KR101373895B1 - A colored photosensitive resin composition, color filter, liquid display device and imaging device having the same - Google Patents

Abstract

This invention is colored photosensitive resin composition containing binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The said binder resin (A) is a following ( It is a copolymer obtained by copolymerizing A1), (A2), (A3), and (A4), or unsaturated group containing resin obtained by making the following (A5) further react with the said copolymer, The colored photosensitive resin composition characterized by the above-mentioned. will be.

(A1): A compound having an unsaturated bond containing at least one skeleton selected from the group consisting of tricyclodecane skeleton and dicyclopentadiene skeleton in one molecule.

(A2): A compound containing an aromatic vinyl compound.

(A3): A compound having an unsaturated bond containing a hydroxyl group skeleton in one molecule.

(A4): unsaturated carboxylic acid.

(A5): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

Colored photosensitive resin composition, color filter

Description

Colored photosensitive resin composition, color filter, liquid crystal display and imaging device having same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER, LIQUID DISPLAY DEVICE AND IMAGING DEVICE HAVING THE SAME}

The present invention relates to a colored photosensitive resin composition, a color filter, a liquid crystal display device and an imaging device including the same.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an imaging device, etc. is uniformly apply | coated uniformly the coloring photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was patterned by spin coating. After that, an operation of exposing and developing a coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) and further heating and curing (hereinafter sometimes referred to as "postfiring") as necessary is repeated for each color. To form pixels of each color. Thereafter, a process of forming an ITO electrode on a surface of the color filter for a liquid crystal display device is essential, and in this process, the color filter is exposed to a high temperature of about 200 ° C or more. Moreover, also when forming an oriented film, it exposes to high temperature 200 degreeC or more.

As a coloring photosensitive resin composition which forms such a color filter, the composition containing a photopolymerizable compound and a photoinitiator with pigment and binder resin is used a lot. Moreover, the photosensitive resin composition containing a black pigment is used also for formation of a black matrix. The acrylic resin which has a carboxyl group in the side chain which is excellent in light resistance and little color change is used for such colored photosensitive composition. As an example, the colored resin composition obtained through the composition of the acrylic resin containing a carboxyl group in a side chain, a pigment, and a polyfunctional acrylate is used. Moreover, in order to raise a sensitivity, the photosensitive resin composition containing the reactive acrylic resin obtained by adding an unsaturated carboxylic acid and adding a basic acid anhydride to the polymer containing the monomer which has an epoxy group and an unsaturated double bond is used.

However, when the pixel is formed using such a conventional composition, the colored layer formed on the base may be deteriorated in brightness and color characteristics due to a high temperature process when the photosensitive resin composition having low heat resistance is used, or the photosensitive resin composition is decomposed. There is a problem that the image and color purity are lowered, such as afterimages generated by the outgas OUTGAS.

In order to improve the above problems, a binder resin containing tricyclodecane skeleton or dicyclopentadiene skeleton may be considered. However, when only the resin is used, developability is insufficient and margins are very insufficient or low adhesion when adjusting acid value and molecular weight. There are disadvantages to losing. In particular, the coloring photosensitive resin which coat | covers said coloring photosensitive resin composition on a glass substrate, is exposed by the exposure amount (365 nm) of 100mJ / cm <2>, and the post-firing film thickness after a baking process is required is 2.5 micrometers or more. In the case of a composition, there is a problem that the developability is insufficient and the margin is very insufficient when the acid value and the molecular weight are adjusted.

An object of the present invention is that development residues do not occur on the substrate or surface defects in the pixel portion when forming pixels using the colored photosensitive resin composition, and the sensitivity is excellent, there is no problem during development, and outgas is remarkably improved. It is to provide a photosensitive resin composition that reduces the problem of afterimage.

Still another object of the present invention is developed even when the film thickness after post-firing when the coloring photosensitive resin composition is coated on a glass substrate and exposed at an exposure dose (365 nm) of 100 mJ / cm 2 is omitted. It is an object to provide the coloring photosensitive resin composition which is excellent in the property and which significantly reduces the outgas which causes an afterimage.

Still another object of the present invention is an insulating film for a liquid crystal display of a high aperture method (hereinafter sometimes referred to as an HA method) and a color filter on array method (hereinafter, referred to as a COA method). It is providing the coloring photosensitive resin composition used for the insulating film for liquid crystal displays, etc.

The present invention for achieving the above object,

A colored photosensitive resin composition containing a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a coloring material (D) and a solvent (E), wherein the binder resin (A) is represented by the following (A1), It is a copolymer obtained by copolymerizing (A2), (A3) and (A4), The coloring photosensitive resin composition characterized by the above-mentioned is provided.

(A1): A compound having an unsaturated bond containing at least one skeleton selected from the group consisting of tricyclodecane skeleton and dicyclopentadiene skeleton in one molecule.

(A2): A compound containing an aromatic vinyl compound.

(A3): A compound having an unsaturated bond containing a hydroxyl group skeleton in one molecule.

(A4): unsaturated carboxylic acid.

Moreover, the said binder resin (A) provides the coloring photosensitive resin composition characterized by that it is unsaturated group containing resin obtained by making the copolymer (A5) which has an unsaturated bond and an epoxy group further react in 1 molecule.

Moreover, the ratio of the component derived from each of said (A1), (A2), (A3), and (A4) with respect to the total number of moles of the component of the said binder resin (A),

The structural unit derived from (A1) is 2-50 mol%,

The structural unit derived from (A2) is 2 to 60 mol%,

The structural unit derived from (A3) is 2-40 mol%,

The structural unit derived from (A4) provides the coloring photosensitive resin composition characterized by the above-mentioned.

Further, the proportion of the constituents derived from the above (A5) is 5 to 80 mol% based on the number of moles of the constituents derived from (A4) in the binder resin (A) provides a colored photosensitive resin composition. .

Furthermore, when the said coloring photosensitive resin composition is coated on a glass substrate, it is exposed by the exposure amount (365 nm) of 100 mJ / cm <2>, and the film thickness after post-firing when the image development process is skipped is colored photosensitive, characterized by the above-mentioned. It provides a resin composition.

The present invention further provides a color filter comprising a color layer formed by exposing and developing a colored photosensitive resin composition in a predetermined pattern, wherein the colored photosensitive resin composition is the colored photosensitive resin composition described above. Provide a filter.

The present invention also provides a liquid crystal display device having the color filter described above.

The present invention also provides an imaging device having the above-described color filter.

Hereinafter, the present invention will be described in detail.

The colored photosensitive resin composition which concerns on this invention is a colored photosensitive resin composition containing binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The said binder resin (A) is a copolymer obtained by copolymerizing following (A1), (A2), (A3), and (A4), or an unsaturated group containing resin obtained by making the said (A5) further react with the said copolymer, It is characterized by the above-mentioned. It relates to a colored photosensitive resin composition. In addition, although it is not restrict | limited, It is good to dissolve or disperse | distribute the other additive (F) arbitrarily in the said solvent (E).

(A1): A compound having an unsaturated bond containing at least one skeleton selected from the group consisting of tricyclodecane skeleton and dicyclopentadiene skeleton in one molecule.

(A2): A compound containing an aromatic vinyl compound.

(A3): A compound having an unsaturated bond containing a hydroxyl group skeleton in one molecule.

(A4): unsaturated carboxylic acid.

(A5): Compound which has an unsaturated bond and an epoxy group in 1 molecule.

The binder resin (A)

The binder resin (A) generally has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of a coloring material.

Binder resin (A) contained in the coloring photosensitive resin composition of this invention can be obtained by superposition | polymerization (this is also a concept including copolymerization) of the compound of said (A1), (A2), (A3) and (A4). It is a copolymer containing a structural unit.

In embodiment of this invention, as a compound (A1) which has an unsaturated bond, a tricyclotecan skeleton, and / or a dicyclopentadiene skeleton in 1 molecule, specifically, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, bdicyclopentenyloxyethyl (meth) acrylate, etc. are mentioned. Here, (meth) acrylate means acrylate and / or methacrylate.

Moreover, as a compound (A2) containing an aromatic vinyl compound, aromatic vinyl compounds, such as styrene, alpha-methylstyrene, and vinyltoluene, are mentioned.

Moreover, 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, etc. are mentioned specifically as a compound (A3) which has an unsaturated bond and a hydroxyl group skeleton in 1 molecule. Moreover, as a compound which has an unsaturated bond and a hydroxyl group skeleton in 1 molecule, the compound containing the hydroxyl group obtained by adding epoxy (meth) acrylate, such as glycidyl (meth) acrylate, to (meth) acrylic acid is also included and applied Possible compounds are not limited and are all included in the present invention.

Moreover, as unsaturated carboxylic acid (A4), acrylic acid, methacrylic acid, etc. are mentioned specifically ,. The acrylic acid and methacrylic acid may be used alone or in combination of two or more.

In addition to the acrylic acid and methacrylic acid, one or more other acids may be used. Specific examples of the other acid include unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, and fumaric acid.

In addition, the present invention is included in the present invention even when the monomers other than the above-mentioned (A1) to (A4) are further included and copolymerized, and the compound having an unsaturated bond copolymerizable with (A1) and (A3) is specifically Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and aminoamino (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic ester compounds including alicyclic substituents such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate;

Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylates;

Unsaturated carboxylic ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate and phenoxy (meth) acrylate;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;

Vinyl cyanide compounds such as (meth) acrylonitrile and alpha-chloroacrylonitrile; And

And maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide. These may be used alone or in combination of two or more.

It is preferable that the ratio of the structural component guide | induced from each of (A1)-(A4) used by this invention exists in the following range in mole fraction with respect to the total mole number of the structural component which comprises said copolymer.

The structural unit derived from (A1) is 2-50 mol%,

The structural unit derived from (A2) is 2 to 60 mol%,

The structural unit derived from (A3) is 2-40 mol%,

The structural unit derived from (A4) provides the coloring photosensitive resin composition characterized by the above-mentioned.

That is, the compound (A1) which has an unsaturated bond containing 1 or more types of frame | skeleton selected from the group which consists of a tricyclodecane skeleton and a dicyclopentadiene skeleton in the said one molecule, the compound (A2) containing an aromatic vinyl compound, 1 The copolymer obtained by the copolymerization reaction containing the compound (A3) which has an unsaturated bond containing a hydroxyl group skeleton in a molecule | numerator, and an unsaturated carboxylic acid compound (A4) is said (A1)-(A4) with respect to the total number-of-moles of a component. In the components derived from each Although not limited, it is preferably included in the range of 2 to 50 mol%, 2 to 60 mol%, 2 to 40 mol% and 2 to 70 mol%, respectively.

In particular, it is more preferable that the ratio of said structural component is the following ranges.

The structural unit derived from (A1) is 2 to 40 mol%,

The structural unit derived from (A2) is 2 to 50 mol%,

The structural unit derived from (A3) is 5 to 30 mol%,

The structural unit derived from (A4) is 2 to 60 mol%.

When the above-mentioned composition ratio is in the above range, a good balance of developability, solubility and heat resistance is obtained, and thus a preferable copolymer can be obtained.

In one embodiment of the present invention, the copolymer can be produced by reacting in the following manner.

To the flask equipped with the stirrer, the thermometer, the reflux cooling tube, the dropping lot and the nitrogen introduction tube, 0.5 to 20 times the amount of the solvent (E) was introduced together with respect to the total amount of (A1) to (A5) and the atmosphere in the flask was introduced. Substitute in nitrogen for air. Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times of the solvent (E) and azobisisobuty by mass basis with respect to the total amount of (A2), (A3), and (A4). A solution obtained by adding 0.1 to 10 mol% of a polymerization initiator, such as ronitrile or terbutyrryloxy 2-ethylhexyl carbonate, to the total moles of (A1), (A2), (A3), and (A4) (room temperature or heating). Under agitation solution) dropwise into the above flask over 0.1 to 8 hours, and further stirred at 40 to 140 ° C for 1 to 10 hours to obtain a copolymer.

In the above process, part or all of the polymerization initiator may be put in the flask, or part or all of (A1), (A2), (A3) and (A4) may be put in the flask. Also, alpha-methylstyrene dimers or mercapto compounds may be used as chain transfer agents to control molecular weight or molecular weight distribution. The use amount of alpha-methylstyrene dimer or mercapto compound is 0.005 to 5% by mass with respect to the total amount of (A1), (A2), (A3) and (A4). In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

Although the binder resin (A) contained in the coloring photosensitive resin composition of this invention is not restrict | limited, An unsaturated bond and an epoxy group in 1 molecule are copolymerized by copolymerizing (A1), (A2), (A3), and (A4). It is more preferable that it is unsaturated group containing resin obtained by making the compound (A5) which has further react. By adding said (A5) to said copolymer, photo / thermosetting property can be provided to binder resin.

As a specific example of the compound (A5) which has an unsaturated bond and an epoxy group in the said 1 molecule of this invention, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3, 4- epoxycyclo Hexyl methyl (meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned. Among these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more.

Moreover, it is preferable that the ratio of the structural unit derived from (A5) in the said binder resin (A) is 5-80 mol% with respect to the number-of-moles of the structural component derived from (A4) in the said binder resin (A), 10 To 70 mol% is more preferable. If the composition ratio of (A5) is in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

In embodiment of this invention, binder resin (A) can be manufactured by making said copolymer and (A5) react by the following methods, for example.

The atmosphere in the flask was replaced by nitrogen to air, and in the copolymer, as a reaction catalyst of 5 to 80 mol% of (A5), a carboxyl group and an epoxy group in a molar fraction with respect to the structural unit derived from (A4), for example, Tris Dimethylaminomethylphenol is 0.01 to 5% by mass relative to the total amount of (A1), (A2), (A3) and (A4) and as a polymerization inhibitor, for example hydroquinone (A1), (A2), The copolymer and (A5) can be reacted by adding 0.001 to 5% in a flask on a mass basis with respect to the total amount of (A3) and (A4) for 1 to 10 hours at 60 to 130 ° C. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

Although the binder resin (A) of this invention is not restrict | limited, It is preferable that the weight average molecular weight in terms of polystyrene is in the range of 3,000-100,000, and it is more preferable to exist in the range of 5,000-50,000. When the weight average molecular weight of binder resin (A) exists in the range of 3,000-100,000, film | membrane decrease hardly arises at the time of image development, and since the missing property of a non-pixel part at the time of image development tends to be favorable, it is preferable.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A), it is more preferable that it is 1.8-4.0. Molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferable because it is excellent in developability when it is 1.5-6.0.

Photopolymerization  The compound (B)

The photopolymerizable compound (B) contained in the colored photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. have.

The photopolymerizable compound (B) used in the present invention may be prepared by mixing two or more photopolymerizable compounds having different functional groups or different functional groups in order to improve developability, sensitivity, adhesion, surface problems, and the like of the colored photosensitive resin composition And does not limit its scope.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, thipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound (B) is used in an amount of usually 1 to 60 parts by mass, preferably 5 to 50 parts by mass based on the total 100 parts by mass of the binder resin (A) and the photopolymerizable compound (B). When the photopolymerizable compound (B) is in the range of 1 to 60 parts by mass based on the above-mentioned criteria, the strength and smoothness of the pixel portion tends to be favorable.

Light curing Initiator (C)

The photopolymerization initiator (C) contained in the colored photosensitive resin composition of the present invention is not limited, but is at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound. The colored photosensitive resin composition containing the photopolymerization initiator (C) described above has a high sensitivity, and the film formed using this composition has good strength and surface smoothness of the pixel portion.

Moreover, when photopolymerization start adjuvant (C-1) is used together with a photoinitiator (C), since the coloring photosensitive resin composition containing these becomes more sensitive and the productivity at the time of forming a color filter using this composition is preferable, it is preferable. .

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Moreover, as said acetophenone type compound, for example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4 -(2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) And oligomers of phenyl] propan-1-one. As an acetophenone type compound, the compound represented by following formula (1) is mentioned, for example.

&Lt; Formula 1 >

In Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms. Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group at 4,4' An imidazole compound substituted by a haloalkoxy group, and the like. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

As said oxime compound, 0-ethoxycarbonyl- (alpha)-oxyimino- 1-phenyl propane- 1-one of following formula (2) is mentioned, for example.

(2)

Further, as long as the effect of the present invention is not impaired, other photopolymerization initiators generally used in this field may be further used in combination. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photopolymerization initiators.

In addition, a photopolymerization initiator having a group capable of chain transfer may be used. As the photopolymerization initiator, for example, those described in Japanese Patent Publication (A) No. 2002-544205 can be cited.

As a photoinitiator which has a group which can cause said chain transfer, the compound represented by following formula (3)-8 is mentioned, for example.

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

In addition, you may use combining a photoinitiator (C-1) with a photoinitiator (C).

As the photopolymerization initiation assistant (C-1), an amine compound and a carboxylic acid compound are preferably used. Specific examples of the amine compound in the photopolymerization initiation assistant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4- 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis Diethylamino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The amount of the photopolymerization initiator (C) to be used is generally 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass based on 100 parts by mass of the total of the binder resin (A) and the photopolymerizable compound (B) 1) is used in an amount of usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass based on the above-mentioned standards.

When the amount of the photopolymerization initiator (C) is in the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion tend to be favorable . Moreover, when the usage-amount of a photoinitiator auxiliary (C-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

Coloring material (D)

The coloring material (D) used in the present invention is preferably an organic pigment or an inorganic pigment usually used as a pigment in a pigment dispersion resist. If necessary, dyes may be used and are included in the present invention.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, oxides or composite metals of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony Oxides; and the like.

Specific examples of the organic pigment and inorganic pigment include compounds classified as pigments in the Color Index (published by The society of Dyers and Colorists), and more specifically, pigments having the following color index (CI) numbers. Although these are mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76

C.I. Pigment Green 7, 10, 15, 25, 36 and 47

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

These coloring materials (D) can be used individually or in combination of 2 or more types, respectively. The content of the coloring material (D) is usually in the range of 3 to 60 mass%, preferably 5 to 55 mass%, based on the total solid content in the colored photosensitive resin composition. When the content of the coloring material (D) is in the range of 5 to 60 mass% based on the above-mentioned criteria, even if a thin film is formed, the color density of the pixel is sufficient and the residue of the non- Which is preferable.

Solvent (E)

The solvent (E) contained in the colored photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of colored photosensitive resin composition can be used.

Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetonitrile three Ketones such as tones, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-meth Ester, such as methyl oxypropionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable. Ester, such as ethyl propionate and 3-methoxy methyl propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned.

These solvents (E) may be used alone or in combination of two or more.

The content of the solvent (E) in the colored photosensitive resin composition of the present invention is usually 60 to 90% by mass, preferably 70 to 85% by mass, based on the total amount of the colored photosensitive resin composition containing the solvent. When the content of the solvent (E) is in the range of 60 to 90% by mass on the basis of the above criteria, it can be applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is preferable since the coating property tends to be good.

Additive (F)

If necessary, additives (F) such as fillers, other polymer compounds, curing agents, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents may be added to the colored photosensitive resin composition of the present invention.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of other polymer compounds include curable resins such as epoxy resin and maleimide resin, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane have.

The curing agent is used for enhancing deep curing and mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins and other aromatic epoxy resins and alicyclic compounds. Epoxy resins, glycidyl ester resins, glycidylamine resins, or aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, Isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

As said oxetane compound in the said hardening | curing agent, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example.

A curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent in the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators.

As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

These adhesion promoters may be used alone or in combination of two or more.

The concentration based on resist solid content is usually 0.01 to 10% by mass, preferably 0.05 to 2% by mass.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The colored photosensitive resin composition of the present invention can be produced, for example, by the following method. The coloring material (D) is mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the coloring material becomes about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (A) may be blended. The remainder of binder resin (A), the photopolymerizable compound (B), the photoinitiator (C), the other components used as needed, and the additional solvent as needed in the obtained dispersion liquid (henceforth a mill base). Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

Hereinafter, a method of forming a pattern of a colored photosensitive resin composition according to the present invention will be described.

The method for forming a pattern of a colored photosensitive resin composition according to the present invention comprises the steps of applying the above-mentioned colored photosensitive resin composition on a substrate, selectively exposing a part of the colored photosensitive resin composition, And removing the exposed region or the non-exposed region.

As an example, it is coated on a substrate as follows to form a pattern by photo-curing and development and can be used as a black matrix or a colored pixel (colored image).

First, the composition of the present invention is applied onto a substrate (including but not limited to a glass or silicon wafer) or a layer containing a solid content of a previously formed colored photosensitive resin composition and preliminarily dried to remove volatile components such as solvents, . The thickness of the coating film at this time is usually about 1 to 3 mu m. Ultraviolet rays are applied to a specific region through a mask to obtain a desired pattern on the thus obtained coating film. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. Thereafter, the coated film after curing is brought into contact with the aqueous alkaline solution to dissolve and expose the non-exposed region, thereby making it possible to produce a desired pattern. After the development, it is possible to carry out post-drying (post-firing) for about 10 to 60 minutes at 150 to 230 ° C as necessary.

More preferably, the coloring photosensitive resin composition of this invention is exposed to a 100 mJ / cm <2> exposure amount (365 nm) on a glass substrate, and it coats so that the film thickness after baking may be 2.5 micrometers or more when the image development process is skipped, and it is preliminary. After drying, the obtained coating film is irradiated to a specific region with an exposure amount (365 nm) of 100 mJ / cm 2 through a photomask, and after the coating film is developed, post-firing is carried out as necessary.

The developing solution used for development after patterned exposure is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be either an inorganic or an organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The preferable concentration of the alkaline compound in the alkali developing solution is in the range of 0.01 to 10 mass%, more preferably 0.03 to 5 mass%.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dode Alkyl aryl sulfonates, such as sodium cinnaphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the alkaline developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

Hereinafter, a color filter according to the present invention will be described.

The color filter according to the present invention is characterized by comprising a color layer formed by exposing and developing the above-mentioned colored photosensitive resin composition in a predetermined pattern.

The pattern forming method of the colored photosensitive resin composition is described above, and a detailed description thereof will be omitted. As described above, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the application of the colored photosensitive resin solution, the drying, the patterned exposure to the dry film obtained, and the development. The color filter can be obtained by repeating the operation for the number of colors required for the color filter. The construction and manufacturing method of the color filter are well known in the art, and a detailed description thereof will be omitted.

The color filter is usually a black matrix and three primary color pixels of red, green and blue arranged on a substrate. However, by performing the above operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to any color A black matrix or pixel of the color is obtained and the same operation is carried out by using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a target color for other colors to arrange the black matrix and the three primary color pixels on the substrate can do. Of course, the photosensitive resin composition of this invention can also be applied only to 1 color, 2 color, or 3 colors of a black matrix and a ternary color.

The black matrix, which is a light-shielding layer, may be a colored resin (colored in black) of the present invention, but may be formed of, for example, a chromium layer. Therefore, the colored photosensitive resin composition .

The color filter produced using the colored photosensitive resin composition of the present invention has a small difference in film thickness within the plane, and can have a thickness difference of 0.15 mu m or less, more preferably 0.05 mu m or less, for example, with a film thickness of 1 to 4 mu m . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device and an image pick-up element of outstanding quality by high yield by assembling this to a color liquid crystal display device and an image pick-up element.

The present invention also includes a liquid crystal display device and an image pickup device provided with the color filter described above.

The liquid crystal display of the present invention includes a configuration known in the art except for the color filter described above. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a TFT (Thin Film Transistor) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed at a position where the TFT substrate overlaps with a color filter can be given. The TFT substrate includes an outer frame made of a light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of a nematic liquid crystal placed in the outer frame, a plurality of pixel electrodes , A transparent glass substrate on which pixel electrodes are formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyimide. Each of the plurality of pixel electrodes is connected to a plurality of thin film transistors formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Accordingly, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

The image pickup device of the present invention is characterized by including the above-described color filter, and in the case of other configurations, the configurations known in the art can be applied without limitation. That is, all the image pickup devices to which the above-described color filter can be applied are included in the present invention. Both a charge coupled device (CCD) and a Complementary Metal Oxide Silicon (CMOS) imaging device are included in the present invention, and both an active pixel sensor and a passive pixel sensor are included in the present invention. Included.

For example, a semiconductor substrate divided into a light receiving area and a light blocking area, a light blocking film formed on the light blocking area, a flattening layer formed over the entire substrate on the light blocking film, a color filter formed on the flattening layer, and a concave lens formed on the color filter. And an image pickup device having a color filter, wherein the color filter is the color filter described above.

The semiconductor substrate is divided into a light receiving region in which light passing through the lens is received and a light blocking region in which light is not received, and a photodiode may be formed in the semiconductor substrate of the light receiving region. An impurity layer may be formed. A charge transfer electrode may be formed on the impurity layer to transfer charges supplied from the photodiode. The light blocking film is made of a material capable of blocking light, and is formed over the entire light blocking area. The planarization layer may be formed to planarize the uneven portion by the elements (eg, the charge transfer electrode, the light blocking film, etc.) formed on the impurity layer, and protect the charge transfer electrode, the light blocking film, and the like. On the planarization layer, color filters are formed in respective colors corresponding to the respective light receiving regions. The pad supplies an external electrical signal to the solid-state image pickup device or transmits an internal electrical signal to the solid-state image pickup device. The lens is a concave lens, and is a hybrid polyamide-based polyimide layer having a refractive index of 0.1 or more lower than the transparent epoxy resin layer formed thereon. The transparent epoxy resin layer having a refractive index higher than 0.1 may be formed on the lens.

As another example, a plurality of photo diodes (PD) for converting a signal of light into an electrical signal are arranged in a matrix form, and are formed between each of the vertical photo diodes arranged in the matrix form. A plurality of vertical charge coupled device (VCCD) for transferring charges generated in the vertical direction, and a horizontal charge transfer region for transferring charges transferred by each of the vertical charge transfer regions in a horizontal direction ( The above-described color filter and micro device are configured to include a horizontal charge coupled device (HCCD) and a sense amplifier configured to output an electrical signal by sensing a charge transmitted in the horizontal direction and formed on a vertical line of the photodiode. It may be configured to include a lens.

As another example, photodiodes (PDs) and MOS transistors, which are light-receiving elements disposed at predetermined intervals on a semiconductor substrate, may form an element layer constituting a pixel and an insulating layer separating each pixel. have. A metal wiring layer having a plurality of metal wires is formed on the semiconductor substrate, and then a color filter array is formed thereon, and a coating layer for adjusting the focal length is formed on the color filter array. The upper portion of the coating layer corresponds to each photodiode PD, and a microlens for concentrating external light to the photodiode PD is formed, and the upper portion of the microlens is supported by a CMOS image sensor module, An objective lens for condensing light can be formed. The color filter may be configured to be the above-described color filter.

< Example >

As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all changes within the meaning and range equivalent to the scope of the claims. Hereinafter, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to the examples. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

&Lt; Synthesis of Resin A &

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. 0.35 mol), 38.7 g (0.45 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 44.0 g (0.2 mol), glycerin methacrylate 16.0 g (0.1 mol) And a solution in which 3.6 g of azobisisobutyronitrile was added to the mixture containing 136 g of propylene glycol monomethyl ether acetate, was added dropwise to the flask over 2 hours from the dropping lot, and further stirring was continued at 100 ° C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown into the flask, reaction was continued at 110 degreeC for 6 hours, and resin A with a solid acid value of 105.7 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 20,000, and molecular weight distribution (Mw / Mn) was 2.3.

&Lt; Synthesis of Resin B >

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. The atmosphere in the flask was changed to nitrogen from air, and the temperature was raised to 100 ° C., followed by alpha-methylstyrene 35.0 g (0.3 mol), methacrylic acid 43.0 g (0.5 mol), monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.1 mol), glycerin methacrylate 16.0 g (0.1 Mole) and 136 g of propylene glycol monomethyl ether acetate were added dropwise to the flask over 2 hours from a dropwise addition of 3.6 g of azobisisobutyronitrile, followed by stirring at 100 DEG C for further 5 hours. . Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin B with a solid acid value of 122.7 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 21,500, and molecular weight distribution (Mw / Mn) was 2.3.

&Lt; Synthesis of resin C >

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., followed by 29.5 g of vinyltoluene ( 0.25 mol), methyl methacrylate 11.0 g (0.1 mol), methacrylic acid 38.7 g (0.45 mol), monomethacrylate (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.1 mol) of tricyclodecane skeleton To a mixture containing 22.0 g (0.15 mol) of 2-hydroxyethyl methacrylate and 136 g of propylene glycol monomethyl ether acetate, a solution containing 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the lot. It dripped and continued stirring at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was added to the flask, and the reaction was continued at 110 DEG C for 6 hours to obtain Resin C having a solid acid value of 122.7 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 23,400, and molecular weight distribution (Mw / Mn) was 2.4.

&Lt; Synthesis of Resin D >

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., followed by 35.0 g of vinyltoluene ( 0.3 mol), 38.7 g (0.45 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.1 mol), glycerin methacrylate 24.0 g (0.15 mol) And a solution in which 3.6 g of azobisisobutyronitrile was added to the mixture containing 136 g of propylene glycol monomethyl ether acetate, was added dropwise to the flask over 2 hours from the dropping lot, and further stirring was continued at 100 ° C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin D with a solid acid value of 122.0 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin E>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., and then 55.6 g of vinyltoluene ( 0.5 mole), methacrylic acid 25.0 g (0.3 mole), monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 22.0 g (0.1 mole), glycerin methacrylate 16.0 g (0.1 mole) And a solution in which 3.6 g of azobisisobutyronitrile was added to the mixture containing 136 g of propylene glycol monomethyl ether acetate, was added dropwise to the flask over 2 hours from the dropping lot, and the stirring was continued for 5 hours at 100 ° C. Resin E having a value of 104.5 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 19,000, and molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin F>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. 0.5 mole), 43.0 g (0.5 mole) of methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate were added dropwise to the flask over 2 hours from a lot by dropping a solution containing 3.6 g of azobisisobutyronitrile. Stirring was continued for 5 hours at 100 ° C. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], and 0.9 g of trisdimethylaminomethylphenol. And 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin F with a solid acid value of 123.5 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 20,000, and molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin G>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. 0.3 mole), 38.7 g (0.45 mole) of methacrylic acid, 8.0 g (0.25 mole) of glycerin methacrylate, and 136 g of propylene glycol monomethyl ether acetate were added to a solution containing 3.6 g of azobisisobutyronitrile. It was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin G with a solid acid value of 107.0 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 22,000, and molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin H>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube. The atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C. Benzyl methacrylate 3.6 g of azobisisobutyronitrile was added to the mixture containing g (0.4 mol), methacrylic acid 43.0 g (0.5 mol), glycerin methacrylate 32.0 g (0.2 mol), and 136 g of propylene glycol monomethyl ether acetate. The solution was added dropwise to the flask over 2 hours from the dropping lot, and the stirring was continued for 5 hours at 100 ° C. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin H of 123.5 mgKOH / g of solid acid value was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 20,000, and molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of Resin I>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., 17.6 g of benzyl methacrylate. (0.1 mol), 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 44.0 g (0.2 mol), glycerin methacrylate 32.0 g (0.2 mol) ) And a solution containing 3.6 g of azobisisobutyronitrile added to the mixture containing 136 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropwise lot, and the stirring was continued at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin I of 124.5 mgKOH / g of solid acid value was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and molecular weight distribution (Mw / Mn) was 2.2.

<Synthesis of Resin J>

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air, and then heated to 100 ° C., and then 41.2 g of vinyltoluene ( 0.35 mol), 38.7 g (0.45 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Kasei Co., Ltd.) 44.0 g (0.2 mol), and 136 g of propylene glycol monomethyl ether acetate The solution which added 3.6 g of azobisisobutyronitrile to the mixture was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 22.5 g of glycidyl methacrylate [0.15 mol, (50 mol% of the carboxyl groups of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone was thrown in the flask, reaction was continued at 110 degreeC for 6 hours, and resin J with a solid acid value of 107.0 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 22,500, and molecular weight distribution (Mw / Mn) was 2.3.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

&Lt; Example 1 >

Of the components shown in Table 1 below, the total amount of the pigment as the coloring material (D) and the pigment dispersant as the additive (F) is mixed so as to be 20% by mass with respect to the mixture of the pigment, the pigment dispersant and the propylene glycol monomethyl ether acetate. After the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

<Table 1>

The coloring material (D) C.I. Pigment Blue15: 6 5.0 parts C.I. Pigment Violet 23 0.5 part The binder resin (A) Resin A (solids content calculation) 6.0 parts Photopolymerizable Compound (B) Dipentaerythritol hexaacrylate
(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 6.0 parts
The photopolymerization initiator (C) 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butanone
(Irgacure 369, manufactured by Ciba Specialty Chemical) 1.5 parts
4,4'-di (N, N'-dimethylamino) -benzophenone
(EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.) 0.5 parts
Solvent (E) Propylene glycol monomethyl ether acetate 78.8 Part Additive (F) Pigment dispersant (polyester type) 1.2 parts Epoxy resin (SUMI-EPOXY ESCN-195XL; Sumitomo Kagaku Kogyo Co., Ltd.) 0.4 part 3-methacryloxypropyltrimethoxysilane 0.1 part

A glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 3.0 µm, and then Preliminary drying was carried out at 100 ° C for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 220 ° C. for 30 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In the non-pixel portion, development residue and poor development did not occur on the substrate. And even if it develops, the minimum required exposure amount required in order to form the pattern without surface roughness was 30mJ / cm <2>.

<Example 2>

It carried out similarly to Example 1 except having changed resin A into resin B in Example 1. The evaluation results are shown in Table 2 below.

<Example 3>

It carried out similarly to Example 1 except having changed resin A into resin C in Example 1. The evaluation results are shown in Table 2 below.

<Example 4>

It carried out similarly to Example 1 except having changed resin A into resin D in Example 1. The evaluation results are shown in Table 2 below.

&Lt; Example 5 >

It carried out similarly to Example 1 except having changed resin A into resin E in Example 1. The evaluation results are shown in Table 2 below.

&Lt; Comparative Example 1 &

It carried out similarly to Example 1 except having changed resin A into resin F in Example 1. The evaluation results are shown in Table 3 below.

Comparative Example 2

It carried out similarly to Example 1 except having changed resin A into resin G in Example 1. The evaluation results are shown in Table 3 below.

&Lt; Comparative Example 3 &

It carried out similarly to Example 1 except having changed resin A into resin H in Example 1. The evaluation results are shown in Table 3 below.

&Lt; Comparative Example 4 &

It carried out similarly to Example 1 except having changed resin A into resin I in Example 1. The evaluation results are shown in Table 3 below.

&Lt; Comparative Example 5 &

It carried out similarly to Example 1 except having changed resin A into resin J in Example 1. The evaluation results are shown in Table 3 below.

<Table 2>

Example 1 Example 2 Example 3 Example 4 Example 5 Sensitivity * 1 (mJ / cm ² ) 40 45 45 30 65 Development residue on the substrate * 2 ○ ○ ○ ○ ○ Sectional shape * 3 ○ ○ ○ ○ ○ Pencil Hardness * 4 5H 5H 5H 4H 4H Outgassing * 5 30% < 33% < 45% < 40% 45% Developability * 6 ○ ○ ○ ○ ○

<Table 3>

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Sensitivity * 1 (mJ / cm ² ) 45 50 120 80 50 Development residue on the substrate * 2 ○ X ○ ○ X Sectional shape * 3 ○ ○ ○ ○ ○ Pencil Hardness * 4 3H 4H 3H 5H 5H Outgassing * 5 100% 85% 110% 80% 45% Developability * 6 X X △ ○ X

* 1: represents the minimum necessary exposure amount necessary to form a pattern having no surface roughness even when developed.

* 2: O: no development residue on the substrate, X: development residue on the substrate

* 3: The cross-sectional shape of the pixel end was observed using SEM.

      ○: Net taper phase, X: Reverse taper phase

* 4: The cured coating film was produced like Example except having not used a photomask. The measurement of pencil hardness is in accordance with JIS K5600-5-4.

* 5: Outgas was analyzed by pyrolysis at 230 ° C. for 30 minutes through Py-GC / FID to analyze the collected compounds. The resultant value was obtained as a percentage based on the value of Comparative Example 1 as 100%.

* 6: Developability is measured at 23 ℃ / 0.04% KOH

      ○: less than 30 seconds, Δ: 30 to 50 seconds X: 50 seconds or more.

Coloring photosensitive resin compositions of Examples 1, 2, 3, 4 and 5 containing the binder resin of the present invention from Table 2 has a high sensitivity and a high development speed, the outgas generation is significantly lowered to solve the afterimage problem It was found that a filter was obtained. On the other hand, the colored photosensitive resin compositions of Comparative Examples 1, 2, 3, 4, and 5, which do not contain the unsaturated group-containing binder resin of the present invention, have insufficient sensitivity or poor development speed, and have a large amount of outgas. It was not possible to obtain a high quality color filter by lowering the quality of the film.

According to the present invention, when a pixel is formed using the colored photosensitive resin composition of the present invention, no development residue occurs on the substrate or surface defects occur in the pixel portion. Since the gas is significantly reduced, the present invention provides a photosensitive resin composition that solves the afterimage problem, thereby providing a high quality color filter.

Further, even when the above-mentioned colored photosensitive resin composition is coated on a glass substrate and exposed at an exposure amount (365 nm) of 100 mJ / cm 2 and the development step is omitted, the developability is excellent even when the film thickness after post-firing is 2.5 µm or more. And it can provide the coloring photosensitive resin composition which significantly reduces the outgas which causes an afterimage.

Moreover, the coloring photosensitive resin composition of this invention can also be used as an ultraviolet curable ink, a photoresist, and a coloring photo spacer. The photosensitive resin composition which removed the coloring material from the coloring photosensitive resin composition of this invention is an insulating film for liquid crystal displays of a high aperture system, the insulating film for liquid crystal displays of a color filter on array system, a photo spacer, an overcoat (flattening film), It can also be used for the projection forming material for liquid crystal alignment control. The coloring photosensitive resin composition of this invention can be preferably used, in order to form the coloring pixel (color image) used for a color liquid crystal display device, an imaging element, etc.

Claims (8)

This invention is colored photosensitive resin composition containing binder resin (A), a photopolymerizable compound (B), a photoinitiator (C), a coloring material (D), and a solvent (E), The said binder resin (A) is a following ( It is a copolymer obtained by copolymerizing A1), (A2), (A3), and (A4), (A1): Compound which has an unsaturated bond containing 1 or more types of frame | skeleton selected from the group which consists of a tricyclodecane skeleton and a dicyclopentadiene skeleton in 1 molecule, (A2) a compound containing an aromatic vinyl compound, (A3): a compound having an unsaturated bond containing a hydroxyl group skeleton in one molecule, (A4): unsaturated carboxylic acid, The ratio of the component derived from each of said (A1), (A2), (A3), and (A4) with respect to the total number of moles of the component of the said binder resin (A), The structural unit derived from (A1) is 2-50 mol%, The structural unit derived from (A2) is 2 to 60 mol%, The structural unit derived from (A3) is 2-40 mol%, The structural unit derived from (A4) is 2 to 70 mol%, The coloring photosensitive resin composition characterized by the above-mentioned. The colored photosensitive resin composition according to claim 1, wherein the binder resin (A) is an unsaturated group-containing resin obtained by further reacting the copolymer with a compound (A5) having an unsaturated bond and an epoxy group in one molecule. delete The coloring photosensitive resin of Claim 2 whose ratio of the component derived from said (A5) is 5-80 mol% with respect to the number-of-moles of the component derived from (A4) in the said binder resin (A). Composition. The film thickness after post-firing at the time of spin-coating the said colored photosensitive resin composition on the glass substrate, exposing at 100mJ / cm <2> of exposure amount (365 nm), and omitting a developing process is characterized by the above-mentioned. Colored photosensitive resin composition to be used. A color filter comprising a color layer formed by applying a colored photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern, The said colored photosensitive resin composition is the colored photosensitive resin composition of any one of Claims 1, 2, 4, and 5, The color filter characterized by the above-mentioned. A liquid crystal display device comprising the color filter of claim 6. An image pickup device comprising the color filter of claim 6.