KR20190093295A - A Red PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE COMPRISING THE SAME - Google Patents

Abstract

The present invention relates to a colorant; and two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having two or more carbon atoms, wherein the number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more by mass average, and the number of alkyleneoxy groups having the two or more carbon atoms is 2.0 to 10.5 by mass average. In addition, the colorant comprises: a compound represented by chemical formula 1; and at least one selected from the group consisting of pigments and dyes other than the compound represented by the chemical formula 1, thereby having excellent luminance, that is, excellent color reproducibility due to high permeability, improving development residues when manufacturing the color filter, and having a good pattern.

Description

Red photosensitive resin composition, a color filter and an image display device including the same {A Red PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE COMPRISING THE SAME}

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

A color filter is a member used for a solid-state image sensor and 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, the image display apparatus tends to be thin, and the color filters included in the image display apparatus also tend to become thin, and accordingly, the size of the colored pattern becomes smaller. In particular, such a tendency is observed in color filters for solid-state image pickup devices. It stands out.

As the colored pattern becomes smaller, inaccuracies in the end portion of the colored pattern and developing residues of the unexposed portion are more problematic than before.

In addition, in order to obtain spectral sensitivity equivalent to that of a conventional color filter, the thinned color filter increases the composition ratio of the colorant in the colored photosensitive resin composition, wherein components other than the colorant (components contributing to photolithographic performance) are relatively high. Will decrease.

Therefore, there is a need for the development of a colored photosensitive resin composition capable of maintaining photolithographic performance of a conventional degree even when the component contributing to photolithography performance is relatively reduced.

In addition, when trying to obtain spectral sensitivity by increasing the composition ratio of the colorant, the composition ratio of the colorant dispersion is increased. Thus, if the composition ratio of the colorant dispersion is increased, the thixotropy of the colored photosensitive resin composition itself containing the colorant dispersion is increased. ) Increases, the film thickness uniformity in the surface of the support tends to decrease when the colored curable composition is applied onto the support to form a colored layer. When the uniformity of the colored layer film thickness is lowered, there is a problem that variations in focal length occur during exposure, inaccurate fine pattern periphery, or development residue in the non-hardened portion.

In order to solve the above problems, Korean Patent Laid-Open Publication No. 10-2009-0073035 contains two or more polymerizable compounds containing a colorant and 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 by mass average, and the number of alkyleneoxy groups of 2 or more carbon atoms is 2.0 or more and 10.0 or less by mass average, thereby having a DOF margin (deep depth of focus) and developing residue. Although described with respect to the colored curable composition that can reduce the occurrence of this, it does not properly solve the problem of development residue generation, there is a problem that the color reproducibility 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, it is possible to implement a high transmissive, that is, the brightness, that is, the color reproducibility is excellent, the development residue is improved, the pattern formation is good red photosensitive resin composition, color filter and image display including the same It is an object to provide a device.

Red photosensitive resin composition of the present invention for achieving the above object is a coloring agent; And two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, wherein the number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more in terms of mass, and alkylene jade having 2 or more carbon atoms. The number of periods is 2.0 to 10.5 by mass average, and the coloring agent includes at least one compound selected from the group consisting of a compound represented by the following Chemical Formula 1 and a pigment and dye other than the compound represented by Chemical Formula 1; do.

[Formula 1]

Moreover, the color filter which concerns on this invention is characterized by including the hardened | cured material of the red photosensitive resin composition mentioned above.

In addition, the image display apparatus according to the present invention is characterized by including the above-described color filter.

 The red photosensitive resin composition of the present invention is capable of implementing high transmittance, that is, has excellent brightness, that is, color reproducibility, development residue in color filter manufacture, and good pattern formation.

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

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

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part is said to "include" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

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

In the present invention, the number of alkyleneoxy groups having 2 or more carbon atoms in the mass average of two or more photopolymerizable compounds is included in the number of 'C2 or more alkyleneoxy groups' each of the photopolymerizable compounds and the red photosensitive resin composition. The mass mean value calculated based on the mass of each photopolymerizable compound is indicated.

For example, the red photosensitive resin composition of this invention is a photopolymerizable compound 1, the photopolymerizable compound 2,. In the case of containing n kinds of photopolymerizable compounds composed of the photopolymerizable compound n, the number of polymerizable groups (J _AVE ) in the mass average of the n kinds of photopolymerizable compounds is calculated by the following equation.

[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 photopolymerizable compound 2 in the red photosensitive resin composition, Jn is the number of polymerizable groups in one molecule of photopolymerizable compound n, and Wn is the total mass of photopolymerizable compound n in the red photosensitive resin composition.

Similarly, the red photosensitive resin composition of this invention is a photopolymerizable compound 1, the photopolymerizable compound 2,... In the case of containing n kinds of photopolymerizable compounds composed of the photopolymerizable compound n, the number of alkyleneoxy groups having 2 or more carbon atoms (A _AVE ) in the mass mean of the n kinds of photopolymerizable compounds is calculated by the following equation (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 1 molecule of the photopolymerizable compound 1, W1 is the total mass of the photopolymerizable compound 1 in the red photosensitive resin composition, A2 is the photopolymerizable compound 2 W2 is the total mass of photopolymerizable compound 2 in the red photosensitive resin composition, An is the number of polymerizable groups in one molecule of photopolymerizable compound n, and Wn is a red photosensitive resin in one molecule. The total mass of 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 which concerns on one aspect of this invention is a coloring agent; And two or more photopolymerizable compounds containing a photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms, wherein the number of polymerizable groups of the two or more photopolymerizable compounds is 4.5 or more in terms of mass, and alkylene jade having 2 or more carbon atoms. The number of phases is 2.0 to 10.5 by mass average, and the colorant comprises at least one compound selected from the group consisting of a compound represented by the following Chemical Formula 1 and a pigment and dye other than the compound represented by Chemical Formula 1; As a result, the luminance, that is, the color reproducibility is excellent, the development residues can be suppressed during the production of the color filter, and the pattern formation is advantageous.

[Formula 1]

In the present invention, 'good pattern formation' means that the pattern smoothness is excellent at the time of pattern formation.

coloring agent

The red photosensitive resin composition according to one embodiment of the present invention includes a colorant, and the colorant comprises a compound represented by the formula (1) to enable high permeability, thereby improving luminance, ie, color reproducibility, and the like. High color reproduction is possible.

According to an embodiment of the present invention, the compound represented by Formula 1 may be included in 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 comprising the same have. When the content of the colorant is less than the above range, the color separation ability of the formed pattern may be lowered. When the content of the colorant exceeds the above range, lithography performance may be lowered, resulting in residue or undeveloped problems.

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

Pigment

The pigment may include an organic pigment or an inorganic pigment, and these may be used alone or in combination of two or more thereof. Among these, using an organic pigment may be more preferable at the point which is excellent in heat resistance and color development. In addition, the organic pigment may be a synthetic or natural pigment.

The organic pigment may be optionally treated with rosin; Surface treatment using a pigment derivative having an acidic group or a basic group introduced therein; Graft treatment on the surface of the pigment using a polymer compound or the like; Fine granulation treatment by sulfuric acid fine granulation 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 (constitution pigments), and the metal compounds are more specifically 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 include a compound classified as a pigment in the Color Index (The Society of Dyers and Colourists), more specifically, the following color index (CI) number Examples of the pigments include, but are not limited to, and one or more selected from them may be co-dispersed using a binder resin, a dispersant, or the like to suit desired chromaticity.

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;

C.I. Specific examples of pigment oranges 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, 254, 255, 264 and 265. However, the present invention is not limited thereto, and these may be used alone or in combination of two or more thereof.

Preferably, 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 be used.

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

Dispersant

The dispersant is added to maintain the stability and deagglomeration of the insoluble colorant can be used without limitation to those commonly used in the art. Specifically, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and the like can be used, but preferably BMA (butyl methacrylate) or DMAEMA (N, N-dimethylamino An acrylate dispersant (hereinafter sometimes referred to as an acrylic dispersant) containing ethyl methacrylate can be used. In this case, it may be desirable to apply the acrylic dispersant prepared by the living control method as shown in Korean Patent Laid-Open Publication No. 2004-0014311, and as a commercial product of the acrylate-based dispersant manufactured by the living control method BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like, but are not limited to these may be used alone or in combination of two or more.

The dispersant may use a pigment dispersant of another resin type in addition to the acrylic dispersant described above. The other resin type pigment dispersants include (partially) known pigment dispersants of known resin types, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. 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 ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, phosphate esters, and the like. As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (Big) Chemi Corporation: 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 name: 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: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Trade name of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORON DOPA-33, FLORON DOPA-44, etc., but are not limited thereto, and each of these is independently or It can be used in combination of 2 or more type, It can also be used in combination 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. If the content of the dispersant exceeds the above range, the viscosity may be increased to cause a process problem. If the dispersant is less than the above range, the atomization of the pigment may be difficult or a problem such as gelation after dispersion may occur.

dyes

The dye may be used without limitation so long as it has solubility in organic solvents or can be dispersed therein. Preferably, it is preferable to use a dye having solubility in an organic solvent and ensuring reliability such as solubility in an alkaline developer, heat resistance and solvent resistance. In the case of the dye which does not have solubility in an organic solvent, it can also disperse and use it.

As the dye, at least one selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes and the like and derivatives thereof can be used. In addition, it can also be selected from azo-based, xanthene-based and phthalocyanine-based acid dyes and derivatives thereof.

Preferred dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (color dyeing yarn).

Specific examples of the dye,

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 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 59; Etc. can be mentioned.

In addition, 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 and 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 and the like;

See 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 and 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 and the like;

In addition, 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 Red dyes such as, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;

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, etc. ;

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 and 58; Although these etc. are mentioned, It is not limited to these, These can be used individually or in mixture of 2 or more types, respectively.

According to an embodiment of the present invention, the compound of Formula 1; and at least one substance 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 Chemical Formula 1 and at least one material selected from the group consisting of pigments and dyes satisfies the above range, high colorability and high brightness may be obtained, and process margins may be improved. There is an advantage that the sensitivity can be excellent.

According to one embodiment of the present invention, the aforementioned colorant may be included in an amount of 5 to 70 wt%, preferably 10 to 50 wt%, based on 100 wt% of the total solids in the red photosensitive resin composition including the same. When the content of the colorant is less than the above range, the color separation ability of the formed pattern may be lowered. When the content of the colorant exceeds the above range, lithography performance may be lowered, resulting in residue or undeveloped problems.

Solid content in a red photosensitive resin composition in this invention means the total content of the remaining component except all the solvent contained in a red photosensitive resin composition.

Photopolymerizable  compound

The red photosensitive resin composition according to one embodiment of the present invention comprises two or more photopolymerizable compounds, the photopolymerizable compound comprises at least one or more photopolymerizable compounds having an alkyleneoxy group having 2 or more carbon atoms, The number of polymerizable groups of the photopolymerizable compound is 4.5 or more by mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 to 10.5 by mass average, so that there is an advantage of preventing development residues or pre-breaking. have.

When the 2 or more types of photopolymerizable compounds contain at least 1 type or more of photopolymerizable compounds which have a C2 or more alkylene oxy group, and the number of polymeric groups and the C2 or more alkyleneoxy group of all the photopolymerizable compounds satisfy | fill the above-mentioned range, It can be used without any particular limitation on the kind.

Carbon number  2 or more Alkyleneoxy group  Having Photopolymerizable  compound

The red photosensitive resin composition according to one embodiment of the present invention includes at least one or more photopolymerizable compounds having an alkyleneoxy group having 2 or more carbon atoms, so that developability is improved, thereby improving development residues, line breaks, and the like. .

The kind 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 Formula 2 and a compound represented by the Formula 3 It may be.

[Formula 2]

(In Formula 2,

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

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

The sum of acryloyl group and methacryloyl group is three or four,

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

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

[Formula 3]

(In Chemical Formula 3,

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

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

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

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

Preferably, in Formula 3, n may be each independently an integer of 0 to 6, more preferably may be an integer of 0 to 4. In addition, the sum of m may preferably be an integer of 3 to 60, more preferably an integer of 3 to 24, 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 is bonded to X at the end of the oxygen atom It may be desirable to be in the form.

The compound represented by the formula (2) or (3) is a step of linking the ring-opening skeleton by 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 synthesize | combine from the process of reacting (meth) acryloyl chloride and introducing a (meth) acryloyl group. Each process is a process well known in the art, the skilled person can easily synthesize the compound represented by the formula (2) or formula (3).

The compound represented by Chemical Formula 2 or Chemical Formula 3 may be more preferably a pentaerythritol derivative and / or dipentaerythritol derivative, and specifically, the compounds represented by the following Chemical Formulas 4 to 9 may be exemplified. The compound represented by 4, Formula 5, Formula 8 or Formula 9 can 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 sum of m is 4.)

[Formula 9]

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

As a commercial item of the compound represented by the said General formula (2) or (3), For example, A-DPH-12E, A-DPH-6P, ATM-4E, SR-494 by Satomer company, Nippon Kayaku Co., Ltd. make DPCA-60, TPA-330, and the like, but is not limited thereto.

Polymerizable groups  Have, Carbon number  2 or more Alkyleneoxy group  Not having Photopolymerizable  compound

The red photosensitive resin composition which concerns on one Embodiment of this invention may further contain the photopolymerizable compound which has a polymeric group and does not have a C2 or more alkyleneoxy group. As described above, in the case of further comprising a photopolymerizable compound having a polymerizable group and not having an alkyleneoxy group having 2 or more carbon atoms, there is an advantage of suppressing the phenomenon of increasing the solubility of the cured portion in the developer and a decrease in line width sensitivity. have.

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

Although the kind of the photopolymerizable compound which has the said polymeric group and does not have a C2 or more alkyleneoxy group is not specifically limited in this invention, For example, monofunctional acrylate and methacrylate (for example, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), trimetholethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, These can be used individually or in mixture of 2 or more types, respectively.

In addition, the photopolymerizable compound having the polymerizable group and no 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 formula (10) or a compound represented by the formula (11).

[Formula 10]

(In Chemical Formula 10,

Each Z is independently acryloyl group, methacroyl group, hydrogen atom or carboxyl group).

When the acryloyl group and the methacroyl group are included in Formula 10, the sum thereof is preferably three or four.

[Formula 11]

(In Chemical Formula 11,

Each Z is independently acryloyl group, methacroyl group, hydrogen atom or carboxyl group).

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

According to one embodiment of the 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 solids in the red photosensitive resin composition comprising the same. It may be 10 to 40% by weight, more preferably 20 to 30% by weight. As such, when the content of the photopolymerizable compound is included in the above range, there is an advantage of preventing development residues and defects in the pattern.

According to one 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 having no alkyleneoxy group having 2 or more carbon atoms The weight ratio of (A: B) may be 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 at the mass mean of the photopolymerizable compound or to control the number of 'alkyleneoxy groups having 2 or more carbon atoms' at the mass mean, thereby preventing development residues and pattern defects from occurring. There is an advantage that can be prevented more effectively.

According to one embodiment of the present invention, the red photosensitive resin composition of the present invention may further include one or more selected from the group consisting of alkali-soluble resins, photopolymerization initiators, 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 function as a dispersion medium of a pigment which may sometimes 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 the carboxyl group, it may be preferable to use a copolymer obtained from the monomer having the 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 a molecule such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, and specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, Itaconic acid, maleic acid, and fumaric acid are mentioned, but it is not limited to these, These can respectively be used individually or in combination of 2 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) acrylates; Vinyl carboxylates such as vinyl acetate and vinyl propionate; Although vinyl cyanide compounds, such as (meth) acrylonitrile and the (alpha)-chloro acrylonitrile, are mentioned, It is not limited to these, These can respectively be used individually or in combination of 2 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 / methacrylate Acid / styrene copolymers, and the like, but are 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 the monomer having the carboxyl group and another monomer copolymerizable therewith, the carboxyl monomer in the copolymer is included in an amount of 10 to 50% by weight, based on 100% by weight of the total copolymer. Preferably it may be included in 15 to 40% by weight.

The alkali-soluble resin may have a weight average molecular weight of 3,000 to 100,000 measured by gel permeation chromatography converted into polystyrene, and preferably 5,000 to 50,000. 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 at the time of development, and there is an advantage that the omission of non-pixel portions can be improved.

The molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) with respect to the number average molecular weight may be 1.5 to 6.0, preferably 1.8 to 4.0, in this case development There is an advantage to improve the sex.

The acid value of the alkali-soluble resin may be 30 to 170 mgKOH / g based on solids, preferably 50 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than the above range, it is difficult to secure a sufficient developing speed of the red photosensitive resin composition including the above. When the acid value exceeds the above range, adhesion to the substrate is reduced to cause a short circuit of the pattern. It is easy, and there exists a problem that the compatibility with a coloring agent may arise, and the coloring agent in a red photosensitive resin composition may precipitate, or the storage stability of a red photosensitive resin composition may fall and a viscosity may rise.

The alkali-soluble resin may be included in 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 comprising the same. When the content of the alkali-soluble resin satisfies the above range, the solubility in the developing solution is sufficient to suppress the development of developing residue on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion at the time of development is prevented. There is an advantage that the omission of the non-pixel portion can be good.

Photopolymerization Initiator

The photopolymerization initiator may be used without particular limitation as long as it can generate radicals capable of initiating the polymerization of the photopolymerizable compound by exposure of light such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, and X-ray. For example, an oxime type compound, an acetophenone type compound, a benzoin type compound, a benzophenone type compound, a biimidazole type compound, a triazine type compound, a thioxanthone type compound, an anthracene type compound, etc. can be mentioned, It is limited to this. In this case, one or more kinds thereof can be selected and used. Among them, it may be more preferable to use an oxime-based compound in consideration of polymerization characteristics, initiation efficiency and absorption wavelength.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and (Z) -2-((benzoyloxy) imino) -1- (4- (Phenylthio) phenyl) octan-1-one (see formula 12), (E) -1-(((1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- (L) ethylidine) amino) oxy) ethanone (see formula 13) 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 (see formula 14 below) and the like, and commercially available products Examples include BASF's OXE-01, OXE-02, but are not limited thereto.

 [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 performing its function, but it 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 in the above range, there is an advantage that can further improve the brightness and sensitivity.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 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 benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like, but are not limited thereto.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like, but are not limited thereto.

As said biimidazole type compound compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 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) And imidazole compounds in which the phenyl group at the -4,4'5,5'-tetraphenyl-1,2'-biimidazole or 4,4 ', 5,5' position is substituted with a carboalkoxy group. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-are more preferable. 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.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 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 is not limited thereto.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. It may include, 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. It may include, but is not limited thereto.

Other specific examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, and phenylclioxyl Acid methyl, a titanocene compound, etc. are mentioned, but it is not limited to this.

The photoinitiator mentioned above can be used individually or in mixture of 2 or more types, respectively.

The content of the photopolymerization initiator 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 solids of the alkali-soluble resin and the photopolymerizable compound. have. When the content of the photopolymerization initiator is included in the above-described range, the red photosensitive resin composition including the same may be highly sensitive to shorten the exposure time, thereby improving productivity, and maintaining the high resolution, and further, the red color of the present invention. There exists an advantage that the intensity | strength of the pixel part formed using the photosensitive resin composition and the smoothness in the surface of the said pixel part can become favorable.

The photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the red photosensitive resin composition of the present invention. The red photosensitive resin composition according to the present invention further contains a photopolymerization initiation adjuvant, whereby the sensitivity is further increased, which has the advantage of further improving productivity.

The photopolymerization start adjuvant may be, for example, one or more compounds 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, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, 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's ketone ), 4,4'-bis (diethylamino) benzophenone and the like can be used, but is not limited thereto.

The carboxylic acid compound is preferably an 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, naphthoxyacetic acid, and the like, but are not limited thereto.

Specific examples of the organic sulfur compound having the 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-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. It may be, but is not limited thereto.

solvent

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

Specific examples of 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, but is not limited thereto.

Specifically, the acetate solvents include 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.

Specific examples of the aromatic hydrocarbon solvent include, but are not limited to, benzene, toluene, xylene, mesitylene, and the like.

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

Specific examples of the alcohol solvent include, but are not limited to, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.

Specific examples of the ester solvents include cyclic esters such as γ-butyrolactone; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and the like, but are not limited thereto.

Specifically, the amide solvents include, but are not limited to, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

The solvent mentioned above can be used individually or in mixture of 2 or more types, respectively.

The solvent may be preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of coatability and dryness, specifically alkylene glycol alkyl ether acetates; Ketones; Ester, such as ethyl 3-ethoxy propionate and methyl 3-methoxy propionate; These are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionic acid Although ethyl, 3-methoxy propionate, etc. are mentioned, It is not limited to these, These can be used individually or in mixture of 2 or more types, respectively.

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

additive

In addition to the above components, the red photosensitive resin composition of the present invention may add additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anti-agglomerating agents as required by those skilled in the art without departing from the object of the present invention. It may further include.

Specific examples of the 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 ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. It may include, but is not limited thereto.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds, and the like, but are not limited thereto.

Specific examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene A) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane, and the like. It doesn't happen.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with this. Specifically, the curing auxiliary compound may be a polyhydric carboxylic acid, a polyhydric carboxylic anhydride, an acid generator, or the like. As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.).

The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and specific examples of the surfactant may include fluorine-based surfactants or silicone-based surfactants.

Examples of the fluorine-based surfactant include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals Co., Ltd. as commercially available products.

The silicone surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460, TSF-4452, and the like.

Surfactant illustrated above can be used individually or in mixture of 2 or more types, respectively.

Specific examples of the adhesion promoter include vinyl trimethoxysilane, 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) ethyltrimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyl One or more types selected from trimethoxysilane, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane can 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 of 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-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop Foxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 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, pentaerythritol tetrakis (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 of the aggregation inhibitor include, but are not limited to, sodium polyacrylate.

The manufacturing method of the above-mentioned red photosensitive resin composition can be used without limitation in the method used in the art, for example as follows.

First, the pigment in the colorant is mixed with a solvent or a dispersant and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 µm or less. Under the present circumstances, a pigment dispersant, a part or all of alkali-soluble resin, or dye can be mixed with a solvent, and can be melt | dissolved or disperse | distributed as needed.

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

In addition, the present invention includes a coloring pattern made of the red photosensitive resin composition. The colored pattern may be prepared by applying 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, in the following manner.

First, the said red photosensitive resin composition is apply | coated on the board | substrate or the layer which consists of solid content of the photosensitive resin composition formed previously, and prebaking from the apply | coated photosensitive resin composition layer removes volatile components, such as a solvent, and obtains a smooth coating film.

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

After the application, a red photosensitive resin composition layer is formed by heating after prebaking (heat drying) or drying under reduced pressure to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC.

The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. Under the present circumstances, it is preferable to use apparatuses, such as a mask aligner and a stepper, in order to irradiate the parallel light uniformly to the whole exposure part and to perform the exact alignment of a mask and a board | substrate.

In addition, the desired pattern shape can be obtained by contacting an alkali developing solution with the coating film after hardening after that, dissolving and developing a non-exposed part. As the developing method, a liquid addition method, a dipping method, a spray method, or the like can be carried out, and the substrate can 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, dihydrogen phosphate, sodium dihydrogen phosphate, diammonium phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, carbonate 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. 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, anionic surfactant, or cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, 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 surfactants 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; Alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Etc. can be mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride; Quaternary ammonium salts; Etc. can be mentioned.

These surfactant 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, more preferably 0.1 to 5% by weight.

After the said image development, it washes with water and you may perform the post-baking for 10 to 60 minutes at 150-230 degreeC as needed.

<Color filter>

The color filter which concerns on another aspect of this invention contains the hardened | cured material of the red photosensitive resin composition mentioned above. The color filter includes a substrate and a coloring pattern made of the red photosensitive resin composition of the present invention on the substrate. The substrate may be a transparent material, and a material having sufficient strength and support for the stability of the color filter may be used. Preferably, glass having high chemical stability and high strength may be used.

As the manufacturing method of the color filter, a conventional method well known in the art may be used.

<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 apparatus may include other components that may be included in the image display apparatus, such as a light emitting device such as a light source, a light guide plate, a liquid crystal display including a color filter according to the present invention, and the like. This is not limiting.

The image display device includes a 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 mobile terminal such as a mobile phone, a display device for a digital camera, and a car. Display devices such as a navigation display device, but are not limited thereto.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. Naturally, such modifications and variations fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" indicating contents are by 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 condenser, a dropping lot, and a nitrogen inlet tube, and the temperature was raised to 80 ° C. The mixture containing 30.0 g was dissolved. 5.0 g 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) was added to 50 parts by weight of propylene glycol monomethyl ether acetate. The added solution was added dropwise to the flask over 1 hour from the dropping lot, and further stirring was continued at 80 ° C for 5 hours. This obtained the alkali-soluble resin solution A-1 whose solid acid value is 103 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 12,800, and the molecular weight distribution (Mw / Mn) was 2.4. At this time, the GPC measurement conditions were as follows.

<GPC measurement condition>

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

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

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

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

Example  And Comparative example : Preparation of Red Photosensitive Resin Composition

Example  One.

5.11 parts by weight of the compound represented by the formula (1) as a pigment, 0.14 parts by weight of CI Pigment Red, 3.42 parts by weight of BYK2001 (Dispervic: manufactured by BYK, BYD, 45.1% by weight) as a dispersant, propylene glycol methyl 77.6 weight part of ether acetate, 8.49 weight part of alkali-soluble resin solution A-1 (solid content concentration 35.1 weight%) of the said synthesis example 1, IRGACURE OXE01 (made by Chiba Specialty Chemicals; photoinitiator) 0.74 weight part, p-methoxyphenol (Polymerization Inhibitor) A red photosensitive resin composition was prepared by mixing 0.001 parts by weight, 3.13 parts by weight of a photopolymerizable compound represented by the following formula (15), and 1.34 parts by weight of A-TMMT (manufactured by Shin-Nakamura Chemicals Co., Ltd., polymerizable compound). In this case, the mass average number of polymerized polymers and the number of alkyleneoxy groups having 2 or more carbon atoms of each or all of the photopolymerizable compounds used are represented by Equation 1 or 2 described in the specification of the present invention. To calculated are shown in Table 1.

[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 according to the same constitution 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 the formula (1) as a pigment, 1.02 parts by weight of CI pigment red 242, 0.14 parts by weight of CI pigment red 177, BYK2001 (Dispervic: manufactured by BYK Co., Ltd., solid content concentration 45.1 weight) as a dispersant. %) 3.42 parts by weight, propylene glycol methyl ether acetate 77.6 parts by weight, 8.49 parts by weight of the alkali-soluble resin solution A-1 (solid content concentration 35.1% by weight) of Synthesis Example 1, IRGACURE OXE01 (manufactured by Chiba Specialty Chemicals Co., Ltd .; 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 the formula (15), 1.34 parts by weight of A-TMMT (manufactured by Shin-Nakamura Chemicals, polymerizable compound), red The photosensitive resin composition was prepared.

Comparative example  One.

4.52 parts by weight of CI Pigment Red 254, 0.73 parts by weight of CI Pigment Red, BYK2001 (Dispervic: manufactured by BYK Co., Ltd., solid content concentration 45.1% by weight) 3.42 parts by weight, propylene glycol methyl ether acetate 77.6 weight 8.49 weight part of alkali-soluble resin solution A-1 (solid content concentration 35.1 weight%) of the said synthesis example 1, 0.74 weight part of IRGACURE OXE01 (made by Chiba Specialty Chemicals; photoinitiator), 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 Co., Ltd.) were prepared to prepare a red photosensitive resin composition.

Comparative example  2.

A red photosensitive resin composition was prepared according to the same constitution and content as in Comparative Example 1 except that the kind and content of the photopolymerizable compound was changed as described in Table 1 below.

Comparative example  3 to 6.

5.11 parts by weight of a compound represented by Chemical Formula 1 (manufactured by BASF Corporation) and 0.14 parts by weight of CI Pigment Red 177 as a pigment, except that the kind and content of the photopolymerizable compound were changed as described in Table 1 below. A red photosensitive resin composition was prepared in the same composition and content as 1.

Photopolymerizable compound (Mass average)
Polymerization number (Mass average)
2 or more carbon atoms
Alkyleneoxy group number Kinds Polymerizable group 2 or more carbon atoms
Alkyleneoxy group number amount
(Mass part) 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 shinnakamura chemicals company
ATM-4E: ATM-4E made by Shin-Nakamura Chemicals

Production Example : Manufacturing of color filter

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, followed by drying. When the red photosensitive resin composition manufactured in the said Example and the comparative example was exposed on this glass substrate at the exposure amount (365 nm) of 50 mJ / cm <2>, the film thickness after baking after 2.5 micrometers was Spin coated as much as possible and then pre-dried for 3 minutes at 100 ° C. in a clean oven. Thereafter, the substrate was coated with the red photosensitive resin composition and a quartz glass photomask (a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm after cooling to room temperature. It was set to 100 micrometers, and it irradiated with the exposure amount (365 nm) of 50 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by the Ushio Denki Corporation.

The UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 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 manufactured in the 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 manufactured in the above production example was measured using a microscopic spectrometer OSP-SP2000, and the standard (Comparative Example 1) was determined to calculate the luminance change therefrom in% and the results are shown in Table 4 below. .

Experimental Example  3. Phenomenon Residue  evaluation

After 500mJ UV irradiation on a substrate having a 2 m square black matrix patterned substrate, the black matrix patterned substrate Spin-coating the red photosensitive resin composition prepared in the above Examples and Comparative Examples at an exposure amount (365 nm) of 50 mJ / cm 2 so that the film thickness after post-firing when the developing step was omitted was 2.5 μm, Subsequently, it was pre-dried at 100 degreeC for 3 minutes in the clean oven. After cooling, the mixture was left in an aqueous developer containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide for 2 minutes, and then washed with distilled water. The criteria are shown in Table 3 below, and the results are shown in Table 4 below.

<Current residue evaluation criteria> ○ ×

Experimental Example  4. Tearing  evaluation

After 500mJ UV irradiation on a substrate having a 2 m square black matrix patterned substrate, the black matrix patterned substrate An ECLIPSE LV100POL Model (manufactured by Nikon Co., Ltd.) optical microscope was used for the color filter manufactured by the same composition and method as the above Preparation Example, except that the red photosensitive resin composition prepared in Example and Comparative Example was coated and exposed on the substrate. To check the straightness in the reflection mode. Line tearing evaluation criteria are as shown in Table 3, and the results are shown in Table 4 below.

<Line tear evaluation criteria> ○ ×

(Color coordinates Rx = 0.650, Ry = 0.335) division Luminance Phenomenon residue Tearing 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 it contains a colorant containing a compound represented by the formula (1) of the present invention (Examples 1 to 8), does not contain a compound represented by the formula (1) (Comparative Examples 1 to 2) It was confirmed that the luminance was more improved, and in the case of using a photopolymerizable compound that satisfies the conditions set forth in the present invention together with the colorant (Examples 1 to 8), photopolymerizability not satisfying the conditions set forth in the present invention. When using the compound (Comparative Examples 3 to 6), it was confirmed that the development residue or line tearing phenomenon was improved.

Claims (10)

coloring agent; And two or more 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 by mass average, and the number of alkyleneoxy groups having 2 or more carbon atoms is 2.0 to 10.5 by mass average,
The colorant is a red photosensitive resin composition comprising: a compound represented by Formula 1; and at least one selected from the group consisting of pigments and dyes other than the compound represented by Formula 1;
[Formula 1]

The method of claim 1,
The photopolymerizable compound further comprises a photopolymerizable compound containing a polymerizable group and not containing an alkyleneoxy group having 2 or more carbon atoms. The method of claim 1,
Wherein the photopolymerizable compound having an alkyleneoxy group having 2 or more carbon atoms comprises at least one selected from the group consisting of a compound represented by Formula 2 and a compound represented by Formula 3:
[Formula 2]

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

(In Chemical Formula 3,
Each E independently represents-((CH ₂ ) yCH ₂ O)-or-((CH ₂ ) yCH (CH ₃ ) O)-, and each independently represents an integer of 1 to 10,
Each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group,
The sum of acryloyl group and methacryloyl group is 5 or 6 pieces,
n is each independently an integer of 0 to 10, and the sum of each n is an integer of 1 to 60). The method of claim 1,
Compound represented by Formula 1 is a red photosensitive resin composition, characterized in that contained in 0.05 to 30% by weight based on 100% by weight of the total red photosensitive resin containing the same. The method of claim 1,
The colorant is a red photosensitive resin composition, characterized in that 5 to 70% by weight based on 100% by weight of the total solid content of the red photosensitive resin composition comprising the same. The method of claim 1,
The red photosensitive resin composition, wherein the two or more photopolymerizable compounds are included in an amount of 5 to 50 wt% based on 100 wt% of the total solids in the red photosensitive resin composition including the same. 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 and 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: 1. It is 9, The red photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The red photosensitive resin composition further comprises one or more selected from the group consisting of alkali-soluble resins, photopolymerization initiators, solvents and additives. The hardened | cured material of the red photosensitive resin composition of any one of Claims 1-8 is contained, The color filter characterized by the above-mentioned. An image display apparatus comprising the color filter of claim 9.