JP6007544B2 - Pigment dispersion, colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

Description

  The present invention resides in a pigment dispersion, a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display 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 them, a manufacturing method (pigment dispersion method) using a photosensitive resin in which a pigment is dispersed, which has excellent properties on average from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like, is most widely adopted.
In the pigment dispersion method, for example, a composition in which a pigment is dispersed in a photosensitive resin is applied onto a transparent substrate such as glass, and the formed coating film is exposed by radiation irradiation through a photomask, and an unexposed portion is organic or A pattern is formed by removal by developing with an inorganic developer.

On the other hand, in recent years, the flow of technological innovation is rapid, and color filters are required to have higher transmittance, higher contrast, and higher density (that is, higher color density) in order to reduce power consumption. .
As the color material used in the color filter, pigments are mainly used from the viewpoints of heat resistance and light resistance. In particular, as the pigment, a pigment whose intrinsic transmission spectrum matches the emission spectrum of the backlight phosphor in the visible light wavelength region is preferably used.

  As such a pigment, when forming a green pixel, it is known to use a combination of a halogenated zinc phthalocyanine green pigment and various yellow pigments. For example, in Patent Documents 1 to 3, a brominated zinc phthalocyanine pigment and C. I. It is disclosed to use together with Pigment Yellow 138.

JP 2003-161827 A JP 2006-184427 A JP 2007-291232 A

However, in Patent Documents 1 to 3, when preparing a pigment dispersion, there is a case where the production yield deteriorates due to a large increase in viscosity of the dispersion and the storage stability of the obtained pigment dispersion becomes a problem. there were.
Accordingly, an object of the present invention is to provide a pigment dispersion which has a small increase in viscosity when preparing a pigment dispersion and is excellent in storage stability.

  The present invention also provides a colored resin composition containing the pigment dispersion, a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an organic EL display device. Let it be an issue.

As a result of intensive studies, the present inventors have found that the above problem can be solved by including a specific amount of propylene glycol monomethyl ether when preparing a pigment dispersion, and have reached the present invention.
That is, the gist of the present invention includes (A) a pigment, (B) a solvent, and (D) a dispersant. The (A) pigment is a zinc halide phthalocyanine green pigment and C.I. I. Pigment Yellow 138, and the solvent (B) contains propylene glycol monomethyl ether (hereinafter sometimes referred to as “PGME”) in an amount of 2% by weight to 6% by weight in the total solvent. It exists in a pigment dispersion, a colored resin composition, a color filter, a liquid crystal display device and an organic EL display device.

The present invention can provide a pigment dispersion having a small increase in viscosity when preparing a pigment dispersion and having excellent storage stability.
The present invention also provides a colored resin composition containing the pigment dispersion, a color filter having pixels formed using the colored resin composition, a high-quality liquid crystal display device, and an organic EL display device. Is possible.

It is a cross-sectional schematic diagram which shows an example of the organic EL element containing the color filter of this invention.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Moreover, terms such as “CI Pigment Green” mean a color index (CI).
The pigment dispersion of the present invention contains (A) a pigment, (B) a solvent, and (D) a dispersant. The (A) pigment is a zinc halide phthalocyanine green pigment and C.I. I. Pigment Yellow 138 is contained, and (B) the solvent contains 2% by weight or more and 6% by weight or less of PGME in all the solvents.

The colored resin composition of the present invention contains the pigment dispersion and (C) a binder resin, and preferably contains (E) a polymerizable monomer and (F) a photopolymerization initiating component and / or a thermal polymerization initiating component. In addition, other components may be contained.
First, (A) the pigment will be described in detail.
[(A) Pigment]
The colored resin composition of the present invention comprises (A) a pigment containing a halogenated zinc phthalocyanine green pigment and C.I. I. Pigment Yellow 138 is contained.
The zinc halide phthalocyanine green pigment in the present invention will be described.

Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule. A zinc halide phthalocyanine green pigment in which these hydrogen atoms are substituted with a bromine atom or a chlorine atom is preferably used in the present invention. This is a brominated zinc phthalocyanine green pigment.
Of these, brominated zinc phthalocyanine containing an average of 13 or more bromine atoms in one molecule is preferable because it exhibits extremely high transmittance and is suitable for forming a green pixel of a color filter. Furthermore, brominated zinc phthalocyanine having 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable, and in particular, an average of 14 bromine atoms in one molecule is 14 Brominated zinc phthalocyanine having ˜16 and not containing chlorine atoms in one molecule or having an average of 2 or less is preferred. Particularly preferably, C.I. I. Pigment Green 58.

  Among such halogenated zinc phthalocyanine green pigments, for example, brominated zinc phthalocyanine green pigments 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 brominated zinc phthalocyanine thus obtained may be used singly, but the brominated zinc phthalocyanine having a different bromination rate or chlorination rate and other metals as long as the effect of the present invention is not impaired. It can be used by mixing with brominated phthalocyanine or the like substituted. Changing the chlorination rate and bromination rate, or changing the central metal changes the color tone of the pigment and increases the number of hues that can be reproduced.
Even with the same green pigment, C.I. I. It may be mixed with a halogenated copper phthalocyanine such as CI Pigment Green 36 or 7.

The average primary particle size of the green pigment containing zinc halide phthalocyanine is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and even more preferably 0.025 μm or less. 005 μm or more. The average primary particle size of other pigments is the same as described above.
By setting the average primary particle size to be equal to or less than the above upper limit value, it is difficult to generate foreign matters in the composition, the depolarization is low, and a pixel having sufficient contrast and light transmittance can be formed. By setting it as the above, the colored resin composition which has favorable dispersion stability and ensured sufficient heat resistance and light resistance can be obtained.

The C.I. used in the pigment dispersion of the present invention. I. The average primary particle size of Pigment Yellow 138 is the same as described above.
The average primary particle size of the pigment can be determined by 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). The primary particle diameter is measured from this image, the number average value is calculated according to the following formula, and the average particle diameter is obtained.

  In the case of an organic pigment, the particle diameter of each pigment particle was determined for each of a plurality of pigment particles, usually about 200 to 300, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area. Thereafter, the number average value is calculated according to the following formula, and the average particle diameter is obtained.

  The brominated zinc phthalocyanine green pigment obtained in this way is dry-ground in a grinder such as an attritor, ball mill, vibration mill, vibration ball mill, etc., if necessary, and then pigmented by the solvent salt milling method or solvent boiling method. By doing so, a brominated zinc phthalocyanine green pigment that develops a green color with high transmittance and contrast can be obtained. There is no particular limitation on the pigmentation method, but it is preferable to employ the solvent salt milling method in that pigment growth can be easily suppressed and pigment particles having a large specific surface area can be obtained.

  The solvent salt milling method 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. The kneading machine at this time has, for example, a kneader, a mix muller, or a pulverizing space in which 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 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 particle diameter 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.
In the pigment dispersion of the present invention, the content of the pigment (A) in the total solid content is usually 10% by weight or more, preferably 12% by weight or more, and usually 20% by weight or less, preferably 16% by weight or less. .

In addition, the content of the pigment (A) in the colored resin composition of the present invention is usually 80% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less in the total solid content. It is 0.1% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more.
Within the above range, the film thickness is appropriate with respect to the color density, and it is preferable in terms of easy gap control when forming a liquid crystal cell.

Further, the content of the halogenated zinc phthalocyanine green pigment contained in the pigment dispersion and colored resin composition of the present invention is usually 30% by weight or more, preferably 35% by weight or more, and more preferably 38% in the total pigment. % By weight or more, usually 99.95% by weight or less, preferably 99.92% by weight or less, more preferably 99.9% by weight or less.
Furthermore, C.I. contained in the pigment dispersion and colored resin composition of the present invention. I. The content of Pigment Yellow 138 is usually 1% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% by weight or less in the total pigment.

Within the above range, it is preferable in that the luminance is high and a desired green color tone can be easily obtained.
Further, the pigment dispersion and the colored resin composition of the present invention include the above-mentioned zinc halide phthalocyanine green pigment and C.I. I. In addition to Pigment Yellow 138, other pigments such as a red pigment, an orange pigment, and a purple pigment may be contained. Examples of these pigments include those described in JP-A-2006-343648. .
Also when other pigments are contained, it is preferably within the above range.

[(B) Solvent]
The pigment dispersion and colored resin composition of the present invention contain propylene glycol monomethyl ether.
In the pigment dispersion of the present invention, the content of propylene glycol monomethyl ether in all the solvents is usually 1% by weight or more, preferably 2% by weight or more, and usually 20% by weight or less, preferably 6% by weight or less.

The pigment dispersion of the present invention may contain other solvents in addition to PGME. The other solvent is not particularly limited as long as it dissolves or disperses each component constituting the pigment dispersion and the viscosity becomes appropriate, and examples thereof include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, Glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl 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;

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as 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;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;

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;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

Of the above solvents, glycol alkyl ether acetates are preferred because the dispersibility of the pigment in the present invention in the solvent (B) is good. Furthermore, propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
The content of the solvent (B) in the pigment dispersion of the present invention is usually 70% by weight or more, preferably 75% by weight or more, and usually 90% by weight or less, preferably 85% by weight or less.
Further, the content of the solvent (B) in the colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is usually 65% by weight or more, preferably 70% by weight or more, and more preferably. It is 75% by weight or more and usually 99% by weight or less.
It is preferable that it is in the above-mentioned range since it has a viscosity suitable for application and can form a coating film satisfactorily.

<Reason for the effect>
By setting it as the structure of this invention, the viscosity increase at the time of preparing a pigment dispersion liquid is suppressed, and the reason why it is excellent in the storage stability of a viscosity is estimated as follows.
The pigment in the pigment dispersion is present in the solution without aggregating because the attractive force between the pigments is canceled by components such as a dispersant and a dispersion resin.
The dispersant has the largest role in canceling the attractive force between the pigments. When preparing the pigment dispersion, it is important that the dispersant is efficiently adsorbed on the pigment.
Here, when PGME which is a highly polar solvent is included, the adsorption site of the dispersant, for example, the primary to tertiary amino groups in the acrylic block copolymer are more easily adsorbed on the pigment surface. Become.

Thereby, the adsorption efficiency of a pigment and a dispersing agent improves, and the pigment which aggregates reduces.
On the other hand, if the adsorption activity of the dispersant is high, desorption and re-adsorption are likely to occur frequently, resulting in a decrease in the average adsorption amount of the dispersant. When the average amount of adsorption decreases, when stored for a long period of time, the aggregation of the pigment gradually increases, and the viscosity of the composition tends to increase.
As described above, by adjusting the content of PGME to an appropriate amount, the viscosity stability is excellent both in the preparation of the pigment dispersion and in storage stability.

[(D) Dispersant]
As the (D) dispersant in the present invention, any known dispersant can be used regardless of the type as long as the (A) pigment can be dispersed and kept stable, and examples thereof include cationic, anionic, and nonionic types. Or a dispersant such as amphoteric can be used, but a polymer dispersant is preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. A block copolymer is particularly preferable. Among them, the block copolymer is composed of an A block having a solvophilic property and a B block having a functional group containing a nitrogen atom, and the amine value thereof is 80 mg-KOH / g or more and 150 mg-KOH. / G or less (effective solid content conversion) is particularly preferable in that the effect of the present invention can be easily obtained. More preferably, they are 100 mg-KOH / g or more and 140 mg-KOH / g or less.
Within the above range, the adsorptive power to the pigment surface is sufficient and the dispersion stability is good.

As the block copolymer, an acrylic block copolymer is preferable. The acrylic block copolymer can disperse the pigment (A) very efficiently. This is presumably because the molecular arrangement is controlled, so that there are few structures that obstruct the dispersant when adsorbing to the pigment.
In the present invention, the acrylic block copolymer is preferably an AB block composed of an A block and a B block and / or an ABA block copolymer.

The B block constituting the acrylic block copolymer preferably has a primary to tertiary amino group as a functional group containing a nitrogen atom, and the amino group is preferably —NR ⁴¹ R ⁴² (provided that R ⁴¹ And R ⁴² are each independently a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. What is preferable as a partial structure containing this is represented by the following formula (1).

^{(However, R 41} and ^{R 42} has the same meaning as above ^{R 41} and ^{R 42, R 43} is one or more alkylene groups having a carbon ^{number, R 44} represents a hydrogen atom or a methyl group.)
Among them, R ⁴¹ and R ⁴² are preferably a methyl group, R ⁴³ is preferably a methylene group or an ethylene group, and R ⁴⁴ is preferably a methyl group. Examples of such a compound include a partial structure represented by the following formula.

Two or more kinds of the partial structure containing an amino group as described above may be contained in one B block. In that case, two or more amino group-containing partial structures may be contained in the B block in any form of random copolymerization or block copolymerization. In addition, a partial structure not containing an amino group may be partially contained in the B block within a range not impairing the effects of the present invention. Examples of such a partial structure include (meth) acrylic acid esters. And a partial structure derived from a monomer.

On the other hand, in the present invention, the A block of the (D) dispersant is not particularly limited as long as it is solvophilic and is composed of a monomer copolymerizable with the monomer constituting the B block described above.
Examples of the A block include polymer structures obtained by copolymerizing comonomers such as styrene monomers, (meth) acrylate monomers, (meth) acrylate monomers, vinyl acetate monomers, glycidyl ether monomers, and the like. It is done.

The (D) dispersant contained in the pigment dispersion and colored resin composition of the present invention is an AB block or ABA block copolymeric polymer compound composed of an A block and a B block as described above. Of these, AB block copolymers are preferred. Such a block copolymer is prepared, for example, by a living polymerization method.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Specifically, for example, a method described in JP-A-2007-270147 can be mentioned.

The amine value of the dispersant (in terms of effective solid content) is represented by the weight of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mg-KOH / g] = (561 × V) / (W × S)
(W: represents the amount of the dispersant sample weighed [g], V: represents the titration amount at the end of titration [mL], and S represents the solid content concentration [wt%] of the dispersant sample.)
Further, the acid value of this block copolymer is preferably lower, although it depends on the presence and type of acidic groups that form the acid value, and is usually 50 mg-KOH / g or less, preferably 40 or less, more preferably. Is 30 or less.
When the average primary particle size of the pigment is small, the specific surface area increases and the amount of adsorbing dispersant per unit area decreases. In this case, the dispersant made of the copolymer is preferably used because it is more effective than the other dispersants.
The dispersant in the present invention is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the colored resin composition.

  The colored resin composition of the present invention may contain other dispersants as long as the effects of the present invention are not impaired. Examples of other dispersants include those described in JP-A-2006-343648, for example.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the pigment. Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of a resin selected from (C) binder resin or other binder resin described later as the following dispersion resin.
Specifically, in the dispersion treatment step to be described later, the (C) binder resin is added to the (D) dispersant by adding the (C) binder resin together with the components such as the (D) dispersant described above. It contributes to the dispersion stability of the pigment (A) by a synergistic effect. As a result, there is a possibility that the amount of (D) dispersant added can be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of pigment in the pigment dispersion and the colored resin composition.
The acid value of the dispersion resin is preferably 0.5 mg-KOH / g or more, more preferably 1 mg-KOH / g or more, most preferably 5 mg-KOH / g or more, and preferably 300 mg-KOH / g or less, 200 mg-KOH / G or less is more preferable, and 150 mg-KOH / g or less is most preferable. By controlling the acid value within the above range, the alkali developability is improved, and the handling becomes easy in synthesis and the like.

  The weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, more preferably 200000 or less, more preferably 50000 or less, and 30000 or less. Most preferred. By controlling the molecular weight within the above range, the alkali developability can be improved and the dispersion stability can be prevented from being lowered.

[(C) Binder resin]
(C) The preferred resin for the binder resin differs depending on the curing means.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, 11-14144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and the like can be used. C-1) to (C-5) resins and the like.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)

Of these, the resin (C-1) is particularly preferable, and the resin will be described below.
The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item in 2009-025813. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a 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 not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.
The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (7) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content ratio of repeating units derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more 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.
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.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

  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 may be used alone or in combination of two or more.

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%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
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, succinic anhydride and tetrahydrophthalic anhydride are preferred. 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%.

It is preferable for it to be within the above-mentioned range since the remaining film ratio during development and the solubility in a developer are 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. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

  The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. 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.

In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g.
Within the above range, the solubility in a developer is good and film roughness is not likely to occur, which is preferable.
Moreover, the content rate of (C) binder resin is 0.1-80 weight% normally in a total solid, Preferably it is 1-60 weight%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(E) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (E) a polymerizable monomer. (E) The polymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).
The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of the photopolymerization initiation component when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (E) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (E) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, 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. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (E) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content ratio of these (E) polymerizable monomers is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of (E) polymerizable monomer to the total pigment is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. % By weight or less, preferably 150% by weight or less, more preferably 110% by weight or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(F) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (F) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In the present invention, the component (F) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) to a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

  In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (E), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (F) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter arbitrarily referred to as (F1) component) and a polymerization accelerator (hereinafter arbitrarily referred to as (F2) component). , Means a mixture in which an additive such as a sensitizing dye (hereinafter, arbitrarily referred to as component (F3)) is used in combination.

(Photopolymerization initiation component)
The colored resin composition of the present invention preferably contains a photopolymerization initiation component. The photopolymerization initiating component is usually used as a mixture of (F1) a photopolymerization initiator and an additive such as (F2) a polymerization accelerator and (F3) a sensitizing dye, which are added as necessary. It is a component having a function of generating a polymerization active radical by directly absorbing or photosensitizing to cause a decomposition reaction or a hydrogen abstraction reaction.

Examples of the (F1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives Oxime ester derivatives described in JP 2000-80068 A (hereinafter referred to as “oxime ester”). It referred to as ether-based initiator "), and the like.
Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.

  Among these photopolymerization initiators, oxime ester initiators include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and a compound represented by the following formula (XI).

(In formula (XI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroaryl group having 4 to 25 carbon atoms. An alkyl group, each of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;

R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

X represents a divalent aromatic hydrocarbon group and / or an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic group which may have a substituent. )
Of the compounds represented by the formula (XI), compounds in which X is a carbazole ring which may have a substituent are preferable. Specifically, compounds represented by the following formula (XII) Among them, the compound represented by the following formula (XIII) is particularly preferable.

(In the formula, R ¹⁰¹ , R ¹⁰² and Z have the same meanings as in formula (XI). R ^{10
3 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent. )

(In the formula, R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (XIIIa).

^{(Wherein, R 103} and ^{R 104} each independently represent a hydrogen atom, a phenyl group or a N- acetyl -N- acetoxy amino group.
* Represents a binding site. )
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group. )
In addition, benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, etc. Examples also include thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester initiators are more preferable, and oxime ester initiators are particularly preferable.
Examples of the (F2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.
These (F1) photopolymerization initiators and (F2) polymerization accelerators may be used alone or in combination of two or more.

Further, (F3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681 JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

(F3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content of these (F) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight based on the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.

(Thermal polymerization initiation component)
Specific examples of the thermal polymerization initiation component (thermal polymerization initiator) that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiator described in International Publication No. 2009/107734 pamphlet or the like can be used.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.

[Optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, and the like. Moreover, when a pigment is contained as a coloring matter, a dispersant or a dispersion aid may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used.

[Preparation method of pigment dispersion and colored resin composition]
In the present invention, the pigment dispersion can be prepared by an appropriate method. For example, a zinc halide phthalocyanine pigment and C.I. I. It can be prepared by mixing (A) a pigment containing Pigment Yellow 138, (D) a dispersant and other additives in a (B) solvent containing PGME.

  More preferable preparation methods include zinc halide phthalocyanine pigments and C.I. I. In the presence of (D) a dispersant and, if necessary, a dispersion aid, (A) a pigment containing Pigment Yellow 138 is contained in (B) a solvent containing 2 to 6% by weight of PGME in the solvent. In some cases (C) A part of the binder resin or other resin, for example, paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. Prepare the solution. The pigment dispersion is mixed with (C) a binder resin, preferably (E) a polymerizable monomer, (F) a photopolymerization initiating component and / or a thermal polymerization initiating component, and, if necessary, a solvent or other components. Thus, a colored resin composition is prepared.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. This colored resin composition is supplied onto the substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a color filter, and a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

The substrate used for forming the pixel is not particularly limited as long as it is transparent and has an appropriate strength. For example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a thermoplastic resin is used. A sheet, an epoxy resin, a thermosetting resin, various glass, etc. are mentioned.
In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.
Exposure of radiation, 10~10,000J / ^{m 2} is preferred.

Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

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 developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is, and is used as a part of a color display, a liquid crystal display device, or the like. Although used, 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. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<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, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is manufactured by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.
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 weight”.
<Reference Synthesis Example 1: Synthesis of Resin A>
Prepare a separable flask with a cooling tube as a reaction tank, charge 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction tank to 90 ° C. did.

Meanwhile, 30 parts by weight of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, t-butylperoxy-2-ethyl Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, charge 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate to the chain transfer agent tank, and temperature of the reaction 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 weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were charged into the reaction vessel at 110 ° C. as it was. For 9 hours. This was cooled to room temperature, weight average molecular weight 8000, acid value 101 mgKOH
/ G of resin A was obtained.

<Preparation of pigment dispersion>
[1] Preparation of green pigment dispersion (1) C.I. I. 6 parts by weight of Pigment Green 58 (manufactured by DIC; hereinafter abbreviated as “G58”), 6 parts by weight of Y138 (manufactured by Dainichi Seika; hereinafter abbreviated as “Y138”), “BYK” manufactured by BYK Chemie as a dispersant. -LPN6919 "(methacrylic acid AB block copolymer, amine value 121 mgKOH / g, acid value 1 mgKOH / g or less) in terms of solid content, 4 parts by weight of resin A of Reference Synthesis Example 1 in terms of solid content Were mixed and propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) was used as a solvent to adjust the solid content concentration to 20%. The ratio of PGMEA to PGME was 95: 5. 100 parts by weight of this mixed solution and 300 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours using a paint shaker to prepare a green pigment dispersion (1). At that time, the viscosity of the dispersion was measured every hour.

[2] Preparation of green pigment dispersion (2) Green pigment dispersion (2) was prepared in the same manner as in Example 1 except that the ratio of PGMEA to PGME was changed to 80:20, and dispersed every hour. The viscosity of the liquid was measured.
[3] Preparation of Green Pigment Dispersion (3) Green Pigment Dispersion (3) was prepared in the same manner as in Example 1 except that the ratio of PGMEA to PGME was changed to 90:10, and dispersed every hour. The viscosity of the liquid was measured.
[4] Preparation of Green Pigment Dispersion (4) Green Pigment Dispersion (4) was prepared in the same manner as in Example 1 except that the ratio of PGMEA to PGME was changed to 100: 0, and dispersed every hour. The viscosity of the liquid was measured.

<Evaluation method>
[Measurement method of viscosity of pigment dispersion]
In the green pigment dispersions (1) to (4) prepared in <Preparation of Pigment Dispersion>, the rate of change in viscosity (μ _max / μ _min ) in the dispersion being prepared, and immediately after preparation and after preparation 35 The viscosity change rate (μ _{7 days} / μ ₀ ) after storage at 7 ° C. for 7 days was measured.
Note that μ _min represents the minimum value of the viscosity in the dispersion liquid being prepared, and μ _max represents the maximum value of the viscosity in the dispersion liquid being prepared.
Further, mu ₀ denotes the viscosity immediately after the preparation of the pigment dispersion, mu _7days represents the viscosity after storage for 7 days at 35 ° C. after preparation.
The viscosity was measured at room temperature (23 ° C.) and 20 rpm using an E-type viscometer “RE-80L” (manufactured by Toki Sangyo Co., Ltd.).
The results are summarized in Table 1.

As shown in Table 1, the pigment dispersion of the present invention has a small increase in viscosity at the time of preparation. Therefore, it is easy to suppress a decrease in the yield of the pigment dispersion due to thickening.
Furthermore, since the storage stability of the pigment dispersion is excellent, it is easy to suppress the yield reduction in the production of the colored resin composition.
Moreover, the color filter containing the pixel formed using the colored resin composition of this invention, the liquid crystal display device and organic electroluminescent display device containing this color filter are high quality.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (8)

(A) a pigment, (B) a solvent, (D) a dispersant,
The (A) pigment is a halogenated zinc phthalocyanine green pigment and C.I. I. Pigment Yellow 138,
(B) A pigment dispersion for producing a colored resin composition, wherein the solvent contains propylene glycol monomethyl ether in an amount of 2% by weight to 6% by weight in all solvents.   The pigment dispersion liquid according to claim 1, wherein the solvent (B) contains propylene glycol monomethyl ether acetate.   The pigment dispersion liquid according to claim 1 or 2, wherein the (D) dispersant is a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom.   The pigment dispersion according to claim 3, wherein the block copolymer has an amine value of 80 mg-KOH / g or more and 150 mg-KOH / g or less.   The pigment dispersion according to any one of claims 1 to 4, wherein the (A) pigment is 10 wt% or more and 20 wt% or less in the total solid content. Method of manufacturing a pigment dispersion liquid according to any one of claims 1 to 5, (C) and having a mixing step of mixing a binder resin, a colored resin composition. The addition in the mixing step, (E) characterized by mixing a polymerizable monomer, the production method of the colored resin composition of claim 6. Further, in the mixing step, (F) characterized by mixing a photopolymerization initiator component and / or the thermal polymerization initiator component, method for producing a colored resin composition according to claim 6 or 7.

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