the commercial products, such as.

The fluorine-based surfactant or silicone-based surfactant of the present invention can be used in the range of 0.1% by mass to 1.5% by mass with respect to the total solid content in the colored photosensitive resin composition. 0.1% by mass to 1.0% by mass is preferable, and 0.1% by mass to 0.7% by mass is particularly preferable.
Within this range, the coatability and the uniformity of the colored film are good.

  The colored photosensitive resin composition of the present invention can be used in combination with various nonionic, cationic, and anionic surfactants in addition to the above-mentioned fluorine-based surfactant or silicone-based surfactant. .

Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene There are nonionic surfactants such as polycondensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd., etc. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

Specific examples of the cationic surfactant include a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo Co., Ltd.)), an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth) acrylic acid (co) polymer. Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  In the colored photosensitive resin composition of the present invention, if necessary, a chain transfer agent, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, a polymer compound other than the above binder resin, adhesion Various additives such as an accelerator, an antioxidant, a UV absorber, and an aggregation inhibitor can be contained.

Examples of the chain transfer agent that can be added to the colored photosensitive resin composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, Examples include mercapto compounds having a heterocyclic ring such as 2-mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

It is also effective to contain a thermal polymerization initiator in the colored photosensitive resin composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketone peroxides. Peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like.

It is also a preferred embodiment that the colored photosensitive resin composition of the present invention contains a thermal polymerization component.
Examples of the thermal polymerization component include polyfunctional epoxy compounds.
The polyfunctional epoxy compound is preferably a compound that thermally crosslinks with a functional group (for example, carboxyl group) of a binder resin such as an alkali-soluble resin. The chemical resistance is improved.
Examples of the polyfunctional epoxy compound that can be used in the present invention include bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.

  For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) Similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC) can also be used.

  As the cresol novolac type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei) can be used. As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl and the like can be used.

Examples of the alicyclic epoxy compound include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), and Santo Tote ST-3000. , ST-4000, ST-5080, ST-5100 and the like (manufactured by Tohto Kasei).
In addition, Epototo YH-434 and YH-434L which are amine type epoxy resins, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can be used.

Among these polyfunctional epoxy compounds, a novolak type epoxy compound represented by the following general formula (III) is preferable, and those having an epoxy equivalent of 200 to 220 are particularly preferable.
Examples of such a compound include epiclone epiclone N-660, N-665, N-670, N-673, N-680, N-690, N-695, N-685-EXP, manufactured by DIC Corporation. N-672-EXP, N-655-EXP-S, N-865, N-865-80M, YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L can be used, Epicron N-660, N-665, N-670, N-673, N-680, N-690, N-695, YDCN-704L and the like are particularly preferable.

In the general formula (III), l is 5 to 100, R is, H, or is CH _3.

The colored photosensitive resin composition of the present invention may contain two or more polyfunctional epoxy compounds.
As content in the colored photosensitive resin composition of the polyfunctional epoxy compound which concerns on this invention, 2 mass%-20 mass% are preferable with respect to the total solid except a pigment, and 3 mass%-10 mass%. Is more preferable. When the content is within the above range, the formed colored film is excellent in solvent resistance.
In addition, when the colored photosensitive resin composition of the present invention is applied to the production of a color filter, if the content of the polyfunctional epoxy compound is more than the above range, the color filter quality is improved by yellow coloring after post-baking. If the amount is too small or too small, there is a problem that the solvent resistance is poor.

A thermal polymerization inhibitor may be added to the colored photosensitive resin composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

  In addition to the above, various additives can be added to the colored photosensitive resin composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

Further, considering the case where the colored photosensitive resin composition of the present invention is applied to the production of a color filter, further improving the developability of the colored photosensitive resin composition, such as promoting alkali solubility of uncured parts. For the purpose of illustration, it is preferable to use an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less.
Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid and caprylic acid; oxalic acid and malon Acids, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic dicarboxylic acids; aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid Aromatic polycarbonate such as acid, trimellitic acid, trimesic acid, melophanoic acid, pyromellitic acid Other acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

[Preparation method of colored photosensitive resin composition]
An example of the preparation method of the colored photosensitive resin composition of this invention is shown below.
First, a mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed into a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single screw or twin screw extruder, etc. After the pigment is ground using a kneader while applying a strong shearing force, the mixture is put into water and made into a slurry with a stirrer or the like. Next, the slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a refined pigment. In the present invention, as described above, it is preferable to obtain a coated pigment by adding a polymer compound to the pigment refining step.
In addition, at the time of preparation of the colored photosensitive resin composition of the present invention, it is possible to omit the above-described pigment refining step.

  Next, bead dispersion is performed with a pigment and a dispersant and / or a pigment derivative and a solvent to obtain a pigment dispersion composition. More specifically, mainly using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., finely dispersed with beads made of glass having a particle diameter of 0.01 mm to 1 mm, zirconia, etc. The pigment dispersion composition is obtained by processing.

For details on kneading and dispersing, see T.W. C. “Paint Flow Pigment Dispersion” by Patton (1964 John Wiley)
and Sons) and the method described herein can also be applied to the present invention.

  Subsequently, the colored photosensitive resin composition of the present invention is prepared by adding a solvent, a photopolymerizable compound, a photopolymerization initiator, a binder resin, and the like to the pigment dispersion composition obtained as described above. can do.

The colored photosensitive resin composition of the present invention is excellent in curing sensitivity and can form a colored film without wrinkles or unevenness even when subjected to heat treatment.
Therefore, the colored photosensitive resin composition of the present invention is preferably used when forming a colored pattern of a color filter, and can also be applied to UV ink and the like.

<Color filter and manufacturing method thereof>
The color filter of the present invention is characterized by having a colored pattern formed on the substrate using the colored photosensitive resin composition of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing a color filter of the present invention comprises a step of applying the colored photosensitive resin composition of the present invention on a substrate to form a colored photosensitive resin composition layer (coating step), and the colored photosensitive resin composition. And a step of exposing the physical layer through a mask (exposure step) and a step of developing the colored photosensitive resin composition layer after exposure to form a colored pattern (development step). .
By such a method, a color filter used in a liquid crystal display device or a solid-state imaging device can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

[Coating process]
In the application step, the colored photosensitive resin composition of the present invention is applied on the substrate directly or via another layer. Thereby, a colored photosensitive resin composition layer is formed on the substrate.
Substrates used for color filters include, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and solid-state imaging Examples of the photoelectric conversion element substrate used for the element include a silicone substrate and a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. In addition, a color pattern formed using the colored photosensitive resin composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

The method for applying the colored photosensitive resin composition of the present invention to a substrate is not particularly limited, and a known application method such as spin coating, slit coating, cast coating, roll coating, bar coating or the like is used. Can do. Among them, a method using a slit nozzle (hereinafter referred to as a slit nozzle coating method) such as a slit-and-spin method or a spinless coating method is preferable. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored photosensitive resin composition from the slit nozzle is usually 500 microliters / second to 2000 microliters / second, preferably 800 microliters / second to 1500 microliters / second, The coating speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second. The solid content of the colored photosensitive resin composition is usually 10 to 20%, preferably 13 to 18%.
When forming a coating film with the colored photosensitive resin composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 μm to 5.0 μm, preferably 0.5 μm. It is ˜4.0 μm, most preferably 0.8 μm to 3.0 μm.
Moreover, when forming the color filter for solid-state image sensors, the thickness (after prebaking process) of a coating film has the preferable range of 0.5 micrometer-5.0 micrometers.

After the coating process as described above is completed, usually, the colored photosensitive resin composition layer is pre-baked. Further, if necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr (13 to 133 Pa), preferably about 0.2 to 0.5 torr (27 to 67 Pa).
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

[Exposure process]
Subsequently, the colored photosensitive resin composition layer pre-baked as described above is exposed through a mask having a predetermined pattern (exposure process).
The radiation used in the exposure step is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferable in a proximity exposure machine and a mirror projection exposure machine, and the exposure amount is 5 mJ / cm ^{2 to} 300 mJ / cm ^2, more preferably ^{10mJ / cm 2 ~150mJ / cm 2} , more preferably from ^{10mJ / cm 2 ~100mJ / cm 2} .
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

[Development process]
After the exposure as described above is completed, development of the colored photosensitive resin composition layer in the unexposed area is performed.
In the development step, the uncured part after exposure is eluted into the developer, leaving only the cured part.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
As the developer, any developer can be used as long as it dissolves the colored photosensitive resin composition layer in the unexposed area and does not dissolve the cured area. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used in the developer include those described above that can be used when preparing the colored photosensitive resin composition of the present invention.
Examples of the alkaline aqueous solution used for the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, Concentration of an alkaline compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001% by mass to 10% by mass %, Preferably 0.01% by mass to 1% by mass, and an alkaline aqueous solution formed by dissolution. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

  The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. It is also possible to develop with the substrate tilted.

After the development step as described above, a rinsing step for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) in order to complete the curing.
The rinsing process is usually performed with pure water. To save liquid, pure water is used in the final cleaning, and used pure water is used at the beginning of cleaning, or the substrate is inclined and cleaned. Irradiation can be used in combination.

After the rinsing step, draining and drying are performed, followed by heat treatment (post-baking).
The post-baking treatment is performed by treating the colored photosensitive resin composition layer after development in an atmosphere at a temperature of 200 ° C. to 250 ° C. for 5 minutes to 60 minutes. This post-baking treatment can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like.

A color filter (in the present invention) in which a colored pattern (colored film) of a plurality of colors (for example, three colors, four colors) is formed by sequentially repeating the above steps for each color according to a desired number of hues. Color filter) can be obtained.
The color filter of the present invention is manufactured using the colored photosensitive resin composition of the present invention, has no wrinkles or unevenness, and has a colored pattern having good light transmittance, and thus becomes a high-quality color filter.

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

<Synthesis example of polymer 1 and polymer 2 which are polymer compounds having a heterocyclic group in the side chain>
(Synthesis of polymer 1)
M-11 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 90 ° C. while flowing nitrogen into the flask. To this, 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 1 was obtained. As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.

(Synthesis of polymer 2)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask and a stirrer (Shinto). The temperature is increased to 90 ° C. by stirring while flowing nitrogen in the flask. To this, 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 90 ° C. for 2 hours. Two hours later, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.

<Preparation of coated pigments 1-4>
(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Red254 Ciba Specialty Chemicals CROMOPHTAL RED BP), 500 g of sodium chloride, 20 g of a 30% by weight solution of the above-described polymer 1 and 100 g of diethylene glycol were added to a 1 gallon kneader (manufactured by Inoue Seisakusho). And kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
In the preparation of the coated pigment 1, C.I. I. A coated pigment 2 was prepared in the same manner as the coated pigment 1 except that Pigment Red 177 (CROMOPHTAL RED A2B manufactured by Ciba Specialty Chemicals) was used.

(Preparation of coated pigment 3)
In the preparation of the coated pigment 1, C.I. I. The coated pigment 3 was prepared in the same manner as the coated pigment 1 except that Pigment Yellow 139 (Pariol Yellow 1819D manufactured by BASF) was used and the polymer 2 was used instead of the polymer 1.

(Preparation of coated pigment 4)
In the adjustment of the coating pigment 3, C.I. I. A coated pigment 4 was prepared in the same manner as the coated pigment 3 except that Yellow Pigment E4GN-GT (manufactured by LANXESS) was used instead of Pigment Yellow 139.

<Measurement of primary particle size distribution of coated pigments 1-4>
The distribution of primary particle sizes of the coated pigments 1 to 4 was measured with a transmission electron microscope, and the ratio of particles having a particle size of 0.08 μm or less is shown in Table 1.

<Evaluation of coverage of coated pigments 1-4>
10 g of the obtained coated pigment was put into 100 mL of 1-methoxy-2-propanol and shaken at room temperature for 3 hours with a shaker. Thereafter, the pigment was precipitated with a centrifugal separator at 80,000 rpm for 8 hours. The solid content of the supernatant was determined from the drying method. The amount of the polymer compound released from the coated pigment was determined, and the release rate (%) was calculated from the ratio with the polymer compound used in the treatment. The smaller the liberation rate, the higher the degree of coverage on the pigment.
As a result, it was found that all of the coated pigments 1 to 4 obtained by the above-described method showed a liberation amount of 20% by mass or less and were high in the degree of coverage with the polymer compound.

<Preparation of pigment dispersion compositions 1 to 4>
With respect to 35 parts of the pigment equivalent of the coated pigment 1, 14.0 parts DispersBYK161 (manufactured by BYK-CHEMIE) as a dispersant, 200 parts propylene glycol monomethyl ether acetate as a solvent, and a rotational speed of 3,000 r. p. m. The mixture was stirred for 3 hours to prepare a mixed solution, and further subjected to a dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads.
Thereby, a pigment dispersion composition 1 was obtained.
Similarly, the pigment dispersion compositions 2 to 4 were obtained by changing the coating pigment type and the amount of the dispersant as shown in Table 1 below.

[Example 1]
Components of the following composition were added to the pigment dispersion composition and mixed by stirring to prepare a colored photosensitive resin composition (color resist solution).
-Pigment dispersion composition 1 39.8 parts-Pigment dispersion composition 2 4.4 parts-(A) Solvent: Propylene glycol monomethyl ether acetate / ethyl ethoxypropionate = 8/2 61.1 parts-(C) Binder Resin: benzyl methacrylate and methacrylic acid (= 70/30 [
Mole ratio]) Weight average molecular weight = 5,000 2.56 parts (D) polymerizable compound: DPHA 3.4 parts made by Nippon Kayaku Co., Ltd. (E-1) Triazine polymerization initiator: 4- [o-Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine
0.89 parts (E-2) hexaarylbiimidazole polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 0.38 parts Diethylaminobenzophenone 0.18 parts, N-phenylmercaptobenzimidazole 0.23 parts, polyfunctional epoxy compound: Epicron 695 manufactured by DIC 0.86 parts, (F) Surfactant: DIC Megafac F781F 0.05 parts・ The following structure 1 0.52 parts

[Examples 2 to 20]
In the composition of the colored photosensitive resin composition of Example 1, the type and amount (unit: part) of the pigment dispersion composition and the type and amount (unit: part) of the photopolymerization initiator are appropriately set as shown in Tables 2 to 2 below. The colored photosensitive resin compositions of Examples 2 to 20 were prepared in the same manner except for the changes as shown in Table 4.

The components described in Tables 2 to 4 and Tables 5 to 9 below are as follows.
(E-1) Triazine-based: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine (triazine-based photopolymerization initiator) )
(E-1) Oxime-based: Oxime-based initiator OXE-01 (oxime-based photopolymerization initiator) manufactured by Ciba Specialty Chemicals
(E-2) Hexaarylbiimidazole type: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (hexaarylbiimidazole type polymerization initiator)
(E-2) Acetophenone series: Irgacure 369 (acetophenone series photopolymerization initiator) manufactured by Ciba Specialty Chemicals
(F) Fluorine series: Megafac F781F (fluorine-based surfactant) manufactured by DIC Corporation
(F) Silicone: Shin-Etsu Silicone KF-6001 (silicone surfactant)

[Evaluation]
Each colored photosensitive resin composition obtained as described above was spin-coated on a glass substrate so that the film thickness after prebaking was 3.0 μm, and dried on a hot plate at 100 ° C. for 80 seconds ( Pre-bake). Thereafter, the entire surface of the colored photosensitive resin composition layer is exposed through a mask at 50 mJ / cm ² (illuminance 20 mW / cm ² ), and the colored photosensitive resin composition layer after exposure is exposed to an alkali developer CDK-1 ( Development was performed by spraying a 1% aqueous solution of Fuji Film Electronics Materials Co., Ltd. in the form of a shower. Thereafter, pure water was sprayed in a shower to wash away the developer. Then, the colored photosensitive resin composition layer that has been exposed and developed as described above is heat-treated in an oven at 220 ° C. for 30 minutes (post-baking), and a colored film (colored) for constituting a color filter is formed on the glass substrate. Pattern) to form a colored substrate.

  The following evaluation was performed using the obtained colored substrate, and the results are summarized in Tables 2 to 4.

-Wrinkles-
The formed colored film (colored pattern) was observed at 500 times using an optical microscope. The evaluation criteria are as follows. Here, ◎, ○, and Δ are ranges where there is no practical problem.
[Evaluation criteria]
A: The surface is very smooth.
○: Although smooth, slight unevenness is seen at the end.
(Triangle | delta): A delicate unevenness | corrugation is seen on the whole surface.
X: Unevenness is clearly seen on the entire surface.

-Mura-
The formed colored film (colored pattern) was observed at 500 times using an optical microscope. The evaluation criteria are as follows. Here, ◎, ○, and Δ are ranges where there is no practical problem.
[Evaluation criteria]
A: The colored film is very uniform with no difference in density.
○: Almost no difference in shade.
(Triangle | delta): A delicate shade difference is seen on the whole surface.
X: A clear contrast is seen on the entire surface.

-Pattern shape-
The colored substrate was cut out by glass cutting, and the cross section was observed at 15,000 times using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). The evaluation criteria are as follows.
[Evaluation criteria]
○: The end of the colored pattern has a gentle slope shape.
(Triangle | delta): The coloring pattern edge part is a rectangle.
X: The cut | notch has generate | occur | produced in the coloring pattern edge part.

-Residual film rate (Evaluation of exposure sensitivity)-
The film thickness of the colored photosensitive resin composition layer exposed and developed as described above was measured with a stylus type film thickness measuring device (DEKTAK manufactured by ULVAC). Furthermore, the film thickness of the colored photosensitive resin composition layer (colored film) after heat treatment in an oven at 220 ° C. for 30 minutes was also measured in the same manner as described above, and the remaining film ratio (%) was calculated using the following formula. did. The higher the remaining film ratio, the better the exposure sensitivity.
Residual film ratio (%) = (film thickness of colored film after heat treatment) / (film thickness of colored photosensitive resin composition layer subjected to exposure and development) × 100

Example 21
Components of the following composition were added to the pigment dispersion composition and mixed by stirring to prepare a colored photosensitive resin composition (color resist solution).
Pigment dispersion composition 1 27.7 parts Pigment dispersion composition 2 11.8 parts Pigment dispersion composition 3 0.47 parts (A) Solvent: propylene glycol monomethyl ether acetate / ethyl ethoxypropionate = 8 / 2 65.6 parts (C) Binder resin: benzyl methacrylate and methacrylic acid (= 70/30 [
Mole ratio]) Weight average molecular weight = 5,000 2.99 parts (D) Polymerizable compound: DPHA 3.5 parts by Nippon Kayaku Co., Ltd. (E-1) Triazine polymerization initiator: 4- [o-Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine
1.34 parts · (E-2) hexaarylbiimidazole polymerization initiator: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 0.38 parts Diethylaminobenzophenone 0.18 parts, N-phenyl mercaptobenzimidazole 0.23 parts, polyfunctional epoxy compound: DIC Corporation Epicron 695 0.86 parts, (F) Surfactant: DIC Corporation Megafac F781F 0.05 parts・ Structure 1 (said structure) 0.52 parts

[Examples 22 to 40]
In the composition of the colored photosensitive resin composition of Example 21, the type and amount (unit: part) of the pigment dispersion composition, the type and amount (unit: part) of the photopolymerization initiator, and the type and amount of surfactant. Colored photosensitive resin compositions of Examples 22 to 40 were prepared in the same manner except that (unit: part) was appropriately changed as shown in Tables 5 to 7 below.

[Evaluation]
Using the colored photosensitive resin compositions of Examples 21 to 40, colored substrates were produced using the same method as in Examples 1 to 20. About the obtained colored substrate, it evaluated by the method similar to Examples 1-20, and the result was put together in Table 5-Table 7. FIG.

Example 41
Components of the following composition were added to the pigment dispersion composition and mixed by stirring to prepare a colored photosensitive resin composition (color resist solution).
-Pigment dispersion composition 1 31.5 parts-Pigment dispersion composition 2 10.7 parts-Pigment dispersion composition 3 3.5 parts-(A) Solvent: Propylene glycol monomethyl ether acetate / ethyl ethoxypropionate = 8 / 2 54.5 parts · (C) Binder resin: benzyl methacrylate and methacrylic acid (= 70/30 [
Mole ratio]) Weight average molecular weight = 5,000 0.82 parts (D) Polymerizable compound: Nippon Kayaku Co., Ltd. DPHA 2.7 parts (E-1) Triazine polymerization initiator: 4- [o-Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine
1.00 part (E-2) hexaarylbiimidazole polymerization initiator: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole 0.33 part 0.14 parts of diethylaminobenzophenone, 0.18 parts of N-phenylmercaptobenzimidazole, polyfunctional epoxy compound: 0.86 part of Epicron 695 manufactured by DIC Corporation (F) Surfactant: MegaFack F781F manufactured by DIC Corporation 05 parts, structure 1 (the above structure) 0.52 parts

[Examples 42 to 53, Comparative Examples 1 to 4]
In the composition of the colored photosensitive resin composition of Example 41, the type and amount (unit: part) of the pigment dispersion composition, the type and amount (unit: part) of the photopolymerization initiator, and the type and amount of surfactant. The colored photosensitive resin compositions of Examples 42 to 53 and Comparative Examples 1 to 4 were prepared in the same manner except that (unit: part) was appropriately changed as shown in Tables 8 to 9 below.

[Evaluation]
Using the colored photosensitive resin compositions of Examples 41 to 53 and Comparative Examples 1 to 4, colored substrates were produced using the same method as in Examples 1 to 20. About the obtained colored substrate, it evaluated by the method similar to Examples 1-20, and the result was put together in Tables 8-9.

From Table 2 to Table 9, the triazine-based or oxime-based photopolymerization initiator which contains the pigment of the (B-1) group and the pigment of the (B-2) group, and is the (E-1) group; And (E-2) group, a colored photosensitive resin composition containing a hexaarylbiimidazole-based photopolymerization initiator or an acetophenone-based photopolymerization initiator in a range where the mass ratio is 80:20 to 40:60. In Examples 1 to 53, it can be seen that wrinkles and unevenness do not occur in the colored pattern (colored film) obtained by the post-baking process. It can also be seen that the formed colored pattern (colored film) has an excellent pattern shape. Furthermore, it turns out that the colored photosensitive resin composition of Examples 1-53 has a high residual film ratio compared with Comparative Examples 1-4, and is excellent also in exposure sensitivity.
Moreover, it turns out that the wrinkles and nonuniformity which generate | occur | produce in the coloring pattern (colored film) obtained by using for a post-baking process can be suppressed more by using a fluorochemical surfactant or a silicone type surfactant.

  As described above, the colored pattern formed using the colored photosensitive resin composition of the present invention is free from wrinkles and unevenness. As a result, the color filter having such a colored pattern has display unevenness when it is panelized. It is assumed that it has no good optical properties.

Claims (5)

(A) a solvent, (B) a pigment comprising one type selected from the following group (B-1) and one selected from the following group (B-2), (C) a binder resin, (D ) A photopolymerizable compound, and (E) one selected from the following (E-1) group and one selected from the following (E-2) group, the (E-1) group: (E-2) group = colored photosensitive resin composition containing a photopolymerization initiator contained in the range of 80:20 to 40:60 (mass ratio) (however, one type selected from group (B-1)) And (B-2) one type selected from the group is not the same pigment).
Group (B-1): Group consisting of diketopyrrolopyrrole pigment, anthraquinone pigment, and perylene pigment (B-2) group: From anthraquinone pigment, disazo pigment, isoindoline pigment, and quinophthalone pigment Group (E-1) group: Triazine photopolymerization initiator and group (E-2) group consisting of oxime photopolymerization initiator: hexaarylbiimidazole photopolymerization initiator and acetophenone photopolymerization initiator Group of   Furthermore, (F) a fluorine-based surfactant or a silicone-based surfactant is contained in a range of 0.1% by mass to 1.5% by mass with respect to the total solid content in the colored photosensitive resin composition. The colored photosensitive resin composition according to 1.   The said (B) pigment contains 1 type selected from the said (B-1) group, and 1 type selected from the said (B-2) group, and is comprised by 3 or more types. Or the coloring photosensitive resin composition of Claim 2.   The color filter which has a coloring pattern which uses the colored photosensitive resin composition of any one of Claims 1-3 on a board | substrate. Applying the colored photosensitive resin composition according to any one of claims 1 to 3 on the substrate to form a colored photosensitive resin composition layer;
Exposing the colored photosensitive resin composition layer through a mask;
Developing the colored photosensitive resin composition layer after exposure to form a colored pattern; and
A method for producing a color filter, comprising: