KR20200114892A - Red colored photosensitive resin composition, color filter and display device having the same - Google Patents

Abstract

The present invention relates to a red colored photosensitive resin composition including an alkali-soluble resin (A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the alkali-soluble resin (A) is a copolymer of a coumarin-based compound (A1), an oxetane functional group-containing compound (A2) and an unsaturated carboxylic acid (A3), and the colorant (B) includes at least two pigments selected from the compounds represented by C.I. pigment 254, C.I. pigment red 269 and C.I. pigment 291. The red colored photosensitive resin composition is inhibited from degradation of reliability and shows high luminance. The present invention also relates to a color filter and a display device including the red colored photosensitive resin composition.

Description

A red photosensitive resin composition, a color filter and a display device including the same TECHNICAL FIELD [RED COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a red photosensitive resin composition, a red color filter and a display device including the same.

The color filter is embedded in the color photographing device of an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), etc., and can be used to actually obtain a color image. . In addition, color filters are widely used in photographing devices, plasma display panels (PDP), liquid crystal displays (LCD), field emission displays (FEL), and light emitting displays (LEDs), and their application range is rapidly expanding.

Such a color filter is a series of processes in which a colored photosensitive resin composition containing a colorant is uniformly coated with a pigment corresponding to each color of red, green and blue on the top of a substrate, then exposed and developed, and heated as necessary to heat cure. It is manufactured by repeating for each color to form a pixel for each color.

Meanwhile, as a conventional method of aligning the liquid crystal, a contact type rubbing method is used in which a polymer film such as polyimide is applied to a substrate such as glass, and the surface is rubbed in a predetermined direction with fibers such as nylon or polyester. However, the liquid crystal alignment by the contact rubbing method as described above has the advantage of obtaining a simple and stable liquid crystal alignment performance, but fine dust or electrostatic discharge (ESD) is generated when the fiber and the polymer film are rubbed, resulting in the occurrence of a substrate substrate. This may be damaged, and as the roll becomes larger due to an increase in processing time and an increase in the size of the glass, it may cause serious problems in manufacturing a liquid crystal panel due to process difficulties such as non-uniformity in rubbing strength.

In order to solve the problem of the contact rubbing method as described above, the photoreactive material bonded to the photoreactive polymer by linearly polarized UV causes a photoreaction (photoisomerization, light dimerization, photodecomposition), and the liquid crystal is aligned. A photo-alignment method through an orientation mechanism has been proposed.

However, since the photo-alignment method cannot maintain or provide stable alignment characteristics in terms of external heat, light, physical impact, and chemical impact, there is a problem in that productivity or reliability is lower than that of the rubbing method. Therefore, when the photo-alignment model is applied, there is a need to develop a red photosensitive resin composition capable of suppressing a decrease in reliability of red PR (photo resist). In addition, in order to realize sufficient color reproducibility and sharpness of a color image, a high-power backlight must be used in accordance with the luminance of the red pixel.

Korean Patent Publication No. 2012-112188 discloses a red coloring composition for a color filter and a color filter, but does not provide an alternative to the above problem.

Korean Patent Publication No. 2012-112188

An object of the present invention is to provide a red photosensitive resin composition having high luminance while suppressing a decrease in reliability of a red photosensitive resin composition when applied to a photo-alignment model.

In addition, an object of the present invention is to provide a color filter manufactured by using the red photosensitive resin composition.

The present invention contains an alkali-soluble resin (A), a colorant (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E), and the alkali-soluble resin (A) is a coumarin compound (A1). ), an oxetane functional group-containing compound (A2) and an unsaturated carboxylic acid (A3) are copolymerized, and the colorant (B) is CI Pigment 254, C.I. It provides a red photosensitive resin composition containing at least two or more types of pigments among the compounds represented by Pigment Red 269 and C.I Pigment 291.

In addition, the present invention provides a color filter and a display device including the red photosensitive resin composition.

The red photosensitive resin composition according to the present invention can suppress the decrease in reliability, particularly when applied to a photo-alignment model, and has excellent luminance and low color shift when implementing a color filter. have.

Accordingly, a color filter manufactured using the red photosensitive resin composition according to the present invention and a display device including the same have an advantage of having excellent reliability by suppressing a decrease in reliability, and an excellent effect of high color reproduction.

The present invention contains an alkali-soluble resin (A), a colorant (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E), and the alkali-soluble resin (A) is a coumarin compound (A1). ), a copolymer comprising a compound (A2) and an unsaturated carboxylic acid (A3) containing an oxetane functional group, and the colorant (B) is CI Pigment 254, C.I. By including at least two or more pigments of the compounds represented by Pigment Red 269 and CI Pigment 291, a red photosensitive resin composition having high luminance while suppressing the decrease in reliability of the red photosensitive resin composition, and a color filter and display comprising the same It relates to the device.

In the present invention, when the repeating unit, compound or resin represented by the formula has its isomers, the corresponding formula representing the repeating unit, compound or resin means a representative formula including the isomer.

Hereinafter, the present invention will be described in detail.

<Red photosensitive resin composition>

The red photosensitive resin composition of the present invention includes an alkali-soluble resin, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and may further include an additive if necessary.

Alkali-soluble resin (A)

The alkali-soluble resin (A) included in the red photosensitive resin composition of the present invention is a copolymerization reaction comprising a coumarin-based compound (A1), a compound (A2) containing an oxetane functional group, and an unsaturated carboxylic acid (A3). It is a copolymer obtained. The alkali-soluble resin (A) can be polymerized together by adding other monomers in addition to the monomers of (A1) to (A3). That is, even when a monomer other than the above (A1) to (A3) is further contained and copolymerized, it is included in the present invention.

In the present invention, the coumarin-based compound (A1) is a compound having a coumarin skeleton structure, and may include at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4, X is the following Formula 5, and R ₁ to R ₂₀ are each independently hydrogen, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, a phenyl group, a benzyl group, or an alkoxy group having 1 to 8 carbon atoms to be.

[Formula 5]

In Formula 5, R ₂₁ is hydrogen or a methyl group, and a dotted line represents a portion bonded to Formulas 1 to 4.

The coumarin-based compound (A1) represented by Chemical Formulas 1 to 4 according to the present invention can be easily prepared according to a known synthesis method in the art, and the present invention does not limit the synthesis method.

In the present invention, the compound (A2) containing an oxetane functional group may include a polymerizable unsaturated group having an oxetane skeleton derived from Formula 6 below.

[Formula 6]

이며, R₆은 수소 또는 메틸기이며, Y는-O-, -CO-, -C(=O)O-, -CONH- 또는 페닐렌기이고, 점선은 상기 Y로부터의 결합을 나타내고, R₇은 수소, 탄소수 1 내지 12의 알킬기, 알릴기, 페닐기, 할로겐 원자 또는 탄소수 1 내지 8의 에톡시기이다.In Formula 6, X is

, R ₆ is hydrogen or a methyl group, Y is -O-, -CO-, -C(=O)O-, -CONH- or a phenylene group, the dotted line represents the bond from Y, and R ₇ is Hydrogen, an alkyl group having 1 to 12 carbon atoms, an allyl group, a phenyl group, a halogen atom or an ethoxy group having 1 to 8 carbon atoms.

As the compound (A2) of Formula 6, for example, 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyl Oxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2 ,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloyloxyethyl)oxetane, 3 -(Methacryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-(methacryloyloxyethyl)oxetane, 3-(methacryloyloxyethyl)-2-trifluoromethyl Oxetane, 3-(methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxyethyl)-2-phenyloxetane, 2,2-difluoro-3- (Methacryloyloxyethyl) oxetane, 3-(methacryloyloxyethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxyethyl)-2,2,4 Methacrylic acid esters such as ,4-tetrafluorooxetane; 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyl Oxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 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 Royloxyethyl)oxetane, 3-(acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(acrylic Royloxyethyl)-2-phenyloxetane, 2,2-difluoro-3-(acryloyloxyethyl)oxetane, 3-(acryloyloxyethyl)-2,2,4-trifluoro Acrylic acid esters, such as looxetane and 3-(acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane, are mentioned. These may be used alone or in combination of two or more.

In this specification, (meth)acrylate means acrylate and/or methacrylate.

The unsaturated carboxylic acid (A3) is not limited as long as it is a carboxylic acid compound having a polymerizable unsaturated double bond, and may be used alone or in combination of two or more. Specific examples of 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 ends, such as ω-carboxypolycaprolactone mono(meth)acrylate. Of the above compounds, acrylic acid and methacrylic acid are preferable because they have excellent copolymerization reactivity and solubility in a developer.

In the copolymer obtained by copolymerizing (A1) to (A3) used in the present invention, that is, an alkali-soluble resin, the ratio of the constituent components derived from each of (A1) to (A3) is the constitution constituting the above copolymer It is preferable that it is in the following range as a mole fraction with respect to the total number of moles of the components.

The structural unit derived from (A1) is 5 to 40 mol%,

The structural unit derived from (A2) is 5 to 70 mol%,

The structural unit derived from (A3) is 5 to 60 mol%.

According to an embodiment of the present invention, the alkali-soluble resin (A) contained in the red photosensitive resin composition is added to a copolymer obtained by copolymerizing (A1), (A2) and (A3) with the above (A1) to (A3). A compound (A4) having an unsaturated bond capable of copolymerization may be further included to be copolymerized.

In the present invention, the compound (A4) having an unsaturated bond is not limited as long as it is a compound having a polymerizable unsaturated double bond, and specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, cyclopentyl (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, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl Unsaturated carboxylic acid ester compounds containing alicyclic substituents such as (meth)acrylate, norbornyl (meth)acrylate, pinenyl (meth)acrylate, and glycols such as oligoethylene glycol monoalkyl (meth)acrylate Unsaturated carboxylic acid ester compounds containing substituents having an aromatic ring such as monosaturated carboxylic acid ester compounds, benzyl (meth)acrylate, phenoxy (meth)acrylate, styrene, α-methylstyrene, vinyltoluene Aromatic vinyl compounds such as, vinyl acetate and carboxylic acid vinyl esters such as vinyl propionate, vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile, N-cyclohexylmaleimide, and N-phenylmaleimide N-substituted maleimide compounds, such as, etc. are mentioned. Among these, aromatic vinyl compounds and N-substituted maleimide compounds are preferable from the viewpoint of improving sensitivity and adhesion. Each of these may be used alone or in combination of two or more.

In the copolymer obtained by copolymerizing (A1) to (A4) used in the present invention, the proportion of the constituent components derived from (A4) is 5 to 40 moles with respect to the total number of moles of the constituent components constituting the copolymer. It is preferably %.

That is, as the alkali-soluble resin (A) according to the present invention, at least one compound (A1) of Formulas 1 to 4, compound (A2) of Formula 6, unsaturated carboxylic acid compound (A3), and a compound having an unsaturated bond In the copolymer obtained by copolymerizing (A4), the monomers of Formulas 1 to 4, the monomers of Formula 6, the unsaturated carboxylic acid monomers, and the monomers having an unsaturated bond are not particularly limited with respect to the total number of moles of the constituents, but each 5 It is preferably contained within the range of to 40 mol%, 5 to 70 mol%, 5 to 60 mol%, and 5 to 40 mol%.

More preferably, the ratio of the constituent components may be in the following range.

Constituent units derived from (A1): 10 to 30 mol%,

Constituent units derived from (A2): 10 to 60 mol%,

Constituent units derived from (A3): 10 to 50 mol%,

Constituent units derived from (A4): 5 to 30 mol%.

If the above-described constitutional ratio is within the above range, it is possible to suppress a decrease in the reliability of the red photosensitive resin composition, particularly when applied to a photo-alignment model, of the red photosensitive resin composition. Accordingly, the color filter made of the red photosensitive resin composition of the present invention has an advantage of excellent luminance and low color shift and thus excellent transmittance.

In the present invention, as an example of the method for producing the copolymer, when obtained by copolymerizing (A1) to (A4), it can be produced by copolymerizing by the following method.

Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, 0.5 to 20 times the amount of solvent (E) by mass relative to the total amount of (A1) to (A3) was introduced, and the atmosphere in the flask was air Is substituted with nitrogen. Thereafter, the solvent (E) was heated to 40 to 140°C, and then 0 to 20 times the amount of the solvent (E) based on the mass relative to the predetermined amount of (A1) to (A3) and the total amount of (A1) to (A3) ), and 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 (A4) (dissolve by stirring at room temperature or under heating) from the dropping lot It is added dropwise to the flask over 0.1 to 8 hours, and stirred at 40 to 140°C for 1 to 10 hours.

Further, in the above step, part or all of the polymerization initiator may be put into the flask, or part or all of (A1) to (A4) may be put into the flask. Further, in order to control the molecular weight or molecular weight distribution, an α-methylstyrene dimernamecapto compound may be used as a chain transfer agent. The amount of α-methylstyrene dimer capto compound used is 0.005 to 5% by mass based on the total amount of (A1) to (A4). In addition, the above polymerization conditions may be appropriately adjusted in the introduction method or reaction temperature in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

According to an embodiment of the present invention, the alkali-soluble resin (A) contained in the red photosensitive resin composition is a compound (A5) having an unsaturated bond and an epoxy group in one molecule in a copolymer obtained by copolymerizing (A1) to (A4). It can be obtained by further reacting. By adding (A5) to the above copolymer, light/thermosetting can be imparted to the binder resin.

In the present invention, specific examples of the compound (A5) having an unsaturated bond and an epoxy group in one molecule are glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclo Hexylmethyl (meth)acrylate, methylglycidyl (meth)acrylate, etc. are mentioned. Among these, glycidyl (meth)acrylate is preferably used. Each of these may be used alone or in combination of two or more.

The compound (A5) having an unsaturated bond and an epoxy group is preferably reacted in an amount of 5 to 80 mol%, more preferably 10 to 80 mol% based on the number of moles of the unsaturated carboxylic acid compound (A3) contained in the copolymer. .

If the composition ratio of (A5) is within the above range, it is preferable because sensitivity and developability are excellent.

In one embodiment of the present invention, the alkali-soluble resin (A) is a copolymer obtained by copolymerizing the above (A1), (A2), (A3) and (A4) and (A5), for example, as follows: It can be produced by reacting in the same way.

As a reaction catalyst between a carboxyl group and an epoxy group, the atmosphere in the flask is replaced with air from nitrogen, and 5 to 80 mol% of (A5) in mole fraction with respect to the constituent unit derived from (A3) in the copolymer, for example, trisdimethyl Aminomethylphenol is 0.01 to 5% by mass based on the total amount of (A1) to (A5) and as a polymerization inhibitor, for example, hydroquinone is 0.001 to 5% by mass based on the total amount of (A1) to (A5). % Is added to the flask and reacted at 60 to 130°C for 1 to 10 hours, whereby the copolymer and (A5) can be reacted. In addition, as with the polymerization conditions, the introduction method and the reaction temperature may be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.

According to the present invention, the above-described alkali-soluble resin (A) may be a copolymer obtained by copolymerization reaction of the compound (A1) of Formula 1 to 4, the compound (A2) of Formula 6, and the unsaturated carboxylic acid compound (A3). And, preferably, it may be a resin obtained by a copolymerization reaction further including a compound (A4) having an unsaturated bond. Most preferably, in the copolymer obtained by the copolymerization reaction of the compound (A1) of Formulas 1 to 4, the compound of Formula 6 (A2), an unsaturated carboxylic acid compound (A3), and a compound (A4) having an unsaturated bond. It is preferable that it is an unsaturated group-containing resin obtained by further reacting the compound (A5) having an unsaturated bond and an epoxy group in one molecule.

In some embodiments, the alkali-soluble resin (A) may be polymerized together by adding other monomers in addition to the monomers of (A1) to (A5). That is, it is not particularly limited as long as it is within the range not departing from the object of the present invention, and it is included in the present invention even when a monomer other than the above (A1) to (A5) is further contained and copolymerized.

In the present invention, the alkali-soluble resin (A) preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin (A) is in the above-described range, film reduction is less likely to occur during development, and the omission of non-pixel portions during development tends to be favorable, so this is preferable.

The acid value of the alkali-soluble resin (A) is preferably in the range of 30 to 150 mgKOH/g based on solid content. If the acid value is less than 30mgKOH/g, developability for alkaline water is lowered and there is a risk of leaving a residue on the substrate. If the acid value exceeds 150mgKOH/g, the possibility of desorption of the pattern increases. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. If the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0, it is preferable because developability is excellent.

The content of the alkali-soluble resin (A) contained in the red photosensitive resin composition of the present invention is usually 5 to 90% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content in the red photosensitive resin composition. When the content of the alkali-soluble resin (A) satisfies the above-described range, the solubility in the developer is sufficient, making it difficult to generate a developing residue on the substrate in the non-pixel portion, and it is difficult to reduce the film in the pixel portion of the exposed portion during development. The omission of non-pixel portions tends to be good, so it is preferable. In addition, the red photosensitive resin composition of the present invention has excellent stability that does not change with time at room temperature for 6 months.

In the present invention, the solid content in the red photosensitive resin composition means the total content of the remaining components excluding the solvent from the red photosensitive resin composition.

Colorant (B)

The colorant (B) according to the present invention is a component capable of expressing colors such as red, green, or blue so that a pattern having a desired color can be prepared.

Pigment (b1 )

The colorant (B) contained in the red photosensitive resin composition of the present invention is a pigment (b1) as C.I. Pigment 254, C.I. It is characterized by containing at least two or more of the compounds represented by Pigment Red 269 and C.I Pigment 291.

The colorant (B) of the present invention is C.I. Pigment Red 269, C.I. When at least two or more of the compounds represented by Pigment 254 and C.I Pigment 291 are included, high transmittance and high color reproduction are possible.

In one embodiment of the present invention, C.I. Pigment Red 269, C.I. Pigments containing at least two or more of the compounds represented by pigment 254 and CI pigment 291 may be included in an amount of 10 to 100% by weight based on the total 100% by weight of the colorant (B), preferably 20 to It may be included in 100% by weight. In the colorant (B) according to the present invention, the C.I. When two or more of Pigment Red 269, 254, and 291 are included in the above range, the luminance characteristics are excellent.

In the aspect of the present invention for realizing more excellent high permeability and high color reproducibility, the colorant used in the present invention is C.I. Including Pigment Red 269, C.I. It is preferable to contain a compound represented by pigment 254 or C.I pigment 291. In this case, the colorant is C.I. Pigment Red 269 and C.I. Pigment Red 254 or C.I. Pigment Red 291 may be included in a weight ratio of 10:90 to 90:10.

The colorant (B) according to the present invention can be used to prepare a pattern having a desired color, the C.I. Pigment Red 254, C.I. In addition to Pigment Red 269 and CI Pigment Red 291, it is a component capable of expressing a color such as red, green, or blue, and is selected from pigments and dyes commonly used in the field within the scope of the present invention. It may further include one or more, which may be manufactured in the form of a mill base.

The pigments that may be used additionally may include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more. It may be more preferable to use an organic pigment in terms of excellent heat resistance and color development. The organic pigment may be a synthetic colorant or a natural colorant.

If necessary, the organic pigment is rosin treated; Surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; Graft treatment on the surface of a pigment using a polymer compound or the like; Fine particle treatment by a sulfuric acid fine particle method or the like; Or a washing treatment with an organic solvent or water to remove impurities; It may have been.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, inorganic salts of barium sulfate (extender pigment), and the like. More specifically, the metal compounds include iron, cobalt, aluminum, cadmium, lead, copper, and titanium. , Oxides of metals such as magnesium, chromium, zinc, antimony, and carbon black, or complex metal oxides.

As a specific example of the pigment that can be further used, more preferably, a compound classified as a pigment in the Color Index (Publisher: The Society of Dyers and Colorists) may be mentioned. More specifically, pigments exemplified by the following color index (CI) numbers may be mentioned, but the present invention is not limited thereto, and at least one selected from them is co-dispersed using a binder resin or a dispersant to suit the desired chromaticity. Can be used.

C.I. Specific examples of pigment yellow include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214, and the like;

C.I. Specific examples of pigment orange include C.I. Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and the like;

C.I. Specific examples of Pigment Red include C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 255, 264 and 265, and the like.

Among the pigments illustrated above, preferably, C.I. Pigment Red 177, C.I. Pigment Red 242, Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. It may be more preferable to include at least one selected from the group consisting of Pigment Yarrow 185.

Dye (b2)

The dye (b2) that may be additionally included in the colorant (B) of the present invention may be used without limitation as long as it has solubility in an organic solvent or is dispersible. It is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, heat resistance, and solvent resistance. In the case of a dye that is not soluble in an organic solvent, it is also possible to disperse and use.

As the dye (b2), one or more selected from acidic dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof may be used. In addition, it is also possible to select from azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof.

As the dye (b2), a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dye note (color dyeing company) are preferably mentioned.

Specific examples of the dye (b2),

C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135;

C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent orange 63;

C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91:1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197;

C.I. Solvent Violet No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59 may be mentioned, but is not limited thereto.

The colorant (B) may be included in a weight fraction of preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the solid content in the colored photosensitive resin composition. If the content of the colorant (A) is less than the above range, the color separation ability of the formed pattern may be deteriorated, and if the content of the colorant (A) is exceeded, the lithography performance may deteriorate, resulting in a problem such as a residue or a non-development.

(b3) dispersant

The dispersant is added to maintain stability and deaggregation of the insoluble colorant, and those generally used in the art may be used without limitation. Specifically, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, etc. can be used, but preferably BMA (butyl methacrylate) or DMAEMA (N,N-dimethylamino Ethyl methacrylate) containing an acrylate-based dispersant (hereinafter, sometimes referred to as an acrylic dispersant) may be used. At this time, it may be preferable to apply the acrylic dispersant prepared by the living control method as suggested in Korean Patent Application Laid-Open No. 2004-0014311, and as a commercial product of the acrylate-based dispersant prepared through the living control method, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. may be mentioned, but are not limited thereto, and these may be used alone or in combination of two or more.

In addition to the above-described acrylic dispersant, the dispersant may use other resin type pigment dispersants. The other resin type pigment dispersants include known resin type pigment dispersants, especially polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) An oily dispersant such as an amide formed by the reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; And phosphate esters and adducts of ethylene oxide/propylene oxide. Commercially available products of the above resin-type dispersants include cationic resin dispersants, for example, BYK (Big) Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co.'s trade name: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc., but are not limited thereto, and each of these Alternatively, it may be used in combination of two or more, and may be used in combination with an acrylic dispersant.

The content of the dispersant may be included in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the pigment solids included together. When the content of the dispersant exceeds the above range, the viscosity may increase, causing a problem in the process. When the content is less than the above range, it may be difficult to atomize the pigment, or problems such as gelation after dispersion may occur.

Photopolymerizable compound (C)

The photopolymerizable compound (C) contained in the red photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other polyfunctional monomers. have. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroly. Such as money. 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, pentaerythritol tri (Meth)acrylate, pentaerythritol tetra(meth)acrylate, thipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylateddipentaerythritol Hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

Among these, a bifunctional or higher polyfunctional monomer is preferably used. Especially preferably, it is a polyfunctional monomer of 5 or more functions.

The photopolymerizable compound (C) is usually used in the range of 1 to 60% by weight, preferably 5 to 50% by weight, based on the total 100% by weight of the alkali-soluble resin (A) and the photopolymerizable compound (C). When the photopolymerizable compound (C) is contained within the above content range, the strength and smoothness of the pixel portion tend to be improved, and thus it is preferable.

Photopolymerization initiator (D)

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention can initiate polymerization of the photopolymerizable compound (C) described above by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays. It is a compound that generates radicals and the like.

The photopolymerization initiator is commonly used in the art within a range that does not impair the object of the present invention, and the type of the photopolymerization initiator is not particularly limited as long as it can polymerize the binder resin and the photopolymerizable compound. Representative examples include, but are limited to, oxime compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, biimidazole compounds, triazine compounds, thioxanthone compounds, and anthracene compounds. It is not, and one or more can be selected and used from this. Among these, it may be more preferable to use an oxime-based compound in consideration of polymerization characteristics, initiation efficiency, and absorption wavelength.

As the oxime compound, for example, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime), o- Oxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z)-2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one ( See Formula 7 below), (E)-1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidine)amino)oxy)ethanone ( See Formula 8 below) and (E)-1-(((1-(6-(4-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-2-methylbenzoyl) )-9-ethyl-9H-carbazol-3-yl)ethylidine)amino)oxy)ethanone (see Formula 9 below), etc., and commercially available products include BASF's OXE-01, OXE-02, etc. However, it is not limited thereto.

[Formula 7]

[Formula 8]

[Formula 9]

In the present invention, the oxime-based compound is not particularly limited in its content as long as it is within the range capable of performing its functions, preferably 10 to 100% by weight, more preferably, based on the total weight of the photopolymerization initiator (D). It may be included in 20 to 100% by weight. When the content of the oxime compound is within the above range, brightness and sensitivity can be maximized.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like, but is not limited thereto.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like, but are not limited thereto.

Examples of the biimidazole-based compound compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group. Among these, more preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole or 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole And the like, but are not limited thereto.

As the triazine-based compound, for example, 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-(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-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like, but are not limited thereto.

As the thioxanthone compound, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. However, it is not limited thereto.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. However, it is not limited thereto.

As other specific examples, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, campoquinone, phenylclioxyl Acid methyl, titanocene compounds, and the like, but are not limited thereto.

The photopolymerization initiators described above may be used alone or in combination of two or more.

The content of the photopolymerization initiator (D) is not particularly limited, but is preferably contained in an amount of 0.1 to 40% by weight based on the total weight of solids in the alkali-soluble resin (A) and the photopolymerizable compound (C), and 1 to 30 It is more preferable to be included in weight percent. When the content of the photopolymerization initiator is within the above range, the red photosensitive resin composition is highly sensitive and thus the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, it is preferable because the strength of the pixel portion formed by using the red photosensitive resin composition of the present invention and the smoothness on the surface of the pixel portion can be improved.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation aid (d1) in order to improve the sensitivity of the red photosensitive resin composition of the present invention. Since the red photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary agent, the sensitivity is further increased and productivity can be improved.

As the photopolymerization initiation aid (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl) Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. I can.

Solvent (E)

As long as the solvent (E) according to the present invention is effective in dissolving other components included in the red photosensitive resin composition, a solvent commonly used in the art may be used without particular limitation. As a specific example, the solvent may be used by selecting one or more from ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and amides, but is not limited thereto.

Specifically, the ether solvents 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; And the like.

The acetate solvents are specifically, alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. ;

Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; And the like.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Specifically, the ketone solvents include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specifically, the alcohol solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specifically, the ester solvents include cyclic esters such as γ-butyrolactone;

3-ethoxy ethylpropionate, 3-methoxy methylpropionate, ethyl 3-ethoxypropionate, etc. are mentioned.

Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) is preferably an organic solvent having a boiling point of 100° C. to 200° C. in terms of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates; Ketones; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionic acid Ethyl, methyl 3-methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent (E) contained in the red photosensitive resin composition of the present invention is preferably included in 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total weight of the red photosensitive resin composition of the present invention. Can be included as When the solvent (E) is included within the above-described range, the coating property becomes good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. It can provide an effect.

(F) additive

In addition to the above components, the red photosensitive resin composition of the present invention is an additive (F) such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents according to the needs of those skilled in the art within a range that does not harm the object of the present invention It may further include.

As a specific example of the other polymer compound, a curable resin such as an epoxy resin or a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. However, it is not limited thereto.

The curing agent is used to increase deep curing and mechanical strength, and specific examples thereof include, but are not limited to, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

As a specific example of the epoxy compound, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxidation, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexane dicarboxylic acid bisoxetane, but are limited thereto. It does not become.

The curing agent may be used in combination with 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. Specifically, as the curing auxiliary compound, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators may be used. The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. As the commercially available epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries, Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700). (Manufactured by Shin-Japan Ewha Corporation), and the like.

The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and as a specific example of the surfactant, a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the fluorine-based surfactant are commercially available products such as Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dai Nippon Ink Kagaku Kogyo.

Examples of the silicone surfactant are commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicon, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460 and TSF-4452.

Each of the above-exemplified surfactants may be used alone or in combination of two or more.

As specific examples of the adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(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-mercaptopropyl At least one selected from trimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane may be used.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight based on the solid content in the red photosensitive resin composition of the present invention.

As a specific example of the antioxidant, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)prop Foxy]- 2,4,8,10 -tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine, 3,9-bis[2-{3-(3-tert) -Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5- Methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''- Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert) -Butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis(4-methyl-6-t-butylphenol), 2 ,6-di-t-butyl-4-methylphenol, and the like, but are not limited thereto.

Specific examples that can be used as an anti-aggregation agent in the present invention may include sodium polyacrylate, but are not limited thereto.

The method for preparing the red photosensitive resin composition of the present invention will be described as follows.

First, the pigment (b1) of the colorant (B) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant, part or all of the alkali-soluble resin (A), or a dye (b2) may be mixed together with a solvent (E) to be dissolved or dispersed.

In the mixed dispersion, the dye (b2), the rest of the alkali-soluble resin (A), the photopolymerizable compound (C) and the photopolymerization initiator (D), and the additive (F) and the solvent (E) as necessary are added to a predetermined concentration. It may be further added to prepare the red photosensitive resin composition according to the present invention.

Further, the present invention includes a colored pattern made of the red photosensitive resin composition. The colored pattern may be prepared by applying the colored photosensitive resin composition of the present invention on a substrate, photocuring, and developing. The thickness of the colored pattern is not particularly limited, and may be, for example, 1 to 6 μm.

The colored pattern may be formed, for example, in the following manner.

First, the red photosensitive resin composition is applied onto a substrate or a layer consisting of a solid content of the previously formed photosensitive resin composition, and prebaked from the applied photosensitive resin composition layer to remove volatile components such as a solvent to obtain a smooth coating film.

As the coating method, for example, spin coating, cast coating, roll coating, slit and spin coating, or slit coating can be performed.

After the application, the red photosensitive resin composition layer is formed by prebaking (heat drying) or drying under reduced pressure and heating to volatilize volatile components such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C.

The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposed portion and accurate positioning of the mask and the substrate is performed.

Further, after that, the cured coating film is brought into contact with an alkali developer to dissolve and develop the non-exposed portion, whereby a desired pattern shape can be obtained. As the developing method, a liquid addition method, a dipping method, a spray method, or the like may be performed, and the substrate may be tilted at an arbitrary angle during development.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and/or organic alkaline compounds.

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, carbonic acid. Potassium, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. 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 alkali developer is, for example, 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

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

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, and sorbitan fatty acids. Ester, 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 sulfuric acid ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; Alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; And the like.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride; Quaternary ammonium salt; And the like.

These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the alkaline developer is, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After the above development, washing with water may be performed, and post-baking for 10 to 60 minutes at 150 to 230° C. may be performed as needed.

<Color filter>

In addition, the present invention provides a color filter including a colored pattern made of the above-described red photosensitive resin composition. The color filter of the present invention is a red color filter and includes a substrate and a colored pattern made of the red photosensitive resin composition of the present invention on the substrate. The substrate is a transparent material, and a material having sufficient strength and support for stability of the color filter may be used. Preferably, glass having excellent chemical stability and high strength can be used. As a method of manufacturing the color filter, a conventional method well known in the art may be used.

<Display device>

In addition, the present invention provides a display device including the color filter. Specific examples of the display device include a liquid crystal display (liquid crystal display; LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, and a display device for a digital camera. , Car navigation display devices, and the like, and color display devices are particularly suitable.

The display device includes a configuration known to those skilled in the art except for the color filter, that is, the present invention includes a display device to which the color filter of the present invention can be applied.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes can be made within the scope of the present invention. The scope of the present invention will be determined by the technical idea of the claims to be described later.

In addition, "%" and "parts" indicating the content in the following Preparation Examples, Examples, and Comparative Examples are based on weight unless otherwise noted.

<Synthesis Example>

Synthesis Example 1: Synthesis of 6-methacryloxycoumarin compound

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was replaced with nitrogen and then 6-hydroxycoumarin 48.6 g (0.3 mol) and triethylamine 23.0 g were added to anhydrous tetrahydrofuran (THF) 320 g. Completely dissolved. Here, 156 g (0.3 mol) of a chloride methacrylate solution diluted 20% (w/w) in tetrahydrofuran was added dropwise from the dropping lot over 1 hour and stirred at room temperature for 4 hours to synthesize a coumarin derivative.

Synthesis Example 2: Synthesis of 7-methacryloxy-3,4,8-trimethylcoumarin compound

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was replaced with nitrogen, and then 61.2 g (0.3 mol) of 7-hydroxy-3,4,8-trimethylcoumarin and 23.0 g of triethylamine were added. It was completely dissolved in 320 g of anhydrous tetrahydrofuran (THF). Here, 156 g (0.3 mol) of a chloride methacrylate solution diluted 20% (w/w) in tetrahydrofuran was added dropwise from the dropping lot to the flask over 1 hour, and stirred at room temperature for 4 hours to synthesize a coumarin derivative.

Synthesis Example 3: Synthesis of alkali-soluble resin (B-1)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after heating to 80°C, vinyl toluene 5.9 g, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1 g and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 70. Resin B-1 of mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 23,000, and the molecular weight distribution (Mw/Mn) was 2.7.

Synthesis Example 4: Synthesis of alkali-soluble resin (B-2)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 54.4 g of the coumarin compound prepared in Synthesis Example 2 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after heating to 80°C, vinyl toluene 5.9 g, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1 g and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100° C. for 6 hours, and the solid acid value was 67 Resin B-2 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 21,000, and the molecular weight distribution (Mw/Mn) was 2.6.

Synthesis Example 5: Synthesis of alkali-soluble resin (B-3)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, and after raising the temperature to 80°C, 5.9 g of vinyl toluene, 21.5 g of methacrylic acid, 85.1 g of 3-ethyl-3-(acryloyloxy)methyloxetane, and propylene glycol monomethyl ether acetate A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 70. Resin B-3 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 24,000, and the molecular weight distribution (Mw/Mn) was 2.7.

Synthesis Example 6: Synthesis of alkali-soluble resin (B-4)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 54.4 g of the coumarin compound prepared in Synthesis Example 2 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, and after raising the temperature to 80°C, 5.9 g of vinyl toluene, 21.5 g of methacrylic acid, 85.1 g of 3-ethyl-3-(acryloyloxy)methyloxetane, and propylene glycol monomethyl ether acetate A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100° C. for 6 hours, and the solid acid value was 67 Resin a-4 of mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 21,000, and the molecular weight distribution (Mw/Mn) was 2.6.

Synthesis Example 7: Synthesis of alkali-soluble resin (B-5)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 23.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after heating up to 80°C, vinyl toluene 5.9 g, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 110.5 g and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol, and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100° C. for 6 hours, and the solid acid value was 73 Resin B-5 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 27,000, and the molecular weight distribution (Mw/Mn) was 2.8.

Synthesis Example 8: Synthesis of alkali-soluble resin (B-6)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 69.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after heating to 80°C, vinyl toluene 5.9 g, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 73.6 g and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid content acid value was 85. Resin B-6 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 25,000, and the molecular weight distribution (Mw/Mn) was 2.7.

Synthesis Example 9: Synthesis of alkali-soluble resin (B-7)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after raising the temperature to 80°C, vinyl toluene 5.9 g, acrylic acid 18.0 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1 g and propylene glycol monomethyl ether acetate 136 g A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 80. Resin B-7 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 21,000, and the molecular weight distribution (Mw/Mn) was 2.6.

Synthesis Example 10: Synthesis of alkali-soluble resin (B-8)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, after heating to 80°C, vinyl toluene 5.9 g, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1 g and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 21.3 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 55. Resin B-8 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 22,000, and the molecular weight distribution (Mw/Mn) was 2.8.

Synthesis Example 11: Synthesis of alkali-soluble resin (B-9)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, and after heating to 80°C, 8.8 g of benzyl methacrylate, 21.5 g of methacrylic acid, 92.1 g of 3-(methacryloyloxymethyl)-3-ethyloxetane and propylene glycol mono A solution in which 3.3 g of azobisisobutyronitrile was added to a mixture containing 136 g of methyl ether acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 21.3 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 55. Resin B-9 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 22,000, and the molecular weight distribution (Mw/Mn) was 2.8.

Synthesis Example 12: Synthesis of alkali-soluble resin (B-10)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 23.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After changing my atmosphere from air to nitrogen, and after heating to 80°C, 5.9 g of vinyl toluene, 30.1 g of methacrylic acid, 92.1 g of 3-(methacryloyloxymethyl)-3-ethyloxetane and propylene glycol monomethyl ether A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture containing 136 g of acetate was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, and 28.4 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100° C. for 6 hours, and the solid content acid value was 55. Resin B-10 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 26,500, and the molecular weight distribution (Mw/Mn) was 2.8.

Synthesis Example 13: Synthesis of alkali-soluble resin (B-11)

137 g of propylene glycol monomethyl ether acetate and 45 g 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 changed from air to nitrogen, and the temperature was raised to 80°C. Then, a solution in which 3.3 g of azobisisobutyronitrile was added to a mixture containing 47.2 g of vinyl toluene, 25.8 g of methacrylic acid, 52.8 g of benzyl methacrylate and 136 g of propylene glycol monomethyl ether acetate was added from the dropping lot in 2 hours. It was added dropwise to the flask over and stirred at 80 DEG C for 5 hours to obtain Resin B-11 having a solid acid value of 120 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 13,100, and the molecular weight distribution (Mw/Mn) was 2.4.

Synthesis Example 14: Synthesis of alkali-soluble resin (B-12)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 46.0 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask Azobisisobutyronitrile in a mixture containing 47.2 g of vinyl toluene, 21.5 g of methacrylic acid, 26.4 g of benzyl methacrylate, and 136 g of propylene glycol monomethyl ether acetate after changing the atmosphere inside the air to nitrogen, and after raising the temperature to 80°C. The solution to which 3.3 g was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol, and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100° C. for 6 hours, and the solid acid value was 75 Resin B-12 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 18,000, and the molecular weight distribution (Mw/Mn) was 2.5.

Synthesis Example 15: Synthesis of alkali-soluble resin (B-13)

137 g of propylene glycol monomethyl ether acetate and 45 g of propylene glycol monomethyl ether were introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, and the atmosphere in the flask was made nitrogen from air, and the temperature was raised to 80°C. After vinyl toluene 29.5g, methacrylic acid 21.5g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1g and propylene glycol monomethyl ether acetate 136g in a mixture containing azobisisobutyronitrile 3.3 The solution to which g was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 14.2 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid content acid value was 85. Resin B-13 of mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 35,000, and the molecular weight distribution (Mw/Mn) was 3.0.

Synthesis Example 16: Synthesis of alkali-soluble resin (B-14)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 57.5 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask After the internal atmosphere was changed from air to nitrogen, after heating to 80°C, methacrylic acid 21.5 g, 3-(methacryloyloxymethyl)-3-ethyloxetane 92.1 g and propylene glycol monomethyl ether acetate 136 g were included. A solution in which 3.3 g of azobisisobutyronitrile was added to the mixture was added dropwise from the dropping lot to the flask over 2 hours, and stirred at 80°C for 5 hours to obtain Resin B-14 having a solid acid value of 120 mgKOH/g. Got it. The weight average molecular weight in terms of polystyrene measured by GPC was 19,000, and the molecular weight distribution (Mw/Mn) was 2.7.

Synthesis Example 17: Synthesis of alkali-soluble resin (B-15)

In a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube, 137 g of propylene glycol monomethyl ether acetate, 45 g of propylene glycol monomethyl ether, and 4.6 g of the coumarin compound prepared in Synthesis Example 1 were mixed and introduced, and the flask Including 15.5 g of methacrylic acid, 147.3 g of 3-(methacryloyloxymethyl)-3-ethyloxetane, and 136 g of propylene glycol monomethyl ether acetate after the internal atmosphere was changed from air to nitrogen and then heated to 80°C. A solution in which 3.3 g of azobisisobutyronitrile was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 80°C for 5 hours. Then, the atmosphere in the flask was made from nitrogen to air, 7.1 g of glycidyl methacrylate, 0.5 parts of trisdimethylaminomethylphenol and 0.1 parts of hydroquinone were added into the flask, and the reaction was continued at 100°C for 6 hours, and the solid acid value was 50 Resin B-15 in mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 43,000, and the molecular weight distribution (Mw/Mn) was 3.2.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins prepared in Synthesis Examples 3 to 17 were measured under the following conditions using the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

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

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 µl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard material 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 taken as molecular weight distribution (Mw/Mn).

Preparation Example 1: Red Pigment Liquid Composition (M-1)

As a colorant (B), C.I. Pigment Red 269 40 parts by weight, BYK2001 as a dispersant (Dispervic: manufactured by BYK, solid content concentration 45.1% by weight) 24 parts by weight (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether acetate 136 as a solvent The mixed solution containing parts was dispersed for 12 hours by a bead mill to prepare a red pigment liquid composition (M-1).

Preparation Example 2: Red Pigment Liquid Composition (M-2 )

As a colorant (B), C.I. Pigment Red 254 40 parts by weight, BYK2001 as a dispersant (Dispervic: manufactured by BYK, solid content concentration 45.1% by weight) 24 parts by weight (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether acetate 136 as a solvent The mixed solution containing parts was dispersed for 12 hours by a bead mill to prepare a red pigment liquid composition (M-2).

Preparation Example 3: Red Pigment Liquid Composition (M-3)

As a colorant (B), C.I. Pigment Red 291 40 parts by weight, BYK2001 as a dispersant (Dispervic: manufactured by BYK, solid content concentration 45.1% by weight) 24 parts by weight (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether acetate as a solvent 136 parts by weight The mixed solution containing parts was dispersed for 12 hours by a bead mill to prepare a red pigment liquid composition (M-3).

Preparation Example 4: Red Pigment Liquid Composition (M-4)

As a colorant (B), C.I. Pigment Yellow 150 40 parts by weight, BYK2001 as a dispersant (Disperbic: manufactured by BYK, solid content concentration 45.1% by weight) 24 parts by weight (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether acetate 136 as a solvent The mixed solution containing parts was dispersed for 12 hours by a bead mill to prepare a red pigment liquid composition (M-4).

Preparation Example 5: Red Pigment Liquid Composition (M-5)

As a colorant (B), C.I. Pigment Red177 40 parts by weight, BYK2001 as a dispersant (Dispervic: manufactured by BYK, solid content concentration 45.1% by weight) 24 parts by weight (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether acetate as a solvent 136 parts by weight The mixed solution containing parts was dispersed for 12 hours by a bead mill to prepare a red pigment liquid composition (M-5).

Examples and Comparative Examples: Preparation of red photosensitive resin composition

Each component was mixed in the composition of Tables 1 and 2 to prepare a red photosensitive resin composition (unit: wt%). In Tables 1 and 2 below, the content of the solvent is the rest excluding the amount of the solvent used in the preparation of the colorant and the synthesis of the alkali-soluble resin.

Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 coloring agent M-1 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 18.5 16.8 M-2 16.8 8.4 M-3 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 8.4 13.4 16.8 M-4 1.7 M-5 alkali
Soluble resin B-1 9.1 9.1 9.1 9.1 B-2 9.1 B-3 9.1 B-4 9.1 B-5 9.1 B-6 9.1 B-7 9.1 B-8 9.1 B-9 9.1 B-10 9.1 B-11 B-12 B-13 B-14 9.1 B-15 Photopolymerizable compound C-1 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 Light polymerization
Initiator D-1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 additive F-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent E-1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 Colorants M-1 to M-5: Red pigment dispersion of Preparation Examples 1 to 5
Alkali-soluble resins B-1 to B-15: Alkali-soluble resins prepared in Synthesis Examples 3 to 17
Photopolymerizable compound C-1: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator D-1: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime), manufactured by Ciba
Solvent E-1: Propylene glycol monomethyl ether acetate
Additive F-1: Silicone surfactant (SH-8400)

Furtherance Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 coloring agent M-1 16.8 16.8 16.8 16.8 M-2 4.7 M-3 16.8 16.8 16.8 16.8 4.7 M-4 1.7 M-5 28.9 28.9 31.9 alkali
Soluble resin B-1 9.1 9.1 9.1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 9.1 B-12 9.1 B-13 9.1 B-14 B-15 9.1 Photopolymerizable compound C-1 3.4 3.4 3.4 3.4 3.4 3.4 3.4 Light polymerization
Initiator D-1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 additive F-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 solvent E-1 53.1 53.1 53.1 53.1 53.1 53.1 53.1 Colorants M-1 to M-5: Red pigment dispersion of Preparation Examples 1 to 5
Alkali-soluble resins B-1 to B-15: Alkali-soluble resins prepared in Synthesis Examples 3 to 17
Photopolymerizable compound C-1: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator D-1: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime), manufactured by Ciba
Additive E-1: Propylene glycol monomethyl ether acetate
Solvent F-1: Silicone surfactant (SH-8400)

Test example

(1) Manufacturing of color filter

After applying the red photosensitive resin composition prepared according to Examples 1 to 14 and Comparative Examples 1 to 7 on a glass substrate by spin coating, place it on a heating plate and hold it at a temperature of 100°C for 3 minutes to form a color layer thin film. Formed. Subsequently, a test photomask having a line/space pattern of 1 to 50 µm was placed, and an ultraviolet ray was irradiated with a distance of 250 µm to the test photomask. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ/cm ² using a high pressure mercury lamp of 1 kW containing all g, h, and i-rays, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass substrate on which the developed color layer thin film is formed was washed with distilled water, dried under a nitrogen gas atmosphere, and heated in a heating oven at 200° C. for 1 hour to heat cure to prepare a color filter.

(2) Evaluation of chromaticity

Measurement was made using a microscopic spectrometer OSP-SP2000, and the amount of change in luminance therefrom was calculated as% based on Example 13 and the results are shown in Table 3 below.

(3) Evaluation of chemical resistance after UV irradiation (photo alignment)

In the method of Experimental Example (1), two coating films having patterns formed using the red photosensitive resin compositions of Examples 1 to 14 and Comparative Examples 1 to 7 were prepared.

One coated film on which the pattern was formed was irradiated with UV (light alignment) of 500 mJ/cm ² or more, and then evaluated for NMP elution using UV/VIS (UV-2550).

In addition, one sheet of the remaining coating film on which the pattern was formed was not irradiated with UV, and NMP elution evaluation was performed. In each of the evaluation results, the difference in the result of the presence or absence of UV irradiation was confirmed, and the result value was calculated by Equation 1 below.

[Equation 1]

Result (%): UV-irradiated substrate measurement value/UV-irradiated substrate measurement value

The criteria for evaluating NMP solvent resistance after UV irradiation (photo-alignment) according to the result values are as follows, and the results are shown in Table 3 below.

<Evaluation criteria>

◎: 100 or more and less than 120%

○: 120 or more and less than 150%

△: 150 or more and less than 250%

X: 250% or more

division Transmittance (Y) Y(%) After photo-alignment (UV)
NMP solvent resistance Example 1 16.9 101.2% ◎ Example 2 16.9 101.2% ◎ Example 3 16.9 101.2% ◎ Example 4 16.9 101.2% ◎ Example 5 16.9 101.2% ◎ Example 6 16.9 101.2% ○ Example 7 16.9 101.2% ◎ Example 8 16.9 101.2% ◎ Example 9 16.9 101.2% ◎ Example 10 16.9 101.2% ◎ Example 11 16.9 101.2% ○ Example 12 16.9 101.2% ○ Example 13 16.7 STD (100%) ◎ Example 14 16.7 100.0% ○ Comparative Example 1 16.6 99.4% X Comparative Example 2 16.6 99.4% X Comparative Example 3 16.6 99.4% △ Comparative Example 4 16.6 99.4% △ Comparative Example 5 16.1 96.4% ○ Comparative Example 6 15.9 95.2% ○ Comparative Example 7 15.7 94.0% ○

As shown in Table 3, in the case of examples using the red photosensitive resin composition according to the present invention, it was confirmed that the transmittance characteristics were excellent, and a color filter excellent in chemical resistance after photo-alignment (UV irradiation) could be realized. .

Specifically, it was confirmed that Examples 1 to 14 of the present invention had a transmittance of at least 0.1 or higher compared to Comparative Examples 1 to 7. Especially as a red pigment, C.I. Pigment Red 269 and C.I. Examples of the present invention using two or more of the compounds represented by Pigment 254 and C.I Pigment 291 showed a remarkably improved luminance of 0.8 or more and 4.8% or more compared to Comparative Examples 6 and 7.

In the present invention, the difference in transmittance of 0.1 can increase the luminance of 0.6%, and it is a value that can improve the transmittance even in a color filter. In the technical field to which the present invention belongs, a very small difference in luminance can cause an image or image of a screen to be displayed outdoors under sunlight. It can be said to be a significant number because it is a factor that affects the clearly visible display performance.

In addition, when comparing Examples 1 to 14 and Comparative Examples 1 to 4 using the alkali-soluble resin according to the present invention, a significant difference in NMP solvent properties after photo-alignment was confirmed.

Therefore, the colored photosensitive resin composition of the present invention can suppress the decrease in reliability, especially the reliability of the red photosensitive resin composition when applied to a photo-alignment model, and has excellent luminance when implementing a color filter, and has excellent transmittance due to less color shift. It can be seen that it can provide

Claims (13)

An alkali-soluble resin (A), a colorant (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E) are included,
The alkali-soluble resin (A) is a copolymer comprising a coumarin-based compound (A1), a compound (A2) containing an oxetane functional group, and an unsaturated carboxylic acid compound (A3),
The colorant (B) contains at least two or more pigments of the compounds represented by CI pigment 254, CI pigment red 269 and CI pigment 291, a red photosensitive resin composition. The red photosensitive resin composition of claim 1, wherein the coumarin-based compound (A1) comprises at least one selected from the group consisting of compounds represented by the following formulas 1 to 4:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4, X is the following Formula 5, and R ₁ to R ₂₀ are each independently hydrogen, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, a phenyl group, a benzyl group, or an alkoxy having 1 to 8 carbon atoms And
[Formula 5]

In Formula 5, R ₂₁ is hydrogen or a methyl group, and a dotted line represents a portion bonded to Formulas 1 to 4. The red photosensitive resin composition of claim 1, wherein the compound (A2) containing an oxetane functional group is represented by the following formula (6):
[Formula 6]

In Formula 6, X is

, R ₂₁ is hydrogen or a methyl group, Y is -O-, -CO-, -C(=O)O-, -CONH- or a phenylene group, the dotted line represents the bond from Y, and R ₂₂ is It is hydrogen, an alkyl group having 1 to 12 carbon atoms, an allyl group, a phenyl group, a halogen atom or an ethoxy group having 1 to 8 carbon atoms. The method according to claim 1, wherein the colorant (B) is C.I. Including Pigment Red 269, and C.I. The red photosensitive resin composition further comprising a compound represented by Pigment 254 or C.I Pigment 291. The method according to claim 4, wherein the colorant (B) is the C.I. Pigment Red 269 and C.I. Pigment Red 254 or C.I. Pigment Red 291 will be included in a weight ratio of 10:90 to 90:10, red photosensitive resin composition. The method according to claim 1, wherein the ratio of the constituent components derived from each of (A1), (A2) and (A3) to the total number of moles of the constituent components of the alkali-soluble resin (A),
The structural unit derived from (A1) is 5 to 40 mol%,
The structural unit derived from (A2) is 5 to 70 mol%,
The structural unit derived from (A3) is 5 to 60 mol%, a red photosensitive resin composition. The method of claim 1, wherein the alkali-soluble resin further comprises a compound (A4) having an unsaturated bond capable of copolymerizing with (A1) and (A3) and a compound (A5) having an unsaturated bond and an epoxy group in one molecule. The red photosensitive resin composition which is a resin obtained as. The method according to claim 7, wherein the ratio of the constituent components derived from each of (A1) to (A5) to the total number of moles of constituent components of the alkali-soluble resin (A),
The structural unit derived from (A1) is 5 to 40 mol%,
The structural unit derived from (A2) is 5 to 70 mol%,
The structural unit derived from (A3) is 5 to 60 mol%,
The structural unit derived from (A4) is 5 to 40 mol%,
The constituent unit derived from (A5) is 5 to 80 mol% with respect to the number of moles of the constituent components derived from (A3), the red photosensitive resin composition The method according to claim 1,
Based on the total weight of solids in the red photosensitive resin composition,
5 to 90% by weight of an alkali-soluble resin (A);
5 to 70% by weight of the colorant (B);
1 to 60 parts by weight of a photopolymerizable compound (C) based on 100 parts by weight of the total of the alkali-soluble resin (A) and the photopolymerizable compound (C); And
It contains 0.1 to 40% by weight based on the total weight of solids in the alkali-soluble resin (A) and the photopolymerizable compound (C),
Based on the total weight of the red photosensitive resin composition,
The red photosensitive resin composition containing 60 to 90 weight% of a solvent (E). The red photosensitive resin composition of claim 1, wherein the colorant further comprises at least one pigment or dye. The red photosensitive resin composition according to claim 1, further comprising at least one additive selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents. A color filter manufactured by using the red photosensitive resin composition according to any one of claims 1 to 11. A display device comprising the color filter of claim 12.