JP2014123008A - Curable composition, color filter, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which is highly curable by irradiation with radiation or heat.SOLUTION: A curable composition contains (A) a polymer having a repeating unit represented by a formula (1) and an iodine number of 21 or more and (B) a photopolymerization initiator. [In the formula (1), Rrepresents a hydrogen atom or a methyl group, X represents -COO-(*) or -CONH-(*), Rand Reach independently represent a substituted or unsubstituted bivalent hydrocarbon group, Rrepresents a bivalent organic group, Z represents a single bond, -CO- or -COO-(*), m represents an integer from 1 to 30, and n represents an integer from 0 to 30, where (*) represents a bonding hand bonded to R, and (*) represents a bonding hand bonded to R.]

Description

  The present invention relates to a curable composition, and more specifically, image forming materials such as three-dimensional stereolithography and holography, color filters, photoresists, lithographic printing plates, and color proofs, insulating film materials, protective film materials, inks, Curable composition that can be used for paints, adhesives, sealing materials, coating agents, dental materials, etc., a color filter comprising a colored layer formed using the curable composition, and a display comprising the color filter It relates to an element.

  Conventionally, curable compositions that cure upon irradiation or heating of radiation are image forming materials such as three-dimensional stereolithography, holography, color filters, photoresists, lithographic printing plates, color proofs, insulating film materials, protective film materials, Widely used as inks, paints, adhesives, sealing materials (liquid crystal display elements, LED elements, organic EL elements, etc.), coating agents, dental materials and the like.

  For example, Patent Documents 1 and 2 disclose that a radiation-sensitive composition using a specific polymer having a polymerizable unsaturated bond is suitable as a material for forming a color filter or a spacer or a colored layer. Yes.

JP 2008-233517 A JP 2010-44365 A

  By the way, with recent demands for energy saving, environmental load reduction, and device productivity improvement, curable compositions are required to have a lower curing temperature and higher sensitivity to radiation. In addition, it is known that it is effective to use a dye as a colorant in order to achieve high contrast and high definition of a color filter. However, in a curable composition containing a dye, further curing is possible. There is a need for improvement in performance.

  Therefore, the subject of this invention is providing the composition excellent in sclerosis | hardenability with respect to irradiation of a radiation or a heating. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer etc. which were formed from the said curable composition, and the said color filter.

  In view of this situation, the present inventors have conducted extensive research and found that the above problems can be solved by using a specific polymer having a carboxy group and a polymerizable unsaturated group. It came to be completed.

  That is, the present invention includes (A) a polymer having a repeating unit represented by the following formula (1) and having an iodine value of 21 or more (hereinafter also referred to as “(A) polymer”), and (B) A curable composition containing a photopolymerization initiator is provided.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
X represents -COO-(* ¹ ) or -CONH-(* ¹ );
R ² and R ³ each independently represent a substituted or unsubstituted divalent hydrocarbon group;
R ⁴ represents a divalent organic group,
Z represents a single bond, -CO- or -COO-(* ² ),
m represents an integer of 1 to 30,
n shows the integer of 0-30.
However, “* ¹ ” indicates a bond that bonds with R ^2, and “* ² ” indicates a bond that bonds with R ³ . ]

  Furthermore, the present invention provides a color filter comprising a colored layer, a protective film layer or a spacer formed using the curable composition, and a display element comprising the color filter. Here, the “colored layer” means each color pixel, black matrix, etc. used in the color filter.

The curable composition of the present invention is extremely excellent in curability against radiation and heating.
Therefore, the curable composition of the present invention starts production of various color filters constituting a color liquid crystal display element, a solid-state imaging element, an organic EL display element, and the like, as well as an insulating film material, a protective film material, an ink, and a paint. It is extremely useful as an adhesive, a sealing material for liquid crystal display elements / LED elements / organic EL elements, a coating agent, a dental material, and the like.

Hereinafter, the present invention will be described in detail.
The following curable compositions, described constituents of the curable composition of the present invention.

-(A) polymer-
In the curable composition of the present invention, (A) a polymer, that is, a polymer having a repeating unit represented by the above formula (1) and having an iodine value of 21 or more is a curing component and a binder resin. Can also function. The curable composition of the present invention has extremely excellent curability by containing the (A) polymer.

  In the polymer constituting the conventional curable composition, (meth) acrylic acid is usually copolymerized. However, in the present invention, the above formula (having a longer side chain than the structure derived from (meth) acrylic acid ( It has a repeating unit represented by 1).

In the above formula (1), the divalent hydrocarbon group according to R ² and R ³ is a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. Etc. The divalent aliphatic hydrocarbon group may be either linear or branched, and the divalent aliphatic hydrocarbon group and divalent alicyclic hydrocarbon group may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. It may be a hydrogen group. In addition, in this specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group substituted on the ring structure. In other words, the structure includes at least an alicyclic hydrocarbon or an aromatic hydrocarbon.

  Examples of the divalent aliphatic hydrocarbon group include an alkanediyl group and an alkenediyl group, and the number of carbon atoms is preferably 1 to 20, and more preferably 2 to 12. Specific examples include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl. Group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,4-diyl group, pentane-1 , 5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane-1,3-diyl group, Ethene-1,1-diyl group, ethene-1,2-diyl group, propene-1,2-diyl group, propene-1,3-diyl group, propene-2,3-diyl group, 1-butene-1 , 2-diyl group, 1-butene-1,3-diyl group, 1-bute 1,4-diyl group, 2-pentene-1,5-diyl group, and a 3-hexene-1,6-diyl group.

  As a bivalent alicyclic hydrocarbon group, a cycloalkylene group and a cycloalkenylene group are mentioned, for example, The carbon number is 3-20, Furthermore, 3-12 are preferable. Specific examples include groups represented by the following formula (I) in addition to a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclobutenylene group, a cyclopentenylene group, and the like.

[In Formula (I),
Y represents a divalent group selected from the group of groups represented by the following formulas (i) to (v),
a and b each independently represent an integer of 0 to 6. ]

  a and b are preferably independently an integer of 0 to 3.

Examples of the divalent aromatic hydrocarbon group include an arylene group, and a monocyclic to tricyclic arylene group having 6 to 14 carbon atoms is preferable. Specific examples include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.
Among them, the divalent hydrocarbon radical according to R ² and R ^3, 1 to 20 carbon atoms, more preferably an alkanediyl group having 1 to 12 carbon atoms. R ² and R ³ may be the same or different, and when a plurality of R ² and R ³ are present, they may be the same or different.

Examples of the substituent group of the divalent hydrocarbon group according to R ² and R ^3, and a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, and a phenoxy group.

In the above formula (1), examples of the divalent organic group related to R ⁴ include a divalent hydrocarbon group and a divalent heterocyclic group. Examples of the divalent hydrocarbon group for R ⁴ include the same divalent hydrocarbon groups as those for R ² and R ³ . On the other hand, examples of the divalent heterocyclic group include pyridinediyl. Among them, a divalent hydrocarbon group is preferable, and further, a C1-C10 alkanediyl group, a C2-C10 alkenediyl group, a C3-C20 cycloalkylene group, and a C3-C20 cycloalkenylene group. , An arylene group having 6 to 14 carbon atoms is preferable, and an alkanediyl group having 1 to 6 carbon atoms is particularly preferable.

In the formula (1), X is preferably —COO — (* ¹ ) among —COO — (* ¹ ) and —CONH — (* ¹ ).
m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.
n is preferably an integer of 0 to 6, more preferably an integer of 1 to 3, and still more preferably 0 or 1.

  More preferable examples of the repeating unit represented by the above formula (1) include repeating units represented by the following formulas (1-1) to (1-4).

[In Formula (1-1)-(1-4),
R ¹ , R ⁴ , X, Y, a, b and m are as defined above,
R ⁸ and R ⁹ each independently represent a substituted or unsubstituted divalent aliphatic hydrocarbon group;
r represents an integer of 1 to 30. ]

The divalent aliphatic hydrocarbon group according to R ⁸ and R ⁹ is preferably an alkanediyl group having 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Incidentally, R ⁸ and R ⁹ each may be the same or different, substituents divalent aliphatic hydrocarbon radical according to R ⁸ and R ⁹ are the same as the substituents in R ² and R ³ Is preferably unsubstituted.
r is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

The repeating unit represented by the above formula (1) is, for example, a (meth) acrylic monomer or (meth) acrylamide monomer having a hydroxyl group, and HOOC-R ⁴ —COOH (R ⁴ is as defined above). It can be introduced by utilizing an esterification reaction with an anhydride of a dibasic acid represented by: As a monomer which gives the repeating unit represented by the above formula (1), for example, succinic acid mono [2- (meth) acryloyloxyethyl], 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( Commercial products such as (meth) acryloyloxyethyl tetrahydrophthalic acid can also be used.

  (A) The polymer is further characterized by an iodine value of 21 or more. That is, (A) the polymer has a polymerizable unsaturated group, and the content of the polymerizable unsaturated group is 21 or more in terms of iodine value. Here, the “iodine value” is a value obtained by converting the amount of halogen bonded to 100 g of the polymer (A) into the number of g of iodine. (A) The iodine value of the polymer is preferably 23 or more, particularly preferably 25 or more, preferably 200 or less, more preferably 150 or less, and particularly preferably 100 or less, from the viewpoint of further enhancing the desired effect. (A) As a range of the iodine value of a polymer, Preferably it is 23-200, Most preferably, it is 25-150.

  (A) The polymer preferably has a polymerizable unsaturated group in its side chain. Moreover, as a polymerizable unsaturated group, although it does not specifically limit, (meth) acryloyl group, an allyl group, a vinylphenyl group etc. can be mentioned, Among these, (meth) acryloyl group is preferable. Here, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.

  (A) In order to introduce a polymerizable unsaturated group into the polymer, for example, a glycidyl group described in JP-A-5-19467, WO96 / 23237, JP-A-2008-181095, In addition to a method using a reaction between an alicyclic epoxy group and a carboxy group, a method using a reaction between an isocyanate group and a hydroxyl group described in JP-A-6-230212, JP-A-2008-233517, etc., allyl ( For example, a method of copolymerizing (meth) acrylate may be employed. In the present invention, the (A) polymer preferably has a polymerizable unsaturated group represented by the following formula (2).

[In Formula (2),
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ represents a (c + 1) -valent hydrocarbon group,
R ⁷ independently of one another represents an ethylene group or a propanediyl group,
c represents 1 or 2,
d shows the integer of 0-5. ]

In the above formula (2), R ⁶ can be a divalent or trivalent hydrocarbon group. Examples of the divalent hydrocarbon group include alkanediyl groups, and the number of carbon atoms is preferably 1 to 12, 1-10 are more preferable and 1-6 are still more preferable. Specific examples include the same ones as described above. Moreover, as a trivalent hydrocarbon group which concerns on R < ⁶ >, alkanetriyl group is mentioned, As for the carbon number, 1-19 are preferable, 1-10 are more preferable, and 1-7 are still more preferable. Specific examples include, for example, methylidyne group, ethylidene group, 1,2,3-propanetriyl group, 1,2,4-butanetriyl group, 1,2,5-pentanetriyl group, 1,3,5- In addition to a pentanetriyl group, a group represented by the following formula (II) can be exemplified.

[In Formula (II),
e, f and g each independently represent an integer of 1 to 6. ]

Examples of the propanediyl group according to R ⁷ include a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group, and among them, a propane-1,2-diyl group Is preferred.
d is preferably an integer of 0 to 3, and more preferably 1 or 2.
e, f and g are each independently preferably an integer of 1 to 3, and more preferably 1 or 2.

  The polymer (A) having a polymerizable unsaturated group represented by the above formula (2) in the side chain is, for example, a polymer having in the side chain a group capable of reacting with an isocyanato group such as a hydroxyl group or an amino group. It can manufacture by making the isocyanate compound represented by following formula (3) react.

In [Equation ^{(3), R 5, R} 6, R 7, c and d are as defined in the formula (2). ]

  (A) The polymer is produced by reacting an isocyanate compound represented by the above formula (3) with a monomer polymer containing an ethylenically unsaturated monomer having a hydroxyl group. It is preferable to have a repeating unit represented by the following formula (4).

[In Formula (4),
R ⁵ , R ⁶ , R ⁷ , c and d are as defined in the above formula (2);
R ¹⁰ represents a hydrogen atom or a methyl group,
X ¹ represents —COO — (* ³ ) or —CONH — (* ³ ),
R ¹¹ and R ¹² each independently represent a substituted or unsubstituted divalent hydrocarbon group;
Z ¹ represents a single bond, —CO— or —COO — (* ⁴ ),
s represents an integer of 1 to 30,
t shows the integer of 0-30.
However, “* ³ ” indicates a bond that bonds with R ^11, and “* ⁴ ” indicates a bond that bonds with R ¹² . ]

In the above formula (4), examples of the divalent hydrocarbon group according to R ¹¹ and R ¹² include the same divalent hydrocarbon groups as those described above for R ² and R ^3. An alkanediyl group having 1 to 20 carbon atoms and more preferably 1 to 12 carbon atoms is preferable. Further, examples of the substituent that the divalent hydrocarbon group according to R ¹¹ and R ¹² has include the same substituents as the substituent that the divalent hydrocarbon group according to R ² and R ³ has.
s is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.
t is preferably an integer of 0 to 6, more preferably an integer of 1 to 3, and still more preferably 0 or 1.

As the ethylenically unsaturated monomer having a hydroxyl group, for example,
(Poly) hydroxyalkyl (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin mono (meth) acrylate and the like (poly) hydroxyalkyl ( (Meth) acrylates and their corresponding (meth) acrylamides;
Polyalkylene glycol mono (meth) acrylates such as polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate and the corresponding (meth) acrylamide;

2- (6-hydroxyhexanoyloxy) ethyl (meth) acrylate, 3- (6-hydroxyhexanoyloxy) propyl (meth) acrylate, 4- (6-hydroxyhexanoyloxy) butyl (meth) acrylate, 5- (Hydroxyhexanoyloxy) alkyl (meth) acrylates such as (6-hydroxyhexanoyloxy) pentyl (meth) acrylate, 6- (6-hydroxyhexanoyloxy) hexyl (meth) acrylate and the like (meta ) Acrylamide;

2- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) ethyl (meth) acrylate, 3- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) propyl (meth) acrylate, 4- (3-hydroxy -2,2-dimethylpropoxycarbonyloxy) butyl (meth) acrylate, 5- (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) pentyl (meth) acrylate, 6- (3-hydroxy-2,2-dimethyl In addition to (3-hydroxy-2,2-dimethylpropoxycarbonyloxy) alkyl (meth) acrylate such as propoxycarbonyloxy) hexyl (meth) acrylate and the corresponding (meth) acrylamide,
Examples include 1,4-cyclohexanedimethanol mono (meth) acrylate and (meth) acrylamide corresponding to these.

  (A) When manufacturing a polymer, the ethylenically unsaturated monomer which has a hydroxyl group can be used individually or in mixture of 2 or more types.

  (A) The polymer may contain a repeating unit other than the repeating unit represented by the above formula (1) and the repeating unit having a polymerizable unsaturated group (hereinafter also referred to as “other repeating unit”). Good. Examples of monomers that give other repeating units include, for example, a maleimide substituted with a cyclic group at the N-position, an aromatic vinyl compound, a (meth) acrylic acid ester having an aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. (Meth) acrylic acid ester having, (meth) acrylic acid ester having an aromatic hydrocarbon group, (meth) acrylic acid ester having a cyclic ether group, (meth) acrylic acid ester having two or more alkyleneoxy groups, etc. Can be mentioned.

Examples of the cyclic group substituted at the N-position of maleimide include an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The alicyclic hydrocarbon group may be a bridged alicyclic hydrocarbon group of 2 to 4 rings, but the number of carbon atoms constituting the ring is 5 or more, more 5 to 20, particularly 6 to 12 alicyclic hydrocarbons. Groups are preferred. Specific examples include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, a norbornyl group, a bornyl group, an adamantyl group, a bicyclooctyl group, etc. Among them, a cyclohexyl group is preferable. The aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include, for example, a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthracenyl group, etc. Among them, a phenyl group is preferable. The “alicyclic hydrocarbon group” and the “aromatic hydrocarbon group” as used herein are not only a group consisting of a ring structure, but also a divalent aliphatic hydrocarbon group in the ring structure as described above. It is a concept that includes a substituted group.
As the aliphatic hydrocarbon group possessed by the (meth) acrylic acid ester, an aliphatic hydrocarbon group having 4 or more carbon atoms, more preferably 4 to 12, particularly 4 to 8 carbon atoms is preferable. Specific examples include alkyls such as n-butyl, isobutyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl. The group can be mentioned.
Examples of the alicyclic hydrocarbon group and aromatic hydrocarbon group possessed by the (meth) acrylic acid ester include those similar to the alicyclic hydrocarbon group and aromatic hydrocarbon group described in the above-mentioned cyclic group. it can.
Examples of cyclic ether groups possessed by (meth) acrylic acid esters include ether bonds such as oxirane groups, oxetane groups, oxolane groups, oxane groups, oxepane groups, oxocan groups, oxonan groups, oxecan groups, oxet groups, and oxole groups. A cyclic ether group having one ether; a cyclic ether group having two ether bonds such as a dioxolane group, a dioxane group, a dioxepane group and a dioxecan group; a cyclic ether group having three ether bonds such as a trioxane group. Among these, a C2-C5 cyclic ether group having one ether bond is preferable.
Examples of the alkyleneoxy group that the (meth) acrylic acid ester has include an ethylene group, a propanediyl group, and a butanediyl group. The propanediyl group is preferably a propane-1,2-diyl group.

Examples of the maleimide having a cyclic group substituted at the N-position include N-phenylmaleimide and N-cyclohexylmaleimide.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, acenaphthylene, and the like.
Examples of the (meth) acrylic acid ester having an aliphatic hydrocarbon group include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Can do.
Examples of the (meth) acrylic acid ester having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meta ) Acrylate and the like.
Examples of the (meth) acrylic acid ester having an aromatic hydrocarbon group include benzyl (meth) acrylate and p-hydroxyphenyl (meth) acrylate.

Examples of the (meth) acrylic acid ester having a cyclic ether group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). Acrylate, 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane, tetrahydrofurfuryl (meth) acrylate, 3-tetrahydrofurfuryl (meth) acrylate, 2- (Tetrahydrofurfuryloxy) ethyl (meth) acrylate and the like can be mentioned.
Examples of the (meth) acrylic acid ester having two or more alkyleneoxy groups include polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) ) Acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, and the like.
(A) When manufacturing a polymer, the monomer which gives these other repeating units can be used individually or in mixture of 2 or more types.

  Among the monomers giving other repeating units, maleimide having a cyclic group substituted at the N-position, (meth) acrylic acid ester having an aliphatic hydrocarbon group having 4 or more carbon atoms, and having an alicyclic hydrocarbon group (Meth) acrylic acid ester, (meth) acrylic acid ester having an aromatic hydrocarbon group, (meth) acrylic acid ester having two or more alkyleneoxy groups are preferred, especially aliphatic hydrocarbon group having 4 or more carbon atoms (Meth) acrylic acid ester having an alicyclic hydrocarbon group and (meth) acrylic acid ester having two or more alkyleneoxy groups are preferred. The (meth) acrylic acid ester having 2 or more alkyleneoxy groups preferably has 2 or more alkyleneoxy groups having 2 or more carbon atoms.

  In the polymer (A), the copolymerization ratio of the repeating unit represented by the formula (1) is preferably 1 to 40 mol%, particularly preferably 10 to 30 mol%. Moreover, the other repeating unit copolymerization ratio is preferably 5 to 95 mol%, particularly preferably 10 to 60 mol%.

  The polymer (A) can be produced, for example, by radical polymerization of a monomer that gives each repeating unit. The polymer can be produced by a living radical polymerization method, a living anion polymerization method, a living cation polymerization method, or the like. The residual amount of Mn and unreacted monomers can also be controlled. Moreover, it can also be set as a star-shaped polymer by radically polymerizing in the presence of a tri- or higher functional low molecular polyfunctional thiol.

(A) You may use a polymer individually or in mixture of 2 or more types.
(A) The molecular weight of the polymer can be measured as a weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. (A) The weight average molecular weight (Mw) of the polymer is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 3,000 to 30,000. By setting it within such a range, the desired effect can be further enhanced.
The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured under the same conditions, that is, the dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1. It is 0.0-3.0, More preferably, it is 1.0-2.5. By setting it within such a range, the desired effect can be further enhanced.

-(B) Photopolymerization initiator-
The photopolymerization initiator used in the present invention is obtained by exposing the polymerizable unsaturated group of the polymer (A) to a polymerizable compound described later by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone compound, a polynuclear quinone compound, a diazo compound, an imide sulfonate compound, an onium salt compound, etc. can be mentioned. Of these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, and the like are preferable.
In this invention, a photoinitiator can be used individually or in mixture of 2 or more types.

Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Examples thereof include diethylthioxanthone and 2,4-diisopropylthioxanthone.
Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.
When a biimidazole compound is used as the photoradical generator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Kishisuchiriru) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and the like.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl) Methoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1, 3-Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), WO08 / 078678, JP 201 And the like oxime ester compounds described in -132,215 JP. As commercial products of O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA) and the like can also be used.

  In this invention, 0.1-500 mass parts is preferable with respect to 100 mass parts of (A) polymers, and, as for content of a photoinitiator, 1-200 mass parts is especially preferable.

  In the present invention, a sensitizer can be used in combination with the photopolymerization initiator. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, Anthracene, 2-tert-butylanthracene, perylene and the like can be mentioned.

-(C) Colorant-
The curable composition of the present invention can contain (C) a colorant. Thereby, it can be set as the colored curable composition for forming the colored layer of a color filter, for example. Here, the “colored layer” means each color pixel, black matrix, etc. used in the color filter. The colorant is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use of the curable composition. When the curable composition of the present invention is used for forming a colored layer of a color filter, the color filter is required to have high color purity, luminance, contrast, etc., and therefore, as the colorant, at least one selected from pigments and dyes is used. Is preferred.

  The pigment may be either an organic pigment or an inorganic pigment. Preferred specific examples of the organic pigment include C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 80, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Pigment orange 38, C.I. I. And CI Pigment Violet 23. Preferable specific examples of the inorganic pigment include carbon black and titanium black.

  As the pigment, a lake pigment is also preferable, and specific examples thereof include a triarylmethane dye or a xanthene dye raked with an isopolyacid or a heteropolysanacid. Triarylmethane-based lake pigments are disclosed in, for example, Japanese Patent Application Laid-Open No. 2011-186043. Xanthene-based lake pigments are disclosed in, for example, JP 2010-191304 A.

The dyes are preferably xanthene dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, and the like. More specifically, JP 2010-32999 A, JP 2010-254964 A, JP 2011-138094 A, International Publication No. 10/123071, Pamphlet 2011-116803, JP 2011. Organic dyes described in JP-A No. 117995, JP-A No. 2011-133844, JP-A No. 2011-174987, and the like.
In the present invention, the pigment and the dye can be used alone or in admixture of two or more.

  In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Further, the organic pigment can be used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  (C) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the colored curable composition from the point of forming a pixel having high brightness and excellent color purity, or a black matrix having excellent light shielding properties. Preferably it is 5-60 mass%. The “solid content” here is a component other than the solvent described later.

  If the curable composition of the present invention is used, a color filter having excellent solvent resistance and electrical characteristics can be obtained even when at least one selected from lake pigments and dyes is used as a colorant.

  In the present invention, when a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant is commercially available. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, Big Chemie (BYK)) Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above, manufactured by BYK Chemy (BYK)), Solplus 76 Solsperse 24000 (manufactured by Lubrizol) and polyester as Addispar PB8 1, AJISPER PB822, and Ajisper PB880 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), can be exemplified respectively. As the acrylic copolymer, copolymers disclosed in JP2011-232735A, 2011-237769A, and JP2012-32767A can also be suitably used. The content of the dispersant can be appropriately determined within a range that does not impair the object of the present invention.

  Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(D) Polymerizable compound-
The curable composition of the present invention can be further improved in curability by containing a polymerizable compound (excluding the polymer (A)). A polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (D) polymeric compound can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the polymerizable compound (D) is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) polymer. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be made favorable.

-(E) Binder resin-
The curable composition of the present invention can contain (E) a binder resin (however, excluding the polymer (A)). Thereby, the alkali solubility, binding property, storage stability, etc. of a curable composition can be improved. The binder resin is not particularly limited as long as it does not correspond to the polymer (A), but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (e1)”) and other copolymers. A copolymer with a possible ethylenically unsaturated monomer (hereinafter referred to as “unsaturated monomer (e2)”) can be mentioned.

Examples of the unsaturated monomer (e1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (e1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (e2), the ethylenic unsaturated monomer which has the said hydroxyl group, the monomer which gives the said other repeating unit, etc. can be mentioned, for example.
These unsaturated monomers (e2) can be used alone or in admixture of two or more.

  Specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In this invention, (E) binder resin can be used individually or in mixture of 2 or more types.

  In the present invention, the content of (E) the binder resin is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of (A) polymer.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. A polyfunctional thiol such as pentaerythritol tetrakis (3-mercaptopropionate);

-Solvent-
The curable composition of the present invention contains the above components (A) to (B) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent. .
As said solvent, (A)-(B) component which comprises a curable composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, and as long as it has moderate volatility, It can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate ;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the curable composition is 5 from the viewpoints of applicability and stability of the obtained curable composition. An amount of ˜50 mass% is preferred, and an amount of 10˜40 mass% is particularly preferred.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed from the curable composition of the present invention.

  As a method for forming the colored layer constituting the color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, after applying a liquid composition of the radiation-sensitive curable composition of the present invention containing, for example, a blue colorant on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns are arranged in a predetermined arrangement.

  Next, each of the radiation-sensitive curable compositions of green or red is used, and in the same manner as described above, each of the radiation-sensitive curable compositions is applied, pre-baked, exposed, developed, and post-baked to obtain a green pixel array. And a red pixel array are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. Using the curable composition, it can be formed in the same manner as in the case of forming the pixel. The curable composition of the present invention can also be suitably used for forming such black tricks.

Examples of the substrate used when forming the colored layer include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive curable composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method or a bar coating method should be adopted. However, it is particularly preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples thereof include a light source, a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The radiation is preferably in the range of 190 to 450 nm.

Exposure of the radiation is generally preferred 10~10,000J / m ^2. When the curable composition of the present invention is used, a color filter having good solvent resistance and electrical characteristics can be produced even when the exposure amount is 500 J / m ² or less.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.
The post-baking conditions are usually 120 to 280 ° C. and about 10 to 60 minutes. The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm. If the curable composition of the present invention is used, a color filter having good solvent resistance and electrical characteristics can be produced even when the post-baking temperature is 200 ° C. or lower.

  Further, as a second method for forming a colored layer on a substrate, a method of obtaining pixels of each color by an ink jet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, etc., is adopted. be able to. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the thermosetting composition of the present invention containing, for example, a red colorant is discharged into the formed partition wall by an inkjet apparatus, pre-baking is performed to evaporate the solvent. Next, the coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

  Next, using each green or blue thermosetting composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing color mixing of the thermosetting composition of each color discharged into the compartment, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the colored layer, the light source of radiation, and the method and conditions such as pre-baking are the same as in the first method described above.
When the curable composition of the present invention is used, a colored layer having good solvent resistance and the like can be obtained even when the post-baking temperature is lower than that in the past.

  In addition, after forming a protective film as needed on the pixel pattern obtained through the above steps, a transparent conductive film is formed by sputtering, and a spacer is further formed to form a color filter. A thermosetting and / or radiation-sensitive resin composition is usually used for forming the protective film and spacer, but the curable composition of the present invention is also suitably used for forming the protective film and spacer. can do. The conditions for forming the protective film layer and the spacer are the same as those for the colored layer.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, a solid-state imaging element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (tin-doped indium oxide) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.
Moreover, the organic EL display element provided with the color filter of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
In addition, the electronic paper including the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(A) Synthesis of polymer Synthesis Example 1
In a flask equipped with a condenser and a stirrer, 16.8 parts by mass of 2-hydroxyethyl methacrylate, 11.2 parts by mass of 2-ethylhexyl methacrylate, 0.3 parts by mass of 2,2′-azobisisobutyronitrile and pyrazole 0.8 parts by mass of cyano (dimethyl) methyl ester of -1-dithiocarboxylic acid was dissolved in 56 parts by mass of propylene glycol monomethyl ether acetate, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 6 hours to perform living radical polymerization.
Next, 29.9 parts by mass of propylene glycol monomethyl ether acetate, 10.0 parts by mass of 2-methacryloyloxyethyl isocyanate, and 0.3 parts by mass of p-methoxyphenol are added to the obtained polymer solution, and oxygen bubbling is performed. After raising the temperature of the reaction solution to 100 ° C., the reaction was carried out for 1 hour.
Next, 4.3 parts by mass of succinic anhydride and 0.3 part by mass of dimethylaminopyridine were added and reacted for 4 hours to obtain a propylene glycol monomethyl ether acetate solution having a solid content concentration of about 33% by mass. The obtained polymer had a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of 7,100, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 1.31. Met. This polymer is referred to as “polymer (A-1)”.

Synthesis Examples 2-5
(A) A polymer (A-2) and a polymer (A-3) were prepared in the same manner as in Synthesis Example 1 except that the types and amounts of monomers used as raw materials for the polymer were changed as shown in Table 1. ), A propylene glycol monomethyl ether acetate solution of the polymer (A-4) and the polymer (A-5). The solid content concentration of each polymer was adjusted to be about 33% by mass. Table 1 shows the physical properties and the like of each polymer obtained.

Synthesis Example 6
Into a flask equipped with a condenser and a stirrer, 10 parts by mass of propylene glycol monomethyl ether acetate was put, the internal temperature was kept at 80 ° C., nitrogen bubbling was performed for 30 minutes, and then dissolved in 26 parts by mass of propylene glycol monomethyl ether acetate in advance. 2,2′-azo dissolved in 22.4 parts by mass of 2-hydroxyethyl methacrylate, 2.8 parts by mass of cyclohexyl methacrylate, 2.8 parts by mass of methyl methacrylate and 20 parts by mass of propylene glycol monomethyl ether acetate in advance. A solution of 1.1 parts by mass of bisisobutyronitrile was added dropwise over 2 hours. Thereafter, radical polymerization was performed at 80 ° C. for 2 hours.
Next, 52.8 parts by mass of propylene glycol monomethyl ether acetate, 23.4 parts by mass of 2-methacryloyloxyethyl isocyanate, and 0.3 parts by mass of p-methoxyphenol were added to the obtained polymer solution, and oxygen bubbling was performed. After raising the temperature of the reaction solution to 100 ° C., the reaction was carried out for 1 hour.
Next, 2.2 parts by mass of succinic anhydride and 0.3 parts by mass of dimethylaminopyridine were added, and the reaction was performed for 4 hours. Thereafter, a propylene glycol monomethyl ether acetate solution having a solid concentration of 33% by mass was obtained by concentration under reduced pressure. The obtained polymer has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of 16,600, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) is 1.99. Met. This polymer is referred to as “polymer (A-6)”. Table 1 shows the physical properties and the like of the polymer (A-6).

Comparative Synthesis Example 1
According to Synthesis Example 9 and Synthesis Example 18 of JP 2010-44365 A, 2-hydroxyethyl methacrylate, benzyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, methacrylic acid, N-phenylmaleimide and succinic acid mono-2- A polymer solution (solid content concentration of about 33% by mass) obtained by adding 2-methacryloyloxyethyl isocyanate to an acryloxyethyl copolymer was obtained. This polymer is referred to as “polymer (A-7)”. The iodine value of the polymer (A-7) was 20 g / 100 g.

Comparative Synthesis Example 2
In a flask equipped with a condenser and a stirrer, 19.6 parts by mass of 2-hydroxyethyl methacrylate, 2.8 parts by mass of methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, trade name: PME-200), methacrylic acid 5.6 parts by mass, 0.3 part by mass of 2,2′-azobisisobutyronitrile and 0.8 part by mass of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were added to 56 parts of propylene glycol monomethyl ether acetate. And nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 6 hours to perform living radical polymerization.
Next, 48.4 parts by mass of propylene glycol monomethyl ether acetate, 23.4 parts by mass of 2-methacryloyloxyethyl isocyanate, and 0.3 parts by mass of p-methoxyphenol were added to the resulting polymer solution, and oxygen bubbling was performed. After raising the temperature of the reaction solution to 100 ° C., reaction was performed for 1 hour to obtain a propylene glycol monomethyl ether acetate solution having a solid content concentration of about 33% by mass. The obtained polymer had a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of 7,200, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 1.27. Met. This polymer is referred to as “polymer (A-8)”. A polymer (A-8) does not have a repeating unit represented by the said Formula (1).

Comparative Synthesis Example 3
A polymer was synthesized in the same manner as in Comparative Synthesis Example 2 except that ω-carboxypolycaprolactone mono (meth) acrylate was used instead of methacrylic acid in Comparative Synthesis Example 2. This polymer is referred to as “polymer (A-9)”. A polymer (A-9) does not have a repeating unit represented by the said Formula (1).

(A) Measurement of iodine value of polymer The iodine value of the polymer (A) obtained in each of the above synthesis examples was measured according to the procedure of JIS K 0070. Table 1 shows the measurement results.

In Table 1, the meanings of the abbreviations are as follows.
HEMA: 2-hydroxyethyl methacrylate EHMA: 2-ethylhexyl methacrylate PME-200: methoxypolyethylenegolicol monomethacrylate (manufactured by NOF Corporation, trade name: PME-200)
BzMA: benzyl methacrylate BMA: butyl methacrylate CHMA: cyclohexyl methacrylate MMA: methyl methacrylate PLACEL FM1D: methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester (manufactured by Daicel Chemical Industries, Ltd., trade name: PLACEL FM1D)
AIBN: 2,2′-azobisisobutyronitrile molecular weight control agent: pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester

Preparation of pigment dispersion Preparation Example 1
As a coloring agent, C.I. I. 9.2 parts by mass of CI Pigment Green 58 and C.I. I. 5.8 parts by mass of Pigment Yellow 150, 12.5 parts by mass (non-volatile component = 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersant, and 64.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent A pigment dispersion (C-1) was prepared by treating with a bead mill using 8 parts by weight of propylene glycol monomethyl ether.

Preparation Examples 2-9
Pigment dispersions (C-2) to (C-9) were prepared in the same manner as in Preparation Example 1, except that the type and amount of the colorant were changed as shown in Table 2.

In Table 2, the meanings of the abbreviations are as follows.
G58: C.I. I. Pigment Green 58
Y150: C.I. I. Pigment Yellow 150
Y138: C.I. I. Pigment Yellow 138
R177: C.I. I. Pigment Red 177
R254: C.I. I. Pigment Red 254
B15: 6: C.I. I. Pigment Blue 15: 6
V23: C.I. I. Pigment Violet 23

Lake pigment: triarylmethane lake pigment represented by the following formula (wherein x = 1 to 2)

Dye 1: Xanthene dye represented by the following formula

Dye 2: Xanthene dye represented by the following formula

PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether LPN21116: BYK-LPN21116 (manufactured by BYK Corporation (BYK))
LPN6919: BYK-LPN6919 (manufactured by BYK Corporation)

(E) Synthesis of binder resin Synthesis Example 7
In a flask equipped with a condenser and a stirrer, 30.0 parts by mass of N-phenylmaleimide, 20.0 parts by mass of butyl methacrylate, 15.0 parts by mass of 2-hydroxyethyl methacrylate, 20.0 parts by mass of styrene and 15.15 parts of methacrylic acid. 0 parts by mass is dissolved in 200 parts by mass of propylene glycol monomethyl ether acetate, and 3.0 parts by mass of 2,2′-azobisisobutyronitrile and 5.0 parts by mass of α-methylstyrene dimer are added, and then 15 parts. Purge with nitrogen for min. After the nitrogen purge, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling, and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (E-1). This binder resin (E-1) has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of 10,000, and a ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight. 2.5.

Example 1
Preparation of colored curable composition 100 parts by mass of pigment dispersion (C-1), 44.3 parts by mass of polymer (A-1) solution, (B) 2-benzyl-2-dimethylamino as a photopolymerization initiator 1.6 parts by mass of -1- (4-morpholinophenyl) -butan-1-one, (D) M-402 as a polymerizable compound (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Toagosei Co., Ltd.) 9.8 parts by mass), 0.1 part by mass of Megafac F-554 (manufactured by DIC) as a fluorosurfactant, and ethyl 3-ethoxypropionate as a solvent are mixed to obtain a solid content concentration A 20% by mass colored curable composition (S-1) was prepared.

Evaluation of contrast The colored curable composition (S-1) was applied on a glass substrate using a spin coater and then pre-baked on a hot plate at 100 ° C. for 2 minutes to obtain three coatings having different film thicknesses. A film was formed. Next, after these substrates are cooled to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and radiation including each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without passing through a photomask. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, post-baking was performed at 220 ° C. for 20 minutes to form a cured film on the substrate. Contrast was measured for the obtained three cured films using a contrast meter (contrast measuring device CT-1 manufactured by Aisaka Electric Co., Ltd.). From the measurement result, the contrast when the chromaticity coordinate value y = 0.570 was obtained. The evaluation results are shown in Table 3. The larger the contrast value in the same chromaticity coordinate value, the better.

Evaluation of sensitivity The colored curable composition (S-1) was applied on a glass substrate using a spin coater, and then pre-baked on a hot plate at 90 ° C. for 2 minutes. A coating film of 5 μm was formed. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing each wavelength of 365 nm, 405 nm, and 436 nm through a photomask having a slit of 30 μm in width using a high-pressure mercury lamp at an exposure of 500 J / m ² . Exposed in quantity. After that, after developing a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) on this substrate, 220 is further developed after shower development. Post-baking was performed at 30 ° C. for 30 minutes to form a stripe pattern on the substrate. At this time, the line width of the formed stripe pattern was measured. The evaluation results are shown in Table 3. A larger line width means higher sensitivity.

Evaluation of solvent resistance The colored curable composition (S-1) was applied on a glass substrate using a spin coater, and then prebaked for 2 minutes on a hot plate at 90 ° C., and the film thickness after prebaking was A coating film of 2.5 μm was formed. Subsequently, after cooling this board | substrate to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film with the exposure amount of 500 J / m < ² > through the photomask using the high pressure mercury lamp. After that, after developing a developer consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm), a shower development is performed, and then 180 °. Post-baking was performed at 30 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.
The substrate on which the dot pattern was formed was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, when the pixel pattern that caused cracks and separation from the substrate was not observed after immersion, “◯”, and when the pixel pattern that caused cracks or separation from the substrate was observed after immersion, “×” , Evaluated as. The evaluation results are shown in Table 3.

Evaluation of voltage holding ratio After a colored curable composition (S-1) was applied on a glass substrate on which ITO (indium-tin oxide alloy) electrodes were deposited in a predetermined shape using a spin coater, a clean oven at 90 ° C. The film was pre-baked for 10 minutes to form a film having a thickness of 1.8 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 500 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 180 ° C. for 30 minutes. The coating film was cured to form green pixels on the substrate.
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica. The applied voltage at this time is a square wave of 5.0 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). The evaluation results are shown in Table 3. It means that it is so favorable that the value of a voltage holding ratio is large.

Examples 2-9 and Comparative Examples 1-5
A colored curable composition was prepared and evaluated in the same manner as in Example 1 except that the type and amount of each component were changed as shown in Table 3 in Example 1. The evaluation results are shown in Table 3. Regarding the evaluation of contrast, in Examples 2 to 3 and Comparative Examples 2 to 3 which are green compositions, the contrast when the chromaticity coordinate value y = 0.570 is set to Example 4 which is a red composition and 9, the contrast when the chromaticity coordinate value x = 0.650, and the contrast when the chromaticity coordinate value y = 0.080 in Examples 5 to 8 and Comparative Example 1 which are blue compositions, respectively. It was measured.

In Table 3, each component is as follows.
D-1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name M-402, manufactured by Toagosei Co., Ltd.)
D-2: monoesterified product of dipentaerythritol pentaacrylate and succinic acid, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name TO-1382, manufactured by Toagosei Co., Ltd.)
B-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by BASF)
B-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, BASF Made)
B-3: 2,4-Diethylthioxanthone F-1: Fluorosurfactant (trade name MegaFuck F-554, manufactured by DIC)
F-2: C.I. I. Solvent Blue 45
EEP: ethyl 3-ethoxypropionate MBA: 3-methoxybutyl acetate

Example 10
100 parts by mass of the polymer (A-6) solution, (B) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name Irgacure 907, BASF Corporation) as a photopolymerization initiator 30 parts by mass, (D) 100 parts by mass of γ-glycidoxypropyltrimethoxy as a polymerizable compound, M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Toagosei Co., Ltd.) 10 parts by mass of silane, 0.05 parts by mass of surfactant FTX-218 (manufactured by Neos), and propylene glycol monomethyl ether acetate as a solvent are mixed to form a curable film for forming a protective film having a solid content of 30% by mass. A composition was prepared.
Next, using the green composition obtained in Example 1, the red composition obtained in Example 4, and the blue composition obtained in Example 7, red, green and blue stripes were formed on the glass substrate. A colored pattern was formed. The above-mentioned curable composition for forming a protective film was applied onto the obtained stripe-shaped colored pattern using a slit and spin coater. Pre-baking was performed for 3 minutes on a hot plate at 80 ° C. to form a coating film having a thickness of 1.2 μm. The obtained coating film was exposed to ultraviolet light having an intensity at 365 nm of 40 W / m ² for 2.5 seconds (1,000 J / m ² ) through a photomask. Then, after developing with a 0.05% by weight aqueous solution of tetramethylammonium hydride (TMAH), it was washed with pure water for 1 minute, and further heated in an oven at 220 ° C. for 30 minutes to form a protective film.

Example 11
100 parts by mass of the polymer (A-2) solution, 100 parts by mass of KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd.) as the polymerizable compound (D), and 1 , 9-nonanediacrylate, (B) 5 parts by mass of NCI-831 (manufactured by ADEKA) as a photopolymerization initiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 5 parts by mass of 1-one (trade name Irgacure 907, manufactured by BASF), and 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-bi 5 parts by mass of imidazole, 5 parts by mass of 4,4′-bis (diethylamino) benzophenone as a sensitizer, and γ-glycidoxypropyl as an adhesion promoter 5 parts by mass of limethoxysilane, 0.5 parts by mass of FTX-218 (manufactured by Neos Co., Ltd.) as a surfactant, 0.5 parts by mass of 4-methoxyphenol as a storage stabilizer, and propylene glycol as a solvent Monomethyl ether acetate was mixed to prepare a curable composition for forming a spacer having a solid content of 30% by mass.
Next, a transparent conductive film was formed by sputtering on the substrate on which the stripe-like colored pattern and protective film obtained in Example 10 were formed, and the above-mentioned radiation-sensitive resin composition for forming a spacer was formed using a slit and spin coater. Applied. Pre-baking was performed on a hot plate at 100 ° C. for 3 minutes to form a film having a thickness of 3.5 μm. The obtained coating film was exposed at an exposure amount of 500 J / m ² through a 10 μm square residual pattern photomask using a high-pressure mercury lamp. Then, after developing at 25 ° C. using a 0.05 wt% aqueous solution of potassium hydroxide, the substrate was washed with pure water for 1 minute and further post-baked in an oven at 180 ° C. for 30 minutes to form a spacer. Thus, a color filter was manufactured.
Next, a liquid crystal display element was manufactured using this color filter. The obtained color liquid crystal display element exhibited excellent display characteristics and reliability.

Claims (9)

(A) A curable composition comprising a polymer having a repeating unit represented by the following formula (1) and having an iodine value of 21 or more, and (B) a photopolymerization initiator.

[In Formula (1),
R ¹ represents a hydrogen atom or a methyl group,
X represents -COO-(* ¹ ) or -CONH-(* ¹ );
R ² and R ³ each independently represent a substituted or unsubstituted divalent hydrocarbon group;
R ⁴ represents a divalent organic group,
Z represents a single bond, -CO- or -COO-(* ² ),
m represents an integer of 1 to 30,
n shows the integer of 0-30.
However, “* ¹ ” indicates a bond that bonds with R ^2, and “* ² ” indicates a bond that bonds with R ³ . ]   The (A) polymer further has a maleimide substituted with a cyclic group at the N-position, a (meth) acrylic acid ester having an aliphatic hydrocarbon group having 4 or more carbon atoms, and a (meth) acrylic having an alicyclic hydrocarbon group. Having a repeating unit derived from at least one selected from the group consisting of acid esters, (meth) acrylic acid esters having an aromatic hydrocarbon group and (meth) acrylic acid esters having two or more alkyleneoxy groups, Item 2. The curable composition according to Item 1. The curable composition according to claim 1 or 2, wherein the (A) polymer has a group represented by the following formula (2).

[In Formula (2),
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ represents a (c + 1) -valent hydrocarbon group,
R ⁷ independently of one another represents an ethylene group or a propanediyl group,
c represents 1 or 2,
d shows the integer of 0-5. ]   The curable composition according to any one of claims 1 to 3, which is used for a color filter.   Furthermore, (C) The curable composition of any one of Claims 1-4 containing a coloring agent.   A color filter comprising a colored layer formed using the curable composition according to claim 5.   The color filter provided with the protective film layer formed using the curable composition of any one of Claims 1-4.   The color filter provided with the spacer formed using the curable composition of any one of Claims 1-4.   The display element which comprises the color filter of any one of Claims 6-8.