TWI781095B - Resin composition, color filter and image display device - Google Patents

Abstract

The object of the present invention is to provide a resin composition that can suppress the precipitation of compounds derived from color materials, has high productivity, and can form a colored layer with low surface roughness. The resin composition formed using this resin composition has high productivity and has a surface A color filter having a colored layer with low thickness, and an image display device equipped with such a color filter.

According to one aspect of the present invention, there is provided a resin composition characterized in that it contains a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and A compound (E) of a group and a crosslinked cycloaliphatic group.

Description

Resin composition, color filter and image display device

This case applies the priority of Japanese Patent Application No. 2016-71496 (application date: March 31, 2016), and the entire disclosure content thereof is cited as a part of the specification of this case.

The invention relates to a resin composition, a color filter and an image display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, and tablet PCs) has also increased, showing that the market for liquid crystal displays is expanding day by day. In addition, recently, organic light-emitting display devices such as organic EL displays with high visibility due to self-luminescence are also attracting attention as next-generation image display devices. With regard to the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility, and reduction in power consumption are strongly desired.

Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, in the formation of a color image in a liquid crystal display device, the light passing through the color filter is directly colored by the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. In addition, in an organic light emitting display device, a color filter is used for color adjustment and the like.

The color filter is mainly composed of a base material, a colored layer formed on the base material, an It consists of a light-shielding layer placed between the colored layers and a transparent electrode layer formed on the colored layers. The coloring layer is formed by coating a resin composition containing a coloring material and a photopolymerizable compound on a substrate, patterning it by photolithography, and then performing heat treatment (post-baking) (for example, refer to Japanese Patent JP-A-2015-49458 Gazette).

However, when such a resin composition is used, compounds derived from the coloring material are precipitated during the heat treatment during the formation of the colored layer, which is detected as irregularity during the visual inspection. Therefore, there is a possibility that the yield of the final color filter product may decrease.

The present invention was made in order to solve the above-mentioned problems. That is, the object is to provide: a resin composition that can suppress the precipitation of a compound derived from a coloring material, has high productivity, and can form a colored layer with a low surface roughness; A color filter with a colored layer having a low surface roughness; and an image display device equipped with such a color filter.

The inventors of the present invention have studied intensively on the above-mentioned subject, and found that the precipitation of a compound derived from a coloring material can be suppressed by adding a precipitation-inhibiting compound to a resin composition. The present invention has been accomplished based on this knowledge.

According to one aspect of the present invention, there is provided a resin composition characterized in that it contains a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), and A compound (E) of a group and a crosslinked cycloaliphatic group.

In the above-mentioned resin composition, the carbon number of the above-mentioned fluorocarbon group is 2 or more and 10 or less.

In the above-mentioned resin composition, the above-mentioned crosslinked cycloaliphatic group may be Any of a substituted adamantyl group and an optionally substituted dicyclopentyl group.

In the above-mentioned resin composition, the above-mentioned compound (E) may contain a constituent unit derived from a compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound derived from a crosslinked cycloaliphatic group and an ethylenically unsaturated group. A copolymer of constituent units of the saturated group compound (E-2).

In the resin composition, the molar ratio of the constituent units derived from the compound (E-1) to the constituent units derived from the compound (E-2) in the compound (E) is 5:95 to 70:30.

The above resin composition may further contain a thiol compound (F).

In the above-mentioned resin composition, the above-mentioned polymerizable compound may be a photopolymerizable compound.

According to another aspect of the present invention, there is provided a color filter characterized by comprising a colored layer made of a cured product of the above-mentioned resin composition.

According to another aspect of the present invention, there is provided an image display device characterized by comprising the above-mentioned color filter.

According to the resin composition of one aspect of the present invention, since it contains a compound having a fluorocarbon group and a cross-linked cycloaliphatic group, it can suppress the precipitation of a compound derived from a coloring material, and can provide high productivity and can form a rough surface. A resin composition for a colored layer with a low density. According to a color filter and an image display device according to another aspect of the present invention, a color filter and an image display device formed using the above-mentioned resin composition, having high productivity and having a colored layer with a low surface roughness can be provided.

10‧‧‧color filter

11‧‧‧Substrate

12‧‧‧coloring layer

13‧‧‧shading layer

20‧‧‧Image display device

21‧‧‧Opposite substrate

22‧‧‧LCD layer

30‧‧‧Image display device

40‧‧‧Organic luminescent body

41‧‧‧Transparent anode

42‧‧‧Hole injection layer

43‧‧‧Electric hole transport layer

44‧‧‧luminescent layer

45‧‧‧Electron injection layer

46‧‧‧cathode

50‧‧‧Organic protective layer

60‧‧‧Inorganic oxide film

Fig. 1 is a schematic configuration diagram showing a color filter according to an embodiment of the present invention.

Fig. 2 is a schematic configuration diagram showing a liquid crystal display device which is an example of an image display device according to an embodiment of the present invention.

3 is a schematic configuration diagram showing an organic light emitting display device as an example of an image display device according to an embodiment of the present invention.

Hereinafter, the resin composition, color filter, and image display device according to the embodiments of the present invention will be described in detail.

<<Resin composition>>

The resin composition contains a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a colorant (D), and a compound (E) having a fluorocarbon group and a cross-linked cycloaliphatic group By. The resin composition may further contain a thiol compound (F), a dispersant (G), and a solvent (H).

<Polymer (A)>

The polymer system has the function of imparting film-forming properties or adhesion to the surface to be coated. A polymer may be used individually by 1 type, and may use it in combination of 2 or more types. The polymer is used to impart sufficient hardness to the coating film, and is preferably a curable polymer. The curable polymer is not particularly limited, and conventional curable polymers used for forming colored layers of known color filters can be appropriately used.

As the curable polymer, for example, a photosensitive polymer that can be polymerized and cured by visible rays, ultraviolet rays, electron beams, etc., a thermosetting polymer that can be polymerized and cured by heating, or a mixture thereof can be used.

The thermosetting polymer is not particularly limited, and examples include phenol resin Grease, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine-urea co-condensation resin, silicone resin, polysiloxane resin, etc. A thermosetting polymer may be used individually by 1 type, and may use it in combination of 2 or more types.

Although it does not specifically limit as a photosensitive polymer, In order to provide sufficient hardness to a coating film, it is preferable that it has an ethylenically unsaturated group. The term "ethylenically unsaturated group" in this specification refers to a group containing a carbon-carbon double bond capable of radical polymerization, such as (meth)acryl, vinyl, allyl, etc. Also, the term "(meth)acryl" includes both "acryl" and "methacryl". A photosensitive polymer may be used individually by 1 type, and may use it in combination of 2 or more types.

When forming a colored layer, when using a photolithography process, as a photosensitive polymer, the alkali-soluble resin which is soluble to an alkali developing solution is used suitably. Moreover, alkali-soluble resin can also be used as a thermosetting polymer. In addition, as a polymer, a thermosetting polymer may be further used in addition to the alkali-soluble resin.

(alkali soluble resin)

Alkali-soluble resins have an acidic group, and can be appropriately selected and used as long as they function as a binder resin and are soluble in an alkali developer used for pattern formation.

As an acidic group of alkali-soluble resin, a carboxyl group is mentioned, for example. As an alkali-soluble resin which has a carboxyl group, the carboxyl group containing copolymer which has a carboxyl group, the epoxy group (meth)acrylate resin which has a carboxyl group, etc. are mentioned, for example. Examples of the carboxyl group-containing copolymer include acrylic copolymers having a carboxyl group and acrylic copolymers such as styrene-acrylic copolymers having a carboxyl group. Among them, the best is the side chain It has a carboxyl group, and further has an ethylenically unsaturated group in a side chain, and the like. This is because the film strength of the cured film formed by containing an ethylenically unsaturated group improves. In addition, these acrylic copolymers and acrylic copolymers such as styrene-acrylic copolymers having a carboxyl group, and epoxy acrylate resins may be used in combination of two or more.

Acrylic copolymers having carboxyl groups and acrylic copolymers having carboxyl groups such as styrene-acrylic copolymers are, for example, carboxyl-containing ethylenically unsaturated monomers and other monomers that can be copolymerized as needed, A (co)polymer obtained by (co)polymerizing by a known method.

Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoate, maleic acid, monoalkyl maleic acid, fumaric acid, and itaconic acid. , crotonic acid, cinnamic acid, acrylic acid dimer, etc. Also, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω -Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature, and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesiveness with the substrate. By using an alkali-soluble resin having a bulky hydrocarbon ring for the alkali-soluble resin, the solvent resistance of the resulting colored layer, especially the swelling of the colored layer can be suppressed. Such a hydrocarbon ring includes, for example, a cyclic aliphatic hydrocarbon ring which may also have a substituent, an aromatic ring which may also have a substituent, and combinations thereof; the hydrocarbon ring may also have a carbonyl group, a carboxyl group, or an oxycarbonyl group. , Amide group and other substituents. However, when an aliphatic ring is contained, the luminance of the resulting colored layer is improved while improving the heat resistance or adhesiveness of the colored layer.

酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯、後述之Cardo樹脂等；由即使在加熱處理中抑制來自色材之化合物之析出效果(以下亦稱為「析出抑制效果」)較大的觀點而言，較佳係(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸苄酯、苯乙烯、後述之Cardo樹脂。 The ethylenically unsaturated monomer having a hydrocarbon ring as an alkali-soluble resin having a hydrocarbon ring is combined with a compound represented by a compound (E) having a fluorocarbon group and a crosslinked cycloaliphatic group , such as cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, iso(meth)acrylate

Ester, phenoxyethyl (meth)acrylate, styrene, Cardo resin described later, etc.; even during heat treatment, the effect of inhibiting the precipitation of compounds from coloring materials (hereinafter also referred to as "separation inhibition effect") is large From the standpoint of methacrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, and Cardo (described later) are preferable. resin.

In the case where the alkali-soluble resin is an acrylic copolymer having a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring, it can be realized by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". modulation.

As a specific example of an acrylic copolymer having a carboxyl group, for example, those described in Japanese Patent Application Laid-Open No. 2013-029832, concrete examples include methyl (meth)acrylate, ethyl (meth)acrylate and the like without carboxyl groups. A monomer, and a copolymer of at least one selected from (meth)acrylic acid and its anhydrides. In addition, among the above-mentioned copolymers, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group can also be exemplified. limited to these. Among them, the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is particularly suitable because the sensitivity of the colored layer, film strength, and the like become more stable.

The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. At this time, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is 5% by mass or more, the decrease in the solubility of the obtained coating film to an alkali developing solution can be suppressed, and pattern formation can be facilitated. Also, in the copolymerization When the compounding ratio is 50% by mass or less, pattern defects or film roughness on the pattern surface are less likely to occur when developing with an alkaline developer.

The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000-50,000, more preferably 3,000-20,000. When the weight average molecular weight of the carboxyl group-containing copolymer is 1,000 or more, the curability of the coating film can be sufficiently obtained; and when it is 50,000 or less, it is easy to form a pattern when developing with an alkaline developer.

The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, but epoxy (meth)acrylate resin obtained by reacting an epoxy compound with an unsaturated group-containing monocarboxylic acid and an acid anhydride is preferred. Acrylate compound. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used.

As a carboxyl-containing epoxy (meth)acrylate resin, it is preferable to contain The following chemical formula (1) shows a structure in which two benzene rings are bonded to the fennel skeleton (Cardo structure).

The correct mechanism of the carboxyl-containing epoxy (meth)acrylate resin (hereinafter referred to as Cardo resin) containing the above-mentioned Cardo structure has not yet been elucidated. It can be considered that because the fennel skeleton contains a π-conjugated system, it is highly sensitive to free radicals; By combining the oxime ester-based photopolymerization initiator described later with Cardo resin, the sensitivity, developability, development adhesion, etc. can be improved The required performance. In addition, since Cardo resin has high solvent resolubility, it is also preferable from the viewpoint that a colored resin composition without aggregates can be designed even at a high color density.

The carboxyl group-containing copolymer has an acid value of 40 mgKOH/g or more in terms of developability (solubility) to an aqueous alkali solution used in a developer. The above-mentioned carboxyl group-containing copolymer is preferably 40 mgKOH/g or more and 300 mgKOH in terms of acid value from the viewpoint of developability (solubility) to the alkaline aqueous solution used in the developer and adhesiveness to the substrate. /g or less, more preferably 60 mgKOH/g or more and 280 mgKOH/g or less, more preferably 70 mgKOH/g or more and 250 mgKOH/g or less.

In the case where the side chain of the carboxyl-containing copolymer has an ethylenically unsaturated group, by combining with the compound (E) having a fluorocarbon group and a cross-linked cyclic aliphatic group used in the present invention, the From the viewpoint of the film strength of the cured film and the effect of suppressing the precipitation of the color material, the ethylenically unsaturated bond equivalent is preferably in the range of 100-2000, and particularly preferably in the range of 140-1500. When the ethylenically unsaturated bond equivalent is 2000 or less, development resistance and adhesiveness are excellent. Moreover, if it is 100 or more, since the ratio of the said structural unit which has a carboxyl group, or the structural unit which has a hydrocarbon ring etc. can be relatively increased, it is excellent in developability and heat resistance. Here, "ethylenically unsaturated bond equivalent weight" refers to the weight average molecular weight per mole of ethylenically unsaturated bonds in the carboxyl group-containing copolymer, and is represented by the following formula (1).

[Number 1] Ethylenic unsaturated bond equivalent (g/mol)=W(g)/M(mol)...(1)

In the above formula (1), W represents the mass (g) of the carboxyl group-containing copolymer, and M represents the mole number (mol) of ethylenic double bonds contained in the carboxyl group-containing copolymer W (g).

The above-mentioned ethylenically unsaturated bond equivalent, for example, can be based on JIS K The test method of iodine value recorded in 0070:1992 is calculated by measuring the number of ethylenic double bonds per 1g of alkali-soluble resin.

In the case of a polymer having an ethylenically unsaturated group, the content of the polymer having an ethylenically unsaturated group in the resin composition is 100 parts by mass relative to the total solid content of the resin composition, preferably 5 parts by mass Part or more and 60 parts by mass or less. When the content of the polymer having an ethylenically unsaturated group is 5 parts by mass or more, sufficient hardening is obtained, and peeling of the coating film of the patterned resin composition can be suppressed. Moreover, when content of the polymer which has an ethylenically unsaturated group is 60 mass parts or less, peeling by hardening shrinkage can be suppressed. The so-called "solid content" in this specification refers to the content other than the solvent. The lower limit of the content of polymers having ethylenically unsaturated groups in the resin composition is relative to 100 parts by mass of the total solid content of the resin composition, preferably more than 10 parts by mass; the upper limit of the content of polymers in the resin composition It is 100 mass parts with respect to the total solid content of a resin composition, More preferably, it is 45 mass parts or less.

<Polymerizable compound (B)>

The polymerizable compound is not particularly limited as long as it can be polymerized by a polymerization initiator described later, and for example, a photopolymerizable compound or a thermally polymerizable compound can be used. As a thermally polymerizable compound, a compound having a thermally polymerizable functional group such as a carboxyl group, an amine group, an epoxy group, a hydroxyl group, a glycidyl group, an isocyanate group, and an alkyl group in the molecule can be used. As the photopolymerizable compound, a compound having two or more ethylenically unsaturated double groups in the molecule can be used, and a polyfunctional (meth)acrylate having two or more acryl groups or methacryl groups is particularly preferable.

As such a polyfunctional (meth)acrylate, it can select and use suitably among those skilled in the art. Specific examples include, for example, those described in Japanese Patent Application Laid-Open No. 2013-029832 Those who wait.

These polyfunctional (meth)acrylates may be used individually by 1 type, and may use it in combination of 2 or more types. Also, when the resin composition for color filters of the present invention requires superior photocurability (high sensitivity), the polyfunctional monomer preferably has 3 or more polymerizable double bonds (trifunctional), and more preferably Poly(meth)acrylates of polyhydric alcohols with a valence of 3 or more or modified dicarboxylic acids of these are preferred. Specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol tri( Meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Succinic acid modification of pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The content of the polymerizable compound in the resin composition is preferably not less than 10 parts by mass and not more than 50 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. If the content of the polymerizable compound is 10 parts by mass or more, poor hardening can be suppressed, so it can suppress the elution of the exposed part during development; if the content of the polymerizable compound is 50 parts by mass or less, poor development can be suppressed, or Heat shrinkage, so fine wrinkles are less likely to occur on the entire surface of the colored layer. The lower limit of the content of the polymerizable compound in the resin composition is relative to 100 parts by mass of the total solid content of the resin composition, preferably more than 20 parts by mass; the upper limit of the content of the polymerizable compound in the resin composition is relative to The total amount of solid content in the resin composition is 100 parts by mass, more preferably 40 parts by mass or less.

<Polymerization initiator (C)>

There is no special limitation as a polymerization initiator, and various initiators known from the prior art can be used Use 1 type or combine 2 or more types. The polymerization initiator may, for example, be a thermal polymerization initiator or a photopolymerization initiator, specifically, those described in JP-A-2013-029832 or the like.

As a polymerization initiator, only 1 type may be used, and 2 or more types of compounds may be used together. As a polymerization initiator, due to the high effect of hardening the film surface, the effect of suppressing the occurrence of pattern defects, and the effect of suppressing the occurrence of water bleeding, by combining with the above-mentioned fluorocarbon group and cross-linked cycloaliphatic From the viewpoint that the combination of compounds represented by the compound (E) of the base group has a high effect of inhibiting the precipitation of the color material, it is preferable to contain an oxime ester photopolymerization initiator. Moreover, when using 2 or more types of oxime ester type photoinitiators together, since color material precipitation can be suppressed more, it is preferable to use 2 or more types of oxime ester type photoinitiators.

As the above-mentioned oxime ester-based photopolymerization initiator, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred from the viewpoint of reducing contamination of the colored resin composition for color filters or equipment contamination caused by decomposition products. Those having a condensed ring containing an aromatic ring are more preferably those having a condensed ring containing a benzene ring and a heterocyclic ring.

Examples of the oxime ester-based photopolymerization initiator include those described in JP-A-2000-80068, JP-A-2001-233842, JP-A-2010-527339, JP-A-2010-527338, JP-A-2013-041153, etc. The oxime ester photopolymerization initiator and so on.

As the above-mentioned oxime ester photopolymerization initiator, it has excellent curability, development resistance, inhibitory effect of pattern defect occurrence, and water bleeding for resin compositions with increased color material concentration in order to achieve a wider color reproduction range. From the viewpoint of superior generation suppression effect and precipitation suppression effect, it is preferable to use an oxime ester-based photoinitiator that generates an alkyl radical, and it is more preferable to use an oxime ester-based photopolymerization initiator that generates a methyl radical. . It is presumed that alkyl radicals are more likely to activate radical movement than aryl radicals. as an alkyl Free radical oxime ester-based photopolymerization initiators, such as 1-(o-acetyl oxime) 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-ethanone (trade name "Irgacure OXE-02", manufactured by BASF Corporation), (2,4,6-trimethylphenyl)[8-[[(acetyloxy)imino] [2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]- Methanone (trade name "Irgacure OXE-03", manufactured by BASF Corporation), 1-(o-acetyloxime) 1-[9-ethyl-6-(1,3-dioxolane,4-(2 -methoxyphenoxy)-9H-carbazol-3-yl]-ethanone (trade name "ADEDA OPT-N-1919", manufactured by ADEKA Corporation), o-acetyloxime (9-ethyl-6 -Nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-methanone (trade name "ADEKA AKLS NCI-831 ", manufactured by ADEKA), 1-(o-acetyloxime) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- Base]-1-acetone (trade name "TR-PBG-304", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 1-(o-acetyloxime) 3-cyclopentyl-1-[2-(2-pyrimidine Thio)-9H-carbazol-3-yl]-1-acetone (trade name "TR-PBG-314", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 1-(o-acetyloxime) 2-cyclohexyl -1-[2-(2-pyrimidinyloxy)-9H-carbazol-3-yl]-ethanone (trade name "TR-PBG-326", manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), 1-( o-Acetyl oxime) 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-ethanone (trade name "TR-PBG-331", Changzhou Qiangli Electronics New Materials Co., Ltd.), 1-(o-acetyloxime) 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6-[4-[(4, 6-Dimethyl-2-pyrimidinyl)thio]-2-methylbenzoyl]-9H-carbazol-9-yl]phenyl]-1-octanone (trade name "EXTA-9" , manufactured by UNION CHEMICAL), etc. Also, as an initiator for generating phenyl radicals, specific examples include Irgacure OXE-01 (manufactured by BASF), etc. Further, as an oxime ester photopolymerizable initiator having a diphenylsulfide skeleton Examples of the initiator include ADEKA AKLS NCI-930 (manufactured by ADEKA), TR-PBG-3057 (manufactured by Changzhou Qiangli Power New Material Co., Ltd.), and the like.

As the above-mentioned oxime ester photopolymerization initiator, it is preferable to use an oxime ester photopolymerization initiator having a diphenylsulfide skeleton from the viewpoint of improving luminance compared with a case having a carbazole skeleton. Moreover, it is preferable to contain at least 2 types of oxime type photoinitiators from a viewpoint which can suppress color material precipitation more.

啉基丙烷-1-酮(例如Irgacure 907、BASF公司製)、2-苄基-2-(二甲基胺基)-1-(4-

啉基苯基)-1-丁酮(例如商品名「Irgacure 369」，BASF公司製)、4,4'-雙(二乙基胺基)二苯基酮(例如商品名「Hicure ABP」，川口藥品公司製)等。 Moreover, in an oxime ester type photoinitiator, it is preferable to use together the polymerization initiator which has a tertiary amine structure from a viewpoint of a sensitivity improvement. The reason is that the polymerization initiator with a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in the molecule, so the free radicals generated by the initiator are not easily inactivated by oxygen, which can increase the sensitivity due to. Examples of commercially available photoinitiators having a tertiary amine structure include 2-methyl-1-(4-methylthiophenyl)-2-

Linylpropan-1-one (for example, Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-

Linylphenyl)-1-butanone (for example, trade name "Irgacure 369", manufactured by BASF Corporation), 4,4'-bis(diethylamino) diphenyl ketone (for example, trade name "Hicure ABP", Kawaguchi Pharmaceutical Co., Ltd.), etc.

The content of the polymerization initiator in the resin composition is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. If the content of the polymerization initiator is 0.1 parts by mass or more, photocuring will proceed sufficiently; and if the content of the polymerization initiator is 15 parts by mass or less, side reactions can be suppressed and stability over time can be maintained. The lower limit of the content of the polymerization initiator in the resin composition is relative to 100 parts by mass of the total solid content of the resin composition, more preferably at least 1 part by mass, and more preferably at least 3 parts by mass; The upper limit of the content of the initiator is relative to 100 parts by mass of the total solid content of the resin composition, more preferably 10 parts by mass or less.

As the polymerization initiator used in the above resin composition, when two or more oxime ester-based photopolymerization initiators are used, from the viewpoint of fully exerting the combined effect of these polymerization initiators, oxime The total content of ester-based photopolymerization initiators is based on The total solid content of the resin composition is preferably within a range of 0.1% by mass to 12.0% by mass, more preferably within a range of 1.0% by mass to 8.0% by mass.

<Color (D)>

The color material is not particularly limited as long as it can develop the desired color when forming the colored layer of the color filter, and various organic pigments and dyes can be used alone or within the range that does not damage the physical properties including optical properties. Mix and use 2 or more types in any proportion. Among them, organic pigments are preferably used because of their high heat resistance.

Various organic pigments are known. Among them, diketopyrrolopyrrole pigments (for example, C.I. Pigment Red 254 or brominated diketopyrrolopyrrole pigments represented by the following chemical formula (2)) or halogenated phthalocyanines Pigment greens such as C.I. Pigment Green 7, 36, 58, and 59 are particularly easy to precipitate, so the precipitation-inhibiting compound of the present invention is particularly effective when diketopyrrolopyrrole-based pigments or halogenated phthalocyanine-based pigments are used as color materials.

Examples of organic pigments include compounds classified as pigments in the color index (C.I., issued by The Society of Dyers and Colourists, Inc.), specifically, those with the following color index (C.I.) numbers.

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185 and derivative pigments of C.I. Pigment Yellow 150; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 ; C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; C.I. pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. Pigment Green 7, 36, 58, 59; C.I. Pigment Brown 23, 25; C.I. Pigment Black 1,7.

Examples of the aforementioned dyes include soluble dyes, dyes with various substituents, or dyes that are insoluble in solvents and dispersible by known lake formation (salt formation) techniques (lake coloring materials) , or dyes that are dispersible by combining solvents with low solubility. By using such a dispersible dye in combination with a dispersant, the dispersibility or dispersion stability of the dye can be improved.

染料、靛青系染料、萘醌染料、醌亞胺染料、亞甲基染料、酞菁染料等。又，作為標準，若染料為對10g溶劑(或混合溶劑)之溶解量為10mg以下，則可判定為於該溶劑(或混合溶劑)中該染料為可分散。 As the dye, it can be appropriately selected from known dyes. Examples of dispersible dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, quinoline yellow dyes, triphenylmethane dyes,

Dyes, indigo dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, phthalocyanine dyes, etc. Also, as a standard, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be judged that the dye is dispersible in the solvent (or mixed solvent).

The relative ions in the color lake material vary depending on the types of dyes mentioned above. The relative ions of acid dyes are cations, and the relative ions of basic dyes are anions.

As the relative cation of the acid dye, metal ions such as ammonium cation, calcium ion, barium ion, strontium ion, manganese ion, aluminum ion, cesium ion, lanthanum ion, neodymium ion, cerium ion, polyaluminum chloride or oxygen Inorganic polymers such as zirconium chloride.

The counter anion of the basic dye may be an organic anion or an inorganic anion. As said organic anion, the organic compound which has an anionic group as a substituent is mentioned, for example. Examples of the above-mentioned anionic group include -SO ₂ N ^- SO ₂ CH ₃ , -SO ₂ N ^- COCH ₃ , -SO ₂ N ^- SO ₂ CF ₃ , -SO ₂ N ^- COCF ₃ , -CF ₂ SO ₂ N ^- SO ₂ CH ₃ , -CF ₂ SO ₂ N ^- COCH ₃ , -CF ₂ SO ₂ N ^- SO ₂ CF ₃ , -CF ₂ SO ₂ N ^- COCF ₃ etc. imidic acid group, or -SO ₃ ^- , -CF ₂ SO ₃ ^- , -PO ₃ ^2- , -COO ^- , -CF ₂ PO ₃ ^2- , -CF ₂ COO ^- and the like. On the other hand, examples of inorganic anions include oxoacid anions (phosphate ions, sulfate ions, chromate ions, tungstate ions (WO ₄ ^2- ), molybdate ions (MoO ₄ ^2- ), etc.), or plural Inorganic anions such as condensed polyoxometallic acid anions or mixtures thereof.

系色材、四氮雜卟啉系色材、酞菁系色材及香豆素系色材所構成群的1種以上。 As the above-mentioned lake color material, from the viewpoint of inhibiting the precipitation of the color material, it is preferably selected from the group consisting of azo color material, anthraquinone color material, quinoline yellow color material, indigo color material, and triphenylmethane color material. material,

One or more of the group consisting of porphyrazine-based color materials, phthalocyanine-based color materials, and coumarin-based color materials.

作為基本骨架、並包含玫瑰紅系色材的

系色材。 In addition, as the above-mentioned dye and the above-mentioned lake coloring material, it is preferable to contain

As the basic skeleton, including rose red color material

Department of color materials.

系酸性染料，其中較佳為下述一般式(3)所示化合物、亦即具有玫瑰紅系酸性染料。 As one of the above dyes and lakes

It is an acid dye, and a compound represented by the following general formula (3), that is, a rose bengal acid dye is preferred.

In the above general formula (3), R ^a to R ^d independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ^a and R ^b , R ^c and R ^d may be bonded to form a ring structure. Also, R ^a to R ^d may be the same or different. R ^c represents an acidic group, and X represents a halogen atom. m represents an integer from 0 to 5. The general formula (3) has one or more acidic groups, and n is an integer of 0 or more.

The alkyl groups in R ^a to R ^d are not particularly limited. Examples include linear or branched alkyl groups with 1 to 20 carbons that may also have substituents, among which linear or branched alkyl groups with 1 to 8 carbons are preferred, and 1 to 20 carbons is more preferred. ~5 linear or branched alkyl groups. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. Examples of the substituted alkyl group include a benzyl group, which may further include a halogen atom or an acidic group as the substituent. Substituents.

The aryl groups in R ^a to R ^d are not particularly limited. Examples thereof include an aryl group which may have a substituent having 6 to 20 carbon atoms, and among them, a group having a phenyl group, a naphthyl group, etc. is preferable. The heteroaryl group in R ^a to R ^d may be, for example, a heteroaryl group having 5 to 20 carbon atoms which may have a substituent. As the heteroatom, one containing a nitrogen atom, an oxygen atom, or a sulfur atom is preferred.

As a substituent which an aryl group or a heteroaryl group may have, there may be mentioned, for example, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, a carbamoyl group, and a carbonate group.

Specific examples of acidic groups or their salts include carboxyl (-COOH), carboxylate (-COO- ⁾ , carboxylate (-COOM, where M represents a metal atom), sulfonate (-SO ₃ ^- ), sulfonic acid group (-SO ₃ H), sulfonic acid salt group (-SO ₃ M, where M represents a metal atom), etc.; among them, it is preferred to have a sulfonic acid group (-SO ₃ ^- ), sulfonic acid at least one of a group (—SO ₃ H) or a sulfonate group (—SO ₃ M). Furthermore, the metal atom M may, for example, be a sodium atom, a potassium atom, or the like.

As the compound represented by the general formula (3), acid red 289, acid violet 9, acid violet 30, etc. are preferable from the viewpoint of high brightness.

Also, from the viewpoint of heat resistance, in the general formula (3), a compound having a betaine structure of m=1 and n=0 is preferable. Also, among them, from the viewpoint of forming a colored layer with excellent luminance and light fastness, it is preferable that m=1 and n=0, R ^a and R ^c are independently alkyl or aryl groups, R ^b and R ^d are independently aryl or heteroaryl.

The method for producing the compound represented by the general formula (3) is not particularly limited, and it can be obtained by referring to, for example, Japanese Patent Application Laid-Open No. 2010-211198.

系酸性染料之色澱色材，適合使用金屬色澱色材。金屬色澱色材係使用含有金屬原子作為色澱化劑者。藉由使用含有金屬原子之色澱化劑，色材之耐熱性變高。作為此種色澱化劑，較佳係含有成為2價以上之金屬陽離子之金屬原子的色澱化劑。 as above

It is a lake color material of acid dye, suitable for metal lake color material. The metallic lake coloring material uses those containing metal atoms as the lakening agent. By using a laking agent containing metal atoms, the heat resistance of the color material becomes high. As such a laking agent, a laking agent containing a metal atom serving as a divalent or higher metal cation is preferable.

The average primary particle size of the above-mentioned color material is not particularly limited as long as it can form the desired color when it is used as the coloring layer of the color filter, and it varies depending on the type of color material used. Preferably it is 10 nm or more and 100 nm or less, More preferably, it is 15 nm or more and 60 nm or less. When the average primary particle diameter of the coloring material is within the above-mentioned range, a display device provided with a color filter manufactured using the above-mentioned resin composition can be made high-contrast and high-quality.

The content of the coloring material in the resin composition is usually not less than 15 parts by mass and not more than 55 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. If the content of the color material is 15 parts by mass or more, desired optical properties can be obtained and desired functions can be exhibited; and if the content of the color material is 55 parts by mass or less, poor hardening can be suppressed, and the coating film of the resin composition can be improved. Patterning is easy. The lower limit of the color material content in the resin composition is 100 mass parts relative to the total solid content of the resin composition, preferably more than 25 mass parts; the upper limit of the color material content in the resin composition is relative to the resin composition The total amount of the solid content is 100 parts by mass, preferably 45 parts by mass or less.

<Compound (E) having a fluorocarbon group and a crosslinked cycloaliphatic group>

A compound having a fluorocarbon group and a crosslinked cycloaliphatic group (hereinafter referred to as a "precipitation inhibiting compound") is a compound having one or more fluorocarbon groups and a crosslinked cycloaliphatic group in the molecule. By containing this precipitation inhibitory compound in a resin composition, precipitation of the compound originating in a coloring material in a colored layer can be suppressed. The fact that the precipitation-inhibiting compound is a compound having a fluorocarbon group and a cross-linked cycloaliphatic group can be confirmed by 1H- and 13C-NMR spectra measured using a nuclear magnetic resonance apparatus.

The above-mentioned "fluorocarbon group" refers to a group having a structure in which at least a part of the hydrogen atoms of the hydrocarbon group are replaced by fluorine atoms. In addition, the fluorocarbon group can be a fluorine atom or a part of a hydrogen atom replaced by a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom (except for a fluorine atom), a hydroxyl group, a thiol group, an alkoxy group, an ether group, an amine group, Nitrile, nitro, sulfonyl, sulfinyl, or ester, amine, acyl, amido, carboxyl, and other carbonyl-containing substituents may also be part of the main chain. Ether bond (-O-) or sulfonyl bond (-SO ₂ -).

The carbon number of the fluorocarbon group in the above-mentioned precipitation inhibiting compound is preferably 2 or more and 10 or less from the viewpoint of improving compatibility with other components or obtaining rheological properties most suitable for resin composition coating . The lower limit of the carbon number of the fluorocarbon group is more preferably 4 or more, and the upper limit is more preferably 7 or less.

The fluorocarbon group may also be a fluorocarbon group in which a part of the hydrogen atoms of the hydrocarbon group is replaced by a fluorine atom, but it is preferable from the viewpoint of making the above-mentioned precipitation inhibiting compound exist on the surface of the colored layer and inhibiting the precipitation of the compound derived from the coloring material. It is a perfluorocarbon group in which all the hydrogen atoms of the hydrocarbon group are replaced by fluorine atoms.

The fluorocarbon group includes, for example, a fluoroalkyl group having a saturated structure, a fluoroalkenyl group having an unsaturated structure, and a fluoroalkylaryl group having an aromatic skeleton. In particular, fluoroalkyl and fluoroalkenyl groups are easy to synthesize and it works.

The fluoroalkyl group includes, for example, a fluoroalkyl group having 2 to 10 carbon atoms. Among the fluoroalkyl groups having 2 to 10 carbon atoms, perfluoroalkyl groups are preferred from the viewpoint of making the above-mentioned precipitation-inhibiting compound exist on the surface of the colored layer and suppressing precipitation of the compound derived from the coloring material. Examples of the perfluoroalkyl group having 2 to 10 carbon atoms include perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, and perfluoroheptyl base, perfluorooctyl, perfluorononyl, perfluorodecyl, etc.

The fluoroalkenyl group includes, for example, a fluoroalkenyl group having 2 to 10 carbon atoms. Among the fluoroalkenyl groups having 2 or more and 10 or less carbon atoms, the above-mentioned precipitation-inhibiting compound It is preferably a perfluoroalkenyl group from the viewpoint of existing on the surface of the colored layer and suppressing precipitation of a compound derived from a coloring material. Examples of the perfluoroalkenyl group having 2 to 10 carbon atoms include perfluoropropenyl, perfluoroisopropenyl, perfluorobutenyl, perfluoroisobutenyl, perfluoropentenyl, and perfluoroisoamyl perfluorohexenyl, perfluoroheptenyl, perfluorooctenyl, perfluorononenyl, perfluorodecenyl, etc.

The above "crosslinked cycloaliphatic group" refers to an aliphatic group having a structure in which two or more rings share two or more atoms. The carbon number of the crosslinked cycloaliphatic group is preferably 5 or more and 12 or less from the viewpoint of compatibility with other materials or solubility in an alkaline developer. The lower limit of the carbon number of the crosslinked cycloaliphatic group is more preferably 7 or more, and the upper limit is more preferably 10 or less.

基、亦可經取代之異

基、亦可經取代之金剛烷基、亦可經取代之三環癸基、亦可經取代之二環戊烯基、亦可經取代之二環戊烷基、亦可經取代之三環戊烯基、及亦可經取代之三環戊基、亦可經取代之三環戊二烯基、及亦可經取代之二環戊二烯基等。此等之中，由耐熱性或析出抑制效果的觀點而言，較佳係亦可經取代之金剛烷基或亦可經取代之二環戊基。在此等基經取代的情況，作為取代基可舉例如烷基、環烷基、烷基環烷基、羥基、酮基、硝基、胺基、鹵原子等。 As the crosslinked cyclic aliphatic group, for example, substituted

group, which can also be substituted

Optionally substituted adamantyl, optionally substituted tricyclodecanyl, optionally substituted dicyclopentenyl, optionally substituted dicyclopentyl, optionally substituted tricyclic Pentenyl, tricyclopentyl which may be substituted, tricyclopentadienyl which may be substituted, dicyclopentadienyl which may be substituted, etc. Among these, an adamantyl group which may be substituted or a dicyclopentyl group which may be substituted is preferable from the viewpoint of heat resistance or a precipitation inhibitory effect. When these groups are substituted, the substituents include, for example, alkyl, cycloalkyl, alkylcycloalkyl, hydroxyl, keto, nitro, amino, halogen atoms and the like.

The glass transition temperature of the precipitation inhibiting compound is preferably not less than 150°C and not more than 250°C. If the glass transition temperature of the precipitation-inhibiting compound is above 150°C, after the precipitation-inhibiting compound seeps onto the surface of the coating film, even if the surface of the coating film is wiped, the wear resistance is still high, so the quality of the color filter can be improved; , if it is below 250°C, the precipitation inhibiting compound moves to the surface of the coating film (bleeding occurs), and the precipitation inhibiting effect can be further obtained fruit. The glass transition temperature of the precipitation inhibiting compound can be obtained by measuring with differential scanning calorimetry (DSC) according to JIS K7121-1987. The lower limit of the glass transition temperature of the precipitation inhibiting compound is more preferably 180°C or higher, and the upper limit is more preferably 230°C or lower.

The above-mentioned precipitation inhibiting compound can be made as a constituent unit derived from a compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound (E-1) derived from a compound (E-1) having a crosslinked cyclic aliphatic group and an ethylenically unsaturated group. - A copolymer of the constituent units of 2).

Among the above precipitation inhibiting compounds, the molar ratio of the constituent unit derived from compound (E-1) to the constituent unit derived from compound (E-2) is preferably 5:95 to 70:30, more preferably 10:80 ~50:50, more preferably 13:87~30:70. When the said molar ratio is in the said range, the compatibility with each component in a resin composition, a precipitation inhibitory effect, and the rheological characteristic of a resin composition become favorable. The molar ratio of each constituent unit in the above precipitation-inhibiting compound can be obtained from the measurement results of nuclear magnetic resonance (NMR) analysis.

The aforementioned precipitation-inhibiting compound is preferably, for example, a copolymer containing constituent units of the following general formulas (4) and (5).

In the above general formula (4) and general formula ( ⁵ ), X1 and X2 represent a single bond, an alkylene group having ¹ to 4 carbon atoms that may be substituted, or an alkylene group with 1 or more carbon atoms that may also be substituted and an oxyalkylene group of 4 or less, Rf represents a fluorocarbon group having 2 or more and 10 or less carbons, R ¹ and R ² represent a hydrogen atom, or an optionally substituted hydrocarbon group of 1 or more and 6 or less carbons, A ¹ Represents a crosslinked cyclic aliphatic group.

The precipitation inhibitory compound is preferably a block copolymer containing a structural unit derived from the compound (E-1) and a structural unit derived from the compound (E-2) from the viewpoint of the precipitation inhibitory effect. When the precipitation inhibiting compound is a block copolymer, the number of constituent units derived from compound (E-1) is preferably 3 or more and 15 or less, and the number of constituent units derived from compound (E-2) is preferably 5 or more and 40 or less. When the structural unit derived from the compound (E-1) and the structural unit derived from the compound (E-2) are within the above range, the precipitation inhibitory effect can be exhibited without impairing the compatibility and rheological properties of the components of the resin composition.

The method for producing the above-mentioned block copolymer is not particularly limited, and the block copolymer can be produced by known methods, among which living polymerization is preferred. This is due to the fact that chain movement or deactivation is not easy to occur, and copolymers with homogeneous molecular weights can be produced, and dispersibility can be improved. The living polymerization method may, for example, be a living anionic polymerization method such as a living radical polymerization method or a radical transfer polymerization method, or a living cationic polymerization method. By these methods, monomers can be sequentially polymerized to produce copolymers. For example, a block (A block) composed of constituent units derived from compound (E-1) is produced first, and a block (B block) composed of constituent units derived from compound (E-2) is polymerized to the A block. segment), whereby block copolymers can be produced. In addition, the order of polymerization in the above production method may be reversed to the above. Moreover, it is also possible to manufacture each block separately, and to couple each block after that.

The arrangement of each block of the block copolymer is not particularly limited, and it can be, for example, an AB block copolymer, ABA block copolymer, BAB block copolymer, or the like. Among these, AB block copolymers or ABA block copolymers are preferred from the viewpoint of excellent dispersibility.

The above precipitation inhibiting compound preferably contains a constituent unit derived from the compound (E-3) having an ethylenically unsaturated group copolymerizable with the compound (E-1) and the compound (E-2). By containing such a structural unit derived from the compound (E-3), it is possible to control the compatibility or the glass transition point of the resin composition.

The above-mentioned precipitation inhibiting compound is preferably a copolymer containing the constituent units of the above-mentioned general formula (6) in addition to the constituent units of the above-mentioned general formulas (4) and (5).

In the above-mentioned general formula (6), ^R represents a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms that may also be substituted, and ^A represents an aryl group that may also be substituted, a pyridyl group that may also be substituted, or A group represented by the following general formula (7). When these groups are substituted, examples of the substituents include the substituents described above.

In the above general formula (7), ^A represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted benzyl group, an optionally substituted cyclopentyl group, or an optionally substituted cyclopentylalkyl group, Optionally substituted cyclohexyl, optionally substituted cyclohexylalkyl, * indicates the bonding position. When these groups are substituted, examples of the substituents include the substituents described above.

The above-mentioned precipitation inhibiting compound can be obtained by making the fluorocarbon group and ethylenic non- A compound (E-1) with a saturated group, obtained by copolymerization with a compound (E-2) with a crosslinked cycloaliphatic group and an ethylenically unsaturated group, as a compound with a fluorocarbon group and an ethylenically unsaturated group , for example, a compound represented by the following general formula (8); as a compound having a crosslinked cyclic aliphatic group and an ethylenically unsaturated group, for example, a compound represented by the following general formula (9).

In the above general formula (8), X ¹ , Rf and R ¹ have the same meanings as above.

In the above general formula (9), X ² , A ¹ and R ² have the same meanings as above.

Specific examples of compound (E-1) include, for example, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluoroisopropyl)ethyl (meth)acrylate, 2 -(perfluorobutyl)ethyl(meth)acrylate, 2-(perfluoropentyl)ethyl(meth)acrylate, 2-(perfluorohexyl)ethyl(meth)acrylate, 2 -(perfluoroheptyl)ethyl(meth)acrylate, 2-(perfluorooctyl)ethyl(meth)acrylate, 2-(perfluorononyl)ethyl(meth)acrylate, 2-(perfluorodecyl)ethyl (meth)acrylate, etc. Among these, 2-(perfluorohexyl)ethyl(methyl) is preferred from the standpoint of precipitation suppression and rheological properties of the resin composition. Acrylate.

基(甲基)丙烯酸酯、異

基(甲基)丙烯酸酯、三環癸基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、三環戊基(甲基)丙烯酸酯、三環戊烯基(甲基)丙烯酸酯、二環戊二烯基(甲基)丙烯酸酯、三環戊二烯基(甲基)丙烯酸酯等。此等之中，由與樹脂組成物之各成分間之相溶性或析出抑制效果的觀點而言，較佳為1-金剛烷基(甲基)丙烯酸酯或二環戊基(甲基)丙烯酸酯。 Specific examples of compound (E-2) include 1-adamantyl (meth)acrylate, 1-methyl-1-adamantyl (meth)acrylate, 2-methyl-2- Adamantyl (meth)acrylate, nor

base (meth)acrylate, iso

Dicyclopentyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclopentyl (meth)acrylate Acrylate, tricyclopentadienyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, tricyclopentadienyl (meth)acrylate, etc. Among them, 1-adamantyl (meth)acrylate or dicyclopentyl (meth)acrylate is preferable from the viewpoint of compatibility with each component of the resin composition or the effect of inhibiting precipitation. ester.

Also, when the above-mentioned precipitation inhibiting compound contains a constituent unit derived from a compound (E-3) having an ethylenically unsaturated group that can be copolymerized with the compound (E-1) and the compound (E-2), as the compound ( E-3), for example, the compound represented by the following general formula (10).

In the above general formula (10), A ² and R ³ have the same meanings as above.

Specific examples of compound (E-3) include methyl (meth)acrylate, styrene, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate , Cyclopentylmethyl (meth)acrylate, Cyclopentylethyl (meth)acrylate, Cyclohexylmethyl (meth)acrylate, Cyclohexyl (meth)acrylate, Vinylpyridine, etc. Among them, from the viewpoint of the compatibility of the resin composition or the precipitation effect, it is preferable to use (a base) methyl acrylate, methacrylate, styrene.

The weight average molecular weight (Mw) of the precipitation inhibitory compound is preferably 3,000 or more and 10,000 or less. If the weight average molecular weight of the precipitation inhibiting compound is not less than 3,000 and not more than 10,000, since the affinity with other materials is excellent, or the viscosity is not too high, it will not hinder the surface exudation caused by the heat during baking, and will not damage the precipitation. Inhibitory effect. The lower limit of the molecular weight of the precipitation-inhibiting compound is more preferably at least 4000, and the upper limit of the molecular weight of the precipitation-inhibiting compound is more preferably at most 8000. The "weight average molecular weight" in this specification is calculated|required as a standard polystyrene conversion value by gel permeation chromatography (GPC). In addition, the weight average molecular weight Mw of a precipitation inhibitory compound was calculated|required by GPC (gel permeation chromatography) as a standard polystyrene conversion value.

The content of the precipitation inhibiting compound in the resin composition is preferably not less than 0.3 parts by mass and not more than 12 parts by mass relative to 100 parts by mass of the total solid content of the resin composition. If the content of the precipitation-inhibiting compound is 0.3 parts by mass or more, the smoothness of the applied resin composition can be improved; and if the content of the precipitation-inhibiting compound is 12 parts by mass or less, separation of components or poor curing can be suppressed. The lower limit of the content of the precipitation-inhibiting compound in the resin composition is relative to 100 parts by mass of the total solid content of the resin composition, more preferably 0.5 parts by mass or more; the upper limit of the content of the precipitation-inhibiting compound in the resin composition is relative to the resin composition The total solid content of the substance is 100 parts by mass, more preferably 10 parts by mass or less.

<Thiol compound (F)>

The thiol compound has a function as a crosslinking agent and is a compound having one or more thiol groups in the molecule. By containing the thiol compound in the resin composition, the surface of the colored layer can be densified, and the precipitation of the compound derived from the coloring material can be further suppressed.

The thiol compound can be appropriately selected from known compounds having one or more thiol groups in the molecule. A thiol compound may be used individually by 1 type, and may use it in combination of 2 or more types.

、2-(N,N-二丁基胺基)-4,6-二巰基-s-三

等。作為硫醇化合物，可單獨或組合2種以上使用，其中，由提升反應速度的觀點而言，較佳係使用2-巰基苯并噻唑。 Specific examples of thiol compounds include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-Octanedithiol, 1,2-Cyclohexanedithiol, Decanedithiol, Ethylene Glycol Diethanethiol Acid, Ethylene Glycol Bis(3-Mercaptopropionate), Ethylene Glycol diethanethiolate, 1,4-butanediol diethanethiolate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane ginsengthiolate, 2 -Mercaptopentathiazole, trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol ethanethiol acid, pentaerythritol 4 (3-mercaptopropionate), pentaerythritol 4 (3-mercaptobutyrate), di Pentaerythritol hexa(3-mercaptopropionate), esters of other polyols and thiol-containing carboxylic acids such as ethanethiolic acid and mercaptopropionic acid, trimercaptopropionic acid ginseng (2-hydroxyethyl) isocyanurate , 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-tri

, 2-(N,N-dibutylamino)-4,6-dimercapto-s-tri

Wait. As a thiol compound, it can use individually or in combination of 2 or more types, Among them, it is preferable to use 2-mercaptobenzothiazole from a viewpoint of raising a reaction rate.

The thiol compound may be a thiol compound having a substituent on a carbon atom at the α-position and/or β-position of the thiol. Such specific examples include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis(1-mercaptoethyl)benzene, phthalic acid bis(1-mercapto) ethyl ester), bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, bis(3-mercaptoisobutyl) phthalate, etc.

As the thiol compound, it can be used alone or in combination of two or more. Among them, it is preferable to use one molecule selected from the group consisting of 2 or more thiols in One or more of the group consisting of polyfunctional thiol compounds. Also, from the standpoint of maintaining a good precipitation suppression effect and low surface roughness after long-term storage, it is preferable to have a secondary sulfur having a carbon atom bonded to a thiol group as a secondary carbon atom. The alcohol-based secondary thiol compound is more preferably a polyfunctional secondary thiol compound having two or more secondary thiol groups in one molecule.

The content of the thiol compound in the resin composition is not less than 0.05 parts by mass and not more than 5 parts by mass, preferably not less than 0.5 parts by mass and not more than 3 parts by mass relative to 100 parts by mass of the total solid content of the resin composition . If the content of the thiol compound is 0.05 parts by mass or more, the coating film can be fully hardened by the hardening acceleration effect of the thiol compound; and if the content of the thiol compound is 3 parts by mass or less, the hardening acceleration can be controlled. It can suppress performance degradation of the resin composition such as shape strain at the edge of the pattern.

<Dispersant (G)>

There are no particular limitations on the dispersant, but from the standpoint of improving the adsorption performance of the color material, improving the dispersibility and dispersion stability of the color material, it is preferable to use a dispersant having a constituent unit represented by the following general formula (11). polymer. The structural unit represented by the following general formula (11) has basicity and functions as an adsorption site for color materials.

In the above general formula (11), R ⁴ represents a hydrogen atom or a methyl group, L represents a divalent bonding group, R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group that may also contain heteroatoms, R ⁵ and R ⁶ They may be bonded to each other to form a ring structure. As the divalent bonding group in L, for example, an alkylene group having 1 to 10 carbon atoms, an arylylene group, a -CONH- group, a -COO- group, an ether group having 1 to 10 carbon atoms (-R '-OR"-: R' and R" are each independently an alkylene group) and combinations thereof. Among them, A in the above formula (10) is preferably a divalent bonding group containing a -CONH- group or a -COO- group from the viewpoint of dispersibility.

^The hydrocarbon groups in the hydrocarbon groups that may also contain heteroatoms in R and R can include, for example, alkyl, aralkyl, aryl, etc., the number of carbon atoms of the above ^- mentioned alkyl is preferably 1 to 18, and more preferably methyl or ethyl.

The heteroatom-containing hydrocarbon group in R ⁵ and R ⁶ refers to a structure in which carbon atoms in the above hydrocarbon group are replaced by heteroatoms. The heteroatom which may be contained as a hydrocarbon group includes, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and the like.

As the structural unit represented by the above-mentioned general formula (11), for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylamine (meth)acrylate (meth)acrylic acid esters containing alkyl-substituted amino groups such as diethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethyl Aminopropyl (meth)acrylamide and other (meth)acrylamides containing alkyl-substituted amino groups. Among them, from the viewpoint of improving dispersibility and dispersion stability, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl Propyl (meth)acrylamide.

The structural unit represented by the above-mentioned general formula (11) may be composed of one type, or may contain two or more types of structural units.

In the polymer having the constituent unit represented by the above-mentioned general formula (11), the absorption of the color material in the salt-forming part is further improved, the dispersion stability of the color material, the suppression of developing residue, and the solvent resolubility are excellent, or by By the above-mentioned fluorocarbon used in the present invention group and a compound (E) represented by a crosslinked cycloaliphatic group, and can further suppress the precipitation of the compound from the coloring material, it is preferable to make the constituent unit represented by the above-mentioned general formula (11) have At least a part of the terminal nitrogen portion forms a salt with one or more compounds selected from the group consisting of compounds represented by the following general formulas (12) to (14). It can be confirmed by known means that the polymer having the structural unit represented by the above general formula (10) has the terminal nitrogen site of the structural unit represented by the general formula (11), and the nitrogen site selected from the above general formula (12) ~ ( 14) Salts formed by more than one compound in the group, and their ratios.

In the general formula (12), R ⁷ represents straight chain, branched chain or cyclic alkyl, vinyl, phenyl or benzyl which may also have substituents, or -OR ^a , R ⁽ Meth)acryl. In the general formula (13), R ⁸ , R ⁹ and R ¹⁰ independently represent a hydrogen atom, an acidic group or its ester group, and a straight chain, branched chain or cyclic carbon number of 1 to 20 that may also have substituents. Alkyl, a vinyl group that may also have a substituent, a phenyl or benzyl group that may also have a substituent, or -OR ^b , where R ^b represents a straight chain or branched chain with 1 to 20 carbon atoms that may also have a substituent Or a cyclic alkyl group, a vinyl group that may also have a substituent, a phenyl or benzyl group that may also have a substituent, or a (meth)acryl group separated by an alkylene group with a carbon number of 1 to 4; Q Represents a chlorine atom, bromine atom, or iodine atom. In the general formula (14), R ¹¹ and R ¹² independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, or a phenyl group that may have a substituent Or benzyl, or -OR ^a , R ^a represents a straight chain, branched chain or cyclic alkyl, vinyl, phenyl or benzyl that may also have a substituent, or a carbon interval of 1 to 20 A (meth)acryloyl group of 1 to 4 alkylene groups. Wherein, at least one of R ¹¹ and R ¹² contains a carbon atom.

The polymer having the constituent units represented by the above-mentioned general formula (11) improves the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition by combining with the above-mentioned fluorocarbon-based and cross-linked polymers used in the present invention. The combination of compounds represented by the compound (E) of the bicyclic aliphatic group can further suppress the precipitation of the compound derived from the coloring material, and can form a high-brightness and high-contrast colored layer, preferably the above general formula A salt-type block in which at least a part of the terminal nitrogen site of the structural unit represented by (11) forms a salt with one or more compounds selected from the group consisting of compounds represented by the above general formulas (12) to (14) copolymer.

In the block copolymer, if the block containing the structural unit represented by the above general formula (11) is used as the A block, then the A block is based on the basic structure of the general formula (11) and functions as the opposite The function of the adsorption part of the color material. In addition, when at least a part of the terminal nitrogen site of the structural unit represented by the general formula (11) forms a salt with one or more compounds selected from the group consisting of the above general formulas (12) to (14) , the salt-forming portion functions as a stronger adsorption site for the color material. On the other hand, the B block not containing the structural unit represented by the general formula (10) functions as a block having solvent affinity. Therefore, the block copolymerization system functions as a color material dispersant by sharing the function between the A block that adsorbs the color material and the B block that has solvent affinity.

The B block is a block that does not contain the structural unit represented by the above-mentioned general formula (11). As the constituent unit constituting the B block, for example, a monomer having an ethylenically unsaturated group that can be copolymerized with a monomer derived from the constituent unit represented by the general formula (11), among which Preferably, it is a structural unit represented by the following general formula (15).

In the above general formula (15), L' represents a direct bond or a divalent bond group, R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ represents a hydrocarbon group, -[CH(R ¹⁵ )-CH(R ¹⁶ )-O ] _x -R ¹⁷ or a monovalent group represented by -[(CH ₂ ) _y -O] _z -R ¹⁷ . R ¹⁵ and R ¹⁶ are independently a hydrogen atom or a methyl group, R ¹⁷ is a monovalent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH ₂ CHO or -CH ₂ COOR ¹⁸ , and R ¹⁸ is a hydrogen atom or a carbon atom Alkyl groups with numbers 1 to 5. The above-mentioned hydrocarbon group may have a substituent. x represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.

The weight-average molecular weight Mw of the above-mentioned block copolymer is not particularly limited. From the viewpoint of good color material dispersibility and dispersion stability, it is preferably 1000~20000, more preferably 2000~15000, and even more preferably 3000~ 12000.

The amine value of the block copolymer before salt formation is not particularly limited, but from the viewpoint of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 60 mgKOH /g or more. Also, the upper limit is preferably not more than 130 mgKOH/g, more preferably not more than 120 mgKOH/g. Dispersion stability is excellent as it is more than the said lower limit. Moreover, when it is below the said upper limit, the compatibility with other components is excellent, and solvent resolubility is favorable. In this specification, the amine value of the block copolymer before salt formation refers to the amount of hydrochloric acid required to neutralize 1 g of the solid content of the block copolymer before salt formation, which becomes an equivalent amount of potassium hydroxide. Mass (mg) is a value measured by the method described in JIS K7237-1995.

The amine value of the obtained salt-type block copolymer is compared with the block copolymer before salt formation, and only the value of the portion forming the salt becomes smaller. However, the salt formation site is the same as the nitrogen site corresponding to the end of the amine group, or the color material adsorption site is more strengthened, so there is a tendency to improve the color material dispersibility or color material dispersion stability by salt formation. . Also, similar to the amine group, the salt-forming site will have an adverse effect on solvent resolubility if it is too large. Therefore, the amine value of the block copolymer before salt formation can be used as an indicator for making the dispersion stability of the coloring material and solvent resolubility favorable. The amine value of the obtained salt-type block copolymer is preferably not less than 0 mgKOH/g and not more than 130 mgKOH/g, more preferably not less than 0 mgKOH/g and not more than 120 mgKOH/g. When it is below the said upper limit, the compatibility with other components is excellent, and solvent resolubility is favorable.

The content of the dispersant is from the viewpoint of dispersibility and dispersion stability, preferably 3-45 parts by mass, more preferably 5-35 parts by mass, relative to 100 parts by mass of the total solids in the color material dispersion Ratio deployment.

The method for producing the above-mentioned block copolymer is not particularly limited, and the block copolymer can be produced by a known method. In addition, as a preparation method of the salt-type block copolymer, for example, in a solvent in which a polymer having a constituent unit represented by the above-mentioned general formula (11) is dissolved or dispersed, adding a compound selected from the above-mentioned general formula (12) to ( 14) A method in which one or more compounds of the group are stirred and heated if necessary, etc.

<Solvent (H)>

The solvent is not particularly limited as long as it is an organic solvent that does not react with the components in the resin composition and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.

Specific examples of solvents include methanol, ethanol, n-propanol, Alcohol-based solvents such as isopropanol, methoxyalcohol, and ethoxyl alcohol; carbitol-based solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, Methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl Acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2 - Ketone solvents such as heptanone; methoxy ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxy Glycol ether acetate solvents such as butyl butyl acetate and ethoxy ethyl acetate; methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, Carbitol acetate-based solvents such as butyl carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-propanediol diacetate; ethylene glycol monomethyl Ether, Ethylene Glycol Monoethyl Ether, Ethylene Glycol Dimethyl Ether, Diethylene Glycol Dimethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Diethyl Ether, Propylene Glycol Monomethyl Ether , dipropylene glycol dimethyl ether and other glycol ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amides Amine solvents; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene, etc.; N-heptane, N-hexane, Saturated hydrocarbon solvents such as N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used from the viewpoint of the solubility of other components. Among them, as the solvent used in the present invention, from the viewpoint of solubility of other components or coating suitability, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol ethyl alcohol, etc. Acid ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethoxy ethyl propionate, ethyl lactate and 3-methoxy butyl acetate Choose one or more.

The solvent content in the resin composition is usually in the range of 55-95% by mass, more preferably in the range of 65-90% by mass, and more preferably in the range of 70-88% by mass, relative to the total amount of the resin composition. Inside. If the content of the solvent is more than 5% by mass, the decrease in dispersibility due to the increase in viscosity can be suppressed; and if the content of the solvent is less than 95% by mass, the decrease in the concentration of the color material can be suppressed, so the target chromaticity can be achieved coordinate.

<other ingredients>

In the resin composition, as long as the effect of the present invention is not impaired, a dispersing aid and other components can be further formulated as needed.

Dispersion aids are used to improve the dispersibility of color materials. As the dispersing aid, dye derivatives such as acidic dye derivatives are preferable. In addition to the function of improving the dispersibility of the color material, the pigment derivatives have a weak effect of inhibiting the precipitation of the compound from the color material, but because they have the effect of the precipitation of the compound from the color material, they can be suppressed by the precipitation of the present invention. The use of pigment derivatives together with the compound can further inhibit the precipitation of the compound from the color material.

色素及酞菁色素所構成群之1種以上之色素骨架、並具有酸性基的色素衍生物。酸性色素衍生物中，由提升分散性的觀點而言，更佳為具有喹啉黃色素骨架、並具有酸性基之色素衍生物的喹啉黃色素衍生物。 The dye derivative may be a basic dye derivative, but is preferably an acidic dye derivative. The so-called "acidic pigment derivative" refers to a pigment derivative having an acidic group in its chemical structure, and is particularly preferably a pigment derivative selected from anthraquinone pigment, diketopyrrolopyrrole pigment, azo pigment, quinoline yellow pigment, and diketopyrrole pigment.

Dye derivatives that have one or more dye skeletons in the group consisting of dyes and phthalocyanine dyes and have an acidic group. Among the acidic dye derivatives, quinoline yellow pigment derivatives, which are dye derivatives having a quinoline yellow pigment skeleton and an acidic group, are more preferable from the viewpoint of improving dispersibility.

As the acidic group of the acidic pigment derivative, it is preferably at least one selected from the group consisting of sulfonic acid group, sulfonamide group, carboxyl group, and metal salt or ammonium salt of the functional group. one. By introducing an acidic group, it can be micro-dispersed. When used in color filters, it can obtain a pigment dispersion with high dispersion stability, high contrast, and high brightness, so it is preferable. Also, by using in combination with the compound (E) having a fluorocarbon group and a crosslinked cycloaliphatic group, a synergistic effect can be produced, and the precipitation of the compound derived from the coloring material can be further suppressed.

The organic pigments described in the column of color materials preferably contain pigments and acidic pigment derivatives. The acidic pigment derivative interacts with the pigment, and is adsorbed on the surface of the pigment or absorbed when producing pigment particles. In addition, since the acidic pigment derivatives are adsorbed on the surface of the pigment, the surface of the pigment becomes acidic, and compared with the organic pigment itself, the affinity between the pigment dispersant and the pigment dispersant is further improved, and it plays an intermediary role with the pigment dispersant. Furthermore, the alkaline dispersant can be efficiently located on the pigment surface by adsorbing the acidic pigment derivative interacting with the alkaline dispersant on the surface of the pigment. Thereby, microdispersion or dispersion stabilization can be performed, which is advantageous when used for color filters.

When the organic pigment contains a pigment and an acidic pigment derivative, the content of the acidic pigment derivative in the entire organic pigment is not particularly limited, but is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the pigment. parts by mass, particularly good 2-10 parts by mass. By setting the content of the acidic pigment derivative to 0.5 parts by mass or more, stable dispersion or microdispersion can be performed, and the synergistic effect with the above-mentioned compound (E) having a fluorocarbon group and a crosslinked cycloaliphatic group can be achieved. It effectively suppresses the precipitation of compounds derived from coloring materials; and, by setting the content of acidic pigment derivatives to 30 parts by mass or less, it is possible to suppress chromaticity changes caused by excess acidic pigment derivatives.

In the present invention, one kind or two or more kinds of the above-mentioned acidic dye derivatives may be used, and one kind or two or more kinds of the above-mentioned acidic dye derivatives may be used for one kind of pigment.

In addition, as other components, for example, an interface for improving wettability Activator, silane coupling agent for improving adhesion, defoamer, anti-fish eye agent, antioxidant, anti-coagulation agent, ultraviolet absorber, etc.

<<Manufacturing method of resin composition>>

The said resin composition can be manufactured as follows, for example. First, a color material dispersion or a color material solution is prepared. The color material dispersion liquid contains at least a color material, a dispersant, and a solvent. The coloring material solution contains at least a coloring material and a solvent. The color material dispersion or the color material solution may further contain a polymer, a thiol compound, and the like.

After preparing the color material dispersion or color material solution, add a polymerizable compound, a precipitation inhibiting compound, a polymerization initiator, etc. to the color material dispersion or color material solution, and mix using a known mixing method to obtain a resin composition thing.

According to this embodiment, since the precipitation suppressing compound having a fluorocarbon group and a crosslinked cycloaliphatic group is contained in the resin composition, the precipitation of the compound originating in the coloring material can be suppressed in the colored layer. That is, heat treatment (post-baking) is performed at the time of forming the colored layer as described later, and when heat is applied, fluorocarbons tend to move to the surface of the coating film based on the formation of the colored layer, so the precipitation inhibiting compound itself moves to the surface of the coating film. surface orientation. On the other hand, since the volume of the crosslinked cycloaliphatic group is large, even if the compound from the color material reaches the surface, the crosslinked cycloaliphatic group present near the surface of the coating film will block the compound from the color material, This suppresses the precipitation of compounds derived from coloring materials. In addition, the compound from the color material in the coating film tends to concentrate at the place where the film strength is weak, but since the volume of the cross-linked cycloaliphatic group is relatively large, the concentration of the compound from the color material can also be suppressed. Thereby, it is estimated that precipitation of the compound originating in a coloring material can be suppressed in a colored layer.

According to this embodiment, since precipitation of the compound originating in a coloring material can be suppressed in a colored layer, roughening of the surface of a colored layer can be suppressed. Thereby, a highly productive, A colored layer with low surface roughness and excellent brightness and contrast. Moreover, since precipitation of the compound originating in a coloring material can be suppressed in a colored layer, levelness can also be improved.

<<Color filter>>

The above-mentioned resin composition can be used as a colored layer of a color filter. Hereinafter, the color filter and the colored layer will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram showing a color filter of the present embodiment.

The color filter 10 shown in FIG. 1 is provided with the base material 11, and the colored layer 12 provided in the surface 11A side of the board|substrate 11 and which consists of hardened|cured material of the said resin composition. In the color filter 10 , there are plural colored layers, and the color filter 10 further includes a light-shielding layer 13 arranged between the colored layers 12 . In addition, the color filter 10 may further include a protective coating layer, a transparent electrode layer, an alignment film or alignment protrusion, a columnar spacer, and the like.

<Substrate>

As the substrate 11 , for example, a light-transmitting substrate or a silicon substrate described later, or a light-transmitting substrate or a silicon substrate having an aluminum, silver, silver/copper/palladium alloy thin film, etc. may be used. On these substrates, other color filter layers, resin layers, transistors such as TFTs, circuits, etc. can also be formed.

There are no particular limitations on the light-transmitting substrate as long as it is a substrate having light-transmitting properties. As the light-transmitting substrate, for example, non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plate, or transparent resin film, optical resin plate, flexible glass, etc. have flexibility or Soft transparent soft material.

The thickness of the light-transmitting substrate is not particularly limited, depending on the color filter For example, those with a thickness of about 100 μm to 1 mm can be used.

<shading layer>

The colored layer 12 is composed of a cured product of the above-mentioned resin composition. Moreover, it is sufficient if only one of the plurality of colored layers 12 is a cured product of the above-mentioned resin composition, and not all of the colored layers 12 may be cured products of the above-mentioned resin composition.

The colored layer 12 is usually formed at the opening of the light-shielding layer on the base material, and usually consists of three colored layers with different colors. Also, the arrangement of the colored layers 12 is not particularly limited, and general arrangements such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type can be used, for example. In addition, the width, area, etc. of the colored layer can be set arbitrarily.

The thickness of the colored layer 12 can be appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the resin composition, etc., and is usually preferably not less than 1 μm and not more than 5 μm.

The colored layer 12 can be formed by the following method, for example. First, the above-mentioned resin composition is coated on a substrate by spray coating, dip coating, bar coating, roll coating, spin coating, die coating or other coating means to form a wet coating film. Among them, the spin coating method and the die coating method are suitably used.

Next, after drying the wet coating film using a heating plate or an oven, the wet coating film is exposed through a mask having a predetermined pattern to cause photopolymerization of polymers and photopolymerizable compounds, and the wet coating film becomes a cured coating film. As a light source used for exposure, ultraviolet rays, such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, electron beam, etc. are mentioned, for example. The exposure amount is appropriately adjusted according to the light source used or the thickness of the coating film.

Moreover, after exposure, in order to accelerate|stimulate a polymerization reaction, you may heat-process. The heating conditions are based on the blending ratio of each component in the resin composition used, Or the thickness of the coating film, etc. and choose appropriately.

Next, a developing treatment is performed using a developing solution to dissolve and remove unexposed portions, whereby the coating film is formed into a desired pattern. As a developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. In this alkaline solution, a suitable amount of surfactant and the like may also be added. In addition, as a developing method, a general method can be used.

After the development treatment, the developing solution is washed off, and finally, heat treatment (post-baking) may be performed at 200°C or higher and 240°C or lower in order to fully harden the coating film. Thereby, a colored layer is formed. It does not specifically limit as a heating condition, It can select suitably according to the use of a coating film.

<shading layer>

The light-shielding layer 13 is formed on the substrate 11 into a predetermined shape by patterning, and can be the same as that used as a light-shielding layer in a general color filter. It does not specifically limit as a shape of a light-shielding layer, For example, shapes, such as a stripe shape and a matrix shape, are mentioned. The light-shielding layer can be a metal film such as chromium formed by sputtering or vacuum evaporation. Alternatively, the light-shielding layer may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a binder resin. In the case of a resin layer containing light-shielding particles, there are, for example, a method of patterning a resin composition by development, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a resin composition, etc. .

The film thickness of the light-shielding layer 13 is set to 0.2 μm to 0.4 μm for a metal thin film, and 0.5 μm to 2 μm for a black pigment dispersed or dissolved in a binder resin.

<<Image display device>>

A color filter can be used, for example, by being incorporated in an image display device. The configuration of the image display device is not particularly limited, and can be appropriately selected from conventional display devices. Examples thereof include liquid crystal display devices, organic light-emitting display devices, and the like. FIG. 2 is a schematic configuration diagram showing a liquid crystal display device which is an example of an image display device according to the present embodiment. FIG. 3 is a schematic configuration diagram showing an organic light emitting display device which is an example of an image display device according to the present embodiment.

<Liquid crystal display device>

The liquid crystal display device 20 shown in FIG. 2 includes a color filter, an opposing substrate 21 having a TFT array substrate, and a liquid crystal layer 22 formed between the color filter 10 and the opposing substrate 21 . Furthermore, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and can be made into a known structure of a liquid crystal display device generally using color filters.

The driving method of the liquid crystal display device 20 is not particularly limited, and a driving method generally used in liquid crystal display devices can be used. Such a driving method includes, for example, a TN method, an IPS method, an OCB method, and an MVA method. Any of these methods may be used as appropriate.

As the counter substrate 21, it can be suitably selected and used according to the driving method of a liquid crystal display device, etc. As the liquid crystal constituting the liquid crystal layer 22, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device and the like.

As a method for forming the liquid crystal layer 21, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is slowly cooled to room temperature, In this way, the sealed liquid crystal can be aligned.

<Organic Light Emitting Display Device>

The organic light-emitting display device 30 shown in FIG. 3 is equipped with a color filter 10 and an organic luminous body 40, and may also have an organic protective layer 50 or an inorganic luminescent layer between the color filter 10 and the organic luminous body 40. Oxide film 60.

As a lamination method of the organic luminescent body 40, for example, a transparent anode 41, a hole injection layer 42, a hole transport layer 43, a light emitting layer 44, an electron injection layer 45, and a cathode 46 are successively formed on the color filter 10. method, or a method of attaching the organic luminescent body 40 formed on another substrate to the inorganic oxide film 60 . The transparent anode 41 , hole injection layer 42 , hole transport layer 43 , light emitting layer 44 , electron injection layer 45 , cathode 46 , and other components in the organic luminescent body 40 can appropriately use known ones. The organic light-emitting display device 30 manufactured in this way can be applied to, for example, a passively driven organic EL display or an actively driven organic EL display. Furthermore, the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3 , and may be a generally known structure of an organic light emitting display device using a color filter.

[Example]

In order to describe the present invention in detail, examples are given below for description, but the present invention is not limited to these descriptions.

(Synthesis Example 1: Synthesis of Precipitation Inhibiting Compound I)

Argon (argon) replacement was carried out after the 500 ml four-necked separation flask was dried under reduced pressure. Under the flow of Ar, add 100 g of dehydrated tetrahydrofuran (THF), 2.0 g of methyltrimethylsilyl dimethyl ketene ketal, and 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) 0.15ml, 0.2g of symmetric trimethylbenzene. There, 34.57 g of 2-(perfluorohexyl)ethyl methacrylate (FOEMA) was dripped over 45 minutes using the dropping funnel. Since heat was generated during the progress of the reaction, the temperature was kept below 40° C. by ice cooling. After 1 hour, 17.62 g of 1-adamantyl methacrylate (1-ADMA) was dripped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain the precipitation-inhibiting compound I which is a block copolymer. The weight average molecular weight of the precipitation inhibiting compound I obtained by GPC measurement (NMP LiBr 10 mM) was 4,600.

The obtained precipitation inhibiting compound I was analyzed by thermal decomposition GCMS, FT-IR, 1H-NMR, 13C-NMR and GPC, thereby confirming the constituent units derived from FOEMA and the constituent units derived from 1-ADMA in the precipitation inhibiting compound I , and confirmed that the molar ratio of the constituent units from FOEMA to the constituent units from 1-ADMA was 1:6.

(Synthesis Example 2: Synthesis of Precipitation Inhibiting Compound II)

In Synthesis Example 2, the precipitation suppression was synthesized in the same manner as in Synthesis Example 1, except that dicyclopentyl methacrylate (DCPMA) (FA-513M manufactured by Hitachi Chemical Co., Ltd.) was used instead of 1-adamantyl methacrylate. Compound II. The weight average molecular weight of the precipitation inhibiting compound II determined by GPC (NMP LiBr 10 mM) was 4,500.

The obtained precipitation inhibiting compound II was analyzed by thermal decomposition GCMS, FT-IR, 1H-NMR, 13C-NMR and GPC, thereby confirming the constituent units derived from FOEMA and DCPMA in the precipitation inhibiting compound II, and It was confirmed that the molar ratio of the constituent units derived from FOEMA to the constituent units derived from DCPMA was 1:6.

(Synthesis Example 3: Synthesis of Dispersant I)

Argon (argon) replacement was carried out after the 500 ml four-necked separation flask was dried under reduced pressure. Under the flow of Ar, add 100 g of dehydrated THF, 2.0 g of methyl trimethylsilyl dimethyl ketene ketal, and 0.15 ml of a 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB), symmetrically Trimethylbenzene 0.2g. There, 36.7 g of methacrylate (MMA) was dripped over 45 minutes using the dropping funnel. Since heat was generated during the progress of the reaction, the temperature was kept below 40° C. by ice cooling. One hour later, 13.3 g of dimethylaminoethyl methacrylate (DMMA) was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain a block copolymer. The weight average molecular weight determined by GPC (NMP LiBr10mM) is 7,600, and the amine value is 95mgKOH/g.

In a 100mL round bottom flask, dissolve 29.35 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 29.35 parts by mass of the block copolymer obtained above, and add the phenylphosphonic acid of the compound represented by the above general formula (13) (PPA, manufactured by Tokyo Chemical Industry Co., Ltd.) 3.17 parts by mass (the compound represented by the above-mentioned general formula (13) is 0.20 moles relative to 1 mole of DMMA unit of block copolymer 1), stirred at a reaction temperature of 30°C for 20 hours, Thereby, a salt-type block copolymer (dispersant I) solution was obtained. Specifically, the amine value after salt formation was calculated as follows.

1 g of a solution obtained by mixing 9 parts by mass of the above-mentioned salt-type block copolymer (solid matter after reprecipitation) and 91 parts by mass of chloroform-D1 for NMR was added to an NMR sample tube, and a nuclear magnetic resonance device (manufactured by JEOL, FT NMR, JNM-AL400) measure the 13C-NMR spectrum at room temperature and accumulate 10,000 times. In the obtained spectral data, at the terminal nitrogen site (amine group), the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom not formed by salt and the peak of the carbon atom adjacent to the nitrogen atom formed by salt is calculated. The ratio of the number of amine groups formed by the salt to the total number of amine groups is indeed consistent with the theoretical There was no difference in the salt formation ratio (all 2 acidic groups of phenylphosphonic acid formed a salt with the terminal nitrogen site of DMMA of block copolymer A-1).

From the amine value of 95 mgKOH/g before salt formation, subtract the amine value of 0.40 mole part of DMMA unit (38 mgKOH/g), and calculate the amine value after salt formation to be 57 mgKOH/g.

(Synthesis Example 4: Synthesis of Alkali-Soluble Resin I Solution)

40 parts by mass of benzyl methacrylate (BzMA), 15 parts by mass of methyl methacrylate (MMA), 25 parts by mass of methacrylic acid (MAA), and 2,2'-azobisisobutyronitrile (AIBN ) 3 parts by mass of the mixed solution was dripped at 100° C. for 3 hours under nitrogen gas into a polymerization tank filled with 150 parts by mass of PGMEA. After the dropping, it was heated at 100° C. for 3 hours to obtain a polymer solution. The weight average molecular weight of this polymer solution was 7000.

Next, 20 parts by mass of glycidyl methacrylate (GMA), 0.2 parts by mass of triethylamine, and 0.05 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and heated at 110° C. for 10 hours. This carries out the carboxylic acid group of the main chain methacrylic acid, and Reaction of the epoxy group of GMA. During the reaction, in order to prevent polymerization of GMA, air was blown in the reaction solution. Also, the reaction was tracked by measuring the acid value of the solution. The obtained alkali-soluble resin I was a resin in which a side chain having an ethylenic double bond was introduced using GMA to the main chain formed by copolymerization of BzMA, MMA, and MAA. The alkali-soluble resin I solution has a solid content of 40% by mass, an acid value of 74 mgKOH/g, and a weight average molecular weight of the alkali-soluble resin I of 12,000.

(Synthesis Example 5: Synthesis of Alkali-Soluble Resin II Solution)

In synthesis example 4, except having used 40 mass parts of 1-adamantyl methacrylates instead of BzMA, it carried out similarly to synthesis example 4, and obtained the alkali-soluble resin II solution. The alkali-soluble resin II solution has a solid content of 42.6% by mass, an acid value of 74 mgKOH/g, and a weight average molecular weight of the alkali-soluble resin II of 12,000.

<Synthesis Example 6: Synthesis of Acid Pigment Derivative I>

374.76 parts by mass of oleum having a sulfur trioxide content rate of 11% by mass was stirred while cooling to 10° C., and 74.96 parts by mass of Pigment Yellow 138 were added thereto. Then, it was stirred at 90° C. for 6 hours. After adding the obtained reaction liquid to 1600 mass parts of ice waters and stirring for 15 minutes, the deposit was filtered.

The obtained wet filter cake was washed 3 times with 800 parts by mass of dechlorinated water. The washed wet filter cake was vacuum-dried at 80° C. to obtain a yellow pigment sulfide derivative belonging to the acidic pigment derivative I. The molecular weight was measured by TOF-MS, and it was confirmed to be the target compound.

(Synthesis Example 7: Synthesis of Lake Color Material 1)

5.0 g of acid red 289 (AR289, dye 1, manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (16) was added to 500 ml of water, and dissolved at 80°C to prepare a dye solution. On the other hand, 3.85 g of polyaluminum chloride (trade name "Takibine #1500" manufactured by Taki Chemical Co., Ltd., Al ₂ (OH) ₅ Cl, alkalinity 83.5% by mass, alumina content 23.5% by mass) was added to water 200ml, stirred at 80°C to prepare polyaluminum chloride aqueous solution. The prepared polyaluminum chloride aqueous solution was dropped into the above-mentioned dye solution at 80° C. for 15 minutes, and then stirred at 80° C. for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained filter cake was dried to obtain 6.30 g (yield: 96.2%) of a metal lake color material of a rose bengal acid dye.

<Example 1> (1) Manufacture of color material dispersion liquid R1

4.93 parts by mass of the dispersant I solution in Synthesis Example 3 as a dispersant, and 12.35 parts by mass of a brominated diketopyrrolopyrrole pigment (Br-DPP, trade name "Irgaphor RED S 3621CF", manufactured by BASF Corporation) as a color material 18.27 parts by mass of alkali-soluble resin I solution, PGMEA63.80 parts by mass, 0.65 parts by mass of acidic pigment derivative I, and 100 parts by mass of zirconia beads with a particle diameter of 2.0 mm were placed in a mayonnaise bottle, Vibrate with a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary crushing, then take out the zirconia beads with a particle size of 2.0 mm, and add zirconia beads with a particle size of 0.1 mm 200 parts by mass of balls were similarly dispersed by a pigment shaker for 4 hours as the main dispersion to obtain a color material dispersion liquid R1.

(2) Manufacture of resin composition R1

啉基苯基)-丁酮-1(光起始劑，商品名「Irgacure 369」，BASF公司製)0.86質量份、1-(鄰乙醯基肟)3-環戊基-1-[9-乙基-6-(2-甲基苄甲醯基)-9H-咔唑-3-基]-1-丙酮(肟酯系光聚合起始劑，商品名「TR-PBG-304」，常州強力電子新材料公司製)0.58質量份、析出抑制化合物I 0.02質量份、PGMEA9.10質量份，得到具有感光性之樹脂組成物R1。 Add 59.40 parts by mass of the color material dispersion R1 obtained in the above (1), 4.83 parts by mass of the alkali-soluble resin I solution obtained in Synthesis Example 4, and 5.82 parts by mass of a photopolymerizable compound (trade name "Aronix M-520D", manufactured by Toagosei Co., Ltd.) Parts by mass, 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1 (photoinitiator, trade name "Irgacure 369", manufactured by BASF Corporation) 0.86 parts by mass, 1-(o-acetyloxime) 3-cyclopentyl-1-[9 -Ethyl-6-(2-methylbenzylmethyl)-9H-carbazol-3-yl]-1-propanone (oxime ester photopolymerization initiator, trade name "TR-PBG-304", (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.) 0.58 parts by mass, 0.02 parts by mass of the precipitation inhibiting compound I, and 9.10 parts by mass of PGMEA to obtain a photosensitive resin composition R1.

(3) Formation of colored layer

The resin composition R1 obtained in the above (2) was coated on a glass substrate (trade name "NA35", manufactured by NH Techno Glass Co., Ltd.) with a thickness of 0.7 mm and 100 mm x 100 mm using a spin coater, and then heated on a hot plate. Dry at 80°C for 3 minutes, irradiate with 60mJ/cm ² ultraviolet rays using an ultra-high pressure mercury lamp, and heat in a dust-free furnace at 230°C for 30 minutes to adjust the film thickness after hardening to 2.2μm to form a colored layer.

<Examples 2~23 and Comparative Examples 1~6>

啉基苯基)-丁酮-1(光起始劑，商品名「Irgacure 369」，BASF公司製)，使用肟酯系光聚合起始劑之TR-PBG-3057(常州強力電子新材料公司製)0.71質量份，且將1-(鄰乙醯基肟)3-環戊基-1-[9-乙基-6-(2-甲基苄甲醯基)-9H-咔唑-3-基]-1-丙酮(肟酯系光聚合起始劑，商品名「ADEKA AKLS NCI-930」，ADEKA公司製)之添加量設為0.71質量份。 In Examples 2-23 and Comparative Examples 1-6, after obtaining the color material dispersion using the color materials shown in Tables 2-4, the photosensitive resin composition R2 was prepared according to the composition shown in Table 2-5 ~R13, G1~G7, B1~B7, except for this, the colored layer was formed in the same manner as in Example 1. Among them, the color material dispersions used in the resin compositions B1 to B7 were 13.00 parts by mass of the color material, and no acidic pigment derivatives were added. Also, in the resin composition B4, the substituted 2-benzyl-2-dimethylamino-1-(4-

Phenylphenyl)-butanone-1 (photoinitiator, trade name "Irgacure 369", manufactured by BASF Corporation), TR-PBG-3057 using oxime ester photopolymerization initiator (Changzhou Qiangli Electronic New Material Co., Ltd. system) 0.71 parts by mass, and 1-(o-acetyl oxime) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 The amount of -yl]-1-acetone (oxime ester-based photopolymerization initiator, trade name "ADEKA AKLS NCI-930", manufactured by ADEKA Corporation) was 0.71 parts by mass.

<Evaluation of averageness>

Using the resin compositions prepared in the Examples and Comparative Examples as the coating solution, apply it to the glass substrate in such a way that the film thickness becomes 2.2 μm after baking by the spin coating method. Heat for 3 minutes to dry. At this time, the uniformity of the coating film was visually confirmed under a sodium lamp. The evaluation criteria are as follows.

Evaluation A: The surface of the coating film is smooth.

Evaluation B: Unevenness of the sea-island pattern was confirmed on a part of the surface of the coating film.

Evaluation C: The unevenness of the sea-island pattern was confirmed on the entire surface of the coating film.

<Evaluation of precipitation and measurement of surface roughness>

Each coating film subjected to the above-mentioned evaluation of uniformity was exposed by irradiating 60 mJ/m ² ultraviolet light from the coating film side with a high-pressure mercury lamp. Afterwards, develop for 60 seconds with a developer solution at 23°C and 0.05% KOH concentration, and then heat in an oven at 230°C for 30 minutes, and perform post-baking to form a colored layer. On the surface of these colored layers, the presence or absence of precipitation was confirmed with an optical microscope (product name "MX61L", manufactured by Olympus Corporation). Next, the surface roughness of this colored layer was measured using an atomic force microscope (product name "AS-7B-M", manufactured by TAKANO Corporation). The evaluation criteria in the precipitation evaluation are as follows.

Evaluation A: Precipitation was not confirmed.

Evaluation B: Slight precipitation was confirmed on the coating film.

Evaluation C: Precipitation was confirmed on the whole coating film.

<Evaluation of Optical Properties>

The resin compositions obtained in each of the Examples and Comparative Examples were placed on a 0.7mm thick glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35"), using a spin coater, and then baked to obtain the desired color. (Under C light source, red coloring layer R1~R13: x=0.650, green coloring layer G1~G2: y=0.620, G3~G7: y=0.503, blue coloring layer B1~B7: y=0.085) cloth. After heating and drying the coating film of the applied resin composition on a hot plate at 80°C for 3 minutes, the coating film was irradiated with 60 mJ/cm ² of ultraviolet rays using an ultra-high pressure mercury lamp to harden the coating film. Afterwards, the hardened coating film was post-baked in a dust-free oven at 230°C for 25 minutes to obtain a colored layer with a film thickness of 2.0 μm, and the contrast, chromaticity (x, y) and brightness (Y) of the obtained colored film were measured . The contrast was measured using "Comparison Measuring Device CT-1B" manufactured by Tsubusaka Electric Co., Ltd., and the chromaticity and luminance were measured using "Microspectroscopic Measuring Device OSP-SP200" manufactured by Olympus Co., Ltd.

<Electrical reliability evaluation> (Formation of colored layer)

Prepare a set of ITO substrates A and B with ITO (indium tin oxide) electrodes on the surface of a glass substrate with a thickness of 0.7 mm (manufactured by NH Techno Glass Co., Ltd., "NA35"), and the ITO substrate surface of one ITO substrate A , The photosensitive colored resin composition obtained in each example and each comparative example was coated with a spin coater, and prebaked on a hot plate at 80° C. for 3 minutes to form a coating film. Next, the coating film was irradiated with ultraviolet rays by an exposure machine of 100 mJ/cm ² through a photomask using an ultra-high pressure mercury lamp. After the irradiation, the substrate was developed with a 0.05% potassium hydroxide aqueous solution at 25° C. for 1 minute with a rotary developing machine, washed with pure water for 1 minute, and dried. After drying, the substrate was post-baked in an oven at 230° C. for 30 minutes to fabricate a patterned colored layer arranged on the substrate. The film thickness of the obtained colored layer was 1.9 μm.

(Production of liquid crystal unit)

In addition, the above-mentioned ITO substrate B was prepared, and an epoxy resin-based sealant containing silica beads with a diameter of 5 μm was coated on the outer periphery of the substrate using a dispenser, and the above-mentioned colored layer arranged in a pattern was formed. The surface of the colored layer of the ITO substrate A is arranged facing to each other so that the outer edge is offset by 3mm, and heated in an oven at 180°C for 2 hours under pressure bonding. A liquid crystal (MLC-6846-000, manufactured by Merck Japan) was injected into the empty cell formed between the above-mentioned pressure-bonded substrates, and the peripheral part was sealed with a UV-curable sealant to prepare a liquid crystal cell for voltage retention measurement. In addition, the above-mentioned liquid crystal system has a voltage retention rate of 98% or more under the following voltage retention rate measurement conditions.

(Voltage retention rate)

Using the liquid crystal unit obtained above, heat the liquid crystal unit in a hot air circulation furnace at 105°C for 2.5 hours. After heating, return to room temperature. The distance between the electrodes of the above liquid crystal unit: 5 μm, the applied voltage pulse amplitude: 5V, Applied voltage pulse frequency: 60Hz, applied voltage pulse width: 16.67msec, for ITO substrate A and ITO A pulse voltage was applied to the substrate B, and the voltage retention was measured using a voltage retention measurement system (manufactured by Toyo Technical Co., Ltd., VHR-1A type) to evaluate the voltage retention. The evaluation criteria are as follows.

AA: The voltage retention rate is above 95% (the display stability of liquid crystal is extremely superior).

A: The voltage retention rate is more than 90% and less than 95% (the display stability of liquid crystal is excellent).

B: The voltage retention rate is more than 80% and less than 90% (the display stability of liquid crystal is slightly poor but still within the practical range).

C: The voltage retention rate is less than 80% (the alignment state of the liquid crystal changes abnormally, and the display failure of the liquid crystal occurs).

<Pressure cooker test (PCT)>

For each coating film subjected to the above-mentioned precipitation evaluation and surface roughness measurement, according to JIS C0096:2001 (IEC-60068-2-66), using a highly accelerated life tester (ESPEC Corporation, EHS-211(M)) according to PCT was carried out under the conditions of temperature 125°C, relative humidity 75%, and 12 hours. Then, the color difference (ΔE*ab) before and after PCT was measured using "Microspectrometry Apparatus OSP-SP200" manufactured by Olympus Co., Ltd.

The results are shown in Tables 2 to 6 below.

The abbreviations in the table are as follows.

‧Br-DPP: brominated diketopyrrolopyrrole pigment

‧R254: C.I. Pigment Red 254

‧G7: C.I. Pigment Green 7

‧G59: C.I. Pigment Green 59

‧Y138: C.I. Pigment Yellow 138

‧Y150: C.I. Pigment Yellow 150

‧B15:3: C.I. Pigment Blue 15:3

‧B15:6: C.I. Pigment Blue 15:6

‧V23: C.I. Pigment Violet 23

‧Precipitation inhibitor compound III: MAGAFAC F575 (a compound containing a fluorocarbon group and a cross-linked cycloaliphatic group, manufactured by DIC Corporation)

‧Precipitation inhibitor compound IV: MAGAFAC F444 (perfluoroalkyl ethylene oxide adduct, manufactured by DIC Corporation)

‧Thiol compound I: 2-Mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

‧Thiol Compound II: Pentaerythritol (3-mercaptobutyrate)

‧Irg369: Irgacure369 (manufactured by BASF Corporation)

‧PBG304: TR-PBG-304 (oxime ester photopolymerization initiator, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.)

‧PBG3057: TR-PBG-3057 (oxime ester photopolymerization initiator, manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.)

‧NCI930: ADEKA AKLS NCI-930 (oxime ester photopolymerization initiator, manufactured by ADEKA)

Below, the results are stated. Compared with Comparative Examples 1-3, the precipitation of the compound derived from the color material was not suppressed. In Examples 1-12, the precipitation of the compound derived from the color material was suppressed, so the surface roughness of the colored layer was lower than that of Comparative Examples 1-3. , and the luminance and contrast are also better than Comparative Examples 1-3. Also, in Examples 1 to 12, the flatness was excellent. Furthermore, the voltage retention rate in Examples 1-12 is also superior to that in Comparative Examples 1-3, and the color difference before and after PCT is smaller.

In addition, compared with Comparative Example 4, which did not inhibit the analysis of the compound from the color material It can be seen that in Examples 13-18, the precipitation of compounds from color materials can be suppressed, so the surface roughness of the colored layer is lower than that of Comparative Example 4, and the brightness and contrast of Examples 15-18 are also better than Comparative Example 4. Also, in Examples 13 to 18, the flatness was excellent. Furthermore, the voltage retention rate in Examples 13-18 is also superior to Comparative Example 4, and the color difference before and after PCT is smaller.

Furthermore, compared to Comparative Examples 5 and 6, the precipitation of the compound from the color material was not inhibited. In Examples 19 to 23, the precipitation of the compound from the color material was suppressed, so the surface roughness of the colored layer was higher than that of Comparative Example 5. . Also, in Examples 19 to 23, the flatness was excellent. Furthermore, the voltage retention rate in Examples 19-23 is also superior to Comparative Examples 5 and 6, and the color difference before and after PCT is smaller.

Claims (8)

A resin composition comprising a polymer (A), a polymerizable compound (B), a polymerization initiator (C), a color material (D), a compound (E) having a fluorocarbon group and a crosslinked cycloaliphatic group ), and the thiol compound (F), the above-mentioned polymerization initiator (C) contains two or more oxime ester-based photopolymerization initiators. The resin composition according to claim 1, wherein the carbon number of the fluorocarbon group is 2 or more and 10 or less. The resin composition according to claim 1 or 2, wherein the above-mentioned crosslinked cycloaliphatic group is any one of adamantyl group which may also be substituted and dicyclopentanyl group which may also be substituted. The resin composition according to claim 1 or 2, wherein the above-mentioned compound (E) contains a constituent unit derived from a compound (E-1) having a fluorocarbon group and an ethylenically unsaturated group, and a compound derived from a crosslinked cyclic aliphatic A copolymer of constituent units of a compound (E-2) having a group group and an ethylenically unsaturated group. Such as the resin composition of claim 4, wherein the molar ratio of the constituent units derived from the aforementioned compound (E-1) to the constituent units derived from the aforementioned compound (E-2) in the aforementioned compound (E) is 5:95~ 70:30. The resin composition according to claim 1 or 2, wherein the polymerizable compound is a photopolymerizable compound. A color filter having a colored layer made of a hardened resin composition according to claim 1 or 2. An image display device comprising the color filter of Claim 7.

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