KR101339626B1 - A colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

The coloring photosensitive resin composition containing (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring material, and (E) solvent, (C) photoinitiator is (1) acetophenone At least one selected from the group consisting of oxime and triazine compounds; And (2) a polyfunctional thiol compound, and (2) the polyfunctional thiol compound relates to a colored photosensitive resin composition in the range of 0.1 to 50 mass% based on the total mass of the photopolymerization initiator.

The colored photosensitive resin composition of the present invention can be completely cured on a glass or plastic substrate even by a low temperature baking process of 150 ° C. or lower, and the color layer formed using the same exhibits excellent sensitivity and chemical resistance.

Colored photosensitive resin composition, low temperature hardening, color filter, heat crosslinking agent

Description

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

The present invention relates to a colored photosensitive resin composition, a color filter comprising a pixel formed of the composition, and a liquid crystal display device having the color filter.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. A color filter used in a color liquid crystal display device or the like is generally formed by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned by spin coating, The coating film formed by drying (hereinafter also referred to as preliminary firing) is exposed and developed, and if necessary, further heat curing (hereinafter also referred to as "post-firing") is repeated for each color to obtain each color Thereby forming a pixel. At this time, the glass substrate is used, but it is fragile, heavy, and thick. In this regard, a description of using a plastic substrate to replace a glass substrate is described in Japanese Patent Laid-Open No. 11-271736.

However, when the plastic substrate is used, low-temperature process introduction is essential. Existing colored photosensitive resin compositions prepared for this purpose do not completely cure, exposing the disadvantages of lack of sensitivity and chemical resistance.

As a method for solving such a problem, Japanese Patent No. 2937208 describes using a melamine resin as a thermal crosslinking agent, and Japanese Laid-Open Patent Publication No. 2003-113224 discloses a method of using an alicyclic epoxy resin as a thermal crosslinking agent. However, even when using this method, if the post-baking still at 150 ℃ or less, there is a problem that the lack of sensitivity and chemical resistance is generated and there is a need for improvement.

An object of the present invention is to provide a colored photosensitive resin composition which can be completely cured on a glass or plastic substrate even by a low temperature baking process of 150 ° C. or less, and the pixels produced using the same exhibit excellent sensitivity and chemical resistance.

It is still another object of the present invention to provide a high quality color filter including a pixel exhibiting excellent sensitivity and chemical resistance.

Another object of the present invention is to provide a high quality liquid crystal display device.

In order to achieve the object of the present invention,

As a coloring photosensitive resin composition containing (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring material, and (E) solvent,

(C) the photopolymerization initiator is (1) at least one member selected from the group consisting of acetophenone, oxime and triazine-based compounds; And (2) a polyfunctional thiol compound, and (2) the polyfunctional thiol compound provides a colored photosensitive resin composition in a range of 0.1 to 50 mass% based on the total mass of the photopolymerization initiator.

In order to achieve another object of the present invention,

A color filter comprising a colored layer comprising a formed pixel formed by coating a colored photosensitive resin composition on a substrate and exposing and forming a predetermined pattern, wherein the colored layer is formed of the colored photosensitive resin composition according to the present invention. It provides a color filter characterized by.

In order to achieve another object of the present invention, there is provided a liquid crystal display device having a color filter according to the present invention.

Since the colored photosensitive resin composition of the present invention can be completely cured on a glass or plastic substrate even by a low temperature baking process of 150 ° C. or lower, the pixels produced using the same exhibit excellent sensitivity and chemical resistance. Moreover, the color filter and liquid crystal display device containing the pixel formed using the coloring photosensitive resin composition of this invention also show high quality.

Hereinafter, the present invention will be described in detail.

The present invention provides a colored photosensitive resin composition containing (A) binder resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) coloring material and (E) solvent, wherein (C) photopolymerization initiator is (1) At least one selected from the group consisting of acetophenone, oxime and triazine-based compounds; And (2) a polyfunctional thiol compound, and (2) the polyfunctional thiol compound relates to a colored photosensitive resin composition in the range of 0.1 to 50 mass% based on the total mass of the photopolymerization initiator.

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) of this invention is resin containing the structural unit which can be obtained by superposing | polymerizing (this is also a concept including copolymerization) of compound (A1) which has an alicyclic epoxy group and an unsaturated bond in a molecule | numerator. That is, the compound (A1) having an unsaturated bond is polymerized alone or together with another compound to form the binder resin (A).

Preferably, the binder resin according to the present invention is a copolymer obtained by copolymerizing the following compounds (A1) to (A3), or an unsaturated group-containing resin obtained by further reacting the following (A4).

The binder resin (A) according to the present invention is described in more detail as follows:

(A1): the compound (A1) which has an alicyclic epoxy group and an unsaturated bond in a molecule | numerator,

(A2): a compound having an unsaturated bond capable of copolymerization with (A1) and (A3)

(A3): unsaturated carboxylic acid compound, and

(A4): A compound having an unsaturated bond and an epoxy group in one molecule.

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.

The compound (A1) having an alicyclic epoxy group and an unsaturated bond in the molecule may be one or more selected from compounds of the following formula.

≪ Formula 1 >

(Wherein R1 is a hydrogen atom or an alkyl group (C1-C12), R2 is a hydrogen atom or an alkyl group (C1-C12), an allyl group, a phenyl group, a benzyl group, a halogen atom or an alkoxy group having 1-8 carbons, n is an integer from 1 to 12.)

≪ EMI ID =

(2b)

(In Formula 2a and Formula 2b, R1 is hydrogen or a C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon with or without a hetero atom of N, O or S, R2 is a hetero atom of N, O or S or Not included C ₁ to C ₂₀ aliphatic or aromatic hydrocarbons.)

Examples of the compound of formula 1 include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyljade Cetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxy Methyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluoro Oxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl ) -3-ethyl oxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryl Loyloxyethyl) -2-pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2, 2-difluoro-3- (methacryloyloxyethyl) Oxetane, 3- (methac Methacrylic acid esters such as liloyloxyethyl) -2,2,4-trifluorooxetane and 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluoro oxetane; 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyl Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (Acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl)- 2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acrylic Loyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (acrylic Loyloxyethyl) -2-phenyl oxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-triflo Rooxetane, 3- (acryloyloxye ) It may be mentioned acrylic acid esters such as -2,2,4,4- tetrahydro flow oxetane.

Examples of the compounds represented by the above formulas (2a) and (2b) include epoxidized dicyclodecaneyl (meth) acrylate (3,4-epoxytricyclodecane-8-yl (meth) acrylate and 3,4-epoxytricyclodecane-8-yl). (Meth) acrylate, epoxidized dicyclopentanyloxyethyl (meth) acrylate (2- (3,4-epoxytricyclodecane-9-yloxy) ethyl (meth) acrylate, 2- (3,4- Epoxy tricyclodecane-8-yloxy) ethyl (meth) acrylate, epoxidized dicyclopentanyloxyhexyl (meth) acrylate, etc. Especially, Preferably, epoxidized dicyclodecaneyl (meth) is mentioned. Acrylate, epoxidized dicyclopentanyloxyethyl (meth) acrylate, etc. are mentioned.

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

In addition, the (meth) acrylate recorded in this specification means an acrylate and / or a methacrylate.

In the present invention, the compound (A2) having an unsaturated bond copolymerizable with (A1) and (A3) is not limited as long as it is a compound having an unsaturated double bond which can be polymerized. As a specific example, methyl (meth) acrylate , Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids, such as ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, and cyclo Pentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate And alicyclic substituents such as isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate Aromatic rings such as monounsaturated carboxylic acid ester compounds of glycols such as unsaturated carboxylic acid ester compounds and oligoethylene glycol monoalkyl (meth) acrylates, benzyl (meth) acrylates, and phenoxy (meth) acrylates. Aromatic vinyl compounds, such as an unsaturated carboxylic acid ester compound containing the substituent which has, styrene, (alpha) -methylstyrene, and vinyltoluene, carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate, (meth) acrylonitrile, (alpha) -chloro N-substituted maleimide compounds, such as vinyl cyanide compounds, such as acrylonitrile, N-cyclohexyl maleimide, and N-phenyl maleimide, etc. are mentioned. The. Among these, an aromatic vinyl compound and an N-substituted maleimide compound are preferable from the viewpoint of improving sensitivity and adhesion. These may be used alone or in combination of two or more.

In the present invention, the unsaturated carboxylic acid compound (A3) is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and may be used alone or in combination of two or more. Specific examples include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate. Among these, acrylic acid and methacrylic acid are preferred because of excellent copolymerization reactivity and solubility in a developing solution.

In the present invention, in the copolymer obtained by copolymerizing (A1) to (A3) used in the present invention (even when monomers other than A1 to A3 are included and copolymerized, the product is included in the present invention), (A1) It is preferable that the ratio of the structural unit derived from each of (A3) exists in the following ranges by mole fraction with respect to the total number of moles of the structural unit which comprises said copolymer.

, 2 to 60 mol% of constituent units derived from the structural unit (A1)

(A2): 2 to 95 mol%,

(A3): 2 to 70 mol%

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

From 10 to 50 mol% of constituent units derived from the structural unit (A1)

, 5 to 80 mol% of constitutional units derived from the structural unit (A2)

(A3): 5 to 65 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 the present invention, as an example of the method for producing the copolymer, copolymers obtained by copolymerizing (A1) to (A3) can be produced by copolymerization in the following manner.

A solvent (E) in an amount of 0.5 to 20 times by mass based on the total amount of (A1) to (A3) was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, . Then, after heating up the solvent (E) at 40-140 degreeC, 0-20 times the solvent (E) by mass basis with respect to the predetermined amount of (A1)-(A3) and the total amount of (A1)-(A3). ) And a solution obtained by adding 0.1 to 10 mol% of a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide with respect to the total number of moles of (A1) to (A3) (agitated and dissolved at room temperature or under heating) from the dropping lot. It is dripped at the said flask over 0.1-8 hours, and it stirs further at 40-140 degreeC for 1 to 10 hours.

In the above step, a part or all of the polymerization initiator may be put into a flask, or a part or all of (A1) to (A3) may be put into a flask. Moreover, in order to control molecular weight and molecular weight distribution, (alpha) -methylstyrene dimer and a mercapto compound can also be used as a chain transfer agent. The amount of the? -methylstyrene dimer or mercapto compound used is 0.005 to 5% by mass based on the total amount of (A1) to (A3). 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.

The binder resin (A) contained in the colored photosensitive resin composition of one embodiment of the present invention can be obtained by further reacting (A4) the copolymer obtained by copolymerizing (A1) to (A3). By adding (A4) to the above copolymer, light / heat curability can be imparted to the binder resin.

In the present invention, specific examples of the compound (A4) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclo. Hexylmethyl (meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned. Of these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more.

It is preferable to react 5 to 80 mol% with respect to the mole number of the unsaturated carboxylic acid compound (A3) contained in the said copolymer, and the compound (A4) which has the said unsaturated bond and an epoxy group is especially 10-80 mol%. When the composition ratio of (A4) is within the above range, it is preferable because it is excellent in sensitivity and developability.

In the present invention, the binder resin (A) can be produced by reacting the above copolymer with (A4), for example, in the following manner.

The atmosphere in the flask is replaced with nitrogen from air, and is a reaction catalyst of 5 to 80 mol% of (A4), a carboxyl group and an epoxy group in a molar fraction with respect to the structural unit derived from (A3) in the copolymer, for example, trisdimethyl 0.01 to 5% by weight of the aminomethylphenol relative to the total amount of (A1) to (A4) and a polymerization inhibitor, for example hydroquinone to 0.001 to 5 on the basis of the total amount of (A1) to (A4) By putting% in the flask and reacting at 60 to 130 ° C. for 1 to 10 hours, the copolymer and (A4) can be reacted. 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.

In the present invention, the binder resin (A) preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the range of 3,000 to 100,000, film reduction is not easily caused at the time of development, and the non-pixel portion tends to be satisfactorily missed at the time of development.

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. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

The acid value of the binder resin (A) is preferably in the range of 30 to 150 mgKOH / g on the solid basis. When the acid value is less than 30 mgKOH / g, the developability against alkaline water is lowered and the residue may remain on the substrate. If the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern increases.

Content of binder resin (A) is 5 to 85 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 10 to 70 mass%. When the content of the binder resin (A) is 5 to 85% by mass based on the above reference, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion occurs during development. It is preferable because it is difficult and the missing property of a non-pixel part tends to be good.

 (B) photopolymerizable compound

The (B) photopolymerizable compound 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.

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

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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

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, dipentaerythritol 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. Particularly preferred is a polyfunctional monomer having five or more functionalities.

(B) A photopolymerizable compound is used in 5-50 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is used in the range of 7-45 mass%.

Since the intensity | strength and smoothness of a pixel part tend to become favorable when (B) photopolymerizable compound is the range of 5-50 mass% on the said reference | standard, it is preferable.

(C) photoinitiator

The (C) photoinitiator contained in the coloring photosensitive resin composition of this invention contains the (2) polyfunctional thiol compound which contains two or more mercapto groups in 1 molecule as an essential component, As a main photoinitiator, acetophenone, an oxime, and a tria It is preferable to use a true compound individually or in combination.

As a polyfunctional thiol compound which contains two or more mercapto groups in 1 molecule of (C) photoinitiator contained in the coloring photosensitive resin composition of this invention, For example, tris- (3- mercaptopropionyloxy) -ethyl Isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like. have.

As mentioned above, the polyfunctional thiol compound containing two or more mercapto groups in one molecule is not limited to the said compound, All are contained in this invention.

As an acetophenone type compound in the (C) photoinitiator contained in the coloring photosensitive resin composition of this invention, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl, for example. Dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-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- And oligomers of methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. As an acetophenone type compound, the compound represented by following formula (3) is mentioned, for example.

<Formula 3>

In Formula 3, 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 3 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-morpholin Nophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1- On, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. have.

As an oxime type compound, the following general formula (4), 5, 6, etc. are mentioned, for example.

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

As a triazine type compound in the (C) photoinitiator contained in the coloring photosensitive resin composition of this invention, it is 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- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- ( 3,4 dimethoxyphenyl) ethenyl] -1,3,5-triazine etc. are mentioned.

The acetophenone, oxime and triazine-based compounds may be used alone or in combination of two or more thereof, or may be used in combination with other types of photopolymerization initiators.

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.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra (tert) -Butyl peroxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

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-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be.

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, you may use combining a photoinitiator (C-A) with a photoinitiator (C). As a photoinitiator adjuvant (C-A), an amine compound and a carboxylic acid compound are used preferably.

Specific examples of the amine compound in the photopolymerization start adjuvant include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid, and 4- 2-ethylhexyl dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis ( Aromatic amine compounds, such as diethylamino) benzophenone, are mentioned. 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.

When the photopolymerization initiator and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 0.01 to 5 moles with respect to 1 mole of the photopolymerization initiator. In the said content 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.

The usage-amount of (C) photoinitiator is 0.1-40 mass% normally with respect to the total amount of (A) binder resin and (B) photopolymerizable compound based on solid content, Preferably it is 0.5-30 mass%. Since the sensitivity and adhesiveness of a pixel part tend to become favorable when the (C) photoinitiator is the range of 0.1-40 mass% on the said reference | standard, it is preferable.

In addition, the polyfunctional thiol compound is included in 0.1 to 50% by mass, preferably 5 to 30% by mass based on the total mass of the photopolymerization initiator. When it is contained in the above range, the chemical resistance and the etching resistance are excellent, and the taper straightness is also good.

 (D) Coloring material

It is preferable that it is an organic pigment or an inorganic pigment used for a pigment dispersion resist as a normal pigment. If desired, 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.

Examples of the organic pigments and inorganic pigments 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, 47 and 58

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

These (D) coloring materials may be used alone or in combination of two or more. (D) Content of a coloring material is 3 to 60 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is the range of 5-55 mass%. (D) When the content of the coloring material is in the range of 3 to 60% by mass based on the above criteria, even if a thin film is formed, the color density of the pixel is sufficient, and the tendency for residue to be less likely to occur because the omission of the non-pixel portion during development is not reduced. This is preferable.

 (E) Solvent

The solvent (E) contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the 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. Propylene glycols such as 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, and propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates such as dialkyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxy pentyl acetate, benzene, Aromatic hydrocarbons such as toluene, xylene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, Alcohols such as glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the above solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferably used in the solvent in view of coatability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-e. Ester, such as ethyl oxypropionate and the methyl 3-methoxypropionate, is mentioned, More preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate,

Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

These (E) solvents can be used individually or in mixture of 2 or more types, respectively.

Content of the (E) solvent in the coloring photosensitive resin composition of this invention is 60-90 mass% normally with a mass fraction with respect to the coloring photosensitive resin composition whole quantity containing it, Preferably it is 70-85 mass%. (E) When content of solvent is in the range of 60-90 mass% on the said reference | standard, when apply | coated with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also called a die coater), and inkjet It is preferable because the coating property tends to be good.

 (F) additive

In the colored photosensitive resin composition of the present invention, fillers, other polymer compounds, curing agents, pigment dispersants, and the like may be added as needed. It is also possible to use (F) additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, in parallel.

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. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The said hardening | curing agent can be used individually or in mixture of 2 or more types.

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 can be used individually or in combination of 2 or more types, respectively. 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.

As the adhesion promoter, for example, 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-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

These adhesion promoters may be used alone or in combination of two or more. It is 0.01-10 mass% normally with respect to solid content of a coloring photosensitive resin composition, Preferably 0.05-5 mass% is included.

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. (D) The coloring material is mixed with the (E) solvent 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 is used as needed, and some or all of (A) binder resin may be mix | blended. In the resulting dispersion (hereinafter sometimes referred to as mill base), the remainder of the (A) binder resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (F) other components used as necessary, and as necessary Therefore, further solvent is further added so that it may become a predetermined concentration, and a desired coloring photosensitive resin composition is obtained.

According to an embodiment of the present invention, a color filter comprising a color layer including a formed pixel formed by coating a colored photosensitive resin composition on a substrate and exposing and forming a predetermined pattern, wherein the color layer is the present invention. It provides a color filter comprising a colored photosensitive resin composition according to.

The pattern forming method includes applying a colored photosensitive resin composition on a substrate, selectively exposing a portion of the colored photosensitive resin composition, and removing an exposed area or a non-exposed area of the colored photosensitive resin composition. It is made to include.

As one example thereof, it is applied to a substrate as described below, photocured and developed to form a pattern, and can be used as a black matrix or a colored pixel (colored image).

First, the base material used to apply the composition is not limited, but is applied to a layer containing the solids of glass, silicon wafer, plastic or the previously formed colored photosensitive resin composition and pre-baked to remove volatile components such as solvents and to smooth them. Get a coating.

At this time, the raw material of the plastic used as the base material is amorphous polyolefin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyether sulfone, polyether ketone and the like.

The thickness of the coating film at this time is usually about 1 to 3 mu m. In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. 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 image development, post-firing of about 10 to 120 minutes can be performed at 150 degrees C or less.

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 organic alkaline compound.

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

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

The concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or cationic surfactant.

Specific examples of the non-ionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

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 dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or 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, the color filter according to the present invention will be described.

The color filter according to the present invention is characterized in that it comprises a pixel formed by exposing and developing the above-described 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 composition, drying, patterned exposure to the resulting dry coating film, and development. The color filter can be obtained by repeating the operation by 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 the present invention may be applied to only one color, two colors, or three colors of the black matrix and three primary colors.

In addition, although the black matrix which is a light shielding layer can also use the coloring (colored black) photosensitive resin of this invention, for example, since it may be formed by the chromium layer etc., in this case, the coloring photosensitive property of this invention is used for formation of a black matrix. It is not necessary to use a resin composition.

The color filter produced by 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 3 mu m . Therefore, the color filter thus obtained has excellent smoothness, and by incorporating it into a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with high yield. In addition, by using the color filter described above, it is possible to manufacture an image pickup device of good quality.

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.

Manufacturing example  1: resin Of A  synthesis

40 parts of propylene glycol monomethyl ether acetate and 140 parts of propylene glycol monomethyl ether were 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 nitrogen in air. After heating to 29.5 parts (0.25 mol) of vinyltoluene, 25.8 parts (0.3 mol) of methacrylic acid, 82.8 parts (0.45 mol) of 3- (methacryloyloxymethyl) -3-ethyl oxetane and propylene glycol monomethyl ether The solution which added 4 parts of azobisisobutyronitrile to the mixture containing 136 parts of acetate was dripped at the flask over 2 hours from the dropping lot, and stirring was further continued at 80 degreeC for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 14.2 parts of glycidyl methacrylate (0.1 mol: 33 mol% based on the carboxyl group of methacrylic acid used in this reaction), 0.5 part of trisdimethylaminomethylphenol and 0.1 of hydroquinone The part was poured into a flask, the reaction was continued at 110 ° C. for 6 hours to obtain a resin A having a solid acid value of 82 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 25,000 and the molecular weight distribution (Mw / Mn) was 2.4.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin was carried out under the following conditions using the 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 to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Example  1-3 in comparison with 1-4 and manufacture of colored photosensitive resin composition

Among the components shown in Table 1 below, the total amount of the pigment (D) coloring material and the pigment dispersant (F) additive is mixed in advance so that the total amount of the pigment, the pigment dispersant, and the propylene glycol monomethyl ether acetate is 20% by mass. 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.

Unit (mass%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Coloring material (D-1) 5.49 5.49 5.49 5.49 5.49 5.49 5.49 Coloring material (D-2) 1.76 1.76 1.76 1.76 1.76 1.76 1.76 (A) Binder Resin 4.57 4.57 4.57 4.57 4.57 4.57 4.57 (B) photopolymerizable compound 4.06 4.06 4.06 4.06 4.06 4.06 4.06 (C1) photoinitiator (C1-1)
0.14 (C1-1)
0.21 (C1-1)
0.28 (C1-2)
0.14 (C1-1)
0.35 (C1-1)
One - (C2) photoinitiator 0.57 0.50 0.43 0.57 - 0.48 0.48 (C3) photoinitiator 0.28 0.28 0.28 0.28 - 0.20 0.30 (C-A) photopolymerization start adjuvant 0.28 0.28 0.28 0.28 0.24 0.24 0.29 (E) Solvent 81.00 81.00 81.00 81.00 81.68 80.35 81.20 (F-1) additive 1.51 1.51 1.51 1.51 1.51 1.51 1.51 (F-2) additive 0.34 0.34 0.34 0.34 0.34 0.34 0.34

(A) Binder Resin: A Synthesized in Preparation Example

(B) photopolymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C) photoinitiator

(C1-1): trimethylolpropane tris-3-mercaptopropionate (TMMP; trifunctional, manufactured by Sakai Chemical Co., Ltd.)

(C1-2): pentaeryltritol tetrakis-3-mercaptopropionate (PEMP; 4-functional, manufactured by Sakai Chemical Co., Ltd.)

(C2): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

(C3): Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; manufactured by Ciba Specialty Chemical

(C-A): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)

(D) Coloring material

(D-1): Red pigment dispersion (C.I. Pigment Red 254)

(D-2): yellow pigment dispersion (C.I. pigment yellow 138)

(E) Solvent: Propylene Glycol Monomethyl Ether Acetate

(F-1) Noblock epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)

 (F-2) Pigment Dispersant (Polyester)

Test Example .

A 2-inch square glass substrate (# 1737, manufactured by Corning Incorporated) was sequentially washed 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 1.9 µm. Preliminary drying (preliminary baking) was performed at 100 degreeC for 3 minutes in the 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) It was made into 100 micrometers, and it irradiated at 100 mJ / cm <2> exposure amount (365 nm) in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, followed by washing with water at 150 ° C. (Table 2) or 140 ° C. (Table 3). After drying for 30 minutes (after firing), the results are shown in Tables 2 and 3 below.

Firing after 150 ℃ (drying process) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Chemical resistance * 1 ○ ○ ○ ○ ○ X X Taper Straightness * 2 ○ ○ ○ ○ X X ○ Etching resistance * 3 ○ ○ ○ ○ ○ ○ X

Firing after 140 ℃ (drying process) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Chemical resistance * 1 ○ ○ ○ ○ ○ X X Taper Straightness * 2 ○ ○ ○ ○ X X ○ Etching resistance * 3 ○ ○ ○ ○ ○ x X

* 1: Chemical resistance is evaluated by measuring the color change value (ΔEab) before and after precipitation for 23 ° C./40 minutes under NMP.

△ Eab is a value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (Japanese Society of Color Science, New Color Science Handbook (1986) p.266).

? Eab = {(? L) 2+ (? A) 2+ (? B) 2} 1/2

  (Circle): (DELTA) Eab = less than 2, X: (DELTA) Eab = 2 or more.

* 2: ○: Good taper straightness, X: Bad taper straightness

* 3: The etching resistance was visually evaluated the degree of swelling of the film at 100 ° C for 5 minutes under a strip etching solution (trade name: PRS-2000, manufactured by Dongwoo Finechem Co., Ltd.).

○: with swelling, X: without swelling

As a result of the test, the pixels obtained from the colored photosensitive resin compositions of Examples 1 to 4 were excellent in chemical resistance, and the phenomenon in which the film was swelled even in the etching resistance evaluation did not occur. Moreover, the taper of a good pattern was able to be formed after image development.

In conclusion, it was confirmed that the colored photosensitive resin composition of the present invention is excellent in sensitivity and chemical resistance even after a low temperature post-firing process.

Claims (8)

As a coloring photosensitive resin composition containing (A) binder resin, (B) photopolymerizable compound, (C) photoinitiator, (D) coloring material, and (E) solvent, (C) at least one photopolymerization initiator selected from the group consisting of (1) acetophenone, oxime and triazine compounds; And (2) a polyfunctional thiol compound, (2) the polyfunctional thiol compound is in the range of 5 to 30 mass% based on the total mass of the photopolymerization initiator, The binder resin (A) is an unsaturated group-containing resin obtained by further reacting a copolymer obtained by the copolymerization reaction of the following (A1), (A2), or (A3) with the following (A4): (A1): a compound having an alicyclic epoxy group and an unsaturated bond in the molecule, (A2): a compound having an unsaturated bond capable of copolymerization with (A1) and (A3) (A3): unsaturated carboxylic acid compound, and (A4): A compound having an unsaturated bond and an epoxy group in one molecule. The polyfunctional thiol compound in (C) the photoinitiator is tris-3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythrate according to claim 1 A coloring photosensitive resin composition, which is lithotella tetrakis-3-mercaptopropionate or dipentaerythritol tetrakis 3-mercaptopropionate. delete The coloring photosensitive resin composition of Claim 1 whose said (A1) is 1 or more types chosen from the compound of a following formula. &Lt; Formula 1 >

(Wherein R1 is a hydrogen atom or an alkyl group (C1-C12), R2 is a hydrogen atom or an alkyl group (C1-C12), an allyl group, a phenyl group, a benzyl group, a halogen atom or an alkoxy group having 1-8 carbons, n is an integer from 1 to 12.) &Lt; EMI ID =

(2b)

(In Formula 2a and Formula 2b, R1 is hydrogen or a C ₁ to C ₂₀ aliphatic or aromatic hydrocarbon with or without a hetero atom of N, O or S, R2 is a hetero atom of N, O or S or Not included C ₁ to C ₂₀ aliphatic or aromatic hydrocarbons.) The coloring photosensitive resin composition of Claim 1 whose said (A2) is N-substituted maleimide or an aromatic vinyl compound. The ratio of the structural unit derived from each of said (A1)-(A3) with respect to the total number of moles of the said copolymer structural unit, Structural unit derived from (A1): 2 to 60 mol%, (A2): 2 to 95 mol%, Structural unit derived from (A3): 2 to 70 mol%, It is a range and the said unsaturated group containing resin is obtained by making 5-A80 mol% of (A4) react with respect to the structural unit guide | induced from (A3), The coloring photosensitive resin composition characterized by the above-mentioned. A color filter comprising a color layer comprising a formed pixel formed by coating a colored photosensitive resin composition on a substrate and exposing and forming a predetermined pattern, wherein the color layer is one of claims 1, 2 and 4. The color filter which consists of the coloring photosensitive resin composition of any one of Claims 6-6. A liquid crystal display device comprising the color filter according to claim 7.