KR20130110925A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

PURPOSE: A colorant photosensitive resin composition has a quick developing rate, excellent storage stability, sensitivity, and adhesion and has excellent productivity of a color filter by preventing the short circuit of pattern in a developing process. CONSTITUTION: A colorant photosensitive resin composition consists of a colorant (A), an alkali soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). The colorant includes one or more pigments, one or more dyes, and a pigment dispersant. The alkali soluble resin has an acid value of 30-150 mgKOH/g. The sum of the alkali soluble resin and the photopolymerizable compound is 30-180 mgKOH/g. The photopolymerization initiator includes a structure unit represented by chemical formula 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for color filters used when manufacturing a color filter for use in a color liquid crystal display device and the like and a color filter manufactured using the same.

Color filters are widely used in imaging devices, liquid crystal displays, and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. is uniformly apply | coated uniformly the coloring photosensitive resin composition containing the coloring agent corresponding to each color of red, green, and blue on the board | substrate with which the black matrix was patterned by spin coating. After that, the coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) is exposed and developed, and if necessary, heat-hardening (hereinafter sometimes referred to as postfiring) is repeated for each color. It is manufactured by forming a pixel of color.

 As the coloring agent in the colored photosensitive resin composition, a pigment dispersion system is generally used. For this purpose, a pigment dispersion method is used. As a pigment dispersion method, there exists a method of producing a color filter by the photolithographic method using the coloring radiation sensitive composition which disperse | distributed the pigment to various photosensitive compositions. Since this method uses a pigment, sufficient reliability can be ensured against light and heat, and it has been widely used as a preferable method for the production of color filters for large screens and high resolution color displays.

However, in recent years, the size of displays has been rapidly increasing and high contrast ratio has been continuously demanded. However, in the conventional pigment dispersion system, the pigment has reached the limit of atomization and color unevenness due to coarse particles is present. The method of using a pigment and a dye simultaneously is examined (Republic of Korea Patent Registration 10-0881860).

However, when a color filter is produced by using a colored photosensitive resin composition containing a dye as a coloring agent, the light resistance and heat resistance of the dye are poor, so that color shifts occur frequently, and the development speed is slow and sensitivity is low. There is a problem that the formed pattern is peeled off during the process.

Therefore, research has been conducted to solve this problem. For example, Korean Patent Application Publication No. 2011-0085005 discloses a good thermal stability ketooxime ester photoinitiator and its manufacture in order to improve the problem that the conventional OXE-1 ketooxime ester photoinitiator has poor application performance and low thermal stability. The method is disclosed.

In addition, Taiwan Patent Publication No. 2010-0088529 discloses that in order to improve the problem that the conventional acrylate monomer cannot meet the adhesion, resolution, developability, sensitivity to the substrate, the hydroxyl value is 70mgKOH / g or more 130mgKOH / The color filter and the photosensitive resin composition for black matrices which use the acrylate of the dipentaerythritol which are g or less are disclosed.

However, it is still necessary to solve the problem of the developing speed and sensitivity, and the problem of delamination of the pattern in the development process by the alkali developing solution.

KR 2011-0085005 A KR 2010-0088529 A

Therefore, an object of this invention is to provide the coloring photosensitive resin composition for color filters which can obtain the color filter excellent in contrast ratio.

In addition, the present invention aims to provide a colored photosensitive resin composition having a high development speed, excellent sensitivity and adhesion, no peeling of the pattern during the developing process, and excellent storage stability, so that there is no decrease in sensitivity or increase in viscosity even during long-term storage. It is done.

The present invention to achieve the above object

A coloring photosensitive resin composition composed of a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the coloring agent (A) is one or more pigments and one kind The above dye is an essential component, and the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g, and the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 30 to 180 mgKOH / g. And the photopolymerization initiator (D) provides a colored photosensitive resin composition, characterized in that the structure of formula (1).

(In Formula 1, R ₁ is represented by the following Formula 2, in Formula 2 R ₄ is C ₁ ~ C ₄ Alkyl, R ₅ is a structure of a ring of C ₃ ~ C ₈ , R ₂ in Formula 1 C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.)

The present invention also provides a color filter made of the colored photosensitive resin composition of the present invention.

The colored photosensitive resin composition of the present invention is excellent in storage stability and excellent in sensitivity and adhesion, so that short circuit of the pattern is hardly generated during the developing process, and thus, the color filter has excellent productivity. In addition, the color filter manufactured using the high contrast ratio.

Hereinafter, the role of each component of the present invention will be described in more detail.

This invention is the coloring photosensitive resin composition comprised from a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The said coloring agent (A) is one or more pigments And at least one dye as an essential component, wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g, and the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 30 to 180 mgKOH / g and the photopolymerization initiator (D) provides a colored photosensitive resin composition, characterized in that the structure of formula (1).

[Formula 1]

(In Formula 1, R ₁ is represented by the following Formula 2, in Formula 2 R ₄ is C ₁ ~ C ₄ Alkyl, R ₅ is a structure of a ring of C ₃ ~ C ₈ , R ₂ in Formula 1 C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.)

(2)

Hereinafter, each structure is demonstrated in detail.

The colorant (A)

The colorant (A) comprises at least one pigment (a1), at least one dye (a2) and a pigment dispersant (a3).

Pigments a1 )

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin Turned pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyrans Pyranthrone pigments, diketopyrrolopyrrole pigments and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide.

In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) number of Although a pigment is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185

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

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264

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

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

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

CI Pigment Black 1 and 7 etc

The pigment may be used an organic pigment or an inorganic pigment generally used in the art, these may be used alone or in combination of two or more.

Among the CI pigment pigments exemplified above, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15: 3, Pigment Blue 15: 6 , Pigments selected from the group consisting of CI pigment green 7, CI pigment green 36 and CI pigment green 58 can be preferably used.

It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. An example of a method for uniformly dispersing the particle size of the pigment is a method of containing and dispersing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. have.

Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more thereof. .

Pigment dispersants ( a3 )

The pigment dispersant (a3) is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Preferably, it contains an acrylate dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Laid-Open Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above may be used alone or in combination of two or more.

The pigment dispersant (a3) may be a pigment dispersant of a resin type other than 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); Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.

As a commercial item of the above-mentioned resin type pigment dispersant, As a cationic resin dispersant, 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; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, 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; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned.

In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more thereof, or may be used in combination with an acrylic dispersant.

The usage-amount of the said pigment dispersant (a3) is 5-60 mass parts with respect to 100 mass parts of solid content of the pigment (a1) used, More preferably, it is the range of 15-50 mass parts. When the content of the pigment dispersant (a3) exceeds 60 parts by mass, the viscosity may be increased. When the amount of the pigment dispersant (a3) is less than 5 parts by mass, it may be difficult to atomize the pigment or may cause problems such as gelation after dispersion.

dyes( a2 )

The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof.

Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dye note (color dyed yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. Blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70 and the like;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49 and the like;

Green dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

CI Solvent Yellow 14, 16, 21, 56, 151, 79, 93 having excellent solubility in organic solvents in CI solvent dyes; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Orange 41, 45, 62; CI solvent blue 35, 36, 44, 45, 70; CI Solvent Violet 13 is preferred, and CI Solvent Yellow 21, 79; CI Solvent Red 8, 122, 132; CI Solvent Orange 45, 62 is more preferred.

Also, C.I. As an acid dye

CI 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 ;

CI 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;

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

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like;

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

Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.

CI acid yellow 42 having excellent solubility in organic solvents in acid dyes; CI Acid Red 92; CI acid blue 80, 90; CI Acid Violet 66; CI Acid Green 27 is preferred.

Also as a C.I. direct dye,

CI 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;

CI 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 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

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

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;

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

Green dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.

Also, C.I. As a modantoic dye

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

CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84;

Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Green dyes, such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.

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

The content of the dye in the coloring agent (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, based on the total weight of solids of the coloring agent (A). Do. When the content of the dye in the colorant (A) is within the above range, it is possible to prevent the problem of lowering the reliability of the dye eluted by the organic solvent after the pattern formation, it is preferable because the sensitivity is excellent.

The content of the coloring agent (A) is 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of solids of the colored photosensitive resin composition. When the colorant (A) is included in the range of 5 to 60% by weight, the color density of the pixel is sufficient even when a thin film is formed, and the residue is unlikely to occur because the omission of the non-pixel portion during development is not reduced. Do.

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

Alkali-soluble resin (B)

In order to have solubility with respect to the alkaline developing solution used at the image development process at the time of forming a pattern, it copolymerizes and manufactures the ethylenically unsaturated monomer (b1) which has a carboxyl group as an essential component. In addition, in order to ensure compatibility with the dye (a2) and storage stability of the coloring photosensitive resin composition, the acid value of the alkali-soluble resin (B) is characterized in that 30 ~ 150mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, , The dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity tends to rise.

A hydroxyl group may be added to secure further developability of the alkali-soluble resin (B). Although there exists an effect that the developing speed which gives a hydroxyl group improves, the sum of the hydroxyl value of alkali-soluble resin (B) and a photopolymerizable compound (C) is limited to 30 mgKOH / g or more and 180 mgKOH / g or less. If the sum of hydroxyl groups is less than 30mgKOH / g, sufficient development speed cannot be secured. If it exceeds 180mgKOH / g, the dimensional stability of the formed pattern is deteriorated, so the linearity of the pattern is poor, and compatibility with dye is reduced. The problem of storage stability is likely to occur.

Specific examples of the ethylenically unsaturated monomer (b1) having the carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid and anhydrides of the dicarboxylic acids; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and the like, and acrylic acid and methacrylic acid are preferred.

In order to provide a hydroxyl group to alkali-soluble resin (B), it can manufacture by copolymerizing the ethylenically unsaturated monomer (b1) which has a carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group, and the ethylenically unsaturated monomer which has a carboxyl group The compound (b3) which has glycidyl group can be made to further react with the copolymer of (b1), and it can manufacture. Moreover, the compound (b3) which has glycidyl group can be manufactured by making the copolymer of the ethylenically unsaturated monomer (b1) which has a carboxyl group, and the ethylenically unsaturated monomer (b2) which has a hydroxyl group react further.

Specific examples of the ethylenically unsaturated monomer (b2) having the hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide, and the like, and 2-hydroxyethyl (meth) acrylate is preferable, and two or more kinds can be used in combination.

Specific examples of the compound (b3) having the glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl Ether, ethylglycidyl ether, glycidyl isopropyl ether, t-butylglycidyl ether, benzylglycidyl ether, glycidyl 4-t-butylbenzoate, glycidyl stearate, arylglycidyl Ether, methacrylic acid glycidyl ester, and the like, butylglycidyl ether, arylglycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds can be used in combination.

The unsaturated monomers (b4) copolymerizable in the preparation of the alkali-soluble resin (B) are illustrated below, but are not necessarily limited thereto.

Specific examples of the copolymerizable unsaturated monomers (b4) include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds and the like.

The monomers exemplified in the above (b4) may be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) must satisfy the condition that the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 30 mgKOH / g or more and 180 mgKOH / g, with respect to solid content in the photosensitive resin composition. The weight fraction is in the range of 10 to 80% by weight, preferably 10 to 70% by weight. When the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above criteria, the solubility in the developing solution is sufficient, so that pattern formation is easy. It is preferable because omission becomes good.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) should be a compound capable of polymerizing under the action of a photopolymerization initiator described below and must satisfy the hydroxyl values described above for developability and compatibility with dyes. Although the number of functional groups is not specifically limited, The bifunctional photopolymerizable compound is preferable, The trifunctional or more than trifunctional polyfunctional photopolymerizable compound which is excellent in polymerization property and which can fully cure is more preferable.

Specific examples of the bifunctional photopolymerizable compound include 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxypropane and the like.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like, and two or more kinds thereof may be used in combination. Commercially available products include trade names 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER), and KAYARAD DPHA (Nippon Kayaku).

The content of the photopolymerizable compound (C) must satisfy the condition that the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 50 mgKOH / g or more and 250 mgKOH / g or less, and the solid content in the colored photosensitive resin composition It is preferable that 5 to 45 weight% is included in a weight fraction with respect to it, and it is more preferable that 7 to 45 weight% is included especially. When the said photopolymerizable compound (C) is contained 5 to 45 weight% by said reference | standard, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

Light curing Initiator (D)

The photopolymerization initiator (D) includes a photopolymerization initiator (d1) having a structure of Formula 1 below.

[Formula 1]

(2)

In Formula 1, R ₁ is represented by Formula 2, in Formula 2, R ₄ is alkyl of C ₁ to C ₄ , R ₅ is a ring structure of C ₃ to C ₈ , R ₂ in Formula 1 is C Alkyl of ₁ to C ₈ , substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.

The photopolymerization initiator (d1) having the structure of Chemical Formula 1 prevents a decrease in sensitivity caused by the dye and expresses effective photopolymerization characteristics in the colored photosensitive resin composition including the dye as a colorant.

Moreover, the photoinitiator (d2) of that excepting the above can also be used together in the range which does not impair the effect of this invention. Typically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-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.

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.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

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. There is this.

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d3) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The coloring photosensitive resin composition which concerns on this invention contains a photoinitiation adjuvant (d3), and can raise a sensitivity further and can improve productivity.

As the photopolymerization initiation assistant (d3), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound and an organosulfur compound having a thiol group can be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, 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.

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.

Specific examples of the organosulfur 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, trimethylolpropane tris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercapto Butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) and the like Can be mentioned.

The photopolymerization initiator (D) is 0.1 to 40% by weight, preferably 1 to 30, based on the content of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the total solids weight of the colored photosensitive resin composition of the present invention. Wt% may be included. When the photoinitiator (D) is included in the range of 0.1 to 40% by weight, the coloring photosensitive resin composition is highly sensitive, and thus the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved. Also in the case of (d1) it should be included 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the total photopolymerization initiator. When the ratio of (d1) is less than 10% by weight based on the total weight of the entire photopolymerization initiator, the decrease in sensitivity due to the dye is not overcome and shorting of the pattern is likely to occur during the developing process.

In addition, when using the said photoinitiator (d3) further, the said photoinitiator (d3) is an alkali-soluble resin (B) and a photopolymerizable compound (C) based on the total weight of solid content of the coloring photosensitive resin composition of this invention. The content of 0.1 to 40% by weight, preferably 1 to 30% by weight may be included. When the usage-amount of (d3) is in the range of 0.1-40 weight% mentioned above, the sensitivity of a coloring photosensitive resin composition becomes high, and the productivity of the color filter formed using this composition improves.

Solvent (E)

If the solvent (E) is effective in dissolving the other components included in the colored photosensitive resin composition, it can be used without particular limitation to the solvent used in the usual colored photosensitive resin composition, especially ethers, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

Specific examples of the solvent (E) 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; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lac Tate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. can be used.

Each of the above-mentioned solvents (E) may be used alone or in combination of two or more. The solvent (E) may include 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention have. If the content of the solvent (E) is within the range of 60 to 90% by weight described above, it is 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, or the like. When applied, the coating property is improved.

Additive (F)

As the additive (F) can be selectively added as needed, for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents and the like.

Specific examples of the other polymer compound 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. Can be mentioned.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

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

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. 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 above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be included in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solids content of the colored photosensitive resin composition.

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

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

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The mixing and dispersing methods for the components are not particularly limited to those known to those skilled in the art. Specifically, the dispersing group used to disperse each component in the solvent is not particularly limited, and kneader, roll mill, attritor, super mill, dissolver, homo Known dispersers such as mixers, sand mills and the like can be used.

The colored photosensitive resin composition thus prepared is advantageous for achieving high concentration and high transmittance, and is useful as a raw material for forming a color pattern constituting the color filter because of its excellent dispersion stability and excellent characteristics over time.

Method for producing colored photosensitive resin composition

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, part or all of the pigment dispersant (a3), the alkali-soluble resin (B), or the dye (a2) can be mixed with the solvent (E) to dissolve or disperse.

In the mixed dispersion, dyes (a2), the remainder of alkali-soluble resins (B), photopolymerizable compounds (C) and photopolymerization initiators (D), and additives (F) and solvents (E), if necessary, have a predetermined concentration. It can be further added and the coloring photosensitive resin composition which concerns on this invention can be manufactured.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, embodiment of this invention disclosed below is an illustration to the last, and the scope of the present invention is not limited to these embodiment. The scope of the invention is indicated in the appended claims, and moreover contains all modifications within the meaning and range equivalent to the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Manufacturing example  1: Preparation of Pigment Dispersion Composition

<Pigment Dispersion Composition M1>

CI pigment blue 15: 6 12.0 parts by weight, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate and 40 parts by weight of propylene glycol methyl ether by means of a bead mill Pigment dispersion composition M1 was prepared by mixing / dispersing for 12 hours.

Synthetic example  1 to 4: Synthesis of Alkali Soluble Resin

&Lt; Synthesis Example 1 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.2 mgKOH / g and a weight average molecular weight Mw of about 15,110 as measured by GPC.

Synthesis Example 2

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 9.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 54.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, 7.0 parts of 2-hydroxyethyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 69.4 mgKOH / g, the hydroxyl value was 29.8 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 13,180.

&Lt; Synthesis Example 3 &

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 3.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 66.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 26.5 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 16,070.

Synthesis Example 4

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 22.5 parts of acrylic acid, 10 parts of benzyl methacrylate, 47.5 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecylmercapto were charged and replaced with nitrogen. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 6 hours. The solid acid value of the alkali-soluble resin thus synthesized was 172.3 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 14,850.

Example  1 to 8 and Comparative Example  1 to 7: Preparation of colored photosensitive resin composition

&Lt; Example 1 >

22.5 parts of the pigment dispersion composition M1, C.I. Solvent blue 44 (trade name: VALIFAST BLUE 2620, product of Orient Chemical Chemical Co., Ltd.) 0.3 parts, 16.8 parts of the resin of Synthesis Example 1, 5.1 parts of the acrylate of dipentaerythritol having a hydroxyl value of 41 mgKOH / g, Irgacure 369 (BASF 0.3 parts, 0.7 parts of TR-PBG-305 (manufactured by TRONLY) of the formula (3), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to prepare a colored photosensitive resin composition.

<Example 2>

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 1, the acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

<Example 3>

22.5 parts of the pigment dispersion composition M1, CI solvent blue 44 (trade name: VALIFAST BLUE 2620, 0.35 parts of Orient Chemical Co., Ltd.), 16.8 parts of the resin of Synthesis Example 1, an acrylate of pentaerythritol having a hydroxyl value of 104 mgKOH / g. 5.1 parts of cargo, 0.3 parts of Irgacure 369 (manufactured by BASF Corporation), 0.7 parts of TR-PBG-305 (manufactured by TRONLY Corporation), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to form a colored photosensitive resin composition. Prepared.

<Example 4>

22.5 parts of the pigment dispersion composition M1, CI solvent blue 44 (trade name: VALIFAST BLUE 2620, product of Orient Chemical Chemical Co., Ltd.) 0.3 parts, 16.8 parts of the resin of Synthesis Example 1, acrylic of dipentaerythritol having a hydroxyl value of 162 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

<Example 5>

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 2, the acrylic of the dipentaerythritol whose hydroxyl group is 41 mgKOH / g. 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

<Example 6>

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 2, acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

&Lt; Example 7 >

22.5 parts of the pigment dispersion composition M1, CI solvent blue 44 (trade name: VALIFAST BLUE 2620, 0.35 parts of Orient Chemical Co., Ltd.), 16.8 parts of the resin of Synthesis Example 2, an acrylate of pentaerythritol having a hydroxyl value of 104 mgKOH / g. 5.1 parts of cargo, 0.3 parts of Irgacure 369 (manufactured by BASF Corporation), 0.7 parts of TR-PBG-305 (manufactured by TRONLY Corporation), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed to form a colored photosensitive resin composition. Prepared.

&Lt; Example 8 >

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 2, the acrylic of the dipentaerythritol whose hydroxyl group is 22 mgKOH / g. 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

&Lt; Example 9 >

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 1, the acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g A colored photosensitive resin composition was prepared by mixing 5.1 parts of a latex, 0.3 parts of Irgacure 369 (manufactured by BASF Corporation), 0.7 parts of a photopolymerization initiator of Formula 4 below, 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether. .

&Lt; Comparative Example 1 &

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 1, the acrylic of the dipentaerythritol whose hydroxyl group is 22 mgKOH / g. 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

Comparative Example 2

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd. product) 0.3 part, 16.8 parts of resin of the synthesis example 2, the acrylic of the dipentaerythritol whose hydroxyl group is 162 mgKOH / g. 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

&Lt; Comparative Example 3 &

22.5 parts of the pigment dispersion composition M1, CI solvent blue 44 (trade name: VALIFAST BLUE 2620, 0.3 parts of Orient Chemical Co., Ltd.), 16.8 parts of the resin of Synthesis Example 3, acrylic of dipentaerythritol having a hydroxyl value of 80 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

&Lt; Comparative Example 4 &

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd. product) 0.3 part, 16.8 parts of resin of the synthesis example 4, the acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF), 0.7 parts of TR-PBG-305 (made by TRONLY), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the coloring photosensitive resin composition Was prepared.

&Lt; Comparative Example 5 &

22.5 parts of the said pigment dispersion composition M1, 16.8 parts of resin of the synthesis example 1, 5.1 parts of acrylates of the dipentaerythritol with a hydroxyl value of 80 mgKOH / g, 0.3 parts of Irgacure 369 (made by BASF), TR-PBG-305 (TRONLY company) Preparation) 0.7 part, propylene glycol monomethyl ether acetate 20.3 parts, and propylene glycol monomethyl ether 34.0 parts were mixed, and the coloring photosensitive resin composition was produced.

&Lt; Comparative Example 6 >

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd.) 0.3 part, 16.8 parts of resin of the synthesis example 1, the acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g 5.1 parts of a latex, 0.3 parts of Irgacure 369 (made by BASF Corporation), 0.7 part of Irgacure OXE-01 (made by BASF Corporation), 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether were mixed, and the colored photosensitive resin composition was mixed. Prepared.

&Lt; Comparative Example 7 &

22.5 parts of said pigment dispersion composition M1, CI solvent blue 44 (brand name: VALIFAST BLUE 2620, Orient Chemical Co., Ltd. product) 0.3 part, 16.8 parts of resin of the synthesis example 4, the acrylic of the dipentaerythritol whose hydroxyl group is 80 mgKOH / g A colored photosensitive resin composition was prepared by mixing 5.1 parts of a latex, 0.3 parts of Irgacure 369 (manufactured by BASF Corporation), 0.7 parts of a photopolymerization initiator of Formula 4 below, 20.3 parts of propylene glycol monomethyl ether acetate, and 34.0 parts of propylene glycol monomethyl ether. .

Example coloring agent bookbinder Monomer (hydroxyl value) Photopolymerization initiator Acid value Hydroxyl value One P + D Synthesis Example 1 41 P 100.2 41 2 P + D Synthesis Example 1 80 P 100.2 80 3 P + D Synthesis Example 1 104 P 100.2 104 4 P + D Synthesis Example 1 162 P 100.2 162 5 P + D Synthesis Example 2 41 P 68 70.8 6 P + D Synthesis Example 2 80 P 68 109.8 7 P + D Synthesis Example 2 104 P 68 133.8 8 P + D Synthesis Example 2 22 P 68 51.8 9 P + D Synthesis Example 1 80 A 100.2 80

P: C.I. Pigment Blue 15: 6

D: C.I. Solvent blue 44

Synthesis Example 1: Acid value 100.2, hydroxyl value 0

Synthesis Example 2: Acid value 69.4, hydroxyl value 29.8

P: TR-PBG-305 (manufactured by TRONLY)

A:

Comparative Example coloring agent bookbinder Monomer (hydroxyl value) Photopolymerization initiator Acid value Hydroxyl value One P + D Synthesis Example 1 22 P 100.2 22 2 P + D Synthesis Example 2 162 P 68 191.8 3 P + D Synthesis Example 3 80 P 25 80 4 P + D Synthesis Example 4 80 P 173 80 5 P Synthesis Example 1 80 P 100.2 80 6 P + D Synthesis Example 1 80 O 100.2 80 7 P + D Synthesis Example 4 80 A 172.5 80

P: C.I. Pigment Blue 15: 6

D: C.I. Solvent blue 44

Synthesis Example 1: Acid value 100.2, hydroxyl value 0

Synthesis Example 2: Acid value 69.4, hydroxyl value 29.8

Synthesis Example 3: Acid value 26.5, hydroxyl value 0

Synthesis Example 4: Acid value 172.5, hydroxyl value 0

P: TR-PBG-305 (manufactured by TRONLY)

O: Irgacure OXE-01 (manufactured by BASF)

A: [Formula 4]

Experimental Example 1 Measurement of Development Speed, Adhesiveness and Line Width

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 7.

Specifically, each of the colored photosensitive resin composition was coated on a 2-inch angle glass substrate ("EAGLE XG" manufactured by Corning Corporation) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. I was. Subsequently, a test photomask having a pattern for changing the transmittance stepwise in a range of 1 to 100% and a line / space pattern of 1 μm to 50 μm was placed on the thin film and the distance from the test photomask was 100 μm. Was investigated. At this time, the ultraviolet light source was irradiated with luminous intensity of 100 mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The UV-irradiated thin film was developed by soaking in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter.

The film thickness of the color filter prepared above was 2.3 탆.

&Lt; Development speed >

The time taken for the non-exposed part to completely dissolve in the developer during development was measured and shown in Tables 3 to 4 below.

&Lt; Adhesion >

When the generated pattern was evaluated through an optical microscope, the degree of tearing was evaluated on the following patterns.

○: no tearing on the pattern

△: 1 to 3 tears on the pattern

×: 4 or more tearing pattern

<Pattern line width>

The line width of the resulting pattern was measured using a scanning electron microscope. When the line width of a pattern is measured more than the line width of a photomask, it can be said that the sensitivity of a coloring photosensitive resin composition is sufficient and the line width expanded. The enlarged line width compared to the photomask is shown in Tables 3 to 4 below.

Experimental Example 2 Measurement of Contrast Ratio

Contrast ratio was measured using the color filter manufactured similarly except having used <Experimental Example 1> and a test photomask.

The substrate of the color filter is sandwiched between two deflection plates, and the maximum and minimum values of the light intensity transmitted by rotating the front deflection plate while illuminating with a fluorescent lamp (wavelength 380 to 780 nm) from the rear side are CS-2000 luminance. The contrast ratio, which is measured using a system (KONICA MINOLTA) and obtained by dividing the maximum value by the minimum value, is shown in Tables 3 to 4 below.

<Experiment 3> Viscosity change measurement and foreign matter evaluation over time

<Viscosity change measurement>

The initial viscosity of the pigment dispersion composition prepared in Examples and Comparative Examples was measured and stored at 5 ° C. for 1 month, and then the viscosity was measured to observe the viscosity change. The viscosity was measured with a Brookfield viscometer (Brookfield Viscometer DVI +, manufactured by BROOKFIELD) at 25 ° C. The measured results are shown as storage stability in Tables 3 to 4 below.

○: viscosity change ± 5% or less

△: viscosity change ± 5% or more ± 10% or less

×: viscosity change ± 10% or more

<Overseas Foreign Material Evaluation>

The pigment dispersion compositions prepared in Examples and Comparative Examples were stored at 5 ° C. for 1 month, and then observed with a reflective optical microscope (2,500 times magnification) in the same manner as the initial foreign material evaluation. It is shown in Tables 3 to 4 below.

◎: two or less foreign bodies

○: 3 to 5 foreign bodies

(Triangle | delta): 6-10 foreign objects

×: 11 or more foreign bodies

Example Developing speed (s) Contrast ratio Line width enlargement (㎛) Adhesiveness Storage stability Over time One 25 5693 2.90 ○ ○ △ 2 23 5871 2.72 ○ ○ ○ 3 19 5865 2.20 ○ ○ ○ 4 16 5826 1.38 △ ○ △ 5 34 5790 3.32 ○ ○ ○ 6 32 5580 3.20 ○ ○ ○ 7 32 5567 2.28 △ △ ○ 8 35 5961 3.49 ○ ○ ○ 9 22 5808 2.65 ○ ○ ○

Comparative Example Developing speed (s) Contrast ratio Line width enlargement (㎛) Adhesiveness Storage stability Foreign matter One 40 5825 3.00 ○ ○ × 2 31 5732 2.11 × × △ 3 70 5811 4.20 ○ ○ ○ 4 14 5755 -1.20 × △ △ 5 23 3509 3.70 ○ ○ ○ 6 22 5540 -2.60 ○ ○ ○ 7 13 5771 -1.40 × △ △

As shown in Table 3, the colored photosensitive resin compositions of Examples 1 to 9 according to the present invention showed excellent results in development speed, contrast ratio, line width enlargement, adhesiveness, storage stability and foreign matter characteristics over time.

On the other hand, as shown in Table 4, Comparative Examples 1 and 2 in which the sum of hydroxyl values is outside the range of 30 to 180 mgKOH / g was poor in adhesion, storage stability, and foreign material characteristics over time. In addition, in the case of Comparative Example 4 in which the acid value greatly deviated from the range of 30 to 150 mgKOH / g, the line width enlargement characteristic and adhesion were particularly poor. In addition, in the case of Comparative Example 5 containing no dye, the contrast ratio characteristics were poor. In addition, in the case of Comparative Examples 6 and 7 in which the photopolymerization initiators were different, the line width expansion characteristic and the adhesion were particularly poor.

Therefore, it can be seen that the colored photosensitive resin composition of the present invention improves process reliability, productivity and yield, and can produce a high quality color filter having a high development speed and excellent sensitivity.

Claims (9)

As colored photosensitive resin composition comprised from a coloring agent (A), alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The coloring agent (A) comprises at least one pigment (a1), at least one dye (a2) and a pigment dispersant (a3), wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g, and the alkali The sum of the hydroxyl value of a soluble resin (B) and a photopolymerizable compound (C) is 30-180 mgKOH / g, and the said photoinitiator (D) contains the coloring photosensitive resin characterized by including the structural unit (d1) of following General formula (1). Composition.
[Formula 1]

(In Formula 1, R ₁ is represented by the following Formula 2, in Formula 2 R ₄ is C ₁ ~ C ₄ Alkyl, R ₅ is a structure of a ring of C ₃ ~ C ₈ , R ₂ in Formula 1 C ₁ -C ₈ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl group, and R ₃ is a substituted or unsubstituted diphenylsulfide group.)
(2)

The method according to claim 1,
The colored photosensitive resin composition contains, based on the total solid weight,
The colorant (A) is contained in an amount of 5 to 60% by weight,
The alkali-soluble resin (B) satisfies the condition that the sum of the hydroxyl value of the alkali-soluble resin (B) and the photopolymerizable compound (C) is 30 mgKOH / g or more and 180 mgKOH / g, and includes 10 to 80 wt%,
Said photopolymerizable compound (C) satisfies the condition that the sum of the hydroxyl value of alkali-soluble resin (B) and a photopolymerizable compound (C) is 50 mgKOH / g or more and 250 mgKOH / g or less, and contains 5 to 45 weight%,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total content of the alkali-soluble resin (B) and the photopolymerizable compound (C),
The solvent (E) is a coloring photosensitive resin composition, characterized in that 60 to 90% by weight based on the total weight of the coloring photosensitive resin composition. The method according to claim 1,
Wherein the content of the dye in the colorant (A) is 0.5 to 80% by weight based on the total weight of the solid content of the colorant (A). The method according to claim 1,
The usage-amount of the said pigment dispersant (a3) is 5-60 mass parts with respect to 100 mass parts of solid content of the pigment (a1) used, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1,
Structural unit (d1) of the formula (1) is a coloring photosensitive resin composition, characterized in that it comprises 10 to 100% by weight based on the total weight of the entire photopolymerization initiator. The method according to claim 1,
The photopolymerization initiator further comprises at least one photoinitiator (d2) selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds. Colored photosensitive resin composition to be used. The method according to claim 1,
The photopolymerization initiator is a colored photosensitive resin composition further comprises at least one photopolymerization initiation aid (d3) selected from the group consisting of an amine compound, a carboxylic acid compound and an organosulfur compound having a thiol group. The method of claim 7,
The photopolymerization initiator (d3) is contained in an amount of 0.1 to 40 wt% based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C) based on the total solid weight of the colored photosensitive resin composition. Composition. The color filter manufactured from the coloring photosensitive resin composition of any one of Claims 1-8.