JP2010243599A - Resin composition for color layer for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for color layer for a color filter which is hardly yellowing and is excellent in transparency and heat resistance. <P>SOLUTION: The resin composition for color layer for the color filter contains at least a binder resin, a polyfunctional monomer, a photopolymerization initiator and a pigment dispersion, wherein the binder resin is obtained by reacting an epoxy group of the following component (D) with a carboxyl group of a copolymer prepared by copolymerizing the following components (A) to (C), and does not contain an aromatic ring. The components are: (A) at least one in 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, and 1-perfluoroadamantyl (meth)acrylate; (B) an alicyclic compound-containing monomer having a monocyclic aliphatic hydrocarbon group and an unsaturated double bond; (C) a carboxyl group-containing monomer having a carboxyl group and an unsaturated double bond; and (D) an epoxy group-containing compound having an epoxy group and an unsaturated double bond. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition for a colored layer for a color filter that has little yellowing and is excellent in transparency and heat resistance.

  Generally, a color filter used in a liquid crystal display device or the like includes a transparent substrate, a black matrix formed on the transparent substrate, and a colored layer formed in an opening of the black matrix. Here, it is known that the colored layer in the color filter is formed into a pattern by a photolithography method or the like using a resin composition for a colored layer for a color filter containing a pigment of each color. Specifically, a colored layer resin composition for a color filter in which a pigment of each color, a binder resin, a polyfunctional monomer, a photopolymerization initiator, and the like are dispersed in a solvent is applied onto a transparent substrate, and the resulting coating is obtained. A method of forming a patterned colored layer by exposing and curing the film in a predetermined pattern and developing with an alkali developer is used.

  Moreover, as a color filter, the color filter which has a colored layer of three colors of red (R), green (G), and blue (B) was common. As color characteristics of such a color filter, high color reproducibility, high contrast, and high luminance have been recently demanded particularly in color television applications.

Here, as the binder resin, an aromatic ring-containing polymer containing an aromatic ring is generally used because of excellent heat resistance (shape stability during post-baking (heating)).
However, when such an aromatic ring-containing polymer is used, there is a problem that yellowing occurs at the time of post-baking, and the luminance of the colored layer becomes low.

For such a problem, a method of using a polycyclic aliphatic group-containing polymer comprising a polycyclic aliphatic hydrocarbon group monomer containing a polycyclic aliphatic hydrocarbon group containing little yellowing and high transparency is disclosed. (Patent Document 1).
However, even when such a polycyclic aliphatic group-containing polymer is used, there is a problem that heat resistance and transparency may be insufficient.

Patent 3887046

  The present invention has been made in view of the above problems, and has as its main object to provide a resin composition for a colored layer for a color filter that has little yellowing and is excellent in transparency and heat resistance. .

  As a result of repeated studies to solve the above problems, the present inventors have used an adamantane or adamantane-containing monomer containing an adamantane derivative as a monomer component among the polycyclic aliphatic hydrocarbon group-containing monomers, and include an aromatic ring. The present inventors have found that a resin composition for a colored layer for a color filter that is less yellowed and excellent in transparency and heat resistance can be obtained by using a non-binder resin, and has completed the present invention.

  That is, the present invention provides a copolymer comprising at least a binder resin, a polyfunctional monomer, a photopolymerization initiator, and a pigment dispersion, wherein the binder resin is obtained by copolymerizing the following (A) to (C). Provided is a resin composition for a colored layer for a color filter, which is obtained by reacting an epoxy group of the following (D) with a carboxyl group having no aromatic ring.

(A) 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl An alicyclic compound-containing monomer (C) having at least one of (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate (B) a monocyclic aliphatic hydrocarbon group and an unsaturated double bond; An epoxy group-containing compound having a carboxyl group-containing monomer (D) epoxy group having an unsaturated double bond and an unsaturated double bond

According to the present invention, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy- A binder resin containing at least one of 1-adamantyl (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate (hereinafter sometimes simply referred to as an adamantane-containing monomer) as a monomer component and not containing an aromatic ring is used. As a result, yellowing during heating can be reduced, and transparency and heat resistance can be improved.
Moreover, the binder resin has an unsaturated double bond and a hydroxyl group by reacting the epoxy group-containing compound with a carboxyl group derived from a carboxyl group-containing monomer. Can do. As a result, the resin composition for a colored layer for a color filter after exposure can be made excellent in heat resistance, and further, it can be made excellent in developability.

  In the present invention, the ratio of (A) to (D) in the binder resin is within the range of (A) 10% by mass to 50% by mass, (B) within the range of 0% by mass to 20% by mass, ( C) It is preferable to be within the range of 10% by mass to 60% by mass, and (D) within the range of 5% by mass to 35% by mass. When the ratio of (A) to (D) in the binder resin is the ratio described above, the binder resin can be reduced in yellowing and excellent in heat resistance.

  In the present invention, the binder resin preferably has a weight average molecular weight in the range of 3000 to 24000. This is because when the weight average molecular weight of the binder resin is within the above-described range, the binder resin can be excellent in heat resistance and developability.

  In the present invention, the pigment dispersion is preferably a blue pigment dispersion containing a blue pigment. When the pigment dispersion is a blue pigment dispersion containing a blue pigment, that is, when used for forming a blue colored layer, blue light is absorbed by the yellow colored material contained in such a blue colored layer. There is a problem that the luminance of blue light is lowered. In general, the blue colored layer of the color filter is set so that the luminance is lower than that of the red or green colored layer by design. For this reason, even a slight decrease in luminance greatly affects optical characteristics such as color reproducibility as a color filter. Therefore, when the pigment dispersion is a blue pigment dispersion, the effect of reducing yellowing can be more effectively exhibited.

  The present invention has an effect that a colored layer resin composition for a color filter that is less yellowed and excellent in transparency and heat resistance can be provided.

Hereinafter, the colored layer resin composition for a color filter of the present invention will be described.
The colored layer resin composition for a color filter of the present invention includes at least a binder resin, a polyfunctional monomer, a photopolymerization initiator, and a pigment dispersion, and the binder resin includes the following (A) to (C). The carboxyl group of the copolymer obtained by polymerization is reacted with the epoxy group (D) below, and does not contain an aromatic ring.
(A) 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl An alicyclic compound-containing monomer (C) having at least one of (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate (B) a monocyclic aliphatic hydrocarbon group and an unsaturated double bond; An epoxy group-containing compound having a carboxyl group-containing monomer (D) epoxy group having an unsaturated double bond and an unsaturated double bond

According to the present invention, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy- By using a binder resin that includes at least one of 1-adamantyl (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate, that is, an adamantane-containing monomer as a monomer component and does not include an aromatic ring, yellowing during heating can be prevented. And it can be excellent in transparency and heat resistance. In addition, since a binder resin with little yellowing and high transparency is used, a colored layer with high luminance can be formed.
Here, the reason why the above-described effects can be obtained by using the adamantane-containing monomer as a monomer component and not including an aromatic ring is presumed as follows.

That is, since the adamantane skeleton contained in the adamantane-containing monomer has a higher melting point than other polycyclic aliphatic compounds not containing such an adamantane skeleton, the heat resistance is improved. In addition, since it does not contain a double bond (conjugated system) like an aromatic ring, it does not easily cause side reactions due to heat or ultraviolet rays.
Moreover, by not containing an aromatic ring, it is possible to make the side reaction due to heat and ultraviolet rays difficult to occur as described above.
For this reason, the above-described effects can be obtained by using a binder resin containing an adamantane-containing monomer having an adamantane skeleton as described above as a monomer component and not containing an aromatic ring.

  Further, by using a binder resin containing the alicyclic compound-containing monomer and the carboxyl group-containing monomer as monomer components, compatibility with each component of the color filter colored layer resin composition and developability during development are achieved. It can be excellent.

  Further, the binder resin is obtained by reacting the epoxy group-containing compound with a carboxyl group derived from a carboxyl group-containing monomer. Thereby, the binder resin can have an unsaturated double bond and a hydroxyl group. As described above, the binder resin has an unsaturated double bond, so that it can be polymerized between the binder resins at the time of exposure or between the binder resin and the polyfunctional monomer. The colored layer resin composition can be made excellent in heat resistance. Moreover, it can be made excellent in developability because the binder resin can have a hydroxyl group.

  The colored layer resin composition for color filter of the present invention has at least a binder resin, a polyfunctional monomer, a photopolymerization initiator, and a pigment dispersion. Hereafter, each component of the resin composition for colored layers for color filters of this invention is demonstrated in detail.

1. Binder Resin The binder resin used in the present invention is obtained by reacting the epoxy group of the following (D) with the carboxyl group of the copolymer obtained by copolymerizing the following (A) to (C) to form an aromatic ring. It is not included.
(A) 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl An alicyclic compound-containing monomer (C) having at least one of (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate (B) a monocyclic aliphatic hydrocarbon group and an unsaturated double bond; An epoxy group-containing compound having a carboxyl group-containing monomer (D) epoxy group having an unsaturated double bond and an unsaturated double bond

(1) Copolymer The copolymer in the present invention includes (A) 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl- At least one of 2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate, (B) an alicyclic compound-containing monomer, and (C) a carboxyl group Although it is what copolymerized the containing monomer, what was copolymerized so that it may become a block copolymer may be used even if it copolymerizes the said each monomer at random.

  In the present invention, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1 -By using an adamantane-containing monomer of adamantyl (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate as a monomer component of the copolymer, the binder resin is less yellowed when heated and is transparent. And it can be excellent in heat resistance.

  Examples of such adamantane-containing monomers include 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 1 -Perfluoroadamantyl (meth) acrylate may be used, but in the present invention, 1-adamantyl (meth) acrylate and 2-adamantyl (meth) acrylate can be preferably used. This is because the binder resin can be made excellent in transparency and heat resistance by using the compound as an adamantane-containing monomer.

  The adamantane-containing monomer in the present invention may consist of only one type or two or more types.

The content of the adamantane-containing monomer in the present invention is not limited as long as the binder resin can have a desired heat resistance, and is preferably in the range of 10% by mass to 50% by mass in the binder resin. In particular, the content is preferably in the range of 20% by mass to 40% by mass. It is because it can be made excellent in transparency and heat resistance because the content is within the above range.
In addition, content of each said monomer component means content of the component originating in each said monomer which occupies for the said binder resin.

  The alicyclic compound-containing monomer in the present invention has a monocyclic aliphatic hydrocarbon group and an unsaturated double bond, and does not contain an aromatic ring.

Here, the monocyclic aliphatic hydrocarbon group is an aliphatic cyclic hydrocarbon group and a monocyclic functional group. Such a monocyclic aliphatic hydrocarbon group is generally excellent in compatibility with each component used in the color filter resin composition for color filter used for forming the color filter color layer, and further with a developer. It has the property of being excellent in compatibility.
Therefore, in the present invention, the alicyclic compound-containing monomer is used as a monomer component of the copolymer, whereby the binder resin is phased with each component of the color filter resin composition for a color filter of the present invention. It is excellent in solubility and the resin composition for a colored layer for a color filter can be made excellent in developability.

  As such an alicyclic compound-containing monomer, any monomer having a monocyclic aliphatic hydrocarbon group and easily copolymerizable with each of the above monomers can be used. Specifically, cyclohexyl (meth) acrylate is used. , Cyclohexylmethyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, 4-isopropylcyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, 3-methylcyclohexyl ( (Meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 4-ethylcyclohexyl (meth) acrylate, 2-tert-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) ) Acrylate, menthyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclononyl (meth) acrylate and cyclodecyl (meth) acrylate be able to. Since the alicyclic compound-containing monomer is the compound, the binder resin can be made excellent in compatibility with each component of the colored filter resin composition for color filters and in developability. It is.

  The alicyclic compound-containing monomer in the present invention may be composed of only one type or may be composed of two or more types.

  The content of the alicyclic compound-containing monomer in the present invention is not limited as long as the binder resin has desired compatibility with each component of the colored filter resin composition for color filters and developability. In the binder resin, the content is preferably in the range of 0% by mass to 20% by mass, and more preferably in the range of 5% by mass to 15% by mass. It is because it can be set as binder resin excellent in compatibility with each component of the said resin composition for colored layers for color filters, and developability because the said content is in the said range.

  The carboxyl group-containing monomer in the present invention has a carboxyl group and an unsaturated double bond, and does not contain an aromatic ring.

  In the present invention, the binder resin can contain a carboxyl group by using the carboxyl group-containing monomer as a monomer component of the binder resin. By having a carboxyl group, the binder resin can be excellent in solubility in an alkaline developer used for development. Moreover, by having such a carboxyl group, the introduction of the epoxy group-containing compound into the copolymer can be facilitated.

  As such a carboxyl group-containing monomer, any monomer having a carboxyl group and easily copolymerizable with each of the above monomers may be used. Specifically, methacrylic acid, acrylic acid, crotonic acid, itaconic acid, Mention can be made of maleic acid, fumaric acid, α- (hydroxymethyl) acrylic acid, (meth) acryloyloxyethyl succinic acid monoester, (meth) acryloyloxyphthalic acid monoester, etc. , Methacrylic acid, and maleic acid can be preferably used, and acrylic acid and methacrylic acid can be particularly preferably used. When the carboxyl group-containing monomer is the compound, polymerization and reaction can be easily controlled. As a result, the copolymer can be synthesized with high accuracy.

  The carboxyl group-containing monomer in the present invention may be composed of only one kind or two or more kinds.

  As content of the carboxyl group-containing monomer in the present invention, it is sufficient that the binder resin has a desired alkali developability, and is within a range of 10% by mass to 60% by mass in the binder resin. It is preferable that it is in the range of 20 mass%-50 mass% especially. It is because it can be made excellent in alkali developability because the content is within the above range.

  The copolymer in the present invention is synthesized using the above adamantane-containing monomer, alicyclic compound-containing monomer, and carboxyl group-containing monomer as monomer components, and if necessary, contains an aromatic ring other than each of the above monomers. A non-ethylenically unsaturated monomer may be used as a monomer component.

The ethylenically unsaturated monomer is not particularly limited as long as it is copolymerizable with the above monomers and does not contain an aromatic ring. Examples of such an ethylenically unsaturated monomer not containing an aromatic ring include methyl (meth) acrylate, n-butyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, allyl (meth) ) Acrylate, hydroxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyl (meth) ethyl acrylate and the like, and their macromonomers; N-methylmaleimide And N-substituted maleimides such as N-cyclohexylmaleimide.
In addition, the said ethylenically unsaturated monomer can be individual or can combine several types.

  The method for synthesizing the copolymer in the present invention may be any method as long as it is a method of copolymerization so that the adamantane-containing monomer, alicyclic compound-containing monomer, and carboxyl group-containing monomer are contained in a desired ratio. The method can be used. Specifically, a method of polymerizing after dissolving or dispersing each of the monomers and the polymerization initiator in a solvent can be mentioned.

  In addition, as a polymerization initiator, what is generally used for the synthesis | combination of a copolymer can be used, For example, the photoinitiator mentioned later can be used.

(2) Epoxy group-containing compound The epoxy group-containing compound in the present invention has an epoxy group and an unsaturated double bond. By binding to the carboxyl group of the copolymer, the unsaturated double bond is obtained. A binder resin having a bond is formed.
Moreover, it does not contain an aromatic ring.

  As such an epoxy group-containing compound, any compound can be used as long as it can be efficiently bonded to the copolymer. Specifically, glycidyl methacrylate, glycidyl acrylate, (3,4-epoxycyclohexyl) methyl acrylate. , (3,4-epoxycyclohexyl) methyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, and the like. Among them, in the present invention, glycidyl methacrylate, glycidyl acrylate, (3 , 4-epoxycyclohexyl) methyl acrylate and (3,4-epoxycyclohexyl) methyl methacrylate can be preferably used, and in particular, glycidyl methacrylate and glycidyl. Acrylate can be preferably used. This is because the reaction with the carboxyl group can be easily controlled.

  The epoxy group-containing compound in the present invention may be composed of only one type or may be composed of two or more types.

  The content of the epoxy group-containing compound in the present invention is only required to have a desired heat resistance, and is preferably in the range of 5% by mass to 35% by mass in the binder resin. It is preferably within the range of 10% by mass to 30% by mass. It is because it can be excellent in heat resistance and developability when the content is within the above range.

  In the present invention, as a method of reacting the carboxyl group of the copolymer with the epoxy group of the epoxy group-containing compound, the carboxyl group of the copolymer and the epoxy group of the epoxy group-containing compound can be reacted accurately. Any method can be used, but a catalyst for an epoxy group-containing compound is usually used.

  Examples of such an epoxy group-containing compound catalyst include triethylamine, N, N-dimethylbenzylamine, triethylammonium chloride, triethylammonium bromide, triphenylphosphine, and phenothiazine.

  The reaction method may be a method in which the epoxy group-containing compound is added and reacted in a solvent containing the copolymer after the copolymerization, and the copolymer is purified from the solvent after the copolymerization. Then, the method of reacting after mixing the copolymer and the epoxy group-containing compound in a newly prepared solvent may be used.

  The reaction conditions such as the temperature when the carboxyl group of the copolymer in the present invention is reacted with the epoxy group of the epoxy group-containing compound are appropriately set according to the type of the compound to be used and the catalyst for the epoxy group-containing compound. Is.

(3) Binder resin The weight average molecular weight of the binder resin used in the present invention is not particularly limited as long as it can exhibit desired heat resistance and developability, but is preferably in the range of 3000 to 24000. In particular, it is preferably in the range of 4000 to 21000, particularly preferably in the range of 6000 to 18000. This is because when the weight average molecular weight is within the above range, the heat resistance and developability can be improved.
In addition, the said weight average molecular weight (Mw) can be calculated | required as a standard polystyrene conversion value by a gel permeation chromatography (GPC).

The acid value of the binder resin used in the present invention is preferably 20 mgKOH / g to 120 mgKOH / g, and more preferably 30 mgKOH / g to 100 mgKOH / g. This is because when the acid value is within the above range, the developability can be improved.
In addition, an acid value shows the acid value per 1g of said binder resins, and says the value calculated | required by the potentiometric titration method according to JISK0070.

The content of the binder resin used in the present invention is not particularly limited as long as it can form a colored layer with high accuracy. Specifically, the solid content of the resin composition for a colored layer for a color filter of the present invention is 100. It is preferably within a range of 30 to 50 parts by weight per part by weight, and particularly preferably within a range of 35 to 45 parts by weight. This is because if the content is less than the above range, curability becomes insufficient and a good pattern may not be formed. On the other hand, if the amount is larger than the above range, developability deteriorates, and a residue that cannot be washed off by development is generated on the substrate, which may deteriorate the quality of the color filter.
In addition, solid content of the resin composition for colored layers for color filters refers to all components other than the solvent contained in the resin composition for colored layers for color filters.

2. Pigment Dispersion The pigment dispersion used in the present invention contains a pigment, a pigment dispersant, and a dispersion resin.

(1) Pigment As the pigment contained in the pigment dispersion in the present invention, a known pigment can be used. Specific examples of organic pigments that can be used in the present invention are shown in Tables 1 and 2 below.

Examples of inorganic pigments that can be used include titanium oxide, zinc white, lead sulfate, yellow lead, zinc yellow, bengara, cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black. And carbon black.
In addition, these pigments may be used independently and may mix and use 2 or more types.

In the present invention, among others, the pigment is a blue pigment such as Pigment Blue (PB) 15, PB15: 3, PB15: 4, PB15: 6, PB60, PB80, and Pigment Violet (PV) 23. The resin composition for a colored layer for a color filter of the present invention is preferably used for forming a blue colored layer, and particularly preferably a phthalocyanine pigment such as PB15: 6.
When the resin or the like contained in the blue colored layer is yellowed, there is a problem that blue light is absorbed by the yellowed material contained in such a blue colored layer and the luminance of the blue light is lowered. In addition, the blue colored layer of the color filter is generally set so that the luminance is lower by design compared to the red or green colored layer. The impact on change will be significant. Therefore, when the said pigment is a blue pigment and the resin composition for colored layers for color filters of this invention is used for formation of a blue colored layer, when yellowing of this invention can be made small. It is because the effect of can be exhibited more effectively.
Moreover, the phthalocyanine pigments described above are characterized in that they tend to aggregate and become low in luminance. Therefore, by using such a phthalocyanine pigment, the effect of reducing the yellowing and increasing the luminance of the present invention can be more effectively exhibited.

  In addition, the dispersion average particle diameter of the pigment used in the present invention is such that a desired color can be formed when the colored layer of the color filter is formed using the resin composition for the colored layer of the color filter of the present invention. Usually, it is preferable to be within a range of 0.01 μm to 0.15 μm, and it is particularly preferable to be within a range of 0.01 μm to 0.10 μm. This is because when the colored layer of the color filter is formed using the resin composition for a colored layer for a color filter of the present invention, a colored layer excellent in luminance and contrast can be obtained.

  The content of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when the colored layer of the color filter is formed using the colored filter resin composition of the present invention. Although it varies depending on the type of pigment, it is preferably in the range of 1 to 20 parts by weight per 100 parts by weight of solid content of the colored layer resin composition for color filters, and in particular, 5 to 10 parts by weight. It is preferably within the range of parts. This is because if the amount is less than the above range, the optical characteristics may not be sufficiently exhibited. On the other hand, when the amount is larger than the above range, the ultraviolet light absorption by the pigment is remarkably increased, and there is a possibility that curing may be insufficient.

(2) Pigment dispersant Any pigment dispersant may be used in the present invention as long as it can uniformly disperse the pigment, and a known pigment dispersant can be used. Specific examples include polymer dispersants such as modified polyurethane, modified polyacrylate, modified polyester, and modified polyamide, and surfactants and pigment derivatives such as phosphate esters, alkylamines, and polyoxyethylene alkylphenyl ethers. .
In the present invention, among them, a modified polyacrylate polymer dispersant is preferable, and as specific trade names, Disperbyk 2000, Disperbyk 2001, LP-N Disperbyk 21116, LP-N Disperbyk 21324 (above, manufactured by BYK Chemie) is preferably used. Can do.

  The content of the pigment dispersant used in the present invention is not particularly limited as long as it can uniformly disperse the pigment, but per 100 parts by weight of the solid content of the color filter resin composition for a color filter of the present invention. It is preferably within the range of 1 to 12 parts by weight, and more preferably within the range of 2 to 10 parts by weight. This is because if the content is less than the above range, dispersion of the pigment may be insufficient, and it may be difficult to obtain desired optical characteristics. Because there is a risk of causing.

(3) Dispersing Resin The dispersing resin used in the present invention is used for efficiently mixing the pigment with the binder resin, photopolymerization initiator, polyfunctional monomer and the like. Specifically, the pigment and the pigment dispersant are added to the dispersion resin to form a pigment dispersion, and then the pigment dispersion is mixed with the binder resin or the like to form a colored layer resin composition for a color filter. It is used for the purpose of preparing.
Such a dispersing resin may be any resin that has excellent compatibility with the pigment and the pigment dispersant, can uniformly disperse the pigment and the pigment dispersant, and has alkali developability.
In the present invention, in particular, from the viewpoint of preventing the yellowing described above, it is preferable that it does not contain an aromatic ring, and among them, an alkali-soluble resin having an acidic functional group such as a carboxyl group is preferably used.

As such an alkali-soluble resin having a carboxyl group, a copolymer of the carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer is preferable, and the epoxy group-containing compound is further added. Those having an ethylenically unsaturated group introduced in the side chain can also be preferably used.
Moreover, as said other monomer, the said alicyclic compound containing monomer, the said ethylenically unsaturated monomer, etc. can be used.

  About the said carboxyl group containing monomer, an alicyclic compound containing monomer, an ethylenically unsaturated monomer, and an epoxy group containing compound, what was described in the said "1. binder resin" item can be used.

  The content of the dispersing resin is not particularly limited as long as it can uniformly disperse the pigment, but is usually 1 to 12 parts by weight per 100 parts by weight of the solid content of the colored filter resin composition for color filters. It is preferably within the range of parts, and particularly preferably within the range of 2 to 10 parts by weight. This is because when the content is within the above range, the pigment can be excellent in uniform dispersibility.

3. Multifunctional monomer The polyfunctional monomer used in the present invention has a plurality of polymerizable functional groups, and is polymerized with the above multifunctional monomers or with the above binder resin by light irradiation, whereby the above color filter is used. The colored layer resin composition is cured.
As such a polyfunctional monomer, a polyfunctional (meth) acrylate having an acryloyl group or a methacryloyl group is usually used.

  Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene di (meth) acrylate, glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate , Polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, methoxylation Cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate, butanediol Bifunctional (meth) acrylates such as di (meth) acrylate, di (meth) acrylate phthalate, di (meth) acrylate phosphate, zinc di (meth) acrylate And the like.

  Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and alkyl-modified dipenta. Erythritol tri (meth) acrylate, tri (meth) acrylate phosphate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxype (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, carboxylic acid-modified dipentaerythritol penta (meth) acrylate, urethane tri Trifunctional or higher functional (meth) acrylates such as (meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, and ester hexa (meth) acrylate may be mentioned.

  These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  The content of the polyfunctional monomer used in the present invention is preferably in the range of 20 to 40 parts by weight per 100 parts by weight of the solid content of the color filter resin composition of the present invention. Especially, it is preferable that it exists in the range of 25 weight part-35 weight part. If the amount is less than the above range, the colored filter resin composition for the color filter cannot be sufficiently cured, and during development, the exposed portion is eluted, or the cured product of the colored filter resin composition for the color filter is peeled off. This is because there is a risk that the adhesiveness may be lowered, for example. Further, if the amount is larger than the above range, there is a risk that development failure such as development failure even at an unexposed portion may occur.

  Moreover, as a content ratio with respect to the said binder resin of the polyfunctional monomer used for this invention, what is necessary is just what can be set as the desired degree of hardening, but it is contained in the said resin composition for colored layers for color filters. The weight ratio of the polyfunctional monomer and the binder resin (binder resin / polyfunctional monomer) is preferably in the range of 30/70 to 59/41, and in particular, in the range of 35/65 to 50/50. Preferably there is. This is because the curability can be optimized.

4). Photopolymerization initiator As the photopolymerization initiator used in the present invention, those generally used for the production of color filters can be used.

  Specifically, as such a photopolymerization initiator, an α-aminoketone-based initiator and a thioxanthone-based initiator can be preferably used. Moreover, you may contain another photoinitiator as needed.

  The content of the photopolymerization initiator used in the present invention is not particularly limited as long as it can form a colored layer of a color filter, but the solid content of the resin composition for a colored layer for a color filter of the present invention is 100% by weight. It is preferably within the range of 5 to 25 parts by weight per part, and more preferably within the range of 8 to 15 parts by weight. If the amount is less than the above range, radical polymerization cannot proceed sufficiently, curing becomes insufficient, and curability may be lowered. On the other hand, if the amount is larger than the above range, yellowing becomes remarkable, and the luminance may be lowered and the optical characteristics may be impaired.

5). Resin composition for colored layer for color filter The resin composition for colored layer for color filter of the present invention only needs to have at least the binder resin, polyfunctional monomer, photopolymerization initiator, and pigment dispersion. It may contain a solvent or an additive as necessary.

  The solvent may be any solvent that does not react with the components of the colored layer resin composition for color filters of the present invention and can dissolve or uniformly disperse them. Specifically, cyclohexyl acetate; methoxybutyl acetate (MBA); ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol mono-n Diethylene glycol monoalkyl ether acetates such as butyl ether acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether; cyclohexanone, 2- Hep Non, ketones such as 3-heptanone; Lactic acid alkyl esters such as ethyl 2-hydroxypropionate; 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Other esters such as ethyl ethoxypropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate; γ-butyrolactone, 3-methoxybutanol, 3-methyl-3-methoxybutyl acetate and the like can be mentioned. These solvents may be used alone or in combination of two or more.

  The content of the solvent used in the present invention is not particularly limited as long as it can form a colored layer with high accuracy, but usually 70% by mass to 95% by mass in the resin composition for a colored layer for a color filter. %, Preferably in the range of 75% by mass to 90% by mass. This is because when the content of the solvent is within the above range, the coating property can be improved.

  Examples of the additive include a sensitizer, a polymerization terminator, a chain transfer agent, a plasticizer, a surfactant, an antifoaming agent, and a silane coupling agent.

  The method for producing the colored layer resin composition for a color filter of the present invention may be any method that can uniformly disperse or dissolve the above-described components, and known mixing and dispersing means can be used.

  As a use of the colored filter resin composition for a color filter of the present invention, it can be used for forming a colored layer of a color filter, and in particular, it is preferably used for forming a colored layer that is required to have high luminance. .

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention more specifically.

[Examples 1-6 and Comparative Examples 1-5]
1. Synthesis of binder resin 60 parts by weight of propylene glycol monomethyl ether acetate (PMA) as a solvent was added to a 3 L separable flask, heated to 120 ° C., and then 8.76 parts by weight of methacrylic acid (MAA) as a monomer component, methyl Methacrylate (MMA) 8.56 parts by weight, cyclohexyl methacrylate (CHMA) 3.44 parts by weight, 1-adamantyl methacrylate (ADAMA) 10.28 parts by weight, t-butylperoxy-2-ethylhexanoate as a radical initiator 0.66 parts by weight and 1.54 parts by weight of n-dodecyl mercaptan as a chain transfer agent were uniformly mixed and added dropwise over 3 hours.
After 3 hours from the end of the dropwise addition, the temperature was raised to 130 ° C. over 10 minutes and kept at a constant temperature of 130 ° C. for 15 minutes to synthesize a copolymer.
A predetermined amount of 0.02 part by weight of a polymerization inhibitor and 8.96 parts by weight of glycidyl methacrylate (GMA) are added to the above copolymer, the temperature is raised to 110 ° C., and when the temperature reaches 110 ° C., N, N -Binder resin G was obtained by adding dimethylbenzylamine and then heating for 10 hours.
Similarly, MAA, MMA, CHMA, ADAMA, dicyclopentanyl methacrylate (DCPMA), isobornyl methacrylate (IBMA), benzyl methacrylate (MzMA), and tertiary butyl cyclohexyl methacrylate (t-BuCHMA) are shown in the following table. Binder resins A to F and H to I were synthesized as the ratio shown in FIG.
Moreover, the weight average molecular weight (Mw) and acid value (AV: mgKOH / g) were measured by the method mentioned above about obtained binder resin AI.
In addition, the numerical value in Table 3 shows the mass%.

2. Preparation of resin composition for colored layer for color filter The binder resin (resins A to I), multifunctional monomer, photopolymerization initiator, pigment, pigment dispersant, resin for dispersion, solvent and additive are shown in Table 4 below. The resin composition for colored layers for color filters was prepared by blending as shown.
In blending, after first preparing a master batch by mixing a pigment, a pigment dispersant and a dispersing resin, this master batch, the binder resin, the polyfunctional monomer, a photopolymerization initiator, a solvent, and an additive are added. This was done by mixing the agent. The numerical values in Table 4 indicate parts by weight.
Moreover, pigment blue 15: 6 (B15: 6) and pigment violet 23 (V23) were used as a pigment. Dispersbyk 2000 (manufactured by Big Chemie) (BYK2001) and LP-N Disperbyk 21116 (manufactured by Big Chemie) (BYK21116) were used as pigment dispersants. The binder resin A was used as the dispersing resin.
In addition, Aronix M403 (manufactured by Toagosei Co., Ltd.) (M403) was used as the multifunctional monomer. Diethylthioxanthone (manufactured by Nippon Kayaku) (DETX-S) and Irgacure 907 (manufactured by Ciba Specialty Chemicals) (Irg907) were used as photopolymerization initiators. As an additive, KBM503 (manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
As a solvent, propylene glycol monomethyl ether acetate (manufactured by Kuraray) was used. The amount of the solvent added was adjusted so that the solid content concentration of the color filter resin composition for color filters was 22.5% by mass.

3. Evaluation After the resin composition for the colored layer for color filter prepared in Examples and Comparative Examples was applied on a glass substrate with a spin coater, it was dried by heating at 80 ° C. for 3 minutes on a hot plate, and the thickness was 1.5 μm to A 2.3 μm coating film was formed. Next, the coating film was exposed and cured through a photomask using a high-pressure mercury lamp. Then, it developed with 0.05 mass% potassium hydroxide developing solution at the temperature of 23 degreeC. Subsequently, it heated for 120 minutes within 230 degreeC oven, the board | substrate was baked (post-baking), and the colored layer was formed.
About the obtained colored layer, Olympus Optical Co., Ltd. product and spectrocolorimeter OSP-SP200 measured the color, and calculated | required chromaticity (x and y) and a brightness | luminance (Y value). The results are shown in Table 5 below. Further, the rate of change in luminance (Y value change rate) with Comparative Example 1 as a reference was evaluated according to the following criteria.
Δ: Less than + 0.5% ○: + 0.5% or more, less than + 1.0% ◎: + 1.0% or more

  From Table 5, it has confirmed that the colored layer formed using the resin composition for colored layers for color filters produced in the Example became high-intensity.

Claims (4)

At least a binder resin, a polyfunctional monomer, a photopolymerization initiator, and a pigment dispersion;
The binder resin is obtained by reacting the epoxy group of the following (D) with the carboxyl group of the copolymer obtained by copolymerizing the following (A) to (C), and does not contain an aromatic ring. A resin composition for a colored layer for a color filter.
(A) 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl An alicyclic compound-containing monomer (C) having at least one of (meth) acrylate and 1-perfluoroadamantyl (meth) acrylate (B) a monocyclic aliphatic hydrocarbon group and an unsaturated double bond; An epoxy group-containing compound having a carboxyl group-containing monomer (D) epoxy group having an unsaturated double bond and an unsaturated double bond   The ratio of (A) to (D) in the binder resin is within the range of (A) 10% by mass to 50% by mass, (B) within the range of 0% by mass to 20% by mass, and (C) 10% by mass. The resin composition for a colored layer for a color filter according to claim 1, wherein the resin composition is in a range of -60 mass% and (D) is in a range of 5 mass% to 35 mass%.   The resin composition for a colored layer for a color filter according to claim 1 or 2, wherein the binder resin has a weight average molecular weight in the range of 3000 to 24000.   The resin composition for a colored layer for a color filter according to any one of claims 1 to 3, wherein the pigment dispersion is a blue pigment dispersion containing a blue pigment.