TW201523145A - Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus - Google Patents

Abstract

An a photosensitive resin composition, a color filter and a method for manufacturing the same, and a liquid crystal display apparatus are provided. The photosensitive resin composition includes a pigment, alkali-soluble resin, a compound containing an ethylenically unsaturated group, a photoinitiator and an organic solvent. The photosensitive resin composition has advantages of high contrast, low post-baking color difference and good linearity of high precision pattern.

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, low post-bake chromatic aberration, and high definition pattern linearity 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 was obtained using C.I. Pigment Red 254 (i.e., a chlorinated diketopyrrolopyrrole pigment) which increased brightness but was poorly contrasted.

Further studies by Japanese Patent Laid-Open No. 1999-231516 and International Publication No. 2009/144115 disclose that the use of brominated diketopyrrolopyrrole pigments can simultaneously improve brightness and contrast, but it has a pattern of large post-bake chromatic aberration and high definition. The shortcomings of poor sex.

Therefore, how to simultaneously improve the problem of poor linearity of the post-baking color difference and high-definition pattern to meet the requirements of the current industry is a problem that the technicians in the field are 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 is capable of improving the problem of poor linearity of a pattern having a large post-baking color difference and high definition.

The present invention provides a photosensitive resin composition for a color filter comprising a pigment (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (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 alkali-soluble resin (B) includes the first alkali-soluble resin (B-1) represented by the formula (2):

In the formula (2), A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-indenylene or a single bond; L represents a tetravalent carboxylic acid residue; Y ¹ represents a trivalent organic group having a carbon number of 1 to 20; and R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; and R ⁴ represents hydrogen. Atom or methyl; and m represents an integer from 1 to 20.

In an embodiment of the invention, the first alkali-soluble resin (B-1) is obtained by reacting the first mixture. The first mixture includes a diol compound (b-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (b-2), and a dicarboxylic anhydride (b-3) represented by the formula (3),

In the formula (3), Y ² represents a trivalent organic group having a carbon number of 1 to 20; and R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.

In one embodiment of the present invention, the molar ratio (b-2) of the above polymerizable unsaturated group-containing diol compound (b-1) to the above tetracarboxylic acid or acid dianhydride (b-2) thereof (b-1) is 0.2 to 1.0.

In one embodiment of the present invention, the molar ratio of the above-mentioned polymerizable unsaturated group-containing diol compound (b-1) to the above-described dicarboxylic acid anhydride (b-3) represented by formula (3) (b-3) ) / (b-1) is 0.02 to 1.6.

In an embodiment of the invention, the alkali-soluble resin (B) further includes a second alkali-soluble resin (B-2) other than the first alkali-soluble resin (B-1). The second alkali-soluble resin (B-2) is obtained by a reaction of the second mixture. The second mixture includes an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group.

In an embodiment of the invention, the above epoxy compound having at least two epoxy groups includes a compound represented by the formula (4), a compound represented by the formula (5), or a combination of the two:

In the formula (4), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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 (5), R ¹² to R ²⁵ 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 weight ratio of the first alkali-soluble resin (B-1) to the second alkali-soluble resin (B-2) is 10:90 or more and less than 100:0.

In an embodiment of the present invention, the use amount of the pigment (A) is 60 parts by weight to 600 parts by weight based on the amount of the alkali-soluble resin (B) used, and the use of the first pigment (A-1) The amount of the ethylenic unsaturated group-containing compound (C) is from 40 parts by weight to 400 parts by weight, and the photoinitiator (D) is used in an amount of from 10 parts by weight to 100 parts by weight, based on 40 parts by weight to 400 parts by weight. And the amount of organic solvent (E) used is 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). The second pigment (A-2) is selected from the group consisting of diketopyrrolopyrrole pigments, azo pigments, anthraquinone pigments, anthraquinone pigments, quinacridone pigments, benzimidazolone pigments, and quinoline pigments. The group of people formed.

In one embodiment of the present invention, the second pigment (A-2) is used in an amount of 20 parts by weight to 200 parts by weight based on 100 parts by weight of the alkali-soluble resin (B).

In an embodiment of the invention, the above ethylenically unsaturated group-containing compound (C) includes the first compound (C-1). The first compound (C-1) is selected from the group consisting of a compound represented by the formula (6), a compound represented by the formula (7), and a compound represented by the formula (8):

In the formulae (6) to (8), R ²⁶ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ²⁷ each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ²⁸ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 1 to 6 carbon atoms; in the formula (6), an acryloyl group and a methacryloyl group The total amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (7) is 3 or 4; in the formula (8), 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 0 to 10 An integer, and the sum of each r is 3 to 30; and x represents an integer of 0 to 3.

In one embodiment of the present invention, the first compound (C-1) is used in an amount of 5 parts by weight to 60 parts by weight based on 100 parts by weight of the alkali-soluble resin (B).

In an embodiment of the invention, the above ethylenically unsaturated group-containing compound (C) includes the second compound (C-2). The second compound (C-2) is a compound represented by the formula (9):

In the formula (9), R ²⁹ and R ³⁰ 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 one embodiment of the present invention, the amount of the second compound (C-2) to be used is 5 parts by weight to 60 parts by weight based on 100 parts by weight of the alkali-soluble resin (B).

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.

In view of the above, when the photosensitive resin composition of the present invention is used for forming a color filter, it is possible to improve the problem that the pattern of the post-baking color difference and the high-definition pattern is not linear, and is further applicable 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

120, 220‧‧‧ first polarizer

130, 230‧‧‧second polarizer

140, 240‧‧‧ light source

150, 250‧‧‧luminometer

140, 240‧‧‧ light source

D1, D2, D3‧‧‧ polarized direction

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a contrast detecting device in an evaluation mode according to the present invention.

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 alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (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 compound represented by the formula (1).

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 parts by weight to 350 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B) to be described later, and More preferably, it is 60 parts by weight to 300 parts by weight.

It is worth noting that when the photosensitive resin composition does not contain the first pigment At (A-1), the color filter produced by the film 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 Diaminodianthraquinone, Anthrapyrimidine, Flavanthrone, Anthanthrone, Indanthrone, Pyranthrone or Violanthrone Anthraquinone pigment; Quinacridone pigment; Dioxazine pigment; Perynone pigment; Perylene pigment; thioindigo pigment; Isoindoline Pigment; Isoindolinone pigment; Quinophthalone pigment; Threen 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). Again, the first 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 quinoline. It is a group of 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 CI 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, 272, Red pigment of 273, 274, 275 or 276.

In order to obtain a better brightness, the red pigment is preferably CI Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254, and more preferably CI Pigment Red 177, 209, 224, 242 or 254.

Specific examples of the yellow pigment of the second pigment (A-2) include C.I. 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, 195, 196, 197, 198, 199, 200, 202, 203, 204, Yellow pigment of 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. Iron, chrome oxide green, cobalt green, amber, titanium black, A metal oxide powder such as iron black, titanium oxide or triiron tetroxide, a metal sulfide powder or a metal powder is synthesized.

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

The second pigment (A-2) may be used in an amount of 20 parts by weight to 200 parts by weight, preferably 30 parts by weight to 180 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B) to be described later, and More preferably, it is 40 parts by weight to 160 parts by weight.

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

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 60 parts by weight to 600 parts by weight, preferably 80 parts by weight to 500 parts by weight, and more preferably 100, based on 100 parts by weight of the alkali-soluble resin (B) to be described later. Parts by weight to 400 parts by weight.

Alkali soluble resin (B)

The alkali-soluble resin (B) includes a first alkali-soluble resin (B-1), a second alkali-soluble resin (B-2), or a combination of the two. Further, the alkali-soluble resin (B) may optionally include other alkali-soluble resins (B-3).

First alkali soluble resin (B-1)

The first alkali-soluble resin (B-1) is a compound represented by the formula (2):

In the formula (2), A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-indenylene or a single bond; L represents a tetravalent carboxylic acid residue; Y ¹ represents a trivalent organic group having a carbon number of 1 to 20; and R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; and R ⁴ represents hydrogen. Atom or methyl; and m represents an integer from 1 to 20.

The first alkali-soluble resin (B-1) is obtained by reacting the first mixture. The first mixture includes a diol compound (b-1) (hereinafter also referred to simply as component (b-1)) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride (b-2) thereof (hereinafter also referred to simply as Component (b-2)) and a dicarboxylic anhydride (b-3) represented by formula (3) (hereinafter also referred to simply as component (b-3)),

In the formula (3), Y ² represents a trivalent organic group having a carbon number of 1 to 20; and R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group.

The diol compound (b-1) containing a polymerizable unsaturated group is a bisphenol compound (b-1-i) having two epoxy groups and having at least one carboxylic acid group and at least one ethylenically unsaturated group. The compound (b-1-ii) is obtained by reacting. The reactant for synthesizing the diol compound (b-1) containing a polymerizable unsaturated group may also contain other compounds.

The bisphenol compound (b-1-i) having two epoxy groups can be obtained, for example, by dehydrohalogenation of a bisphenol compound with a halogenated propylene oxide in the presence of an alkali metal hydroxide.

Specific examples of the bisphenol used to synthesize the bisphenol compound (b-1-i) having two epoxy groups include bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-di Methylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)anthracene, bis(4-hydroxy-3,5-dimethylphenyl) Bismuth, bis(4-hydroxy-3,5-dichlorophenyl)fluorene, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane , bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethyloxane, bis(4-hydroxy-3,5-dimethylphenyl)di Methyl decane, bis(4-hydroxy-3,5-dichlorophenyl)dimethyl decane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane , bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylbenzene Propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-dual ( 4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5- Dichlorophenyl)ether; 9,9-bis(4-hydroxyphenyl)anthracene, 9,9-double ( 4-hydroxy-3-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-chlorophenyl)anthracene, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3-fluoro Phenyl) ruthenium, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene or a combination of the above compounds.

Specific examples of the halogenated propylene oxide used to synthesize the bisphenol compound (b-1-i) having two epoxy groups include 3-chloro-1,2-epoxypropane and 3-bromo-1,2- Propylene oxide or a combination of the above compounds. The above halogenated propylene oxide may be used in an amount of from 1 equivalent to 20 equivalents, and preferably from 2 equivalents to 10 equivalents, based on 1 equivalent of the total hydroxyl group in the bisphenol compound.

Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide or a combination of the above compounds. The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 to 15 equivalents, and preferably from 0.9 to 11 equivalents, based on 1 equivalent of the total hydroxyl group in the bisphenol compound. .

It is to be noted that 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 operation temperature for the dehydrohalogenation reaction is from 20 ° C to 120 ° C, and the operation time ranges from 1 hour to 10 hours.

In one embodiment, an aqueous solution of the alkali metal hydroxide added to the above dehydrohalogenation reaction may also be used. 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, at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction, tetramethyl ammonium chloride, tetramethyl ammonium bromide, and trimethylbenzyl chloride may be added. A quaternary ammonium salt such as ammonium chloride is used as a catalyst. Next, the reaction is carried out at 50 ° C to 150 ° C for 1 hour to 5 hours, and an alkali metal hydroxide or an aqueous solution thereof is further added. Then, 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.

Further, in order to smoothly carry out the above-described dehydrohalogenation reaction, an aprotic such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. The reaction is carried out by a polar solvent or the like. In the case of using an alcohol, the alcohol may be used in an amount of 2% by weight to 20% by weight, based on the total amount of the above-mentioned halogenated propylene oxide, and preferably 4% by weight to 15% by weight. In the case of using an aprotic polar solvent, the total amount of the halogenated propylene oxide is 100% by weight, and the aprotic polar solvent may be used in an amount of 5 to 100% by weight, preferably 10% by weight. 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 heating and depressurizing, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

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 benzene, toluene or methyl isobutyl ketone, and sodium hydroxide or potassium hydroxide may be added. An aqueous alkali metal hydroxide solution is used to carry out the dehydrohalogenation reaction again. In the dehydrohalogenation reaction, the alkali metal hydroxide may be used in an amount of from 0.01 mol to 1 mol, preferably from 0.05 mol to 0.9 mol, based on the total equivalent of the hydroxyl group in the above bisphenol compound. ear. another 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 completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as benzene, toluene or methyl isobutyl ketone can be distilled off by heating and decompression to obtain a bisphenol compound (b-1-i) having two epoxy groups.

The bisphenol compound (b-1-i) having two epoxy groups is preferably a bisphenol compound having two epoxy groups represented by the following formula (2-1), or by the following formula ( The bisphenol compound having two epoxy groups represented by 2-2) is a polymer obtained by polymerizing a monomer.

In the formulae (2-1) and (2-2), A ¹ to A ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

B represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9 - Amidino or a single bond. M1 may represent an integer of 1 to 10, and m1 is more preferably an integer representing 1 to 2.

The bisphenol compound having two epoxy groups represented by the formula (2-1) is particularly preferably a bisphenol compound having two epoxy groups represented by the following formula (2-3).

In the formula (2-3), A ¹ to A ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

The bisphenol compound having two epoxy groups represented by the formula (2-3) is, for example, a two epoxy group obtained by reacting a bisphenol fluorene with an epihalohydrin. Bisphenolphthalein type compound.

Specific examples of the bisphenol quinoid type compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methyl Phenyl) 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- 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene [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)indole [9,9-bis(4-hyd) Roxy-3,5-dichlorophenyl)fluorene],9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene] Or a combination of the above compounds.

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxyhydrin, 3-bromo-1,2-epoxyhydrin (epibromohydrin) or a combination of the above compounds.

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) a product manufactured by Osaka Gas: for example, PG-100, EG- 210 or an analogue thereof; or (3) a product manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG or the like.

The compound (b-1-ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is at least one compound selected from the group consisting of acrylic acid, methacrylic acid, and 2-methyl propylene hydride. 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutylsuccinic acid, 2-methylpropenyloxyethyl adipate, 2-methylpropenyloxybutylene Acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropene oxime Oxybutyl butyl maleic acid, 2-methyl propylene methoxy succinic acid, 2-methyl propylene oxypropyl adipate, 2-methyl propylene oxypropyl tetrahydro phthalic acid, 2 -Methyl propylene oxime propyl phthalate, 2-methyl propylene oxy butyl phthalic acid, or 2-methyl propylene oxy butyl hydrogen phthalic acid; a compound obtained by reacting an acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, ortho-benzene Formic acid; a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes but is not limited to 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, or pentaerythritol trimethacrylate. Further, the carboxylic anhydride compound described herein may be the same as the above component (b-2) and the following component (b-4), and therefore will not be further described.

The tetracarboxylic acid or its acid dianhydride (b-2) is selected from the group consisting of a saturated linear hydrocarbon tetracarboxylic acid, an alicyclic tetracarboxylic acid, an aromatic tetracarboxylic acid, and an acid dianhydride of the above carboxylic acid. At least one.

Specific examples of the saturated linear hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid or a combination of the above compounds. The saturated linear hydrocarbon tetracarboxylic acid may also have a substituent.

Specific examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid or a combination of the above compounds. The alicyclic tetracarboxylic acid may also have a substituent.

Specific examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylphosphonium tetracarboxylic acid, 1,2,3,6 - tetrahydrophthalic acid or a combination of the above compounds.

The tetracarboxylic acid or its acid dianhydride (b-2) is preferably biphenyltetracarboxylic acid or benzophenone IV. A carboxylic acid, a diphenyl ether tetracarboxylic acid or an acid dianhydride of the above carboxylic acid, and more preferably a biphenyltetracarboxylic acid, a diphenyl ether tetracarboxylic acid or an acid dianhydride of the above carboxylic acid.

When the first alkali-soluble resin (B-1) of the present invention is used as a component of a photosensitive resin composition described later, the polymerizable unsaturated group-containing diol compound (b-1) and the When the molar ratio (b-2)/(b-1) of the tetracarboxylic acid or the acid dianhydride (b-2) is from 0.2 to 1.0, the high-definition pattern linearity of the photosensitive composition is preferable.

Specific examples of the dicarboxylic anhydride (b-3) represented by the formula (3) include trimethoxydecyl propyl succinic anhydride, triethoxy decyl propyl succinic anhydride, and methyl dimethoxy decyl alkyl group. Propyl succinic anhydride, methyl diethoxy decyl propyl succinic anhydride, trimethoxy decyl butyl succinic anhydride, triethoxy decyl butyl succinic anhydride, methyl diethoxy decane Butyl succinic anhydride, p-(trimethoxydecyl)phenyl succinic anhydride, p-(triethoxydecyl)phenyl succinic anhydride, p-(methyldimethoxydecyl)phenyl butyl Diacid anhydride, p-(methyldiethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride, (Methyldiethoxydecylalkyl)phenylsuccinic anhydride or a combination of the above compounds.

The dicarboxylic anhydride (b-3) represented by the formula (3) is preferably trimethoxydecyl propyl succinic anhydride, triethoxy decyl propyl succinic anhydride, p-(trimethoxydecyl) benzene Butadiene anhydride, p-(triethoxydecyl)phenyl succinic anhydride, m-(trimethoxydecyl)phenyl succinic anhydride, m-(triethoxydecyl)phenyl succinic anhydride or the above A combination of compounds.

When the first alkali-soluble resin (B-1) of the present invention is used as a component of a photosensitive composition described later, the diol compound containing a polymerizable unsaturated group (b-1) When the molar ratio (b-3)/(b-1) of the dicarboxylic anhydride (b-3) represented by the formula (3) is from 0.02 to 1.6, the photosensitive composition High definition patterns are more linear.

In the mixture for the synthesis reaction of the alkali-soluble resin, if the dicarboxylic anhydride (b-3) represented by the formula (3) is not contained, when the alkali-soluble resin is used as a component of the photosensitive composition described later, The pattern with large color difference and high definition has poor linearity.

In addition to the above-mentioned diol compound (b-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or its acid dianhydride (b-2), and a dicarboxylic acid anhydride (b-3) represented by the formula (3), The component (b-4) may be contained in the alkali-soluble resin of the invention.

The component (b-4) contains a dicarboxylic acid or an anhydride thereof, but does not contain the dicarboxylic anhydride (b-3) represented by the formula (3). Specific examples of the dicarboxylic acid include a saturated linear hydrocarbon dicarboxylic acid, a saturated cyclic hydrocarbon dicarboxylic acid, an unsaturated dicarboxylic acid, or a combination of the above compounds.

Specific examples of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, sebacic acid, Citramalic acid, malonic acid, glutaric acid, citric acid, and tartaric acid. , oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid or a combination of the above compounds. The hydrocarbon group in the above saturated linear hydrocarbon dicarboxylic acid may also be substituted.

Specific examples of the saturated cyclic hydrocarbon dicarboxylic acid include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid or A combination of the above compounds. The above saturated cyclic hydrocarbon dicarboxylic acid may also be a saturated hydrocarbon-substituted alicyclic dicarboxylic acid.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl bridged methylenetetrahydrophthalic acid (methyl) Endo-methylene tetrahydrophthalic acid), chlorendic acid, trimellitic acid or a combination of the above compounds.

These dicarboxylic acids preferably include a combination of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid or the above dicarboxylic acid, more preferably These include succinic acid, itaconic acid, tetrahydrophthalic acid or a combination of the above dicarboxylic acids.

The component (b-4) preferably includes a combination of succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic anhydride or the above dicarboxylic anhydride, more preferably These include succinic anhydride, itaconic anhydride, tetrahydrophthalic anhydride or a combination of the above dicarboxylic anhydrides.

The method for synthesizing the first alkali-soluble resin (B-1) is not particularly limited as long as the above-mentioned polymerizable unsaturated group-containing diol compound (b-1), tetracarboxylic acid or acid dianhydride (b-2) thereof It can be obtained by reacting with a dicarboxylic acid anhydride (b-3) represented by the formula (3). For example, a bisphenol fluorene type epoxy (meth) acrylate which is a diol compound (b-1) containing a polymerizable unsaturated group is heated in a solvent such as propylene glycol monomethyl ether acetate to cause The first alkali-soluble resin (B-1) of the present invention can be obtained by reacting a tetracarboxylic acid or its acid dianhydride (b-2) with a dicarboxylic acid anhydride (b-3) represented by the formula (3).

Further, the reaction conditions of the solvent, catalyst, and the like used in the synthesis of the polymerizable unsaturated group-containing diol compound (b-1) and the first alkali-soluble resin (B-1) of the present invention are not particularly limited. However, it is preferred to use a solvent which does not have a hydroxyl group and has a boiling point higher than the reaction temperature as a solvent for the reaction. Preferred specific examples of the solvent include Ethyl cellosolve acetate and 2-butoxyethyl acetate (butyl c) Elosolve acetate), such as a cellosolve solvent; diglyme, Ethylcarbitol acetate, and Butylcarbitol acetate; a high boiling point ether or ester solvent such as Propylene glycol monomethyl ether acetate; a ketone solvent such as cyclohexanone or diisobutyl ketone; or 2-hydroxy-2-methyl Methyl propyl propionate, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 - Ethyl 3-ethoxypr opionate, other ester solvents such as ethyl ethoxyacetate. The above solvent for the polymerization reaction may be used singly or in combination of two or more. Further, specific examples of the catalyst include ammonium salts such as Tetraethylammonium bromide, Benzyltriethylammonium chloride, triphenylphosphine or tris(2,6-di). A catalyst such as a phosphine such as Tris (2,6-dimethoxyphenyl) phosphine. The above catalysts may be used singly or in combination. Further, in order to control the degree of polymerization, an inhibitor is usually added to the reaction solution. Specific examples of the above polymerization inhibitor include methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di- T-butyl-p-cresol), phenothiazine or an analogue thereof. The above polymerization inhibitors can be generally used singly or in combination of two or more.

Further, the diol compound (b-1) containing a polymerizable unsaturated group and the tetracarboxylic acid or its acid dianhydride (b-2), the dicarboxylic acid anhydride (b-3) represented by the formula (3) and/or The method of the reaction of the component (b-4) is not particularly limited. Specifically, for example, as described in Japanese Laid-Open Patent Publication No. Hei 9-325494, the reaction temperature is from 90 ° C to 140 ° C. A known method of reacting an alcohol compound with a tetracarboxylic dianhydride. Preferably, the terminal of the compound is a carboxylic acid group, and the diol compound (b-1) containing a polymerizable unsaturated group, a tetracarboxylic acid or an acid dianhydride (b-2) thereof, The molar ratio of the dicarboxylic anhydride (b-3) and the component (b-4) represented by (3) is (b-1): (b-2): (b-3): (b-4) = ( 1): (0.2 to 1): (0.02 to 1.6): (0 to 0.3) quantitatively reacts these components. Further, preferably, these components are uniformly dissolved and reacted at a reaction temperature of from 90 ° C to 130 ° C, followed by reaction and aging at a reaction temperature of from 40 ° C to 80 ° C.

The first alkali-soluble resin (B-1) is measured by a gel permeation chromatography (GPC) and has a polystyrene-equivalent number average molecular weight of preferably 1,000 or more and 10,000 or less. When the number average molecular weight of the first alkali-soluble resin (B-1) is less than 1,000, there is a possibility that alkali resistance is deteriorated, so that the pattern after alkali development tends to be chipped and the reproducibility of the fine line pattern is remarkably lowered. When the number average molecular weight of the first alkali-soluble resin (B-1) is more than 10,000, the developability is likely to occur after development.

Further, when the photosensitive composition does not contain the first alkali-soluble resin (B-1), the post-baking color difference is large and the high-definition pattern has poor linearity.

Second alkali soluble resin (B-2)

The second alkali-soluble resin (B-2) is obtained by a reaction of the second mixture. The second mixture includes an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. Further, the second mixture may further include a carboxylic anhydride compound, a compound having an epoxy group, or both of the above Combination of compounds.

The epoxy compound having at least two epoxy groups is a compound represented by the formula (4), a compound represented by the formula (5), or a combination of the two.

Specifically, the compound represented by the formula (4) is as follows:

In the formula (4), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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 (4) can be obtained by reacting a bisphenol fluorene with a halogenated propylene oxide (epihalohydrin).

Specific examples of the bisphenol quinone type compound include: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methyl) 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) -9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)anthracene (9, 9-bis(4-hydroxy-3-methoxyphenyl)fluorene), 9,9-bis(4-hydroxy-3,5- 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)anthracene (9, 9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)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. .

Further, specifically, the compound represented by the formula (5) is as follows:

In the formula (5), R ¹² to R ²⁵ 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 (5) can be obtained by reacting a compound represented by the formula (5-1) with a halogenated propylene oxide in the presence of an alkali metal hydroxide.

In the formula (5-1), and are respectively of formula (. 5) R ¹² to R ²⁵ and n are as defined R ¹² and n are as defined to R ^25, here not described herein.

The synthesis method of the compound represented by the formula (5-1) can be as follows: First, in the acid In the presence of a catalyst, a compound represented by the formula (5-2) is subjected to a condensation reaction with a phenol to form a compound represented by the formula (5-1). Next, an excess amount of the halogenated propylene oxide is added to subject the halogenated propylene oxide to a dehydrohalogenation reaction with the compound represented by the formula (5-1) to obtain a compound represented by the formula (5).

In the formula (5-2), the same as the definition of R ¹⁴ to R ¹⁷ defined in formula R (5) is ¹⁴ to R ^17, and this is not described 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 is preferably 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 amount of the compound represented by the above formula (5-2) is 1 mol, and the phenol is used. The class is used in an amount of from 0.5 moles to 20 moles, and preferably from 2 moles to 15 moles.

Specific examples of the acid catalyst include: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, chlorination 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 (5-2) is 100% by weight (% by weight), and the acid catalyst is preferably used in an amount of 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 from 50% by weight to 300% by weight, based on the total weight of the compound represented by the formula (5-2) and the phenol, of 100% by weight, preferably from 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; diethylenetriamine (diethylene triamine), organic amine of triethylenetetramine, aniline, phenylene diamine or the like; ammonia, sodium dihydrogen phosphate or the like A combination of compounds. The above neutralizing agents may be used singly or in combination of two or more. The above water washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction, and carrying out the extraction repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off under reduced pressure and concentrated, whereby the compound represented by the formula (5-1) 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. Then, at a temperature of 20 ° C to 120 ° C, it is allowed to react for 1 hour to 10 Hours to carry out the 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 (5-1). The total equivalent weight of the hydroxyl group in the compound having the structure of the formula (5-1) is 1 equivalent, and the alkali metal hydroxide added in the above dehydrohalogenation reaction is used in an amount of 0.8 to 15 equivalents, and preferably From 0.9 equivalents 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 heating and depressurizing, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

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 equivalent weight of the hydroxyl group in the compound represented by the formula (5-1) is 1 equivalent, and the alkali metal hydroxide The amount of the compound used is from 0.01 mol to 0.3 mol, and preferably from 0.05 mol to 0.2 mol. 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 completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. In addition, a solvent represented by the formula (5) can be obtained by distilling off a solvent such as toluene or methyl isobutyl ketone by heating and pressure reduction. Specific examples of the compound represented by the above formula (5) include those commercially available from Nippon Kayaku, such as NC-3000, NC-3000H, NC-3000S, and NC-3000P.

Specific examples of the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group in the second mixture and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group in the above first mixture (b- The specific examples of 1-ii) are the same, and therefore will not be described again.

The carboxylic anhydride compound in the second mixture includes a tetracarboxylic acid or an acid dianhydride thereof and/or a dicarboxylic acid or an anhydride thereof, wherein a specific example of the tetracarboxylic acid or its acid dianhydride and a component in the above first mixture (b) -2) The specific example of the dicarboxylic acid or its anhydride is the same as the component (b-4) in the above first mixture, and will not be further described herein.

Specific examples of the epoxy group-containing compound in the second mixture include glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, a glycidyl ether compound having an unsaturated group, and an epoxy group. A group of unsaturated compounds or a combination of the above compounds. Specific examples of the glycidyl ether compound having an unsaturated group include the trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171 or Denacol EX- 192 (The above is the product of Changchun Chemical Industry Co., Ltd.).

The second alkali-soluble resin (B-2) may be polymerized by reacting an epoxy compound having at least two epoxy groups in the second mixture with a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group. A reaction product having a hydroxyl group. Next, a carboxylic anhydride compound is further added and the reaction is carried out. The equivalent weight of the acid group based on the above-mentioned reaction product having a hydroxyl group is 1 equivalent, and the equivalent weight of the acid anhydride group contained in the carboxylic anhydride compound is preferably from 0.4 equivalent to 1 equivalent, and more preferably from 0.75 equivalent to 1 equivalent. When a plurality of carboxylic anhydride compounds are used, a carboxylic anhydride compound may be added sequentially or simultaneously in the reaction. Further, the above reaction has an operating temperature in the range of 50 ° C to 130 ° C.

The second alkali-soluble resin (B-2) may also be reacted with an epoxy compound having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a reaction product having a hydroxyl group. Then, a carboxylic anhydride compound and/or a compound having an epoxy group is further added to carry out a polymerization reaction. The acid equivalent of the above compound having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably 0.8 equivalents based on 1 equivalent of the total epoxy group on the epoxy compound having at least two epoxy groups. To 1.5 equivalents, more preferably from 0.9 equivalents to 1.1 equivalents. The total amount of hydroxyl groups based on the above-mentioned reaction product having a hydroxyl group is 100 mol% (mol%), and the carboxylic anhydride compound is used in an amount of 10 mol% to 100 mol%, preferably 20 mol% to 100 mol. Ear %, and more preferably 30 mole % to 100 mole %.

In the preparation of the first alkali-soluble resin (B-1) described above, in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The above reaction Specific examples of the catalyst include triphenyl phosphine, tris(2,6-dimethoxyphenyl)phosphine, triphenyl stibine, Triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride or a combination of the above reaction catalysts. The above reaction catalysts may be used singly or in combination.

Further, in order to control the degree of polymerization, an inhibitor is usually added to the reaction solution. Specific examples of the above polymerization inhibitor include methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di- T-butyl-p-cresol), phenothiazine or an analogue thereof. The above polymerization inhibitors can be generally used singly or in combination of two or more.

In the preparation of the above first alkali-soluble resin (B-1), a solvent for polymerization reaction can be used as necessary. Specific examples of the solvent for the above polymerization include: alcohol compounds of ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, ethylene glycol or the like; methyl ethyl ketone, ring a ketone compound of ketone or an analogue thereof; an aromatic hydrocarbon compound of toluene, xylene or the like; cellosolve of celecin, butyl cellosolve or the like a compound of the formula; a carbitol compound of carbitol, butyl carbazine or the like; a propylene glycol alkyl ether compound of propylene glycol monomethyl ether or the like; dipropylene glycol monomethyl ether (di(propylene glycol) Poly(propylene glycol alkyl ether) compound of methyl ether) or the like; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol Acetate compound of propylene glycol methyl ether acetate, propylene glycol methyl monoether acetate or the like; ethyl lactate, butyl lactate or An alkyl lactate compound of the same; or a dialkyl glycol ether; or methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate, etc. Other esters. The above solvent for the polymerization reaction may be used singly or in combination of two or more. Further, the acid value of the first alkali-soluble resin (B-1) is from 50 mgKOH/g to 200 mgKOH/g, preferably from 60 mgKOH/g to 180 mgKOH/g.

The second alkali-soluble resin (B-2) is preferably manufactured by Nippon Steel Chemical Co., Ltd. under the name of V259ME or V301ME.

The photosensitive resin composition preferably has a high-precision pattern collimation property by including the second alkali-soluble resin (B-2).

Further, when the alkali-soluble resin (B) contains both the first alkali-soluble resin (B-1) and the second alkali-soluble resin (B-2), the first alkali-soluble resin (B-1) and the second alkali-soluble resin The weight ratio of (B-2) is 10:90 or more and less than 100:0. At this time, the high-precision pattern collimation property obtained from the photosensitive resin composition is more preferable.

Other alkali soluble resin (B-3)

The alkali-soluble resin (B) may more preferably include other alkali-soluble resins (B-3). The other alkali-soluble resin (B-3) is the first alkali-soluble resin (B-1) and the second alkali A resin other than the soluble resin (B-2), but is not limited to a resin having a carboxylic acid group or a hydroxyl group. Specific examples of the other alkali-soluble resin (B-3) include resins such as an acrylic resin, a urethane resin, or a novolac resin.

Compound containing ethylenically unsaturated group (C)

The ethylenically unsaturated group-containing compound (C) includes the first compound (C-1), the second compound (C-2), the third compound (C-3) or a combination of the above compounds.

First compound (C-1)

The first compound (C-1) is selected from the group consisting of a compound represented by the formula (6), a compound represented by the formula (7), and a compound represented by the formula (8):

In the formulae (6) to (8), R ²⁶ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ²⁷ each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ²⁸ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 1 to 6 carbon atoms; in the formula (6), an acryloyl group and a methacryloyl group The total amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (7) is 3 or 4; in the formula (8), 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 0 to 10 An integer, and the sum of each r is 3 to 30; and x represents an integer of 0 to 3.

In the formula (6), the formula (7) or the formula (8), -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)- of R ²⁶ is preferably an end on the oxygen atom side. Bond to R ²⁷ .

In the formula (6), all of the six R ^{27 are} preferably an allyl group.

The compound represented by the formula (6) or the compound represented by the formula (7) 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 (6) and the compound represented by the formula (7) are more preferably a pentaerythritol derivative, a dipentaerythritol derivative or a combination of the two.

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

Specific examples of the compound represented by the formula (7) include a compound represented by the formula (7-1), a compound represented by the formula (7-2), Ethoxylated Pentaerythritol tetraacrylate or propoxy oxygen. Propoxylated Pentaerythritol tetraacrylate. In the formula (7-1), the sum of each k is 4. The sum of k in the formula (7-2) is 12. The compound represented by the formula (7) 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 (8) include Ethoxylated Trimethylolpropane triacrylate, Ethoxylated Trimethylolpropane trimethacrylate, Propoxylated Trimethylolpropane Triacrylate, Propoxylated Glyceryl triacrylate. The compound represented by the formula (8) 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 (above, manufactured by Toyo Chemical Co., Ltd.) or a combination of the above compounds.

The first compound (C-1) may be used in an amount of 5 parts by weight to 60 parts by weight, preferably 8 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B), and more preferably It is 10 parts by weight to 40 parts by weight.

When the first compound (C-1) is contained in the ethylenically unsaturated group-containing compound (C), the high-definition pattern linearity of the photosensitive resin composition is preferable.

Second compound (C-2)

The second compound (C-2) may be a compound represented by the formula (9):

In the formula (9), R ²⁹ and R ³⁰ 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 second compound (C-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. Above The polyfunctional alcohol 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 (C-2) include pentaerythritol caprolactone-modified tetra(meth)acrylate compound, ditrimethylolpropane caprolactone-modified tetra(meth)acrylate compound A poly(meth) acrylate compound modified with 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 (C-2) is, for example, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

The second compound (C-2) may be used in an amount of 5 parts by weight to 60 parts by weight, preferably 8 parts by weight to 50 parts by weight, and more preferably 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (B). Parts to 40 parts by weight.

When the second compound (C-2) is contained in the ethylenically unsaturated group-containing compound (C), the high-definition pattern linearity of the photosensitive resin composition is preferable.

Third compound (C-3)

The third compound (C-3) has a functional group represented by the formula (10).

In the formula (10), R ³¹ represents hydrogen or a methyl group.

Specific examples of the third compound (C-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) propyl Acid phenoxyethyl ester, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, ( Methyl acrylate 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 Acrylic acid Ester, trimethylolpropyl tri(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate, Pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate , dipentaerythritol tetra(meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(A) Acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylic acid Ester, phenolic polyglycidyl ether (meth) acrylate or a combination of the above compounds.

The third compound (C-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 ethylenically unsaturated group-containing compound (C) may be used in an amount of 40 parts by weight to 400 parts by weight, preferably 50 parts by weight to 350 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). More preferably, it is 60 parts by weight to 300 parts by weight.

Photoinitiator (D)

The photoinitiator (D) is, for example, an acetophenone, a biimidazole, an acyl oxime or the above compound a combination of things.

Specific examples of the acetophenone-based compound include p-dimethylamine acetophenone (p-dimethylamino-acetophenone), α,α'-dimethoxy azo acetophenone (α,α'-dimethoxyazoxy-acetophenone), 2,2'-dimethyl-2-phenylacetophenone (2,2'-dimethyl-2-phenyl-acetophenone), p-methoxy-acetophenone, 2-methyl-1-(4-methylthiophenyl)-2- Morpholino-1-propanone [2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone], 2-benzyl-2-nitrogen, nitrogen-dimethylamine-1-(4-? A combination of the above compounds. 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

Specific examples of the diimidazole-based compound include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-chlorophenyl)- 4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole [2,2'-bis (o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Imidazole [2,2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl)-4,4' ,5,5'-o-methoxyphenyl-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-ethyl Phenyl)-4,4',5,5'-tetraphenyl-biimidazole [2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2 '-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(p-methoxyphenyl)-4,4',5,5'- Tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2-chlorobenzene 4,4',5,5'-tetraphenyl-imimidazole [2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2' - bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4-dichlorophenyl)-4,4',5, 5'-tetraphenyl-biimidazole] or a combination of the above compounds.

Specific examples of the lanthanoid compound include ethane ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9-hydro-oxazol-3- substituent]-, 1-(oxygen) -Ethrone, [Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as CGI- manufactured by Ciba Specialty Chemicals 242, the structure of which is represented by formula (11)], 1-(4-(phenylthio)phenyl)-octane-1,2-dione 2-indole-oxy-benzoate [1- (4-phenyl-thio-phenyl)-octane-1,2-dion-2-oxime-O-benzoate, such as CGI-124 manufactured by Ciba Specialty Chemicals, the structure of which is represented by formula (12)], ethane ketone ,1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzhydryl)-9hydro-oxazol-3-substituted]-, 1-(oxy-B醯肟)[Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), by Asahi Manufactured by an electrochemical company, the structure of which is represented by formula (13)] or a combination of the above compounds.

The photoinitiator (D) is preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholine. 1-acetone, 2-benzyl-2-nitrogen, nitrogen-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetraphenyldiimidazole, ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9hydro-carbazole-3 a substituent]-, 1-(oxy-acetamidine) or a combination of the above compounds.

The photoinitiator (D) may further be further added with the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone-4-indole (thioxanthone-4-sulfone), benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double a benzophenone-based compound such as (diethylamine) benzophenone [4,4'-bis(diethylamino)benzophenone]; an α -diketone such as benzil or acetyl ( α- diketone); benzoin and other acyloin; benzoin methylether, benzoin ethylether, benzophenone isopropyl a acyloin ether such as benzoin isopropyl ether; 2,4,6-trimethyl-benzoyl-diphenyl-phosphine oxide, double -(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl -phosphineoxide] acylphosphine oxides; anthraquinone, 1,4-naphthyl (1,4-naphth) Oquinone) quinone class; phenacyl chloride, tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine [tris(trichloromethyl)-s -triazine] a halide such as a halide; a di-tertbutylperoxide; or a combination of the above compounds. The compound to be added to the photoinitiator (D) is preferably a benzophenone-based compound, and more preferably 4,4'-bis(diethylamine)benzophenone.

The photoinitiator (D) may be used in an amount of 10 parts by weight to 100 parts by weight, preferably 12 parts by weight to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B), and more preferably It is preferably from 15 parts by weight to 60 parts by weight.

Organic solvent (E)

The organic solvent (E) means that the pigment (A), the alkali-soluble resin (B), the ethylenically unsaturated group-containing compound (C), and the photoinitiator (D) can be dissolved without reacting with the above components. An organic solvent, and preferably one having a suitable volatility.

The organic solvent (E) is, for example, a (poly)alkylene glycol monoalkyl ether, a (poly)alkylene glycol monoalkyl ether acetate, other ethers, a ketone, an alkyl lactate, and others. An ester, an aromatic hydrocarbon, a carboxylic acid amide or a combination of the above solvents.

Specific examples of the (poly)alkylene glycol monoalkyl ethers include 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 Propylene glycol methyl ether, tripropylene glycol diethyl ether or a combination of the above solvents.

Specific examples of the (poly)alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Propylene glycol A combination of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or the above solvents.

Specific examples of the other ethers include diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or a combination of the above solvents.

Specific examples of the ketone include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or a combination of the above solvents.

Specific examples of the alkyl lactate include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate or a combination of the above solvents.

Specific examples of other esters include methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, and 3-methoxypropionic acid. Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP), ethyl ethoxyacetate, ethyl hydroxyacetate, 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 Ester, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate Ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxybutyrate or a combination of the above solvents.

Specific examples of the aromatic hydrocarbons include toluene, xylene or a combination of the above solvents.

Specific examples of the carboxylic acid amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or a combination of the above solvents.

The organic solvent (E) is preferably propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate or a combination of the above solvents. The above organic solvent (E) may be used singly or in combination of two or more.

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 (B), 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 surfactant, a filler, a polymer (refer to a polymer other than the above-described alkali-soluble resin (B)), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.

The surfactant helps to improve the coatability of the photosensitive resin composition. The surfactant is, for example, polyethylene oxide alkyl ether such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; polyethylene oxide octane Polyethylene oxide alkyl phenyl ethers such as phenylene ether and polyethylene oxide decyl phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate Classes; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; KP products manufactured by Shin-Etsu Chemical Co., Ltd., by Dow Corning SF-8427 manufactured by Toray Co., Ltd., a Polyflow product manufactured by Kyoritsu Oil & Fat Chemical Industry, manufactured by Tochem Products Co., Ltd. F-Top products, by the big day Megafac products manufactured by the Ink Chemical Industry, Fluorade products manufactured by Sumitomo 3M, Asahi Guard products manufactured by Asahi Glass, or Safir manufactured by Asahi Glass Co., Ltd. Surflon products.

Specific examples of the filler include glass, 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-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 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 amount of the alkali-soluble resin (B) used is 100 parts by weight, the additive (F) The amount used is from 1 part by weight to 10 parts by weight, preferably from 1.5 parts by weight to 8 parts by weight, and more preferably from 2 parts by weight to 6 parts by weight.

<Preparation Method of Photosensitive Resin Composition for Color Filter>

A method which can be used for preparing a photosensitive resin composition, for example, a pigment (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (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 photosensitive resin composition is prepared by, for example, dispersing a part of the alkali-soluble resin (B) and the ethylenically unsaturated group-containing compound (C) in a part of the organic solvent (E) to form a dispersion solution; and then The remaining pigment (A), the alkali-soluble resin (B), the ethylenically unsaturated group-containing compound (C), the photoinitiator (D), and the organic solvent (E) are mixed.

Alternatively, the photosensitive resin composition may be formed by first dispersing a part of the pigment (A) in a mixture of the partially alkali-soluble resin (B) and a part of the organic solvent (E) to form a pigment dispersion; (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (C), a photoinitiator (D), and an 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 drying under reduced pressure is carried out at a pressure of from 0 mmHg to 200 mmHg for from 1 second to 60 seconds, and the prebaking is performed by heating the coating film at a temperature of from 70 ° C to 110 ° C for from 1 minute to 15 minutes.

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 pre-baked film is immersed at a temperature of 23 ± 2 ° C The stain is applied to the developer to remove unnecessary portions 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 is performed by a heating device such as a hot plate or an oven. The post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time using the oven is from 15 minutes to 150 minutes. After the above-described processing steps, a specific pattern can be fixed, 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 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 finally the injection hole is sealed to form a liquid crystal layer. Subsequently, a liquid crystal display is fabricated by providing a polarizing plate on the other side of the color filter that contacts the liquid crystal layer and the other side of the substrate that contacts the liquid crystal layer. 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.

Preparation example of diol compound (b-1) containing a polymerizable unsaturated group

Hereinafter, Preparation Examples 1 to 6 of the diol compound (b-1) containing a polymerizable unsaturated group will be described:

Preparation Example 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 are added in a continuous manner to 500 ml In a 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, the light yellow transparent mixed solution is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound of Preparation Example 1 having a solid content of 99.9% by weight (b-1- 1).

Preparation Example 2

First, 100 parts by weight of an oxime epoxy compound (Model PG-100, manufactured by Osaka Gas; epoxy equivalent 259), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight A portion of 2,6-di-t-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition 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 content of 50% by weight was obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (b-1-2) of Preparation Example 2 having a solid content of 99.9% by weight. .

Preparation Example 3

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 100 parts by weight of 2-methylpropenyl ethoxy succinate, 0.3 parts by weight of chlorine Benzyltriethylammonium, 0.1 parts by weight of 2,6-di third Butyl p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition 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 content of 50% by weight was obtained. The light yellow transparent mixed liquid was subjected to a step of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (b-1-3) of Preparation Example 3 having a solid content of 99.9% by weight.

Preparation Example 4

First, 0.3 mol of bis(4-hydroxyphenyl)phosphonium, 9 mol of 3-chloro-1,2-epoxypropane was added to a 1000 ml three-necked flask equipped with mechanical stirring, a thermometer and a reflux condenser. And 0.003 mol of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Then, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (30 wt% aqueous solution formed in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Next, the reaction solution was washed with water repeatedly until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain an bis(4-hydroxyphenyl)fluorene epoxy compound.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)fluorene (epoxy equivalent 181), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 part by weight of 2, 6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether Acetate was added to a 500 ml four-necked flask in a continuous addition. 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 content of 50% by weight was obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (b-1-4) of Preparation Example 4 having a solid content of 99.9% by weight. .

Preparation Example 5

Add 0.3 mol of bis(4-hydroxyphenyl)hexafluoropropane, 9 mol of 3-chloro-1,2-epoxypropane and a 1000 ml three-necked flask equipped with mechanical stirring, thermometer and reflux condenser. 0.003 mole of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Next, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (30 wt% aqueous solution formed in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Next, the reaction solution was washed with water repeatedly until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)hexafluoropropane.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)hexafluoropropane (epoxy equivalent 224), 35 parts by weight of methacrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 weight a portion of 2,6-di-t-butyl-p-cresol and 135 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition to a 500 ml four-necked flask. in. 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 content of 50% by weight was obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (b-1-5) of Preparation Example 5 having a solid content of 99.9% by weight. .

Preparation Example 6

Add 0.3 mol of bis(4-hydroxyphenyl)dimethyl decane, 9 mol of 3-chloro-1,2-epoxypropane to a 1000 ml three-necked flask equipped with mechanical stirring, thermometer and reflux condenser. And 0.003 mol of tetramethylammonium chloride. Subsequently, the mixture was heated to 105 ° C while stirring, and reacted at 105 ° C for 9 hours. Next, unreacted 3-chloro-1,2-epoxypropane was distilled off under reduced pressure. Thereafter, the reaction system was cooled to room temperature, and 9 mol of benzene and 0.5 mol of sodium hydroxide (30 wt% aqueous solution formed in water) were added with stirring. Then, the temperature was raised to 60 ° C and maintained for 3 hours. Next, the reaction solution was washed with water repeatedly until there was no chloride ion (checked with silver nitrate). The solvent benzene was distilled off under reduced pressure, and then dried at 75 ° C for 24 hours to obtain an epoxy compound of bis(4-hydroxyphenyl)dimethyl decane.

100 parts by weight of an epoxy compound of bis(4-hydroxyphenyl)dimethyl decane (epoxy equivalent 278), 100 parts by weight of 2-methylpropenyl ethoxy succinate, 0.3 parts by weight Benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 200 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous addition to a 500 ml four-necked flask. The feed rate is controlled at 25 parts by weight per minute, and the reverse The temperature of the process was maintained at 100 ° C to 110 ° C for 15 hours, and a pale yellow transparent mixture having a solid content of 50% by weight was obtained. The light yellow transparent mixed liquid is subjected to the steps of extraction, filtration, and heat drying to obtain a polymerizable unsaturated group-containing diol compound (b-1-6) having a solid content of 99.9% by weight. .

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

Synthesis Example 1 to Synthesis Example 10 of the first alkali-soluble resin (B-1) will be described below:

Synthesis Example 1

1.0 mol of the polymerizable unsaturated group-containing diol compound (b-1), 1.9 g of benzyltriethylammonium chloride, and 0.6 g of 2,6-di-t-butyl-p-cresol were dissolved. 900 g of ethylene glycol ethyl ether acetate, and simultaneously added 0.2 mol of 3,3',4,4'-biphenyltetracarboxylic dianhydride (b-2-1) and 1.6 mol of trimethoxy Based on alkyl propyl succinic anhydride (b-3-1) (added simultaneously; here, "simultaneous addition" means adding 3,3',4,4'-biphenyltetracarboxylic acid at the same reaction time The dianhydride (b-2-1) and trimethoxydecyl propyl succinic anhydride (b-3-1) are formed to form a reaction solution. Next, the reaction solution was heated to 110 ° C and reacted for 2 hours to obtain a first alkali-soluble resin of Synthesis Example 1 having an acid value of 100 mg KOH/g and a number average molecular weight of 1566 (hereinafter referred to as first alkali solubility) Resin B-1-1).

Synthesis Example 2

1.0 mol of a polymerizable unsaturated group-containing diol compound (b-1-2), 2.0 g of triphenylphosphine, 0.7 g of methoxyphenol, dissolved in 900 g of ethylene glycol ethyl ether acetate In the ester. Next, 0.3 mol of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (b-2-2) was added and reacted at 90 ° C for 2 hours. Then, 1.4 mol of triethoxydecyl propyl succinic anhydride (b-3-2) was added and reacted at 90 ° C for 4 hours (segmented addition method; here, "segmented addition" means Add 3,3',4,4'-benzophenonetetracarboxylic dianhydride (b-2-2) and triethoxydecylpropyl succinic anhydride (b-3-) at different reaction times 2)), that is, first adding 3,3',4,4'-benzophenonetetracarboxylic dianhydride (b-2-2), followed by adding triethoxysulfonylpropyl succinic anhydride ( B-3-2). Thus, a first alkali-soluble resin (hereinafter referred to as a first alkali-soluble resin B-1-2) of Synthesis Example 8 having an acid value of 90 mg KOH/g and a number average molecular weight of 1981 was obtained.

Synthesis Example 3 to Synthesis Example 10

The first alkali-soluble resin of Synthesis Example 3 to Synthesis Example 10 was prepared in the same manner as in Synthesis Example 2, and was different in that the composition of the first alkali-soluble resin and the amount thereof, the reaction time, and the reaction temperature were changed. And the reactant addition time (as shown in Table 1), wherein the compounds corresponding to the labels in Table 1 are as follows.

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

Synthesis Example 11 to Synthesis Example 13 of the second alkali-soluble resin (B-2) will be described below:

Synthesis Example 11

1.0 mol of the polymerizable unsaturated group-containing diol compound (b-1), 1.9 g of benzyltriethylammonium chloride, and 0.6 g of 2,6-di-t-butyl-p-cresol were dissolved. 700 grams of ethylene glycol ethyl ether acetate, and simultaneously added 0.3 moles of 3,3',4,4'-biphenyltetracarboxylic dianhydride (b-2-1) and 1.4 moles of dibutyl Anhydride (b-4-1). Subsequently, the mixture was heated to 110 ° C and reacted for 2 hours to obtain a second alkali-soluble resin of Synthesis Example 11 having an acid value of 130 mg KOH/g and a number average molecular weight of 1888 (hereinafter referred to as a second alkali-soluble resin B-2). -1).

Synthesis Example 12 to Synthesis Example 13

The second alkali-soluble resin of Synthesis Example 12 to Synthesis Example 13 was prepared in the same manner as in Synthesis Example 17, and was distinguished by changing the kind of the component of the second alkali-soluble resin and the amount thereof, the reaction time, and the reaction temperature. And the reactant addition time (as shown in Table 2).

Synthesis Example 14

An equivalent reaction product of 198.53 g of bisphenol fluorene type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution, solid content concentration: 50% by weight, and acid value in terms of solid content: 1.28 mg KOH/g 50% by weight of propylene glycol monomethyl ether acetate solution having an epoxy equivalent of 21,300), 24.15 g of benzophenone tetracarboxylic dianhydride, 8.13 g of succinic anhydride, 48.12 g of propylene glycol monomethyl ether acetate, and 0.45 a gram of triphenylphosphine added to a 500 ml four-necked flask with a reflux condenser in. Next, the mixture was heated and stirred at 120 ° C to 125 ° C for 1 hour. Then, the mixture was stirred under heating at 75 ° C to 80 ° C for 6 hours. Thereafter, 7.14 g of 3-glycidoxypropyltrimethoxydecane was added and stirred at 80 ° C for 8 hours to synthesize a second alkali-soluble resin (B-2-4). The solid content of the obtained resin solution was 53.2% by weight, and the acid value (in terms of solid content) was 110 mgKOH/g. The area % of the second alkali-soluble resin (B-2-4) in the resin solution analyzed by GPC was 91%, and the number average molecular weight was 6621.

Example of photosensitive resin

Hereinafter, Examples 1 to 10 and Comparative Examples 1 to 7 of the photosensitive resin will be described:

Example 1

40 parts by weight of the first pigment (A-1) represented by the above formula (1) (hereinafter abbreviated as A-1), 100 parts by weight of the first alkali-soluble resin (B-1-1), and 40 parts by weight KAYARAD TPA-330 (manufactured by Nippon Kayaku Co., Ltd.; hereinafter referred to as C-1-2), 5 parts by weight of 2-methyl-1-(4-methylthiophenyl)-2-morpholine 1-acetone (hereinafter abbreviated as D-1), 10 parts by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (hereinafter referred to as D-2), 5 parts by weight of 4,4'-bis(diethylamine)benzophenone (hereinafter abbreviated as D-3) and 1 part by weight of sodium polyacrylate (hereinafter referred to as F-) 1) 500 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as E-1), and shake-type After the stirring 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 3.

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 distinguished by changing the kinds of components of the photosensitive resin composition and the amounts thereof used (as shown in Table 3). ), wherein the compounds corresponding to the labels in Table 3 are as follows. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 3.

Comparative Example 1 to Comparative Example 7

The photosensitive resin compositions of Comparative Examples 1 to 7 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 4). ), wherein the compounds corresponding to the labels in Table 4 are as follows. The obtained photosensitive resin composition was evaluated by the following evaluation methods, and the results are shown in Table 4.

Evaluation method 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 polarizing plate 120 and the polarization direction of the second polarizing plate 130 are projected on the same plane, the polarization direction of the first polarizing plate 120 is parallel to the polarizing of the second polarizing plate 130. Direction (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. When in one plane, 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 (14), and evaluated based on the following criteria.

◎: 1500 ≦ contrast

○: 1200 ≦ contrast <1500

△: 900 ≦ contrast <1200

×: contrast <900

Post-bake color difference

The photosensitive resin composition was applied by spin coating on a glass substrate having a length and a width of 100 mm. At about 100 mm Hg (mmHg) The pressure was dried under reduced pressure for about 30 seconds. Next, the above glass substrate was prebaked at 80 ° C for 2 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 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. Next, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model MCPD). Then, after baking at 235 ° C for 30 minutes, a photosensitive resin layer having a film thickness of 2.0 μm was formed on the glass substrate. Next, the chromaticity was measured again. The chromaticity change after baking and before baking was defined by the formula (15) as the post-baking color difference, and the baking color difference ΔEab* was evaluated according to the following criteria.

△Eab*=[(ΔL) ² +(Δa) ² +(△b) ² ] ^1/2 (15)

◎: post-bake color difference △Eab*<2

○: 2 ≦ after baking color difference △ Eab * < 4

△: 4 ≦ after baking color difference △ Eab * < 6

×: 6≦ baked color difference △Eab*

High definition pattern linearity

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. Next, using a photomask having a strip pattern of 25 μm width (pitch 50 μm), an exposure machine (manufactured by Canon, model: PLA-501F) was used at 300 mJ/cm ² (mJ/cm ² ). The ultraviolet light illuminates the above pre-baked coating film. 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 strip pattern formed by the above method was observed by an optical microscope, and the high definition pattern linearity was evaluated in accordance with the following criteria.

☆: More than 90% of the strip patterns have good linearity

◎: 80% or more, less than 90% of the strip pattern has good linearity

○: 70% or more, less than 80% of the strip pattern has good linearity

△: 60% or more, less than 70% of the strip pattern has good linearity

×: less than 60% of the strip pattern has good linearity

<evaluation result>

Table 3 and Table 4 show that the photosensitive resin composition containing the first pigment (A-1) (Examples 1 to 10) and the photosensitive resin composition not containing the first pigment (A-1) (Comparative Example 1, Comparative Example 6, and Comparative Example 7) contain the first The photosensitive resin composition of the 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 2 and the comparative example 3).

Further, a photosensitive resin composition containing the first alkali-soluble resin (B-1) (Examples 1 to 10) and a photosensitive resin composition containing only the second alkali-soluble resin (B-2) (Comparative Example) 2 to Comparative Example 7), the photosensitive resin composition containing the first alkali-soluble resin (B-1) had a small baking color difference and a high definition pattern linearity.

Further, a photosensitive resin composition containing the second alkali-soluble resin (B-2) (Examples 6 to 8) and a photosensitive resin composition containing only the first alkali-soluble resin (B-1) (implementation) In the examples 1 to 5, the examples 9, the examples 10 and the comparative example 1), the high-definition pattern linearity of the photosensitive resin composition containing the second alkali-soluble resin (B-2) is preferable.

Further, the photosensitive resin composition containing the first compound (C-1) (Example 1, Example 3, and Example 4) and the photosensitive resin composition not containing the first compound (C-1) (Example) 2. High-definition pattern of the photosensitive resin composition containing the first compound (C-1) as compared with Example 5 to Example 10, Comparative Example 3, Comparative Example 5, Comparative Example 6, and Comparative Example 7) Straightness is preferred.

Further, the photosensitive resin composition containing the second compound (C-2) (Examples 2 to 5) and the photosensitive resin composition not containing the second compound (C-2) (Example 1, Example 6 to Example 10, Comparative Example 2, Comparative Example 4, Comparative Example 6, and Comparative Example 7) High-definition of the photosensitive resin composition containing the second compound (C-2) The degree of linearity of the pattern is better.

Further, the photosensitive resin composition in which the molar ratio (b-2)/(b-1) of the component (b-1) and the component (b-2) in the alkali-soluble resin falls within 0.2 to 1.0 (Example) 1 to 8) A photosensitive resin composition having a molar ratio (b-2)/(b-1) of the component (b-1) and the component (b-2) in the alkali-soluble resin of 0.15 (implemented) In the case of Example 9), the high-definition pattern linearity of the photosensitive resin compositions of Examples 1 to 8 is preferable.

Further, the photosensitive resin composition in which the molar ratio (b-3)/(b-1) of the component (b-1) and the component (b-3) in the alkali-soluble resin falls between 0.02 and 1.6 (Example 1) Example 8) A photosensitive resin composition having a molar ratio (b-3)/(b-1) of 0.01 to the component (b-1) and the component (b-3) in the alkali-soluble resin (Example) 10) The high-definition pattern linearity of the photosensitive resin compositions of Examples 1 to 8 is preferable.

As described above, since the photosensitive resin composition of the present invention contains a specific pigment and a specific alkali-soluble resin, it has the characteristics of good contrast, small post-baking chromatic aberration, and high-definition pattern linearity, and thus is suitable for use. Color filter and liquid crystal display device.

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 (17)

A photosensitive resin composition for a color filter comprising: a pigment (A); an alkali-soluble resin (B); an ethylenically unsaturated group-containing compound (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 alkali-soluble resin (B) includes a first alkali-soluble resin (B-1) represented by the formula (2); In the formula (2), A represents a phenyl group or a substituted phenyl group having a substituent, wherein the substituent is an alkyl group having a carbon number of 1 to 5, a halogen atom or a phenyl group; and B represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, 9,9-indenylene or a single bond; L represents a tetravalent carboxylic acid residue; Y ¹ represents a trivalent organic group having a carbon number of 1 to 20; and R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group; and R ⁴ represents hydrogen. Atom or methyl; and m represents an integer from 1 to 20. The photosensitive resin composition for color filters according to claim 1, wherein the first alkali-soluble resin (B-1) is obtained by reacting the first mixture, and the first mixture includes a diol compound (b-1) containing a polymerizable unsaturated group; a tetracarboxylic acid or an acid dianhydride thereof (b-2); and a dicarboxylic acid anhydride (b-3) represented by the formula (3), In the formula (3), Y ² represents a trivalent organic group having a carbon number of 1 to 20; and R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group. The photosensitive resin composition for color filters according to the second aspect of the invention, wherein the polymerizable unsaturated group-containing diol compound (b-1) and the tetracarboxylic acid or acid dianhydride thereof The molar ratio (b-2)/(b-1) of (b-2) is 0.2 to 1.0. The photosensitive resin composition for color filters according to the second aspect of the invention, wherein the polymerizable unsaturated group-containing diol compound (b-1) and the two represented by the formula (3) The molar ratio (b-3)/(b-1) of the carboxylic anhydride (b-3) is 0.02 to 1.6. The photosensitive resin composition for color filters according to claim 1, wherein the alkali-soluble resin (B) further comprises a second alkali-soluble other than the first alkali-soluble resin (B-1) Resin (B-2), and the second alkali-soluble resin (B-2) is obtained by a reaction of a second mixture, wherein the second mixture comprises: an epoxy compound having at least two epoxy groups; and having at least one carboxylic acid group and at least one ethylenically unsaturated group Compound. The photosensitive resin composition for color filters according to claim 5, wherein the epoxy compound having at least two epoxy groups includes a compound represented by the formula (4), and the formula (5) a compound represented or a combination of the two, In the formula (4), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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 (5), R ¹² to R ²⁵ 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 weight of the first alkali-soluble resin (B-1) and the second alkali-soluble resin (B-2) The ratio is 10:90 or more and less than 100:0. Photosensitive resin group for color filters as described in claim 1 An article wherein the amount of the pigment (A) used is from 60 parts by weight to 600 parts by weight based on 100 parts by weight of the alkali-soluble resin (B), the first pigment (A-1) The amount of the ethylenically unsaturated group-containing compound (C) used is 40 parts by weight to 400 parts by weight, and the photoinitiator (D) is used in an amount of 10 parts by weight to 400 parts by weight. The parts by weight to 100 parts by weight, and the organic solvent (E) is used in an amount of from 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 comprises 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 9, wherein the second pigment (A-2) is used based on 100 parts by weight of the alkali-soluble resin (B). The amount used is from 20 parts by weight to 200 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated group-containing compound (C) comprises a first compound (C-1), and the first The compound (C-1) is selected from the group consisting of a compound represented by the formula (6), a compound represented by the formula (7), and a compound represented by the formula (8). In the formulae (6) to (8), R ²⁶ each independently represents -(CH ₂ CH ₂ O)- or -(CH ₂ CH(CH ₃ )O)-; and R ²⁷ each independently represents an acryloyl group or a methyl group. a propylene fluorenyl group or a hydrogen atom; each of R ²⁸ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 1 to 6 carbon atoms; in the formula (6), an acryloyl group and a methacryloyl group The total amount of the propylene sulfhydryl group and the methacryl fluorenyl group in the formula (7) is 3 or 4; in the formula (8), 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 0 to 10 An integer, and the sum of each r is 3 to 30; and x represents an integer of 0 to 3. The photosensitive resin composition for color filters according to claim 11, wherein the amount of the first compound (C-1) is 100 parts by weight based on the amount of the alkali-soluble resin (B) used. The amount used is from 5 parts by weight to 60 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated group-containing compound (C) comprises a second compound (C-2), and the second The compound (C-2) is a compound represented by the formula (9). In the formula (9), R ²⁹ and R ³⁰ 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 color filters according to claim 13, wherein the second compound (C-2) is used based on 100 parts by weight of the alkali-soluble resin (B). The amount used is from 5 parts by weight to 60 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 fourteenth aspects of the invention. A color filter produced by the manufacturing method described in claim 15 of the patent application. A liquid crystal display device comprising the color filter of claim 16 of the patent application.