TWI506368B - Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus - Google Patents

Description

Photosensitive resin composition, color filter, method for producing the same, and liquid Crystal display device

The present invention relates to a photosensitive resin composition for a color filter and a color filter formed therefor. In particular, a photosensitive resin composition for a color filter having high contrast and excellent development resistance is provided.

Currently, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, and color cameras. Moreover, as the market demand for image devices such as color liquid crystal displays is expanding, the production techniques of color filters are also diversified to meet the above market demands.

The color filter can usually be formed on a transparent glass substrate by a method such as a dyeing method, a printing method, an electrophoresis method, or a pigment dispersion method to obtain a color filter. In general, in order to further improve the contrast of the color filter, a light shielding layer (or a black matrix) may be disposed between the pixel colored layers formed by the pixels.

A photosensitive resin group used for red pixels in a general color filter The product is a C.I. Pigment Red 254 (i.e., a chlorinated diketopyrrolopyrrole pigment) which improves brightness but has poor contrast.

Further studies by Japanese Patent Laid-Open No. 1999-231516 and International Publication No. 2009/144115 disclose that the use of a brominated diketopyrrolopyrrole pigment can simultaneously improve brightness and contrast, but it has the disadvantage of poor developability.

Therefore, how to improve the problem of poor developability of the photosensitive resin composition under the premise of high contrast of the photosensitive resin composition to meet the requirements of the current industry is a problem that a person skilled in the art is currently trying to solve.

In view of the above, the present invention provides a photosensitive resin composition for a color filter used in a liquid crystal display device, which can improve the above problem of poor development resistance.

The present invention provides a photosensitive resin composition for a color filter comprising a pigment (A), an ethylenically unsaturated group-containing compound (B), an alkali-soluble resin (C), a photoinitiator (D), and an organic compound. Solvent (E). The pigment (A) includes the first pigment (A-1) represented by the formula (1).

The ethylenically unsaturated group-containing compound (B) includes the first compound (B-1) or the second compound (B-2) or a combination of the two. The first compound (B-1) is selected from the group consisting of a compound represented by the formula (2), a compound represented by the formula (3), and a compound represented by the formula (4). The second compound (B-2) is a compound represented by the formula (5).

In the formulae (2) to (4), R ¹ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ² each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 carbon atoms; and the total number of propylene fluorenyl groups and methacryl fluorenyl groups in the formula (2) The amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (3) is 3 or 4; in the formula (4), the total amount of the acryl fluorenyl group and the methacryl fluorenyl group is 3; p each independently represents an integer of 0 to 6, and the sum of each p is 3 to 24; q each independently represents an integer of 0 to 6, and the sum of each q is 2 to 16; r each independently represents an integer of 0 to 10, And the sum of each r is 3 to 30; and x represents an integer of 0 to 3,

In the formula (5), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group; y represents an integer of 1 to 2; s represents an integer of 1 to 6; t represents an integer of 0 to 5; and the sum of s and t It is 2 to 6.

In an embodiment of the present invention, the use amount of the pigment (A) is 40 parts by weight to 800 parts by weight based on the amount of the alkali-soluble resin (C) used, and the use of the first pigment (A-1) The amount of the ethylenically unsaturated group-containing compound (B) is from 50 parts by weight to 500 parts by weight, and the photoinitiator (D) is used in an amount of from 15 parts by weight to 150 parts by weight, based on 40 parts by weight to 400 parts by weight. And the organic solvent (E) is used in an amount of 500 parts by weight to 5000 parts by weight.

In an embodiment of the invention, the pigment (A) further includes a second pigment (A-2) other than the first pigment (A-1), and the second pigment (A-2) is selected from two A group consisting of a ketopyrrolopyrrole pigment, an azo pigment, an anthraquinone pigment, an anthraquinone pigment, a quinacridone pigment, a benzimidazolone pigment, and a quinoline pigment.

In one embodiment of the present invention, the second pigment (A-2) is used in an amount of 40 parts by weight to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin (C).

In an embodiment of the invention, the alkali-soluble resin (C) includes a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is obtained by reacting the first mixture, A mixture includes an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.

In one embodiment of the present invention, the above epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (6), a compound represented by the formula (7) or both combination,

In the formula (6), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12,

In the formula (7), R ¹⁰ to R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and n represents an integer of 0 to 10.

In an embodiment of the invention, the amount of the alkali-soluble resin (C) used is 100 parts by weight, and the amount of the first alkali-soluble resin (C-1) is from 3 parts by weight to 60 parts by weight.

In one embodiment of the present invention, the first compound (B-1) is used in an amount of 10 parts by weight to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (C), and the second compound (B) The amount of -2) used is from 10 parts by weight to 100 parts by weight.

The present invention further provides a method of producing a color filter comprising using a pixel layer formed of the above-described photosensitive resin composition for a color filter.

The present invention further provides a color filter which is produced by the above-described manufacturing method.

The present invention further provides a liquid crystal display device comprising the above-described color filter.

When the photosensitive resin composition of the present invention is used for forming a color filter, the problem of poor development resistance can be improved, and it can be applied to a color filter and a liquid crystal display device.

The above described features and advantages of the invention will be apparent from the following description.

100,200‧‧‧Detection device

110‧‧‧Photosensitive resin layer

120, 220‧‧‧ first polarizer

130, 230‧‧‧second polarizer

140‧‧‧Light source

150‧‧‧luminometer

D1, D2, D3‧‧‧ polarized direction

1 is a diagram showing a contrast detecting device in an evaluation mode according to the present invention. Schematic diagram.

Fig. 2 is a schematic view showing a contrast detecting device in an evaluation mode according to the present invention.

<Photosensitive Resin Composition for Color Filters>

The present invention provides a photosensitive resin composition for a color filter comprising a pigment (A), an ethylenically unsaturated group-containing compound (B), an alkali-soluble resin (C), a photoinitiator (D), and an organic compound. Solvent (E). Further, if necessary, the photosensitive resin composition for a color filter may further include an additive (F).

Each component of the photosensitive resin composition for color filters (hereinafter also referred to as a photosensitive resin composition) used in the present invention will be described in detail below.

Here, the following description means that acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid, and acrylate and/or methacrylate is represented by (meth)acrylate; similarly, (meth) The acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group.

Pigment (A)

The pigment (A) includes the first pigment (A-1). Further, the pigment (A) may optionally include the second pigment (A-2).

First pigment (A-1)

The first pigment (A-1) is a red pigment, and the first pigment (A-1) is a formula (1) A compound represented.

The first pigment (A-1) represented by the formula (1) is a brominated diketopyrrolopyrrole pigment, which can be produced by a synthesis method disclosed in a conventional patent document (Publication No. WO 2009/144115).

The above synthesis method is, for example, a method for synthesizing a brominated diketopyrrolopyrrole pigment using a succinic acid diester as a raw material. Specifically, 2 moles of 4-bromobenzonitrile and 1 mole of succinic acid diester are added to an inert organic solvent (for example, tert-amylalcohol). Next, a condensation reaction is carried out in the presence of an alkali metal or an alkali metal alkoxide and at a high temperature of from 80 ° C to 110 ° C to form an alkali metal salt of a brominated diketopyrrolopyrrole compound. Then, an alkali metal salt of a brominated diketopyrrolopyrrole compound is protonated using water, an alcohol or an acid or the like to obtain a brominated diketopyrrolopyrrole pigment. At the stage of protonation, the size of the primary particle size can be controlled by the temperature of protonation, the water used, the ratio of alcohol to acid, and the amount of addition. The above synthesis method is merely illustrative, and the synthesis method of the brominated diketopyrrolopyrrole pigment of the present invention is not limited thereto.

The first pigment (A-1) may be used in an amount of 40 parts by weight to 400 parts by weight, preferably 50%, based on 100 parts by weight of the alkali-soluble resin (C) to be described later. The amount is 350 parts by weight, and more preferably 60 parts by weight to 300 parts by weight.

It is to be noted that when the photosensitive resin composition does not contain the first pigment (A-1), the color filter produced thereof has a problem of poor contrast.

Second pigment (A-2)

In addition to the above-mentioned first pigment (A-1), the pigment (A) of the present invention may be optionally mixed with two or more kinds of the second pigments (A-2). The second pigment (A-2) is usually an organic pigment or an inorganic pigment, and it is preferred to use a pigment having high coloring property and high heat resistance.

Specific examples of the second pigment (A-2) include a diketopyrrolopyrrole pigment other than the first pigment (A-1); azo (Azo), disazo (Disazo) or polyazo (Polyazo) Azo pigment; etc.; Phthalocyanine pigment such as copper phthalocyanine, Halogenated copper phthalocyanine or metal-free phthalocyanine; aminoguanidine (Aminoanthraquinone), diaminoanthracene Diamino dianthraquinone, Anthrapyrimidine, Flavanthrone, Anthanthrone, Indanthrone, Pyranthrone or Violathrone Anthraquinone pigment; Quinacridone pigment; Dioxazine pigment; Perynone pigment; Perylene pigment; thioindigo pigment; isoporphyrin Isoindoline pigment; Isoindolinone pigment; Quinophthalone pigment; Threne pigment; Quinoline pigment; Benzimidazolone pigment, metal complex pigment Or a combination of the above pigments.

The second pigment (A-2) is preferably different from the first pigment (A-1). Further, the second pigment (A-2) is preferably selected from the group consisting of diketopyrrolopyrrole pigments, azo pigments, anthraquinone pigments, anthraquinone pigments, quinacridone pigments, benzimidazolone pigments. And a group consisting of quinoline pigments. The pigment can be adjusted by adjusting the mixing ratio of the first pigment (A-1) and the second pigment (A-2) in the pigment (A) and the mixing ratio of the various pigments in the second pigment (A-2). )s color.

Specific examples of the red pigment of the second pigment (A-2) include C.1. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21 , 22, 23, 31, 32, 37, 37, 41, 47, 48, 48:1, 48:2, 48:2, 48:4, 49, 49:1, 49:2, 50:1, 52 : 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64 : 1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112 , 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 174, 176, 177, 178, 179, 181, 184, 185, 187 , 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239 , 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271 Red pigment such as 272, 273, 274, 275 or 276.

In order to obtain a better brightness, the red pigment is preferably C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 Or 254, and more preferably C.I. Pigment Red 177, 209, 224, 242 or 254. It is worth noting that C.I. Pigment Red 254 is a chlorinated diketopyrrolopyrrole pigment (the substituent on the benzene ring is chlorine), which improves brightness but has poor contrast. On the other hand, the first pigment (A-1) in the present case is a brominated diketopyrrolopyrrole pigment (the substituent on the benzene ring is bromine), which not only improves the brightness but also has a good contrast.

Specific examples of the yellow pigment of the second pigment (A-2) include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 127, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, A yellow pigment of 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207 or 208.

In order to obtain a preferred brightness, the yellow pigment is preferably CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185, and more preferably CI Pigment Yellow 83, 138, 139, 150 or 180.

The orange pigment of the second pigment (A-2) specifically includes CI pigments of orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79.

For better brightness, the orange pigment is preferably C.I. Pigment Orange 38 or 71.

The inorganic pigment of the second pigment (A-2) specifically includes barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide red [red iron oxide (III)], cadmium red, ultramarine blue, and low iron cyanidation. Metal oxide powder such as iron, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium dioxide or triiron tetroxide, metal sulfide powder or metal powder.

In order to obtain a balance between brightness and saturation, and to obtain good coatability, sensitivity, and development resistance, an inorganic pigment may be used in combination with an organic pigment.

The second pigment (A-2) may be used in an amount of 40 parts by weight to 400 parts by weight, preferably 60 parts by weight to 360 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C) to be described later, and More preferably, it is 80 parts by weight to 320 parts by weight.

When the photosensitive resin composition contains the second pigment (A-2), the contrast of the color filter is preferable.

The photosensitive resin composition of the present invention can further adjust the chromaticity by using a dye without reducing the heat resistance. This is well known to those of ordinary skill in the art to which the present invention pertains, and is not described herein.

The pigment (A) may be used in an amount of 40 parts by weight to 800 parts by weight, preferably 60 parts by weight to 700 parts by weight, and more preferably 80, based on 100 parts by weight of the alkali-soluble resin (C) to be described later. Parts by weight to 600 parts by weight.

Compound containing ethylenically unsaturated group (B)

The ethylenically unsaturated group-containing compound (B) includes the first compound (B-1) or The second compound (B-2) or a combination of the above compounds.

First compound (B-1)

The first compound (B-1) is selected from the group consisting of a compound represented by the formula (2), a compound represented by the formula (3), and a compound represented by the formula (4):

In the formulae (2) to (4), R ¹ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ² each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 carbon atoms; and the total number of propylene fluorenyl groups and methacryl fluorenyl groups in the formula (2) The amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (3) is 3 or 4; in the formula (4), the total amount of the acryl fluorenyl group and the methacryl fluorenyl group is 3; p each independently represents an integer of 0 to 6, and the sum of each p is 3 to 24; q each independently represents an integer of 0 to 6, and the sum of each q is 2 to 16; r each independently represents an integer of 0 to 10, And the sum of each r is 3 to 30; and x represents an integer of 0 to 3.

In the formula (2), the formula (3) or the formula (4), -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)- of R ¹ is preferably an end on the oxygen atom side. Bond to R ² .

In the formula (2), all of the six R ^{2 are} preferably an allyl group.

The compound represented by the formula (2) or the compound represented by the formula (3) can be synthesized by the following steps: First, pentaerythritol or dipentaerythritol is opened by Ethylene oxide or Propylene oxide. A step of bonding a ring-opening skeleton by a cycloaddition reaction. Next, a step of introducing a (meth)acryl fluorenyl group by reacting, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton.

The compound represented by the formula (2) and the compound represented by the formula (3) are more preferably a pentaerythritol derivative, a dipentaerythritol derivative or a combination of the two.

Specific examples of the compound represented by the formula (2) include compounds represented by the formula (2-1) to the formula (2-4). In the formulae (2-1) and (2-4), the sum of each n is 6. The sum of each n in the formula (2-2) and the formula (2-3) is 12. The compound represented by the formula (2) is preferably the formula (2-1) or the formula (2-2). The compound represented by the formula (2) is, for example, a commercially available product (such as KAYARAD DPEA-12 manufactured by Nippon Kayaku Co., Ltd.).

Specific examples of the compound represented by the formula (3) include a compound represented by the formula (3-1), a compound represented by the formula (3-2), Ethoxylated Pentaerythritol tetraacrylate or propoxy oxygen. Propoxylated Pentaerythritol tetraacrylate. In the formula (3-1), the sum of each k is 4. The sum of k in the formula (3-2) is 12. The compound represented by the formula (3) is, for example, a commercially available product (for example, EM 2411, EM2421 manufactured by Changxing Chemical Industry Co., Ltd. or Miramer M4004 manufactured by Toyo Chemical Co., Ltd.).

Specific examples of the compound represented by the formula (4) include Ethoxylated Trimethylolpropane triacrylate, Ethoxylated Trimethylolpropane trimethacrylate, and Ethoxylated Trimethylolpropane trimethacrylate. Propoxylated Trimethylolpropane Triacrylate, Propoxylated Glyceryl triacrylate. The compound represented by the formula (4) is, for example, a commercially available product (for example, KAYARAD GPO-303, KAYARAD THE-330, KAYARAD TPA-320, KAYARAD TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), M-310 , M-321, M-350, M-360, M-460 (above, manufactured by Toagosei Co., Ltd.), SR415, SR454, SR492, SR499, CD501, SR502, SR9020, SR9021, SR9035 (above, by Sha Manufactured by Toma Co., Ltd.), EM2380, EM2381, EM2382, EM2383, EM2384, EM2385, EM2386, EM2387, EM3380 (above, manufactured by Changxing Chemical Industry Co., Ltd.), Miramer M3130, Miramer M3160, Miramer M3190, Miramer M360 ( The above, manufactured by Toyo Chemical Co., Ltd.) or a combination of the above compounds.

The amount of the alkali-soluble resin (C) to be described later is 100 parts by weight, and the first compound (B-1) may be used in an amount of 10 parts by weight to 100 parts by weight, preferably 12 parts by weight. The parts by weight are 80 parts by weight, and more preferably 15 parts by weight to 60 parts by weight.

Second compound (B-2)

The second compound (B-2) may be a compound represented by the formula (5):

In the formula (5), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group; y represents an integer of 1 to 2; s represents an integer of 1 to 6; t represents an integer of 0 to 5; and the sum of s and t It is 2 to 6.

In detail, the second compound (B-2) is a (meth) acrylate-based compound obtained by reacting a caprolactone-modified polyol with (meth)acrylic acid.

The above caprolactone-modified polyol is obtained by reacting caprolactone with a polyol having four or more functional groups. The above caprolactone may be γ-caprolactone, δ-caprolactone, ε-caprolactone or a combination of the above compounds, and is preferably ε-caprolactone. The above polyol having four or more functional groups is, for example, pentaerythritol, ditrimethylolpropane, dipentaerythritol or a combination of the above compounds. The amount of the above-mentioned caprolactone is preferably from 1 mole to 12 moles, based on the amount of the polyol having four or more functional groups being 1 mole.

Specific examples of the second compound (B-2) include pentaerythritol caprolactone-modified tetra(meth)acrylate compound, ditrimethylolpropane caprolactone modified tetra(methyl) A poly(meth)acrylate compound modified with an acrylate compound or dipentaerythritol caprolactone or a combination of the above compounds. Specific examples of the above-mentioned dipentaerythritol caprolactone-modified poly(meth)acrylate compound include dipentaerythritol caprolactone-modified di(meth)acrylate compound and dipentaerythritol caprolactone modified tri ( Methyl) acrylate compound, dipentaerythritol caprolactone modified tetra(meth) acrylate compound, dipentaerythritol caprolactone modified penta (meth) acrylate compound, dipentaerythritol caprolactone A hexa(meth) acrylate compound or a combination of the above compounds. Specifically, the second compound (B-2) is, for example, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

The amount of the alkali-soluble resin (C) to be described later is 100 parts by weight, and the second compound (B-2) may be 10 parts by weight to 100 parts by weight, preferably 12 parts by weight to 80 parts by weight, and more preferably 15 parts by weight to 60 parts by weight.

When the first compound (B-1) or the second compound (B-2) is not contained in the compound (B) containing an ethylenically unsaturated group, the development resistance of the photosensitive resin composition is poor.

It is to be noted that the first compound (B-1) or the second compound (B-2) can effectively improve the shortcomings of the conventional brominated diketopyrrolopyrrole pigment, and the photosensitivity The resin composition facilitates the formation of a color filter.

Third compound (B-3)

The third compound (B-3) has a functional group represented by the formula (I).

In the formula (I), Y ¹ represents hydrogen or a methyl group.

Specific examples of the third compound (B-3) include acrylamide, (meth) propylene morpholine, (meth) acrylate-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethylene glycol (A) Acrylate, octyl octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl amino (meth) acrylate, dodecyl (meth) acrylate, (a) Dicyclopentyloxyethyl acrylate, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl(meth)acrylamide, tetrachlorophenyl (meth)acrylate, (methyl) )-2-tetrachlorophenoxyethyl acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, ( 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, nitrogen-vinyl tyrosone, (methyl) Phenyloxyethyl acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol poly (meth) acrylate, (meth)acrylic acid borneol ester, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, three (2-Hydroxyethyl)isocyanate di(meth)acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate III ( Methyl) acrylate, trimethylolpropyl tri(meth)acrylate, triethylene glycol di(meth)acrylate, new Pentandiol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropyl triacrylate ( Trimethylolpropane triacrylate), pentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(methyl) ) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylol propyl (meth) acrylate, EO modification Bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, EO modified hydrogenated bisphenol A di(meth) acrylate, PO modified hydrogenation double Phenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, phenolic polyglycidyl ether (meth) acrylate or a combination of the above compounds.

The third compound (B-3) is preferably trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, tetraacrylic acid. Ditrimethylolpropyl propyl ester, TO-1382 manufactured by Japan East Asia Synthetic Co., Ltd. or a combination of the above compounds.

The third compound (B-3) may be 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C) to be described later, and more preferably 50 parts by weight to 200 parts by weight.

The ethylenically unsaturated group-containing compound (B) may be used in an amount of 50 parts by weight to 500 parts by weight, preferably 60 parts by weight to 400 parts by weight based on 100 parts by weight of the alkali-soluble resin (C) to be described later. Parts, and more preferably from 70 parts by weight to 300 parts by weight.

Alkali soluble resin (C)

The alkali-soluble resin (C) includes a first alkali-soluble resin (C-1), a second alkali-soluble resin (C-2), or a combination of the two.

First alkali soluble resin (C-1)

The first alkali-soluble resin (C-1) is obtained by reacting the first mixture. The first mixture includes an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. Further, the first mixture may more optionally include a carboxylic anhydride compound (c-3), an epoxy group-containing compound (c-4), or a combination of the two.

Epoxy compound having at least two epoxy groups (c-1)

The epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (6), a compound represented by the formula (7), or a combination of the two.

Specifically, the compound represented by the formula (6) is as follows:

In the formula (6), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12.

The compound represented by the formula (6) can be obtained by reacting a bisphenol fluorene with a halogenated propylene oxide (epihalohydrin).

In detail, specific examples of the bisphenol quinoid type compound include: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyl) 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene (9,9-bis (4-hydroxy-3-chlorophenyl)fluorene), 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9 - bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl) 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene (9,9-bis(4-hydroxy) -3,5-dimethylphenyl)fluorene), 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene or an analog thereof, or a combination of the above compounds.

Specific examples of the epoxidized propylene oxide (epihalohydrin) include 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin or the like, or a combination thereof. .

Specific examples of the bisphenol quinoid compound having an epoxy group include (1) a product manufactured by Nippon Steel Chemical Co., Ltd.: ESF-300 or the like; (2) Osaka Natural Gas (Osaka) Goods manufactured by Gas Co., Ltd.: for example, PG-100, EG-210 or the like; (3) SMS Technology (SMS Technology) Commercial products manufactured by Co., Ltd.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

Further, specifically, the compound represented by the formula (7) is as follows:

In the formula (7), R ¹⁰ to R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and n represents an integer of 0 to 10.

The compound represented by the formula (7) can be obtained by reacting a compound represented by the formula (7-1) with a halogenated propylene oxide in the presence of an alkali metal hydroxide.

In the formula (7-1), ¹⁰ is identical to R ²³ and n are as defined with formula R (7) in the definition of R ²³ and R ¹⁰ to n, which is not repeated herein.

The method for synthesizing the compound represented by the formula (7-1) is as follows. First, a compound represented by the formula (7-2) is subjected to a condensation reaction with a phenol in the presence of an acid catalyst to form a formula. Compound represented by (7-1). Next, an excess amount of the halogenated propylene oxide is added to carry out dehydrohalogenation of the halogenated propylene oxide with the compound represented by the formula (7-1) to obtain a compound represented by the formula (7).

In the formula (7-2), the same as defined in R ¹² to R ¹⁵ defined in formula (. 7) of the R ¹² to R ^15, which is not repeated herein. X ¹ and X ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. The above halogen atom may be chlorine or bromine. The above alkyl group is preferably a methyl group, an ethyl group or a tert-butyl group. The above alkoxy group is preferably a methoxy group or an ethoxy group.

Specific examples of the phenols include: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol , octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol, propylene Propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, cyclohexylcresol or the like. The above phenols may be used singly or in combination of two or more.

The compound represented by the formula (7-2) is used in an amount of 1 mol, and the phenol is used in an amount of 0.5 mol to 20 mol, and preferably 2 mol to 15 mol.

Specific examples of the acid catalyst include: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, chlorination Zinc (zinc chloride) or an analogue thereof. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or a combination of the above compounds. The acid catalysts may be used singly or in combination of two or more.

Further, the amount of the above acid catalyst used is not particularly limited. However, the amount of the compound represented by the above formula (7-2) is 100% by weight (% by weight), and the amount of the acid catalyst used is preferably from 0.1% by weight to 30% by weight.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Further, specific examples of the above organic solvent include toluene, xylene, methyl isobutyl ketone or the like. The above organic solvents may be used singly or in combination of two or more.

The organic solvent is used in an amount of 50% by weight to 300% by weight, based on the total weight of the compound represented by the formula (7-2) and the phenol, of 100% by weight, preferably 100% by weight to 250% by weight. Further, the above condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the condensation reaction has an operation time of 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be performed. The above neutralization treatment adjusts the pH of the solution after the reaction to pH 3 to pH 7, and preferably pH 5 to pH 7. The above water washing treatment can be carried out using a neutralizing agent, wherein the neutralizing agent is an alkaline substance, and specifically includes: an alkali metal hydrogen of sodium hydroxide, potassium hydroxide or the like. Oxide; alkaline earth metal hydroxide of calcium hydroxide, magnesium hydroxide or the like; diethylene triamine, triethylenetetramine, aniline (aniline), an organic amine of phenylene diamine or an analogue thereof; ammonia, sodium dihydrogen phosphate or a combination of the above. The above neutralizing agents may be used singly or in combination of two or more. abovementioned The water washing treatment can be carried out by a conventional method, for example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction is repeated. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off under reduced pressure and concentrated, and thus, the compound represented by the formula (7-1) can be obtained.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or a combination of the above compounds. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In one embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, while the above aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing. Water, and the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or its The quaternary ammonium salt of the analog is used as a catalyst, and after reacting at 50 ° C to 150 ° C for 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Next, the reaction is allowed to proceed for 1 hour to 10 hours at a temperature of from 20 ° C to 120 ° C to carry out a dehydrohalogenation reaction.

The above-mentioned halogenated propylene oxide is used in an amount of 1 equivalent to 20 equivalents, and preferably 2 equivalents to 10 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the formula (7-1). Hydroxyl in a compound having the structure of the formula (7-1) above The total equivalent weight of the base is 1 equivalent, and the alkali metal hydroxide to be added in the above dehydrohalogenation reaction is used in an amount of from 0.8 to 15 equivalents, and preferably from 0.9 to 11 equivalents.

Further, in order to allow the above-described dehydrohalogenation reaction to proceed smoothly, an alcohol of methanol, ethanol or the like may be added. In addition to this, an aprotic polar solvent of dimethyl sulfone, dimethyl sulfoxide or the like may be added to carry out the reaction. In the case of using an alcohol, the total amount of the halogenated propylene oxide is 100% by weight based on the above, and the alcohol is used in an amount of 2% by weight to 20% by weight, and preferably 4% by weight to 15% by weight. In the case of using an aprotic polar solvent, the total amount of the aprotic polar solvent is from 5% by weight to 100% by weight, and preferably 10% by weight, based on 100% by weight of the total amount of the halogenated propylene oxide. Up to 90% by weight.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by distillation under reduced pressure, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg).

In order to prevent the formed epoxy resin from containing a hydrolyzable halogen, the dehydrohalogenated reaction solution may be added to a solvent such as toluene or methyl isobutyl ketone, or an alkali metal such as sodium hydroxide or potassium hydroxide. An aqueous hydroxide solution is used and the dehydrohalogenation reaction is carried out again. In the dehydrohalogenation reaction, the total hydroxyl group equivalent weight in the compound represented by the formula (7-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and preferably 0.05 moles to 0.2 moles. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After the dehydrohalogenation reaction is completed, the salt is removed by filtration, washing, and the like. class. Further, a solvent represented by the formula (7) can be obtained by removing a solvent such as toluene or methyl isobutyl ketone by distillation under reduced pressure. Specific examples of the compound represented by the above formula (7) include those commercially available from Nippon Kayaku, such as NC-3000, NC-3000H, NC-3000S, and NC-3000P.

a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c-2)

Specific examples of the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group are selected from the group consisting of (1) to (3): (1) acrylic acid, methyl group Acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyloxyethyl adipate, 2-methyl Acryloxybutylene adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl malay Acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropenyloxypropyl Tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate or 2-methyl propylene oxybutyl phthalic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound comprises adipic acid, succinic acid, maleic acid or phthalic acid; (3) by hydroxyl group-containing (methyl) Ester with the carboxylic acid anhydride compound (c-3) obtained by reacting a half ester compound, wherein the hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl acrylate [(2-hydroxyethyl) Acrylate], 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate [(2- Hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol trimethacrylate, and the like. Further, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (c-3) contained in the first mixture of the aforementioned first alkali-soluble resin (C-1).

Carboxylic anhydride compound (c-3)

The carboxylic anhydride compound (c-3) may be selected from the group consisting of (1) to butanedioic anhydride, maleic anhydride, and itacona. Anhydride (phthalic anhydride), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride, trimellitic anhydride a dicarboxylic anhydride compound such as (1,3-dioxoisobenzofuran-5-carboxylic anhydride); and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride, double A tetracarboxylic anhydride compound such as phenyl ether tetracarboxylic dianhydride.

Epoxy group-containing compound (c-4)

The epoxy group-containing compound (c-4) may be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and an epoxy group. A group of unsaturated compounds or a combination of the above compounds. The above-mentioned unsaturated group-containing glycidyl ether compound is manufactured by Nagase Chemical Co., Ltd., and is modeled as Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171 or Products such as Denacol EX-192.

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The hydroxyl group-containing reaction product formed by the polymerization reaction, wherein the epoxy compound (c-1) having at least two epoxy groups is a compound represented by (6). Next, the carboxylic anhydride compound (c-3) is added to the reaction solution to carry out a polymerization reaction. The number of equivalents of the hydroxyl group of the hydroxy group-containing reaction product is 1 equivalent, and the number of equivalents of the acid anhydride group contained in the carboxylic anhydride compound (c-3) is preferably from 0.4 equivalents to 1 equivalent, more preferably from 0.75 equivalents to 1 equivalent. . When a plurality of carboxylic anhydride compounds (c-3) are used, these carboxylic anhydride compounds may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (c-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/10. And more preferably 5/95 to 80/20. Further, the above reaction may be operated at a temperature of from 50 ° C to 130 ° C.

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1) having at least two epoxy groups and a compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. The hydroxyl group-containing reaction product formed by the reaction, wherein the epoxy compound (c-1) having at least two epoxy groups is a compound represented by the formula (6). Next, a polymerization reaction is carried out by adding a carboxylic anhydride compound (c-3), an epoxy group-containing compound (c-4), or a combination of the two to the reaction solution. The total number of equivalents of the epoxy groups in the compound represented by the formula (6) is 1 equivalent, and the number of acid equivalents of the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably the same. It is from 0.8 equivalents to 1.5 equivalents, and more preferably from 0.9 equivalents to 1.1 equivalents. The total amount of the hydroxyl group based on the above hydroxyl group-containing reaction product is 100 mol%, and the carboxylic anhydride compound (c-3) is used in an amount of 10 mol% to 100 mol%, preferably 20 mol% to 100%. Mohr%, and more preferably 30 mol% to 100 mol%.

When the first alkali-soluble resin (C-1) described above is prepared, in order to shorten the reaction time, a basic compound is generally added to the reaction solution as a reaction catalyst. The reaction catalyst includes triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride or benzyl chloride. Benzylethylethylammonium chloride or the like. The reaction catalysts may be used singly or in combination of two or more.

The total amount of the epoxy compound (c-1) having at least two epoxy groups and the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, and the reaction is carried out. The amount of the catalyst used is preferably from 0.01 part by weight to 10 parts by weight, and more preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor may be added to the reaction solution. Polymerization inhibitors include Methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol, phenanthrene Phenothiazine and the like. The polymerization inhibitors may be used singly or in combination of two or more.

The total amount of the epoxy compound (c-1) having at least two epoxy groups and the compound (c-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, polymerized. The inhibitor is preferably used in an amount of from 0.01 part by weight to 10 parts by weight, and more preferably from 0.1 part by weight to 5 parts by weight.

When the first alkali-soluble resin (C-1) is prepared, a polymerization solvent can be optionally used. The polymerization solvent includes an alcohol solvent such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; a ketone solvent such as methyl ethyl ketone or cyclohexanone; toluene; An aromatic hydrocarbon solvent such as xylene; a cellophane solvent such as cellosolve or butyl cellosolve; carbitol and butyl carbitol a carbopol-type solvent such as propylene glycol monomethyl ether; a polypropylene glycol alkyl ether such as dipropylene glycol monoether [poly(propylene glycol alkyl ether)] (propylene glycol) alkyl ether] solvent; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, etc. Solvent-like solvent; alkyl lactate-based solvent such as ethyl lactate or butyl lactate; or dialkyl glycol ether solvent. The polymerization solvent may be used singly or in combination of two or more. Further, the acid value of the first alkali-soluble resin (C-1) is preferably from 50 mgKOH/g (mgKOH/g) to 200 mgKOH/g, and more preferably 60 mg. KOH / gram to 150 mg KOH / gram.

The first alkali-soluble resin (C-1) may be used in an amount of 3 parts by weight to 60 parts by weight, preferably 4 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and More preferably, it is 5 parts by weight to 40 parts by weight. When the alkali-soluble resin (C) contains the first alkali-soluble resin (C-1), the obtained photosensitive resin composition is preferably excellent in developability.

Second alkali soluble resin (C-2)

The second alkali-soluble resin (C-2) is copolymerized by an ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group and other copolymerizable ethylenically unsaturated monomer (c-6). The total amount of the ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group and the other copolymerizable ethylenically unsaturated monomer (c-6) is 100 parts by weight.

Specific examples of the ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acrylonitrile ethoxylate An unsaturated monocarboxylic acid compound such as butyl succinate, 2-methyl propylene ethoxy succinate or 2-isobutyl ethoxy succinate; maleic acid, maleic anhydride, and fumar An unsaturated dicarboxylic acid (anhydride) compound such as acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride; or a trivalent or higher unsaturated polyvalent carboxylic acid (anhydride) compound. The above ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group may be used singly or in combination of two or more.

The ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group is preferably acrylic acid, methacrylic acid, 2-acrylonitrile ethoxy succinate, 2-methyl Alkyl propylene ethoxy succinate, 2-isobutyl hydrazine ethoxy succinate or a combination of the above compounds. When a carboxylic acid group-containing ethylenic unsaturation such as 2-propenyl ethoxy succinate, 2-methyl propylene ethoxy succinate, 2-isobutyl oxime ethoxy succinate or the like is used In the case of a monomer, the ethylenically unsaturated monomer (c-5) having at least one carboxylic acid group can improve the pigment dispersibility of the photosensitive resin composition for a color filter, improve the development resistance, and reduce the generation of residue.

Specific examples of the other copolymerizable ethylenically unsaturated monomer (c-6) include dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate (hereinafter referred to as FA-511A). , dicyclopentenyloxyethyl acrylate (hereinafter referred to as FA-512A), dicyclopentyl methacrylate, dicyclopentyl ethoxy methacrylate, dicyclopentenyl methacrylate, An aromatic vinyl compound such as dicyclopentenyl ethoxy methacrylate, styrene, α-methyl styrene, vinyl toluene, p-chlorostyrene, methoxystyrene; N-phenyl Malay Yttrium, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylbenzene Kamalyimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Maleic imine compound such as N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexylmaleimide Methyl acrylate, methyl methacrylate, benzyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate Ester, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, methacrylic acid Tributyl ester, 2-hydroxyethyl acrylate, 2-hydroxy methacrylate Ethyl ethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, methyl 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, A Allyl acrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, methoxy triethylene glycol acrylate, triethylene glycol methacrylate Methoxy triethylene glycol methacrylate, lauryl methacrylate, tertadecyl methacrylate, cetyl methacrylate, An unsaturated carboxylic acid ester compound such as octadecylmethacrylate, eicosyl methacrylate, docosyl methacrylate; acrylic acid-N, N-dimethylaminoethyl , N,N-dimethylaminoethyl methacrylate, N-N-diethylaminopropyl acrylate, N,N-dimethylaminopropyl methacrylate, Acrylic-N,N- Dibutylaminopropyl ester, N-isobutylaminoethyl methacrylate; unsaturated carboxylic acid glycidyl ester compound such as glycidyl acrylate or glycidyl methacrylate; vinyl acetate a vinyl carboxylate compound such as ester, vinyl propionate or vinyl butyrate; vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether, methallyl epoxypropyl ether, etc. a saturated vinyl compound; a vinyl cyanide compound such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N- An unsaturated decylamine compound such as hydroxyethyl acrylamide or N-hydroxyethyl methacrylamide; an aliphatic conjugated diene such as 1,3-butadiene, isoamylene or chlorinated butadiene A compound or a combination of the above compounds. Other copolymerizable Specific examples of the ethylenically unsaturated monomer (c-6) to be combined may be used singly or in combination of two or more.

The other copolymerizable ethylenically unsaturated monomer (c-6) is preferably selected from the group consisting of dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxylate. Acrylate, dicyclopentyl methacrylate, dicyclopentylethoxy methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl ethoxy methacrylate, styrene, N-benzene a group consisting of carbamazepine, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, and benzyl methacrylate .

The solvent used to prepare the second alkali-soluble resin (C-2) includes ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, Triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, triple (poly)alkylene glycol monoalkyl ether solvent such as tripropylene glycol mono methyl ether or tripropylene glycol mono ethyl ether; ethylene glycol methyl ether acetate, ethylene glycol a (poly)alkylene glycol monoalkyl ether acetate solvent such as diethyl ether acetate, propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate; diglyme, diethylene glycol methyl ether, diethylene glycol Other ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Ethyl lactate solvent; 2-hydroxy-2-methylpropionic acid methyl ester, 2-hydroxy-2-methylpropionic acid , methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, glycolic acid Ethyl ester, methyl 2-hydroxy-3-methylbutanoate, 3-methyl 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate Ester, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate Other ester solvents such as n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbon solvents such as toluene and xylene; or N- A carboxylic acid guanamine solvent such as methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide. The above solvents may be used singly or in combination of two or more.

The solvent for preparing the second alkali-soluble resin (C-2) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the two.

The initiator used to prepare the second alkali-soluble resin (C-2) is generally a radical type polymerization initiator. The radical polymerization initiator includes 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile) [2, 2'-azobis-(2,4-dimethylvaleronitrile)], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)[2,2'-azobis-(4- Azo (azo) compound such as methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile; a peroxy compound such as benzoylperoxide or a combination of the above compounds.

The second alkali-soluble resin (C-2) may be used in an amount of 40 parts by weight to 97 parts by weight, preferably 50 parts by weight to 96 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and More preferably 60 parts by weight to 95 parts by weight Share.

Photoinitiator (D)

The photoinitiator (D) may be a radical photoinitiator. Specifically, the photoinitiator (D) is, for example, an O-oxime compound, a triazine compound, or a benzene. An acetophenone-based compound, a biimidazole-based compound, or a benzophenone-based compound.

Specific examples of the O-mercaptoquinone compound include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-phenylhydrazinium), 1-[ 4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinium), 1-[4-(phenylindenyl)phenyl]-heptane- 1,2-dione-2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazol-3-yl]-ethane Keto-1-(O-ethylindenyl), 1-[9-ethyl-6-(3-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-( O-acetinyl), 1-[9-ethyl-6-phenylindenyl-9H-indazol-3-yl]-ethanone-1-(O-ethylindenyl), ethane ketone -1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazol-3-yl]-1-(O-acetylindenyl), ethane ketone -1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-carbazol-3-yl]-1-(O-ethylindenyl), Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-indazol-3-yl]-1-(O-ethenyl)肟), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)-9H-indazol-3-yl]-1-(O- Ethyl ketone), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)phenylhydrazine }}-9H-carbazol-3-yl]-1-(O-B Ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxy Phenylhydrazinyl}-9H-indazol-3-yl]-1-(O-acetamidoguanidine) or a combination of the above compounds.

Specific examples of triazine compounds include 2,4-bis(trichloromethane) ,6-(p-methoxy)styryl-s-triazine, 2,4-bis(2,4-Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine] Trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine [2,4-Bis(trichloromethyl)-6-(1- P-dimethylaminophenyl-1,3-butadienyl)-s-triazine], 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine [2-trichloromethyl-4- Amino-6-(p-methoxy)styryl-s-triazine] or a combination of the above compounds.

Specific examples of the acetophenone compound include p-dimethylacetonone, α , α' -dimethoxy oxy acetophenone, 2,2'-dimethyl-2-phenylbenzene Ethyl ketone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-benzyl-2-N, N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone or a combination of the above compounds.

Specific examples of the diimidazole compound include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2 , 2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4' , 5,5'-tetraphenyldiimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4 , 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole or the above compounds The combination.

Specific examples of the benzophenone compound include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-anthracene, benzophenone, and 4,4'-bis(dimethylamine) Benzophenone, or 4,4'-bis(diethylamine)benzophenone or a combination of the above compounds.

The photoinitiator (D) is preferably 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylindenyl), 1-[9 -ethyl-6-(2-methylphenylindenyl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidoxime), ethane ketone-1-[9- Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoinyl)-9H-indazol-3-yl]-1-(O-ethylindenyl), ethane ketone-1- [9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone}-9H-carbazole-3 -yl]-1-(O-acetamidoxime), 2,4-bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine, 2-benzyl- 2-N,N-dimethylamine-1-(4-morpholinylphenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4,4',5, 5'-tetraphenylimidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole], 4,4'-double ( Diethylamine) benzophenone or a combination of the above compounds.

The above photoinitiator (D) may be used singly or in combination of two or more.

Further, in the range without affecting the physical properties of the photosensitive resin composition of the present invention can also need to add further initiator other than the photo-initiator (D), for example: α - dione (α -diketone) compound, A acyloin-based compound, a acyloin ether-based compound, an acylphosphine oxide-based compound, a quinone-based compound, a halogen-containing compound, or a peroxide.

Specific examples of the α -diketone compound include a benzil or an acetyl group-based compound or a combination of the above compounds.

Specific examples of the ketol compound include benzoin or a combination of the above compounds.

Specific examples of the ketol ether compound include benzoin methylether, benzoin ethylether, benzoin isopropyl ether or a combination of the above compounds.

Specific examples of the phosphonium oxide compound include 2,4,6-trimethyl-benzoyl diphenylphosphine oxide, bis-(2,6-dimethoxy Bismuthene-2,4,4-trimethoxy-benzoyl-2,4,4-trimethylbenzyl phosphineoxide or a combination of the above compounds.

Specific examples of the quinone compound include anthraquinone or 1,4-naphthoquinone or a combination of the above compounds.

Specific examples of the halogen-containing compound include phenacyl chloride, tribromomethyl phenylsulfone, tris(trichloromethyl)-s-triazine [tris(trichloromethyl)-s-triazine Or a combination of the above compounds.

Specific examples of the peroxide include di-tertbutylperoxide or a combination of the above compounds.

The above photoinitiator (D) may be used singly or in combination of two or more.

When the photoinitiator (D) is not used, the development resistance of the photosensitive resin composition is not good.

The photoinitiator (D) may be used in an amount of 15 parts by weight to 150 parts by weight, preferably 20 parts by weight to 120 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and more preferably 25 parts by weight to 90 parts by weight.

Organic solvent (E)

The organic solvent (E) means that the pigment (A), the ethylenically unsaturated group-containing compound (B), the alkali-soluble resin (C), and the photoinitiator (D) can be dissolved, but not in the above The organic solvent to be reacted with the component, and preferably has a suitable volatility.

Further, the organic solvent (E) may be the same as the organic solvent used to prepare the second alkali-soluble resin (C-2), and will not be described herein. The organic solvent (E) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the above solvents.

The organic solvent (E) may be used in an amount of 500 parts by weight to 5000 parts by weight, preferably 800 parts by weight to 4,500 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C), and more preferably 1000 parts by weight to 4000 parts by weight.

Additive (F)

The photosensitive resin composition of the present invention can be further optionally further added with the additive (F) without affecting the efficacy of the present invention. Specific examples of the additive (F) include a filler, a polymer (refer to a polymer other than the above-described alkali-soluble resin (C)), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.

Specific examples of the filler include glass or aluminum and the like.

Specific examples of the polymer include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or a combination of the above polymers.

Specific examples of the adhesion promoter include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxy Propyl propyl trimethoxy decane, 3-glycidyl propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane, 3-chloropropyl group Dimethoxy decane, 3-chloropropyltrimethoxy decane, 3-Methacryloxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane or a combination of the above compounds.

Specific examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol or a combination of the above compounds.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone or the above compounds. combination.

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

The additive (F) is used in an amount of 2 parts by weight to 20 parts by weight, preferably 3 parts by weight to 16 parts by weight, and more preferably 4 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). 12 parts by weight.

<Preparation Method of Photosensitive Resin Composition for Color Filter>

A method for preparing a photosensitive resin composition, for example, a pigment (A), an ethylenically unsaturated group-containing compound (B), an alkali-soluble resin (C), a photoinitiator (D), and an organic solvent (E) The mixture is placed in a stirrer to be stirred, and uniformly mixed into a solution state. If necessary, an additive (F) may be added and uniformly mixed to obtain a photosensitive resin composition in a solution state.

Further, the method for preparing the photosensitive resin composition is not particularly limited. The method for preparing the photosensitive resin composition is, for example, first dispersing a part of the alkali-soluble resin (C) and the ethylenically unsaturated group-containing compound (B) in a part of the organic solvent (E). Medium to form a dispersion solution; and then mixing the remaining pigment (A), the ethylenically unsaturated group-containing compound (B), the alkali-soluble resin (C), the photoinitiator (D), and the organic solvent (E) preparation.

Alternatively, the photosensitive resin composition may be obtained by dispersing a part of the pigment (A) in a part of the organic solvent (E) to form a pigment dispersion; and mixing the remaining pigment (A), containing ethylenic unsaturation The compound (B), the alkali-soluble resin (C), the photoinitiator (D), and the remaining organic solvent (E) are prepared. Further, the dispersion step of the above pigment (A) can be carried out by mixing, for example, a mixer such as a beads mill or a roll mill.

<Method for Manufacturing Pixel Layer and Color Filter>

The color filter is prepared by sequentially pre-baking, exposing, developing, and baking the photosensitive filter with a photosensitive composition on a substrate on which a black matrix has been formed, wherein the black matrix is used to isolate each The pixel layer (hereinafter, the pixel layer is also called a pixel coloring layer). The preparation method of the color filter will be described in detail below.

First, a photosensitive resin composition for a color filter in a solution state is uniformly applied onto a substrate by a coating method such as spin coating or cast coating or roll coating to form a coating film. The substrate is, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, and the like to which a transparent conductive film is attached, which is used for a liquid crystal display device, and the like, and is used for a photoelectric conversion device (such as a solid). A substrate (for example, a ruthenium substrate) of the photographic device; or a substrate having a black matrix for shielding light that can isolate a pixel colored layer such as red, green, or blue.

After the coating film is formed, most of the solvent is removed by drying under reduced pressure, and then the residual solvent is completely removed by pre-baking to form a pre-baked coating film. It is worth noting that the conditions of drying under reduced pressure and pre-baking vary depending on the type and ratio of each component. In general, the vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the prebaking is performed at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes. Heat treatment.

Next, the prebaked coating film is exposed by a photomask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, h-line or i-line, and the ultraviolet irradiation device may be a (ultra) high-pressure mercury lamp and a metal halide lamp.

Then, the exposed prebaked coating film is immersed in a developing solution at a temperature of 23 ± 2 ° C to remove an unnecessary portion of the prebaked coating film, whereby a specific pattern can be formed on the substrate. Specific examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, dimethyl Basic compounds such as ethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5,4,0)-7-undecene Alkaline aqueous solution. The concentration of the developer is from 0.001% by weight to 10% by weight, preferably from 0.005% by weight to 5% by weight, and more preferably from 0.01% by weight to 1% by weight.

After the prebaked coating film is developed, the substrate having the specific pattern is washed with water, and the above specific pattern is air-dried with compressed air or compressed nitrogen. Then, post-bake (that is, heat treatment) is performed by a heating device such as a hot plate or an oven. The post-baking temperature is 100 to 280 ° C, and the heating time is 1 minute to 15 minutes. The volatile component in the coating film is removed and the unreacted ethylenic unsaturated double bond is subjected to a thermosetting reaction. After the above-described processing steps, a specific pattern can be fixed on the substrate, thereby forming a pixel colored layer. Repeating the above steps, sequentially forming red, green, blue and other pixel colored layers on the substrate.

Finally, an ITO (Indium Tin Oxide) protective film (evaporated film) was formed on the surface of the pixel colored layer by sputtering under a vacuum atmosphere at a temperature of 220 ° C to 250 ° C. When necessary, the ITO protective film is etched and wired, and a liquid crystal alignment film (polyimine for liquid crystal alignment film) is applied onto the surface of the ITO protective film, thereby forming a color filter having a pixel layer.

<Method of Manufacturing Liquid Crystal Display Device>

First, a color filter formed by the above-described method of forming a color filter and a substrate provided with a thin film transistor (TFT) are disposed oppositely, and a gap is provided between the two (crystal) Cell gap). Next, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Then, liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and the injection hole is sealed to form a liquid crystal layer. Subsequently, a polarizing plate is provided by contacting the other side of the color filter in contact with the other side of the liquid crystal layer in the color filter to form a liquid crystal display element. Next, a surface light source is provided on one side of the liquid crystal display element to form a liquid crystal display device. The liquid crystal used, that is, the liquid crystal compound or the liquid crystal composition, is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used in the production of the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

Synthesis example of first alkali soluble resin (C-1)

Synthesis Example C-1-1 to Synthesis Example C-1-3 of the first alkali-soluble resin (C-1) will be described below:

Synthesis Example C-1-1

First, 100 parts by weight of a ruthenium epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500-mL four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was added to 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heated to 110 ° C to 115 ° C. After reacting for 2 hours, the first alkali-soluble resin B-1-1 having an acid value of 98 mgKOH/g and a weight average molecular weight of 2,205 was obtained.

Synthesis Example C-1-2

100 parts by weight of ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., model ESF-300; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500-mL four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature of the reaction was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate while 13 parts by weight of benzophenonetetracarboxylic dianhydride was added, and heated to 90 ° C to 95 ° C. After reacting for 2 hours, 6 parts by weight of tetrahydrophthalic anhydride is added, and the reaction is carried out at 90 ° C to 95 ° C for 4 hours to obtain a first alkali-soluble resin (C-1-2) having an acid value of 99.0 mgKOH/g and a weight average molecular weight of 2,630.

Synthesis Example C-1-3

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model: NC-3000; epoxy equivalent: 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight A portion of triphenylphosphine and 264 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction flask and the temperature was maintained at 95 °C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic acid was added. The tetrahydrophthalic anhydride was reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin (C-1-3) having an acid value of 102 mgKOH/g and a weight average molecular weight of 3,200.

Synthesis example of second alkali soluble resin (C-2)

Synthesis Example C-2-1 to Synthesis Example C-2-3 of the second alkali-soluble resin (C-2) will be described below:

Synthesis Example C-2-1

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and nitrogen gas was introduced. Then, 5 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOMS), 5 parts by weight of dicyclopenteny acrylate (hereinafter abbreviated as FA-511A), 40 Parts by weight of styrene monomer (hereinafter abbreviated as SM) and 50 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) are dissolved in 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as EEP). The manner in which the monomer mixture is fed is continuously added.

After stirring evenly, the temperature of the oil bath was raised to 100 °C. Then, 6 parts by weight of a polymerization initiator 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) was dissolved in the EEP, and added in an interval of one hour in five equal parts. Into the four-necked flask.

The reaction temperature of the polymerization process was maintained at 100 °C. After 6 hours, The second alkali-soluble resin C-2-1 was obtained by taking out the polymerization product from a four-necked flask and devolatilizing the solvent.

Synthesis Example C-2-2 to Synthesis Example C-2-4

The second alkali-soluble resin of Synthesis Example C-2-2 to Synthesis Example C-2-4 was prepared in the same manner as in Synthesis Example C-2-1, and was distinguished by changing the second alkali-soluble resin. The types of components and their amounts used, the reaction time, the reaction temperature, and the reaction addition time (as shown in Table 1), wherein the compounds corresponding to the reference numerals in Table 1 are shown below.

Example of photosensitive resin composition

Hereinafter, Examples 1 to 10 and Comparative Examples 1 to 8 of the photosensitive resin composition will be described:

Example 1

40 parts by weight of the first pigment (A-1) represented by the formula (1) (hereinafter abbreviated as A-1) and 10 parts by weight of the compound represented by the formula (2-1) (hereinafter abbreviated as B-1) -1), 40 parts by weight of dipentaerythritol hexaacrylate (hereinafter abbreviated as B-3-1), 100 parts by weight of the first alkali-soluble resin (C-1-1), and 5 parts by weight of 2-methyl- 1-(4-methylthiophenyl)-2-morpholino-1-propanone (hereinafter abbreviated as D-1), 5 parts by weight of 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyldiimidazole (hereinafter abbreviated as D-2), 5 parts by weight of 4,4'-bis(diethylamine)benzophenone (hereinafter referred to as D-3) and 2 parts by weight of sodium polyacrylate (hereinafter abbreviated as F-1) are added to 500 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as E-1), and After the shaking type stirrer was uniformly stirred, the photosensitive resin composition of Example 1 was obtained. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 2.

Embodiment 2 to Embodiment 10

The photosensitive resin compositions of Examples 2 to 10 were prepared in the same manner as in Example 1, and were different in that the composition of the photosensitive resin composition and the amount thereof were changed (as shown in Table 2). ), wherein the compounds corresponding to the labels in Table 2 are as follows. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 2.

Comparative Example 1 to Comparative Example 8

The photosensitive resin compositions of Comparative Examples 1 to 8 were prepared in the same manner as in Example 1, and were distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof used (as shown in Table 3). ). The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 3.

Evaluation method Development resistance

The photosensitive resin compositions of the above respective Examples and Comparative Examples were applied by spin coating to a glass substrate having a length and a width of 100 mm. Then, it was dried under reduced pressure at a pressure of about 100 mmHg for about 30 seconds. Next, the glass substrate was prebaked at a temperature of 80 ° C for 2 minutes to form a prebaked film having a film thickness of 2.5 μm. Thereafter, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., model MCPD).

Next, the above prebaked coating film was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F). After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution at 23 °C. After 1 minute, it was washed with pure water. Then, the chromaticity was measured again, and the chromaticity change (ΔEab*) was calculated by the following formula (8). The smaller the measured chromaticity change (ΔEab*), the better the developability of the photosensitive resin composition, and the evaluation is based on the following criteria.

ΔEab*=[(ΔL) ² +(Δa) ² +(Δb) ² ] ^1/2 (8)

◎: ΔEab*<2

○: 2≦ΔEab*<4

△: 4≦ΔEab*<6

╳:6≦ΔEab*

Contrast

The photosensitive resin compositions of the above respective Examples and Comparative Examples were applied by spin coating to a glass substrate having a length and a width of 100 mm. Then, it was dried under reduced pressure at a pressure of about 100 mmHg (mmHg) for about 30 seconds. Next, the above glass substrate was prebaked at 80 ° C for 3 minutes to form a prebaked coating film having a film thickness of 2.5 μm. Thereafter, the above prebaked coating film was irradiated with ultraviolet light of 300 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F). After irradiation with ultraviolet light, the prebaked coating film was immersed in a developing solution at 23 ° C for 2 minutes. Thereafter, the prebaked coating film was washed with pure water, and the prebaked coating film was post-baked at 200 ° C for 80 minutes to form a photosensitive resin layer having a film thickness of 2.0 μm on the glass substrate.

The photosensitive resin layer having a film thickness of about 2.0 μm was measured for the luminance value of the photosensitive resin layer by the detecting device shown in FIGS. 1 and 2, and the ratio of the luminance was calculated.

In the detecting device 100 of FIG. 1, the photosensitive resin layer 110 obtained above is provided between the first polarizing plate 120 and the second polarizing plate 130. The light emitted from the light source 140 sequentially passes through the first polarizing plate 120, the photosensitive resin layer 110, and the second polarizing plate 130. Then, the luminance value (cd/cm ² ) of the light penetrating the second polarizing plate 130 was measured by a luminance meter 150 (manufactured by Topcon Corporation, model number BM-5A). It should be noted that when the polarization direction of the first polarizer 120 and the polarization direction of the second polarizer 130 are projected on the same plane, the polarization direction of the first polarizer 120 is parallel to the polarization direction of the second polarizer 130. (such as the polarization direction D1). The luminance value measured by the detecting device 100 of FIG. 1 is A.

The detecting device 200 illustrated in FIG. 2 is substantially the same as the detecting device 100 illustrated in FIG. 1 except that the polarizing direction D2 of the first polarizing plate 220 and the polarizing direction D3 of the second polarizing plate 230 are projected. a plane In the upper direction, the polarization direction D2 of the first polarizing plate 220 is perpendicular to the polarization direction D3 of the second polarizing plate 230. The luminance value measured by the device 200 is B. Next, the contrast of the photosensitive resin composition was calculated by the formula (9), and evaluated based on the following criteria.

◎: 1500 ≦ contrast

○: 1200 ≦ contrast <1500

△: 900 ≦ contrast <1200

╳: Contrast <900

<evaluation result>

It is known from Table 2 and Table 3 that the photosensitive resin containing the first pigment (A-1) The composition (Examples 1 to 10) was compared with the photosensitive resin composition (Comparative Example 1, Comparative Example 2, Comparative Example 7, and Comparative Example 8) which did not contain the first pigment (A-1). The photosensitive resin composition of one pigment (A-1) has a good contrast.

Further, the photosensitive resin composition containing the second pigment (A-2) (Examples 7 to 10) and the photosensitive resin composition not containing the second pigment (A-2) (Examples 1 to 1) 6. The photosensitive resin composition containing the second pigment (A-2) has a better contrast than the comparative example 3 and the comparative example 4).

Further, the photosensitive resin composition containing the first compound (B-1) (Examples 1 to 6) and the photosensitive resin composition not containing the first compound (B-1) (Comparative Example 3 to Comparative Example) 8) The photosensitive resin composition containing the first compound (B-1) has better development resistance.

Further, a photosensitive resin composition containing the second compound (B-2) (Examples 7 to 10) and a photosensitive resin composition not containing the second compound (B-2) (Comparative Example 3 to Comparative Example) 8) The photosensitive resin composition containing the second compound (B-2) has better development resistance.

Further, a photosensitive resin composition containing the first alkali-soluble resin (C-1) (Examples 1 to 3, Examples 7 to 10) and the second alkali-soluble resin (C-2) only ( In the case of Example 4 to Example 6), the photosensitive resin composition containing the first alkali-soluble resin (C-1) is preferably excellent in developability.

As described above, the present invention solves the problem of poor development resistance by adding the above-mentioned first compound and the above-mentioned second compound to a photosensitive resin composition containing a brominated diketopyrrolopyrrole pigment. In other words, the photosensitive light of the present invention Since the resin composition contains a specific pigment and a specific ethylenically unsaturated group-containing compound, it has both good contrast and excellent development resistance, and is therefore suitable for use in color filters and liquid crystal display devices.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (11)

A photosensitive resin composition for a color filter comprising: a pigment (A); an ethylenically unsaturated group-containing compound (B); an alkali-soluble resin (C); a photoinitiator (D); and an organic solvent (E) wherein the pigment (A) comprises the first pigment (A-1) represented by the formula (1), The ethylenically unsaturated group-containing compound (B) includes a first compound (B-1) or a second compound (B-2) or a combination of the two, wherein the first compound (B-1) is selected a compound represented by the formula (2), a compound represented by the formula (3), and a compound represented by the formula (4), and the second compound (B-2) is represented by the formula (5) Compound, In the formulae (2) to (4), R ¹ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ² each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 carbon atoms; and the total number of propylene fluorenyl groups and methacryl fluorenyl groups in the formula (2) The amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (3) is 3 or 4; in the formula (4), the total amount of the acryl fluorenyl group and the methacryl fluorenyl group is 3; p each independently represents an integer of 0 to 6, and the sum of each p is 3 to 24; q each independently represents an integer of 0 to 6, and the sum of each q is 2 to 16; r each independently represents an integer of 0 to 10, And the sum of each r is 3 to 30; and x represents an integer of 0 to 3, In the formula (5), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group; y represents an integer of 1 to 2; s represents an integer of 1 to 6; t represents an integer of 0 to 5; and the sum of s and t It is 2 to 6. The photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the amount of the pigment (A) used is 40 based on 100 parts by weight of the alkali-soluble resin (C). The first pigment (A-1) is used in an amount of 40 parts by weight to 400 parts by weight, based on 800 parts by weight, of the ethylenically unsaturated group-containing The compound (B) is used in an amount of 50 parts by weight to 500 parts by weight, the photoinitiator (D) is used in an amount of 15 parts by weight to 150 parts by weight, and the organic solvent (E) is used in an amount of 500 parts by weight to 5000 parts by weight. The photosensitive resin composition for color filters according to claim 1, wherein the pigment (A) further includes a second pigment (A-2) other than the first pigment (A-1) And the second pigment (A-2) is selected from the group consisting of a diketopyrrolopyrrole pigment, an azo pigment, an anthraquinone pigment, an anthraquinone pigment, a quinacridone pigment, a benzimidazolone pigment, and A group consisting of quinoline pigments. The photosensitive resin composition for color filters according to claim 3, wherein the second pigment (A-2) is used based on the amount of the alkali-soluble resin (C) used in an amount of 100 parts by weight. The amount used is from 40 parts by weight to 400 parts by weight. The photosensitive resin composition for color filters according to claim 1, wherein the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is obtained by reacting a first mixture comprising: an epoxy compound (c-1) having at least two epoxy groups; and having at least one carboxylic acid group and at least one ethyl group Unsaturated group compound (c-2). The photosensitive resin composition for color filters according to claim 5, wherein the epoxy compound (c-1) having at least two epoxy groups includes a compound represented by the formula (6), a compound represented by the formula (7) or a combination of the two, In the formula (6), R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of An aryl group of 6 to 12 or an aralkyl group having a carbon number of 6 to 12, In the formula (7), R ¹⁰ to R ²³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and n represents an integer of 0 to 10. The photosensitive resin composition for color filters according to claim 5, wherein the first alkali-soluble resin (C-1) is used based on 100 parts by weight of the alkali-soluble resin (C). The amount used is from 3 parts by weight to 60 parts by weight. The photosensitive resin composition for color filters according to claim 1, wherein the amount of the alkali-soluble resin (C) used is 100 parts by weight based on the first compound (B-1). The amount used is from 10 parts by weight to 100 parts by weight, and the second compound (B-2) is used in an amount of from 10 parts by weight to 100 parts by weight. A method of producing a color filter comprising the pixel layer formed of the photosensitive resin composition for a color filter according to any one of the first to eighth aspects of the invention. A color filter produced by the manufacturing method described in claim 9 of the patent application. A liquid crystal display device comprising the color filter according to claim 10 of the patent application.