JP2012007025A - Carboxy group-containing modified phenol resin and colored composition for color filter, containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carboxy group-containing modified phenol resin that both satisfies high sensitivity and maintenance of physical properties such as excellent dispersion stability, patternability, and chemical resistance, and a colored composition for a color filter, using the same.SOLUTION: The carboxy group-containing modified phenol resin is obtained by reacting a modified phenol resin (A), prepared by polymerizing a compound (a) containing a phenolic hydroxy group modified with a substituent containing a (meth) acryloyl group and a hydroxy group using an aldehyde (b) and an acid catalyst (c), with a polybasic acid anhydride.

Description

  The present invention relates to a carboxyl group-containing modified phenol resin from which a highly sensitive photosensitive coloring composition can be obtained, and in particular, high sensitivity used in the manufacture of color filters used in color liquid crystal display devices, color image pickup tube elements, and the like. The present invention also relates to a phenol resin suitable for a color filter coloring composition having good compatibility, and a color filter formed using the phenol resin.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundred microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist material) in which a pigment is dispersed in a photosensitive resin composition is applied to a transparent substrate such as glass, and the solvent is removed by drying. Perform pattern exposure, and then remove the unexposed areas in the development process to form the first color pattern. If necessary, apply heat and other treatments, and then repeat the same operation for all filter colors in sequence. Can be manufactured.

In forming a filter segment using a photosensitive coloring composition containing a pigment, high photosensitivity, solubility in a developer in a non-image area, and chemical resistance in an image area are important characteristics. In recent years, there has been an increasing demand for color filters with higher color density and black matrix with higher optical density (OD value), and there is a tendency for the colorant concentration in the photosensitive coloring composition to increase. However, when the concentration of the colorant is increased, it affects other characteristics such as insufficient curing of the exposed area due to an increase in light absorption of the colorant itself.
Thus, there is a trade-off relationship between the increase in the colorant concentration and the maintenance of the characteristics derived from the photosensitive resin composition including the photosensitivity.

In order to solve such a trade-off relationship, an epoxy compound having an ethylenically unsaturated double bond is subjected to an addition reaction with a polymer having a carboxyl group, and an ethylenically unsaturated diazo group is added to the hydroxyl group formed by the addition reaction. A composition using an acrylic polymer obtained by addition reaction of an isocyanate having a heavy bond as a binder resin has been studied (for example, Patent Document 1).
Since this method uses an acrylic polymer as a binder resin, compatibility with the photopolymerizable monomer used in the composition is improved, but there is a limit to increasing the amount of ethylenically unsaturated groups introduced. Therefore, there is a problem that the sensitivity when the colorant concentration increases is insufficient.

Also, carboxyl group-containing epoxy (meth) acrylate polymerization obtained by adding an unsaturated monocarboxylic acid to the epoxy group of a novolak type epoxy resin having 4 to 7 nuclei and further reacting with a polybasic acid anhydride. The thing is examined (for example, patent document 2).
In this method, a highly sensitive coloring composition suitable for a composition that requires a large amount of a colorant such as a black matrix can be obtained, but the compatibility with the photopolymerizable monomer used in the composition deteriorates. Storage stability is poor. Further, since a uniform cured film cannot be obtained, there is a problem that the cured film has insufficient chemical resistance and cannot be practically used.

In order to use the above compounds as a photosensitive resin composition, the types and ratios of the monomers constituting the photosensitive transparent resin are adjusted to improve stability, solubility, and chemical resistance. A design that satisfies the characteristics is required.
In the photosensitive coloring composition, while maintaining the dispersion stability of the colorant, the sensitivity of the photosensitive coloring composition with high concentration, good patternability (solubility of unexposed areas, photocured areas) In order to achieve the shape maintenance, etc.), the change of the photosensitive resin composition alone has reached its limit.

JP 2002-014468 A JP 2003-43685 A

  Accordingly, the present invention provides a carboxyl group-containing modified phenolic resin that achieves both high sensitivity and excellent dispersion stability, patterning properties, maintenance of physical properties such as chemical resistance, and a coloring composition for a color filter using the same. For the purpose.

  That is, in the first invention, a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group is polymerized using an aldehyde (b) and an acid catalyst (c). It is related with the carboxyl group-containing modified phenol resin obtained by making the modified phenol resin (A) and polybasic acid anhydride react.

  The second invention is a compound (B) obtained by reacting a compound (a) in which a phenolic hydroxyl group is modified with a substituent having a (meth) acryloyl group and a hydroxyl group and a polybasic acid anhydride, The present invention relates to a carboxyl group-containing modified phenol resin obtained by polymerization using an aldehyde (b) and an acid catalyst (c).

The third invention relates to the carboxyl group-containing modified phenolic resin of the first invention, wherein the modified phenolic resin (A) is obtained by copolymerizing a compound represented by the following general formula (1).
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.)

Moreover, 4th invention is related with the carboxyl group containing modified phenol resin of 2nd invention characterized by copolymerizing the compound shown by following General formula (1).
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.)

The fifth invention relates to the carboxyl group-containing modified phenolic resin of any one of the first to fourth inventions, wherein the aldehyde (b) is paraformaldehyde or a compound represented by the following general formula (3).
General formula (3)

(R ⁵ may be substituted with hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a hydroxyl group. (A good aromatic hydrocarbon group having 6 to 12 carbon atoms is shown.)

  The sixth invention relates to the carboxyl group-containing modified phenol resin of any one of the first to fifth inventions, wherein the acid catalyst (c) is an organic sulfonic acid or sulfuric acid.

  The seventh invention relates to the carboxyl group-containing modified phenolic resin of any one of the first to sixth inventions having a weight average molecular weight of 3,000 to 1,000,000.

  Moreover, 8th invention is related with the coloring composition for color filters containing the carboxyl group containing modified phenol resin of any one of 1st-7th invention, and a coloring agent.

  Moreover, 9th invention is related with the color filter characterized by including the filter segment formed from the coloring composition of 8th invention.

In the tenth invention, a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group is polymerized using an aldehyde (b) and an acid catalyst (c). To obtain a modified phenolic resin (A),
Then
The present invention relates to a method for producing a carboxyl group-containing modified phenolic resin, characterized by reacting a modified phenolic resin (A) with a polybasic acid anhydride.

The eleventh aspect of the invention comprises reacting a compound (a) in which a phenolic hydroxyl group is modified with a substituent having a (meth) acryloyl group and a hydroxyl group and a polybasic acid anhydride to obtain a compound (B),
Then
The present invention relates to a method for producing a carboxyl group-containing modified phenol resin, wherein the compound (B) is polymerized using an aldehyde (b) and an acid catalyst (c).

In addition, the twelfth aspect of the invention relates to a compound represented by the following general formula (1) when polymerizing a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group. The present invention relates to a method for producing a carboxyl group-containing modified phenolic resin according to a tenth aspect of the invention.
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.)

The thirteenth invention is the production of a carboxyl group-containing modified phenolic resin according to the eleventh invention, wherein the compound represented by the following general formula (1) is copolymerized when the compound (B) is polymerized. Regarding the method.
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.)

Furthermore, the fourteenth invention is a method for producing a carboxyl group-containing modified phenolic resin according to any of the tenth to thirteenth inventions, wherein the aldehyde (b) is paraformaldehyde or a compound represented by the following general formula (3): About.
General formula (3)

(R ⁵ may be substituted with hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a hydroxyl group. (A good aromatic hydrocarbon group having 6 to 12 carbon atoms is shown.)

  Furthermore, the fifteenth invention relates to a method for producing a carboxyl group-containing modified phenolic resin of any of the tenth to fourteenth inventions, wherein the acid catalyst (c) is an organic sulfonic acid or sulfuric acid.

Since the coloring composition for color filters of the present invention contains a carboxyl group-containing modified phenolic resin as an essential component, it achieves dispersion stability, high sensitivity, excellent patterning properties, and chemical resistance as a coloring composition for color filters. be able to.
In addition, the carboxyl group-containing modified phenolic resin used in the present invention has a high molecular weight unlike conventional novolak type epoxy (meth) acrylate, and can easily control Tg (glass transition temperature), double bond equivalent, and acid value. Therefore, chemical resistance and durability can be enhanced by dramatically increasing sensitivity and improving compatibility with acrylic resin.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not specified in the contents.

The carboxyl group-containing modified phenolic resin of the present invention uses a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group, using an aldehyde (b) and an acid catalyst (c). It is obtained by reacting a modified phenolic resin (A) obtained by polymerization with a polybasic acid anhydride.
Moreover, the carboxyl group-containing modified phenolic resin of the present invention is a compound obtained by reacting a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group and a polybasic acid anhydride. (B) can also be obtained by polymerizing using aldehydes (b) and acid catalyst (c).
That is, the carboxyl group-containing modified phenolic resin of the present invention is different from the conventional method of introducing a (meth) acryloyl group into a novolac type epoxy resin, and the phenolic hydroxyl group of phenols used in advance as a monomer is (meth) acryloyl. A novolak-type phenol resin is synthesized by using as a monomer a compound modified with a substituent having a group and a hydroxyl group.

  This makes it possible to obtain a modified phenolic resin having a (meth) acryloyl group and a hydroxyl group without undergoing a process of modifying a novolak type epoxy resin with (meth) acrylic acid or the like as in the prior art.

  In the present invention, the phenolic hydroxyl group of the monomer used in synthesizing the carboxyl group-containing modified phenolic resin is protected with a (meth) acryloyl group and a substituent having a hydroxyl group, and thus has a hydroxyl group used in conventional synthesis. Compared with phenols, the reactivity of the monomer is low and addition condensation with aldehyde is suppressed, so that it is possible to design the main chain structure and control the molecular weight that cannot be achieved by the conventional method for synthesizing novolak type phenol resins. Therefore, when the carboxyl group-containing modified phenolic resin of the present invention is used, it is possible to provide a coloring composition having excellent dispersion stability, high sensitivity, excellent patterning properties, and chemical resistance, which has been difficult to achieve in the past. .

<Compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group>
The compound (a) in which the phenolic hydroxyl group used in the present invention is modified with a (meth) acryloyl group and a substituent having a hydroxyl group,
If it is a compound modified by the substituent which has a 1 or more (meth) acryloyl group and a hydroxyl group in a molecule | numerator, there will be no restriction | limiting in particular.

As the compound (a) used in the present invention, for example,
(1) a compound obtained by ring-opening addition of (meth) acrylic acid and one or more functional aromatic epoxy compound,
(2) Compounds obtained by ring-opening addition of glycidyl (meth) acrylate and a phenoxy group-containing compound having one or more functional phenolic hydroxyl groups, carboxyl groups, and thiol groups, and the like.

Specifically, the compound obtained in the above (1) can be obtained by using the raw materials described below.
As an aromatic epoxy compound having one or more functions,
Examples thereof include phenyl glycidyl ether, bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and epoxidized product of dicyclopentadiene-modified phenol resin.

Specifically, the compound obtained in the above (2) can be obtained by using the raw materials described below.
As a phenoxy group-containing compound having a monofunctional or higher phenolic hydroxyl group,
Examples include phenol, nonylphenol, o-cresol, m-cresol, p-cresol, bisphenol A, α-naphthol, β-naphthol, 9-hydroxyphenanthrene, resorcinol,
As a phenoxy group-containing compound having a carboxyl group having one or more functions,
Acetylsalicylic acid, p-methoxybenzoic acid, m-methoxybenzoic acid, o-methoxybenzoic acid, 3-phenoxypropionic acid, 4-phenoxybutyric acid, 4- (phenylmethoxy) phenoxyacetic acid, m-phenylenedioxydiacetic acid, etc. Can be mentioned,
As a phenoxy group-containing compound having a thiol group having one or more functions,
Examples thereof include p-methoxythiophenol, m-methoxythiophenol, o-methoxythiophenol, 3,4-dimethoxythiophenol, 2,5-dimethoxythiophenol, 4-methoxy-α-toluenethiol and the like.

  Among the compounds obtained by these methods, 2-hydroxy-3-phenoxypropyl methacrylate obtained by the reaction of methacrylic acid and phenyl glycidyl ether, or the reaction of glycidyl methacrylate and phenol, can suppress gelation during polymerization. preferable.

  The said compound (a) can be used individually by 1 type or in combination of 2 or more types.

<Compound (a) in which phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group, or a compound capable of copolymerizing with compound (B)>

As the compound (a) in which the phenolic hydroxyl group is modified with a substituent having a (meth) acryloyl group and a hydroxyl group, or a compound that can be copolymerized with the compound (B), a compound represented by the general formula (1) , Aromatic monofunctional maleimides, aromatic (meth) acrylamides, and aromatic urethane (meth) acrylates, and a copolymer thereof is one of the preferred embodiments of the present invention.
This makes it possible to control the molecular weight, glass transition temperature, double bond equivalent, and acid value of the resin, and provide desired dispersion stability, high sensitivity, excellent patterning properties, and resistance to color compositions for color filters. It becomes possible to obtain a carboxyl group-containing modified phenolic resin that satisfies chemical properties.
Among these, the compound represented by the general formula (1) can be particularly preferably used from the viewpoint that the glass transition temperature and the double bond equivalent can be easily controlled.
General formula (1)

In the compound represented by the general formula (1), R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, carbon A cyclic alkyl group having 3 to 12 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, carbon number A 3-12 cyclic alkyl group, a C6-C12 aromatic hydrocarbon group, or a C1-C10 alkoxyl group is shown, j shows the integer of 0-3. R ² existing in one molecule may be the same or different.

The compound represented by the general formula (1) can be used as long as it is within the above range. Specifically,
Phenyl ester compounds such as phenyl acetate, phenyl propionate, phenyl benzoate, phenyl cyclohexanecarboxylate,
Phenyl ether compounds such as anisole, ethyl phenyl ether, bismethoxybenzene, allyl phenyl ether,
phenyl carbonate compounds such as tert-butoxycarbonyloxyphenyl,
Phenyl acetal compounds such as ethoxyethyl phenyl ether can be used, and two or more kinds of compounds may be used.

As the aromatic monofunctional maleimides,
N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N- (2,6-diethylphenyl) maleimide, N-2-chlorophenylmaleimide, N- (4-hydroxyphenyl) maleimide, N-2-trifluoromethylphenylmaleimide and the like can be used, and one kind can be used alone, or two or more kinds can be used in combination.

  The aromatic (meth) acrylamides can be used as long as they are represented by the general formula (2).

General formula (2)
CH ₂ = CR ³ (CO) NR ⁴ C ₆ H ₅
In the compound represented by the general formula (2), R ³ represents hydrogen or a methyl group, and R ⁴ represents hydrogen, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

The compound represented by the general formula (2) is one in which at least one of the two substituents on the nitrogen atom of the amide bond is substituted with a phenyl group, and any compound within the above range can be used. ,In particular,
N-phenyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N, N-diphenyl (meth) acrylamide and the like can be used, and one kind can be used alone, or two or more kinds can be used in combination. Can be used.

  The aromatic urethane (meth) acrylate is a (meth) acrylate having one or more urethane bonds, and is a compound obtained by a reaction between a hydroxy compound having at least one (meth) acryloyl group and an aromatic isocyanate. If available, it can be used.

Examples of the hydroxy compound having at least one (meth) acryloyl group include:
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono ( (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) (Meth) acrylate compounds having various hydroxyl groups such as acrylate- (meth) acrylic acid adducts and 2-hydroxy-3-phenoxypropyl (meth) acrylate ,
Examples thereof include a ring-opening reaction product of the above (meth) acrylate compound having a hydroxyl group and ε-caprolactone.

As the aromatic isocyanate, for example,
Aromatic isocyanates such as phenyl isocyanate,
aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
One or more burettes of isocyanate monomers,
Alternatively, polyisocyanates such as isocyanurates obtained by trimerization of the above diisocyanate compounds can be used.

<Aldehydes (b)>
As the aldehydes (b) used in the present invention, it is preferable to use paraformaldehyde and a compound represented by the general formula (3) from the viewpoint of easy availability of raw materials and industrial versatility.
General formula (3)

In general formula (3), R ⁵ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a hydroxyl group. The C6-C12 aromatic hydrocarbon group which may be substituted by is shown.

The compound represented by the general formula (3) can be used as long as it is within the above range. Specifically,
Alkyl aldehydes such as formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, dodecyl aldehyde,
Alkenyl aldehydes such as crotonaldehyde,
Aromatic aldehydes such as benzaldehyde, hydroxybenzaldehyde and naphthaldehyde can be used, and one kind can be used alone, or two or more kinds can be used in combination.

<Acid catalyst (c)>
The acid catalyst (c) used in the present invention is not particularly limited as long as it is an acidic compound. Specifically,
Inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid,
Organic carboxylic acids such as oxalic acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid,
An organic sulfonic acid such as trifluoromethanesulfonic acid can be used, and one kind can be used alone, or two or more kinds can be used in combination.
Of these, organic sulfonic acid and sulfuric acid are preferably used from the viewpoint of catalytic activity.

  The polymerization reaction for obtaining the carboxyl group-containing modified phenolic resin of the present invention may be performed using a solvent, and the solvent is not limited as long as it does not inhibit the reaction. Examples thereof include organic carboxylic acids such as acetic acid; ethyl acetate, Esters such as butyl acetate; cellosolves such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; cellosolves such as ethylene glycol monoethyl ether acetate; carbitols such as diethylene glycol monoethyl ether; diethylene glycol monoethyl ether acetate and the like Carbitol acetates; ethers such as diethyl ether and tetrahydrofuran; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide; acetone, methyl ethyl ketone Ketones such as ethylene and cyclohexanone; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene; and halogen solvents such as methylene chloride, chloroform, monochlorobenzene, and dichlorobenzene. It may be a single solvent or a mixture of two or more.

Then, the manufacturing method of the modified phenol resin (A) of this invention is demonstrated. The modified phenolic resin (A) of the present invention polymerizes a compound (a) obtained by modifying a phenolic hydroxyl group with a substituent having a (meth) acryloyl group using an aldehyde (b) and an acid catalyst (c). (Hereinafter, this manufacturing method may be referred to as “first aspect of manufacturing method”).
The modified phenolic resin of the present invention is a compound (B) obtained by reacting a compound (a) having a phenolic hydroxyl group modified with a (meth) acryloyl group and a substituent having a hydroxyl group and a polybasic acid anhydride. Can also be obtained by polymerizing using an aldehyde (b) and an acid catalyst (c) (hereinafter, this production method may be referred to as “second aspect of the production method”).

First, the 1st aspect of a manufacturing method is demonstrated. Specifically, the compound (a) and the aldehyde (b) are put in a reactor equipped with a cooling device and a stirring device, and then the acid catalyst (c) is added to perform stirring and reaction.
The charging molar ratio between the compound (a) and the aldehyde (b) is not particularly limited, but it is preferable that [compound (a) / aldehyde (b)] = 1 / 0.1 to 1/10, Particularly preferably, it is 1 / 0.2 to 1/8.
In addition, when using the compound which can be copolymerized with a compound (a), it calculates using the number of moles totaled with the compound (a).
When the ratio of aldehydes (b) exceeds 10, the molecular weight of the obtained resin may not be sufficiently increased.
On the other hand, when the ratio of the aldehydes (b) is less than 0.1, the molecular weight becomes too large, the handling becomes difficult, and depending on the reaction conditions, it may gel and become insoluble and infusible.
When paraformaldehyde is used as the aldehyde (b), since paraformaldehyde is melted or depolymerized by heat in the reaction system to form formaldehyde during the reaction, the number of moles of formaldehyde generated here is changed to the aldehydes (b ) Is calculated as the number of moles.

  The amount of the acid catalyst (c) to be added varies depending on the type and activity of the acid used, but the total of the compound (a) and the compound that can be used and copolymerized with the compound (a) is used as necessary. 10 to 500 mol% is preferable with respect to 100 mol%, and can be set as appropriate. From the viewpoint of economical aspect and removal operation after completion of the reaction, it is particularly preferably 30 to 300 mol%.

  The reaction is preferably carried out within the range of room temperature to about 150 ° C, particularly preferably 40 to 100 ° C. If the temperature becomes too high, the raw material compound cannot be trapped by the cooling device, and a side reaction may occur in some cases. On the other hand, when the temperature is too low, the progress of the reaction becomes very slow, which is not preferable from an economical viewpoint.

  Although reaction time is not specifically limited, It can set suitably with conditions, such as reaction temperature, a catalyst seed | species, and quantity. It is preferable to complete in about 1 to 20 hours from an economical viewpoint, and it is particularly preferably 1 to 10 hours.

Although it is difficult to react the monomers charged at the time of reaction 100%, the remaining monomers can be removed by refining and refining operations such as dialysis.
Specifically, a method in which the resin produced at the end of the reaction is added to a poor solvent for the resin such as a large amount of water, and the amount of the poor solvent such as water and other conditions can be appropriately set.
The catalyst species can be removed by neutralizing the liquid after being put in the poor solvent and then washing the resin with water.
When performing the water washing treatment, it is desirable that the pH value is 3 to 7, preferably 5 to 7, with a basic compound. As basic compounds,
Inorganic alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide,
Various basic substances such as organic alkalis such as triethylamine, dimethylbenzylamine and pyridine can be used.
Further, in the case of washing treatment, it may be carried out according to a regular method, and the amount and number of washing water are not particularly limited, but may be set according to the required level.

  After the neutralization treatment, the product obtained by distilling off the solvent under reduced pressure is concentrated to obtain the desired curable modified phenolic resin. When the obtained resin is stored, it is preferable from the viewpoint of storage stability that it is put in a light-shielding bottle or a small amount of a polymerization inhibitor.

<Carboxyl group-containing modified phenolic resin>
Then, reaction of the obtained modified phenol resin (A) and polybasic acid anhydride is demonstrated.
The polybasic acid anhydride used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule.
Specifically, for example, phthalic anhydride, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, Examples thereof include a compound containing an acid anhydride group having an alicyclic structure such as heptic anhydride or tetrabromophthalic anhydride, or an aromatic ring structure.
Other acid anhydride group-containing compounds include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride , Pentylmaleic anhydride, hexylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, butylglutamic anhydride, decylglutamic anhydride, dodecylglutamic acid An anhydride etc. are mentioned.
In the present invention, the acid anhydride group-containing compound may be used alone or in combination.

The synthesis conditions for obtaining the carboxyl group-containing modified phenolic resin of the present invention are not particularly limited, and can be performed under known conditions.
For example, a modified phenolic resin (A), a polybasic acid anhydride and, if necessary, a solvent are charged in a flask and heated at 60 ° C. to 100 ° C. with stirring to obtain a carboxyl group-containing modified phenolic resin. At this time, a catalyst such as a tertiary amino group-containing compound may be used as necessary.

Here, in the case where the ratio of reacting the polybasic acid anhydride with respect to 1.0 mol of the hydroxyl group in the modified phenol resin (A) is less than 0.1, in the resulting carboxyl group-containing modified phenol resin of the present invention. In some cases, the carboxyl group functioning as the solubility of the non-image area in the developer is reduced, and desired physical properties may not be exhibited.
In addition, it cannot be made to react with the quantity which makes a polybasic acid anhydride react with 1.0 mol with respect to 1.0 mol of hydroxyl groups in the said modified phenol resin (A).

Next, a second aspect of the manufacturing method will be described.
First, a compound (B) is obtained by reacting a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group and a polybasic acid anhydride.
As the polybasic acid anhydride, the same compounds as those exemplified in the first aspect of the production method can be used, and the reaction conditions are the reaction conditions of the modified phenol resin (A) and the polybasic acid anhydride. According to
Next, the carboxyl group-containing modified phenolic resin of the present invention can be obtained by polymerizing the compound (B) using the aldehydes (b) and the acid catalyst (c).
The reaction conditions at this time are the same as those for the compound (a) and the aldehydes (b).
In each of the above steps, the ratio between the components is in accordance with the first aspect of the production method.

  The carboxyl group-containing modified phenolic resin of the present invention preferably has a weight average molecular weight of 3,000 to 1,000,000, particularly preferably 5,000 to 100,000. When the weight average molecular weight is less than 3,000, chemical resistance, durability, and heat resistance may not be sufficiently obtained. When the weight average molecular weight exceeds 1,000,000, for example, the molecular weight becomes too high and handling becomes a problem. There is a case.

  In the present invention, several kinds of carboxyl group-containing modified phenolic resins having different weight average molecular weights and double bond equivalents may be used together. For example, as one effective means for improving various physical properties, the weight average molecular weight is 3 , 000 compounds and 100,000 compounds may be used in combination.

  In addition, since the carboxyl group-modified phenol resin obtained in the present invention has a high molecular weight and has a phenyl group in the main chain, the 5% weight loss temperature is 300 ° C. or higher, and the conventional acrylic polymer is 250 ° C. Compared to the degree, the heat resistance is very good.

The glass transition temperature of the carboxyl group-containing modified phenolic resin obtained in the present invention is preferably −50 to 150 ° C., particularly preferably −30 to 100 ° C. The glass transition temperature affects the patterning property. When the glass transition temperature is less than −50 ° C., the hardness of the photocured portion is lowered, and the pattern may be chipped. Moreover, when a glass transition temperature exceeds 150 degreeC, the solubility of an unexposed part falls and an unexposed part may remain as a residue.
Therefore, specifically, when the glass transition temperature of the carboxyl group-containing modified phenolic resin is too low, the hardness of the photocured portion can be increased by increasing the glass transition temperature by using anisole as a compound that can be copolymerized. The decrease can be suppressed.
On the other hand, when the glass transition temperature of the carboxyl group-containing modified phenolic resin is too high, the glass transition temperature can be lowered by using diphenyl ether, and the solubility reduction of the uncured portion can be suppressed.

<Photosensitive coloring composition>
The photosensitive coloring composition of this invention is characterized by including the carboxyl group containing modified phenol resin mentioned above. If necessary, the photosensitive coloring composition of the present invention is a compound other than the carboxyl group-containing modified phenolic resin of the present invention having one or more ethylenically unsaturated groups in one molecule, a colorant, and a resin-type pigment dispersion. Various additives such as an agent, a pigment derivative, a surfactant, a storage stabilizer, a solvent, and a photoinitiator can be contained.

Among the compounds other than the curable modified phenolic resin of the present invention having one or more ethylenically unsaturated groups in one molecule, examples of the compound having one ethylenically unsaturated group in one molecule include:
Unsaturated compounds such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, Alkyl (meth) acrylate compounds having an alkyl group having 1 to 22 carbon atoms such as octadecyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) ) Hydroxyl-containing unsaturated compounds such as acrylates;
(Meth) acrylate compounds having a hydroxyl group at the terminal and having a polyoxyalkylene chain, such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate;
Mono (meth) acrylate compounds having an alkoxy group at the terminal and a polyoxyalkylene chain, such as methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and methoxytriethylene glycol (meth) acrylate;
Polyoxyalkylene (meth) acrylate compounds having a phenoxy or aryloxy group at the terminal, such as phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, and phenoxytriethylene glycol (meth) acrylate;
Acrylamide unsaturated compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxymethyl- (meth) acrylamide;
Unsaturated compounds having a dialkylamino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene;
Nitrogen content such as quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having a halogen ion such as Cl ⁻ , Br ⁻ , I ⁻ or the like as a counter ion or QSO ₃ ⁻ (Q: an alkyl group having 1 to 12 carbon atoms) (Meth) acrylic compounds;
Examples thereof include perfluoroalkylalkyl (meth) acrylate compounds having a perfluoroalkyl group having 1 to 20 carbon atoms, such as perfluoromethylmethyl (meth) acrylate and perfluoroethylmethyl (meth) acrylate.

As a compound having two ethylenically unsaturated groups in one molecule, for example,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethyl Glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified Diacrylate, 2-acryloyloxyethyl acid phosphate diester, p-bis [β- (meth) acryloyloxyethylthio] xylylene, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl sulfone, etc. It is done.

As a compound having three or more ethylenically unsaturated groups in one molecule, for example,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (acrylic) Roxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) Of polyhydric alcohol and (meth) acrylic acid, such as acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra (meth) acrylate, etc. Ester compounds;
Among the above compounds, those having one or more hydroxyl groups in the molecule, compounds having two or more isocyanate groups in one molecule, and compounds having two or more hydroxyl groups in one molecule other than the above, if necessary Polyfunctional urethane (meth) acrylates obtained by reacting;
Polyfunctional (meth) acrylates obtained by modifying a styrene-maleic anhydride copolymer with a hydroxyl group-containing (meth) acrylic compound having one or more hydroxyl groups in the molecule;
Polyfunctional polyester (meth) acrylates formed by ester-linking (meth) acrylic acid to an alcohol residue in a polyester obtained by dehydration condensation of a dibasic acid and a polyhydric alcohol;
Examples include polyfunctional (meth) acrylates obtained by adding (meth) acrylic acid to an acrylic copolymer of an epoxy group-containing (meth) acrylate compound.

  The compounds other than the carboxyl group-containing modified phenolic resin of the present invention having one or more ethylenically unsaturated groups in one molecule can be used singly or in combination of two or more.

  The colored composition for a color filter of the present invention contains at least a compound other than the carboxyl group-containing modified phenolic resin of the present invention and a colorant.

As the colorant contained in the color filter coloring composition of the present invention, organic or inorganic red, magenta or yellow pigments can be used alone or in admixture of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.
When forming a red filter segment using the coloring composition of the present invention, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 can be used. The red coloring composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.
When forming a magenta color filter segment, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 81, 122, 144, 146, 169, 177, 207, and red pigments can be used.
When forming a yellow filter segment, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 It can be used yellow pigments such 181,182,185,187,188,193,194,198,199,213,214.
Examples of inorganic pigments include yellow lead, zinc yellow, red bean (red oxide (III)), and cadmium red. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.
In the coloring composition of the present invention, the coloring agent is finely dispersed in the photosensitive resin composition using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. Can be manufactured. When a pigment is used as the colorant, a dispersion aid such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition obtained by dispersing the pigment in the photosensitive resin composition using the dispersion aid is used. If so, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the colorant.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the resin composition. Resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, their modified products, poly (lower alkyleneimine) formed by reaction of polyester having free carboxyl group, amide or its salt, etc. are used It is done. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

 Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as laurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

 The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Further, in the coloring composition of the present invention, the coloring agent is sufficiently dispersed in the photosensitive resin composition, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate forming the filter segment. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the colorant.

  When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the colored composition of the present invention. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropyloxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used. The photopolymerization initiator can be used in an amount of preferably 5 to 20 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the colorant.

  These photopolymerization initiators are used alone or in admixture of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

The colorant is preferably contained in a proportion of 5 to 70% by weight, more preferably 20 to 50% by weight, in a total of 100% by weight of the solid content of the coloring composition.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed from the coloring composition for color filters of this invention.

  Each color coloring composition other than red, magenta or yellow can be formed using ordinary color coloring compositions containing each color pigment, the non-photosensitive transparent resin, and the polyfunctional monomer. Examples of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

Examples of the green coloring composition include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 are used. The green coloring composition includes
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.

  Examples of cyan coloring compositions include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 81 are used.

The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the coloring composition of this invention and each normal color coloring composition by the photolithographic method.
As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, each color-colored photosensitive composition prepared as a color resist material of the above-mentioned solvent development type or alkali development type that is cured by light irradiation is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”, and “%” represents “% by weight”.

<Preparation of resin solution>
IR and GPC were used for confirmation of the structure of the carboxyl group-containing modified phenolic resin of the present invention.

(A) GPC
A TSKgel column and an HLC-8120GPC manufactured by Tosoh Corporation equipped with an RI detector were used, and the molecular weight in terms of polystyrene when THF was used as a developing solvent was used.

(B) IR
For the measurement of FT-IR spectrum, Shimadzu FT-IR-8200PC was used, and it was confirmed whether or not the absorption of acid anhydride near 1845 cm ⁻¹ disappeared.

(Synthesis Example 1)
In a 1 L flask, 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), 88.8 g (0.4 mol), paraformaldehyde 25.2 g (0.8 mol), chloroform 80 mL was added, and sulfuric acid (20 mL) diluted with acetic acid (80 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 90 g of a modified phenolic resin. To this was added 0.045 g of methoquinone as a polymerization inhibitor, 100 g of cyclohexanone, 22.91 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of acid anhydride absorption by IR, Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-1 having an acid value of 74.9 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 13600, and the weight average molecular weight (Mw) was 37200.

(Synthesis Example 2)
In a 1 L flask, 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), 88.8 g (0.4 mol), paraformaldehyde 25.2 g (0.8 mol), chloroform 80 mL was added, and sulfuric acid (4 mL) diluted with acetic acid (80 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 90 g of a modified phenolic resin. To this was added 0.045 g of methoquinone as a polymerization inhibitor, 100 g of cyclohexanone, and 41.40 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of absorption of acid anhydride by IR, Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-2 having an acid value of 116.2 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 17200, and the weight average molecular weight (Mw) was 46500.

(Synthesis Example 3)
2-hydroxy-3-phenoxypropyl methacrylate (product name: “Aronix M-5700”, manufactured by Toagosei Co., Ltd.) 44.4 g (0.2 mol), diphenyl ether 34.0 g (0.2 mol) paraformaldehyde 25 0.2 g (0.8 mol) and 75 mL of chloroform were added, and sulfuric acid (4 mL) diluted with acetic acid (75 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 70 g of a modified phenolic resin. To this was added 0.035 g of methoquinone as a polymerization inhibitor, 70 g of cyclohexanone, and 10.15 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of absorption of acid anhydride by IR. Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-3 having an acid value of 46.70 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 12400, and the weight average molecular weight (Mw) was 21100.

(Synthesis Example 4)
2-hydroxy-3-phenoxypropyl methacrylate (product name: “Aronix M-5700”, manufactured by Toagosei Co., Ltd.) 44.4 g (0.2 mol), diphenyl ether 34.0 g (0.2 mol) paraformaldehyde 25 0.2 g (0.8 mol) and 75 mL of chloroform were added, and sulfuric acid (4 mL) diluted with acetic acid (75 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 70 g of a modified phenolic resin. To this was added 0.035 g of methoquinone as a polymerization inhibitor, 70 g of cyclohexanone, and 17.85 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of acid anhydride absorption by IR. Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-4 having an acid value of 70.47 mg KOH / g. The number average molecular weight (Mn) of the obtained resin was 15600, and the weight average molecular weight (Mw) was 28000.

(Synthesis Example 5)
In a 1 L flask, 22.22 g (0.1 mol) of 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), 15.21 g (0.1 mol) of tetrahydrophthalic anhydride Then, 0.022 g of methoquinone as a polymerization inhibitor and 0.40 g of dimethylbenzylamine as a catalyst were added, heated to 90 ° C. and reacted for about 6 hours, and disappearance of acid anhydride absorption was confirmed by IR. To this was added 57.75 g (0.3 mol) of phenol EO-modified acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: “light acrylate PO-A”), 25.2 g (0.8 mol) of paraformaldehyde, and 80 mL of chloroform, and iced. While stirring at 4 ° C. in a bath, sulfuric acid (4 mL) diluted with acetic acid (80 mL) was slowly added dropwise. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried under reduced pressure at room temperature to obtain 70 g of a carboxyl group-containing modified phenol resin having an acid value of 40.1 mgKOH / g. Cyclohexane was added thereto and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenol resin solution P-5. The number average molecular weight (Mn) of the obtained resin was 11500, and the weight average molecular weight (Mw) was 35600.

(Synthesis Example 6)
In a 1-L flask, 40.00 g (0.18 mol) of 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), 27.38 g (0.18 mol) of tetrahydrophthalic anhydride Then, 0.035 g of methoquinone as a polymerization inhibitor and 0.70 g of dimethylbenzylamine as a catalyst were added, heated to 90 ° C., reacted for about 6 hours, and disappearance of acid anhydride absorption was confirmed by IR. To this, 42.35 g (0.22 mol) of phenol EO-modified acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: “light acrylate PO-A”), 25.2 g (0.8 mol) of paraformaldehyde, and 80 mL of chloroform were added, and iced. While stirring at 4 ° C. in a bath, sulfuric acid (4 mL) diluted with acetic acid (80 mL) was slowly added dropwise. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 70 g of a carboxyl group-containing modified phenol resin having an acid value of 72.4 mgKOH / g. Cyclohexane was added thereto and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenol resin solution P-6. The number average molecular weight (Mn) of the obtained resin was 14000, and the weight average molecular weight (Mw) was 31600.

(Synthesis Example 7)
2-hydroxy-3-phenoxypropyl methacrylate (product name: “Aronix M-5700” manufactured by Toagosei Co., Ltd.) 44.4 g (0.2 mol), anisole 21.6 g (0.2 mol), paraformaldehyde in a 1 L flask 25.2 g (0.8 mol) and 75 mL of chloroform were added, and sulfuric acid (4 mL) diluted with acetic acid (75 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 70 g of a modified phenolic resin. To this was added 0.035 g of methoquinone as a polymerization inhibitor, 70 g of cyclohexanone, and 11.52 g of succinic anhydride, and the mixture was heated to 90 ° C. and reacted for about 6 hours. After confirming the disappearance of acid anhydride absorption by IR, cyclohexanone. Was added to dilute to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-7 having an acid value of 71.4 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 12400, and the weight average molecular weight (Mw) was 21100.

(Synthesis Example 8)
2-hydroxy-3-phenoxypropyl methacrylate (product name: “Aronix M-5700” manufactured by Toagosei Co., Ltd.) 44.4 g (0.2 mol), anisole 21.6 g (0.2 mol), paraformaldehyde in a 1 L flask 25.2 g (0.8 mol) and 75 mL of chloroform were added, and sulfuric acid (4 mL) diluted with acetic acid (75 mL) was slowly added dropwise while stirring at 4 ° C. in an ice bath. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 70 g of a modified phenolic resin. To this was added 0.035 g of methoquinone as a polymerization inhibitor, 70 g of cyclohexanone, and 17.85 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of acid anhydride absorption by IR. Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenol resin solution P-8 having an acid value of 74.1 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 15600, and the weight average molecular weight (Mw) was 25400.

(Synthesis Example 9)
In a 1 L flask, 83.36 g (0.38 mol) of 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), bisphenol F EO-modified acrylate (manufactured by Toagosei Co., Ltd.) , Product name: “Aronix M-208”) 9.69 g (0.02 mol), paraformaldehyde 25.2 g (0.8 mol), chloroform 80 mL, acetic acid (80 mL) with stirring at 4 ° C. in an ice bath Sulfuric acid diluted with (4 mL) was slowly added dropwise. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 90 g of a modified phenolic resin. To this was added 0.045 g of methoquinone as a polymerization inhibitor, 100 g of cyclohexanone, 22.91 g of tetrahydrophthalic anhydride, heated to 90 ° C., reacted for about 6 hours, and confirmed the disappearance of acid anhydride absorption by IR, Cyclohexanone was added and diluted to a solid content of 30% to obtain a carboxyl group-containing modified phenol resin solution P-9 having an acid value of 70.1 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 34500, and the weight average molecular weight (Mw) was 115000.

(Synthesis Example 10)
In a 1 L flask, 83.36 g (0.38 mol) of 2-hydroxy-3-phenoxypropyl methacrylate (manufactured by Toagosei Co., Ltd., product name: “Aronix M-5700”), bisphenol F EO-modified acrylate (manufactured by Toagosei Co., Ltd.) , Product name: “Aronix M-208”) 9.69 g (0.02 mol), paraformaldehyde 25.2 g (0.8 mol), chloroform 80 mL, acetic acid (80 mL) with stirring at 4 ° C. in an ice bath Sulfuric acid diluted with (4 mL) was slowly added dropwise. After completion of dropping, the flask was gradually heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol, washed several times, and collected by filtration. Thereafter, the reaction product was dried at room temperature under reduced pressure to obtain 90 g of a modified phenolic resin. To this was added 0.045 g of methoquinone as a polymerization inhibitor, 100 g of cyclohexanone, and 15.30 g of succinic anhydride, and the mixture was heated to 90 ° C. and reacted for about 6 hours. After confirming the disappearance of acid anhydride absorption by IR, cyclohexanone. Was added to dilute to a solid content of 30% to obtain a carboxyl group-containing modified phenolic resin solution P-10 having an acid value of 74.5 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 34500, and the weight average molecular weight (Mw) was 104000.

(Comparative Synthesis Example 1)
Cresol novolak glycidyl ether (manufactured by DIC Corporation, product name: “Epiclon N-665”, epoxy equivalent 208, number of nuclei 6-7) 104 g, acrylic acid 36 g, p-methoxyphenol as a polymerization inhibitor in a 1 L flask After adding 0.14 g and 61 g of diethylene glycol ethyl ether acetate, the flask was heated to 100 ° C., and after confirming that the above mixture was uniformly dissolved, 0.8 g of triphenylphosphine was charged and allowed to react for about 10 hours. . This was charged with 24.3 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for about 6 hours. After confirming the disappearance of acid anhydride absorption by IR, 322.4 g of diethylene glycol ethyl ether acetate was added and the solid content was 30. To obtain a novolac type epoxy acrylate resin solution R-1 having a solid acid value of 67 mgKOH / g.

(Comparative Synthesis Example 2)
Cresole novolak glycidyl ether (product name: “Epototo YDCN-704”, epoxy equivalent 210, number of nuclei 9 to 10) 105 g, acrylic acid 36 g, p-methoxy as a polymerization inhibitor in a 1 L flask After adding 0.14 g of phenol and 116 g of diethylene glycol ethyl ether acetate, the temperature of the flask was raised to 100 ° C. After confirming that the above mixture was uniformly dissolved, 0.8 g of triphenylphosphine was charged and reacted for about 10 hours. It was. This was charged with 24.3 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for about 6 hours. After confirming the disappearance of acid anhydride absorption by IR, 269.7 g of diethylene glycol ethyl ether acetate was added and the solid content was 30. To obtain a novolac type epoxy acrylate resin solution R-2 having a solid content acid value of 67 mgKOH / g.

(Comparative Synthesis Example 3)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 150 g of cyclohexanone and heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Then, 40 g of methacrylic acid and 25 g of methyl methacrylate were added from the dropping vessel. , N-butyl methacrylate 35 g, and N, N-azobisisobutyronitrile 1.33 g in advance are mixed dropwise over 2 hours, followed by stirring at the same temperature for 3 hours, A containing acrylic polymer was obtained. This was charged with 0.17 g of methoquinone, 53.5 g of cyclohexanone and 35.7 g of glycidyl methacrylate as a polymerization inhibitor, heated to 90 ° C. and allowed to react for about 10 hours, confirming that the acid value had dropped to 3 mg KOH / g. . Further, 40.9 g of cyclohexanone, 27.2 g of 2-methacryloyloxyethyl methacrylate, and 0.02 g of dibutyltin dilaurate were charged, heated to 60 ° C., reacted for about 6 hours, and the disappearance of isocyanate group absorption was confirmed by IR. Cyclohexanone was added and diluted to a solid content of 30% to obtain a photosensitive acrylic resin solution R-3 having an acid value of 73.6 mgKOH / g. The number average molecular weight (Mn) of the obtained resin was 11600, and the weight average molecular weight (Mw) was 24300.

<Production Example of Dispersed Resin Solution>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 233 parts of cyclohexanone and heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. A mixed solution in which 10 parts of methacrylate, 77 parts of n-butyl methacrylate and 1.33 parts of N, N-azobisisobutyronitrile are uniformly mixed in advance is dropped over 2 hours, and then stirred at the same temperature for 3 hours. Then, a resin solution having a weight average molecular weight of 25000 was obtained. After cooling to room temperature, it was diluted with cyclohexanone to obtain a dispersed resin solution having a solid content of 20%.

<Preparation of coloring composition for red color filter>
[Example 1]
First, P.I. R. 254 (CI Pigment Red 254 diketopyrrolopyrrole red pigment) 1.66 parts, P.I. R. 177 (CI Pigment Red 177 anthraquinone red pigment) 2.2 parts, P.I. Y. 150 (CI Pigment Yellow 150 azomethine yellow pigment) 0.51 part, dispersant (“Solspers 20000” manufactured by Nippon Lubrizol) 0.87 part, dispersion resin solution 4.5 part, solvent (propylene glycol monomethyl) 23.3 parts of ether acetate) were mixed and dispersed in a planetary ball mill using zirconia beads to obtain a pigment dispersion. To this pigment dispersion, 7.25 parts of carboxyl group-containing modified phenol resin solution P-1 as a resin solution, 3.38 parts of an ethylenically unsaturated compound (dipentaerythritol hexaacrylate), a photopolymerization initiator (2- (dimethyl Amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) 1.08 parts, sensitizer (2,4-diethylthioxanthone) 0. 27 parts and 55 parts of a solvent (propylene glycol monomethyl ether acetate) were stirred and mixed, and then filtered through a 1 μm filter to prepare a coloring composition for a red color filter.

[Examples 2 to 10, Comparative Examples 1 to 3]
The resin solution was changed from the carboxyl group-containing modified phenol resin solution P-1 to the carboxyl group-containing modified phenol resin solution P-2 to 10, the novolac type epoxy acrylate resin solution R-1, 2, and the photosensitive acrylic resin solution R-3. A colored composition for a red color filter was prepared in the same manner as in Example 1 except that.

<Preparation of coloring composition for green color filter>
[Example 11]
First, P.I. G. 36 (CI Pigment Green 36 Halogenated Copper Phthalocyanine Green Pigment) 3.94 parts, P.I. Y. 150 (CI Pigment Yellow 150 azomethine yellow pigment) 1.00 part, dispersant (“Solspers 20000” manufactured by Nippon Lubrizol) 0.99 parts, dispersion resin solution 4.69 parts, solvent (propylene glycol monomethyl) 26.06 parts of ether acetate) were mixed and dispersed in a planetary ball mill using zirconia beads to obtain a pigment dispersion. To this pigment dispersion, 4.80 parts of a carboxyl group-containing modified phenol resin solution P-1 as a resin solution, 3.38 parts of an ethylenically unsaturated compound (dipentaerythritol hexaacrylate), a photopolymerization initiator (2- (dimethyl Amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) 1.08 parts, sensitizer (2,4-diethylthioxanthone) 0. 27 parts and 53.8 parts of a solvent (propylene glycol monomethyl ether acetate) were stirred and mixed, and then filtered through a 1 μm filter to prepare a coloring composition for a green color filter.

[Examples 12 to 20, Comparative Examples 4 to 6]
The resin solution was changed from the carboxyl group-containing modified phenol resin solution P-1 to the carboxyl group-containing modified phenol resin solution P-2 to 10, the novolac type epoxy acrylate resin solution R-1, 2, and the photosensitive acrylic resin solution R-3. A colored composition for a green color filter was prepared in the same manner as in Example 11 except that.

<Preparation of coloring composition for blue color filter>
[Example 21]
First, P.I. B. 15: 6 (C.I. Pigment Blue 15: 6 copper phthalocyanine-based blue pigment) 2.10 parts, P.I. V. 23 (CI Pigment violet 23 dioxazine-based purple pigment) 1.04 parts, dispersant ("Solspers 20000" manufactured by Nippon Lubrizol) 0.48 parts, dispersion resin solution 3.75 parts, solvent (propylene glycol monomethyl) 16.40 parts of ether acetate) were mixed and dispersed in a planetary ball mill using zirconia beads to obtain a pigment dispersion. To this pigment dispersion, 10.00 parts of a carboxyl group-containing modified phenol resin solution P-1 as a resin solution, 4.20 parts of an ethylenically unsaturated compound (dipentaerythritol hexaacrylate), a photopolymerization initiator (2- (dimethyl Amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) 1.30 parts, sensitizer (2,4-diethylthioxanthone) 0. 32 parts and 60.4 parts of solvent (propylene glycol monomethyl ether acetate) were stirred and mixed, and then filtered through a 1 μm filter to prepare a colored composition for a blue color filter.

[Examples 22 to 30, Comparative Examples 7 to 9]
The resin solution was changed from the carboxyl group-containing modified phenol resin solution P-1 to the carboxyl group-containing modified phenol resin solution P-2 to 10, the novolac type epoxy acrylate resin solution R-1, 2, and the photosensitive acrylic resin solution R-3. A colored composition for a blue color filter was prepared in the same manner as in Example 21 except that.

<Evaluation of coloring composition for color filter>
The prepared colored composition for color filter (red, green, blue) was evaluated by the following evaluation method, and the results are shown in the table. In addition, about the coloring composition obtained by the Example and the comparative example, the dispersion stability, developability, sensitivity, and chemical resistance were evaluated by the following method.

(Dispersion stability evaluation)
The viscosity at 25 ° C. of the prepared coloring composition for color filter was measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO). The viscosity on the day of preparation of the color filter coloring composition was measured as the initial viscosity (η0: mPa · s), and the viscosity after storage for 7 days in a constant temperature room at 40 ° C. (η7: mPa · s) was measured. The dispersion stability was evaluated according to the following criteria.
○: “η7 / η0 is 0.8 or more and less than 1.20, and viscosity increase hardly occurs and dispersion stability is good.”
Δ: “η7 / η0 is 1.20 or more and less than 1.60, the viscosity is slightly increased and the dispersion stability is slightly inferior”
×: “η7 / η0 is less than 0.8 or 1.60 or more, a change in viscosity is observed, and dispersion stability is inferior.”

(Developability evaluation)
The color filter coloring composition was spin-coated on a 10 × 10 cm, 1.1 mm thick transparent glass substrate and pre-baked at 70 ° C. for 20 minutes to form a coating film having a dry film thickness of about 2.0 μm. Then, UV pattern exposure was performed at 8 levels of exposure doses of 20, 30, 40, 50, 60, 80, 100, and ²⁰⁰ mJ / cm ² through a mask having a fine line pattern of 50 μm. The time (T1) for dissolving the entire pattern of the unexposed area was calculated with an alkaline developer. The alkaline developer used was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao) and 90% by weight of water. The thing which consists of% was used.
○: “T1 is 40 seconds or less.”
Δ: “T1 is longer than 40 seconds and shorter than 60 seconds.”
×: “Unexposed part cannot be removed even after 60 seconds”

(Sensitivity evaluation)
The exposed substrate produced in the development evaluation was extended to 1.5 times T1 and developed to form a stripe-shaped filter segment. The film thickness of the unexposed / undeveloped part and the film thickness of the obtained filter segment at each exposure level were measured with a surface shape measuring device “Dektak150” (manufactured by ULVAC, Inc.), and [remaining film ratio] = [ The film thickness of the filter segment] / [film thickness of unexposed / undeveloped portion] was calculated. From the obtained residual film rate curve, the exposure amount at which the residual film rate reached saturation was determined as the saturated exposure amount, and the residual film rate was determined as the saturated residual film rate. In addition, the sensitivity is higher as the saturation exposure amount is smaller and the saturation residual film ratio is closer to 100%.

(Chemical resistance evaluation)
A filter segment was formed in the same manner as the sensitivity evaluation except that the exposure amount was set to the saturated exposure amount + 50 mJ / cm ² . After heat treatment at 230 ° C. for 60 minutes, a part of the substrate was immersed in N-methylpyrrolidone (NMP) for 30 minutes, and then the state of the pattern surface was observed with an optical microscope, and chemical resistance was evaluated according to the following criteria.
○: “No change was observed.”
Δ: “Slightly cracks were observed”
×: “Severe cracks were observed.”

  As shown in the table, when the novolac type epoxy acrylate resin was used, the molecular weight and Tg were not appropriate, so that the dispersion stability and chemical resistance were poor. When a photosensitive acrylic resin was used, the sensitivity was poor because the amount of ethylenically unsaturated groups introduced was not appropriate. When the carboxyl group-containing modified phenolic resin of the present invention is used, the molecular weight, Tg, and ethylenically unsaturated group amount can be designed in an appropriate range, so the sensitivity is high, and the dispersion stability and chemical resistance are excellent. A colored composition could be obtained.

Claims (15)

  Modified phenol resin (A) obtained by polymerizing a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group using an aldehyde (b) and an acid catalyst (c) And a carboxyl group-containing modified phenolic resin obtained by reacting polybasic acid anhydride.   A compound (B) obtained by reacting a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group and a polybasic acid anhydride is converted into an aldehyde (b), an acid catalyst. A carboxyl group-containing modified phenolic resin obtained by polymerization using (c). The carboxyl group-containing modified phenol resin according to claim 1, wherein the modified phenol resin (A) is obtained by copolymerizing a compound represented by the following general formula (1).
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.) The carboxyl group-containing modified phenolic resin according to claim 2, which is obtained by copolymerizing a compound represented by the following general formula (1).
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6 to 12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.) The carboxyl group-containing modified phenolic resin according to any one of claims 1 to 4, wherein the aldehyde (b) is paraformaldehyde or a compound represented by the following general formula (3).
General formula (3)

(R ⁵ may be substituted with hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a hydroxyl group. (A good aromatic hydrocarbon group having 6 to 12 carbon atoms is shown.)   The carboxyl group-containing modified phenol resin according to any one of claims 1 to 5, wherein the acid catalyst (c) is an organic sulfonic acid or sulfuric acid.   The carboxyl group-containing modified phenolic resin according to any one of claims 1 to 6, which has a weight average molecular weight of 3,000 to 1,000,000.   The coloring composition for color filters containing the carboxyl group-containing modified phenol resin in any one of Claims 1-7, and a coloring agent.   A color filter comprising a filter segment formed from the colored composition according to claim 8. A compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group is polymerized using an aldehyde (b) and an acid catalyst (c) to obtain a modified phenol resin (A). Get
Then
A method for producing a carboxyl group-containing modified phenol resin, comprising reacting the modified phenol resin (A) with a polybasic acid anhydride. The compound (a) having a phenolic hydroxyl group modified with a (meth) acryloyl group and a substituent having a hydroxyl group is reacted with a polybasic acid anhydride to obtain a compound (B).
Then
A method for producing a carboxyl group-containing modified phenol resin, wherein the compound (B) is polymerized using an aldehyde (b) and an acid catalyst (c). A compound represented by the following general formula (1) is copolymerized when polymerizing a compound (a) in which a phenolic hydroxyl group is modified with a (meth) acryloyl group and a substituent having a hydroxyl group. Item 11. A method for producing a carboxyl group-containing modified phenolic resin according to Item 10.
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.) 12. The method for producing a carboxyl group-containing modified phenolic resin according to claim 11, wherein the compound represented by the following general formula (1) is copolymerized when the compound (B) is polymerized.
General formula (1)

(R ¹ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or An optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, wherein R ² is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a carbon number; 6-12 aromatic hydrocarbon group, or an alkoxyl group having 1 to 10 carbon atoms, j is different even each R ² together present in the. one molecule represents an integer of 0 to 3 identical May be.) The method for producing a carboxyl group-containing modified phenol resin according to any one of claims 10 to 13, wherein the aldehyde (b) is paraformaldehyde or a compound represented by the following general formula (3).
General formula (3)

(R ⁵ may be substituted with hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or a hydroxyl group. (A good aromatic hydrocarbon group having 6 to 12 carbon atoms is shown.)   The method for producing a carboxyl group-containing modified phenol resin according to any one of claims 10 to 14, wherein the acid catalyst (c) is an organic sulfonic acid or sulfuric acid.