JP5157522B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display element. The present invention relates to a radiation-sensitive composition used for forming a colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display element including the color filter.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and 2) are known.

  In recent years, a brighter screen with better color reproducibility has been desired for monitors and televisions, and the brightness of the backlight is improved and the content of colorants, particularly pigments, contained in the radiation-sensitive composition is increased. The need has arisen (Non-Patent Document 1). Furthermore, liquid crystal monitor screens and liquid crystal television screens are becoming higher definition, and the number of pixels per unit area on the screen tends to increase. Therefore, a radiation-sensitive composition that can form a finer pattern for both black matrix formation and pixel formation has been required.

In response to this requirement, for example, Patent Document 3 discloses that a pattern having high resolution can be formed by incorporating an alkali-soluble resin having a specific structure in the radiation-sensitive composition. However, in the so-called negative radiation-sensitive composition, the line width of the pattern to be formed becomes thicker than the design dimension of the photomask due to the influence of diffracted light during proximity exposure. There was a problem that a difficult pattern could not be obtained.
On the other hand, as a technique for eliminating the pattern line width widening of the negative radiation sensitive composition, for example, reducing the exposure amount, strengthening the development conditions, of the radiation sensitive polymerization initiator in the radiation sensitive composition Techniques such as reducing the content or adding a polymerization inhibitor into the radiation-sensitive composition are known. However, any method tends to cause pattern chipping, peeling, or undercutting during development, and is particularly applicable when the content of the colorant contained in the radiation-sensitive composition becomes high. It was not possible.
JP-A-2-144502 JP-A-3-53201 JP 2004-205862 A Published by Kei Murakami, “New Development of LCD Front and Backlight”, 1st Edition, Toray Research Center, Inc., September 2002

An object of the present invention is to provide a pixel and a black matrix having excellent pattern shape, excellent adhesion to a substrate, even when the content of the colorant contained in the radiation-sensitive composition is high. An object of the present invention is to provide a radiation-sensitive composition for forming a colored layer that can be formed and does not increase the pattern line width even in proximity exposure.
A further object of the present invention is to provide a color filter comprising a colored layer formed from the radiation-sensitive composition for forming the colored layer, and a color liquid crystal display device comprising the color filter.

  In view of such circumstances, the present inventors have conducted intensive research and have solved the above problems by including a phenolic compound having a specific structure in the radiation-sensitive composition for forming a colored layer. As a result, the present invention has been completed.

  That is, the present invention includes (A) a colorant, (B) an alkali-soluble resin, (C) a monomer having two or more radically polymerizable unsaturated bonds, (D) a radiation-sensitive radical generator, and ( E) The following formulas (1) to (5)

[In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a phenyl group, a naphthyl group, or a — (CH ₂ ) x -COOZ group, R ¹ may be the same or different from each other, Z represents an alkoxyalkyl group, a cyclic ether group, a vinyloxyalkyl group or a t-alkoxycarbonylalkyl group, and a plurality of Z may be the same or different from each other , X is an integer of 0 to 4, and A is a single bond, -S- group, -O- group, -CO- group, -COO- group, -SO- group, -SO ₂ -group, -C ( R ² ) (R ³ ) -group or

A group (wherein k is an integer of 0 to 4), R ² and R ³ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or an acyl having 6 or less carbon atoms. A group, a phenyl group, a naphthyl group or a — (CH ₂ ) x —COOZ group, m, n, p and q are integers of 0 or more and satisfy the relationship of m + n ≦ 5, p + q ≦ 5 and n + q ≧ 1. ]

In [formula (2), R ¹ represents the same group as R ¹ of formula (1), R ⁴ represents the same group as R ² of formula (1), m, n, p, q, r and s Is an integer of 0 or more and satisfies the relationship of m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, and n + q + s ≧ 1. ]

In [formula (3), R ¹ represents the same group as R ¹ of formula (1), R ⁴ represents the same group as R ² of formula (1), the two R ⁴ are identical to each other A may be different, A represents the same group as A in Formula (1), m, n, p, q, r, s, t, and u are integers of 0 or more, and m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, n + q + s + u ≧ 1 are satisfied. ]

In [Formula (4), R ¹ represents the same group as R ¹ of formula ^{(1), R 2, R} 3 and R ⁴ each equation ^{(1), R 2, R} 3 and the formula (2) R ⁴ represents the same group, m, n, p, q, r, s, t and u are integers of 0 or more, and m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 4, n + q + s + u ≧ 1 Satisfy the relationship. ]

Wherein, R ^1, R ^2, and R ³ are R ^1, R ^2, and shows the same group as ^{R 3, m, n, p} , q, r and s is an integer of 0 or more of the formula (1) Therefore, the relationship of m + n ≦ 5, p + q ≦ 4, r + s ≦ 5, and n + q + s ≧ 2 is satisfied, and l represents an integer of 1 to 5. ]
A phenolic compound having a flavan skeleton, a phenolic compound having a spirobiindane skeleton, and at least one compound selected from the group consisting of phenolic compounds having a spirobiindene skeleton A radiation-sensitive composition for forming a colored layer is provided.

  The present invention also provides a color filter having a colored layer formed by using the radiation-sensitive composition for forming a colored layer, and a color liquid crystal display device comprising the color filter.

By using the radiation-sensitive composition containing the component (E) of the present invention, even when the content of the colorant contained in the radiation-sensitive composition is high, the adhesiveness to the substrate is excellent and high. Pixels and black matrices having fine and excellent pattern shapes can be formed, and pattern line width does not increase even in proximity exposure.
Therefore, the color filter of the present invention is useful for, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

(Radiation-sensitive composition for forming colored layer)
The “colored layer” in the radiation-sensitive composition for forming a colored layer of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”) comprises pixels and / or a black matrix used for a color filter. Means layer.
Hereafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) Colorant-
The colorant (A) in the present invention is not particularly limited and may be either an organic pigment or an inorganic pigment.
The organic pigment is, for example, divided into pigments in the color index (CI; issued by The Society of Dyers and Colorists), and the (A) colorant in the present invention is not particularly limited. Specific examples of such compounds include those having color index (CI) numbers as shown below.

  C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, 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 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and chromium oxide Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

These colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876, various commercially available polymers or oligomers for dispersing pigments, and the like. The polymer coating method on the carbon black surface is disclosed in, for example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like.
The colorants can be used alone or in admixture of two or more.

When the radiation-sensitive composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and heat resistance, (A) the coloring agent has high color development and high heat resistance. An agent, particularly a colorant having high heat decomposition resistance is preferable, specifically an organic colorant is preferable, and an organic pigment is particularly preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).

  According to the radiation-sensitive composition of the present invention, even if the content of the colorant is 30% by weight or more in the total solid content of the radiation-sensitive composition, no chipping or peeling occurs and the line A pattern that does not increase in width can be formed. In the present invention, the upper limit of the content of the colorant is preferably 60% by weight or less, particularly preferably 50% by weight or less in the total solid content of the radiation-sensitive composition from the viewpoint of ensuring developability. . Here, solid content is components other than the solvent mentioned later.

The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired.
As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), EFKA4046 (manufactured by Ciba Specialty Chemicals), Solsperse 76500 (manufactured by Lubrizol Corporation) As a cationic comb-shaped graft polymer, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Ajisper PB821, Ajisper PB822 (Ajinomoto Fine Techno Co., Ltd.) Mention may be made of the Company, Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 100 parts by weight of the (A) colorant. 50 parts by weight. In this case, when the content of the dispersant exceeds 100 parts by weight, developability and the like may be impaired.

  Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

-(B) Alkali-soluble resin-
The (B) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is particularly limited as long as it is soluble in the alkali developer used in the development processing step when forming the colored layer. Although not intended, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Especially, it is preferable to contain the polymer which has a carboxyl group, and especially the polymer (henceforth "polymer (B1)") which has a repeating unit represented by following formula (6), and a following formula. It is preferable to contain at least one selected from the group consisting of a polymer having a repeating unit represented by (7) (hereinafter referred to as “polymer (B2)”).

(In the formula, R ⁵ represents a hydrogen atom or a methyl group.)

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a monovalent organic group having an acryloyl group or a methacryloyl group, a vinyl group, or 1- M represents a methylvinyl group, Y represents a divalent organic group, and h represents an integer of 1 to 5.)

In the above formula (7), R ⁶ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ⁷ and R ⁸ are preferably hydrogen atoms. h is preferably 1.

  In the above formula (7), the monovalent organic group having an acryloyl group or a methacryloyl group of X is preferably a group represented by the following formula (X-1) or the following formula (X-2). X in the above formula (7) is preferably a vinyl group or a 1-methylvinyl group.

(In the formula, R ¹⁶ represents a hydrogen atom or a methyl group, i represents an integer of 2 to 5, j represents an integer of 1 to 10, and “*” represents a bond.)

(In the formula, R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, a cyclohexane-1,2-diyl group, or a 1,2-phenylene group. , “*” Indicates a bond.)

Y in the above formula (7) is a methylene group, an alkylene group having 2 to 6 carbon atoms, or an alkenylene group having 2 to 6 carbon atoms (however, these alkylene groups and alkenylene groups may be interrupted by oxygen atoms in the middle). A cyclohexanediyl group, a cyclohexenediyl group, or an arylene group having 6 to 12 carbon atoms (wherein the arylene group may have a carboxyl group or an acid anhydride group), and a methylene group , Ethylene group, 1,3-propylene group, 1,2-ethenylene group, 1,2-propenylene group, 1,3-propenylene group, 2,3-propenylene group, cyclohexane-1,2-diyl group, 4- Cyclohexene-1,2-diyl group, 1,2-phenylene group, biphenyl-2,2′-diyl group or —CH ₂ —O—CH ₂ — The bivalent group represented by these is more preferable.

  The (B) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is represented by the following formula (8) in addition to the repeating unit represented by the above formula (6) or the above formula (7). A polymer having at least one repeating unit selected from the group consisting of a repeating unit and a repeating unit represented by the following formula (9) is preferable.

(In the formula, R ⁹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

(In the formula, R ^{10 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group.)

In the above formula (8), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ⁹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- Butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- An undecyl group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned.

The aryl group having 6 to 12 carbon atoms R ^9, for example, a phenyl group, o- tolyl group, m- tolyl group, p- tolyl group, a 1-naphthyl group, there may be mentioned 2-naphthyl group it can.

R ⁹ in the above formula (8) is preferably a cyclohexyl group, a phenyl group or the like, and particularly preferably a phenyl group.

As a halogen atom of R < ¹⁰ > -R < ¹⁵ > in the said Formula (9), a chlorine atom, a bromine atom, or an iodine atom is mentioned, A chlorine atom is preferable.
In the above formula (9), R ^{10 to} R ¹⁵ are all hydrogen atoms, or R ¹² is a chlorine atom, a hydroxyl group or a hydroxymethyl group, and R ¹⁰ and R ¹¹ and R ^{13 to} R ¹⁵ It is preferable that all are hydrogen atoms, and it is more preferable that all of R ^{10 to} R ¹⁵ are hydrogen atoms.

  In the polymer (B1), the repeating unit represented by the formula (6) is preferably 1 to 40% by weight, and 5 to 30% by weight with respect to all the repeating units of the polymer (B1). It is more preferable. In the polymer (B2), the repeating unit represented by the formula (7) is preferably 5 to 80% by weight, and preferably 10 to 60% by weight, based on all the repeating units of the polymer (B2). It is more preferable that (B) By making the ratio of the repeating unit represented by formula (6) or formula (7) in the alkali-soluble resin within such a range, the developability of the radiation-sensitive composition containing the same becomes better. Suppression of the generation of residues during development becomes more effective, which is preferable.

  In the polymer (B1) and the polymer (B2) in the present invention, the repeating unit represented by the above formula (8) is 50% by weight with respect to all the repeating units of the polymer (B1) or the polymer (B2). The content is preferably within the following range, and more preferably within the range of 5 to 40% by weight. In addition, the polymer (B1) and the polymer (B2) contain 60% by weight or less of the repeating unit represented by the above formula (9) based on the entire repeating unit of the polymer (B1) or the polymer (B2). It is preferable to have it in the range of 5 to 40% by weight. Furthermore, the polymer (B1) and the polymer (B2) may have both the repeating unit represented by the above formula (8) and the repeating unit represented by the above formula (9). The total content of both is preferably 80% by weight or less, more preferably 10 to 70% by weight, based on all repeating units of the polymer (B1) or the polymer (B2). In this case, it is preferable that the individual content ratio of the repeating unit represented by the above formula (8) or the repeating unit represented by the above formula (9) is within the above-described range of values.

  By setting the content ratio of the repeating unit represented by the above formula (8) and the repeating unit represented by the above formula (9) in the polymer (B1) and the polymer (B2) within the above range, it is more suitable for the substrate. The advantage that adhesion is improved is obtained, which is preferable.

The polystyrene-reduced weight average molecular weight (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of (B) alkali-soluble resin in the present invention is usually 1,000. -45,000 are preferable, and 3,000 to 20,000 are particularly preferable.
In addition, the (B) alkali-soluble resin gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the present invention has a polystyrene-equivalent number average molecular weight (hereinafter sometimes referred to as “Mn”) of 1 in general. 5,000 to 45,000, and particularly preferably 3,000 to 20,000.
In this case, if the Mw is less than 1,000, the remaining film ratio of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. If it exceeds 000, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

  The polymer (B1) is, for example, a radically polymerizable compound containing (meth) acrylic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be produced by polymerization in the presence of a radical polymerization initiator.

The polymer (B1) can be purified through a reprecipitation method using two or more organic solvents having different polarities after radical polymerization of the radical polymerizable compound as described above. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution volume) of a precipitant ( The polymer is purified by pouring into a poor solvent and reprecipitating the polymer. At that time, out of the impurities remaining in the polymer solution, impurities soluble in the precipitating agent remain in the liquid phase and are separated from the purified polymer (B1).
Examples of the good solvent / precipitant combination used in this reprecipitation method include cyclohexanone / n-hexane, propylene glycol monoethyl ether / n-hexane, cyclohexanone / n-heptane, propylene glycol monoethyl ether / n- And heptane.

  In addition, the polymer (B1) contains the above radical polymerization initiator, pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazole-1- Ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (5-methyl-pyrazol-1-ylthio) Molecular weight systems that act as iniferters such as carbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide The presence of agents, in an inert solvent, the reaction temperature, usually, 0 to 150 ° C., preferably as a 50 to 120 ° C., can also be produced by living radical polymerization.

  In the polymer (B1), another radical polymerizable compound that is preferably copolymerized with (meth) acrylic acid is a compound represented by the following formula (8-1) (hereinafter referred to as “compound (b1)”. ), A compound represented by the following formula (9-1) (hereinafter sometimes referred to as “compound (b2)”), (meth) acrylic acid, compound (b1) and compound (b2) And other radical polymerizable compounds (hereinafter referred to as “compound (b3)”). In the polymer (B1), for example, 2- (meth) acryloyloxyethyl isocyanate is added to the polymer (B1) obtained by copolymerizing a radical polymerizable compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. A polymerizable unsaturated bond can also be introduced into the polymer side chain by reacting an unsaturated isocyanate compound such as.

(Wherein, R ⁹ has the same meaning as R ⁹ in the formula (8).)

(Wherein, R ¹⁰ to R ¹⁵ have the same meanings as R ¹⁰ to R ¹⁵ in the formula (9).)

  The compound (b1) leads the repeating unit represented by the formula (8) to the (B) alkali-soluble resin. Specific examples of the compound (b1) include, for example, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Examples thereof include Nn-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like. Of these compounds (b1), N-cyclohexylmaleimide and N-phenylmaleimide are preferable, and N-phenylmaleimide is particularly preferable. In the polymer (B1), the compound (b1) can be used alone or in admixture of two or more.

  The compound (b2) leads the repeating unit represented by the formula (9) to the (B) alkali-soluble resin. Specific examples of the compound (b2) include acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene, 5-hydroxyacenaphthylene and the like. Of these compounds (b2), acenaphthylene and 5-chloroacenaphthylene are preferable, and acenaphthylene is particularly preferable. In a polymer (B1), an unsaturated compound (b2) can be used individually or in mixture of 2 or more types.

As the compound (b3), for example,
Unsaturated monocarboxylic acids such as crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

In the polymer (B1), the compound (b3) includes a mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more, and a polymer mono (meta) having a carboxy group and a hydroxyl group at both ends. ) Acrylates, unsaturated phenols, aromatic vinyl compounds, unsaturated carboxylic acid esters, macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain, and the like. (Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate , Allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, polystyrene macro Monomers, polymethyl methacrylate macromonomers and the like are preferred.
In the polymer (B1), the compound (b3) can be used alone or in admixture of two or more.

  In addition, the polymer (B2) is a polymer of a radical polymerizable compound (hereinafter referred to as “compound (b4)”) represented by the following formula (7-1) (hereinafter referred to as “compound (b4)”). , A compound represented by the following formula (7-2) (hereinafter referred to as “unsaturated monocarboxylic acid (X)”), and then the following formula (7-2). It can manufacture by adding the compound (henceforth "polybasic acid anhydride (y)") represented by (7-3).

(Wherein, R ^6, R ^7, R ⁸ and h are respectively the same as R ^6, R ^7, R ⁸ and h in the formula (7).)

(In the formula, X has the same meaning as X in the formula (7)).

(In the formula, Y has the same meaning as Y in the above formula (7).)

  Specific examples of the compound (b4) include, for example, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl. Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethyl styrene, 2,4-diglycidyloxymethyl styrene, 2,5-diglycidyloxymethyl styrene, 2,6-di Glycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxy Methylstyrene, 2, 4 6- tri glycidyloxy-methylstyrene, and the like. Of these compounds (b4), o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferable, and p-vinylbenzyl glycidyl ether is particularly preferable. In the polymer (B2), the compound (b4) can be used alone or in admixture of two or more.

In the styrene epoxy polymer, examples of other radical polymerizable compound that is preferably copolymerized with the compound (b4) include the compound (b1), the compound (b2), and the compound (b3). In the styrene epoxy polymer, the compound (b1) and the compound (b2) are preferably the same compounds as exemplified in the polymer (B1). In the styrene epoxy polymer, the compound (b3) is preferably an aromatic vinyl compound, an unsaturated carboxylic acid ester, or a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain. , Α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (Meth) acrylate, glycerol mono (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like are preferable.
In the styrene epoxy polymer, the compound (b1), the compound (b2) and the compound (b3) can be used alone or in admixture of two or more.

  The styrene epoxy polymer can be produced in the same manner as the polymer (B1), and the Mw and Mn thereof can be appropriately set according to the Mw and Mn of the desired (B) alkali-soluble resin.

The unsaturated carboxylic acid (X) can be appropriately selected according to the desired type of X in the formula (7). Preferred unsaturated carboxylic acids (X) include, for example, acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyl Roxyethyl succinic acid and the like can be mentioned. In the ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate, the number of repeating units of polycaprolactone is preferably 1 to 10, more preferably 2 to 5. Among the unsaturated carboxylic acids (X), acrylic acid or methacrylic acid is more preferable because of its high reactivity, and acrylic acid is particularly preferable.
Unsaturated carboxylic acid (X) can be used individually or in mixture of 2 or more types.

  The addition reaction of unsaturated monocarboxylic acid (X) to the styrene epoxy polymer can be carried out according to a known method. The amount of unsaturated monocarboxylic acid (X) used is preferably in the range of 0.7 to 1.3 equivalents relative to 1 equivalent of epoxy groups of the styrene epoxy polymer, and 0.9 to 1.2 equivalents More preferably, it is the range.

  The polybasic acid anhydride (y) can be appropriately selected according to the desired type of Y in the formula (7). Preferred polybasic acid anhydrides (y) include, for example, malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, phthalic anhydride , Cyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, diphenic anhydride and the like. Of these, succinic anhydride, glutaric anhydride, phthalic anhydride or 4-cyclohexene-1,2-dicarboxylic anhydride is particularly preferable because of its high reactivity.

  The addition reaction of the polybasic acid anhydride (y) to the styrene epoxy polymer can be performed according to a known method. The addition amount of the polybasic acid anhydride (y) is preferably in the range of 0.2 to 1.0 equivalent, more preferably 0.4 to 0, relative to 1 equivalent of the epoxy group of the styrene epoxy polymer. .9 equivalent range.

In this invention, a polymer (B1) and a polymer (B2) can be used individually or in mixture of 2 or more types, respectively. Further, as the alkali-soluble resin, for example, a copolymer of (meth) acrylic acid and the above compound (b3) can be used together with the polymer (B1) and / or the polymer (B2).
In the present invention, the content of the alkali-soluble resin is usually preferably from 10 to 1,000 parts by weight, particularly preferably from 20 to 500 parts by weight, based on 100 parts by weight of the colorant (A). In this case, if the content of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed part of the substrate or the light shielding layer. When the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.

-(C) Monomer having two or more radically polymerizable unsaturated bonds-
Examples of the monomer having two or more radically polymerizable unsaturated bonds in the present invention (hereinafter sometimes referred to as “polyfunctional monomer”) include:
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone,
Examples thereof include tris [2- (meth) acryloyloxyethyl] phosphate and isocyanuric acid ethylene oxide-modified triacrylate.

Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol triacrylate and amber Monoesterified product with acid, monoester with pentaerythritol trimethacrylate and succinic acid Preferred are monoesterified products of dipentaerythritol pentaacrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol hexaacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, and the surface of the colored layer is smooth. It is preferable in that it has excellent properties and hardly causes scumming or film residue on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  In the present invention, the content of the (C) polyfunctional monomer is usually preferably from 5 to 500 parts by weight, particularly preferably from 20 to 300 parts by weight, per 100 parts by weight of the (B) alkali-soluble resin. In this case, if the content of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or the light shielding layer.

In the present invention, a part of the polyfunctional monomer is replaced with a monomer having one radical polymerizable unsaturated bond (hereinafter sometimes referred to as “monofunctional monomer”). You can also.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] esters, mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, N- (meth) acryloylmorpho In addition to phosphorus, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more. The content ratio of the monofunctional monomer is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the content ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.

-(D) Radiation sensitive radical generator-
The radiation-sensitive radical generator in the present invention is a polyfunctional monomer and a monofunctional monomer optionally used by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active radical capable of initiating polymerization.
Examples of such a radiation sensitive radical generator include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, benzoin compounds, α-diketone compounds, and the like.

  In the present invention, the radiation-sensitive radical generator can be used alone or in admixture of two or more kinds. Examples of the radiation-sensitive radical generator in the present invention include acetophenone compounds, biimidazole compounds, At least one selected from the group consisting of triazine compounds and O-acyloxime compounds is preferred.

  In the present invention, the general content of the radiation-sensitive radical generator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer. Part. In this case, if the content of the radiation-sensitive radical generator is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 120 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Among the preferred radiation-sensitive radical generators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2- Examples include dimethoxy-1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, the content when an acetophenone-based compound is used as the radiation-sensitive radical generator is usually preferably 0.01 to 80 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer. Especially preferably, it is 1-70 weight part, More preferably, it is 1-60 weight part. In this case, if the content of the acetophenone compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, On the other hand, when the amount exceeds 80 parts by weight, the formed colored layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .

Among these biimidazole compounds, 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) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is preferred.
These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the content when the biimidazole compound is used as the radiation-sensitive radical generator is usually 0.01 to 40 parts by weight with respect to 100 parts by weight of the total of (C) polyfunctional monomers. Is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the content of the biimidazole compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

In the present invention, when a biimidazole compound is used as the radiation-sensitive radical generator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
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.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

In the present invention, the hydrogen donor 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 formed colored layer does not easily fall off from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

  In the present invention, the content when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of the total of (C) polyfunctional monomers. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be reduced. On the other hand, if the content exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

The amine hydrogen donor can function as a sensitizer when used in combination with a radiation sensitive radical generator other than a biimidazole compound such as an acetophenone compound. When an amine hydrogen donor is used as a sensitizer, its content is usually preferably 300 parts by weight or less, particularly preferably 200 parts by weight, based on 100 parts by weight of a radiation sensitive radical generator other than a biimidazole compound. However, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight, since it is difficult to obtain a sufficient effect if the content is too small. It is desirable to do.

  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- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the content in the case of using a triazine-based compound as the radiation-sensitive radical generator is preferably 0.01 to 40 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer, Preferably it is 1-30 weight part, Most preferably, it is 1-20 weight part. In this case, if the content of the triazine compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

  Specific examples of the O-acyloxime compound include, for example, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl. -6-benzoyl-9H-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -Nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O -Acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9H-carbazol-3-yl ] -Ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -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) and the like. it can.

Among these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 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- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the content in the case of using an O-acyloxime compound as a radiation-sensitive radical generator is preferably 0.01 to 80% by weight with respect to 100 parts by weight of the (C) polyfunctional monomer. Parts, more preferably 1 to 60 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, if the content of the O-acyloxime compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 80 parts by weight, the formed colored layer tends to fall off from the substrate during development.

-(E) component-
The component (E) in the present invention includes compounds represented by the above formulas (1) to (5), a phenolic compound having a flavan skeleton, a phenolic compound having a spirobiindane skeleton, and a phenolic compound having a spirobiindene skeleton. At least one compound selected from the group consisting of: By containing such a component, it is possible to prevent the pattern line width from becoming thicker than the design dimension of the photomask in proximity exposure without causing pattern chipping, peeling, or undercut during development.

In the compound represented by the formula (1), the group A in the formula is preferably a -CO- group, a methylene group or an isopropylidene group. R ¹ is preferably a hydrogen atom or an alkyl or alkoxy group having 4 or less carbon atoms.
Specific examples of the compound represented by the above formula (1) include, for example,
(Polyhydroxy) benzophenones include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3 ′ -Tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3 ' -Methoxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, 3,4,5,3', 4 ' , 5'-hexahydroxybenzophenone, etc .;
Examples of bis (hydroxyphenyl) alkanes include bis (p-hydroxyphenyl) methane;
Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) as bis (polyhydroxyphenyl) alkanes ) Propane and the like.

In the compound represented by the formula (2), R ¹ in the formula is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ^{4 in} the formula is a hydrogen atom or an alkyl group having 6 or less carbon atoms. preferable.
Specific examples of the compound represented by the above formula (2) include, for example,
Tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 2- [bis {( 5-isopropyl-4-hydroxy-2-methyl) phenyl} methyl] phenol and the like.

In the compound represented by the above formula (3), the group A in the formula is preferably a methylene group. In the formula, R ¹ is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ⁴ is preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.
Specific examples of the compound represented by the above formula (3) include, for example,
Examples thereof include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane.

In the compound represented by the above formula (4), R ¹ in the formula is preferably a hydrogen atom, and R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.
Specific examples of the compound represented by the above formula (4) include, for example,
4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like can be mentioned.

In the compound represented by the above formula (5), R ¹ in the formula is preferably a hydrogen atom, and R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.
Specific examples of the compound represented by the above formula (5) include, for example,
4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl } -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1- Methylethyl) benzene and the like.

Specific examples of the phenolic compound having the flavan skeleton include, for example,
2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2,4,4-trimethyl-7,2 ′, 4′-trihydroxyflavan, etc. Can be mentioned.
Specific examples of the phenolic compound having the spirobiindane skeleton include, for example, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane-5,6,7,5 ′, 6 ′, 7 ′. -Hexanol etc. can be mentioned.
Specific examples of the phenolic compound having a spirobiindene skeleton include, for example, 3,3′-dimethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol. Etc.

  Among these compounds, (polyhydroxy) benzophenones, compounds represented by the above formula (4), and compounds represented by phenolic compounds having a flavan skeleton are preferable, and 2,3,4-trihydroxybenzophenone, 2 , 3,4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 6′-pentahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1 -Methylethyl] phenyl] ethylidene] bisphenol, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman are particularly preferred.

  In the present invention, the content of the component (E) is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, and particularly preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Parts by weight. In this case, if the content of the component (E) is less than 0.1 part by weight, the desired effect may not be obtained. On the other hand, when the amount exceeds 10 parts by weight, the formed pattern tends to drop off from the substrate during development.

-Additives-
Although the radiation sensitive composition of this invention contains the said (A)-(E) component, it can further contain another additive as needed.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulation agents such as sodium acrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention contains the components (A) to (E) as essential components, and optionally contains the additive component. Prepared as a composition.
As the solvent, as long as the components (A) to (E) and the additive component constituting the radiation-sensitive composition are dispersed or dissolved and do not react with these components and have appropriate volatility. 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;

(Poly) alkylene glycol mono, such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate Alkyl ether acetates;
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;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl 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, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.
The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually The amount is preferably 5 to 50% by weight, and particularly preferably 10 to 40% by weight.

Color filter The color filter of this invention is provided with the colored layer formed from the radiation sensitive composition for colored layer formation of this invention.
The method for forming the color filter of the present invention will be described below.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the 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 the pixels of each color is not limited to the above.
The black matrix can be formed in the same manner as in the pixel formation using the radiation-sensitive composition for forming a colored layer of the present invention.

Examples of the substrate used when forming the pixel and / or the black matrix 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 a liquid composition of a radiation sensitive composition to a substrate, an appropriate application 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, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
Exposure of radiation is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 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 color filter of the present invention thus obtained is extremely useful for high-definition color liquid crystal surface elements, color image pickup tube elements, color sensors and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one embodiment of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed on a thin film transistor substrate array as described above using the radiation-sensitive composition for forming a colored layer of the present invention. In particular, a high-definition color liquid crystal display element can be manufactured.

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.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Elution solvent: tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis synthesis example 1 of alkali-soluble resin
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and 30 parts by weight of N-phenylmaleimide. Then, 30 parts by weight of benzyl methacrylate, 20 parts by weight of styrene, and 5 parts by weight of α-methylstyrene dimer which is a chain transfer agent as a molecular weight control agent were charged, and after purging with nitrogen, the reaction solution was stirred at 80 ° C. with gentle stirring. The temperature was raised to 3, and the polymerization was carried out for 3 hours while maintaining this temperature. By adding 0.5 part by weight of 2,2′-azobisisobutyronitrile, polymerization was further performed for 1 hour, and then the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid content Concentration = 33.0 wt%). The obtained resin was Mw = 9,500 and (Mw / Mn) = 2.0. This resin is referred to as “resin (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 20 parts by weight of N-phenylmaleimide. , 35 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 6 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent. After substituting with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring and polymerized for 3 hours while maintaining this temperature. By adding 0.5 part by weight of 2,2′-azobisisobutyronitrile, polymerization was further performed for 1 hour, and then the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid content Concentration = 33.0 wt%). The obtained resin was Mw = 7,500 and (Mw / Mn) = 2.1. This resin is referred to as “resin (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid, 30 parts by weight of acenaphthylene, and benzyl methacrylate. 40 parts by weight, 10 parts of glycerol monomethacrylate, 5 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 5 parts by weight of α-methylstyrene dimer, which is a chain transfer agent, as a molecular weight control agent were added and gently purged. While stirring, the temperature of the reaction solution was raised to 80 ° C., and this temperature was maintained for polymerization for 3 hours. By adding 0.5 part by weight of 2,2′-azobisisobutyronitrile, polymerization was further performed for 1 hour, and then the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid content Concentration = 33.0 wt%). The obtained resin was Mw = 11,000 and (Mw / Mn) = 2.2. This resin is referred to as “resin (B-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 25 parts by weight of N-phenylmaleimide. , 25 parts by weight of benzyl methacrylate, 15 parts by weight of styrene, 10 parts by weight of glycerol monomethacrylate, 10 parts by weight of ω-carboxypolycaprolactone monoacrylate, and 5 parts by weight of α-methylstyrene dimer which is a chain transfer agent as a molecular weight control agent. After substituting with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring and polymerized for 3 hours while maintaining this temperature. By adding 0.5 part by weight of 2,2′-azobisisobutyronitrile, polymerization was further performed for 1 hour, and then the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid content Concentration = 33.0 wt%). The obtained resin was Mw = 10,000 and (Mw / Mn) = 2.2. This resin is referred to as “resin (B-4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monoethyl ether, followed by 15 parts by weight of methacrylic acid, 30 parts by weight of acenaphthylene, and benzyl methacrylate. 35 parts by weight, 20 parts of glycerol monomethacrylate and 6 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent were charged, and after nitrogen substitution, the reaction solution was heated to 80 ° C. while gently stirring. The polymerization was carried out for 3 hours while maintaining this temperature. By adding 0.5 part by weight of 2,2′-azobisisobutyronitrile, polymerization was further performed for 1 hour, and then the temperature was raised to 100 ° C. and polymerization was continued for 1 hour to obtain a resin solution (solid content Concentration = 33.0 wt%). The obtained resin was Mw = 12,000 and (Mw / Mn) = 2.2. This resin is referred to as “resin (B-5)”.

Synthesis Example 6
In a flask equipped with a condenser and a stirrer, 40 parts by weight of p-vinylbenzylglycidyl ether, 27 parts by weight of N-phenylmaleimide, 17 parts by weight of styrene and 16 parts by weight of benzyl methacrylate are dissolved in 300 parts by weight of propylene glycol monomethyl ether acetate. Further, 4 parts by weight of 2,2′-azobisisobutyronitrile and 6 parts by weight of α-methylstyrene dimer were added, and then purged with nitrogen for 15 minutes. After purging with nitrogen, the reaction kettle was heated to 80 ° C. with stirring and reacted for 5 hours to obtain a resin solution containing 25% by weight of styrene epoxy resin. This styrene epoxy resin had Mw = 6,000 and (Mw / Mn) = 2.5.
200 parts by weight of a resin solution containing the obtained styrene epoxy resin, 10 parts by weight of methacrylic acid as unsaturated monocarboxylic acid (X), 0.2 part by weight of p-methoxyphenol, 0.2 part by weight of tetrabutylammonium bromide and 300 parts by weight of propylene glycol monomethyl ether acetate was charged in a flask and reacted at a temperature of 120 ° C. for 9 hours. Thereby, 1 equivalent of methacrylic acid reacted with 1 equivalent of epoxy group of the styrene epoxy resin. Furthermore, 16 parts by weight of 4-cyclohexene-1,2-dicarboxylic acid anhydride as the polybasic acid anhydride (y) was added and reacted at 80 ° C. for 6 hours. The reaction mixture was washed twice with the liquid temperature kept at 80 ° C. and concentrated under reduced pressure to obtain a resin solution containing 20% by weight of an alkali-soluble resin. The obtained resin was Mw = 7,800 and (Mw / Mn) = 2.6. This resin is referred to as “resin (B-6)”.

Preparation 1 of pigment dispersion
(A) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 80/20 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content), 6 parts by weight of (B-1) as an alkali-soluble resin (solid) The pigment dispersion (r) was prepared by treating 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent with a bead mill.

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment yellow 138 / C.I. I. Pigment Yellow 150 = 50/40/10 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content), (B) 5 parts by weight of (B-2) as an alkali-soluble resin A pigment dispersion (g) was prepared by treating (in terms of solid content) and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent in the same manner as in Example 1.

Preparation Example 3
(A) C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Violet 23 = 95/5 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Disperbyk-2001 as a dispersant (in terms of solid content), 5 parts by weight of (B-2) as an alkali-soluble resin (solid) A pigment dispersion (b) was prepared by treating 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent in the same manner as in Example 1.

Preparation Example 4
(A) 20 parts by weight of carbon black (manufactured by Mikuni Dye Co., Ltd.) as a colorant, 2 parts by weight of Disperbyk-2001 (in terms of solid content) as a dispersant, and (B) 4 of (B-3) as an alkali-soluble resin A pigment dispersion (bk1) was prepared by treating in the same manner as in Example 1 with parts by weight (in terms of solid content) and 74 parts by weight of 3-methoxybutyl acetate as a solvent.

Preparation Example 5
(A) 20 parts by weight of carbon black (manufactured by Mikuni Dye Co., Ltd.) as a colorant, 2 parts by weight of Disperbyk-167 as a dispersant (in terms of solid content), (B) 3 of (B-3) as an alkali-soluble resin A pigment dispersion (bk2) was prepared by treating in the same manner as Example 1 with parts by weight (in terms of solid content) and 75 parts by weight of 3-methoxybutyl acetate as a solvent.

Example 1
Preparation of liquid composition 100 parts by weight of pigment dispersion (r), (B) 6 parts by weight of resin (B-4) as an alkali-soluble resin (in terms of solid content), (C) dipentaerythritol as a polyfunctional monomer 8 parts by weight of hexaacrylate, (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, Ciba Specialty Chemicals) as photopolymerization initiator 3 parts by weight), 4,5 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol as component (E) 0.15 parts by weight, and solvent As a liquid composition for forming a colored layer, 150 parts by weight of ethyl 3-ethoxypropionate and 25 parts by weight of propylene glycol monomethyl ether acetate are mixed. The (R1) was prepared.
The liquid composition (R1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

Formation of pattern The liquid composition (R1) was applied on the surface of a glass substrate using a spin coater and then pre-baked at 90 ° C for 2 minutes to form a coating film having a thickness of 2.5 µm. Then, this board | substrate was cooled to room temperature, and it exposed by the exposure amount of 1000 J / m < ² > by making the exposure gap into 200 micrometers through the photomask using the high pressure mercury lamp on the coating film on a board | substrate. Thereafter, a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. was discharged onto the coating film on the substrate at a development pressure of 2 kgf / cm ² (nozzle diameter 1 mm) to perform shower development for 50 seconds, and then 230 ° C. Was post-baked for 30 minutes to form a pixel array in which red line and space (L / S) patterns were arranged on the substrate.

Evaluation When the pixel array on the substrate was observed with an optical microscope, the edge of the pixel pattern was not chipped. Further, when the cross section of the pixel pattern on the substrate was observed with a scanning electron microscope (SEM), no undercut was observed. It was 93.0 micrometers when the line | wire width of the pixel pattern formed through the photomask with a slit width of 90 micrometers was measured with the optical microscope.

Examples 2-17 and Comparative Examples 1-6
In Example 1, the liquid compositions (R2) to (R3), (G1) to (G3), () are the same as Example 1 except that the types and amounts of the constituent components are changed as shown in Table 2. B1) to (B3) and (BK1) to (BK14) were prepared.
Next, in place of the liquid composition (R1), the liquid compositions (R2) to (R3), (G1) to (G3), (B1) to (B3), and (BK1) to (BK14) were used. Were evaluated in the same manner as in Example 1. The results are shown in Table 2.

In Table 1, each component is as follows.
C-1: Dipentaerythritol hexaacrylate C-2: Tris (2-hydroxyethyl) isocyanurate triacrylate (trade name M-315, manufactured by Toagosei Co., Ltd.)
D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
D-3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
E-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol E-2: 2,3,4-trihydroxybenzophenone E- 3: 2,3,4,4′-tetrahydroxybenzophenone E-4: 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman E-5: 2,3,4,2 ′, 6′-pentahydroxybenzophenone F-1: malonic acid F-2: nonionic surfactant (trade name A-60, manufactured by Kao Corporation)
F-3: Polymerization inhibitor phenothiazine EEP: Ethyl 3-ethoxypropionate PGMEA: Propylene glycol monomethyl ether acetate MBA: 3-methoxybutyl acetate

The radiation-sensitive composition containing the component (E) of the present invention has excellent adhesion to the substrate, high definition and excellent even when the content of the colorant contained in the radiation-sensitive composition is high. In addition, a pixel and a black matrix that have a different pattern shape and do not increase in pattern line width even in proximity exposure can be formed.
Therefore, the radiation-sensitive composition of the present invention is extremely preferably used for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. Can do.

Claims (6)

Selected from the group consisting of (A) a colorant, (B) an alkali-soluble resin, (C) a monomer having two or more radically polymerizable unsaturated bonds, (D) an acetophenone compound and an O-acyloxime compound. A radiation-sensitive radical generator containing at least one selected from the above formulas, and (E) the following formulas (1) to (5)

[In the formula (1), R ¹ represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a phenyl group, a naphthyl group, or a — (CH ₂ ) x -COOZ group, R ¹ may be the same or different from each other, Z represents an alkoxyalkyl group, a cyclic ether group, a vinyloxyalkyl group or a t-alkoxycarbonylalkyl group, and a plurality of Z may be the same or different from each other , X is an integer of 0 to 4, and A is a single bond, -S- group, -O- group, -CO- group, -COO- group, -SO- group, -SO ₂ -group, -C ( R ² ) (R ³ ) -group or

A group (wherein k is an integer of 0 to 4), R ² and R ³ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or an acyl having 6 or less carbon atoms. A group, a phenyl group, a naphthyl group or a — (CH ₂ ) x —COOZ group, m, n, p and q are integers of 0 or more and satisfy the relationship of m + n ≦ 5, p + q ≦ 5 and n + q ≧ 1. ]

In [formula (2), R ¹ represents the same group as R ¹ of formula (1), R ⁴ represents the same group as R ² of formula (1), m, n, p, q, r and s Is an integer of 0 or more and satisfies the relationship of m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, and n + q + s ≧ 1. ]

In [formula (3), R ¹ represents the same group as R ¹ of formula (1), R ⁴ represents the same group as R ² of formula (1), the two R ⁴ are identical to each other A may be different, A represents the same group as A in Formula (1), m, n, p, q, r, s, t, and u are integers of 0 or more, and m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, n + q + s + u ≧ 1 are satisfied. ]

In [Formula (4), R ¹ represents the same group as R ¹ of formula ^{(1), R 2, R} 3 and R ⁴ each equation ^{(1), R 2, R} 3 and the formula (2) R ⁴ represents the same group, m, n, p, q, r, s, t and u are integers of 0 or more, and m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 4, n + q + s + u ≧ 1 Satisfy the relationship. ]

Wherein, R ^1, R ^2, and R ³ are R ^1, R ^2, and shows the same group as ^{R 3, m, n, p} , q, r and s is an integer of 0 or more of the formula (1) Therefore, the relationship of m + n ≦ 5, p + q ≦ 4, r + s ≦ 5, and n + q + s ≧ 2 is satisfied, and l represents an integer of 1 to 5. ]
Component (E) containing at least one compound selected from the group consisting of: a compound represented by the formula: a phenolic compound having a flavan skeleton; a phenolic compound having a spirobiindane skeleton; and a phenolic compound having a spirobiindene skeleton. The radiation-sensitive composition for forming a colored layer , wherein the content of is 0.1 to 10 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin . (B) As an alkali-soluble resin, contains at least one selected from the group consisting of a polymer having a repeating unit represented by the following formula (6) and a polymer having a repeating unit represented by the following formula (7) The radiation-sensitive composition for forming a colored layer according to claim 1 .

(In the formula, R ⁵ represents a hydrogen atom or a methyl group.)

(Wherein R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X represents a monovalent organic group having an acryloyl group or a methacryloyl group, a vinyl group, or 1- A methyl vinyl group, Y represents a divalent organic group, and h represents an integer of 1 to 5.) (B) As an alkali-soluble resin, further contains a polymer having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula (9) The radiation-sensitive composition for forming a colored layer according to claim 2 .

(In the formula, R ⁹ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

(In the formula, R ^{10 to} R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group.) (A) Content of a coloring agent is 30 to 60 weight% in a total solid, The radiation sensitive composition of any one of Claims 1-3 . The color filter which has a colored layer formed using the radiation sensitive composition for colored layer formation of any one of Claims 1-4 . A color liquid crystal display device comprising the color filter according to claim 5 .