KR20070103036A - Radiation-sensitive resin composition and color filter - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition containing a coloring agent, an alkali-soluble resin, a polyfunctional monomer and a radiation-sensitive radical generator. The alkali-soluble resin is produced by living radical polymerization of a polymerizable unsaturated compound, and has a weight average molecular weight (Mw) of 1,000-45,000 in terms of polystyrene as determined by gel permeation chromatography. A color filter which does not suffer from image burn-in can be produced from this radiation-sensitive resin composition with high production yield.

Description

Radiation-sensitive resin composition and color filter {RADIATION-SENSITIVE RESIN COMPOSITION AND COLOR FILTER}

The present invention comprises a radiation sensitive resin composition useful for the production of color filters used in a transmissive or reflective color liquid crystal device, a color image tube element, and the like, a method for producing the same, a color filter formed from the radiation sensitive resin composition, and the color filter. It relates to a color liquid crystal display device.

As a method of forming a color filter using a colored radiation-sensitive resin composition, a photo film having a desired pattern shape is formed by forming a coating film of a colored radiation-sensitive resin composition on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance. A method of obtaining pixels of each color by irradiating radiation through a mask (hereinafter referred to as "exposure"), developing with an alkaline developer, dissolving and removing unexposed portions, and then postbaking using a clean oven or hot plate. (See Japanese Patent Laid-Open No. 2000-329929 and Japanese Patent No. 3639859).

Since the size of the substrate used for forming the color filter has been increased in recent years, the liquid projecting portion for applying the radiation-sensitive resin composition is more suitable from the method in which the method of applying the radiation-sensitive resin composition employs a central dropping spin coater. It is being replaced by using a smaller diameter slit nozzle. In the latter slit nozzle method, since the diameter of the liquid protrusion is small and narrow, the radiation-sensitive resin composition is often left in the vicinity of the nozzle tip after the completion of coating. When it dries, since it falls on a color filter as a dry foreign material at the next application | coating, and the quality of a color filter will fall remarkably, jet cleaning is performed by spraying a cleaning solvent to a nozzle front part before application | coating normally. Nevertheless, deterioration of the quality of the color filter due to dry foreign matters cannot be effectively prevented, which is a major factor in decreasing product yield.

Therefore, in order to cope with such a problem, the radiation-sensitive resin composition for color filters which is high in the solubility with the washing | cleaning solvent after washing | cleaning, ie, even after drying in recent years, is calculated | required.

In addition, in recent years, the liquid crystal display device having a color filter is required to increase the lifespan, and accordingly, there is an increasing demand for the ability to prevent "burn out" of the color filter.

"Small" is a kind of display defect of a liquid crystal display device, in which an image that should not be displayed on the screen is displayed on the screen, or a black or white "fog" shape is displayed superimposed on the image to be displayed. This phenomenon is thought to be due to the diffusion of the charged impurities in the liquid crystal into the liquid crystal and the potential difference applied to align the liquid crystal molecules is not maintained for a certain period of time. It has recently been found to elute from among the formed color filters.

As described in Japanese Unexamined Patent Publication No. 2000-329929, it is known that it is effective to increase the pigment purity. However, impurities may be derived from components other than the pigment in the radiation-sensitive resin composition, Raising the pigment purity is not necessarily enough.

Therefore, the development of the radiation sensitive resin composition for color filters which does not generate | occur | produce "baking" while satisfying the demand of the high product yield at the time of recent color filter manufacture is strongly demanded.

An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a color filter that does not generate "baking" with a high product yield.

Another object of the present invention is to provide a method for producing the radiation-sensitive resin composition.

Still another object of the present invention is to provide a color filter having no burnout formed from the radiation-sensitive resin composition and a color liquid crystal display device including the filter.

The above objects and advantages of the present invention firstly,

(A) A radiation sensitive resin composition containing a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation-sensitive radical generator, (B) alkali-soluble resin is a polymerizable unsaturated compound It is produced by living radical polymerization, and it is achieved by the radiation sensitive resin composition characterized by the polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) being 1,000-45,000 resin.

The above objects and advantages of the present invention are secondly a radiation-sensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a radiation-sensitive radical generator, B) The polystyrene reduced weight average molecular weight (Mw) which alkali-soluble resin has group represented by general formula (I) or group represented by general formula (ii) mentioned later on at least one terminal of the polymer chain which comprises this, and it measured by the gel permeation chromatography. It is achieved by the radiation sensitive resin composition characterized by these being 1,000-45,000.

Third, the above object and advantage of the present invention is that (A) the colorant is a pigment, and the pigment dispersion obtained by mixing and dispersing the pigment while grinding in the presence of a dispersant in a solvent (B) alkali-soluble resin, (C) polyfunctionality It is achieved by the manufacturing method of the said radiation sensitive resin composition characterized by mixing with a monomer and (D) radiation sensitive radical generator.

Fourth, the above object and advantages of the present invention,

It is achieved by the said radiation sensitive resin composition (henceforth "the radiation sensitive resin composition for color filters") used for color filters.

Fifth, the above objects and advantages of the present invention are achieved by a color filter formed from a radiation sensitive resin composition for a color filter.

Sixth, the above objects and advantages of the present invention are achieved by a color liquid crystal display device comprising the color filter.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Radiation  Resin composition

-(A) colorant-

The coloring agent in this invention is not specifically limited, It may be any of a pigment, dye, or a natural pigment. Since a color filter is high purity, and high light transmittance color development and heat resistance are calculated | required, a pigment is preferable and especially an organic pigment or carbon black is preferable.

As said organic pigment, the compound classified by the pigment in the color index, for example, the thing of which the following color index (C.I.) numbers are given is mentioned.

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 Brown 23, C.I. Pigment brown 25;

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

Among these organic pigments, C.I. Pigment Yellow 83, C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment green 36; C.I. Pigment Violet 23, C.I. Pigment Blue 60 or C.I. Pigment Blue 80 is preferred.

The said organic pigment can be used individually or in mixture of 2 or more types, and can also mix and use an organic pigment and carbon black.

In this invention, a radiation sensitive resin composition can be manufactured by a suitable method. In the case of using a pigment as a colorant, the pigment is mixed and dispersed in the solvent in the presence of a dispersant, for example, using a bead mill, a roll mill, or the like, to obtain a pigment dispersion, which is to be described later. It is preferable to manufacture by adding and mixing a component, (D) component, and the additional solvent and other additive mentioned later as needed.

As a dispersant used in the preparation of the pigment dispersion, an appropriate dispersant such as cationic, anionic, nonionic or amphoteric can be used, but a compound having a urethane bond (hereinafter referred to as "urethane-based dispersant") The dispersant which contains is preferable.

The urethane-based dispersant is, for example, the formula R-NH-COO-R '(wherein R and R' is a monovalent or polyvalent organic group of aliphatic, alicyclic or aromatic, the polyvalent organic group is another urethane bond Bound to another group or to other groups). That is, the urethane bond may be present in the lipophilic group and / or hydrophilic group in the urethane-based dispersant, may also be present in the main and / or side chains of the urethane-based dispersant, and may also be present in one or more of the urethane-based dispersant. When two or more urethane bonds are present in the urethane-based dispersant, the groups to which each urethane bond is bonded may be the same or different.

As such a urethane type dispersing agent, the reaction product of diisocyanate and / or triisocyanate, the polyester which has a hydroxyl group at one terminal, and / or the polyester which has a hydroxyl group at both terminal is mentioned, for example.

As said diisocyanate, For example, benzene diisocyanate, such as benzene-1, 3- diisocyanate and benzene-1, 4- diisocyanate; Toluene diisocyanate such as toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,5-diisocyanate; 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-di Other aromatic diisocyanates such as isocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2,5-diisocyanate, and xylene diisocyanate such as 1,4-xylene-2,6-diisocyanate Isocyanate etc. are mentioned.

Moreover, as said triisocyanate, For example, benzene triisocyanate, such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3,5-triisocyanate; Toluene triisocyanates such as toluene-2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate; 1,2-xylene-3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene -2,4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate, 1,4-xylene-2,3,5-triisocyanate, 1,4-xylene-2,3, Other aromatic triisocyanate, such as xylene triisocyanate, such as 6-triisocyanate, etc. are mentioned.

These diisocyanate and triisocyanate can be used individually or in mixture of 2 or more types, respectively.

Examples of the polyester having a hydroxyl group at one end and the polyester having a hydroxyl group at both ends include, for example, polycaprolactone having a hydroxyl group at one end or both ends, polyvalerolactone having a hydroxyl group at one end or both ends, Polylactone having a hydroxyl group at one or both ends, such as polypropiolactone having a hydroxyl group at one or both ends; And polycondensed polyesters having a hydroxyl group at one or both ends, such as polyethylene terephthalate having a hydroxyl group at one or both ends, and polybutylene terephthalate having a hydroxyl group at one or both ends.

The polyester which has a hydroxyl group at these one terminal, and the polyester which has a hydroxyl group at both terminal can be used individually or in mixture of 2 or more types, respectively.

As the urethane-based dispersant in the present invention, a reaction product of an aromatic diisocyanate with a polylactone having a hydroxyl group at one end and / or a polylactone having a hydroxyl group at both ends is preferable, and particularly has a toluene diisocyanate and a hydroxyl group at one end. Preference is given to reaction products with polycaprolactone and / or polycaprolactone having hydroxyl groups at both ends.

As a specific example of such a urethane-based dispersant, Disperbyk 161, Disperbyk 170 (above, manufactured by BYK Corporation), EFKA (manufactured by EFKA Corporation, Inc.), and disparon (formerly, for example) The thing of series, such as the Sumitoga Kasei Co., Ltd. product, is mentioned.

The polystyrene reduced weight average molecular weight (Mw) measured by GPC of the urethane-based dispersant in the present invention is preferably 5,000 to 50,000, more preferably 7,000 to 20,000.

The urethane-based dispersants may be used alone or in combination of two or more thereof.

Moreover, the (meth) acrylic-type dispersing agent containing the (co) polymer of a (meth) acrylic-type monomer is also preferable as a dispersing agent.

As a specific example of such a (meth) acrylic-type dispersing agent, Disperbyk 2000, Disperbyk 2001 (above, the Big Chemical Co., Ltd. product) etc. are mentioned.

The said (meth) acrylic-type dispersing agent can be used individually or in mixture of 2 or more types.

The amount of the dispersant used in preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, particularly preferably 10 based on 100 parts by weight of the pigment. To 50 parts by weight. In this case, when the usage-amount of a dispersing agent exceeds 100 weight part, there exists a possibility that developability etc. may be impaired.

Moreover, as a solvent used when manufacturing a pigment dispersion liquid, the same thing as the solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later is mentioned, for example.

The amount of the solvent used when preparing the pigment dispersion is preferably 500 to 1,000 parts by weight, more preferably 700 to 900 parts by weight based on 100 parts by weight of the pigment.

In the production of the pigment dispersion, when producing by using a bead mill, for example, using a glass bead, titania bead or the like of about 0.5 to 10 mm in diameter, and preferably a pigment mixture containing a pigment, a solvent and a dispersant The mixture can be mixed and dispersed while cooling with cooling water or the like.

In this case, the filling rate of the beads is preferably 50 to 80% of the mill capacity, and the injection amount of the pigment mixed liquid is preferably about 20 to 50% of the mill capacity. In addition, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

In addition, when manufacturing using a roll mill, it can process, for example, using a triaxial roll mill, a biaxial roll mill, etc., cooling a pigment mixture liquid with cooling water etc. preferably.

In this case, it is preferable that a roll space | interval is 10 micrometers or less, and a shear force becomes like this. Preferably it is about 10 ⁸ dyn / sec. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

-(B) alkali-soluble resin-

Alkali-soluble resins in the present invention are produced through living radical polymerization of a polymerizable unsaturated compound, and have a resin having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 45,000 as measured by gel permeation chromatography (GPC). Resin (B) ".

Resin (B) acts as a binder with respect to (A) pigment, and when it manufactures a color filter, it is preferable to have solubility with respect to the developing solution used at the developing process, Preferably alkaline developing solution. As the resin (B), for example, an acidic functional group, for example, a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, and the like, and / or an alcoholic hydroxyl group (hereinafter, these acidic functional groups and alcoholic hydroxyl groups are integrated to form an "alkali soluble functional group"). And a copolymer of a polymerizable unsaturated compound having an acidic functional group with another copolymerizable unsaturated compound (hereinafter, referred to as "alkali-soluble copolymer").

Preferred alkali-soluble copolymers include, for example, (b1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides (hereinafter collectively referred to as "unsaturated compounds (b1)") and (b2) other copolymerizable unsaturated compounds. And copolymers of monomer mixtures (hereinafter referred to as "unsaturated compounds (b2)") (hereinafter referred to as "alkali soluble copolymers (I)").

As an unsaturated compound (b1), for example

Unsaturated monocarboxylic acids such as (meth) acrylic acid, 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;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acid, such as monosuccinic acid [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

Mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, such as (omega)-carboxy polycaprolactone mono (meth) acrylate, etc. are mentioned.

Among these unsaturated compounds (b1), (meth) acrylic acid, monosuccinate mono [2- (meth) acryloyloxyethyl],? -Carboxypolycaprolactone mono (meth) acrylate, and the like are particularly preferable.

The said unsaturated compound (b1) can be used individually or in mixture of 2 or more types.

Next, as an unsaturated compound (b2), for example

Styrene, α-methylstyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy- α-methylstyrene, p-styrenesulfonic acid, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- Aromatic vinyl compounds such as vinyl benzyl methyl 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;

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No- N- (substituted) aryl maleimides such as methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N-position substituted maleimide such as N-cyclohexyl maleimide;

Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc. (hereinafter, simply referred to as "macromonomer" box);

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-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, methoxy propylene glycol (meth) acrylate, Messenger CD propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl Unsaturated carboxylic acid esters such as (meth) acrylate and glycerol (meth) acrylate; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl (meth) acrylate;

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

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

Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

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;

And aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene and isoprenesulfonic acid.

Among these unsaturated compounds (b2), styrene, macromonomer, N-position substituted maleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylic Elate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, etc. are preferable. Moreover, in a macromonomer, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer are especially preferable, and N-phenylmaleimide and N-cyclohexyl maleimide are especially preferable in N-position substituted maleimide.

The said unsaturated compound (b2) can be used individually or in mixture of 2 or more types.

As preferable alkali-soluble copolymer (I), More specifically, in the group which consists of (meth) acrylic acid, mono succinate mono [2- (meth) acryloyloxyethyl], and (omega) -carboxypolycaprolactone mono (meth) acrylate At least one unsaturated compound (b1) selected, a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, It contains at least one unsaturated compound (b2) selected from the group consisting of benzyl (meth) acrylate and glycerol mono (meth) acrylate, and optionally styrene, methyl (meth) acrylate, allyl (meth) acrylate And a copolymer of a monomer mixture further containing at least one unsaturated compound (b2) selected from the group consisting of phenyl (meth) acrylates (hereinafter, "carboxyl" Containing copolymer (I-1) "can be referred to hereinafter).

As a more preferable alkali-soluble copolymer (I-1), Unsaturation which specifically contains (meth) acrylic acid as an essential component and further contains monosuccinate mono [2- (meth) acryloyloxyethyl] as the case may be Compound (b1), polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate And at least one unsaturated compound (b2) selected from the group consisting of glycerol (meth) acrylate, and optionally styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. And copolymers of monomer mixtures further containing one or more unsaturated compounds (b2) selected from the group consisting of hereinafter (hereinafter referred to as "carboxyl group-containing copolymer (I-2)"). .

As a specific example of a carboxyl group-containing copolymer (I-2),

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / polystyrene macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / polymethyl (meth) acrylate macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / polystyrene macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / polymethyl (meth) acrylate macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / N-cyclohexylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / mono succinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer, etc. are mentioned.

In addition, as a specific example of a carboxyl group-containing copolymer (I-1),

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / polystyrene macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / polymethyl (meth) acrylate macromonomer / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / polystyrene macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / polymethyl (meth) acrylate macromonomer / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-cyclohexylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono succinate mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / allyl (meth) acrylate / styrene copolymer ,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monosuccinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer ,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth ) Acrylate / styrene copolymer, etc. are mentioned.

The polymerization ratio of the unsaturated compound having an alkali-soluble functional group in the resin (B) is preferably 1 to 100% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight based on the total unsaturated compounds. to be. When the polymerization ratio of the unsaturated compound which has an acidic functional group is less than 1 weight%, there exists a tendency for the solubility with respect to the alkaline developing solution of resin obtained to fall.

In addition, the copolymerization ratio of the unsaturated compound having an alkali-soluble functional group in the alkali-soluble copolymer is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30 to the total unsaturated compound. % By weight. When the copolymerization ratio of the unsaturated compound having an acidic functional group is less than 1% by weight, the solubility of the alkali-soluble copolymer obtained in the alkali developer tends to decrease, while when it exceeds 40% by weight, the alkali developer of the alkali-soluble copolymer obtained. The solubility with respect to too high may damage a pattern shape etc.

Next, living radical polymerization which manufactures resin (B) is demonstrated.

Resin (B) can be produced, for example, by living radical polymerization of a polymerizable unsaturated compound having an acidic functional group in the presence of a radical polymerization initiator system which generates living radicals in a solvent together with other copolymerizable unsaturated compounds. .

In living radical polymerization, when it is going to use the compound which has functional groups which may inactivate active radicals, such as a carboxyl group, as a polymerizable unsaturated compound, in order to prevent a growth terminal from deactivating, it is polymerizable as needed. Resin (B) can also be obtained by deprotecting the said functional group in an unsaturated compound, for example by esterification etc., after superposing | polymerizing.

As a radical polymerization initiator system for living radically polymerizing a polymerizable unsaturated compound, for example, TEMPO system (MKGeorges, RPNVeregin, PMKazmaier, GKHamer, Macromolecules, 1993, Vol. 26, p. 2987), a system comprising a combination of copper bromide and bromine-containing ester compounds proposed by Matyjaszewski et al. (Matyjaszewski, K. Coca, S. Gaynor, G.wei , M. Woodworth, BE Macromolecules, 1997, Vol. 30, p.7348), a system comprising a combination of carbon tetrachloride and ruthenium (II) complexes proposed by Hamasaki et al. (Hamasaki, S. Kamigaito, M. Sawamoto, M. Macromolecules, 2002, Vol. 35, p. 2934), Japanese Patent No. 3939859, Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004-518773 Thio having a chain transfer constant greater than 0.1, as disclosed in And a system including a combination of a carbonyl compound and a radical initiator.

As a preferable radical polymerization initiator type | system | group used for a living radical polymerization, the type | system | group in which the active radical which is a growth terminal is inactivated is selected suitably according to the kind of polymerizable unsaturated compound used, but considering a polymerization efficiency, a metal-free system, etc., it is a molecular weight control agent. Combinations of thiocarbonylthio compounds and radical initiators are preferred.

The combination of the thiocarbonylthio compound and the radical initiator is described in detail in the following patent documents, in addition to Japanese Patent No. 3639859, Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004-518773. .

Thiocarbonylthio compounds and radicals, as described in Japanese Patent No. 3639859, Japanese Patent Publication No. 2002-500251, Japanese Patent Publication No. 2004-518773, and Japanese Patent Publication No. 2002-508409 By living radical polymerization of a polymerizable unsaturated compound in the presence of an initiator, a random copolymer or a block copolymer having a narrow molecular weight distribution can be obtained. Moreover, since a functional group can be introduce | transduced into the obtained random copolymer and block copolymer, this copolymer is used as an aqueous gel (refer Japanese Unexamined-Japanese-Patent No. 2002-512653), and a photoresist (Japanese Unexamined-Japanese-Patent No. 2003-527458). And surfactants (see Japanese Patent No. 3634843), and the like.

In the present invention, preferred resin (B) is a group represented by the following formula (i) (hereinafter referred to as "terminal group (i)") or a group represented by formula (ii) at at least one end of the polymer chain constituting the same And a resin having a "terminal group (ii)" (hereinafter referred to as "resin (B1)").

In Formula i, Z ¹ is a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total of 3 to 3 atomic atoms of a carbon atom and a hetero atom 20 monovalent heterocyclic group, -OR, -SR, -N (R) ₂ , -OC (= 0) R, -C (= 0) OR, -C (= 0) N (R) ₂ ,- P (= O) (OR) ₂ , -P (= 0) (R) ₂ or a monovalent group having a polymer chain, each R is independently of each other an alkyl group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms , A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 atoms in total between a carbon atom and a hetero atom, wherein the alkyl group having 1 to 20 carbon atoms and the monovalent aromatic group having 6 to 20 carbon atoms Hydrocarbon group, monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted]

In formula (ii), Z <^2> is a m-valent group derived from C1-C20 alkanes, the m-valent group derived from a C6-C20 aromatic hydrocarbon, and 3-20 total atoms of a carbon atom and a hetero atom A m-valent group derived from a heterocyclic compound or an m-valent group having a polymer chain, and an m-valent group derived from the alkane having 1 to 20 carbon atoms, a m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and the total number of atoms M-valent groups derived from 3 to 20 heterocyclic compounds may each be substituted, and m is an integer of 2 or more]

When resin (B1) has only one polymer chain which comprises it, the terminal group (i) is couple | bonded with either terminal of the said polymer chain. At the other end, terminal group (i), terminal group (ii) or chain stop group may be bonded. This "chain stop group" is a group determined according to the reaction conditions at the time of living radical polymerization, and when the end group (ii) is bonded to the polymer chain, it is not bonded to the polymer chain in the end group (ii) (m -1) coupling numbers S- are combined with the chain stopper. In addition, a chain stopper may be R <^{1> in} Formula ( ¹⁾ or R <^2> in Formula (2) mentioned later.

In addition, when there are two or more polymer chains constituting the polymer chain, the polymer chain is bonded to the terminal group (ii) at one end thereof so that the resin (B1) has a branched structure. The other end of the polymer chain may be bonded to end groups (i), end groups (ii) or chain stop groups. When the end group (ii) is bonded to the other end of the polymer chain, (m-1) number of bonds (S-) which are not bonded to the polymer chain in the end group (ii) are further end groups. (i), end groups (ii) or chain stop groups. In addition, a chain stopper may be R <^{1> in} Formula ( ¹⁾ or R <^2> in Formula (2) mentioned later.

In Formula (I), Z ¹ A substituted C1-20 alkyl group, Substituted C6-C20 monovalent aromatic hydrocarbon group, Substituted carbon atoms and hetero atoms in total 3 to Examples of the monovalent group having 20 monovalent heterocyclic groups, substitutable R, and polymer chains include those preferable ones, for example, the same ones as the corresponding groups of Z ¹ in the general formula (1) described below. Can be.

In formula (ii), m-valent group derived from Z ² substituted alkanes having 1 to 20 carbon atoms, m-valent group derived from substitutable aromatic hydrocarbons having 6 to 20 carbon atoms, and carbon atoms which may be substituted Examples of the m-valent group derived from the heterocyclic compound having 3 to 20 atoms in total with a hetero atom and the m-valent group having a polymer chain include these preferable ones, and examples of Z ² in Chemical Formula 2 described below The same thing as the corresponding group is mentioned, respectively.

Resin (B1) can be manufactured through the process of living radical polymerization, for example using a thiocarbonylthio compound represented by following formula (1) or (2) as a molecular weight control agent using a polymerizable unsaturated compound. In this living radical polymerization, a radical initiator is also preferably used.

In the general formula (1), the definition of Z ¹ is the same as the formula (i), p is an integer of 1 or more, when R ¹ is p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic having 3 to 20 carbon atoms. A hydrocarbon group, a C 6-20 monovalent aromatic hydrocarbon group, a carbon atom and a hetero atom monovalent heterocyclic group having 3 to 20 carbon atoms, -OR, -SR, -N (R) ₂ or a polymer chain Represents a monovalent group having, and each R is, independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 3 atomic atoms of a carbon atom and a hetero atom; 18 monovalent heterocyclic group, and when p≥2, the p-valent group derived from C1-C20 alkanes, the p-valent group derived from C6-C20 aromatic hydrocarbons, and a carbon atom and a hetero atom Heterocyclic compounding with 3 to 20 atoms in total A p-valent group having a p-valent group or a polymer chain derived from water, the alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total atom Derived from a monovalent heterocyclic group having 3 to 20 carbon atoms, a pvalent group derived from an alkan having 1 to 20 carbon atoms, a pvalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total Each p-valent group may be substituted]

In Formula 2, Z ² and m are the same as defined above in Formula ii, R ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent having 6 to 20 carbon atoms. Represents an aromatic hydrocarbon group, a monovalent heterocyclic group having 3 to 20 carbon atoms in total and a hetero atom, -OR, -SR, -N (R) _2, or a monovalent group having a polymer chain, wherein each R is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 atoms in total between a carbon atom and a hetero atom; The alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may be substituted. has exist]

In the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include 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, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethylbutyl group, n -Nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. are mentioned.

Further, as the first phase-valent aromatic hydrocarbon group having 6 to 20 Z ^1, for example, phenyl, 1-naphthyl, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, benzyl group, methyl α- A benzyl group, the (alpha), (alpha)-dimethyl benzyl group, a phenethyl group etc. are mentioned.

As the monovalent heterocyclic group having 3 to 20 carbon atoms in total between Z ¹ carbon atoms and hetero atoms, for example, an epoxy group, an aziridinyl group, 2-furanyl group, 3-furanyl group, and 2-tetrahydrofura Nyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3-pyrazole group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-tianyl group, 4-tianyl group, 2 -Pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, etc. are mentioned. have.

Further, Z ¹ is -OR, -SR, -N (R) ₂ , -OC (= 0) R, -C (= 0) OR, -C (= 0) N (R) ₂ , -P (= O) (OR) ₂ and -P (= O) (R) ₂ The alkyl group of 1 to 18 carbon atoms of R, the monovalent aromatic hydrocarbon group of 6 to 18 carbon atoms or the total number of atoms of carbon atoms and hetero atoms 3 Examples of the monovalent heterocyclic group of 18 to 18 include, for example, an alkyl group having 1 to 20 carbon atoms as illustrated for Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a total number of atoms of 3 to 20 carbon atoms and a hetero atom. Examples of monovalent heterocyclic groups include groups having 18 or less carbon atoms in total.

Moreover, as a C2-C18 alkenyl group of the same R, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. are mentioned.

Examples of the alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, and a substituent to R include a hydroxyl group, -OR, -SR, -N (R) ₂ exemplified for Z ¹ in addition to a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, an isocyanate group, a cyano group, a vinyl group, an epoxy group, a silyl group, and a halogen atom -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ or -P (= O) (R) ₂ , An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic ring having 3 to 18 atoms in total between a carbon atom and a hetero atom It can select suitably from the same group as tableware. One or more of these substituents may be present in the substituted derivative. However, it is preferable that the total carbon number-the total atom number of the substituent in a substituted derivative do not exceed 20.

Moreover, as monovalent group which has a polymer chain of Z <^1> , For example, alpha-olefins, such as ethylene and propylene; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl halides such as vinyl fluoride, vinyl chloride and vinylidene chloride; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; Esters of unsaturated alcohols such as vinyl acetate and allyl acetate; Unsaturated carboxylic acids such as (meth) acrylic acid and p-vinylbenzoic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n- (meth) acrylate (Meth) acrylic acid esters, such as hexyl and cyclohexyl (meth) acrylate;

(Meth) acrylamides such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; Unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; Monovalent group which has addition polymerization type polymer chain formed from 1 or more types of unsaturated compounds, such as conjugated diene, such as butadiene and isoprene; Polyethers such as polyoxyethylene capable of etherifying the terminal and polyoxypropylene capable of etherifying the terminal; Monovalent groups which have polyaddition polymer chain | strands, polycondensation-type polymer chains, such as polyester, a polyamide, and polyimide, etc. are mentioned. In monovalent groups having these polymer chains the polymer chain can be directly attached to the carbon atom of the thiocarbonyl group of the formula (1), and is also for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ It may be bonded to the carbon atom of the thiocarbonyl group represented by the formula (1) via a linking water such as CH ₂ -COO-. In this case, it should be understood as a monovalent group having a polymer chain including these linking numbers.

In Formula 1, a plurality of Z ¹ present may be the same or different from each other.

In the general formula (1), when p = 1, R ¹ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom and a hetero atom; Represents a monovalent heterocyclic group having 3 to 20 carbon atoms in total, -OR, -SR, -N (R) ₂ or a polymer chain, and having an alkyl group having 1 to 20 carbon atoms and 1 having 3 to 20 carbon atoms. The valent alicyclic hydrocarbon group, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 carbon atoms and the total atoms of the carbon atom and the hetero atom, and R may each be substituted.

The alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -SR, -N (R) ₂ or a substituted derivative thereof or As a monovalent group which has a polymer chain | strand, the thing similar to the group illustrated about the corresponding group of said Z <^1> is mentioned, for example. In a monovalent group having a polymer chain of R ¹ (p = 1), the polymer chain can be directly bonded to the sulfur atom in formula (1), for example -CH ₂ -COO-, -C (CH ₃ ) It may be bonded to the sulfur atom in the formula (1) through a linking water such as (CN) CH ₂ CH ₂ -COO-. In this case, it is understood as in the case of Z ¹ .

Moreover, as said C3-C20 monovalent alicyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, a cyclohexenyl group etc. are mentioned, for example.

Examples of substituents for groups monovalent alicyclic of the C 3 -C 20 hydrocarbons, e.g., total atoms with the Z ¹ groups of the monovalent aromatic hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 6 to 20, carbon atoms and heteroatoms, It can select suitably from the same thing as the group illustrated about the monovalent heterocyclic group of the number 3-20, and the substituent to R. One or more of these substituents may be present in the substituted derivative. However, it is preferable that the total carbon number-the total atom number of the substituent in a substituted derivative do not exceed 20.

Further, when p≥2, R ¹ represents a p-valent group derived from alkane having 1 to 20 carbon atoms, a p-valent group derived from aromatic hydrocarbon having 6 to 20 carbon atoms, and a total of 3 to 3 atomic atoms of a carbon atom and a hetero atom. P-valent group having a p-valent group or a polymer chain derived from a heterocyclic compound of 20, p-valent group derived from the alkane, p-valent group derived from an aromatic hydrocarbon, and a heterocyclic compound having 3 to 20 atoms in total Derivative p-valent groups may each be substituted.

Examples of the alkanes having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, n-octane, n -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eichoic acid, etc. are mentioned.

Further, as the aromatic hydrocarbon having 6 to 20 carbon atoms, for example, benzene, 1,4-dimethylbenzene (in this case, for example, the carbon atom of each methyl group in the 1,4-position is bonded to the sulfur atom in the formula (1). ), 1,2,4,5-tetramethylbenzene (in this case, for example, the carbon atom of each methyl group in 1,2,4,5-position is bonded to the sulfur atom in formula 1), 1,2, 3,4,5,6-hexamethylbenzene (in this case, for example, the carbon atom of each methyl group in 1,2,3,4,5,6-position is bonded to a sulfur atom in formula 1), 1, 4-di-i-propylbenzene (in this case, for example, a carbon atom at 2-position of each i-propyl group at 1,4-position is bonded to a sulfur atom in formula 1), naphthalene, anthracene group Can be mentioned.

Moreover, as said total heterocyclic compound of 3-20 atoms, for example, oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thian, pyridine, piperi Dean, morpholine, etc. are mentioned.

As a substituent for the p-valent group derived from the said C1-C20 alkane, the p-valent group derived from a C6-C20 aromatic hydrocarbon, and the p-valent group derived from the heterocyclic compound of 3 to 20 atoms in total, Examples include the alkyl groups of 1 to 20 carbon atoms of Z ¹ , monovalent aromatic hydrocarbon groups of 6 to 20 carbon atoms, monovalent heterocyclic groups having 3 to 20 carbon atoms and heteroatoms, and substituents for R. It can select suitably from the same thing as one group. One or more of these substituents may be present in the substituted derivative. However, it is preferable that the total carbon number-the total atom number of the substituent in a substituted derivative do not exceed 20.

Moreover, as a polymer chain which provides the p-valent group of R <^1> , the same thing as the addition polymerization type polymer chain, polyaddition type polymer chain, and polycondensation type polymer chain which were illustrated about the monovalent group which has the said polymer chain of Z <^1> is mentioned. In p-valent groups having a polymer chain of R ¹ , the polymer chain may be directly bonded to a sulfur atom in formula (1), for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ CH ₂ It may be bonded to the sulfur atom of the formula (1) via a linking water such as -COO-. In this case, it can be understood in the same manner as in the case of Z ¹ .

Next, in the formula (2), examples of the alkane having 1 to 20 carbon atoms that provide the m-valent group of Z ² include the same compounds as those exemplified for the alkani having 1 to 20 carbon atoms that provide the p-valent group of R ¹ . Can be mentioned.

Further, as the aromatic hydrocarbon having 6 to 20 carbon atoms to provide an m-valent of Z ^2, such may be mentioned example is the same as illustrated with respect to the aromatic hydrocarbon group having 6 to 20 carbon atoms compound to provide an p-valent of the R ^1.

In addition, as a heterocyclic compound having 3 to 20 carbon atoms in total having a carbon atom and a hetero atom providing an m-valent group of Z ² , for example, a total atom of a carbon atom and hetero atom having a p-valent group as described above in R ¹ The same thing as the compound illustrated about the heterocyclic compound of the number 3-20 is mentioned.

Examples of substituents for groups m monovalent derived from the heterocyclic compounds of the m-valent group, and a total atom number of from 3 to 20 that is derived from an aromatic hydrocarbon of the m-valent group, having 6 to 20 carbon atoms is derived from alkanes having a carbon number of 1 to 20, Z ^2, For example, the Z ¹ alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms and a hetero atom, and a substituent to R It can select suitably from the same thing as the group illustrated about the. One or more of these substituents may be present in the substituted derivative. However, it is preferable that the total carbon number-the total atom number of the substituent in a substituted derivative do not exceed 20.

Further, as the polymer chain to provide an m-valent of Z ^2, for example, the Z include ¹ to the same as the addition polymerization-based polymer chain, heavy household polymer swaena polycondensation polymer chain illustrated for groups monovalent having a polymer chain have. In m-valent groups having a polymer chain of Z ² , the polymer chain may be directly bonded to a carbon atom of a thiocarbonyl group of the formula (2), for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH It may be bonded to the carbon atom of the thiocarbonyl group in the formula (2) via a linking water such as ₂ CH ₂ -COO-. Even in this case it can be understood in the same manner as in the case of Z ^1.

In the formula (2), an alkyl group having 1 to 20 carbon atoms for R ² , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, and a total atom of a carbon atom and a hetero atom, -OR,- As a monovalent group which has SR, -N (R) _2, and a polymer chain, and these substituted derivatives, the same thing as the group illustrated about the corresponding group of said Z <^1> is mentioned, for example. In monovalent groups having a polymer chain of R ² , the polymer chain may be directly bonded to a sulfur atom in formula (2), for example —CH ₂ —COO—, —C (CH ₃ ) (CN) CH ₂ CH ₂ It may be bonded to the sulfur atom of the formula (2) through a linking water such as -COO-. This case is understood in the same manner as in the case of Z ¹ .

Moreover, as a C3-C20 monovalent alicyclic hydrocarbon group of R <^2> and its substitution derivative, For example, said C1-C20 monovalent alicyclic hydrocarbon group of R <^1> (p = 1) and its substituted derivatives are mentioned, for example. The same thing as the group illustrated about is mentioned.

In Formula 2, a plurality of R ² may be the same or different from each other.

In Chemical Formula 2, when the connecting portion between Z ² and —C (═S) —SR ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ^{2 is} bonded to —C (═S) —SR ^2, and the connecting portion In the case of this aromatic carbon atom, the aromatic carbon atom in Z ^{2 is} bonded to -C (= S) -SR ^2, and in the case where the linking moiety is a sulfur atom, the sulfur atom in -SR representing Z ² is -C (= S )-Combined with SR ² .

As a specific example of the especially preferable thiocarbonylthio compound in this invention, the compound etc. which are represented by following General formula (3)-(22) are mentioned.

These thiocarbonylthio compounds can be used individually or in mixture of 2 or more types.

In the present invention, in the living radical polymerization, one or more kinds of other molecular weight controlling agents such as α-methylstyrene dimer and t-dodecyl mercaptan may be used together with the thiocarbonylthio compound.

It does not specifically limit as a radical initiator used for living radical polymerization, What is generally known as a radical polymerization initiator can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2,4-dimethylvaleronitrile), 2,2'- azobis (4-methoxy-2,4 Azo compounds such as -dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, 1,1'-bis (t-butylperoxy) cyclohexane and t-butylperoxy pivalate; Hydrogen peroxide; And redox initiators containing these peroxides and reducing agents.

These radical initiators can be used individually or in mixture of 2 or more types.

The solvent used for the living radical polymerization is not particularly limited as long as the active radical is not inactivated, for example

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Poly) alkylene glycol alkyl ether acetates such as acetates;

(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, and dipropylene glycol diethyl ether ;

Other ethers such as tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Ketoalcohols such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-pentyl formate, i-pentyl 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 such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene from the viewpoints of solubility, pigment dispersibility, coating properties, etc. of each component in the radiation-sensitive resin composition. Glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, N-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferred.

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

In the living radical polymerization, the amount of the thiocarbonylthio compound to be used is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 16 parts by weight based on 100 parts by weight of the total polymerizable unsaturated compound. The amount of the radical polymerization initiator to be used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total polymerizable unsaturated compound.

Moreover, polymerization temperature becomes like this. Preferably it is 0-150 degreeC, More preferably, it is 50-120 degreeC. The polymerization time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 6 hours.

The Mw of the resin (B) (wherein Mw is a polystyrene reduced weight average molecular weight measured by gel permeation chromatography (GPC)) is 1,000 to 45,000, preferably 3,000 to 20,000, particularly preferably 4,000 to 10,000.

In addition, Mw / Mn of the resin (B) (this Mn is a polystyrene reduced number average molecular weight measured by GPC) is preferably 1 to 2.0, more preferably 1 to 1.7, particularly preferably 1 to 1.4. .

By using an alkali-soluble resin having such a predetermined Mw and preferably further having the specific Mn and / or Mw / Mn, a radiation-sensitive resin composition excellent in developability is obtained, thus having a sharp pattern end. At the time of development, a residue, ground contamination, film residues, etc. are less likely to occur on the substrate and the light shielding layer of the unexposed portion during development, and at the time of manufacturing a color filter because of high cleaning property by an organic solvent. It is possible to realize high product yield without generating dry foreign matters, and to more effectively prevent "burning" of the color filter.

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

The amount of the resin (B) used in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight based on 100 parts by weight of the pigment (A). In this case, when the usage-amount of resin (B) is less than 10 weight part, alkali developability may fall, for example, there may be a background contamination or a film residue on the substrate or the light shielding layer of the unexposed part, If it exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, so there is a fear that it is difficult to achieve the target color concentration as a thin film.

-(C) polyfunctional monomer-

The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.

As such a polyfunctional monomer, 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 having a degree of polymerization of at least 1 degree and polypropylene glycol having a degree of polymerization of at least 1 degree;

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and modified dicarboxylic acids thereof;

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

Di (meth) acrylates of polymers having hydroxyl groups at both ends, such as poly-1,3-butadiene having hydroxyl groups at both ends, polyisoprene having hydroxyl groups at both ends, and polycaprolactone having hydroxyl groups at both ends;

Tris [2- (meth) acryloyloxyethyl] phosphate etc. are mentioned.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified substances are preferable, and specifically, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth). ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferred, among which trimethylolpropane triacrylate, Pentaerythritol triacrylate and dipentaerythritol hexaacrylate have high pixel intensity, excellent smoothness of the pixel surface, and also cause background contamination, film residue, etc. on the substrate and the light shielding layer of the unexposed part. It is especially preferable at a difficult point.

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

The amount of the polyfunctional monomer used in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the resin (B). In this case, when the usage-amount of a polyfunctional monomer is less than 5 weight part, the intensity | strength and surface smoothness of a pixel will fall, and when it exceeds 500 weight part, alkali developability will fall, for example, on the board | substrate of an unexposed part. Or there exists a tendency for background contamination, a film | membrane residue, etc. to occur easily on a light shielding layer.

In the present invention, a monofunctional monomer having one polymerizable unsaturated bond together with the polyfunctional monomer can also be used.

As said monofunctional monomer, N-vinyl succinimide, N-vinyl pyrrolidone, N- besides the unsaturated monomer (b1) and unsaturated monomer (b2) which were illustrated, for example with respect to the said alkali-soluble copolymer (I) Vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl indole, N-vinyl indolin, N-vinyl benzimidazole, N-vinylcarbazole, N-vinyl piperidine, N-vinyl piperazine, N-vinylmorpholine, N-vinylphenoxazine, etc. N-vinyl nitrogen-containing heterocyclic compound; Examples of N- (meth) acryloyl morpholine and commercially available products include M-5300, M-5400, and M-5600 (above, manufactured by Toagosei Co., Ltd.).

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The use ratio of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a tendency for the intensity | strength and surface smoothness of a pixel to fall.

-(D) radiation sensitive radical generator-

The radiation sensitive radical generator (hereinafter, simply referred to as a "radical generator") in the present invention is the (C) polyfunctional monomer by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like. It is a compound which generate | occur | produces the radical which can start the superposition | polymerization of the monofunctional monomer used in some cases.

Examples of such radical generators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds and the like. Can be.

In the present invention, the radical generator may be used alone or in combination of two or more thereof. As the radical generator in the present invention, one kind selected from the group consisting of an acetophenone compound, a biimidazole compound, and a triazine compound The above is preferable.

In the present invention, the amount of the radical generator used is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight based on 100 parts by weight of the total amount of the (C) polyfunctional monomer or monofunctional monomer. In this case, when the amount of the radical generator is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the pixel pattern is arranged in accordance with a predetermined arrangement. There exists a tendency for a pixel to fall easily from a board | substrate at the time of image development.

As a specific example of the acetophenone compound among the preferable radical generators in this invention, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropaneone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy- 1,2-diphenylethan-1-one, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) Butanone-1, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and the like.

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

In the present invention, the amount of use of the acetophenone compound as the radical generator is preferably 0.01 to 80 parts by weight, more preferably based on 100 parts by weight in total of the (C) polyfunctional monomer or monofunctional monomer. Is 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. In this case, when the amount of the acetophenone compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the pixel patterns are arranged in accordance with a predetermined arrangement. There exists a tendency for a pixel to fall easily from a board | substrate at the time of image development.

Moreover, as a specific example of the said biimidazole 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'-biimidazole, 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, 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 (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred.

These biimidazole compounds are excellent in solubility in solvents and do not generate foreign matters such as undissolved matters or precipitates. Furthermore, these biimidazole compounds have a high sensitivity and allow the curing reaction to sufficiently proceed by exposure of a small amount of energy, and at the same time, the curing reaction is unexposed. Since it does not occur, the coating film after exposure is clearly divided into an insoluble hardened portion for the developing solution and an uncured portion having high solubility for the developing solution, whereby a high-precision fine color in which pixel patterns without undercuts are arranged in accordance with a predetermined arrangement. A filter can be formed.

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

In the present invention, the amount of use of the biimidazole compound as the radical generator is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight in total of the (C) polyfunctional monomer or monofunctional monomer. It is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, when the usage-amount of a biimidazole 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 a pixel pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 40 weight part, When developing, it tends to be easy to cause the formed pixels to fall off from the substrate and to have film roughness of the pixel surface.

In this invention, when using a biimidazole compound as a radical generator, using the following hydrogen donor 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 compound by exposure.

As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like 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 bonded directly to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, " Mercaptan hydrogen donor ".

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 hydrogen Donor ".

On the other hand, these hydrogen donors may have a mercapto group and an amino group simultaneously.

The hydrogen donor will be described in more detail below.

The mercaptan hydrogen donor may have one or more benzene rings or heterocycles, and may also have both a benzene ring and a heterocycle. 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 hydrogen donor has two or more mercapto groups, under conditions in which 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, and further, 1 Under the condition that at least two free mercapto groups remain, the two sulfur atoms may have a structural unit bonded through a divalent organic group such as an alkylene group, or two sulfur atoms in a disulfide form.

In addition, the mercaptan 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 portions other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine etc. are mentioned.

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

In addition, the amine hydrogen donor may have one or more benzene rings or heterocycles, respectively, and may have both a benzene ring and a heterocycle. In the case of having two or more of these rings, a condensed ring may or may not be formed.

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

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

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

On the other hand, the amine hydrogen donor also acts 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. The combination of at least one mercaptan hydrogen donor and at least one amine hydrogen donor is preferable because it is difficult to drop off from the substrate during development, and pixels with high pixel intensity and sensitivity are formed.

Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis (Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone Etc. can be mentioned. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, in particular Preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

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

In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total of (C) the polyfunctional monomer or the monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed pixels tend to fall off the substrate during development.

In addition, specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 , 6-bis (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)- Triazine compounds which have halomethyl groups, such as 4, 6-bis (trichloromethyl) -s-triazine, are mentioned.

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

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

In the present invention, the amount of the triazine compound used as the radical generator is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total amount of the (C) polyfunctional monomer or a monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, when the amount of the triazine compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which pixel patterns are arranged in accordance with a predetermined arrangement. There exists a tendency for a pixel to fall easily from a board | substrate at the time of image development.

Other additives

Although the radiation sensitive resin composition of this invention makes the said (A)-(D) component an essential component, you may further contain another additive as needed.

As another 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; Agglomeration inhibitors, such as sodium polyacrylate, etc. are mentioned.

Preparation of Liquid Composition

The radiation sensitive resin composition of this invention is manufactured as a liquid composition normally by mix | blending a solvent.

The solvent may be appropriately selected and used as long as it does not react with these components while dispersing or dissolving the components (A) to (D) or other additive components constituting the radiation sensitive composition.

As such a solvent, for example

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Poly) alkylene glycol alkyl ether acetates such as acetates;

(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, and dipropylene glycol diethyl ether ;

Other ethers such as tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Ketoalcohols such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-pentyl formate, i-pentyl 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 such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 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 dipropylene glycol methyl ether acetate in terms of solubility, pigment dispersibility, and coating properties. , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-butyric acid Propyl, n-butyl butyrate, ethyl pyruvate and the like are preferred.

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.

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

Although the usage-amount of a solvent is not specifically limited, From a viewpoint of the coating property, stability, etc. of the liquid composition obtained, the total concentration of each component except the solvent of the said composition becomes like this. Preferably it is 5-50 weight%, Especially preferably, it is 10- The amount which becomes 40 weight% is preferable.

Formation method of the color filter

Next, the method of forming the color filter of this invention using the radiation sensitive resin composition of this invention is demonstrated.

The method for forming the color filter usually includes at least the following steps (1) to (4).

(1) The process of forming the coating film of the radiation sensitive resin composition for color filters of this invention on a board | substrate.

(2) The process of exposing to at least one part of the said coating film.

(3) The process of developing the said coating film after exposure.

(4) A step of subjecting the coating film after development to heat treatment (hereinafter referred to as "post baking").

Hereinafter, these processes are demonstrated in order.

(1) process

First, a light shielding layer is formed on the surface of a board | substrate so that the part which forms a pixel may be divided as needed, and the liquid composition of the radiation sensitive resin composition for color filters containing a red pigment, for example is apply | coated on this board | substrate. Thereafter, prebaking is performed to evaporate the solvent to form a coating film.

As a board | substrate used at this process, a ring-opening polymer of cyclic olefin, its hydrogenated substance, etc. other than glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyether sulfone are mentioned, for example. have.

If desired, 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.

When apply | coating a liquid composition to a board | substrate, the appropriate application | coating methods, such as rotational application | coating, ie, application | coating by a spin coater, casting | flow_spread coating, roll coating, and slit nozzle, can be employ | adopted. The radiation sensitive resin composition of this invention has high solubility to a washing | cleaning solvent even after drying, and is also suitable for application | coating by a slit nozzle.

Prebaking conditions are preferably about 2 to 4 minutes at 70 to 110 ° C.

The coating thickness is preferably 0.1 to 10 m, more preferably 0.2 to 8.0 m, still more preferably 0.2 to 6.0 m as the film thickness after solvent removal.

(2) process

Thereafter, at least part of the formed coating film is exposed through a photomask having a suitable pattern, for example.

As the radiation used in this step, for example, visible rays, ultraviolet rays, far 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.

The exposure dose of radiation is preferably about 10 to 10,000 J / m 2.

(3) process-

Thereafter, the exposed coating film is preferably developed using an alkali developer, and the unexposed portions of the coating film are dissolved and removed to form a pattern.

Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabi, and the like. Aqueous solutions, such as cyclo- [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. On the other hand, after alkali development, it washes with water preferably.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid soaking) developing method, and the like can be applied.

As for image development conditions, about 5 to 300 second is preferable at normal temperature.

(4) process

Subsequently, by post-baking the coating film after image development, the board | substrate with which the pixel pattern containing the hardened | cured material of a radiation sensitive resin composition was arrange | positioned in a predetermined array can be obtained.

As for the conditions of post-baking, 20 to 40 minutes are preferable at 180-230 degreeC.

The film thickness of the pixel thus formed is preferably 0.5 to 5.0 m, more preferably 1.5 to 3.0 m.

In addition, the process of said (1)-(4) is repeated using each liquid composition of the radiation sensitive resin composition for color filters containing a green or a blue pigment, and a green pixel pattern and a blue pixel pattern are repeated on the same board | substrate. By forming on it, the colored layer in which the pixel pattern of three primary colors of red, green, and blue are arrange | positioned in a predetermined | prescribed arrangement can be formed on a board | substrate. However, the formation order of the pixel pattern of each color in this invention is not limited to the said order.

Color filter

The color filter of this invention is formed from the radiation sensitive resin composition for color filters of this invention.

The color filter of the present invention is very useful, for example, in a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Color liquid crystal display

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

The color liquid crystal display device of this invention can take a suitable structure. For example, the color filter may be formed on a substrate different from the driving substrate on which the thin film transistor TFT is disposed, and the substrate on which the driving substrate and the color filter are formed may have an opposite structure through the liquid crystal layer. In addition, a substrate in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed may be opposed through a liquid crystal layer. have. The latter structure can further improve the aperture ratio and has the advantage of obtaining a bright and high precision fine liquid crystal display element.

Radiation  Resin composition ( II )

On the other hand, it is a radiation sensitive resin composition containing (A) pigment, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive radical generator,

(B) Alkali-soluble resin has the content rate of the component whose Mw is less than 1,000 is 0-30 weight%, and the content rate of the component whose Mw is 1,000-10,000 is 50-100 weight%, Preferably it is 70-100 weight%, More preferable Preferably, the content is 90 to 100% by weight, the content of components having a Mw of more than 10,000 and 45,000 or less is 0 to 45% by weight, the content of components having a Mw of more than 45,000 is 0 to 5% by weight, and the Mw of the whole resin is A radiation sensitive resin composition (hereinafter referred to as "radiation sensitive resin composition (II)") which is a resin of 1,000 to 10,000, preferably 2,000 to 8,000 (hereinafter referred to as "resin (ii)") also includes a color filter. It can be used for formation.

As (A) component, (C) component, and (D) component in a radiation sensitive resin composition (II), the said (A) component used for the radiation sensitive resin composition of this invention, (C) component, for example And the same thing as (D) component can be used, Moreover, the said other additive illustrated about the radiation sensitive resin composition of this invention can be mix | blended with a radiation sensitive resin composition (II), and also a radiation sensitive resin composition ( II) is also usually prepared as a liquid composition by blending the solvents exemplified for the liquid composition of the radiation-sensitive resin composition of the present invention.

The resin (ii) is, for example, after radical polymerization of the monomer mixture containing the unsaturated monomer (b1) and the unsaturated monomer (b2), and then using a reprecipitation method using two or more kinds of organic solvents having different polarities. It can obtain by the method of refine | purifying via, a "refining method" hereafter, etc.

Hereinafter, the purification method will be described.

The radical polymerization which manufactures resin (ii) is not specifically limited, It can carry out by a conventional method.

The copolymer after the polymerization can be used as a polymer solution for purification as long as the solvent used for the polymerization is a good solvent in the following reprecipitation method or after adjusting the concentration, and the copolymer from the polymer solution obtained by polymerization. May be separated by conventional methods and provided to the purification treatment as a solid.

After radical polymerization, the obtained copolymer is refine | purified by the reprecipitation method using 2 or more types of organic solvent from which polarity differs. That is, the solution in the good solvent of the copolymer is removed, if necessary, by filtration or centrifugation, or the like, and then poured in a large amount, for example, 5 to 10 times the amount of the precipitant (poor solvent) in the volume of the copolymer solution and the copolymer is poured. Purify by reprecipitation. At this time, among the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the copolymer.

As a good solvent / precipitator combination used for this reprecipitation method, for example, diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, methyl Ethyl ketone / n-heptane; and the like.

In reprecipitation of the copolymer, it is preferable to add the copolymer solution as little as possible while vigorously stirring the precipitant, whereby the amount of impurities contained in the precipitation can be minimized. In addition, by repeating the reprecipitation treatment a plurality of times, the purity can be made higher, and the precipitation which is very fine and unsuitable for filtration can be separated by centrifugation or the like.

In the case where more precise purification is required, the fractional precipitation method is preferable as a method of the reprecipitation method. That is, the copolymer is dissolved in a good solvent, and the solvent is sequentially precipitated with a solute copolymer while varying the kind, composition, and temperature of the solvent. Aliquot and divide. For this method, it is common to add a precipitant to the copolymer solution. In addition, the composition of the good solvent and the precipitant, that is, the mixing ratio of the good solvent may be sequentially changed at a constant temperature, or the temperature may be changed by making the mixing ratio of the good solvent constant. By using such a method, a copolymer of a narrow molecular weight range can be fractionated in a good yield. Each fraction of the copolymer fractionated by the fractional precipitation method can be obtained as a solid by concentrating and drying one or a plurality of fractions according to the value of these Mw.

Moreover, the copolymer obtained by such a reprecipitation method can also be refine | purified by adsorption / affinity chromatography, a dialysis method, etc. as needed.

The Mn of the resin (ii) is preferably 600 to 10,000, more preferably 1,200 to 8,000.

The Mw / Mn of the resin (ii) is preferably 1 to 2.0, more preferably 1 to 1.7, particularly preferably 1 to 1.4.

By using the resin (ii) having such a predetermined Mw and preferably further having the specific Mn and / or Mw / Mn, a developable radiation-sensitive resin composition (II) is obtained, and thus sharp Since it is possible to form a pixel having a patterned end, residue, ground contamination, film residue, etc. are generated on the substrate and the light shielding layer of the unexposed part at the time of development, and furthermore, since the cleaning property by the organic solvent is high, It is possible to realize a high product yield without generating dry foreign matters during the production of the color filter, and to effectively prevent "burning" of the color filter.

In radiation sensitive resin composition (II), resin (ii) can be used individually or in mixture of 2 or more types.

As mentioned above, the radiation sensitive resin composition of this invention can form the color filter which a "baking" does not generate | occur | produce in a high product yield, and is also suitable for application | coating by a slit nozzle.

On the other hand, the radiation sensitive resin composition of this invention is used suitably also for manufacture of the color filter for CCD.

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.

Mobile phase: Tetrahydrofuran comprising 0.5% by weight phosphoric acid.

Comparative Synthesis Example 1

10 parts by weight of 2,2'-azobisisobutyronitrile and 400 parts by weight of diethylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 30 parts by weight of methacrylic acid and N-phenylmaleimide. 31.2 parts by weight, benzyl methacrylate, 20 parts by weight of styrene, 18.8 parts by weight of styrene and 10 parts by weight of α-methylstyrene dimer as a molecular weight control agent were added thereto, followed by nitrogen replacement, and the reaction solution was heated to 80 ° C. with gentle stirring. The polymerization was carried out for 3 hours while maintaining this temperature. Then, the reaction solution was heated up at 100 degreeC, 2 weight part of 2,2'- azobisisobutyronitrile were added, and superposition | polymerization was continued for 1 hour, and the resin solution (solid content concentration = 20.1 weight%) was obtained. This resin was Mw = 5,000 and Mw / Mn = 3.6. This resin was referred to as "resin (b-1)".

Synthesis Examples 1 to 20

2 parts by weight of 2,2'-azobisisobutyronitrile, a compound represented by each of the above formulas (3) to (22) as a molecular weight controlling agent in a flask equipped with a cooling tube and a stirrer, the amount shown in Table 1 And 200 parts by weight of diethylene glycol monomethyl ether acetate, followed by 30 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of benzyl methacrylate and 18.8 parts by weight of styrene, followed by nitrogen replacement. The reaction solution was heated to 80 ° C. with gentle stirring, and polymerized for 3 hours while maintaining this temperature. Thereafter, the reaction solution was heated to 100 ° C, 1 part by weight of 2,2'-azobisisobutyronitrile was added, and the polymerization was further continued for 1 hour, whereby the resins (B-1) to resins shown in Table 1 ( Each solution of B-20) was obtained. It was as having shown in Table 1 when the value of solid content, Mw, and Mw / Mn of each obtained resin was measured.

Evaluation of Voltage Retention

Comparative Example 1

(A) As a pigment, C.I. Pigment Red 254 and C.I. A mixed liquid containing 40 parts by weight of a 50/50 (weight ratio) mixture of Pigment Yellow 139, 10 parts by weight of disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent, was added to a diamond fine mill (trade name, Mitsubishi Matherial). The pigment dispersion liquid was manufactured and mixed for 12 hours by the bead mill (bead diameter 1.0mm) of the corporation | Co., Ltd. product.

Subsequently, 100 weight part of this pigment dispersion liquid, 70 weight part of resin (b-1) as alkali-soluble resin, (C) 80 weight part of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2- as a radical generator 50 parts by weight of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were prepared to prepare a liquid composition (r-1). It was.

Subsequently, the liquid composition (r-1) is formed on a surface of a SiO ₂ film which prevents elution of sodium ions, and is further spinned onto a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After apply | coating using a coater, it prebaked for 10 minutes in 90 degreeC clean oven, and formed the coating film of 2.0 micrometers in thickness.

Subsequently, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film by the exposure amount of 5,000 J / m <2> using the high pressure mercury lamp, without passing through a photomask. Subsequently, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and post-baked at 250 ° C. for 30 minutes to cure the coating film. Red pixels were formed on the substrate. The film thickness of this pixel was 1.60 mu m.

Subsequently, after bonding the board | substrate which formed this pixel and the board | substrate which only deposited the ITO electrode to a predetermined shape with the sealing agent which mixed 0.8 mm glass beads, the liquid crystal cell made by Merck Corporation was injected, and a liquid crystal cell was injected. Prepared.

Subsequently, the liquid crystal cell was put into the 60 degreeC constant temperature layer, and the voltage retention of the liquid crystal cell was measured by the liquid crystal voltage retention measurement system VHR-1A type (brand name) by Toyo Technica. At this time, the applied voltage was a 5.5 V square wave and the measurement frequency was 60 Hz. Here, voltage retention is a value of (the voltage applied by the liquid crystal cell potential difference / 0 millisecond after 16.7 milliseconds). The results are shown in Table 2 below.

When the voltage retention of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds and cannot align the liquid crystal sufficiently. Therefore, the liquid crystal display device provided with the color filter formed using such a liquid composition is likely to cause "baking".

The above result is shown in Table 2.

Examples 1-20

Liquid compositions (R-1) to (R-20) were prepared in the same manner as in Comparative Example 1, except that 70 parts by weight of resins (B-1) to (B-20) were used instead of resin (b-1), respectively. Except having manufactured, it carried out similarly to the comparative example 1, and produced the liquid crystal cell and measured the voltage retention, and it was all 92%. Therefore, the liquid crystal display device provided with the color filter formed using liquid composition (R-1)-(R-20) is less likely to produce "baking." The above result is shown in Table 2.

Although the radiation sensitive resin composition using a red pigment was evaluated here, the same result was obtained also in the case of the radiation sensitive resin composition using a blue, green, yellow, or black pigment.

Comparative Synthesis Example 2

2.5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of diethylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 30 parts by weight of methacrylic acid and N-phenylmaleimide. 31.2 parts by weight, 20 parts by weight of benzyl methacrylate, 18.8 parts by weight of styrene and 3 parts by weight of α-methylstyrene dimer (chain transfer agent) were added thereto, followed by nitrogen substitution, and the reaction solution was heated to 80 ° C. with gentle stirring. The polymerization was carried out for 3 hours while maintaining the temperature. Thereafter, the reaction solution was heated to 100 ° C, 0.5 part by weight of 2,2'-azobisisobutyronitrile was added, and polymerization was continued for 1 hour to obtain a resin solution (solid content concentration = 33.2% by weight). This resin was Mw = 14,000 and Mw / Mn = 2.1. This resin was referred to as "resin (b-2)".

Immersion test

Comparative Example 2

The liquid composition (r-1) a, was applied using a spin coater on a soda glass substrate having a diameter of 4 inches SiO ₂ film is formed to prevent the elution of sodium ions on the surface, allowed to stand 12 hours in a 23 ℃ clean room And drying to form a coating film.

Subsequently, this board | substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and the coating film melt | dissolved completely.

Examples 21-40

A coating film was formed on a soda glass substrate in the same manner as in Comparative Example 2 except that the liquid compositions (R-1) to (R-20) were used instead of the liquid composition (r-1), respectively.

Subsequently, this board | substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes, and the coating film melt | dissolved completely.

Comparative Example 3

A liquid composition (r-2) was prepared in the same manner as in Comparative Example 1 except that 70 parts by weight of the resin (b-2) was used instead of the resin (b-1). Then, the coating film was formed on the soda glass substrate similarly to the comparative example 2 except having used the liquid composition (r-2) instead of the liquid composition (r-1).

Subsequently, this substrate was immersed in 100 cc of propylene glycol monomethyl ether acetate for 2 minutes. As a result, the coating film was not completely dissolved, and a large amount of foreign matter was observed in the liquid.

Application test

Comparative Example 4

To the coating device TR63210S-CL (brand name) of the slit nozzle type color filter manufactured by Tokyo Oka Kogyo Co., Ltd. on a soda glass substrate having a SiO ₂ film formed thereon on the surface of which a liquid composition (r-1) prevents elution of sodium ions. After coating, the coating film was formed by standing at room temperature for 1 hour and drying.

Subsequently, after the slit nozzle was blow-cleaned with propylene glycol monomethyl ether acetate, a liquid composition (r-1) was applied to the new soda glass substrate by TR63210S-CL again, and foreign matter was generated on the formed coating film again. It could apply without making it.

Examples 41 to 60

The coating test was carried out in the same manner as in Comparative Example 4 except that the liquid compositions (R-1) to (R-20) were used instead of the liquid composition (r-1). It could be applied without.

Comparative Example 5

The coating test was carried out in the same manner as in Comparative Example 4 except that the liquid composition (r-2) was used instead of the liquid composition (r-1). As a result, a foreign matter occurred on the formed coating film, and a preferable coating film could be formed. There was no.

Claims (10)

(A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive radical generator, (B) Alkali-soluble resin is manufactured through living radical polymerization of a polymerizable unsaturated compound, The polystyrene reduced weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000-45,000, The radiation sensitive resin composition characterized by the above-mentioned. . The radiation sensitive resin composition of Claim 1 whose ratio of Mw / Mn is 1-2.0, when the polystyrene conversion number average molecular weight measured by the gel permeation chromatography of (B) alkali-soluble resin is Mn. The radiation sensitive according to claim 1 or 2, wherein (B) the alkali-soluble resin is a copolymer of a monomer mixture containing (b1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride and (b2) another unsaturated compound. Resin composition. The radiation-sensitive radiation according to any one of claims 1 to 3, wherein the alkali-soluble resin (B) has a group represented by the following formula (i) or a group represented by the following formula (ii) at at least one end of the polymer chain constituting it. Resin composition. <Formula i>

In formula (i), Z ¹ represents a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total of 3 to 20 atoms of a carbon atom and a hetero atom Monovalent heterocyclic groups of -OR, -SR, -N (R) ₂ , -OC (= 0) R, -C (= 0) OR, -C (= 0) N (R) ₂ , -P (= O) (OR) ₂ , -P (= O) (R) ₂ or a monovalent group having a polymer chain, each R is independently of each other an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, A monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 atoms having a carbon atom and a hetero atom, and the alkyl group having 1 to 20 carbon atoms and a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. The group, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted. <Formula ii>

In formula (ii), Z ² is a m-valent group derived from alkane having 1 to 20 carbon atoms, a m-valent group derived from aromatic hydrocarbon having 6 to 20 carbon atoms, a complex having 3 to 20 atoms in total of carbon atoms and hetero atoms M-valent group derived from a cyclic compound or m-valent group having a polymer chain, m-valent group derived from the above-mentioned alkanes having 1 to 20 carbon atoms, m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and the total number of atoms The m-valent groups derived from the heterocyclic compound of 3 to 20 may each be substituted, and m is an integer of 2 or more. The resin produced according to claim 4, wherein the alkali-soluble resin (B) is produced through a step of living radical polymerization using a thiocarbonylthio compound represented by the following general formula (1) or (2) as a molecular weight control agent: A radiation sensitive resin composition characterized by the above-mentioned. <Formula 1>

In formula (1), the definition of Z ¹ is the same as formula (i), p is an integer of 1 or more, and when R ¹ is p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon having 3 to 20 carbon atoms Group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, and -OR, -SR, -N (R) ₂ or a polymer chain Represents a monovalent group, and each R is, independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of a carbon atom and a hetero atom; A monovalent heterocyclic group of p, wherein p≥2, a pvalent group derived from an alkan having 1 to 20 carbon atoms, a pvalent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and a hetero atom Heterocyclic compounding with 3 to 20 atoms in total A p-valent group having a p-valent group or a polymer chain derived from water, the alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total atom Monovalent heterocyclic group having 3 to 20 carbon atoms, R, pvalent group derived from C1-20 alkanes, pvalent group derived from C6-20 aromatic hydrocarbons and heterocyclic compound having 3 to 20 atoms in total Each p-valent group derived from may be substituted. <Formula 2>

In Chemical Formula 2, Z ² and m have the same definition as in Chemical Formula ii, R ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. Group, a monovalent heterocyclic group having 3 to 20 carbon atoms in total and a hetero atom, -OR, -SR, -N (R) ₂ or a monovalent group having a polymer chain, each R independently of one another An alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a monovalent heterocyclic group having 3 to 18 carbon atoms in total having a carbon atom and a hetero atom; The alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may be substituted. (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation-sensitive radical generator, and (B) alkali-soluble resin contains at least one terminal of the polymer chain which comprises it A radiation sensitive resin composition having a group represented by the formula (i) or a group represented by the formula (ii), wherein the polystyrene reduced weight average molecular weight (Mw) measured by gel permeation chromatography is 1,000 to 45,000. (A) The coloring agent is a pigment, and the pigment dispersion obtained by mixing and dispersing the said pigment in the presence of a dispersing agent in a solvent, dispersing (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation-sensitive radical generator It mixes with the manufacturing method of the radiation sensitive resin composition in any one of Claims 1-6. The radiation sensitive resin composition of any one of Claims 1-6 for color filters. The color filter formed from the radiation sensitive resin composition of Claim 8. The color liquid crystal display device provided with the color filter of Claim 9.