KR102383520B1 - A Red PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE COMPRISING THE SAME - Google Patents

Abstract

The present invention is a colorant; and two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms; the number of polymerizable groups in the two or more photopolymerizable compounds is 4.5 or more on a mass average, and an alkylene oxide having 2 or more carbon atoms. The number of periods is 2.0 to 10.5 on a mass average, and the colorant is a compound represented by the following Chemical Formula 1; and at least one selected from the group consisting of pigments and dyes other than the compound represented by Chemical Formula 1; By including, high permeability is realized The present invention relates to a red photosensitive resin composition having excellent luminance, that is, color reproducibility, improved development residue during the manufacture of color filters, and good pattern formation, color filters and image display devices including the same.
[Formula 1]

Description

Red photosensitive resin composition, color filter and image display device comprising the same

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

A color filter is a member used for a solid-state image sensor or a liquid crystal display device, and is generally produced by forming a coloring pattern using a coloring photosensitive resin composition on a support body.

In recent years, there is a tendency for image display devices to become thinner, and color filters included in image display devices also tend to become thinner, and accordingly, the size of the coloring pattern is becoming more miniaturized. appears conspicuously.

According to the miniaturization of the coloring pattern, impreciseness at the end of the coloring pattern or the development residue in the unexposed portion is more problematic than before.

In addition, in the thin-layered color filter, the composition ratio of the colorant in the colored photosensitive resin composition increases in order to obtain spectral sensitivity equivalent to that of the conventional color filter. In this case, components other than the colorant (components contributing to photolithography performance) are relatively will decrease

Accordingly, there is a need for development of a colored photosensitive resin composition capable of maintaining photolithography performance comparable to that of the prior art even when a component contributing to photolithography performance is relatively reduced.

In addition, when the composition ratio of the colorant is increased to obtain spectral sensitivity, the composition ratio of the colorant dispersion is increased. As such, when the composition ratio of the colorant dispersion is increased, the thixotropy (thixotropy) of the colored photosensitive resin composition itself containing the colorant dispersion is increased. ) increases, so when the colored curable composition is applied on a support to form a colored layer, the film thickness uniformity in the surface of the support tends to decrease. When the uniformity of the thickness of the colored layer is lowered, there are problems in that the focal length varies during exposure, inaccuracies in the periphery of a fine pattern occur, and development residues in the non-hardened portion occur.

In order to solve the above problems, Korean Patent Application Laid-Open No. 10-2009-0073035 discloses a colorant and at least two polymerizable compounds containing a polymerizable compound having an alkyleneoxy group having 2 or more carbon atoms; The number of polymerizable groups of the two or more polymerizable compounds is 4.5 or more on a mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 or more and 10.0 or less on a mass average. Although it has been described with respect to a colored curable composition that can reduce the occurrence of , this does not properly solve the problem of the generation of the development residue, and there is a problem that the color gamut does not meet the recently required standards.

Republic of Korea Patent Publication No. 10-2009-0073035 (2009.07.02.)

The present invention is to solve the above problems, and it is possible to realize high transmittance, so that it has excellent luminance, that is, color reproducibility, improved development residue, and good pattern formation, a red photosensitive resin composition comprising the same, and a color filter and image display including the same The purpose is to provide a device.

The red photosensitive resin composition of the present invention for achieving the above object is a colorant; and two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms; the number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more on a mass average, and an alkylene oxide having 2 or more carbon atoms. The number of periods is 2.0 to 10.5 on a mass average, and the colorant comprises a compound represented by the following formula (1); and at least one selected from the group consisting of pigments and dyes other than the compound represented by formula (1) do.

[Formula 1]

In addition, the color filter according to the present invention is characterized in that it includes a cured product of the above-described red photosensitive resin composition.

In addition, the image display apparatus according to the present invention is characterized in that it includes the above-described color filter.

The red photosensitive resin composition of the present invention can realize high transmittance, so that it has excellent luminance, that is, color reproducibility, improved development residue during color filter manufacturing, and good pattern formation.

The color filter of the present invention has the same advantages as described above.

The image display apparatus of the present invention has the same advantages as described above.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present invention, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In the present invention, the number of polymerizable groups in the mass average of the two or more types of photopolymerizable compounds is a mass calculated based on the number of polymerizable groups each photopolymerizable compound has and the mass of each photopolymerizable compound contained in the red photosensitive resin composition mean the average value.

In addition, in the present invention, the number of alkyleneoxy groups having 2 or more carbon atoms in the mass average of two or more types of photopolymerizable compounds is the number of 'alkyleneoxy groups having 2 or more carbon atoms' each photopolymerizable compound has, and contained in the red photosensitive resin composition It points out the mass average value computed based on the mass of each photopolymerizable compound.

For example, the red photosensitive resin composition of this invention is photopolymerizable compound 1, photopolymerizable compound 2, ... When it contains n types of photopolymerizable compounds which consist of , photopolymerizable compound n, the number of polymerizable groups (J _AVE ) in the mass average of the n types of photopolymerizable compounds is calculated by the following formula (1).

[Equation 1]

J _AVE =(J1·W1 + J2·W2 + … +Jn·Wn)/(W1 + W2 + … + Wn)

In Equation 1, J1 is the number of polymerizable groups in one molecule of the photopolymerizable compound 1, W1 is the total mass of the photopolymerizable compound 1 in the red photosensitive resin composition, and J2 is the number of polymerizable groups in one molecule of the photopolymerizable compound 2 , W2 is the total mass of the photopolymerizable compound 2 in the red photosensitive resin composition, Jn is the number of polymerizable groups in one molecule of the photopolymerizable compound n, Wn is the total mass of the photopolymerizable compound n in the red photosensitive resin composition.

Similarly, the red photosensitive resin composition of the present invention is a photopolymerizable compound 1, a photopolymerizable compound 2, ... , the number of alkyleneoxy groups having 2 or more carbon atoms in the mass average of the n types of photopolymerizable compounds (A _AVE ) is calculated by the following formula (2) .

[Equation 2]

A _AVE =(A1·W1 + A2·W2 + … +An·Wn)/(W1 + W2 + … + Wn)

In Equation 2, A1 is the 'number of alkyleneoxy groups having 2 or more carbon atoms' in one molecule of the photopolymerizable compound 1, W1 is the total mass of the photopolymerizable compound 1 in the red photosensitive resin composition, and A2 is the photopolymerizable compound 2 'The number of alkyleneoxy groups having 2 or more carbon atoms' in one molecule, W2 is the total mass of the photopolymerizable compound 2 in the red photosensitive resin composition, An is the number of polymerizable groups in one molecule of the photopolymerizable compound n, Wn is the red photosensitive resin It is the total mass of the photopolymerizable compound n in the composition.

Hereinafter, the present invention will be described in more detail.

<Red photosensitive resin composition>

The red photosensitive resin composition according to an aspect of the present invention includes a colorant; and two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms; the number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more on a mass average, and an alkylene oxide having 2 or more carbon atoms. The number of phases is 2.0 to 10.5 on a mass average, and the colorant is a compound represented by the following formula (1); and at least one selected from the group consisting of pigments and dyes other than the compound represented by formula (1). It is possible to have excellent luminance, that is, color reproducibility, it is possible to suppress the occurrence of development residues during the manufacture of color filters, and there are advantages of good pattern formation.

[Formula 1]

In the present invention, 'good pattern formation' means excellent smoothness of the pattern during pattern formation.

coloring agent

The red photosensitive resin composition according to an embodiment of the present invention includes a colorant, and the colorant includes a compound represented by Chemical Formula 1, thereby enabling high transmission, thereby improving luminance, that is, color reproducibility. There is an advantage that high color reproduction is possible.

According to an embodiment of the present invention, the compound represented by Formula 1 may be included in an amount of 5 to 70% by weight, preferably 10 to 50% by weight, based on 100% by weight of the total solid content in the red photosensitive resin composition including the same. there is. If the content of the colorant is less than the above range, the color separation ability of the formed pattern may be reduced, and if it exceeds the above range, the lithography performance may be deteriorated to cause problems such as residues or non-development.

According to one aspect of the present invention, the red photosensitive resin composition of the present invention contains one or more selected from the group consisting of pigments and dyes so that the colorant can exhibit a desired color such as red, in addition to the compound represented by Chemical Formula 1 above. Further included, and at this time, the pigment or dye that may be further included may be used without particular limitation as long as it is a pigment or dye commonly used in the art, and these may be prepared in the form of a mill base, but are not limited thereto.

pigment

The pigment may include an organic pigment or an inorganic pigment, which may be used alone or in combination of two or more. Among these, it may be more preferable to use an organic pigment from the viewpoint of excellent heat resistance and color development. In addition, the organic pigment may be a synthetic pigment or a natural pigment.

The organic pigment may be treated with rosin, if necessary; surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; graft treatment to the surface of the pigment using a polymer compound or the like; fine-graining treatment by a sulfuric acid fine-graining method or the like; or 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, and inorganic salts of barium sulfate (physical pigment). More specifically, the metal compounds include iron, cobalt, aluminum, cadmium, lead, copper, and titanium. and oxides of metals such as magnesium, chromium, zinc, antimony, and carbon black, or composite metal oxides.

As a specific example of the pigment, more preferably a compound classified as a pigment in the Color Index (Publisher: The Society of Dyers and Colorists) may be mentioned, and more specifically, the following color index (C.I.) number Examples of pigments may be mentioned, but the present invention is not limited thereto, and one or more selected from them may be co-dispersed using a binder resin, a dispersant, etc. to match the desired chromaticity.

C.I. As a specific example of pigment yellow, 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;

C.I. As a specific example of the pigment orange, C.I. pigment orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. As a specific example of pigment red, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265. However, it is not limited thereto, and these may be used alone or in combination of two or more.

Preferably, the C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 242, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185 or mixtures thereof may also be used.

The pigment is preferably used in the form of a pigment dispersion composition in which particle diameters are uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing treatment by containing a pigment dispersant can be given. According to this method, a pigment dispersion composition in which the pigment is uniformly dispersed in a solution can be obtained.

dispersant

The dispersing agent is added for deagglomeration and stability maintenance 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, and polyamine may be used, but preferably BMA (butyl methacrylate) or DMAEMA (N,N-dimethylamino An acrylate-based dispersing agent (hereinafter, sometimes referred to as an acrylic dispersing agent) containing ethyl methacrylate) can be used. At this time, it may be preferable to apply the acrylic dispersant prepared by the living control method as presented in Korean Patent Application Laid-Open No. 2004-0014311. 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.

As the dispersant, a pigment dispersant of a resin type other than the above-mentioned acrylic dispersant may be used. The pigment dispersants of the other resin types include known resin type pigment dispersants, in particular polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); 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 polyacrylates; adducts of ethylene oxide/propylene oxide and phosphate esters; and the like. As a commercially available product of the above-mentioned resin type dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade 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 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 from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Kyoeisha Chemical Company's trade name: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, and the like may be mentioned, but are not limited thereto, and these are each alone or It can be used in combination of 2 or more type, and can also be used together with an acrylic dispersing agent.

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. If the content of the dispersant exceeds the above range, the viscosity may increase and process problems may occur.

dyes

The dye may be used without limitation as long as it has solubility in organic solvents or is dispersible. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance and solvent resistance. In the case of dyes that are not soluble in organic solvents, it is also possible to disperse them and use them.

As the dye, at least one selected from acid dyes having an acid group such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof may be used. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof may be selected.

Preferred examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists), and well-known dyes described in the dyeing notes (color dyes).

Specific examples of the dye include,

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 No. 135;

C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 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 No. 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; and the like.

Also, C.I. as an acid dye

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. orange dyes such as acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Violet dyes, such as acid violet 6B, 7, 9, 17, 19, 66;

Also C.I. As a direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, yellow dyes such as 136, 138, and 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. orange dyes such as direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Violet dyes, such as direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Also, C.I. As modanto dye

C.I. yellow dyes such as modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 red dye;

C.I. Orange dyes such as modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ;

C.I. Violet dyes, such as modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; and the like, but is not limited thereto, and these may be used alone or in combination of two or more.

According to an embodiment of the present invention, the compound of Formula 1; and at least one material selected from the group consisting of pigments and dyes; may be mixed in an amount of 1:0.05 to 1:18 by weight, preferably It may be mixed in a weight ratio of 1:0.1 to 1:9, more preferably 1:0.2 to 1:4.

As such, when the mixing ratio of the compound of Formula 1 and at least one material selected from the group consisting of pigments and dyes satisfies the above ranges, the effect of high coloration and high brightness can be exhibited, and the process margin is improved, There is an advantage that the sensitivity can be improved.

According to an embodiment of the present invention, the above-described colorant may be included in an amount of 5 to 70% by weight, preferably 10 to 50% by weight, based on 100% by weight of the total solid content of the red photosensitive resin composition including the same. If the content of the colorant is less than the above range, the color separation ability of the formed pattern may be reduced, and if it exceeds the above range, the lithography performance may be deteriorated to cause problems such as residues or non-development.

In the present invention, the solid content in the red photosensitive resin composition means the total content of the remaining components excluding all solvents included in the red photosensitive resin composition.

photopolymerization compound

The red photosensitive resin composition according to an embodiment of the present invention includes two or more types of photopolymerizable compounds, wherein the photopolymerizable compound includes at least one type of photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, the two or more types The number of polymerizable groups of the photopolymerizable compound is 4.5 or more on a mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 to 10.5 on a mass average. there is.

The two or more photopolymerizable compounds contain at least one photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, and the number of polymerizable groups and the number of alkyleneoxy groups having 2 or more carbon atoms in the total photopolymerizable compound satisfies the above-mentioned ranges. It can be used without any special restrictions on its type.

carbon number 2 or more alkyleneoxy group having photopolymerization compound

The red photosensitive resin composition according to an aspect of the present invention includes at least one photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, thereby improving developability and improving development residues and line tearing. .

The type of the 'photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms' is not particularly limited, but includes, for example, at least one selected from the group consisting of a compound represented by the following Chemical Formula 2 and a compound represented by Chemical Formula 3 may be doing

[Formula 2]

(In Formula 2,

Each E independently represents -((CH ₂ )yCH ₂ O)-, or -((CH ₂ )yCH(CH ₃ )O)-, and y each independently represents an integer from 1 to 10,

X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group,

The sum of the acryloyl group and the methacryloyl group is 3 or 4,

each m is independently an integer from 0 to 10, and the sum of each m is an integer from 1 to 40).

Preferably, in Formula 2, m may be each independently an integer of 0 to 6, more preferably an integer of 0 to 4. In addition, the sum of m may be an integer of preferably 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.

[Formula 3]

(In Formula 3,

Each E independently represents -((CH2)yCH2O)-, or -((CH2)yCH(CH3)O)-, y each independently represents an integer from 1 to 10;

X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group,

The sum of the acryloyl group and the methacryloyl group is 5 or 6,

each n is independently an integer from 0 to 10, and the sum of each n is an integer from 1 to 60).

Preferably, in Formula 3, n may be each independently an integer of 0 to 6, more preferably an integer of 0 to 4. In addition, the sum of m may be preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.

In addition, -((CH ₂ )yCH ₂ O)-, or -((CH ₂ )yCH(CH ₃ )O)- in the compound represented by Formula 2 or Formula 3 has an oxygen atom-side terminal bonded to X It may be desirable to be in the form of

The compound represented by Formula 2 or Formula 3 includes a process of bonding a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process, and a terminal hydroxyl group of the ring-opening skeleton. , for example, it can be synthesized from a step of introducing a (meth)acryloyl group by reacting (meth)acryloyl chloride. Each process is a process well known in the art, and those skilled in the art can easily synthesize the compound represented by Chemical Formula 2 or Chemical Formula 3.

The compound represented by Formula 2 or Formula 3 may be more preferably a pentaerythritol derivative and/or a dipentaerythritol derivative, and specifically, include compounds represented by Formulas 4 to 9 below, among others, A compound represented by Formula 4, Formula 5, Formula 8, or Formula 9 may be used more preferably.

[Formula 4]

(In Formula 4, the total sum of n is 6.)

[Formula 5]

(In Formula 5, the total sum of n is 12.)

[Formula 6]

(In Formula 6, the total sum of n is 12.)

[Formula 7]

(In Formula 7, the total sum of n is 6.)

[Formula 8]

(In Formula 8, the total sum of m is 4.)

[Formula 9]

(In Formula 9, the total sum of m is 12.)

Commercially available products of the compound represented by the formula (2) or (3) include, for example, Shin-Nakamura A-DPH-12E, A-DPH-6P, ATM-4E, Sartomer SR-494, Nippon Kayaku Co., Ltd. DPCA-60, TPA-330, etc. may be mentioned, but is not limited thereto.

polymerizable group Have, carbon number 2 or more alkyleneoxy group not having photopolymerization compound

The red photosensitive resin composition according to an embodiment of the present invention may further include a photopolymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms. As described above, when a photopolymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms is further included, a phenomenon in which the solubility of the cured part in a developer is increased or a phenomenon in which the line width sensitivity is lowered can be suppressed. there is.

It is preferable that it is 2 or more, and, as for the number of the polymeric groups of the photopolymerizable compound which has the said polymerizable group, it is more preferable that it is 3 or more.

The type of the photopolymerizable compound having the polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms is not particularly limited in the present invention, but for example, a monofunctional acrylate or methacrylate (eg, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, and these may be used alone or in mixture of two or more.

In addition, the photopolymerizable compound having the polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms may include at least one selected from the group consisting of a compound represented by the following Chemical Formula 10 or a compound represented by Chemical Formula 11.

[Formula 10]

(In Formula 10,

Z is each independently an acryloyl group, a methacroyl group, a hydrogen atom, or a carboxyl group).

When the acryloyl group and the methcroyl group are included in Formula 10, the sum thereof is preferably 3 or 4.

[Formula 11]

(In Formula 11,

Z is each independently an acryloyl group, a methacroyl group, a hydrogen atom, or a carboxyl group).

When the acryloyl group and the methcroyl group are included in Formula 11, the sum thereof is preferably 5 or 6.

According to an embodiment of the present invention, the content of the total photopolymerizable compound included in the red photosensitive resin composition of the present invention is 5 to 50% by weight, preferably based on 100% by weight of the total solid content in the red photosensitive resin composition including the same 10 to 40% by weight, more preferably 20 to 30% by weight. As such, when the content of the photopolymerizable compound is included within the above range, there is an advantage in that it is possible to prevent the development of residues and defective patterns.

According to an embodiment of the present invention, the content (A) of the photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms and the content (B) of the photopolymerizable compound having the polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms A weight ratio (A:B) of 9:1 to 1:9, preferably 8:2 to 2:8. When the weight ratio satisfies the above range, it is easier to control the number of polymerizable groups in the mass average of the photopolymerizable compound or to control the number of 'alkyleneoxy groups having 2 or more carbon atoms' in the mass average, thereby reducing the occurrence of defective development residues and patterns. There is an advantage that it can be prevented more effectively.

According to an embodiment of the present invention, the red photosensitive resin composition of the present invention may further include at least one selected from the group consisting of alkali-soluble resins, photoinitiators, solvents and additives.

Alkali-soluble resin

The alkali-soluble resin may be removed by making the non-exposed part alkali-soluble after curing of the red photosensitive resin composition including the same, and may also serve as a dispersion medium for pigments that may be included together.

The alkali-soluble resin may be used without particular limitation as long as it is used in the art, but preferably includes a monomer having a carboxyl group. As the polymer including the monomer having a carboxyl group, it may be preferable to use a copolymer obtained from the monomer having a carboxyl group and another monomer copolymerizable with the monomer, but is not limited thereto.

The monomer having a carboxyl group may be, for example, an unsaturated carboxylic acid having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, specific examples of which include acrylic acid, methacrylic acid, crotonic acid, Itaconic acid, maleic acid and fumaric acid may be mentioned, but are not limited thereto, and these may be used alone or in combination of two or more.

The other copolymerizable monomer may mean a compound having a polymerizable carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as α-methylstyrene and vinyltoluene; unsaturated carboxylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and benzyl (meth)acrylate; Unsaturated glycidyl carboxylates, such as unsaturated aminoalkyl carboxylates, such as aminoethyl acrylate, and glycidyl (meth)acrylate; vinyl carboxylates such as vinyl acetate and vinyl propionate; and vinyl cyanide compounds such as (meth)acrylonitrile and α-chloroacrylonitrile, but is not limited thereto, and these may be used alone or in combination of two or more.

Preferred examples of the copolymer include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / methacrylic acid copolymer, methyl methacrylate / methacrylic acid acid/styrene copolymer, and the like, but is not limited thereto, and these may be used alone or in combination of two or more.

When the alkali-soluble resin is a copolymer obtained from a monomer having a carboxyl group and another monomer copolymerizable therewith, the carboxyl group monomer in the copolymer is included in an amount of 10 to 50% by weight with respect to 100% by weight of the total copolymer, Preferably, it may be included in an amount of 15 to 40% by weight.

The alkali-soluble resin may have a weight average molecular weight of 3,000 to 100,000, preferably 5,000 to 50,000, measured by gel permeation chromatography in terms of polystyrene. When the weight average molecular weight of the alkali-soluble resin satisfies the above range, it is possible to suppress the occurrence of film reduction during development, and there is an advantage in that the omission property of the non-pixel portion can be improved.

The molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight relative to the number average molecular weight (weight average molecular weight (Mw)/number average molecular weight (Mn)) may be 1.5 to 6.0, preferably 1.8 to 4.0, in this case development There are advantages to improving performance.

The alkali-soluble resin may have an acid value of 30 to 170 mgKOH/g based on solid content, preferably 50 to 150 mgKOH/g. When the acid value of the alkali-soluble resin is less than the above range, it is difficult for the red photosensitive resin composition including the same to secure a sufficient development speed. It is easy, there is a problem in that compatibility with the colorant occurs, the colorant in the red photosensitive resin composition is precipitated, or the storage stability of the red photosensitive resin composition is reduced and the viscosity may increase.

The alkali-soluble resin may be included in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on 100% by weight of the total solid content of the red photosensitive resin composition including the same. When the content of the alkali-soluble resin satisfies the above range, the solubility in the developer is sufficient to suppress the generation of development residues on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion during development is prevented. Thus, there is an advantage that the omission property of the non-pixel portion can be improved.

light curing initiator

The photopolymerization initiator may be used without particular limitation, as long as it can generate radicals that can initiate polymerization of the above-mentioned photopolymerizable compound by exposure to light such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. For example, an oxime-based compound, an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, a biimidazole-based compound, a triazine-based compound, a thioxanthone-based compound, and an anthracene-based compound may be mentioned, but the present invention is not limited thereto. No, one or more types may be selected and used therefrom. Among them, in consideration of polymerization characteristics, initiation efficiency and absorption wavelength, it may be more preferable to use an oxime-based compound.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z)-2-((benzoyloxy)imino)-1-(4- (phenylthio)phenyl)octan-1-one (see formula 12 below), (E)-1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl)ethylidine)amino)oxy)ethanone (see formula 13 below) and (E)-1-(((1-(6-(4-((2,2-dimethyl-1,3-dioxolane-) 4-yl) methoxy) -2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethylidin) amino) oxy) ethanone (refer to the following formula 14), and the like, and commercially available products may include, but are not limited to, OXE-01 and OXE-02 manufactured by BASF.

[Formula 12]

[Formula 13]

[Formula 14]

The content of the oxime-based compound is not particularly limited as long as it is within a range capable of fulfilling its functions, but is 10 to 100% by weight, preferably 20 to 100% by weight, based on 100% by weight of the total photopolymerization initiator. may be included. When the content of the oxime-based compound is included within the above range, there is an advantage in that luminance and sensitivity can be further improved.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 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, but are not limited thereto.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 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 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 the imidazole compound in which the phenyl group at the 4,4',5,5'-position was substituted with a carboalkoxy group, etc. are mentioned. Among these, 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 is not limited thereto.

Examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(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.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. may be mentioned, but 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, and the like. may be mentioned, but is not limited thereto.

As other specific examples, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, phenylclioxyl methyl acid, a titanocene compound, and the like, but is not limited thereto.

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

The content of the photoinitiator is not particularly limited in the present invention, but may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total solid content of the alkali-soluble resin and the photopolymerizable compound. there is. When the content of the photopolymerization initiator is included within the above range, the red photosensitive resin composition including the same is highly sensitive and the exposure time is shortened, so productivity can be improved, and there is an advantage that high resolution can be maintained, and the red color of the present invention There is an advantage in that the strength of the pixel portion formed using the photosensitive resin composition and smoothness on the surface of the pixel portion can be improved.

The photopolymerization initiator may further include a photopolymerization initiator adjuvant 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 further contains a photopolymerization initiation auxiliary, the sensitivity is further increased and productivity can be further improved.

The photopolymerization initiation adjuvant may be, 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, but is not limited thereto.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. may be used, but the present invention is not limited thereto.

The carboxylic acid compound is preferably aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid, but are not limited thereto.

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), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like. However, the present invention is not limited thereto.

solvent

The solvent can be used without particular limitation as long as it can dissolve other components included in the red photosensitive resin composition, as long as it is a solvent used in the art, for example, ethers, acetates, aromatic hydrocarbons, ketones, alcohols , esters, amides, etc., but are not limited thereto, and these may be used alone or in combination of two or more.

The ether solvent is specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, 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, but is not limited thereto.

The acetate solvent is 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, but is not limited thereto.

Specifically, the aromatic hydrocarbon solvent may include benzene, toluene, xylene, mesitylene, and the like, but is not limited thereto.

Specifically, the ketone solvent may include, but is not limited to, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specifically, the alcohol solvent may include, but is not limited to, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specifically, the ester solvents include cyclic esters such as γ-butyrolactone; 3-ethoxy ethyl propionate, 3-methoxy methyl propionate, ethyl 3-ethoxy propionate and the like may be mentioned, but is not limited thereto.

Specifically, the amide solvent may include, but is not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The above-mentioned solvents may be used alone or in combination of two or more.

It may be preferable to use an organic solvent having a boiling point of 100° C. to 200° C. in terms of coating properties and drying properties, and specifically, alkylene glycol alkyl ether acetates; ketones; Esters, such as 3-ethoxy ethyl propionate and 3-methoxy methyl propionate; are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxy propionic acid are mentioned. Ethyl, 3-methoxymethyl propionate, etc. may be mentioned, but is not limited thereto, and these may be used alone or in combination of two or more.

The content of the solvent may be included in an amount of 60 to 90% by weight, preferably 70 to 85% by weight, based on 100% by weight of the total red photosensitive resin composition including the solvent. When the content of the solvent is included within the above range, the applicability may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, etc. There is an advantage.

additive

The red photosensitive resin composition of the present invention adds additives such as other high molecular compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-aggregation agents according to the needs of those skilled in the art in the range that does not impair the purpose of the present invention in addition to the above components may contain more.

Specific examples of the above other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. may be mentioned, but is not limited thereto.

The curing agent is used to enhance 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, and an oxetane compound.

Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolak epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester-based resins, glycidylamine-based 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 epoxide, isoprene (co) ) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but is not limited thereto.

Specific examples of the oxetane compound include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like, but limited thereto. it is not going to be

The curing agent may be used together 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, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, acid generators, and the like may be used. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. The commercially available epoxy resin curing agent includes, for example, a trade name (Adecahadona EH-700) (manufactured by Adeka Industrial Co., Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin-Nippon Ewha Co., Ltd.), trade name (MH-700) (manufactured by Nippon Ewha Co., Ltd.) and the like.

The curing agent and 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.

The fluorine-based surfactants include, for example, Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone as commercially available products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF- from GE Toshiba Silicone. 4460 and TSF-4452.

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

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, 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 100% by weight of the total solid content in the red photosensitive resin composition of the present invention.

Specific examples of the antioxidant include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)prop Foxy]- 2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphospepine, 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, pentaerythritoltetrakis[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 of the aggregation inhibitor include, but are not limited to, sodium polyacrylate.

The method for preparing the above-described red photosensitive resin composition may be used without limitation any method used in the art, but as an example, it is as follows.

First, the pigment among the colorants is mixed with a solvent or a dispersing agent and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, if necessary, a pigment dispersant, part or all of the alkali-soluble resin, or a dye may be mixed with a solvent to be dissolved or dispersed.

The red photosensitive resin composition according to the present invention may be prepared by further adding a dye, the remainder of the alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, and, if necessary, additives and solvents to a predetermined concentration in the mixed dispersion.

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

The coloring pattern may be formed, for example, by the following method.

First, the red photosensitive resin composition is applied on a substrate or a layer made of the solid content of the previously formed photosensitive resin composition, and volatile components such as a solvent are removed by prebaking from the applied photosensitive resin composition layer to obtain a smooth coating film.

As said coating method, spin coating, the casting|flow_spread coating method, the roll coating method, the slit-and-spin coating, or slit coating method etc. can be implemented, for example.

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

An ultraviolet-ray is irradiated to the coating film obtained in this way through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are precisely aligned.

Further, after that, the cured coating film is brought into contact with an alkali developing solution to dissolve the unexposed portion and develop the desired pattern shape. As the developing method, a liquid addition method, a dipping method, a spraying method, etc. may be performed, and the substrate may be tilted at an arbitrary angle during development.

The said developing solution used for image development after patterning exposure is an aqueous solution containing an alkaline compound and surfactant normally. Any of inorganic and/or organic alkaline compounds may be sufficient as the said alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, carbonate Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, 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. You may use these inorganic and organic alkaline compounds individually or in combination of 2 or more types, respectively.

The concentration of the alkaline compound in the alkaline 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 copolymer, sorbitan fatty acid Ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc. are mentioned.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylarylsulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; and the like.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride; quaternary ammonium salts; and the like.

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

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 development, it may be washed with water and, if necessary, may be post-baked at 150 to 230°C for 10 to 60 minutes.

<Color filter>

A color filter according to another aspect of the present invention includes a cured product of the above-described red photosensitive resin composition. The color filter 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 the stability of the color filter may be used. Preferably, a glass having excellent chemical stability and high strength may be used.

A method of manufacturing the color filter may use a conventional method well known in the art.

<Image display device>

An image display apparatus according to another aspect of the present invention includes the color filter described above.

Specifically, the image display device may include other components that may be included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention. It does not limit this.

The image display device includes a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display device for a digital camera, and a car display device. A display device such as a display device for navigation may be included, but the present invention is not limited thereto.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are based on weight unless otherwise specified.

Synthesis example 1. Synthesis of alkali-soluble resin A-1

180 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, and then the temperature was raised to 80 ° C., 21.6 g of acrylic acid, 70.4 g of benzyl methacrylic acid, and methyl methacrylic acid A mixture containing 30.0 g was dissolved. 5.0 g parts by weight of α-methylstyrene dimer (chain transfer agent) was added to the mixture, and 3.3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) to 50 parts by weight of propylene glycol monomethyl ether acetate. was added dropwise from the dropping funnel to the flask over 1 hour, and stirring was continued at 80° C. for 5 hours. Thereby, the alkali-soluble resin solution A-1 whose solid content acid value is 103 mgKOH/g was obtained. The polystyrene equivalent weight average molecular weight measured by GPC was 12,800, and the molecular weight distribution (Mw/Mn) was 2.4. In this case, the GPC measurement conditions were as follows.

<GPC measurement conditions>

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

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 wt% (solvent = tetrahydrofuran)

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

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

Example and comparative example : Preparation of red photosensitive resin composition

Example One.

5.11 parts by weight of the compound represented by Formula 1 as a pigment, 0.14 parts by weight of C.I. Pigment Red 177, BYK2001 as a dispersing agent (Dispervic: manufactured by BYK, solid content concentration 45.1% by weight) 3.42 parts by weight, propylene glycol methyl 77.6 parts by weight of ether acetate, 8.49 parts by weight of alkali-soluble resin solution A-1 of Synthesis Example 1 (solid content concentration of 35.1% by weight), 0.74 parts by weight of IRGACURE OXE01 (Ciba Specialty Chemicals; photopolymerization initiator) 0.74 parts by weight, p-methoxyphenol (Polymerization inhibitor) 0.001 parts by weight, 3.13 parts by weight of the photopolymerizable compound represented by the following formula 15, and 1.34 parts by weight of A-TMMT (Shin-Nakamura Chemicals, polymerizable compound) were mixed to prepare a red photosensitive resin composition, At this time, the mass average number of polymerization groups and the number of alkyleneoxy groups having 2 or more carbon atoms of each or all of the photopolymerizable compounds used at this time were calculated from Equation 1 or Equation 2 described in the specification of the present invention and are shown in Table 1 below.

[Formula 15]

(In Formula 15, n is 2, and the sum of n is 12.)

Example 2 to 7.

A red photosensitive resin composition was prepared in the same configuration and content as in Example 1, except that the type and content of the photopolymerizable compound were changed as described in Table 1 below.

Example 8.

4.09 parts by weight of the compound represented by Formula 1 as a pigment, 1.02 parts by weight of C.I. Pigment Red 242, 0.14 parts by weight of C.I. Pigment Red 177, and BYK2001 (Dispervic: manufactured by BYK) as a dispersant, solid content concentration of 45.1 weight %) 3.42 parts by weight, 77.6 parts by weight of propylene glycol methyl ether acetate, 8.49 parts by weight of alkali-soluble resin solution A-1 of Synthesis Example 1 (solid content concentration 35.1% by weight) 8.49 parts by weight, IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals; photopolymerization initiator) 0.74 parts by weight, 0.001 parts by weight of p-methoxyphenol (polymerization inhibitor), 3.13 parts by weight of the compound represented by the above formula 15, and 1.34 parts by weight of A-TMMT (manufactured by Shin-Nakamura Chemicals, polymerizable compound) are mixed, red A photosensitive resin composition was prepared.

comparative example One.

C.I. Pigment Red 254 4.52 parts by weight, C.I. Pigment Red 177 0.73 parts by weight, BYK2001 as a dispersant (Dispervic: manufactured by BYK, solid content concentration 45.1 wt%) 3.42 parts by weight, propylene glycol methyl ether acetate 77.6 weight part, 8.49 parts by weight of alkali-soluble resin solution A-1 of Synthesis Example 1 (solid content concentration of 35.1% by weight), IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals; photopolymerization initiator) 0.74 parts by weight, p-methoxyphenol (polymerization inhibitor) ) 0.001 parts by weight, 3.13 parts by weight of the compound represented by Formula 15, and 1.34 parts by weight of A-TMMT (manufactured by Shin-Nakamura Chemicals, polymerizable compound) were mixed to prepare a red photosensitive resin composition.

comparative example 2.

A red photosensitive resin composition was prepared in the same configuration and content as in Comparative Example 1, except that the type and content of the photopolymerizable compound were changed as described in Table 1 below.

comparative example 3 to 6.

As a pigment, 5.11 parts by weight of the compound represented by Formula 1 (manufactured by BASF) and 0.14 parts by weight of C.I. Pigment Red 177 were used, and the type and content of the photopolymerizable compound were changed as described in Table 1 below, except that the above Comparative Example A red photosensitive resin composition was prepared with the same composition and content as in 1.

photopolymerizable compound (mass average)
number of polymerization groups (mass average)
carbon number 2 or more
alkyleneoxy group type polymeric group carbon number 2 or more
number of alkyleneoxy groups sheep
(parts by mass) Example 1 5.4 8.4 A-TMMP 4 0 1.40 Formula 15 6 12 3.26 Example 2 4.6 3.6 A-TMMP 4 0 3.26 Formula 15 6 12 1.40 Example 3 6.0 8.4 DPHA 6 0 1.40 Formula 15 6 12 3.26 Example 4 6.0 3.6 DPHA 6 0 3.26 Formula 15 6 12 1.40 Example 5 5.0 2.0 DPHA 6 0 2.33 ATM-4E 4 4 2.33 Example 6 4.6 2.8 DPHA 6 0 1.40 ATM-4E 4 4 3.26 Example 7 5.0 8.0 Formula 15 6 12 2.33 ATM-4E 4 4 2.33 Example 8 5.0 8.0 Formula 15 6 12 2.33 ATM-4E 4 4 2.33 Comparative Example 1 5.4 8.4 A-TMMP 4 0 1.40 Formula 15 6 12 3.26 Comparative Example 2 5.4 8.4 A-TMMP 4 0 1.40 Formula 15 6 12 3.26 Comparative Example 3 5.8 10.8 A-TMMP 4 0 0.47 Formula 15 6 12 4.19 Comparative Example 4 4.2 1.2 A-TMMP 4 0 4.19 Formula 15 6 12 0.47 Comparative Example 5 6.0 1.2 DPHA 6 0 4.19 Formula 15 6 12 0.47 Comparative Example 6 5.6 0.8 DPHA 6 0 3.73 ATM-4E 4 4 0.93 DPHA: dipentaerythritol hexaacrylate
A-TMMP: A-TMMP made by Shin-Nakamura Chemicals
ATM-4E: ATM-4E made by Shin-Nakamura Chemicals

production example : Manufacture of color filters

A glass substrate of 2 square inches (manufactured by Corning, #1737) was sequentially washed with a neutral detergent, water and alcohol, and then dried. On this glass substrate, each of the red photosensitive resin compositions prepared in Examples and Comparative Examples was exposed at an exposure dose (365 nm) of 50 mJ/cm 2 and the post-baking film thickness was 2.5 μm when the development process was omitted. Spin coating was carried out as much as possible, followed by preliminary drying in a clean oven at 100° C. for 3 minutes. After that, it is cooled to room temperature, and the substrate to which the red photosensitive resin composition is applied and a quartz glass photomask (a pattern that changes the transmittance in a stepwise manner in the range of 1 to 100% and a line/space pattern from 1 μm to 50 μm) ), and was irradiated with light at an exposure dose (365 nm) of 50 mJ/cm 2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd.

The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 2 minutes. The thin film-coated substrate was washed with distilled water, dried by blowing nitrogen gas, and dried at 220° C. for 30 minutes to prepare a color filter.

Experimental example One. color coordinates Measure

The color coordinates of the color filter prepared in Preparation Example were measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 4 below.

Experimental example 2. Luminance measurement

The luminance of the color filter prepared in Preparation Example was measured using a microscopic spectrometer OSP-SP2000, and the standard (Comparative Example 1) was set and the luminance change amount was calculated in %, and the results are shown in Table 4 below. .

Experimental example 3. Phenomenon residue evaluation

After irradiating a 2 square inch black matrix patterned substrate with 500mJ UV, the black matrix patterned substrate The red photosensitive resin composition prepared in Examples and Comparative Examples was exposed to an exposure dose (365 nm) of 50 mJ/cm 2 on the upper surface, and the film thickness after firing after omitting the development process was 2.5 μm. Then, it was pre-dried in a clean oven at 100 degreeC for 3 minutes. After cooling, it was left in an aqueous developer solution containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide for 2 minutes, washed with distilled water, and the level of residue was checked using an ECLIPSE LV100POL Model (manufactured by Nikon Corporation) optical microscope. The standards are shown in Table 3 below, and the results are shown in Table 4 below.

<Development Residue Evaluation Criteria> ○ ×

Experimental example 4. line tear evaluation

After irradiating a 2 square inch black matrix patterned substrate with 500mJ UV, the black matrix patterned substrate Except for applying and exposing the red photosensitive resin composition prepared in Examples and Comparative Examples on the color filter prepared in the same configuration and method as in Preparation Example, ECLIPSE LV100POL Model (manufactured by Nikon Corporation) using an optical microscope Thus, straightness was confirmed in the reflection mode. Line tearing evaluation criteria are shown in Table 3 below, and the results are shown in Table 4 below.

<Line tear evaluation criteria> ○ ×

(color coordinates Rx=0.650, Ry=0.335) division luminance development residue line tear Example 1 21.7 104.8% ○ ○ Example 2 21.6 104.3% ○ ○ Example 3 21.6 104.3% ○ ○ Example 4 21.8 105.3% ○ ○ Example 5 21.5 103.9% ○ ○ Example 6 21.7 104.8% ○ ○ Example 7 21.6 104.3% ○ ○ Example 8 21.3 102.9% ○ ○ Comparative Example 1 20.7 100% (std) ○ ○ Comparative Example 2 18.6 89.9% ○ ○ Comparative Example 3 21.5 103.9% ○ × Comparative Example 4 21.3 102.9% × × Comparative Example 5 21.3 102.9% ○ × Comparative Example 6 21.3 102.9% ○ ×

Referring to Table 4, when the colorant containing the compound represented by Formula 1 of the present invention is included (Examples 1 to 8), and when the compound represented by Formula 1 is not included (Comparative Examples 1 to 2) It was confirmed that the luminance was further improved, and in the case of using a photopolymerizable compound satisfying the conditions presented in the present invention together with the colorant (Examples 1 to 8), photopolymerization that does not satisfy the conditions presented in the present invention It was confirmed that the development residue or line tearing phenomenon was improved compared to the case of using the compound (Comparative Examples 3 to 6).

Claims (10)

coloring agent; and two or more types of photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms;
The total number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more on a mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 to 10.5 on a mass average,
The colorant is a red photosensitive resin composition comprising a compound represented by the following Chemical Formula 1; and at least one selected from the group consisting of CI Pigment Red 177 and 242:
[Formula 1]

According to claim 1,
The photopolymerizable compound includes a polymerizable group, the red photosensitive resin composition, characterized in that it further comprises a photopolymerizable compound that does not contain an alkyleneoxy group having 2 or more carbon atoms. The method of claim 1,
The photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms is a red photosensitive resin composition comprising at least one selected from the group consisting of a compound represented by Formula 2 and a compound represented by Formula 3 below:
[Formula 2]

(In Formula 2,
Each E independently represents -((CH ₂ )yCH ₂ O)-, or -((CH ₂ )yCH(CH ₃ )O)-, and y each independently represents an integer from 1 to 10,
X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group,
The sum of the acryloyl group and the methacryloyl group is 3 or 4,
m is each independently an integer from 0 to 10, and the sum of each m is an integer from 1 to 40.)
[Formula 3]

(In Formula 3,
Each E independently represents -((CH ₂ )yCH ₂ O)-, or -((CH ₂ )yCH(CH ₃ )O)-, and y each independently represents an integer from 1 to 10,
X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group,
The sum of the acryloyl group and the methacryloyl group is 5 or 6,
each n is independently an integer from 0 to 10, and the sum of each n is an integer from 1 to 60). The method of claim 1,
The compound represented by Formula 1 is a red photosensitive resin composition, characterized in that it is included in an amount of 0.05 to 30% by weight based on 100% by weight of the total red photosensitive resin including the compound. The method of claim 1,
The red photosensitive resin composition, characterized in that the colorant is contained in an amount of 5 to 70% by weight based on 100% by weight of the total solid content of the red photosensitive resin composition including the same. According to claim 1,
The two or more types of photopolymerizable compounds are red photosensitive resin composition, characterized in that it is contained in an amount of 5 to 50% by weight based on 100% by weight of the total solid content of the red photosensitive resin composition comprising the same. 3. The method of claim 2,
The weight ratio of the content (A) of the photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms to the content (B) of the photopolymerizable compound having the polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms is 9:1 to 1: The red photosensitive resin composition, characterized in that 9. The method of claim 1,
The red photosensitive resin composition is a red photosensitive resin composition, characterized in that it further comprises at least one selected from the group consisting of alkali-soluble resins, photoinitiators, solvents and additives. A color filter comprising a cured product of the red photosensitive resin composition according to any one of claims 1 to 8. An image display device comprising the color filter of claim 9 .