JP2017137483A - Coloring resin composition, color filter and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition which can expand a color reproduction range and can form a pattern with good surface quality; a color filter having a pixel formed using the coloring resin composition; and an image display device having the color filter.SOLUTION: There is provided a coloring resin composition which contains (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator, where (A) the pigment contains a zinc halide phthalocyanine pigment, has an average hydrogen atom number contained in one molecule of the zinc halide phthalocyanine pigment of 3 or more, and further contains (F) a chain transfer agent.SELECTED DRAWING: None

Description

  The present invention relates to a colored resin composition, a color filter, and an image display device. More specifically, a colored resin composition containing a specific zinc halide phthalocyanine pigment and further containing a chain transfer agent, a color filter having pixels created using the colored resin composition, and an image display having the color filter Relates to the device.

  Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for producing color filters used in liquid crystal display devices and the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.

  In recent years, color filters are required to have higher transmission, higher luminance, higher contrast, and higher color gamut. As the color material that determines the color of the color filter, pigments are generally used from the viewpoints of heat resistance, light resistance, etc., among which the intrinsic transmission absorption spectrum matches the phosphor spectrum of the backlight in the visible light wavelength region. Those are preferably used. For example, a combination of a copper halide phthalocyanine green pigment and various yellow pigments has long been used for forming a green pixel.

With regard to increasing the brightness of green pixels, as described in Patent Documents 1 to 3, for example, as a new green pigment having a specific hue, C.I. is a kind of a halogenated zinc phthalocyanine green pigment. I. Pigment Green 58 is described.
Patent Document 4 describes a new zinc halide phthalocyanine green pigment capable of expanding the color reproduction range.

JP 2004-70342 A JP 2004-70343 A JP 2009-52010 A International Publication No. 2015/118720 Pamphlet

  When the present inventors examined the colored resin composition using the specific zinc halide phthalocyanine pigment described in Patent Document 4, it was confirmed that the coloring power was high and the color reproduction range could be expanded. , C.I. I. Unlike the colored resin composition using Pigment Green 58, it was found that the surface of the cured film obtained was undulated, the surface smoothness was poor, and there was a problem in practical use.

  The present invention has been made in view of the above-mentioned problems, and the object thereof is a colored resin composition capable of expanding a color reproduction range and capable of forming a pattern having a good surface property, and this coloring. A color filter having pixels formed using a resin composition and an image display device having the color filter are provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific zinc halide phthalocyanine green pigment and using a chain transfer agent, thereby completing the present invention. It came to do. That is, the gist of the present invention is as follows.

[1] A colored resin composition comprising (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
The (A) pigment contains a halogenated zinc phthalocyanine pigment, the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more, and
Further, (F) a colored resin composition containing a chain transfer agent.
[2] The colored resin composition according to [1], wherein the (F) chain transfer agent contains a compound represented by the following formula (i).

(In said formula (i), p represents the integer of 2-4.
R ^a1 represents a hydrogen atom or an alkyl group which may have a substituent.
X represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent heterocyclic group or a 2-4 valent aromatic ring group.
In addition, a plurality of structures represented by the following general formula (i ′) contained in one molecule

May be the same or different. )
[3] The colored resin composition according to [1] or [2], wherein the content ratio of the (F) chain transfer agent is 0.01% by mass or more based on the total solid content.
[4] The colored resin composition according to any one of [1] to [3], wherein the (E) photopolymerization initiator contains an oxime ester compound.

[5] The colored resin composition according to any one of [1] to [4], wherein the content ratio of the pigment (A) is 20% by mass or more based on the total solid content.
[6] The colored resin composition according to any one of [1] to [5], wherein the (A) pigment further contains a yellow pigment.
[7] The colored resin composition according to any one of [1] to [6], wherein the (B) dispersant includes a block copolymer having a functional group containing a nitrogen atom.
[8] A color filter having pixels created using the colored resin composition according to any one of [1] to [7].
[9] An image display device having the color filter according to [8].

  According to the present invention, a colored resin composition capable of expanding a color reproduction range and capable of forming a pattern having a good surface property, and a color having pixels formed using the colored resin composition A filter and an image display device having the color filter can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having the color filter of the present invention.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
In addition, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” is “ It means “acrylic acid and / or methacrylic acid”. Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.

In the present invention, “weight average molecular weight” refers to polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. .

[1] Constituent Components of Colored Resin Composition Each constituent component of the colored resin composition of the present invention will be described below. The colored resin composition according to the present invention includes (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator as essential components. Other additives other than the above components may be blended.
Hereinafter, each component will be described.

[1-1] (A) Pigment The (A) pigment used in the colored resin composition of the present invention includes a halogenated zinc phthalocyanine pigment (hereinafter sometimes referred to as “green pigment a”). The average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more.
Thus, it is thought that high coloring and high luminance can be achieved by including the green pigment a as the (A) pigment. The detailed mechanism is unknown, but the half-width of the peak is narrow due to the change in the transmission spectrum due to the inclusion of many hydrogen atoms, and the red and blue transmitted light is effectively blocked. Is presumed to be realized.

  Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule, and the halogenated zinc phthalocyanine pigment used in the present invention is one obtained by substituting some of these hydrogen atoms with halogen atoms. In particular, from the viewpoint of high coloring and high brightness, a chlorinated brominated zinc phthalocyanine pigment is preferable.

  The average number of hydrogen atoms in one pigment molecule is a value calculated using the average number of halogen atoms measured by the fluorescent X-ray fundamental parameter method (FP method). Specifically, first, the average number of halogen atoms is calculated by the FP method. Since there are 16 sites occupied by halogen atoms and hydrogen atoms in the halogenated zinc phthalocyanine, the average number of hydrogen atoms can be obtained by calculating the remaining sites not occupied by halogen atoms. It is preferable to perform measurement by adopting the apparatus and conditions used in the examples. Specifically, the average number of halogen atoms is obtained by calculating the average number of halogen atoms per zinc atom from the mass ratio of zinc atoms and halogen atoms measured by the FP method, and subtracting the average number of halogen atoms from 16. .

  The green pigment a has an average number of hydrogen atoms contained in one molecule of usually 3 or more, preferably 3.5 or more, more preferably 4.0 or more, still more preferably 4.2 or more, and particularly preferably 4. It is 5 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5.5 or less. There exists a tendency which becomes highly colored by setting it as the said lower limit or more. Moreover, there exists a tendency which can improve the stability of a dispersion liquid by setting it as the said upper limit or less.

  The green pigment a has an average number of chlorine atoms contained in one molecule of preferably 0.5 or more, more preferably 1 or more, further preferably 1.5 or more, and preferably 14 or less, more preferably It is 12 or less, more preferably 10 or less, even more preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. There exists a tendency which becomes highly colored by setting it as the said lower limit or more. Moreover, there exists a tendency for it to become high-intensity by setting it as the said upper limit or less.

  Further, the green pigment a preferably has an average number of bromine atoms contained in one molecule of 1 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 6 or more, particularly preferably 7 or more, most preferably The number is preferably 8 or more, and is preferably 14 or less, more preferably 13 or less, still more preferably 12 or less, still more preferably 11 or less, and particularly preferably 10 or less. There exists a tendency for it to become high-intensity by setting it as the said lower limit or more. Moreover, there exists a tendency which becomes highly colored by setting it as the said upper limit or less.

  Further, in the green pigment a, the ratio of the average number of chlorine atoms contained in one molecule to the average number of bromine atoms contained in one molecule is preferably 0.1 or more, and is 0.15 or more. Is more preferably 0.2 or more, preferably 7 or less, more preferably 3 or less, further preferably 1 or less, and 0.5 or less. Is particularly preferred. There exists a tendency which becomes highly colored by setting it as the said lower limit or more, and there exists a tendency for it to become high-intensity by setting it as the said upper limit or less.

  Such a halogenated zinc phthalocyanine pigment can be produced by a known production method disclosed in JP-A-50-130816. For example, a method of synthesizing a pigment using phthalic acid or phthalonitrile in which some or all of the hydrogen atoms of the aromatic ring are substituted with a halogen atom such as chlorine in addition to bromine as an appropriate starting material. In this case, a catalyst such as ammonium molybdate may be used as necessary.

As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt of about 110 to 170 ° C. composed of a mixture of aluminum chloride, sodium chloride, sodium bromide and the like can be mentioned. In this method, the ratio of various brominated zinc phthalocyanines with different bromine contents can be adjusted by adjusting the ratio of chloride and bromide in the molten salt, or by changing the amount of chlorine gas introduced and the reaction time. Can be controlled arbitrarily.
When the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid after the reaction is completed, the produced brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing and drying is performed to obtain brominated zinc phthalocyanine.

  The zinc halide phthalocyanine pigment thus obtained is dry-ground in a grinder such as an attritor, ball mill, vibration mill, vibration ball mill or the like as necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. Thus, a zinc halide phthalocyanine pigment that develops a green color with high transmittance and contrast can be obtained. The pigmentation method is not particularly limited, but it is preferable to employ a solvent salt milling treatment from the viewpoint that crystal growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  Solvent salt milling means kneading and grinding a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. As a kneading machine at this time, for example, a kneader, a mix muller, a planetary mixer, or a gap portion of a rotating disk concentric with an annular fixed disk as described in JP-A-2006-77062 is formed. A continuous kneader or the like having a grinding space is preferably used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Further, the average particle size of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  (A) The pigment may contain other green pigments besides the green pigment a. Other green pigments include, for example, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. And CI Pigment Green 58.

  The content ratio of the green pigment a contained in the green pigment is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, and 50% by mass or more. More preferably, it is more preferably 80% by mass or more, most preferably 90% by mass or more, and usually 100% by mass or less. When the amount is not less than the lower limit, the effect of the pigment tends to be obtained more.

  The content ratio of the green pigment contained in (A) the pigment is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and 55% by mass. % Or more, more preferably 60% by weight or more, most preferably 65% by weight or more, and usually 100% by weight or less, preferably 90% by weight or less, More preferably, it is less than 70% by mass, and still more preferably less than 70% by mass. There exists a tendency which can be made wide color gamut by setting it as the said lower limit or more. Moreover, there exists a tendency which can improve platemaking property by setting it as the said upper limit or less.

  The content ratio of the pigment (A) in the colored resin composition of the present invention is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass with respect to the total solid content. In addition, it is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, still more preferably 45% by mass or less, and particularly preferably 40% by mass or less. is there. Within the above range, the dispersion stability is good and there is a tendency that more effects of the green pigment can be obtained.

  The average primary particle size of the green pigment containing the green pigment a is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and usually 0.005 μm or more. By setting the average primary particle size within the above range, there is a tendency that deterioration in depolarization characteristics and reduction in transmittance can be suppressed.

  In addition, the average primary particle diameter of a pigment can be calculated | required with the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). In the case of an organic pigment, the particle diameter of each pigment particle is defined as an area equivalent circle diameter converted to the diameter of a circle having the same area, and after calculating the particle diameter for each of the plurality of pigment particles, the following formula Calculate the average particle size by calculating the number average value as follows.

Particle size of individual pigment particles:
X ₁ , X ₂ , X ₃ , X ₄ ,..., X _i ,... X _m average particle diameter = ΣX _i / m

  In order to adjust the hue, the (A) pigment can contain a yellow pigment. Examples of yellow pigments include C.I. I. Pigment Yellow (P.Y.) 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 16 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a 1: 1 complex of azobarbituric acid represented by the following formula (I) with nickel or compatible isomers thereof And a compound in which another compound is inserted (hereinafter referred to as “nickel azo complex represented by the formula (I)”).

  Examples of the other compounds include compounds represented by the following formula (II).

  Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and a nickel azo complex represented by the formula (I), more preferably C.I. I. And CI pigment yellow 83, 138, 139, 180, 185 and nickel azo complexes represented by formula (I).

  The average primary particle diameter of these yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less. When the pigment is atomized, a technique such as the solvent salt milling described above is preferably used.

  (A) The content of the yellow pigment contained in the pigment is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and 60% by mass or less. Is more preferably 50% by mass or less, most preferably 40% by mass or less, usually 0% by mass to 10% by mass, more preferably 20% by mass or more, and further preferably 25% by mass or more, 30 mass% or more is still more preferable, and 40 mass% or more is especially preferable. When the amount is not more than the above upper limit value, the effect of the green pigment a tends to be obtained more.

  Moreover, in addition to the colored resin composition (A) pigment of the present invention, a dye may be included. In particular, it is preferable to include a yellow dye from the viewpoint of luminance.

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in JP 2010-168531 A.
Examples of those classified as dyes by color index include C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94 98, 99, 162, 163, C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. Solvent orange 2, 7, 11, 15, 26, 45, 56 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and derivatives thereof. Can be mentioned. In addition, C.I. I. C. as a direct dye I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 136, 138, 141, C.I. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, C.I. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, C.I. I. Modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251,23,25 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and derivatives thereof.
Among these, from the viewpoint of handleability, C.I. I. Solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163 are preferred.

  Although the content rate of a yellow dye is not specifically limited, 1 mass% or more is preferable with respect to the total solid of a colored resin composition, 5 mass% or more is more preferable, 10 mass% or more is further more preferable, 30 mass% The following is preferable, 20% by mass or less is more preferable, and 15% by mass or less is more preferable. There exists a tendency which becomes high brightness by setting it as the said lower limit or more, and there exists a tendency which can suppress a durable fall by setting it as the said upper limit or less.

[1-2] (B) Dispersant The colored resin composition of the present invention contains (B) a dispersant for the purpose of stably dispersing the (A) pigment. Of these, the use of a polymer dispersant is preferred because of excellent dispersion stability over time.
Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester. There may be mentioned system dispersants. Specific examples of these dispersants are trade names of EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), SOLPERSE (registered trademark, Louvre). Zol), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.) and the like.

Among the polymer dispersants, a block copolymer having a functional group containing a nitrogen atom is preferable from the viewpoint of dispersibility and storage stability, and an acrylic block copolymer is more preferable.
The block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium base and / or amino group in a side chain and a B block having no quaternary ammonium base and / or amino group. An AB block copolymer and / or a BAB block copolymer are preferable.

Examples of the functional group containing a nitrogen atom include a primary to tertiary amino group and a quaternary ammonium base. From the viewpoint of dispersibility and storage stability, the functional group preferably has a primary to tertiary amino group. It is more preferable to have a group.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but is preferably a repeating unit represented by the following general formula (1) from the viewpoint of dispersibility and storage stability. .

In the above formula (1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An aralkyl group which may be present, and R ¹ and R ² may be bonded to each other to form a cyclic structure. R ³ is a hydrogen atom or a methyl group. X is a divalent linking group.

  The number of carbon atoms of the alkyl group that may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. Preferably, it is 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

  The number of carbon atoms of the aryl group that may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. Preferably, it is 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

  In the above formula (1), the carbon number of the aralkyl group which may have a substituent is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Preferably, it is 9 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoints of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are preferably each independently an alkyl group which may have a substituent, a methyl group or More preferably, it is an ethyl group.

  Examples of the substituent that the alkyl group, aralkyl group, or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, and the like. Substitution is preferred.

In the above formula (1), examples of the cyclic structure formed by combining R ¹ and R ² with each other include, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. Is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specific examples include the following (IV).

  These cyclic structures may further have a substituent.

In the above formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ¹³ — group, a —COOR ¹⁴ — group [ However, R <^13> and R < ¹⁴ > is a single bond, a C1-C10 alkylene group, or a C2-C10 ether group (alkyloxyalkyl group)] etc., etc. are mentioned, Preferably -COO-R < ¹⁴ >. -Group.

  Further, the content ratio of the repeating unit represented by the formula (1) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, More preferably, it is 10 mol% or more, more preferably 15 mol% or more, particularly preferably 20% or more, most preferably 25 mol% or more, and 90 mol% or less. Preferably, it is 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. If it is within the above range, both dispersion stability and high luminance tend to be compatible.

  Moreover, it is preferable that the said block copolymer has a repeating unit represented by following formula (2) from a viewpoint of improving the compatibility with binder components, such as a solvent of a dispersing agent, and improving dispersion stability.

In the above formula (2), R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an alkyl group which may have a substituent, and R ¹² is a hydrogen atom or a methyl group.
n is an integer of 1-20.

The number of carbon atoms of the alkyl group which may have a substituent in R ¹¹ of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. Is preferably 6 or less, more preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. Examples of the substituent that may be included include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.

  Further, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. More preferably, it is 5 or less.

  Further, the content ratio of the repeating unit represented by the formula (2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, 4 mol% or more is more preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is more preferable. When the amount is within the above range, compatibility with a binder component such as a solvent tends to be compatible with dispersion stability.

  Moreover, it is preferable that the said block copolymer has a repeating unit represented by following formula (3) from a viewpoint of improving the compatibility with binder components, such as a solvent of a dispersing agent, and improving dispersion stability.

In the above formula (3), R ⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁹ is a hydrogen atom or a methyl group.

The carbon number of the alkyl group which may have a substituent in R ⁸ in the above formula (3) is not particularly limited, but is usually 1 or more, preferably 1 or more, and 10 or less. It is preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ⁸ of the above formula (3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. It is more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, a phenyl group, a methylphenyl group, and an ethylphenyl group , A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ⁸ in the above formula (3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. It is more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group.
Examples of the substituent that the alkyl group may have in R ⁸ include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. The linear alkyl group represented by R ⁸ includes both linear and branched chains.

  Further, the content ratio of the repeating unit represented by the formula (3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, It is further preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less. If it is within the above range, both dispersion stability and high luminance tend to be compatible.

  The block copolymer includes a repeating unit other than the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). You may have. Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

  From the viewpoint of further improving dispersibility, the A block having a repeating unit represented by the general formula (1) and a B block having no repeating unit represented by the general formula (1). A block copolymer is preferred. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Moreover, it is more preferable that B block has a repeating unit represented by the said General formula (2) and a repeating unit represented by the said General formula (3).

  Moreover, repeating units other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such repeating units include the (meth) acrylic acid ester group described above. Examples thereof include a monomer-derived repeating unit. The content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the A block.

  A repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) may be contained in the B block. Examples of such a repeating unit include: Styrene monomers such as styrene, α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamides such as (meth) acrylamide and N-methylolacrylamide Monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably Although it is 0-20 mol%, it is most preferable that this repeating unit is not contained in B block.

  The acid value of the block copolymer is preferably lower from the viewpoint of dispersibility, and particularly preferably 0 mgKOH / g. Here, the acid value represents the number of mg of KOH necessary for neutralizing 1 g of the solid content of the dispersant.

  Furthermore, the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of dispersibility and developability. More preferably, it is more preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, most preferably 110 mgKOH / g or more, and preferably 150 mgKOH / g or less, 130 mgKOH / G or less is more preferable. Here, the amine value represents an amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant.

  The molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene-converted weight average molecular weight (hereinafter sometimes referred to as “Mw”). When it is within the above range, the dispersion stability is good, and there is a tendency that dry foreign matters are less likely to be generated during coating by the slit nozzle method.

Although the said block copolymer can be manufactured by a well-known method, for example, it can manufacture by carrying out the living polymerization of the monomer which introduce | transduces said each repeating unit. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986)
), Koichi Right, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M. et al. Kuroki, T .; Aida, J .; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

  In the colored resin composition of the present invention, the content ratio of the (B) dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the (A) pigment. 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 70 parts by mass or less, more preferably 50 parts by mass or less, Preferably it is 40 mass parts or less, Most preferably, it is 30 mass parts or less. By being in the said range, there exists a tendency which can be excellent in dispersion stability and can obtain a high-intensity coloring resin composition.

[1-3] Dispersion aid The colored resin composition according to the present invention may contain a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability. As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

Among them, a pigment derivative that has less interference with the hue of the green pigment is preferable, and a sulfonic acid derivative of Pigment Yellow 138, a sulfonic acid derivative of Pigment Yellow 139, and a sulfonic acid derivative of Pigment Blue 15 are more preferable.
The amount of the pigment derivative used is usually 0.1 parts by mass or more, usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 100 parts by mass of the pigment (A). Is 5 parts by mass or less.

[1-4] (C) Solvent (C) The solvent has a function of adjusting the viscosity by dissolving or dispersing the pigment, the dispersant, and other components in the colored resin composition of the present invention.
The solvent (C) may be any solvent that can dissolve or disperse each component.

  Examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl -3-Methoxybutanol Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa], hereinafter the same applies to the boiling point) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C.
Glycol alkyl ether acetates are preferred from the viewpoints of good balance between the solvent, applicability, surface tension, etc., and relatively high solubility of the components in the composition.

  In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersion liquid to break down due to rapid drying. The content of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent. If the amount of the high-boiling solvent is too small, for example, coloring material components may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too much, the drying temperature of the composition will be slow, which will be described later. There is a concern that it may cause problems such as tact defects in the vacuum drying process and pre-baked pin marks in the color filter manufacturing process.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be separately contained.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

When forming a pixel of a color filter by the ink jet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is appropriate. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. On the other hand, if the boiling point is too high, the effect of inhibiting drying of the curable resin composition is high as described later, but there are many residual solvents in the coating film even after heat firing, which may cause quality problems. In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.
The solvent vapor pressure is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In addition, in the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more in the total solvent contained in the pigment dispersion and / or the colored resin composition described later. 90 mass% or more is the most preferable. When the high boiling point solvent is less than 50% by mass, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the pigment dispersion and the colored resin composition described later and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

  On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, it is preferable that alcohol is 20 mass% or less in all the solvents, 10 mass% or less is more preferable, and 5 mass% or less is especially preferable.

  Moreover, the content ratio of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. There exists a tendency which becomes easy to form a coating film by setting it as the said lower limit or less. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in consideration of viscosity suitable for application.

[1-5] (D) Binder resin The colored resin composition of the present invention contains (D) a binder resin. (D) By containing a binder resin, film curability by photopolymerization and solubility by a developer can be compatible.
(D) As the binder resin, a preferable resin tends to be different depending on what means is used for the colored resin composition to be cured. In the case of the photopolymerizable resin composition, examples of the binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11. Known polymer compounds described in publications such as JP-A-174224, JP-A-2000-56118, and JP-A-2003-233179 can be used, but preferably [1-5-1 ]: An unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer. Alkali-soluble resin [1-5-2] obtained by adding a polybasic acid anhydride to at least a part of the resin or the hydroxyl group generated by the addition reaction. Linear alkali-soluble resin containing a boxyl group Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin described in [1-5-3] [1-5-2] [1-5 -4] (Meth) acrylic resin [1-5-5] Epoxy (meth) acrylate resin having a carboxyl group, and the like. Hereinafter, each of these resins will be described.

[1-5-1] Unsaturated monobasic acid in at least part of the epoxy group of the copolymer with respect to the copolymer of the epoxy group-containing (meth) acrylate and other radical polymerizable monomer Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. As one of particularly preferred resins, “epoxy group-containing (meth) acrylate” Unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% and other radical polymerizable monomer 10 to 95 mol%. Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following general formula (V).

In formula (V), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring.
In the formula (V), the ring formed by connecting R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and carbon The number is preferably 5-6.

Especially, as a structure represented by general formula (V), the structure represented by following formula (Va), (Vb), or (Vc) is preferable.
By introducing these structures into the binder resin, when the colored resin composition of the present invention is used for a color filter or an image display element, the heat resistance of the colored resin composition is improved, or the colored resin composition is used. It is possible to increase the intensity of the pixel formed by using.

  In addition, the mono (meth) acrylate which has a structure represented by general formula (V) may be used individually by 1 type, and may use 2 or more types together.

  As the mono (meth) acrylate having the structure represented by the general formula (V), various known ones can be used as long as the structure has the structure, and those represented by the following general formula (VI) are particularly preferable. .

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents the structure of the general formula (V).
In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (VI) is: Among repeating units derived from “other radical polymerizable monomers”, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

  The “other radical polymerizable monomer” other than the mono (meth) acrylate having the structure represented by the general formula (VI) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoroe Chill, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as cumyl, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic acid amides such as N-di-iso-propylamide and (meth) acrylic acid anthracenylamide; Vinyl compounds such as anilic rilates, (meth) acryloylnitriles, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

  Among these “other radically polymerizable monomers”, at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is used to impart excellent heat resistance and strength to the colored resin composition. It is effective to use In particular, in the repeating unit derived from “another radical polymerizable monomer”, the content of the repeating unit derived from at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. %, Preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Propylene glycol monoalkyl ether acetates; Acetic esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl Ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane and decane Petroleum petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more.

The amount of these solvents to be used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, with respect to 100 parts by mass of the resulting copolymer. When the amount of the solvent used is outside this range, it becomes difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can do. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

  Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, and t-butyl peroxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxide Oxydicarbonate, diisopropyl -Oxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.
Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 mass parts with respect to a total of 100 mass parts of the monomer used for a copolymerization reaction, Preferably it is 1-10 mass parts.

  The copolymerization reaction may be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator has been added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Further, the monomer may be added dropwise while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

By making the amount of the epoxy group-containing (meth) acrylate more than the lower limit value, there is a tendency that the additional amount of the polymerizable component and the alkali-soluble component described later can be made sufficient, while the epoxy group-containing By making the amount of (meth) acrylate not more than the above upper limit value, there is a tendency that the amount of other radical polymerizable monomer can be sufficiently secured and the heat resistance and strength can be made sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radical polymerizable monomer. A soluble component).

As the “unsaturated monobasic acid” to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These 1 type may be used independently and may use 2 or more types together.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. There exists a tendency which can suppress the influence of the residual epoxy group with respect to aging stability of a colored resin composition by making the addition ratio of unsaturated monobasic acid more than the said lower limit. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, as the “polybasic acid anhydride” to be added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. When the amount is not more than the above upper limit value, there is a tendency that a decrease in the remaining film ratio during development can be suppressed, and when the amount is not less than the above lower limit value, the solubility tends to be sufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be.
Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups.

Both of these may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol (registered trademark, the same shall apply hereinafter) EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Nagase Kasei Kogyo Co., Ltd.” There are “Denacol EX-146”, “Denacol EX-171”, “Denacol EX-192”, and the like.

The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
The above-mentioned binder resin has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of preferably 3000 or more, more preferably 5000 or more, still more preferably 10,000 or more, and more preferably 100,000 or less, more preferably 50,000 or less. 30000 or less is more preferable, and 20000 or less is particularly preferable. By setting it to the above lower limit value or more, the heat resistance and film strength tend to be favorable, and by setting the upper limit value or less, insufficient solubility in the developer tends to be suppressed. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[1-5-2] Linear alkali-soluble resin containing a carboxyl group in the main chain The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group. Usually, it is obtained by polymerizing a polymerizable monomer containing a carboxyl group.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2 -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meta Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; Monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or Examples thereof include monomers added with acids or anhydrides such as anhydrides thereof. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
The linear alkali-soluble resin containing a carboxyl group in the main chain may be copolymerized with the above-mentioned polymerizable monomer having no carboxyl group to the carboxyl group-containing polymerizable monomer. .

  Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobonyl (meth) acrylate (Meth) acrylic esters such as adamantyl (meth) acrylate; vinyl aromatics such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide N-substituted maleimides such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. And the like. These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  The linear alkali-soluble resin containing a carboxyl group in the main chain may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. Is mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  Specifically, as a linear alkali-soluble resin containing a carboxyl group in the main chain, for example, (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Polymeric monomers that do not contain hydroxyl groups such as meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. A copolymer with a hydroxyl group-containing monomer; such as (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. (Meta) Acry Copolymer of acid ester; copolymer of (meth) acrylic acid and styrene; copolymer of (meth) acrylic acid, styrene and α-methylstyrene; copolymer of (meth) acrylic acid and cyclohexylmaleimide A polymer etc. are mentioned.

From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
The acid value of the linear alkali-soluble resin containing a carboxyl group in the main chain in the present invention is usually 30 to 500 mgKOH / g, preferably 40 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g.

  Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. By setting it as the above lower limit value or more, there is a tendency that the stability of the colored resin composition tends to be favorable, and when it is set to the upper limit value or less, it is used for a developer when used in a color filter or an image display device described later. There is a tendency to suppress the deterioration of solubility.

[1-5-3] Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin described in [1-5-2] The above-described linear alkali-soluble resin containing a carboxyl group in the main chain A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin is also particularly preferable.

The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoints of heat resistance and dispersibility of the pigment described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. In addition, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group. Suitable alicyclic epoxy group-containing unsaturated compounds include the following general formulas (5a) to (5m). The compound which is made is mentioned.

In formulas (5a) to (5m), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group, R ²³ represents a divalent hydrocarbon group, and m is an integer of 1 to 10.
In the general formulas (5a) to (5m), the alkylene group represented by R ²² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable. As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (5c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin described in [1-5-2], a known method can be used. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc. in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000.

[1-5-4] (Meth) acrylic resin As a (meth) acrylic resin, a polymer obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic acid ester as monomer components Say. Preferred (meth) acrylic resins include, for example, a polymer obtained by polymerizing monomer components including (meth) acrylic acid and benzyl (meth) acrylate, and the following general formulas (6) and / or (7). A polymer obtained by polymerizing a monomer component essentially comprising the compound represented, and a polymer obtained by polymerizing the monomer component essentially comprising the compound represented by the general formulas (5a) to (5l) Can be mentioned.

In formula (6), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (7), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (8). Or an adamantyl group which may be substituted. L ³ may be bonded to R ^3b or R ^4b in the following formula (8) to form a ring.

In formula (8), R ^2b , R ^3b and R ^4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² are each independently a direct bond or 2 Represents a valent linking group, and L ¹ , L ² and two or more of L ³ in the above formula (7) may be bonded to each other to form a ring.

[1-5-4a] A polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate. A monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is polymerized. The polymer is preferably used in that it has a high affinity with the pigment.

  The ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component is not particularly limited, but (meth) acrylic acid in the total monomer component is usually 10 to 90% by mass, preferably 15%. It is -80 mass%, More preferably, it is 20-70 mass%. Moreover, benzyl (meth) acrylate is 5-90 mass% normally in all the monomer components, Preferably it is 15-80 mass%, More preferably, it is 20-70 mass%. By making the amount of (meth) acrylic acid not more than the above upper limit value, there is a tendency to easily suppress the roughness of the coating film surface during development, and by making the amount not less than the above lower limit value, good developability is obtained. It tends to be easy. Moreover, it exists in the tendency which makes a dispersibility favorable by making the quantity of benzyl (meth) acrylate into the said range.

[1-5-4b] A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (6) and / or (7). First, the compound of the general formula (6) will be described.
In the ether dimer represented by the general formula (6), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  Although the ratio of the ether dimer in the monomer component when obtaining the acrylic resin is not particularly limited, it is generally 2 to 60% by mass, preferably 5 to 55% by mass in the total monomer component, Preferably it is 5-50 mass%. When the amount is not more than the upper limit value, it tends to be difficult to obtain a low molecular weight product during polymerization, or it is easy to suppress gelation, and on the other hand, to be equal to or more than the lower limit value. It tends to make the film performance such as transparency and heat resistance sufficient.

Then, the compound of General formula (7) is demonstrated.
In General Formula (7), R ^1b preferably represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.
In the general formula (8), the organic groups represented by R ^2b , R ^3b and R ^4b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group. Group, carboxyl group, acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cyclohexane having 3 to 18 carbon atoms. An alkenyl group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, Preferably, it is a C1-C10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^2b , R ^3b and R ^4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are divalent linking groups, L ³ is not particularly limited as long as it is a divalent linking group or a direct bond, but at least either L ¹ or L ² is a linking group having 1 or more carbon atoms. Is preferred. L ¹ , L ² , and L ³ are each independently a direct bond, alkylene having 1 to 15 carbons, —O—, —S—, —C (═O) —, or alkenylene having 1 to 15 carbons. , Phenylene, or combinations thereof are preferred.

As a preferable combination of L ¹ , L ² and L ³ , L ³ is a direct bond, alkylene having 1 to 5 carbon atoms, or a ring formed by combining with R ^3b or R ^4b, and L ¹ and L ² are Each independently represents a direct bond or alkylene having 1 to 5 carbon atoms.
Moreover, as a preferable thing of General formula (8), the compound represented by following General formula (9) can be mentioned.

In the formula (9), R ^2b , R ^3b , R ^4b , L ¹ and L ² have the same meaning as in the formula (8), and R ^5b and R ^6b are each independently a hydrogen atom, a hydroxyl group or a halogen atom. Represents an amino group or an organic group.
In general formula (9), the organic groups represented by R ^5b and R ^6b are each independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, Or an acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and a carbon number An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, or an acyloxy group having 1 to 15 carbon atoms, and more preferably a carbon number. It is a 1-10 alkyl group or a C3-C15 cycloalkyl group.

Preferred substituents among R ^5b and R ^6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
In addition, the alkyl group of R ^1b , each organic group of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ , and the adamantyl group of X are each independently a substituent. Specific examples thereof may include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-heptyl group, n-octyl group and t-octyl group; carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group A cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyl A linear or branched alkoxy group having 1 to 18 carbon atoms such as a xyl group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, Ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, a linear or branched alkylthio group having 1 to 18 carbon atoms such as t-octylthio group; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group and mesityl group; carbon such as benzyl group and phenethyl group Aralkyl group having 7 to 18 carbon atoms; straight chain or branched chain having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group Alkenyloxy group; represented by -OCOR ^18; carboxyl group; an acyl group represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group An acyloxy group represented by —NR ¹⁹ R ²⁰ ; an acylamino group represented by —NHCOR ²¹ ; a carbamate group represented by —NHCOOR ²² ; a carbamoyl group represented by —CONR ²³ R ²⁴ ; Carboxylic acid ester group represented by ²⁵ ; sulfamoyl group represented by —SO ₃ NR ²⁶ R ²⁷ ; sulfonic acid ester group represented by —SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridyl group, furyl group , Oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide A saturated or unsaturated heterocyclic group such as a side group; a trialkylsilyl group such as a trimethylsilyl group;

R ^{17 to} R ²⁸ are each a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or The aralkyl group which may have a substituent is shown.
Moreover, the positional relationship of the said substituent is not specifically limited, When it has a some substituent, it may be same or different.

  Specific examples of the compound represented by the general formula (7) include the following.

  In the monomer component constituting the [1-5-4b] polymer according to the present invention, the ratio of the general formula (7) is not particularly limited, but is usually 0.5 to 60 mass in the total monomer components. %, Preferably 1 to 55% by mass, more preferably 5 to 50% by mass. When it is used as a dispersant by setting it to the upper limit or less, there is a tendency to easily suppress a decrease in dispersion stability of the dispersion. On the other hand, by setting it to the upper limit or more, a decrease in soiling suitability is suppressed. It tends to be easy.

  The (meth) acrylic resin of [1-5-4] in the present invention preferably has an acid group, including the polymers described in [1-5-4a] and [1-5-4b]. . By having an acid group, the resulting colored resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter abbreviated as acid-epoxy curing). Or a composition in which an uncured part can be visualized with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce an acid group into the (meth) acrylic resin, for example, a monomer having an acid group and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter, “monomer for introducing an acid group”) May be used as a monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

These monomers for introducing an acid group may be only one type or two or more types.
When the monomer component for obtaining the (meth) acrylic resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but usually 5% of all the monomer components. -70 mass%, Preferably it is 10-60 mass%.

[1-5-4] (Meth) acrylic resin may have a radical polymerizable double bond.
In order to introduce a radical polymerizable double bond into the (meth) acrylic resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “for introducing a radical polymerizable double bond”). May be referred to as a “monomer”.) Is polymerized as a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

In the case where the monomer component for obtaining the (meth) acrylic resin of [1-5-4] also contains a monomer for introducing the radical polymerizable double bond, the content ratio is particularly limited. However, it is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on all monomer components.
When the (meth) acrylic resin of the present invention is a polymer having the compound of the general formula (6) as an essential monomer component described in the section [1-5-4a], it has an epoxy group. It is preferable.

In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

When the monomer component for obtaining the (meth) acrylic resin of [1-5-4] also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but usually Is 5 to 70% by mass, preferably 10 to 60% by mass, based on all monomer components.
The monomer component for obtaining the (meth) acrylic resin of [1-5-4] contains, in addition to the essential monomer component, other copolymerizable monomers as necessary. May be.

  Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
In particular, when a part or all of the (meth) acrylic resin is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. It is good that it is 1 to 70% by mass, preferably 5 to 60% by mass.

When the monomer component for obtaining the (meth) acrylic resin also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by mass or less, and 85% by mass or less. Is more preferable.
Next, the production method (polymerization method) of [1-5-4] (meth) acrylic resin will be described.

  There is no particular limitation on the method for polymerizing the monomer component, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and polymerization concentration (polymerization concentration = [total mass of monomer components / (total mass of monomer components + solvent mass)] × 100) are the types and ratios of the monomer components used. , Depending on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. The polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

  Moreover, what is necessary is just to use the solvent used by normal radical polymerization reaction when using a solvent at the time of superposition | polymerization. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; Dimethyl sulfoxide and the like Is mentioned. These solvents may be used alone or in combination of two or more.

  When the monomer component is polymerized, a polymerization initiator may be used as necessary. Although there is no restriction | limiting in particular in a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) and the like. These polymerization initiators may be used alone or in combination of two or more.

The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. It is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to the total monomer components in that several thousand to several tens of thousands of polymers can be obtained.
Moreover, you may add a chain transfer agent for molecular weight adjustment. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all monomer components.

In addition, when the compound of the general formula (6) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction. The conversion rate is not necessarily 100 mol%.
When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting the acid group described above as the monomer component, it is necessary to perform a treatment for imparting the acid group after polymerization. . The treatment varies depending on the type of monomer used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride An acid anhydride such as a product may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or first ( An acid such as meth) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the (meth) acrylic resin of [1-5-4] is obtained, a radical polymerizable double bond is formed by using the monomer capable of imparting the radical polymerizable double bond described above as a monomer component. When introducing, it is necessary to perform a treatment for imparting a radically polymerizable double bond after polymerization.
The treatment varies depending on the type of monomer used. For example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond such as (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, ) A compound having an acid group such as acrylic acid and a radical polymerizable double bond may be added.

  The weight average molecular weight of the [1-5-4] (meth) acrylic resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. It is. By setting it as the said upper limit or less, there exists a tendency which becomes easy to suppress that it becomes high viscosity and it becomes difficult to form a coating film, and there exists a tendency for sufficient heat resistance to be easy to express by setting it as the said lower limit or more.

When the said (meth) acrylic-type resin has an acid group, a preferable acid value is 30-500 mgKOH / g, More preferably, it is 50-400 mgKOH / g. When the amount is not less than the lower limit value, the alkali developability tends to be favorable, and when the amount is not more than the upper limit value, it tends to be suppressed that the viscosity becomes too high to form a coating film.
Among the (meth) acrylic resin components, the polymer having the compound represented by the general formula (6) as an essential monomer component is a compound known per se, for example, JP-A-2004-300203. And the compounds described in JP-A-2004-300204.

[1-5-5] Epoxy acrylate resin having carboxyl group Epoxy acrylate resin is an α, β-unsaturated monocarboxylic acid in an epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester moiety. It is synthesized by addition and further reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin is a raw material, and “acrylate” is a representative example. It is named like this according to common usage.

  As an epoxy resin used as a raw material, for example, a bisphenol A type epoxy resin (for example, “Epicoat (registered trademark, the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004”, etc., manufactured by Mitsubishi Chemical Corporation) , Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin ( For example, “Epicoat 807”, “EP-4001”, “EP-4002”, “EP-4004 etc.” manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (For example, “NER- manufactured by Nippon Kayaku Co., Ltd. 406 "(epoxy equivalent 350, softening point 66 ° C)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku Co., Ltd.) "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m, p-) cresol novolac type epoxy resin (For example, “EOCN (registered trademark, the same shall apply hereinafter) -102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC manufactured by Nissan Chemical Co., Ltd.) (Registered trademark) "), trisphenol methane type epoxy resin (for example," EPPN (registered trademark)-"manufactured by Nippon Kayaku Co., Ltd.) 01 ”,“ EPN-502 ”,“ EPPN-503 ”), fluorene epoxy resin (for example, cardo epoxy resin“ ESF-300 ”manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (manufactured by Daicel Chemical Industries, Ltd.) "Celoxide (registered trademark, the same shall apply hereinafter) 2021P", "Celoxide EHPE"), a dicyclopentadiene type epoxy resin obtained by glycidylation of a phenol resin by the reaction of dicyclopentadiene and phenol (for example, "manufactured by Nippon Kayaku Co., Ltd." XD-1000 "," EXA-7200 "manufactured by Dainippon Ink," NC-3000 "," NC-7300 "manufactured by Nippon Kayaku Co., Ltd.), and an epoxy resin represented by the following structural formula 355450) and the like can be preferably used.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymer type epoxy resin. Examples of the copolymerization type epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “first component of copolymerization type epoxy resin”) and one other than these. Functional ethylenically unsaturated group-containing compound (hereinafter referred to as “second component of copolymerization type epoxy resin”), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (10 Compound represented by Al one or more selected, reacting the city include a copolymer obtained by.

In formula (10), R ⁶¹ represents a hydrogen atom or a methyl group, R ⁶² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10. Examples of the compound of the general formula (10) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; methoxydiethylene glycol mono ( Examples thereof include alkoxy polyethylene glycol (meth) acrylates such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

As for the molecular weight of the said copolymerization type epoxy resin, about 1000-200000 is preferable. Further, the amount of the first component of the copolymerization type epoxy resin used is preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 70%, based on the second component of the copolymerization type epoxy resin. It is at most 50% by mass, particularly preferably at most 50% by mass.
As such a copolymerization type epoxy resin, specifically, “CP-15”, “CP-30”, “CP-50”, “CP-20SA”, “CP-510SA” manufactured by NOF Corporation, “CP-50S”, “CP-50M”, “CP-20MA” and the like are exemplified.

  The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, as the weight average molecular weight in terms of polystyrene measured by GPC. When the amount is not less than the above lower limit value, the film formability tends to be good, and when it is not more than the above upper limit value, gelation hardly occurs during the addition reaction of α, β-unsaturated monocarboxylic acid. It tends to be easy to manufacture.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid and the like, preferably acrylic acid and methacrylic acid, and particularly acrylic acid is highly reactive. Therefore, it is preferable.
The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

  The addition reaction of an α, β-unsaturated monocarboxylic acid or ester thereof with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

  The amount of α, β-unsaturated monocarboxylic acid or ester thereof used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, relative to 1 equivalent of the epoxy group of the raw material epoxy resin. Equivalent range. By setting it to the lower limit value or more, insufficient introduction of unsaturated groups can be easily suppressed, and the subsequent reaction with polybasic acid anhydride tends to be sufficient. In addition, the remaining of a large amount of epoxy groups can be reduced. On the other hand, there exists a tendency which can suppress that (alpha), (beta)-unsaturated monocarboxylic acid or its ester remains as an unreacted substance by setting it as the said upper limit or less.

  The polybasic acid anhydride to be further added to the epoxy resin to which the α, β-unsaturated carboxylic acid or ester thereof is added includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetra Carboxylic dianhydride, etc. are mentioned, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride Particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or ester thereof.
The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, more preferably in the range of 20 to 140 mgKOH / g. There exists a tendency for alkali developability to become favorable by setting it as the said lower limit or more, and the tendency to make it easy to make it harden | cure performance by setting it as the said upper limit or less is recognized.

  In addition, as an epoxy acrylate resin having a carboxyl group, for example, a naphthalene-containing resin described in JP-A-6-49174; JP-A-2003-89716, JP-A-2003-165830, JP-A-2005-325331, Examples include fluorene-containing resins described in JP-A No. 2001-354735; resins described in JP-A Nos. 2005-126684, 2005-55814, and 2004-295084.

Moreover, the commercially available epoxy acrylate resin which has a carboxyl group can also be used, and "ACA-200M" by Daicel Corporation etc. can be mentioned as a commercial item, for example.
As the binder resin, for example, an acrylic binder described in JP-A-2005-154708 can also be used.
Of the various binder resins described above, particularly preferred is a copolymer of [1-5-1] “epoxy group-containing (meth) acrylate and other radical polymerizable monomer. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the coal, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction " It is.

As binder resin in this invention, 1 type may be used independently among the above-mentioned various binder resins, and 2 or more types may be used together.
The above-mentioned various binder resins contribute to the dispersion stability due to the synergistic effect particularly in combination with the above-mentioned dispersant and the like, and as a result, the amount of the dispersant added can be reduced, so that the developability is improved. Specifically, for example, it is preferable because an effect of being able to form a high-density color pixel having excellent adhesion to the substrate without remaining undissolved material in the non-image portion on the substrate is preferable.

Specifically, a part of the binder resin is used in the dispersion treatment step described later together with the above-described dispersant and dispersion aid. At this time, the binder resin is preferably used in an amount of about 5 to 200% by mass, more preferably about 10 to 100% by mass, based on the total amount of pigment in the pigment dispersion.
As described above, as the binder resin used in the dispersion treatment step, the various resins described above can be used, and the (meth) acrylic resin of [1-5-4] is particularly preferable. A polymer obtained by polymerizing a monomer component essentially comprising the compound represented by (6) is most preferable.

  When used in the dispersion treatment step together with a dispersant, the acid value of the binder resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, 500 mgKOH / g or less is preferable, 300 mgKOH / g or less is more preferable, 200 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is particularly preferable. By setting it to the upper limit or less, there is a tendency that it is easy to prevent the composition from becoming highly viscous and difficult to be synthesized, and by setting it to the upper limit or more, it tends to be easily applied to alkali development.

  Moreover, when using it for a dispersion | distribution process with a dispersing agent, 1000 or more are preferable, as for the weight average molecular weight of polystyrene conversion measured by GPC of the binder resin, 3000 or more are more preferable, 5000 or more are further more preferable, and 7000 or more are Particularly preferable, 200,000 or less is preferable, 50000 or less is more preferable, 30000 or less is more preferable, 20000 or less is further more preferable, and 15000 or less is particularly preferable. By setting it to the upper limit value or less, there is a tendency to be easily applied to alkali development, and by setting the upper limit value or more, there is a tendency to suppress a decrease in dispersion stability.

  In the colored resin composition of the present invention, the content ratio of the binder resin in the total solid content is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass. Above, particularly preferably 25% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, particularly preferably 30% by mass or less. It is. By setting it to the lower limit value or more, a strong film can be obtained and the adhesion to the substrate tends to be excellent. Moreover, by setting it as the said upper limit or less, there exists a tendency for the permeability of the developing solution to an exposure part to be low, and to suppress the deterioration of the surface smoothness and sensitivity of a pixel.

[1-6] (E) Photopolymerization initiator The colored resin composition of the present invention contains (E) a photopolymerization initiator. (E) By containing a photopolymerization initiator, film curability by photopolymerization can be obtained.
(E) The photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, radical activators such as N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone compounds and oxime ester initiators described in JP-A No. 2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,1,1 An acetophenone derivative such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentaenyl-Ti-bis-2,4,6-trifluorophen-1-yl, Dicyclopentagenyl-Ti-2,6-diplorophen-1-yl, dicyclopentagenenyl-Ti-2,4-difluorophen-1-yl, dimethylcyclopentaenyl-Ti-bis-2,3 , 4,5,6-pentafluorophen-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentaje Le -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (O-acetyloxime).

Among these, an oxime ester compound is preferable from the viewpoint of sensitivity and surface properties.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in small amounts and stable against thermal reactions. Therefore, it is possible to design a photosensitive resin composition with high sensitivity in a small amount. In particular, an oxime ester-based compound having a carbazole ring which may have a substituent is preferable from the viewpoint of light absorption with respect to i-line (365 nm) of an exposure light source.

  As an oxime ester type compound, the compound represented by the following general formula (I-1) is mentioned, for example.

In the formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R ^22a represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, more preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Group or N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Examples of the aromatic ring group for R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxyl group, a halogen atom, and an amino group. , An amide group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group and a halogen atom.
Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .

R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoints of solubility in a solvent and sensitivity to exposure, R ^21b has an optionally substituted carbazolyl group or substituent. Preferred examples include a thioxanthonyl group which may be substituted or a diphenyl sulfide group which may have a substituent, and a group obtained by linking these groups and a carbonyl group. Among these, from the viewpoint of light absorption with respect to i-line (365 nm) of the exposure light source, a carbazolyl group which may have a substituent, or a carbazolyl group which may have a substituent and a carbonyl group are linked. Groups are preferred.

The number of carbon atoms of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent or sensitivity. 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.

The number of carbon atoms of the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted. .

  Among the compounds represented by the general formula (I-1), the compound is represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption with respect to i-line (365 nm) of the exposure light source. Compounds.

In said formula (I-2) or (I-3), R ^<21a> and R ^<22a> are synonymous with the said general formula (I-1).
R ^23a represents an alkyl group which may have a substituent.
R ^24a represents an alkyl group that may have a substituent, an aryloyl group that may have a substituent, a heteroaryloyl group that may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms of the alkyl group in R ^23a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent. Preferably it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of ease of synthesis, there is no substitution. It is preferable that

The carbon number of the aryloyl group in R ^23a is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. Preferably it is 10 or less, More preferably, it is 9 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of ease of synthesis, an ethyl group It is preferable that

The carbon number of the heteroaryloyl group in R ^23a is not particularly limited, but is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. More preferably, it is 10 or less, More preferably, it is 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
Examples of the substituent that the heteroaryloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. Substitution is preferred.
Among these, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoint of solubility in a solvent and ease of synthesis.

  The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

  As commercially available products of such oxime ester compounds, OXE-02, OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Power Electronics, or N-1919 manufactured by ADEKA, NCI-930, NCI-831, etc.

  Specific examples of the oxime ester-based compound include compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.

  Moreover, the chain transfer agent mentioned later is used as an accelerator constituting the photopolymerization initiation system component.

  These photopolymerization initiators and accelerators may be used alone or in combination of two or more.

The blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably, in the total solid content of the colored resin composition of the present invention. Is 1.5% by mass or more, more preferably 2% by mass or more, particularly preferably 2.5% by mass or more, most preferably 3% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less. There is a tendency that the sensitivity to the exposure light beam can be sufficiently secured by setting it to the lower limit value or more, and suppressing the decrease in solubility in the developing solution of the unexposed portion by preventing the development failure by setting the upper limit value or less. There is a tendency to be able to.
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiation system component for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335. 3-ketocoumarin compounds described in JP-A-3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54- No. 155292, Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Publication No. 52-112682, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088, Japanese Unexamined Patent Publication No. 5-107761, Japanese Unexamined Patent Publication No. 5-210240. Distribution, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred.

A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.
The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% in the total solid content of the colored resin composition. It is in the range of not less than mass%, usually not more than 20 mass%, preferably not more than 15 mass%, more preferably not more than 10 mass%.

[1-7] (F) Chain transfer agent The colored resin composition of the present invention further contains (F) a chain transfer agent. (F) The chain transfer agent is a compound having a function of receiving a generated radical and transferring the radical to another compound.
As the (F) chain transfer agent, various compounds can be used as long as they have the above functions. For example, mercapto group-containing compounds, carbon tetrachloride and the like can be mentioned, and the chain transfer effect tends to be high. For this reason, it is more preferable to use a compound having a mercapto group. This is probably because bond cleavage is likely to occur due to the small S—H bond energy, and hydrogen pulling reaction and chain transfer reaction are likely to occur. Effective for improving sensitivity and surface curability.

  Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β- Mercapto group-containing compounds having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyl Lutristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate) Rate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and other aliphatic mercapto group-containing compounds can be mentioned, and in particular, from the viewpoint of surface smoothness, mercapto groups can be used. A compound having a plurality is preferred.

  Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trion is Masui.

In terms of sensitivity, an aliphatic mercapto group-containing compound is preferable, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol. Tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5- Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3 Mercaptobutylate) is more preferable.
Various types of these can be used alone or in combination of two or more.

  Among these, it is preferable to contain the compound represented by the following general formula (i) from the viewpoint that the chain transfer reaction is likely to occur and the surface smoothness is easily improved.

In said formula (i), p represents the integer of 2-4.
R ^a1 represents a hydrogen atom or an alkyl group which may have a substituent.
X represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent heterocyclic group or a 2-4 valent aromatic ring group.
In addition, a plurality of structures represented by the following general formula (i ′) contained in one molecule

May be the same or different.

(About R ^a1 )
R ^a1 represents a hydrogen atom or an alkyl group which may have a substituent.
The alkyl group usually has 1 to 8 carbon atoms, and is preferably 1 or 2 from the viewpoint of high sensitivity.
R ^a1 is preferably a hydrogen atom in that the reactivity of the compound is high and the surface curability of the resulting film is high.
Examples of the substituent that the alkyl group in R ^a1 may have include those described in the following (Substituent Group W1) section.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms A carboxyl group, a sulfonic acid amide group, a sulfone alkylamide group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.

(About X)
In formula (i), X represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent heterocyclic group or a 2-4 valent aromatic ring group.
The case where X is a secondary to quaternary carbon atom means that X has any one of the following structures.

Examples of the aromatic ring group for X include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and is not particularly limited as long as it has 5 to 18 carbon atoms to form the ring. Examples thereof include groups having a valence such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
In addition, the aromatic heterocyclic group may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10. For example, a furan ring, a benzofuran ring, Thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, fluropyrrole ring, furofuran Ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring , Benzimidazole ring, perimidi Ring, quinazoline ring, a quinazolinone ring, and azulene ring.

On the other hand, the heterocyclic group (that is, non-aromatic heterocyclic group) may be a single ring or a condensed ring.
The heterocyclic group is a non-aromatic ring containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom.
When the heterocyclic group has a plurality of heteroatoms constituting the ring, these may be the same or different.
Specific examples include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimidoyl group, a piperidinyl group, and a pyrrolidinyl group.
X is preferably a 2 to quaternary carbon atom, and particularly preferably a quaternary carbon atom, from the viewpoint of good storage stability of the compound (i).
Note that the carbon atom, heterocyclic group and aromatic ring group in X have a substituent represented by other than the following structural formula (i ′) (hereinafter sometimes referred to as “sulfanyl group-containing structure”). Examples of the substituent include those described in the above section (Substituent group W1).

(About p)
p represents an integer of 2 to 4.
In the compound (i), it is particularly preferable that p is 4 in that the sulfanyl group which is a reactive site is increased, the reactivity of the compound is increased, and the resulting pixel has sufficient curability.

Although the specific example of compound (i) is shown below, it is not limited to these.
Compounds having two sulfanyl group-containing structures: ethylene glycol bis (3-mercaptopropionate), etc.
Compounds having three sulfanyl group-containing structures: trimethylolpropane tris (3-mercaptopropionate), etc.
Examples include compounds having four sulfanyl group-containing structures: pentaerythritol tetrakis (3-mercaptopropionate) and the like.
Among the above, pentaerythritol tetrakis (3-mercaptopropionate) is particularly preferable from the viewpoint of sensitivity.

  In the colored resin composition of the present invention, the content ratio of the (F) chain transfer agent is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass with respect to the total solid content. Or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, particularly preferably 0.4% by mass or more, most preferably 0.5% by mass or more, and preferably 10% by mass. It is at most 5% by mass, more preferably at most 5% by mass, further preferably at most 3% by mass, particularly preferably at most 1% by mass. When the amount is not less than the lower limit, the surface roughness tends to be improved, and when the amount is not more than the upper limit, the storage stability tends to be improved.

[1-8] Other solid content The colored resin composition of the present invention may further contain a solid content other than the above components as necessary. Such components include photopolymerizable monomers, organic carboxylic acids, organic carboxylic acid anhydrides, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protectants, adhesion improvers, development improvers, And dyes.

[1-8-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “polymerizable monomer”) (Referred to as “ethylenic compound”). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. . In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds of the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less. Yes, more preferably 7 or less. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit or less.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. There is a tendency that the development and dissolution characteristics can be made favorable by setting it to the lower limit value or more, and the production and handling become good by making the upper limit value or less the photopolymerization performance, the surface smoothness of the pixel, etc. There is a tendency to improve the curability. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer. Also, those described in paragraphs [0056] and [0057] of JP2013-140346A can be used.

  Moreover, in this invention, it is preferable to use the polymerizable monomer of Unexamined-Japanese-Patent No. 2013-195971 from a viewpoint of making the chemical resistance of a pixel and the linearity of the edge of a pixel favorable. From the viewpoint of achieving both sensitivity of the coating film and shortening of the development time, it is preferable to use a polymerizable monomer described in JP2013-195974A.

  The content of these photopolymerizable monomers is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass in the total solid content of the colored resin composition of the present invention. % Or more, particularly preferably 20% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less. is there. The ratio of (A) to 100 parts by mass of the pigment is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and still more preferably 40 parts by mass or more. The amount is particularly preferably 60 parts by mass or more, usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.

[1-8-2] Organic carboxylic acid, organic carboxylic acid anhydride The colored resin composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

The addition amount of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more in the total solid content. Yes, 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less.
By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved matter of the colored resin composition while maintaining high pattern adhesion. .

[1-8-3] Surfactant A variety of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, which may adversely affect various properties. It is preferable to use a nonionic surfactant from the viewpoint of low. The content ratio of the surfactant is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0%, based on the total solid content of the colored resin composition. The range of 1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.3% by mass or less is used.

[1-8-4] Thermal polymerization inhibitor As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. . The blending amount of the thermal polymerization inhibitor is preferably in the range of 3% by mass or less based on the total solid content of the composition.

[1-8-5] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. Is used. The blending amount of these plasticizers is preferably in the range of usually 10% by mass or less with respect to the total solid content of the composition.

[2] Preparation of Colored Resin Composition Next, a method for preparing the colored resin composition according to the present invention (hereinafter sometimes referred to as a resist) will be described.

  First, a predetermined amount of each of the pigment, the solvent and the dispersant is weighed, and in the dispersion treatment step, a pigment containing zinc halide phthalocyanine pigment is dispersed to prepare a pigment dispersion. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, the coloring material is made fine particles, so that the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

When dispersing the pigment, as described above, it is preferable to use a dispersion aid or a dispersion resin in combination as appropriate.
In addition, it is essential that the pigment contains a pigment containing the above-described zinc halide phthalocyanine pigment, but the pigment may be mixed and dispersed with other pigments for toning.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted appropriately.

  The pigment dispersion obtained by the above dispersion treatment is mixed with a solvent, a binder resin, a photopolymerization initiator, a chain transfer agent, and in some cases, a predetermined amount of a photopolymerizable monomer and components other than those described above, and uniform. Disperse solution. In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, the obtained pigment dispersion is preferably filtered with a filter or the like.

[3] Production of Color Filter Substrate Next, the color filter according to the present invention will be described.
The color filter which concerns on this invention has a pixel formed using the above-mentioned colored resin composition.
[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass or heat resistant resin is preferable from the viewpoint of heat resistance.

  For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

[3-2] Black Matrix A color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green, and blue normally. The colored resin composition is preferably used as a coating solution for forming a green pixel (resist pattern) among red, green and blue pixels (hereinafter sometimes abbreviated as “green resist”). Using the green resist, on a resin black matrix forming surface formed on a transparent substrate, or on a metal black matrix forming surface formed using a chromium compound or other light shielding metal material, coating, heat drying, image exposure, Each process of development and thermosetting is performed to form a pixel image.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a colored resin composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repeated pattern such as stripes, mosaics, and triangles to form a resist image. Thereafter, this coating film can be etched to form a black matrix.

  When using the photosensitive coloring resin composition for black matrix, a black matrix is formed using the coloring resin composition containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a colored resin composition containing a black color material by mixing.

[3-3] Formation of Pixels The pixel formation method varies depending on the type of the colored resin composition to be used. Here, a case where a photopolymerizable composition is used as the colored resin composition will be described as an example.
On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film, and image exposure is performed through this photomask. A pixel image is formed by development and, if necessary, thermal curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The color resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating solution used is greatly reduced, there is no influence of mist adhering when using the spin coating method, and the generation of foreign matter is further suppressed. It is preferable from a viewpoint.

  If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

[3-4] Drying of Coating Film The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

  The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-6] Development Step The color filter according to the present invention is an organic solvent or surfactant after image exposure with the above-mentioned light source to the coating film using the colored resin composition according to the present invention. By carrying out development using an aqueous solution containing an alkaline compound and an alkaline compound, an image can be formed on a substrate for production. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, further 40 ° C. or lower. Is preferred. The development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.

[3-7] Thermosetting treatment The color filter after development is subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and the time is 5 minutes or more and 60 minutes or less. Selected by range. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

  In addition to the manufacturing method described above, the color filter according to the present invention includes (1) a curable coloring resin composition containing a solvent, a halogenated zinc phthalocyanine pigment as a coloring material, and a polyimide resin as a binder resin. It can also be manufactured by a method of applying a substrate and forming a pixel image by an etching method. In addition, (2) a method of forming a pixel image directly on a transparent substrate using a colored resin composition containing a halogenated zinc phthalocyanine pigment as a colored ink, and (3) a color containing a halogenated zinc phthalocyanine pigment. Examples thereof include a method of using a resin composition as an electrodeposition solution and depositing a colored film on an ITO electrode having a predetermined pattern by dipping the substrate in the electrodeposition solution. Further, (4) a method in which a film coated with a colored resin composition containing a zinc halide phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development to form a pixel image, and (5) zinc halide. Examples thereof include a method of forming a pixel image with an ink jet printer using a colored resin composition containing a phthalocyanine pigment as a colored ink. As a method for producing the color filter, a method suitable for the color resin composition is adopted depending on the composition of the colored resin composition.

[3-8] Formation of Transparent Electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of a component such as a color display or a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[4] Image display device (panel)
Next, the image display apparatus of the present invention will be described. The image display device of the present invention has the color filter described above. Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as the image display device.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

[4-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a pixel 20 is formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 therebetween.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by mass”.

<Green pigment>
In Examples and Comparative Examples, green pigments A and B described in Table 1 were used.
In addition, the average number of chlorine atoms and the average number of bromine atoms in the table are values measured by a fluorescent X-ray fundamental parameter method (FP method), and the number of chlorine atoms in 16 substitution sites of one molecule of zinc phthalocyanine, The average number of bromine atoms. In addition, since chlorinated brominated zinc phthalocyanine is obtained by substituting all or a part of 16 hydrogen atoms of one molecule of zinc phthalocyanine with chlorine atoms or bromine atoms, the average of 16 from the number of hydrogen atoms. The average number of hydrogen atoms was calculated by subtracting the sum of the number of chlorine atoms and the average number of bromine atoms. Moreover, the average number of chlorine atoms and the average number of bromine atoms were calculated as relative values per zinc atom from the mass ratio of zinc atom, chlorine atom and bromine atom measured by the FP method. The fluorescent X-ray evaluation apparatus used was RIX-3000 manufactured by Rigaku Denki Kogyo Co., Ltd., the X-ray tube was used at Rh 50 kV / 50 mA, and measurement was performed in a measurement diameter of 30 mmφ in a vacuum atmosphere. The amount of the measurement sample was 2 g and used after being pressure-molded (30 mmφ, 200 kN). Further, the average number of chlorine atoms and the average number of bromine atoms in one molecule were the average values in the entire measurement sample. Table 2 shows other detailed conditions set on the RIX-3000 screen. The green pigment B is C.I. I. Pigment Green 58.

<Yellow pigment>
Nickel azo obtained by inserting a compound represented by the following formula (II-1) into a 1: 1 complex of azobarbituric acid represented by the following formula (II) with nickel or a compatible isomer thereof as a yellow pigment A complex (E4GN-GT, manufactured by LANXESS) was used.

<Yellow dye A>
Orasol (registered trademark) Yellow 081 (BASF)

<Yellow dye B>
Oracle (registered trademark) Yellow GHS (manufactured by BASF)

<Dispersion resin A>
Dispersion resin A was synthesized by the following procedure.
First, a separable flask equipped with a cooling tube as a reaction vessel was prepared, charged with 400 parts by mass of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated in an oil bath with stirring until the temperature of the reaction vessel reached 90 ° C. The temperature rose.

  Meanwhile, 30 parts by mass of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, t-butylperoxy-2-ethyl in the monomer tank Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate in a chain transfer agent tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C.

After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel and left at 110 ° C. For 9 hours.
After cooling to room temperature, a polymer solution having a weight average molecular weight Mw of 8000 and an acid value of 101 mgKOH / g was obtained as dispersion resin A.

<Dispersant A: Dispersant “BYK-LPN6919” manufactured by Big Chemie>
A methacrylic acid AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a B block having solvophilicity. It has repeating units of the following formulas (2b) and (3b) and does not have a repeating unit of the following formula (1b). The amine value is 120 mgKOH / g, and the acid value is 1 mgKOH / g or less.

  The content ratios of the following formulas (2b) and (3b) in all repeating units are 33.3 mol% and 6.7 mol%, respectively.

<Binder resin A>
Binder resin A was synthesized by the following procedure.
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2.2′-azobis-2-methylbutyro A mixture of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, and 67.0 parts by mass of acrylic acid, 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, tetrahydrophthalic anhydride (THPA) and triethylamine were added as shown in the table and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin A thus obtained was about 8,000. The structure of the binder resin A was as shown below (polymer compound containing the following four types of repeating units).

<Photopolymerization initiator A>
Oxime ester-based compound having the following chemical structure (methyl 4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoate)

<Preparation of pigment dispersion>
Fill a stainless steel container with 225 parts by mass of the green pigment, yellow pigment, dispersant A, dispersion resin A, solvent (propylene glycol monomethyl ether acetate) and 0.5 mm diameter zirconia beads listed in Table 3, and use a paint shaker. It was dispersed for 6 hours to prepare a green pigment dispersion A, a green pigment dispersion B, and a yellow pigment dispersion. In addition, the compounding quantity of components other than the "solvent" in a table | surface is a solid content conversion value.

<Preparation of colored resin composition>
(Examples 1 and 2 and Comparative Examples 1 to 3)
Other components shown in Table 4 were mixed with each of the pigment dispersions described above to prepare a colored resin composition.
In Table 4, the amounts of the green pigment dispersion A, the green pigment dispersion B, the yellow pigment dispersion, the resin, and the photopolymerizable monomer are solid amounts. Moreover, the compounding quantity of the solvent 1 and the solvent 2 is a value containing the solvent amount contained in the green pigment dispersion liquid A, the green pigment dispersion liquid B, the yellow pigment dispersion liquid, resin, and a photopolymerizable monomer.

In addition, the meaning of the symbol in Table 4 is as follows.
PE-4A: Light acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.)
IRG907: IRGACURE907 (manufactured by BASF)
PET-P: Pentaerythritol tetra (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.)
F475: Megafuck F475 (manufactured by DIC)
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl 3-ethoxypropionate

<Evaluation of film thickness and coloring power>
Each colored resin composition described above was applied on a 50 mm square, 0.6 mm thick glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then dried at 80 ° C. for 3 minutes. Subsequently, the whole surface exposure process was performed with the exposure amount of 40 mJ / cm < ² > with the 2kW high pressure mercury lamp. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes.

  For the coated substrate thus obtained, the chromaticity (sx, sy) and luminance (LY) when the film thickness was 2.50 μm were calculated from the transmission spectrum measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd. The results are shown in Table 5.

  From Table 5, compared with the comparative examples 2 and 3 using the green pigment B, Examples 1 and 2 using the green pigment A had small sx and large sy. This shows that the color reproduction range is widened.

<Surface roughness evaluation>
Each colored resin composition described above was applied on a 50 mm square, 0.6 mm thick glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then dried at 80 ° C. for 3 minutes. Subsequently, the whole surface exposure process was performed with the exposure amount of 40 mJ / cm < ² > with the 2kW high pressure mercury lamp.
Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes.

  The surface roughness Sa (arithmetic mean roughness, nm) of the coated substrate thus obtained with a film thickness of 2.50 μm is a micromap (manufactured by Ryoka Systems Inc., 3D non-contact surface shape measurement system) ). The measurement was performed in a 70 μm × 70 μm visual field in the Focus mode using a 50 × optical lens. The results are shown in Table 6.

From Table 6, it was confirmed that Comparative Examples 2 and 3 using the green pigment B had low surface roughness Sa and good surface smoothness regardless of the presence or absence and content ratio of the chain transfer agent. On the other hand, the comparative example 1 which uses the green pigment A and does not contain a chain transfer agent has a surface roughness Sa of 7 nm or more, has poor surface smoothness, and has a practical problem.
On the other hand, Examples 1 and 2 using the green pigment A and including a chain transfer agent have a surface roughness Sa of less than 7 nm and good surface smoothness.

  Compared to the green pigment B, the green pigment A has a higher average number of hydrogen atoms, and due to the difference in the light absorption characteristics that accompanies it, the inside of the coating film is not easily photocured. Although smoothness tends to be insufficient, by using a chain transfer agent, the heat flow due to post-baking can be suppressed by curing to the inside of the coating film, and the surface smoothness is improved. It is thought that it was possible.

<Preparation of colored resin composition>
(Examples 3 and 4 and Comparative Example 4)
Other components shown in Table 7 were mixed with each pigment dispersion described above to prepare a colored resin composition.
In Table 7, the blending amounts of the green pigment dispersion A, the yellow dye, the resin, and the photopolymerizable monomer are solid amounts. Moreover, the compounding quantity of the solvent 1 and the solvent 2 is a value containing the solvent amount contained in the green pigment dispersion liquid A, resin, and a photopolymerizable monomer.

  Using each colored resin composition of Examples 3 and 4 and Comparative Example 4, the surface roughness Sa was measured by the method described in <Surface Roughness Evaluation>. The results are shown in Table 8.

From the comparison between Table 6 and Table 8, the same tendency was observed when a yellow dye was used instead of the yellow pigment.
When Example 3 and Comparative Example 4 are compared, Comparative Example 4 containing green pigment A and yellow dye A and not containing a chain transfer agent has a surface roughness Sa of 7 nm or more and surface smoothness. In contrast to being defective and practically problematic, Example 3 containing a chain transfer agent has a surface roughness Sa of less than 7 nm and good surface smoothness. Similarly in Example 4 containing yellow dye B instead of yellow dye A, the surface smoothness was good. From this, it was found that even when the green pigment A and the yellow dye are included, the surface smoothness can be improved by using the chain transfer agent regardless of the kind of the yellow dye.

  From the above, by sharing the zinc halide phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule with a predetermined amount or more and the chain transfer agent, it is possible to achieve both expansion of the color reproduction range and surface properties.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (9)

A colored resin composition comprising (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator,
The (A) pigment contains a halogenated zinc phthalocyanine pigment, the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more, and
Further, (F) a colored resin composition containing a chain transfer agent. The colored resin composition according to claim 1, wherein the (F) chain transfer agent contains a compound represented by the following formula (i).

(In said formula (i), p represents the integer of 2-4.
R ^a1 represents a hydrogen atom or an alkyl group which may have a substituent.
X represents a direct bond, a 2-4 quaternary carbon atom, a 2-4 valent heterocyclic group or a 2-4 valent aromatic ring group.
In addition, a plurality of structures represented by the following general formula (i ′) contained in one molecule

May be the same or different. )   The colored resin composition according to claim 1 or 2, wherein the content ratio of the (F) chain transfer agent is 0.01% by mass or more based on the total solid content.   The colored resin composition according to any one of claims 1 to 3, wherein the (E) photopolymerization initiator contains an oxime ester-based compound.   The colored resin composition according to any one of claims 1 to 4, wherein a content ratio of the (A) pigment is 20% by mass or more based on a total solid content.   The colored resin composition according to claim 1, wherein the (A) pigment further contains a yellow pigment.   The colored resin composition according to any one of claims 1 to 6, wherein the (B) dispersant includes a block copolymer having a functional group containing a nitrogen atom.   The color filter which has a pixel created using the colored resin composition of any one of Claims 1-7.   An image display device comprising the color filter according to claim 8.

Images