JP2018087910A - Coloring radiation-sensitive composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring radiation-sensitive composition that can form a colored layer having excellent brightness.SOLUTION: A coloring radiation-sensitive composition contains a colorant, a dispersant, a dispersion medium, a binder resin, a crosslinker and a photopolymerization initiator. The dispersant is a block copolymer that has an A block having a structural unit derived from an alicyclic alkyl group-containing vinyl monomer and an aliphatic alkyl group-containing vinyl monomer of 80 mass% or more in total, and a B block having a structural unit derived from an amino group-containing vinyl monomer, where the sum (δ+δ) of dipole-dipole force term and hydrogen bond force term of Hansen solubility parameter (HSP) of the B block is larger than the sum (δ+δ) of dipole-dipole force term and hydrogen bond force term of HSP of the A block. A distance (Ra) between HSP of the A block of the block copolymer and HSP of the binder resin is 1.0-4.0.SELECTED DRAWING: None

Description

  The present invention relates to a colored radiation-sensitive composition, and particularly relates to a technique for improving a dispersant.

  In the production of a color filter using a radiation-sensitive composition, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known as methods for applying a coloring material to a substrate. Among these, the pigment dispersion method is widely used from the viewpoint of spectral characteristics, durability, pattern shape, and accuracy. In the pigment dispersion method, for example, a coating film made of a colored radiation-sensitive composition in which a pigment, a dispersant, a dispersion medium (solvent), a binder resin, and the like are mixed is formed on a substrate, and is passed through a photomask having a desired pattern shape. Are irradiated with radiation (hereinafter referred to as “exposure”), and alkali development is performed.

  Such a colored radiation-sensitive composition is required to have excellent coating properties. Therefore, Patent Document 1 includes an A block having an acidic group in the side chain and a B block having an amino group in the side chain in order to improve coating properties, long-term storage stability, and alkali developability. It has been proposed to use a -B block copolymer as a pigment dispersant (see Patent Document 1 (Claim 1)).

JP 2013-203887 A

  However, although the colored radiation-sensitive composition using the dispersant of Patent Document 1 improves coating properties, long-term storage stability, and alkali developability, a specific solution for improving the luminance of the color filter is Not proposed. This invention is made | formed in view of the said situation, and makes it a main objective to provide the colored radiation-sensitive composition which can form the colored layer which has the outstanding brightness | luminance.

The colored radiation-sensitive composition of the present invention contains a colorant, a dispersant, a dispersion medium, a binder resin, a crosslinking agent and a photopolymerization initiator, and the dispersant is derived from a vinyl monomer having an alicyclic alkyl group. A block containing a total of 80% by mass or more of structural units derived from a vinyl monomer having a structural unit and an aliphatic alkyl group, and a B block containing a structural unit derived from a vinyl monomer having an amino group The sum (δ _pB + δ _hB ) of the dipole force term (δ _pB ) and the hydrogen bond force term (δ _hB ) of the Hansen solubility parameter in the B block is the dipole force of the Hansen solubility parameter in the A block. term ([delta] _pA) the sum of the hydrogen bonding term _{(δ hA) (δ pA +} δ hA) is greater than the block copolymer, the Hansen a blocks of the block copolymer Distance parameters and Hansen parameters of the binder resin (Ra) is characterized in that 1.0 to 4.0.

  The total content of the structural unit derived from the vinyl monomer having an aromatic group and the structural unit derived from a vinyl monomer having a crosslinkable functional group in the A block of the block copolymer is 2% by mass or less. preferable. The block copolymer is preferably an AB type block copolymer. The amine value of the block copolymer is preferably 10 mgKOH / g to 200 mgKOH / g.

  It is preferable that the content rate of the structural unit derived from the vinyl monomer which has the said alicyclic alkyl group is 20 mass%-70 mass% in 100 mass% of said A blocks. The content of the A block is preferably 50% by mass to 90% by mass in 100% by mass of the entire block copolymer. The molecular weight distribution (PDI) of the block copolymer is preferably 2.0 or less. The block copolymer is preferably polymerized by living radical polymerization.

  The colored radiation-sensitive composition can be used for a color filter. The present invention also includes a color filter provided with a colored layer formed using the colored radiation-sensitive composition.

  By using the colored radiation-sensitive composition of the present invention, a colored layer having excellent luminance can be formed. Therefore, the colored radiation-sensitive composition for color filters of the present invention includes color filters for color liquid crystal displays, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used suitably for production of various color filters.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

<Colored radiation-sensitive composition>
The colored radiation-sensitive composition of the present invention contains a colorant, a dispersant, a dispersion medium, a binder resin, a crosslinking agent, and a photopolymerization initiator. The dispersant has an amino group and an A block containing a total of 80% by mass or more of a structural unit derived from a vinyl monomer having an alicyclic alkyl group and a structural unit derived from a vinyl monomer having an aliphatic alkyl group. B block containing a structural unit derived from a vinyl monomer, and the sum of dipole force term (δ _pB ) and hydrogen bond force term (δ _hB ) of Hansen solubility parameter in the B block (δ _pB + δ _hB ) is a block copolymer in which the Hansen solubility parameter in the A block is larger than the sum of the dipole force term (δ _pA ) and the hydrogen bond force term (δ _hA ) (δ _pA + δ _hA ). In the colored radiation-sensitive composition, the distance (Ra) between the Hansen solubility parameter of the A block of the dispersant and the Hansen solubility parameter of the binder resin is 1.0 to 4.0.

  In the present invention, “A block” can be rephrased as “A segment”, and “B block” can be rephrased as “B segment”. The “vinyl monomer” is a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from a vinyl monomer” refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is a carbon-carbon single bond. “(Meth) acryl” means “at least one of acrylic and methacrylic”. “(Meth) acrylate” means “at least one of acrylate and methacrylate”. “(Meth) acryloyl” refers to “at least one of acryloyl and methacryloyl”.

  The Hansen solubility parameter (HSP) is a value used to predict the solubility of a substance calculated by the method proposed by Hansen et al.

Specifically, HSP is a value calculated by the following formula (formula (1)). In formula (1), δ represents the HSP of the polymer block. δ _d represents the London dispersion force term of the HSP. [delta] _p denotes the polar term of HSP. δ _h represents a hydrogen bond term of HSP.
δ ² = δ _d ² + δ _p ² + δ _h ² (1)

δ _d , δ _p, and δ _h are expressed by the following formula (formula (2) using each molar attractive force multiplier (F _di , F _pi , E _hi ) of the atomic group i constituting the structural unit of the polymer block and the molar volume V _i. ) To (4)).
δ _d = ΣF _di / ΣV _i (2)
δ _p = (ΣF _pi ² ) ^1/2 / ΣV _i (3)
δ _h = (ΣE _hi / ΣV _i ) ^1/2 (4)

Table 1 shows the molar attractive force multipliers (F _di , F _pi , E _hi ) and the molar volume V _i of typical atomic groups.

  For a polymer block having a plurality of structural units, the HSP of each homopolymer constituting each polymer unit is calculated, and the HSPs multiplied by the mole fractions of the respective structural units of these HSPs are added together. Calculated.

The three parameters δ _d , δ _p and δ _h can be regarded as coordinates in a three-dimensional space (Hansen space). When the HSPs of the two substances are placed in the Hansen space, the closer the distance between the two points is, the more easily they are dissolved or compatible with each other. The distance (Ra) between the HSP of the first polymer and the HSP of the second polymer can be calculated by the following formula (Formula (5)). In Equation (5), δ _d1 represents the London dispersion force term of the HSP of the first polymer. δ _p1 represents the HSP dipole force term of the first polymer. δ _h1 represents the hydrogen bond term of the HSP of the first polymer. δ _d2 represents the London dispersion force term of the second polymer HSP. δ _p2 represents the HSP dipole force term of the second polymer. δ _h2 represents the hydrogen bond term of the second polymer HSP.
(Ra) ² = 4 (δ _d1 −δ _d2 ) ² + (δ _p1 −δ _p2 ) ² + (δ _h1 −δ _h2 ) ² (5)

  Various components of the colored radiation-sensitive composition of the present invention (hereinafter sometimes simply referred to as “colored composition”) will be described below.

-1. Coloring agent
The coloring composition of the present invention contains a pigment as a colorant. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferable. Examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment. The structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The pigment contained in the coloring composition may be only one type or a plurality of types.

  Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38, 43; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like; C.I. I. Green pigments such as Pigment Green 7, 36, 58; I. And purple pigments such as Pigment Violet 23, 32, and 50. Among these pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 and the like are preferable.

  In the present invention, the dispersant is C.I. I. Pigment Yellow 138 is preferably used together with a colorant containing a quinophthalone yellow pigment, particularly C.I. I. It is preferably used with a colorant comprising Pigment Green 58 (brominated chlorinated zinc phthalocyanine).

  The upper limit of the content of the colorant in the coloring composition is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass in the total solid content of the coloring composition from the viewpoint of luminance. It is more preferable. Further, the lower limit of the content of the colorant in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass in the total solid content of the coloring composition. preferable. Here, solid content is components other than the dispersion medium mentioned later.

-2. Dispersant-
The dispersant used in the coloring composition of the present invention is a block copolymer having an A block and a B block. In the block copolymer used in the present invention, the sum (δ _pB + δ _hB ) of the HSP dipole force term (δ _pB ) and the hydrogen bond force term (δ _hB ) in the B block is HSP dipole in the A block. It is characterized by being larger than the sum (δ _pA + δ _hA ) of the inter-child force term (δ _pA ) and the hydrogen bond force term (δ _hA ) ((δ _pB + δ _hB )> (δ _pA + δ _hA )).

The sum (δ _pB + δ _hB) minus the sum (δ _pA + δ _hA) from _{((δ pB + δ hB)} - (δ pA + δ hA)) is preferably 0.4 or more, more preferably 0.5 Above, it is preferably 3.0 or less, more preferably 2.0 or less. Adsorption between the dispersant and the colorant is mainly caused by the acid-base action on the B block and the colorant, but may be affected by hydrogen bonds. Therefore, the sum of the dipole force term of the H block of the B block and the hydrogen bond force is larger than the sum of the dipole force term of the H block of the A block and the hydrogen bond force. It is considered to have a high affinity. The sum of the HSP dipole force term and the hydrogen bond force term can be adjusted by appropriately selecting the type and molar fraction of each structural unit of the A block and B block.

  The distance (Ra) between the H block of the A block and the HSP of the binder resin described later is 1.0 or more, preferably 1.5 or more, more preferably 2.0 or more, and 4.0 or less, preferably 3 .5 or less, more preferably 3.0 or less. The A block is considered to have a function of dissolving or compatibilizing the colorant in the dispersion medium and preventing aggregation of the colorant due to the steric repulsion and electrical properties of the A block. Furthermore, since the A block and the binder resin are considered to be compatible, controlling the distance to an appropriate distance prevents aggregation of the colorants and adsorption of the colorant to the binder resin, thereby improving luminance. I think that. The distance (Ra) can be adjusted by appropriately selecting the type and molar fraction of each structural unit of the A block and the binder resin.

  Hereinafter, various constituent components of the block copolymer used in the colored composition of the present invention will be described below.

(2.1 A block)
The A block contains a structural unit derived from a vinyl monomer having an alicyclic alkyl group and a structural unit derived from a vinyl monomer having an aliphatic alkyl group. The total content of the structural unit derived from the vinyl monomer having an alicyclic alkyl group and the structural unit derived from a vinyl monomer having an aliphatic alkyl group is 80% by mass or more in 100% by mass of the A block. 85 mass% or more is preferable.

  The content of the structural unit derived from the vinyl monomer having an alicyclic alkyl group is preferably 20% by mass or more, more preferably 25% by mass or more, and preferably 70% by mass or less in 100% by mass of the A block. More preferably, it is 65 mass% or less.

  As said alicyclic alkyl group, 3 or more are preferable, as for the number of carbon atoms which comprises it, More preferably, it is 6 or more, 20 or less is preferable, More preferably, it is 15 or less. The ring structure of the alicyclic alkyl group may be any of a single ring, a condensed ring, a bridged ring, and a spiro ring. The alicyclic alkyl group preferably has a 6-membered or higher ring structure. Specific examples of the alicyclic hydrocarbon group include a cyclohexyl group, a methylcyclohexyl group, a cyclododecyl group, a bornyl group, and an isobornyl group. Among these, an aliphatic alkyl group having a monocyclic structure such as a cyclohexyl group, a methylcyclohexyl group, or a cyclododecyl group is preferable from the viewpoint of luminance.

  The vinyl monomer having an alicyclic alkyl group is preferably a (meth) acrylic monomer having an alicyclic alkyl group, for example, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) Examples include acrylate, bornyl (meth) acrylate, and isobornyl (meth) acrylate.

  The content of the structural unit derived from the vinyl monomer having an aliphatic alkyl group is preferably 10% by mass or more, more preferably 20% by mass, and further preferably 30% by mass or more in 100% by mass of the A block. 80 mass% or less is preferable, More preferably, it is 70 mass% or less.

  The aliphatic alkyl group may be linear or branched, and the number of carbon atoms constituting the aliphatic alkyl group is preferably 1 or more, preferably 20 or less, more preferably 10 or less. Specific examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 2-ethylhexyl group.

  The vinyl monomer having an aliphatic alkyl group is preferably a (meth) acrylic monomer having an aliphatic alkyl group, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The A block preferably has a structural unit derived from a vinyl monomer having an acidic group from the viewpoint of alkali developability. A block copolymer in which the A block has an acidic group is useful for a color resist. Examples of the acidic group include a carboxy group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—OPO ₃ H ₂ ), a phosphonic acid group (—PO ₃ H ₂ ), and a phosphinic acid group (— PO ₂ H ₂ ). There may be only one type of structural unit derived from a vinyl monomer having these acidic groups, or two or more types of structural units.

  The vinyl monomer having an acidic group is preferably at least one selected from a vinyl monomer having a carboxy group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group. Among these, at least one selected from a (meth) acrylic monomer having a carboxy group, a (meth) acrylic monomer having a sulfonic acid group, or a (meth) acrylic monomer having a phosphoric acid group is preferable.

  Examples of the vinyl monomer having a carboxy group include (meth) acrylic acid; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, hydroxy groups such as 2- (meth) acryloyloxyethyl phthalate A monomer obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride with a vinyl monomer (preferably hydroxyalkyl (meth) acrylate) having a carboxylic acid; crotonic acid, maleic acid, itaconic acid and the like.

  Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, ethyl disulfonate (meth) acrylate, methyl propyl sulfonic acid (meth) acrylamide, and ethyl sulfonate (meth) acrylamide.

  Examples of the vinyl monomer having a phosphoric acid group include 2- (phosphonooxy) ethyl (meth) acrylate.

  The content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and 20% by mass in 100% by mass of the A block. % Or less is preferable, more preferably 18% by mass or less, and still more preferably 16% by mass or less. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with an alkali is increased in alkali development, and if it is 20% by mass or less, the hydrophilicity is high. However, it is possible to prevent the formed pixels from becoming messy.

  The A block is a structural unit other than a structural unit derived from a vinyl monomer having an alicyclic alkyl group, a structural unit derived from a vinyl monomer having an aliphatic alkyl group, and a structural unit derived from a vinyl monomer having an acidic group. You may have a unit.

  Other structural units that can be included in the A block are copolymerized with a vinyl monomer having an alicyclic alkyl group, a vinyl monomer having an aliphatic alkyl group, a vinyl monomer having an acidic group, and a vinyl monomer that forms a B block described later. There is no particular limitation as long as it is formed of a vinyl monomer that can be used. Vinyl monomers that can form other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, vinyl monomers containing heterocycles, vinyl amides, vinyl carboxylates, dienes, (meth) acrylic monomers, and the like. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, 1-decene and the like.
Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-captolactam and the like.
Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  As (meth) acrylic monomers, (meth) acrylamide; (meth) acrylate having a polyethylene glycol structural unit; (meth) acrylate having a hydroxy group; caprolactone adduct of (meth) acrylate having a hydroxy group; having an alkoxy group (Meth) acrylate etc. are mentioned.

  Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.

  Examples of the (meth) acrylate having a polyethylene glycol structural unit include polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n = 1-5) ethyl ether (meth) acrylate, polyethylene glycol (n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1-5) ethyl ether (meth) acrylate, polypropylene glycol (n = 1-1) 5) Propyl ether (meth) acrylate and the like.

  As (meth) acrylate having a hydroxy group, hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (Meth) acrylate etc. are mentioned.

  As the caprolactone adduct of (meth) acrylate having a hydroxy group, 1 mol of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2 mol of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) Examples include acrylate caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, and the like.

  Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.

  The vinyl monomer that can form another structural unit that can be included in the A block is preferably a (meth) acrylic monomer, and has a (meth) acrylate having a polyethylene glycol structural unit, a (meth) acrylate having a hydroxy group, and a hydroxy group. More preferably, it is at least one selected from the group consisting of caprolactone adducts of (meth) acrylates. The vinyl monomer that can be used in the A block can be used alone or in combination of two or more.

  The total content of the structural unit derived from the vinyl monomer having an aromatic group in the A block and the structural unit derived from the vinyl monomer having a crosslinkable functional group is preferably 2% by mass or less, more preferably 1% by mass or less. More preferably, it is 0.1% by mass or less, and most preferably 0% by mass. The A block preferably does not substantially contain a structural unit derived from a vinyl monomer having an aromatic group and a structural unit derived from a vinyl monomer having a crosslinkable functional group. Here, “substantially does not contain” means that the content is 0.1% by mass or less in 100% by mass of the A block. By having an aromatic group, it tends to be colored yellow and the brightness may be lowered. By having a crosslinkable functional group, there is a possibility that the distance from the binder resin cannot be controlled to an appropriate distance by reacting with the binder resin.

  Examples of the aromatic group include a phenyl group, a naphthyl group, an anthryl group, and a benzyl group. Examples of the crosslinkable functional group include oxygen-containing saturated heterocyclic groups such as oxiranyl group, oxetanyl group, tetrahydrofuranyl group, and tetrahydropyranyl group, ethylenically unsaturated group, epithio group, and (dithio) carbonate group. .

  The content of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably 0% by mass. %. When a large amount of amino groups are present in the A block, when used as a dispersant, the colorant is adsorbed on both the A block and the B block, and the dispersion performance of the colorant decreases. Moreover, it is preferable that A block does not contain the structural unit derived from the vinyl monomer which has an amino group substantially.

  When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any form such as random copolymerization and block copolymerization in the A block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

(2.2 B block)
The B block is a polymer block containing a structural unit derived from a vinyl monomer having an amino group. Since the B block has an amino group, it has a high affinity with the colorant and is considered to exhibit a function of adsorbing to the colorant treated with the colorant or the acid group-containing dye derivative.

  As the vinyl monomer having an amino group, conventionally known ones can be exemplified, and (meth) acrylates having an amino group are preferred. As the form of the amino group used, primary, secondary, tertiary and quaternary ammonium salts are used.

  Specific examples of the (meth) acrylate having a primary amino group include 7-amino-3,7-dimethyloctyl (meth) acrylate; the (meth) acrylate having a secondary amino group includes isopropylaminoethyl ( (Meth) acrylate, t-butylaminoethyl (meth) acrylate; (meth) acrylate having a tertiary amino group includes 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dibutyl Aminoethyl (meth) acrylate, 2-dicyclohexylaminoethyl (meth) acrylate; (meth) acrylate having a quaternary ammonium salt includes methyl chloride salt of 2-dimethylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (Meta) Acry And benzyl chloride salts of over bets.

  Only the vinyl monomer which has an amino group may be sufficient as B block, and the other structural unit may be contained. From the viewpoint of maintaining affinity with the colorant, the total content of vinyl monomers having an amino group in the B block is preferably 80% by mass or more, more preferably 90% by mass or more in 100% by mass of the B block. More preferably, it is 93 mass% or more.

  Specific examples of the vinyl monomer capable of forming another structural unit of the B block include the same ones as exemplified as specific examples of the vinyl monomer capable of forming the other structural unit of the A block. Moreover, it is preferable that B block does not have substantially the structural unit derived from the vinyl monomer which has the acidic group which A block has. The content of the structural unit derived from the vinyl monomer having an acidic group in the B block is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably 0% by mass. %.

  When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any form such as random copolymerization and block copolymerization in the B block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(2.3 Block copolymer)
The structure of the block copolymer used in the present invention is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. when expressed as, _{(a-B) m} type, _(a-B) m -A type, the group consisting of _(B-a) m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferably a copolymer having at least one structure selected from Among these, a diblock copolymer represented by AB is preferable from the viewpoint of handleability during processing and physical properties of the composition. A structural unit derived from a vinyl monomer having an aliphatic alkyl group and a structural unit derived from a vinyl monomer having an alicyclic alkyl group in the A block by constituting a diblock copolymer represented by AB And the structural unit derived from the vinyl monomer having an amino group in the B block is localized, and it is thought that the colorant, the dispersion medium, and the binder resin (alkali-soluble resin) can be effectively operated suitably. It is done.

  The content of the A block is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 90% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less. The content of the B block is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less. By adjusting the content ratios of the A block and the B block within the above range, the dispersion performance when used as a dispersant becomes better.

  The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as “GPC”) method. The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 6,000 or more, preferably 15,000 or less, more preferably 12, 000 or less, more preferably 10,000 or less. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

  The molecular weight distribution (PDI) of the block copolymer is preferably 2.0 or less, and more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the more uniform the copolymer. When the value is 1.0, the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the block copolymer of the present invention exceeds 2.0, one having a low molecular weight or one having a high molecular weight is included.

  The amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of adsorbability to the colorant and pigment dispersibility. g or less is preferable, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.

  The acid value of the block copolymer is preferably 10 mgKOH / g or more, and preferably 60 mgKOH / g or less. By setting the acid value within this range, the binder resin (alkali-soluble resin) can be suitably acted on without impairing the affinity with the colorant of the block copolymer.

  In the coloring composition, the content of the dispersant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and 200 parts by mass or less with respect to 100 parts by mass of the colorant. Preferably, it is 100 parts by mass or less, more preferably 50 parts by mass or less.

(2.3 Production method of block copolymer)
The block copolymer used in the present invention is produced by a method of first producing an A block by polymerizing a vinyl monomer, and then polymerizing a B block monomer into the A block; A method of polymerizing A block monomers into blocks; a method of separately producing A blocks and B blocks and then coupling the A blocks and B blocks;

  The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer used in the present invention is preferably a polymer obtained by polymerization using living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the termination of the growth end occurs due to the termination reaction and the chain transfer reaction, and the polymer tends to be a mixture of polymers having various molecular weights and heterogeneous compositions. While the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, the termination reaction and chain transfer are unlikely to occur, and the growth end grows without being deactivated. This is preferable in that it is easy to produce a polymer having a uniform composition.

  In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); There is a method to be used (TERP method). Since the ATRP method uses an amine-based complex, it may not be used unless the acidic group of the vinyl monomer having an acidic group is protected. In the RAFT method, when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be a problem such as sulfur odor or coloring. Among these methods, the TERP method is preferably used from the viewpoints of diversity of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.

  The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) A method in which a vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (1).
(B) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (1) and an azo polymerization initiator.
(C) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (1) and an organic ditellurium compound represented by the general formula (2).
(D) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (1), an azo polymerization initiator, and an organic ditellurium compound represented by the general formula (2).

〔一般式（１）において、Ｒ¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素数１〜８のアルキル基を示す。Ｒ⁴は、炭素数１〜８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。〕

In [general formula (1), R ¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group. ]

〔一般式（２）において、Ｒ¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。〕

In [general formula (2), R ¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴ is a C 1-8 alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or A propargyl group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as an octyl group, a cyclic alkyl group such as a cyclohexyl group, and the like. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ⁴¹ (R ⁴¹ has 1 carbon atom). -8 alkyl groups, aryl groups, C1-8 alkoxy groups or aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like. These substituents are preferably substituted by 1 or 2 substituents.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tet- A butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include —CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
As the oxycarbonyl group, a group represented by —COOR ⁴³ (R ⁴³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable. For example, a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group. Group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
As the allyl group, —CR ⁴⁴¹ R ⁴⁴² —CR ⁴⁴³ ═CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are Are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure).
As the propargyl group, —CR ⁴⁵¹ R ⁴⁵² —C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁵³ is a hydrogen atom and an alkyl group having 1 to 8 carbon atoms) , Aryl group or silyl group).

  Specific examples of the organic tellurium compound represented by the general formula (1) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2- Methyl-2-n-butylterranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl ) -2-methyl-2-methylterranyl-propinate, etc., organics described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 Illustrate all tellurium compounds It is possible.

  Specific examples of the organic ditellurium compound represented by the general formula (2) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, Di-n-butylditelluride, di-s-butylditelluride, di-t-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, Examples thereof include bis- (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride.

  The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile) (V-70), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propyl Pan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Examples include azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), and the like.

In the polymerization methods (a), (b), (c) and (d), the amount of vinyl monomer used may be appropriately adjusted depending on the physical properties of the target copolymer. The vinyl monomer is preferably 5 to 10,000 mol per mol of the organic tellurium compound.
In the polymerization method (b), when the organic tellurium compound of the general formula (1) and the azo polymerization initiator are used in combination, the amount of the azo polymerization initiator used is usually an organic compound of the general formula (1). The azo polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol of the tellurium compound.
In the polymerization method of (c), when the organic tellurium compound of the general formula (1) and the organic ditellurium compound of the general formula (2) are used in combination, The organic ditellurium compound of the general formula (2) is preferably 0.01 mol to 100 mol per 1 mol of the organic tellurium compound of the general formula (1).
In the polymerization method (d), when the organic tellurium compound of the general formula (1), the organic ditellurium compound of the general formula (2) and the azo polymerization initiator are used in combination, Usually, the azo polymerization initiator is preferably 0.01 to 100 mol with respect to 1 mol in total of the organic tellurium compound of the general formula (1) and the organic ditellurium compound of the general formula (2).

  The polymerization reaction can be carried out without a solvent, but it may be carried out using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropol, propylene glycol monomethyl. Examples include ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, and diacetone alcohol.

  The amount of the solvent used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less with respect to 1 g of vinyl monomer. More preferably, it is 10 ml or less, More preferably, it is 1 ml or less.

  The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually stirred at 0 to 150 ° C. for 1 minute to 100 hours. The TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time.

After completion of the polymerization reaction, the desired copolymer can be separated from the obtained reaction mixture by a usual separation and purification means.
The growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ (wherein R ¹ is the same as above), and it is deactivated by the operation in the air after the completion of the polymerization reaction. , Tellurium atoms may remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or inferior in thermal stability, it is preferable to remove the tellurium atom.

  As a method for removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbent, etc .; Method of adsorbing metal: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose tellurium atoms at the end of the copolymer. A liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less can be used. These methods can also be used in combination.

-3. Dispersion medium
The colored composition of the present invention is suitably used as a dispersion medium as long as it disperses or dissolves other components constituting the colored composition and does not react with these components and has moderate volatility. You can select and use. For example, conventionally known organic solvents can be used, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol. Mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, 3-methyl- -Glycol monoalkyl ethers such as methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether Glycol dialkyl ethers such as diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether Teracetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono -Glycol alkyl ether acetates such as n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol Glycol diacetates such as diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether , Ethers such as butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, Ketones such as methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone; Monovalent or polyhydric alcohols such as diol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, and benzyl alcohol Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, acetic acid Mill, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3 -Chain or cyclic esters such as ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone; 3-methoxypropion Acids, alkoxycarboxylic acids such as 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile, etc. Nitriles and the like. The organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of the colorant and the like, solubility of the dispersant, coatability of the colored composition, and the like. The solvent contained in the coloring composition may be only one type or a plurality of types.

  Content of the dispersion medium in a coloring composition is not specifically limited, It can adjust suitably. The upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the colored composition is usually 70% by mass and preferably 75% by mass in consideration of the viscosity suitable for application of the colored composition. The said dispersion medium can be used as a solvent for melt | dissolving and removing the precipitate formed from a coloring composition.

-4. Binder resin
The colored composition of the present invention contains a binder resin (excluding the dispersant). Thereby, the alkali developability of a coloring composition and the binding property to a board | substrate can be improved. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group.

  The binder resin is preferably a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from a (meth) acrylic acid ester. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate.

  In the binder resin, the total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from the (meth) acrylic acid ester is preferably 50% by mass or more, more preferably 60% by mass or more, Preferably it is 70 mass% or more. Further, the binder resin preferably has a structure content derived from a carboxy group-containing vinyl monomer of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass or less. Is more preferable, and 70% by mass or less is more preferable.

  Among these, a random copolymer of a carboxy group-containing vinyl monomer and a (meth) acrylic acid ester is preferable. Specific examples of such a copolymer include a random copolymer of (meth) acrylic acid and butyl (meth) acrylate, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate, Examples include random copolymers of (meth) acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the colorant, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

  In the copolymer of a carboxy group-containing vinyl monomer and a (meth) acrylic acid ester, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to 70% in all monomer components. It is preferable that it is mass%, and it is more preferable that it is 20 mass%-70 mass%.

  The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the coating film has an alkaline aqueous solution. The developability becomes even better.

  The acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and still more preferably 90 mgKOH / g to 150 mgKOH / g. When the acid value of the binder resin is 20 mgKOH or more / g, the alkali developability when the colored composition is used as a colored layer is further improved, and when it is 170 mgKOH / g or less, the heat resistance is improved.

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the pigment dispersion composition, the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, and more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the colorant. More preferably, it is 80 parts by mass.

-5. Cross-linking agent
The coloring composition of the present invention contains a crosslinking agent. In the present invention, the crosslinking agent 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 crosslinking agent 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 caprolactone-modified polyfunctional ( (Meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group and polyfunctional isocyanate, (meth) acrylate having hydroxy group And a polyfunctional (meth) acrylate having a carboxy group obtained by reacting an acid anhydride with the acid anhydride.

  Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Of the aliphatic polyhydroxy compound. 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 dipenta. Examples include erythritol hexa (meth) acrylate and glycerol dimethacrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid And tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic dianhydride.

  In the colored composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the crosslinking agent is too large, the alkali developability of the colored composition of the present invention is lowered, and background stains, film residues, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer. .

-6. Photopolymerization initiator
The coloring composition of the present invention contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beam, and X-ray.

  Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones. Compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

  In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure. On the other hand, if the content is too large, the formed colored layer tends to easily fall off from the substrate during development. .

-7. Other compounding agents
The pigment dispersion composition of the present invention further contains an acidic dye derivative having an acidic group so as to be ion-bonded and adsorbed with the amino group in the block copolymer characterizing the present invention used for the dispersant. Is preferred. This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, the same or similar skeleton as the colorant constituting the coloring composition and the same or similar skeleton as the compound used as the raw material of the pigment are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. In addition, a sulfonic acid group is preferable from the viewpoint of synthesis and the strength of acidity. The acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond.

<Method for producing colored radiation-sensitive composition and color filter>
The coloring composition contains a coloring agent, a dispersing agent, a dispersing medium, a binder resin, a crosslinking agent, a photopolymerization initiator, and other additives as necessary. For example, a paint shaker, a bead mill, a ball mill, a dissolver, a kneader It is manufactured by mixing using a mixing and dispersing machine such as. The coloring composition is preferably filtered after mixing. Examples of other additives include pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, and fungicides. By using the colored radiation-sensitive composition of the present invention, a colored layer having excellent luminance can be formed. Therefore, the colored radiation-sensitive composition of the present invention can be suitably used for forming a color filter.

  The color filter of this invention is provided with the colored layer formed using the said coloring composition.

  Examples of the method for producing the color filter include the following methods. First, for example, after applying the coloring composition of the present invention in which a red pigment is dispersed on a 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 red pixel patterns are arranged in a predetermined arrangement.

  Next, using each colored composition of green or blue, and applying each colored composition, pre-baking, exposing, developing and post-baking in the same manner as described above, the green pixel array and the blue pixel array are formed on the same substrate. Sequentially formed on top. Thereby, a color filter in which pixel arrays 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.

  When applying the coloring 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, a bar coating method, etc. can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter.

  Since the color filter of the present invention has extremely high luminance, it can be suitably used for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, and the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these specific examples. Various physical properties were measured with the following equipment. The abbreviations have the following meanings.
BTEE: ethyl-2-methyl-2-n-butylteranyl-propionate DBDT: dibutylditelluride AIBN: 2,2′-azobis (isobutyronitrile)
MMA: methyl methacrylate BMA: butyl methacrylate EHMA: 2-ethylhexyl methacrylate CHMA: cyclohexyl methacrylate BzMA: benzyl methacrylate HPMA: methacrylate 2-hydroxypropyl THFMA: methacrylate tetrahydrofurfuryl MAA: methacrylate DMAEMA: methacrylic acid Dimethylaminoethyl PMA: propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

(Polymerization rate)
¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) measuring apparatus (manufactured by Bruker, model: AVANCE500 (frequency: 500 MHz)). About the obtained NMR spectrum, the integration ratio of the monomer-derived vinyl group and the peak of the polymer-derived ester side chain was determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It calculated | required by the gel permeation chromatography (GPC) using the high performance liquid chromatograph (The Tosoh company make, model: HLC-8320GPC). Two columns, TSKgel SuperAW3000 (Φ4.6 mm × 150 mm) (manufactured by Tosoh Corporation) and TSKgel SuperAW4000 (Φ4.6 mm × 150 mm), 10 mmol / L lithium bromide / dimethylformamide solution for mobile phase, differential refractive index detection for detector A vessel was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 1 mg / mL, a sample injection amount of 10 μL, and a flow rate of 0.6 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (manufactured by Tosoh Corporation, TSK Standard) as a standard substance, and a weight average molecular weight (Mw) and a number average molecular weight (Mn) were measured. Molecular weight distribution (PDI) was calculated from these measured values.

(Amine number)
The amine value is represented by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
B = 56.11 × Vs × 0.1 × f / w
B: Amine value (mgKOH / g)
Vs: Amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)
f: 0.1 mol / L hydrochloric acid / 2-propanol solution titer w: mass (g) of measurement sample (in solid content)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.5 mol / L potassium hydroxide / ethanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The acid value was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
A = 56.11 × Vs × 0.5 × f / w
A: Acid value (mgKOH / g)
Vs: 0.5 mol / L potassium hydroxide / ethanol solution used for titration (mL)
f: Potency of 0.5 mol / L potassium hydroxide / ethanol solution w: Measurement sample weight (g) (solid content conversion)

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), a cone rotor (1 ° 34 ′ × R24) was used, and the viscosity was measured at 25 ° C. and a rotor rotational speed of 60 rpm. Those having an initial viscosity of less than 20 cps were rated as “◯”, and those having an initial viscosity of 20 cps or more as “x”.

(Luminance)
Measurement was performed using a CF contrast measuring device (trade name: CM-50) manufactured by Otsuka Electronics. About the obtained brightness | luminance, the brightness | luminance of each sample was indexed by setting the brightness | luminance of the comparative example 1 to 100, and the following reference | standard evaluated.
“◎”: 100.2 or more “◯”: 100.1 or more, less than 100.2 “Δ”: 99.9 or more, less than 100.1 “X”: less than 99.9

<Manufacture of copolymer>
(Block copolymer No. 1)
A flask equipped with an argon gas introduction tube and a stirrer was charged with MMA 9.45 g, MAA 1.65 g, CHMA 3.63 g, AIBN 0.148 g, PMA 14.73 g, and after substitution with argon, BTEE 0.90 g, DBDT 0.55 g was added and reacted at 60 ° C. for 16 hours. The polymerization rate was 99%.

  A mixed solution of DMAEMA 3.87 g, AIBN 0.0493 g, and PMA 3.17 g previously substituted with argon was added to the obtained solution, and the mixture was reacted at 60 ° C. for 20 hours. The polymerization rate was 100%.

  After completion of the reaction, the reaction solution was poured into n-heptane which was being stirred. The precipitated polymer was suction filtered and dried to obtain a block copolymer No. 1 was obtained. Block copolymer No. 1 had an Mw of 6,530, a PDI of 1.60, an amine value of 75 mgKOH / g, and an acid value of 59 mgKOH / g.

(Block copolymer Nos. 2 to 8)
Block copolymer No. The block copolymer No. 1 was prepared in the same manner as in the production method of No. 1. 2-8 were produced. Table 2 shows the raw material monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates used. Table 3 shows the composition, Mw, PDI, acid value, and amine value of each block copolymer.

<Manufacture of coloring composition and color filter>
Example 1
C. I. Pigment Green 58 (1.33 parts by mass), C.I. I. Pigment Yellow 138, 0.57 parts by mass, a block copolymer No. 0.76 parts by mass of 1 and 0.76 of binder resin (random copolymer of BzMA and MAA (mass ratio 80:20), Mw = 9,800, PDI = 1.93, acid value 127 mgKOH / g) A SUS container was filled with 1.90 parts by mass of MP, 1.90 parts by mass of MP, 13.68 parts by mass of PMA, and 114 g of 0.3 mm zirconia beads, and dispersed in a vertical bead mill for 3 hours to prepare a pigment dispersion. did.

  70.0 parts by mass of the pigment dispersion obtained above, binder resin (random copolymer of BzMA and MAA (mass ratio 80:20), Mw = 9,800, PDI = 1.93, acid value 127 mgKOH / 2.2 parts by weight of g), 5.0 parts by weight of dipentaerythritol hexaacrylate, 1.0 part by weight of 1-hydroxycyclohexyl phenyl ketone, and 21.8 parts by weight of PMA were mixed to obtain a colored composition. The viscosity of the obtained colored composition was measured and evaluated as “◯”.

The obtained colored composition was applied onto a glass substrate using a spin coater and dried at 60 ° C. for 10 minutes to form a green colored layer having a thickness of 1.0 μm. This colored layer was irradiated with 60 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp and post-baked at 200 ° C. to produce a color filter substrate. The luminance evaluation of the obtained color filter substrate was “◯”.

(Examples 2-3, Comparative Examples 1-5)
The same procedure as in Example 1 was followed, except that the dispersant was changed to the block copolymers listed in Table 4. Table 4 shows the evaluation results of the viscosity of the colored composition obtained and the luminance of the color filter substrate.

In Examples 1 to 3, the block copolymer used as a dispersant is derived from a vinyl monomer having a structural unit derived from a vinyl monomer having an appropriate amount of an alicyclic alkyl group and an aliphatic alkyl group. The distance (Ra) from the binder resin is appropriate, and the sum (δ _pB + δ _hB ) is larger than the sum (δ _pA + δ _hA ). In these Examples 1 to 3, the viscosity of the colored composition is low and the luminance of the color filter is excellent.

  In Comparative Examples 1 and 3, the brightness of the color filter is poor because the distance from the binder resin is not appropriate. In Comparative Example 2, although the distance from the binder resin is appropriate, the luminance of the color filter is poor because the A block has many aromatic groups. In Comparative Example 5, although the distance from the binder resin is appropriate, the luminance of the color filter is poor because the A block has many crosslinkable groups.

In Comparative Example 4, since the sum (δ _pB + δ _hB ) is smaller than the sum (δ _pA + δ _hA ), the viscosity of the coloring composition is high. This is because if the sum of the dipole force term and the hydrogen bond force term of the Hansen solubility parameter of the B block is smaller than the sum of the dipole force term and the hydrogen bond force term of the Hansen solubility parameter of the A block, A This is because the block adversely affects the interaction between the B block and the pigment.

Claims (10)

A colored radiation-sensitive composition containing a colorant, a dispersant, a dispersion medium, a binder resin, a crosslinking agent and a photopolymerization initiator,
The dispersant has an amino group having an A group containing 80 mass% or more in total of a structural unit derived from a vinyl monomer having an alicyclic alkyl group and a structural unit derived from a vinyl monomer having an aliphatic alkyl group. B block containing a structural unit derived from a vinyl monomer, and the sum of dipole force term (δ _pB ) and hydrogen bond force term (δ _hB ) of Hansen solubility parameter in the B block (δ _pB + δ _hB ) is a block copolymer in which the Hansen solubility parameter in the A block is greater than the sum of the dipole force term (δ _pA ) and the hydrogen bond force term (δ _hA ) (δ _pA + δ _hA ),
A colored radiation-sensitive composition, wherein the distance (Ra) between the Hansen solubility parameter of the A block of the block copolymer and the Hansen solubility parameter of the binder resin is 1.0 to 4.0.   The total content of structural units derived from a vinyl monomer having an aromatic group and a vinyl monomer having a crosslinkable functional group in the A block of the block copolymer is 2% by mass or less. The colored radiation-sensitive composition according to 1.   The colored radiation-sensitive composition according to claim 1 or 2, wherein the block copolymer is an AB type block copolymer.   The colored radiation-sensitive composition according to any one of claims 1 to 3, wherein the block copolymer has an amine value of 10 mgKOH / g to 200 mgKOH / g.   The content rate of the structural unit derived from the vinyl monomer which has the said alicyclic alkyl group is 20 mass%-70 mass% in the said A block 100 mass%, As described in any one of Claims 1-4. Colored radiation-sensitive composition.   The colored radiation-sensitive composition according to any one of claims 1 to 5, wherein the content of the A block is 50% by mass to 90% by mass in 100% by mass of the entire block copolymer.   The colored radiation-sensitive composition according to claim 1, wherein the block copolymer has a molecular weight distribution (PDI) of 2.0 or less.   The colored radiation-sensitive composition according to any one of claims 1 to 7, wherein the block copolymer is polymerized by living radical polymerization.   The colored radiation-sensitive composition according to any one of claims 1 to 8, which is used for a color filter.   The color filter provided with the colored layer formed using the colored radiation-sensitive composition as described in any one of Claims 1-8.