KR20090093822A - Radiation-sensitive composition for forming colored layer, color filter and color liquid crystal display device - Google Patents

Abstract

A radiation sensitive composition for forming a colored layer, a color filter using the composition, and an LCD device containing the color filter are provided to improve the adhesion to a substrate even in case the content of a colorant is high and to foam a black matrix having no thick pattern line width even in proximity exposure. A radiation sensitive composition for forming a colored layer comprises a colorant; 100 parts by weight of an alkali-soluble resin; a monomer having at least two radical polymerizable unsaturated bonds; a radiation sensitive radical generator; and 0.1-10 parts by weight of at least one compound selected from the group consisting of a compound represented by the formulas 1-5, a phenolic compound having a flavan skeleton, a phenolic compound having a spirobiindan skeleton, and a phenolic compound having a spirobiindene skeleton.

Description

Radiation-sensitive composition, color filter, and color liquid crystal display device for forming a colored layer {RADIATION-SENSITIVE COMPOSITION FOR FORMING COLORED LAYER, COLOR FILTER AND COLOR LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display device, and more particularly, the formation of a colored layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color image tube device, or the like. It relates to a color filter comprising a radiation-sensitive composition used in the above, a colored layer formed by using the radiation-sensitive composition, and a color liquid crystal display device comprising the color filter.

A method of forming a color filter using a colored radiation-sensitive composition, wherein a coating film of a colored radiation-sensitive composition is formed on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, thereby forming a photomask having a predetermined pattern. A method of obtaining pixels of each color is known (see, for example, Patent Documents 1 and 2 below) by irradiating radiation (hereinafter referred to as "exposure"), developing, dissolving and removing unexposed portions, and post-baking. .

In recent years, a brighter screen with better color reproducibility has been demanded for monitors and televisions, and the content of colorants, especially pigments, contained in the radiation-sensitive composition has to be increased while improving the brightness of the backlight ( The following nonpatent literature 1). In addition, liquid crystal monitor screens and liquid crystal television screens are more highly finer, and the number of pixels per unit area on the screen tends to increase. For this reason, it is calculated | required that a radiation sensitive composition can form a finer pattern for both black matrix formation and pixel formation.

For this request, Patent Document 3, for example, discloses that a pattern having a high resolution can be formed by containing an alkali-soluble resin having a specific structure in the radiation-sensitive composition. However, in the so-called negative radiation-sensitive composition, since the line width of the formed pattern becomes thicker than the design dimension of the photomask under the influence of diffracted light at the time of proximity exposure, there is a problem that a fine pattern having a desired line width cannot be obtained. there was.

On the other hand, as a method of eliminating the increase in the pattern line width of the negative radiation-sensitive composition, for example, the exposure amount is reduced, the development conditions are enhanced, and the content of the radiation-sensitive polymerization initiator in the radiation-sensitive composition is reduced. Or a polymerization inhibitor is contained in the radiation-sensitive composition. However, either of these methods tends to easily cause defects, peeling and undercut of the pattern during development, and in particular, it cannot be applied when the content of the colorant contained in the radiation sensitive composition is increased.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Application Laid-Open No. 3-53201

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2004-205862

[Non-Patent Document 1] Tadakazu Murakami, "New Development of Front Back Light for LCD," First Edition, Toray Research Center, September, 2002.

An object of the present invention is to form a pixel and a black matrix having excellent adhesion with a substrate, high precision and excellent pattern shape even when the content of the colorant contained in the radiation sensitive composition is high, Also in providing the radiation sensitive composition for colored layer formation in which a pattern line width does not become thick.

Moreover, the objective of this invention is providing the color filter which comprises the colored layer formed from the radiation sensitive composition for colored layer formation, and the color liquid crystal display element provided with this color filter.

In view of such circumstances, the present inventors have made intensive studies and found that the above problems can be solved by including a phenolic compound having a specific structure in the radiation-sensitive composition for forming a colored layer, thereby completing the present invention. Reached.

That is, the present invention provides (A) a colorant, (B) an alkali-soluble resin, (C) a monomer having two or more radical polymerizable unsaturated bonds, (D) a radiation sensitive radical generator, and (E) the following Chemical Formulas 1 to 5 It is characterized by containing at least one compound selected from the group consisting of a compound represented by: a phenolic compound having a flavan skeleton, a phenolic compound having a spirobiindane skeleton, and a phenolic compound having a spirobiindene skeleton It is providing the radiation sensitive composition for colored layer formation.

[In 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, and a plurality of R ¹ 's are the same as each other, or And Z may represent an alkoxyalkyl group, a cyclic ether group, a vinyloxyalkyl group or a t-alkoxycarbonylalkyl group, and a plurality of Z's 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 Group (wherein k is an integer of 0 to 4), R ² and R ³ may be the same or different from each other, a hydrogen atom, an alkyl group of 6 or less carbon atoms, an acyl group of 6 or less carbon atoms, a phenyl group or a naphthyl group Or a-(CH ₂ ) x-COOZ group, m, n, p and q are integers greater than or equal to 0 and satisfy a relationship of m + n ≦ 5, p + q ≦ 5 and n + q ≧ 1]

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

[In the formula 3, R ¹ represents a group the same as R ¹ of formula I, R ⁴ is represents a group the same as R ² of formula (I), two R ⁴ may be the same as or different from each other, A is the formula (I) Represents the same group as A, and m, n, p, q, r, s, t and u are integers greater than or equal to 0, m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, n + q + s + u≥1 is satisfied.]

[In the formula 4, R ¹ represents a group the same as R ¹ of formula 1, R ^2, R ³ and R ⁴ each represent the same group with the general formula (I) of R ^2, R ³ and R ⁴ of formula 2, m, n, p, q, r, s, t and u are integers greater than or equal to 0, m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 4, n + q + s + u Satisfying a relationship of ≥1]

[Wherein, R ¹ , R ² and R ³ is R ¹ , R ² and Represents the same group as R ^3, and m, n, p, q, r and s are integers of 0 or more, and m + n ≦ 5, p + q ≦ 4, r + s ≦ 5 and n + q + s ≧ 2. Satisfying the relationship, and l represents an integer of 1 to 5]

Moreover, this invention also provides the color filter which has a colored layer formed using the said radiation sensitive composition for colored layer formation, and the color liquid crystal display element provided with the said 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 adhesion to the substrate is excellent, the pixel having a high precision and excellent pattern shape, and The black matrix can be formed, and the pattern line width does not become thick even in proximity exposure.

Therefore, the color filter of this invention is useful for a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, etc., for example.

(Radiation composition for colored layer formation)

The "coloring layer" in the radiation sensitive composition for forming a colored layer of the present invention (hereinafter also referred to simply as "radiation sensitive composition") means a layer containing a pixel and / or a black matrix used in a color filter. do.

Hereinafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) colorant-

It does not specifically limit as (A) coloring agent in this invention, Any of an organic pigment and an inorganic pigment may be sufficient.

Examples of the organic pigments include compounds classified as pigments in color indices (issued by The Society of Dyers and Colorists, Inc.), specifically those having the following color index (CI) numbers. Can be.

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

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

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

 C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60, C.I. Pigment blue 80;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment green 58;

C.I. Pigment Brown 23, C.I. Pigment brown 25;

C.I. Pigment Black 1, C.I. Pigment Black 7.

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

As the inorganic pigment, for example, titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, bengal (red iron oxide (III)), cadmium, ultramarine blue, blue blue, chromium oxide Green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc. are mentioned.

These colorants can also be used by modifying the particle surface with a polymer as desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, the polymer for disperse | distributing various pigments, or oligomer etc. are mentioned, for example. About the polymer coating method of the carbon black surface, it is disclosed by Unexamined-Japanese-Patent No. 9-71733, Unexamined-Japanese-Patent No. 9-95625, Unexamined-Japanese-Patent No. 9-124969, etc., for example. It is.

The said coloring agent can be used individually or in mixture of 2 or more types.

In the case where the radiation-sensitive composition of the present invention is used for forming a pixel, since the pixel requires high color development and heat resistance, the (A) colorant is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance. Specifically, an organic colorant is preferable, and an organic pigment is especially used preferably.

On the other hand, when the radiation sensitive composition of this invention is used for formation of a black matrix, since a light shielding property is calculated | required by a black matrix, organic pigment or carbon black is used suitably as (A) coloring agent.

According to the radiation sensitive composition of this invention, even when content of a coloring agent becomes 30 weight% or more in the total solid of a radiation sensitive composition, a pattern which does not generate a defect or peeling and does not become thick can be formed. In addition, in this invention, the upper limit of content of a coloring agent is 60 weight% or less in total solids of a radiation sensitive composition from a viewpoint of ensuring developability, Preferably it is 50 weight% or less. Solid content is components other than the solvent mentioned later here.

The coloring agent in this invention can be used with a dispersing agent and a dispersal auxiliary agent as needed.

As the dispersant, suitable dispersants such as cationic, anionic, nonionic or amphoteric, may be used, but a polymer dispersant is preferable. Specifically, an alkyl ammonium salt or a phosphate ester salt of a modified acrylic copolymer, an acrylic copolymer, a polyurethane, a polyester, a polymer copolymer, a cationic comb graft polymer, etc. may be mentioned. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branch polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups). The polymer which a polymer part consists of a ring-opening polymer of (epsilon) -caprolactone is mentioned. Of these dispersants, modified acrylic copolymers, polyurethanes, and cationic comb graft polymers are preferred.

Such dispersants are commercially available, for example, as a modified acrylic copolymer, Disperbyk-2000, Dispervic-2001 (above, manufactured by BYK Corporation), and polyurethane, 161, dispervic -162, dispervic -165, dispervic -167, dispervic -170, dispervic -182 (above, manufactured by BYK Corporation), EFKA4046 (manufactured by Ciba Specialty Chemicals), Solsperth 76500 (Lubricazole Co., Ltd.), as a cationic comb graft polymer, Solsper 24000 (Lubricol Co., Ltd.), Azisper PB821, Azisper PB822 (manufactured by Ajinomoto Fine Techno Co., Ltd.) Etc. can be mentioned.

These dispersants can be used individually or in mixture of 2 or more types. Content of a dispersing agent is 100 weight part or less normally with respect to 100 weight part of (A) coloring agents, Preferably it is 0.5-100 weight part, More preferably, it is 1-70 weight part, Especially preferably, it is 10-50 weight part. In this case, when content of a dispersing agent exceeds 100 weight part, there exists a possibility that developability etc. may be impaired.

As said dispersing adjuvant, a blue pigment derivative, a yellow pigment derivative, etc. are mentioned, for example, Specifically, a copper phthalocyanine derivative etc. are mentioned, for example.

-(B) alkali-soluble resin-

(B) Alkali-soluble resin contained in the radiation sensitive composition of this invention will not be specifically limited if it has solubility with respect to the alkaline developing solution used at the image development process at the time of forming a colored layer, but is normally carboxyl group and phenolic It is a polymer which has acidic functional groups, such as a hydroxyl group. Especially, it is preferable to contain the polymer which has a carboxyl group, Especially the polymer which has a repeating unit represented by following formula (6) (hereinafter "polymer (B1)"), and the polymer which has a repeating unit represented by following formula (7) (Hereinafter, referred to as "polymer (B2)") It is preferable to contain 1 or more types chosen from the group which consists of.

(Wherein R ⁵ represents a hydrogen atom or a methyl group)

(In formula, R <^6> , R <^7> and R <^8> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, X is a monovalent organic group, vinyl group, or 1- which has acryloyl group or methacryloyl group. Methylvinyl group, Y represents a divalent organic group, h represents an integer of 1 to 5)

In the formula (7), R ⁶ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. It is preferable that R <^7> and R <^8> is a hydrogen atom. h is preferably 1.

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

<Formula X-1>

(Wherein, 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)

<Formula X-2>

(Wherein, R ¹⁷ represents a hydrogen atom or a methyl group, 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, "*" Represents a bonding hand)

As Y in the said Formula (7), a methylene group, a C2-C6 alkylene group, a C2-C6 alkenylene group (however these alkylene groups and alkenylene groups may be interrupted by an oxygen atom in the middle), cyclo It is preferable that it is a hexanediyl group, a cyclohexene diyl group, or an arylene group of 6 to 12 carbon atoms (however, this arylene group may have a carboxyl group or an acid anhydride group), and 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, 1,2-phenylene group, biphenyl-2,2'-diyl group or a -CH ₂ -O-CH ₂ - _2-valent group represented by is more preferable.

(B) alkali-soluble resin contained in the radiation sensitive composition of this invention is a repeating unit represented by following formula (8), and a repeating unit represented by following formula (9) other than the repeating unit represented by the said Formula (6) or (7). It is preferable that it is a polymer which has 1 or more types of repeating units chosen from the group which consists of.

(Wherein 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)

(Wherein R ¹⁰ to R ¹⁵ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group)

In the above formula (8), as the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ⁹ , for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl Group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodec A real group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Moreover, as a C6-C12 aryl group of R <^9> , a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, 2-naphthyl group etc. are mentioned, for example.

As R <^9> in the said Formula (8), a cyclohexyl group, a phenyl group, etc. are preferable, and a phenyl group is especially preferable.

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 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 are all hydrogen atoms. More preferably, all of R ¹⁰ to R ¹⁵ are hydrogen atoms.

In the polymer (B1), the repeating unit represented by the above formula (6) is preferably 1 to 40% by weight, and more preferably 5 to 30% by weight based on all the repeating units of the polymer (B1). In addition, it is preferable that it is 5 to 80 weight% with respect to the all the repeating units of the polymer (B2), and, as for the repeating unit represented by the said Formula (7) in a polymer (B2), it is more preferable that it is 10 to 60 weight%. By setting the ratio of the repeating unit represented by the formula (6) or the formula (7) in the alkali-soluble resin to such a range, the developability of the radiation-sensitive composition containing it is better, and the suppression of the occurrence of residuals at the time of development is more. It is preferable to become effective.

The polymer (B1) and the polymer (B2) in the present invention have a repeating unit represented by the formula (8) in a range of 50% by weight or less relative to the total repeating units of the polymer (B1) or the polymer (B2). It is preferable and it is more preferable to have it in 5 to 40weight% of a range. In addition, it is preferable that polymer (B1) and polymer (B2) have a repeating unit represented by the said Formula (9) in 60 weight% or less with respect to all the repeating units of a polymer (B1) or a polymer (B2), It is more preferable to have it in 5 to 40weight% of a range. In addition, the polymer (B1) and the polymer (B2) may have both the repeating unit represented by the said Formula (8) and the repeating unit represented by the said Formula (9), In this case, the sum total of the content rate of both is the polymer (B1) or The total repeating units of the polymer (B2) are preferably 80% by weight or less, and more preferably 10 to 70% by weight. In this case, it is preferable that the individual content rate of the repeating unit represented by the said Formula (8) or the repeating unit represented by the said Formula (9) exists in the range of said value, respectively.

By making the content ratio of the repeating unit represented by the formula (8) and the repeating unit represented by the formula (9) in the polymer (B1) and the polymer (B2) within the above ranges, an advantage that the adhesion to the substrate is improved is obtained more. It is preferable to lose.

Polystyrene conversion weight average molecular weight (henceforth "Mw") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of (B) alkali-soluble resin in this invention is 1,000-45,000 normally. Preferred, in particular 3,000 to 20,000.

In addition, the polystyrene reduced number average molecular weight (henceforth "Mn") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of (B) alkali-soluble resin in this invention is 1,000-1000 normally. 45,000 is preferred, particularly 3,000 to 20,000.

In this case, if Mw is less than 1,000, the remaining film ratio or the like of the resulting film may be reduced, the pattern shape, heat resistance, or the like may be impaired, or the electrical properties may be deteriorated. In addition, there exists a possibility that a dry foreign material may arise easily at the time of application | coating by a slit nozzle system.

The polymer (B1) is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-) in a radically polymerizable compound containing (meth) acrylic acid, a suitable solvent. It can manufacture by polymerizing in presence of radical polymerization initiators, such as dimethylvaleronitrile) and 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile).

In addition, a polymer (B1) can be refine | purified via the reprecipitation method using two or more types of organic solvents from which polarity differs, after radically polymerizing a radically polymerizable compound as mentioned above. That is, after removing the solution in the good solvent after polymerization, insoluble impurities are removed by filtration or centrifugation, if necessary, and then poured into a large amount (usually 5 to 10 times the volume of the polymer solution) in the precipitant (poor solvent), the polymer Purify by reprecipitation. At that time, among the impurities remaining in the polymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified polymer (B1).

As a combination of the good solvent / precipitator used for this reprecipitation method, for example, cyclohexanone / n-hexane, propylene glycol monoethyl ether / n-hexane, cyclohexanone / n-heptane, propylene glycol monoethyl ether / n-heptane etc. are mentioned.

In addition, the polymer (B1) is a radical polymerization initiator, pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (Pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide Feed, bis (5-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrole-1- Living in the presence of a molecular weight controlling agent that acts as an initiator such as ilthiocarbonyl) disulfide and bisthiobenzoyldisulfide, the reaction temperature is usually 0 to 150 캜, preferably 50 to 120 캜 in an inert solvent. It can also manufacture by radical polymerization.

In the polymer (B1), as another radically polymerizable compound which is preferably copolymerized with (meth) acrylic acid, a compound represented by the following formula (8-1) (hereinafter also referred to as "compound (b1)"), the following formula 9- Compounds represented by 1 (hereinafter also referred to as "compound (b2)") and radically polymerizable compounds other than (meth) acrylic acid, compound (b1) and compound (b2) (hereinafter referred to as "compound (b3)") Can be mentioned. In addition, in polymer (B1), 2- (meth) acryloyl to polymer (B1) which copolymerized radically polymerizable compounds which have hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, for example. A polymerizable unsaturated bond can also be introduce | transduced into a polymer side chain by making unsaturated isocyanate compounds, such as oxyethyl isocyanate, react.

<Formula 8-1>

(Wherein, R ⁹ is R ⁹ and agreement in the above formula (8))

<Formula 9-1>

(In the formula, R ¹⁰ to R ¹⁵ is R ¹⁰ to R ¹⁵ and consent for Formula 9)

The compound (b1) is to induce a repeating unit represented by the formula (8) to the (B) alkali-soluble resin. As a specific example of a compound (b1), for example, N-methyl maleimide, N-ethyl maleimide, Nn-propyl maleimide, Ni-propyl maleimide, Nn-butyl maleimide, Nt-butyl maleimide, Nn -Hexyl maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-1- naphthyl maleimide, etc. are mentioned. Among these compounds (b1), N-cyclohexylmaleimide and N-phenylmaleimide are preferable, and N-phenylmaleimide is particularly preferable. In a polymer (B1), a compound (b1) can be used individually or in mixture of 2 or more types.

The compound (b2) is to induce a repeating unit represented by the formula (9) to the alkali-soluble resin (B). As a specific example of a compound (b2), acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene, 5-hydroxyacenaphthylene, etc. are mentioned, for example. Among 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 and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] Esters;

mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate;

o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-iso Unsaturated phenols such as propenyl phenol;

2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1- Unsaturated naphthols such as naphthol;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and 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, methoxypropyl Lenglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Unsaturated carboxyl such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as acrylate and 3-dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and 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 and chloroprene;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

In the polymer (B1), as the compound (b3), mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyhydric carboxylic acid, mono (meth) acryl of a polymer having a carboxyl group and a hydroxyl group at both terminals Preferred are acrylates, unsaturated phenols, aromatic vinyl compounds, unsaturated carboxylic acid esters, macromonomers having a mono (meth) acryloyl group at the ends of the polymer molecular chain, and especially monosuccinic acid [2- (meth) acrylic acid. Yloxyethyl], 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 T) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like are preferable.

In polymer (B1), a compound (b3) can be used individually or in mixture of 2 or more types.

In addition, the polymer (B2) is a polymer of a radically polymerizable compound containing a compound represented by the following Chemical Formula 7-1 (hereinafter also referred to as "compound (b4)") (hereinafter also referred to as "styrene epoxy polymer") To the compound represented by the following formula (7-2) (hereinafter referred to as " unsaturated monocarboxylic acid (X) "), a compound represented by the following formula (7-3) (hereinafter referred to as “polybasic anhydride (y) It can be prepared by adding "."

<Formula 7-1>

^{(Wherein, R 6, R 7, R} 8 , and h is the R ^6, R ^7, R ⁸ and h and consent for Formula 7, respectively)

<Formula 7-2>

(Wherein X is synonymous with X in the formula (7))

<Formula 7-3>

(Wherein Y is synonymous with Y in the formula (7))

As a specific example of a compound (b4), o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, (alpha) -methyl-o-vinyl benzyl glycidy, Dil ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxy Methylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxy Methyl styrene, 2,3,6-triglycidyloxymethyl styrene, 3,4,5-triglycidyloxymethyl styrene, 2,4,6-triglycidyloxymethyl styrene, and the like. Of these compounds (b4), o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether are preferable, and p-vinyl benzyl glycidyl ether is particularly preferable. In a polymer (B2), a compound (b4) can be used individually or in mixture of 2 or more types.

In the styrene epoxy polymer, examples of the other radically polymerizable compound which is preferably copolymerized with the compound (b4) include the compound (b1), the compound (b2) and the compound (b3). In a styrene epoxy polymer, as a compound (b1) and a compound (b2), the compound similar to what was illustrated in the polymer (B1) is preferable. Moreover, in a styrene epoxy polymer, as a compound (b3), an aromatic vinyl compound, unsaturated carboxylic acid ester, macromonomers which have a mono (meth) acryloyl group in the terminal of a polymer molecular chain, etc. are preferable, especially 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, ethylene oxide modified (meth) acrylate of paracumylphenol, polystyrene macromonomer, polymethylmethacrylate macromonomer, etc. are preferable.

In the styrene epoxy polymer, the compound (b1), the compound (b2) and the compound (b3) may be used alone or in combination of two or more thereof.

A styrene epoxy polymer can be manufactured similarly to a polymer (B1), and its Mw and Mn can be suitably set according to Mw and Mn of desired (B) alkali-soluble resin.

The said unsaturated carboxylic acid (X) can be suitably selected according to the kind of desired X in the said General formula (7). Preferable unsaturated carboxylic acid (X) is acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, for example. And 2-methacryloyloxyethyl succinic acid are 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. In said unsaturated carboxylic acid (X), acrylic acid or methacrylic acid is more preferable because it is rich in reactivity, and acrylic acid is especially preferable.

Unsaturated carboxylic acid (X) can be used individually or in mixture of 2 or more types.

Addition reaction of unsaturated monocarboxylic acid (X) to the said styrene epoxy polymer can be performed according to a well-known method. It is preferable that it is the range of 0.7-1.3 equivalent with respect to 1 equivalent of epoxy groups of a styrene epoxy polymer, and, as for the usage-amount of unsaturated monocarboxylic acid (X), it is more preferable that it is 0.9-1.2 equivalent.

The said polybasic acid anhydride (y) can be suitably selected according to the kind of desired Y in the said General formula (7). As preferable polybasic acid anhydride (y), for example, malonic anhydride, maleic anhydride, citraconic acid, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, diglycolic anhydride, phthalic anhydride, cyclo Hexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, diphenic anhydride, etc. are mentioned. Among these, succinic anhydride, glutaric anhydride, phthalic anhydride, or 4-cyclohexene-1,2-dicarboxylic acid anhydride is particularly preferable because it is rich in reactivity.

Addition reaction of the polybasic acid anhydride (y) to a styrene epoxy polymer can be performed according to a well-known method. The addition amount of the polybasic acid anhydride (y) is preferably in the range of 0.2 to 1.0 equivalents, more preferably 0.4 to 0.9 equivalents relative to 1 equivalent of the epoxy group of the styrene epoxy polymer.

In this invention, a polymer (B1) and a polymer (B2) can be used individually or in mixture of 2 or more types, respectively. Moreover, as alkali-soluble resin, the copolymer of (meth) acrylic acid and the said compound (b3) can also be used with a polymer (B1) and / or a polymer (B2), for example.

In this invention, 10-1,000 weight part is preferable normally with respect to 100 weight part of (A) coloring agents, and, as for content of alkali-soluble resin, 20-500 weight part is especially preferable. In this case, when content of alkali-soluble resin is less than 10 weight part, alkali developability may fall, for example, residue or ground contamination may arise on the board | substrate or light-shielding layer of an unexposed part, and it exceeds 1,000 weight part When the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.

(C) monomers having two or more radically polymerizable unsaturated bonds

As a monomer which has two or more radically polymerizable unsaturated bonds in this invention (henceforth a "multifunctional monomer"), it is, for example

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 these dicarboxylic acid modified substances;

Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin;

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate

Isocyanurate ethylene oxide modified triacrylate, and the like.

Among these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tree Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, monoester of pentaerythritol triacrylate with succinic acid, monoester of pentaerythritol trimethacrylate with succinic acid, dipentaerythritol pentaacrylate with succinic acid Monoester, Dipentaerythritol pentamethacryl Monoesters of whey and succinic acid are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and pentaerythritol triacrylate are particularly preferred. Monoesters of and succinic acid and monoesters of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the substrate and the light shielding layer of the unexposed part. It is preferable in that contamination, film residues, etc. are difficult to occur.

The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

As for content of the (C) polyfunctional monomer in this invention, 5-500 weight part is preferable normally with respect to 100 weight part of (B) alkali-soluble resin, Especially 20-300 weight part is preferable. In this case, when content of a polyfunctional monomer is less than 5 weight part, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall, and when it exceeds 500 weight part, alkali developability will fall, for example, or the board | substrate of an unexposed part will be. Background contamination, film residues, and the like tend to be easily generated on the phase or the light shielding layer.

In addition, in this invention, a part of polyfunctional monomer can also be replaced by the monomer which has one radically polymerizable unsaturated bond (henceforth "monofunctional monomer").

Examples of the monofunctional monomer include monovalent monovalent polyvalent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl]. [(Meth) acryloyloxyalkyl] esters, mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate, N- (meth) In addition to acryloyl morpholine, N-vinylpyrrolidone, and N-vinyl- epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types. The content rate of a monofunctional monomer is 90 weight% or less normally, Preferably it is 50 weight% or less with respect to the sum total of a polyfunctional monomer and a monofunctional monomer. In this case, when the content rate of a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

-(D) radiation sensitive radical generator-

The radiation sensitive radical generator in the present invention initiates polymerization of the polyfunctional monomer and the monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. It is a compound that generates an active radical.

Examples of such radiation-sensitive radical generators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, benzoin compounds, α-diketone compounds, and the like.

In the present invention, the radiation-sensitive radical generator may be used alone or in combination of two or more thereof. Examples of the radiation-sensitive radical generator in the present invention include acetophenone compounds, biimidazole compounds, and triazine compounds. At least one selected from the group consisting of compounds and O-acyl oxime compounds is preferable.

In this invention, the general content of a radiation sensitive radical generating agent is 0.01-120 weight part normally with respect to 100 weight part of (C) polyfunctional monomers, Preferably it is 1-100 weight part. In this case, when content of a radiation sensitive radical generating agent is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, and it is 120 weight When the portion is exceeded, the formed colored layer tends to fall off the substrate during development.

As a specific example of an acetophenone type compound among the preferable radiation sensitive radical generators in this invention, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methyl Benzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane -1-one, 1,2-octanedione, etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1,2-octanedione, etc. desirable.

The acetophenone compounds may be used alone or in combination of two or more thereof.

In the present invention, the content in the case of using an acetophenone-based compound as the radiation-sensitive radical generator is preferably 0.01 to 80 parts by weight, particularly preferably 1 to 100 parts by weight of the (C) polyfunctional monomer. To 70 parts by weight, more preferably 1 to 60 parts by weight. In this case, when content of an acetophenone type compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, while exceeding 80 weight part The colored layer formed on the lower surface tends to fall off from the substrate during development.

Moreover, as a specific example of the said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1 , 2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-ratio Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 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, etc. are 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 preferred, in particular 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl -1,2'-biimidazole is preferred.

These biimidazole-based compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved products and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure of a small amount of energy. Since no curing reaction occurs, the coating film after exposure is clearly divided into an insoluble hardened portion with respect to the developer and an uncured portion with high solubility with the developer, whereby a colored layer pattern without undercut is placed in a predetermined arrangement. Therefore, the high precision fine color filter arrange | positioned can be formed.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

In the present invention, the content in the case of using a biimidazole-based compound as the radiation-sensitive radical generator is preferably 0.01 to 40 parts by weight, particularly preferably 100 parts by weight of the total (C) polyfunctional monomer. Is 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, when content of a biimidazole type compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, and it is 40 weight When it exceeds a part, when developing, there exists a tendency which becomes easy to induce dropping from the board | substrate of the formed colored layer and film | membrane roughness of the colored layer surface.

In this invention, when using a biimidazole type compound as a radiation sensitive radical generator, using the hydrogen donor mentioned below together is preferable at the point which can improve a sensitivity further.

The "hydrogen donor" as used here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As a hydrogen donor in this invention, a mercaptan type compound, an amine compound, etc. which are defined below are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, &Quot; mercaptan-based hydrogen donors ").

The amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, 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 may also have a mercapto group and an amino group at the same time.

The hydrogen donor will be described in more detail below.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, a condensed ring may or may not be formed. .

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group, In addition, as long as at least one free mercapto group remains, it may have a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or a structural unit in which two sulfur atoms are bound in the form of disulfide.

The mercaptan-based hydrogen donor may be substituted by 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 position other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, and 2,5-dimercapto-1,3,4- Thiadiazole, 2-mercapto-2,5-dimethylaminopyridine, and the like.

Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, it may or may not form a condensed ring. have.

In addition, the amine-based hydrogen donor may be substituted with at least one amino group by an alkyl group or a substituted alkyl group, and at a position other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, nitrile group or the like. It may be substituted by.

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropy. Phenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzo is particularly preferred. Phenones are preferred.

The amine hydrogen donor also has a function as a sensitizer even in the case of radical generators other than the biimidazole compound.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof, but the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors may be used when developing the colored layer. It is difficult to drop off from the substrate, and is preferable in that the colored layer strength and sensitivity are also high.

Specific examples of the combination of the mercaptan-based hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4 '-Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino Benzophenone, and the like, and more preferred combinations include 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzooxazole / 4,4'-bis ( Diethylamino) benzophenone and a particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The weight ratio of the mercaptan-based hydrogen donor and the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

In this invention, content when using a hydrogen donor together with a biimidazole type compound becomes like this. Preferably it is 0.01-40 weight part, More preferably, 1-30 with respect to 100 weight part of (C) polyfunctional monomers in total. Parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the content of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the content of the hydrogen donor exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

The amine hydrogen donor can function as a sensitizer when used in combination with a radiation sensitive radical generator other than nonimidazole compounds such as acetophenone compounds. When using an amine hydrogen donor as a sensitizer, the content is preferably 300 parts by weight or less, particularly preferably 200 parts by weight, relative to 100 parts by weight of the radiation-sensitive radical generator other than the biimidazole compound. Hereinafter, although it is more preferably 100 parts by weight or less, since such a content is too small, sufficient effects are difficult to be obtained. Therefore, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight.

In addition, specific examples of the triazine-based 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 (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl And triazine-based compounds having halomethyl groups, such as) -4,6-bis (trichloromethyl) -s-triazine.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.

The said triazine type compound can be used individually or in mixture of 2 or more types.

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, more preferably 1 to 1 to 100 parts by weight of the (C) polyfunctional monomer. 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when content of a triazine type compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, and when it exceeds 40 weight part There exists a tendency for the formed colored layer to fall easily from a board | substrate at the time of image development.

As specific examples of the O-acyl oxime compound, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl] -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-carbazole- 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-Methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-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- Onoxime-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.

Among these O-acyl oxime compounds, in particular, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyl oxime), 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-acyl oxime compounds may be used alone or in combination of two or more thereof.

In the present invention, the content in the case of using an O-acyl oxime compound as the radiation sensitive radical generator is preferably 0.01 to 80 parts by weight, more preferably to 100 parts by weight of the (C) polyfunctional monomer. Is 1 to 60 parts by weight, particularly preferably 1 to 50 parts by weight. In this case, when content of an O-acyl oxime type compound is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the colored layer pattern was arrange | positioned according to a predetermined | prescribed arrangement, and it is 80 weight When the portion is exceeded, the formed colored layer tends to fall off the substrate during development.

(E) component-

The component (E) in the present invention is a compound 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, defect, peeling, and undercut of a pattern do not generate | occur | produce at the time of image development, and it can suppress that pattern line width is thicker than the design dimension of a photomask in proximity exposure.

In the compound represented by the formula (1), the group A in the formula is preferably -CO- group, methylene group or isopropylidene group. Moreover, as R <^1> , a hydrogen atom or a C4 or less alkyl or alkoxy group is preferable.

As a specific example of the compound represented by the said Formula (1), for example

As (polyhydroxy) benzophenones, 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 and the like;

As bis (hydroxyphenyl) alkane, bis (p-hydroxyphenyl) methane etc .;

As bis (polyhydroxyphenyl) alkanes, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4 -Trihydroxyphenyl) propane etc. are mentioned.

In the compound represented by 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 preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

As a specific example of the compound represented by the said Formula (2), 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 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.

As a specific example of the compound represented by the said Formula (3), for example

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane etc. are mentioned.

In the compound represented by the formula (4), R ¹ is preferably a hydrogen atom in the formula, and R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

As a specific example of the compound represented by the said Formula (4), for example

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol etc. are mentioned.

In the compound represented by the above formula (5), R ¹ is preferably a hydrogen atom in the formula, and R ² , R ³ , or R ⁴ is preferably a hydrogen atom or an alkyl group having 6 or less carbon atoms.

As a specific example of the compound represented by the said Formula (5), 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 etc. are mentioned.

As a specific example of the phenolic compound which has the said flavan skeleton, it is, for example

2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2,4,4-trimethyl-7,2 ', 4'- Trihydroxy flavan etc. are mentioned.

As a specific example of the phenolic compound which has the said spirobiindane frame | skeleton, it is 3,3,3 ', 3'- tetramethyl- 1,1'- spirobiindane-5,6,7,5', 6 ', 7'- hexanol etc. are mentioned.

As a specific example of the phenolic compound which has the said spirobiindene frame | skeleton, it is 3,3'- dimethyl- 1,1'-spirobiindene-5,6,7,5 ', 6', 7'-, for example. Hexanol and the like.

Among these compounds, compounds represented by (polyhydroxy) benzophenones, compounds represented by the above formula (4), and phenolic compounds having a flavan skeleton are preferred, and 2,3,4-trihydroxybenzophenone and 2 , 3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone, 4,4'-[1- [4- [1- [4-hydroxy Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychromeman Particularly preferred.

In this invention, content of (E) component becomes like this. Preferably it is 0.1-10 weight part, More preferably, it is 1-5 weight part, Especially preferably 1-3 with respect to 100 weight part of (B) alkali-soluble resin. Parts by weight. In this case, when content of (E) component is less than 0.1 weight part, there exists a possibility that a desired effect may not be acquired. On the other hand, when it exceeds 10 weight part, there exists a tendency for the formed pattern to fall easily from a board | substrate at the time of image development.

-additive-

Although the radiation sensitive composition of this invention contains the said (A)-(E) component, it may further contain other additives as needed.

As said other additive, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) s; Surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; And alkali solubility improving agents such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

menstruum

Although the radiation sensitive composition for colored layer formation of this invention makes the said (A)-(E) component an essential component, and contains the said additive component as needed, it is normally manufactured as a liquid composition by mix | blending a solvent.

The solvent may be appropriately selected and used as long as it disperses or dissolves the components (A) to (E) and the additive component constituting the radiation-sensitive composition, and does not react with these components and has suitable volatility.

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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether;

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 (Poly) alkylene glycol monoalkyl ether acetates, such as these;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 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 Methyl hydroxy-3-methylbutane, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, 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-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxybutyl acetate from the viewpoint of solubility, pigment dispersibility, and applicability. , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxy propionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionic acid Ethyl, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n -Butyl, ethyl pyruvate, etc. are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Although content of a solvent is not specifically limited, From a viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition is normally 5-50 weight% normally, Especially 10-10 The amount which becomes 40 weight% is preferable.

Color filter

The color filter of this invention is equipped with the colored layer formed from the radiation sensitive composition for colored layer formation of this invention.

Below, the method of forming the color filter of this invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a portion for forming a pixel, if necessary, and then, for example, a liquid composition of a radiation-sensitive composition in which a red pigment is dispersed is applied to the substrate. Prebaking is carried out to evaporate the solvent to form a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes to form the pixel array in which the red pixel pattern was arrange | positioned in the predetermined | prescribed arrangement.

Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is applied, prebaked, exposed to light, developed and postbaked in the same manner as described above, and the green pixel array and By sequentially forming a blue pixel array on the same substrate, a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on the substrate is obtained. However, in this invention, the order which forms the pixel of each color is not limited to the said thing.

In addition, a black matrix can be formed similarly to the case of formation of the said pixel using the radiation sensitive composition for colored layer formation of this invention.

As a board | substrate used when forming a pixel and / or a black matrix, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

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, vapor phase reaction, vacuum deposition, or the like as desired.

When the liquid composition of the radiation sensitive composition is applied to a substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating or inkjet may be employed. In particular, the spin coating method and the slit die coating method are preferable.

The coating thickness is a film thickness after drying, which is usually 0.1 to 10 µm, preferably 0.2 to 8.0 µm, particularly preferably 0.2 to 6.0 µm.

As radiation used for forming the pixel and / or black matrix, for example, visible rays, ultraviolet rays, ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. Do.

The exposure amount of radiation becomes like this. Preferably it is 10-10,000 J / m <2>.

Moreover, as said alkaline developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8- diazabicyclo- [5.4.0] -7-undecene, 1,5 Aqueous solutions, such as -diazabicyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali image development, it washes with water normally.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

The color filter of this invention obtained in this way is very useful for a highly precise color liquid crystal display element, a color imaging tube element, a color sensor, etc.

Color liquid crystal display element

The color liquid crystal display element of this invention is equipped with the color filter of this invention.

Moreover, as one Embodiment of the color liquid crystal display element of this invention, using the radiation sensitive composition for colored layer formation of this invention, a pixel and / or a black matrix are formed as mentioned above on a thin film transistor substrate array. By doing this, a highly precise color liquid crystal display element can be manufactured especially.

<Example 1>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

Mw and Mn of resin obtained by each following synthesis example were measured by the gel permeation chromatography (GPC) by the following specification.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.).

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.

Elution solvent: tetrahydrofuran comprising 0.5% by weight phosphoric acid.

Synthesis of Alkali Soluble Resin

Synthesis Example 1

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and N-phenylmaleimide. 30 parts by weight, 30 parts by weight of benzyl methacrylate, 20 parts by weight of styrene, and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent were added thereto, followed by nitrogen replacement, and then the reaction solution was stirred at 80 ° C. with gentle stirring. It heated up and maintained at this temperature and superposed | polymerized for 3 hours. After adding 0.5 weight part of 2,2'- azobisisobutyronitrile, and also superposing | polymerizing for 1 hour, heating up at 100 degreeC and continuing superposition | polymerization for 1 hour, resin solution (solid content concentration = 33.0 weight%) Got. Obtained resin was Mw = 9,500 and (Mw / Mn) = 2.0. This resin is referred to as "resin (B-1)".

Synthesis Example 2

4 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and N-phenylmaleimide. 20 parts by weight, 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 α-methylstyrene which is a chain transfer agent as a molecular weight control agent. 6 weight part of sieves were added, and after nitrogen substitution, the reaction solution was heated to 80 ° C. with gentle stirring, and maintained at this temperature to polymerize for 3 hours. After adding 0.5 weight part of 2,2'- azobisisobutyronitrile, and also superposing | polymerizing for 1 hour, heating up at 100 degreeC and continuing superposition | polymerization for 1 hour, resin solution (solid content concentration = 33.0 weight%) Got. Obtained resin was Mw = 7,500 and (Mw / Mn) = 2.1. This resin is referred to as "resin (B-2)".

Synthesis Example 3

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and 30 parts by weight of acenaphthylene. Parts, 40 parts by weight of benzyl methacrylate, 10 parts of glycerol monomethacrylate, 5 parts by weight of ω-carboxypolycaprolactone monoacrylate and 5 parts by weight of α-methylstyrene dimer as a chain transfer agent as a molecular weight control agent, After nitrogen replacement, the reaction solution was heated to 80 ° C. with gentle stirring, and maintained at this temperature to polymerize for 3 hours. After adding 0.5 weight part of 2,2'- azobisisobutyronitrile, and also superposing | polymerizing for 1 hour, heating up at 100 degreeC and continuing superposition | polymerization for 1 hour, resin solution (solid content concentration = 33.0 weight%) Got. Obtained resin was Mw = 11,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-3)".

Synthesis Example 4

3 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and N-phenylmaleimide. 25 parts by weight, 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 α-methylstyrene as a chain transfer agent as a molecular weight control agent 5 weight part of sieves were added, nitrogen-substituted, the reaction solution was heated up to 80 degreeC with gentle stirring, and it maintained this temperature and superposed | polymerized for 3 hours. After adding 0.5 weight part of 2,2'- azobisisobutyronitrile, and also superposing | polymerizing for 1 hour, heating up at 100 degreeC and continuing superposition | polymerization for 1 hour, resin solution (solid content concentration = 33.0 weight%) Got. Obtained resin was Mw = 10,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-4)".

Synthesis Example 5

4 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monoethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of methacrylic acid and 30 parts by weight of acenaphthylene. , 35 parts by weight of benzyl methacrylate, 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 added thereto, and after nitrogen replacement, the reaction solution was stirred at 80 ° C. with gentle stirring. It heated up and maintained at this temperature and superposed | polymerized for 3 hours. After adding 0.5 weight part of 2,2'- azobisisobutyronitrile, and also superposing | polymerizing for 1 hour, heating up at 100 degreeC and continuing superposition | polymerization for 1 hour, resin solution (solid content concentration = 33.0 weight%) Got. Obtained resin was Mw = 12,000 and (Mw / Mn) = 2.2. This resin is referred to as "resin (B-5)".

Synthesis Example 6

40 parts by weight of p-vinylbenzyl glycidyl ether, 27 parts by weight of N-phenylmaleimide, 17 parts by weight of styrene and 16 parts by weight of benzyl methacrylate in a flask equipped with a cooling tube and a stirrer 300 parts by weight of propylene glycol monomethyl ether acetate 4 parts by weight of 2,2'-azobisisobutyronitrile and 6 parts by weight of α-methylstyrene dimer were added thereto, followed by nitrogen purging for 15 minutes. After nitrogen purging, the reaction vessel was heated to 80 ° C while stirring and reacted for 5 hours to obtain a resin solution containing 25% by weight of styrene epoxy resin. This styrene epoxy resin was Mw = 6,000 and (Mw / Mn) = 2.5.

200 parts by weight of the resin solution containing the obtained styrene epoxy resin, 10 parts by weight of methacrylic acid as unsaturated monocarboxylic acid (X), 0.2 parts by weight of p-methoxyphenol, 0.2 parts by weight of tetrabutylammonium bromide and propylene glycol monomethyl 300 parts by weight of ether acetate was placed in a flask and reacted at a temperature of 120 ° C. for 9 hours. Thereby, 1 equivalent of methacrylic acid reacted with respect to 1 equivalent of epoxy groups of the styrene epoxy resin. Further, 16 parts by weight of 4-cyclohexene-1,2-dicarboxylic acid anhydride as polybasic acid anhydride (y) was added and reacted at 80 ° C for 6 hours. About this reaction mixture, the resin solution containing 20 weight% of alkali-soluble resin was obtained by washing twice with the liquid temperature at 80 degreeC, and concentrating under reduced pressure. Obtained resin was Mw = 7,800 and (Mw / Mn) = 2.6. This resin is referred to as "resin (B-6)".

Preparation of Pigment Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 177 = 80/20 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Dispervic-2001 as a dispersant (solid content), (B) 6 parts by weight (B-1) as the alkali-soluble resin (solid content) ) And 75 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to prepare a pigment dispersion (r).

Preparation Example 2

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 138 / C.I. Pigment Yellow 150 = 50/40/10 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Dispervic-2001 as a dispersant (solid content), (B) 5 parts by weight of (B-2) as the alkali-soluble resin ( Solid content conversion) and 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated in the same manner as in Example 1 to prepare a pigment dispersion (g).

Preparation Example 3

(A) As a coloring agent, C.I. Pigment Blue 15: 6 / C.I. Pigment Violet 23 = 95/5 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Dispervic-2001 as a dispersant (solid content), (B) 5 parts by weight (B-2) as the alkali-soluble resin (solid content) ) And 76 parts by weight of propylene glycol monomethyl ether acetate as a solvent were treated in the same manner as in Example 1 to prepare a pigment dispersion (b).

Preparation Example 4

(A) 20 parts by weight of carbon black (manufactured by Mikuni Shikiso Co., Ltd.) as a colorant, 2 parts by weight of Dispervic-2001 as a dispersant (solid equivalent), and (B) 4 parts by weight of (B-3) as an alkali-soluble resin. 74 parts by weight of 3-methoxybutyl acetate as a part (solid content conversion) and a solvent were treated in the same manner as in Example 1 to prepare a pigment dispersion (bk1).

Preparation Example 5

(A) 20 parts by weight of carbon black (manufactured by Mikuni Shikiso Co., Ltd.) as a coloring agent, 2 parts by weight of Dispervic-167 as a dispersant (solid content conversion), and (B) 3 parts by weight of (B-3) as an alkali-soluble resin. A pigment dispersion (bk2) was prepared by treating 75 parts by weight of 3-methoxybutyl acetate as a part (solid content conversion) and a solvent in the same manner as in Example 1.

Example 1

Preparation of Liquid Composition

100 parts by weight of the pigment dispersion (r), (B) 6 parts by weight of the resin (B-4) (solid content conversion) as the alkali-soluble resin, (C) 8 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D ) 3 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photoinitiator, (E) component 0.15 parts by weight of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol as 150 parts by weight of ethyl 3-ethoxypropionate, 25 parts by weight of propylene glycol monomethyl ether acetate was mixed to prepare a liquid composition for forming a colored layer (R1).

The liquid composition (R1) was evaluated according to the following procedure. The evaluation results are shown in Table 2 below.

Formation of patterns

After apply | coating a liquid composition (R1) on the surface of a glass substrate using a spin coater, it prebaked at 90 degreeC for 2 minutes, and formed the coating film of 2.5 micrometers in thickness. Then, this board | substrate was cooled to room temperature, the high pressure mercury lamp was used for the coating film on the board | substrate, and the exposure gap was 200 micrometers through the photomask, and it exposed at the exposure amount of 1,000 J / m <2>. Thereafter, a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. was discharged at a developing pressure of 2 kgf / cm 2 (nozzle diameter of 1 mm) to the coating film on the substrate. A pixel array in which red line and space (L / S) patterns were arranged on a substrate was formed.

evaluation

When the pixel array on the board | substrate was observed with the optical microscope, the defect was not found in the edge of a pixel pattern. In addition, when the cross section of the pixel pattern on the board | substrate was observed with the scanning electron microscope (SEM), the undercut was not found. It was 93.0 micrometers when the line width of the pixel pattern formed through the photomask of 90 micrometers of slit widths was measured with the optical microscope.

Examples 2 to 17 and Comparative Examples 1 to 6

In Example 1, except having changed the kind and quantity of components as shown in Table 2, it carried out similarly to Example 1, and liquid composition (R2)-(R3), (G1)-(G3), ( B1) to (B3) and (BK1) to (BK14) were prepared.

Subsequently, except for using liquid compositions (R2) to (R3), (G1) to (G3), (B1) to (B3), (BK1) to (BK14), respectively, instead of the liquid composition (R1), Evaluation was performed similarly to 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 (brand name M-315, Toagosei Co., Ltd. make)

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-morpholinopropane-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 Chemicals Co., Ltd.)

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 (brand name A-60, manufactured by Cao Co., Ltd.)

F-3: polymerization inhibitor phenothiazine

EEP: 3-Ethoxy Propionate

PGMEA: propylene glycol monomethyl ether acetate

MBA: 3-methoxybutyl acetate

Industrial availability

The radiation sensitive composition containing (E) component of this invention is excellent in adhesiveness with a board | substrate even when content of the coloring agent contained in a radiation sensitive composition is high, has a high precision fine and excellent pattern shape, and exposes proximity Also in the pixel, a pixel and a black matrix in which the pattern line width is not thickened can be formed.

Therefore, the radiation sensitive composition of this invention can be used very suitably for manufacture of various color filters, including the color filter for color liquid crystal display devices in the electronic industry, and the color filter for color separation of a solid-state image sensor.

Claims (7)

(A) a coloring agent, (B) alkali-soluble resin, (C) the monomer which has a 2 or more radically polymerizable unsaturated bond, (D) a radiation sensitive radical generator, and (E) the compound represented by following formula (1), Persimmon for forming a colored layer, characterized by containing at least one compound selected from the group consisting of a phenolic compound having a flavane skeleton, a phenolic compound having a spirobiindane skeleton, and a phenolic compound having a spirobiindene skeleton Radioactive composition. <Formula 1> [In 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, and a plurality of R ¹ 's are the same as each other, or And Z may represent an alkoxyalkyl group, a cyclic ether group, a vinyloxyalkyl group or a t-alkoxycarbonylalkyl group, and a plurality of Z's 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 Group (wherein k is an integer of 0 to 4), R ² and R ³ may be the same or different from each other, a hydrogen atom, an alkyl group of 6 or less carbon atoms, an acyl group of 6 or less carbon atoms, a phenyl group or a naphthyl group Or a-(CH ₂ ) x-COOZ group, m, n, p and q are integers greater than or equal to 0 and satisfy a relationship of m + n ≦ 5, p + q ≦ 5 and n + q ≧ 1] <Formula 2> [In the formula 2, R ¹ represents a group the same as R ¹ of formula 1, R ⁴ is represents the same groups as R ² of formula 1, m, n, p, q, r and s are an integer of 0 or more, m satisfies the relationship of + n ≦ 5, p + q ≦ 5, r + s ≦ 5, n + q + s ≧ 1] <Formula 3> [In the formula 3, R ¹ represents a group the same as R ¹ of formula I, R ⁴ is represents a group the same as R ² of formula (I), two R ⁴ may be the same as or different from each other, A is the formula (I) Represents the same group as A, and m, n, p, q, r, s, t and u are integers greater than or equal to 0, m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, n + q + s + u≥1 is satisfied.] <Formula 4> [In the formula 4, R ¹ represents a group the same as R ¹ of formula 1, R ^2, R ³ and R ⁴ each represent the same group with the general formula (I) of R ^2, R ³ and R ⁴ of formula 2, m, n, p, q, r, s, t and u are integers greater than or equal to 0, m + n ≦ 5, p + q ≦ 5, r + s ≦ 5, t + u ≦ 4, n + q + s + u Satisfying a relationship of ≥1] <Formula 5> [Wherein, R ¹ , R ² and R ³ is R ¹ , R ² and Represents the same group as R ^3, and m, n, p, q, r and s are integers of 0 or more, and m + n ≦ 5, p + q ≦ 4, r + s ≦ 5 and n + q + s ≧ 2. Satisfying the relationship, and l represents an integer of 1 to 5] The radiation sensitive composition for coloring layer formation of Claim 1 whose content of (E) component is 0.1-10 weight part with respect to 100 weight part of (B) alkali-soluble resin. (B) At least 1 sort (s) chosen from the group which consists of a polymer which has a repeating unit represented by following formula (6) as a alkali-soluble resin, and a polymer which has a repeating unit represented by following formula (7). The radiation sensitive composition for colored layer formation containing the above. <Formula 6> (Wherein R ⁵ represents a hydrogen atom or a methyl group) <Formula 7> (In formula, R <^6> , R <^7> and R <^8> respectively independently represents a hydrogen atom or a C1-C10 alkyl group, X is a monovalent organic group, vinyl group, or 1- which has acryloyl group or methacryloyl group. Methylvinyl group, Y represents a divalent organic group, h represents an integer of 1 to 5) The polymer (B) according to claim 3, further comprising (B) an alkali-soluble resin further comprising a polymer having at least one repeating unit selected from the group consisting of repeating units represented by the following formula (8) and repeating units represented by the following formula (9): Radiation sensitive composition for colored layer formation. <Formula 8> (Wherein 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) <Formula 9> (Wherein R ¹⁰ to R ¹⁵ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group or a carboxyl group) The radiation sensitive composition of any one of Claims 1-4 whose content of (A) coloring agent is 30 to 60 weight% in total solid. The color filter which has a colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-5. The color liquid crystal display element provided with the color filter of Claim 6.