TW201814401A - Photosensitive resin composition and uses thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, and a color filter and a liquid crystal display device manufactured using said photosensitive resin composition. The photosensitive resin composition includes a pigment (A), an alkali-soluble resin (B), a compound including an unsaturated ethylenically group (C), a photoinitiator (D), a compound (E) selected from the group consisting of a thermal acid generator and a thermal base generator, and a solvent (F). The color filter formed by the photosensitive resin composition has the advantage of improved sputtering resistance.

Description

Photosensitive resin composition and application thereof

The present invention relates to a photosensitive resin composition, and a color filter and a liquid crystal display device produced by using the photosensitive resin composition; in particular, a photosensitive resin composition provided by the photosensitive resin composition The color filter obtained has the advantage of excellent splash resistance.

At present, color filters have been widely used in the fields of color liquid crystal display devices, color facsimile machines, color cameras, and the like. As the market demand is expanding, the production technology of color filters is also diversified. At present, dyeing methods, printing methods, electroplating methods, and dispersion methods have been developed, among which the dispersion method is the mainstream process.

In the dispersion method, the coloring pigment is first dispersed in a photosensitive resin, and the photosensitive resin is applied onto a glass substrate, and a specific pattern can be obtained by exposure, development, and the like. By repeating the operation three times, a pattern of red, green, and blue pixel-colored layers can be obtained, and then a protective film can be applied to the pattern of the pixel-colored layer as needed.

Japanese Laid-Open Patent Publication No. 2001-075273 discloses a photosensitive resin composition comprising a polymer obtained by polymerizing an unsaturated monomer of a carboxylic acid group and a monomer containing a glycidyl group as an alkali solubility of a photosensitive resin. Resin. However, in the sputtering forming process of the subsequent transparent conductive film, the color filter obtained by using the photosensitive resin composition of the prior art described above has a problem of poor sputtering resistance, especially the pixel coloring layer is After being subjected to the sputtering process of a strong electron beam, problems such as chromaticity loss are liable to occur.

In view of the above, there is a need to develop a photosensitive resin composition to overcome the problem of poor sputtering resistance of a conventional photosensitive resin composition.

In the present invention, a photosensitive resin composition excellent in sputter resistance is obtained by using a special alkali-soluble resin in combination with the remaining components.

Accordingly, the present invention provides a photosensitive resin composition comprising: a pigment (A); an alkali-soluble resin (B); an ethylenically unsaturated group-containing compound (C); a photoinitiator (D); a compound (E) And a solvent (F); wherein: the alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1) having a formula (I-1) The structure shown and/or the structure shown in the formula (I-2): Formula (I-1) In the formula (I-1): D represents a hydrogen atom, a glycidyl group or a structure as shown in the formula (I-1-1), wherein at least one D represents a formula (I-1-). 1) the structure shown, and at least two D represent glycidyl groups; a represents an integer from 1 to 100; In the formula (I-1-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer up to 3; and d represents an integer from 1 to 10; Formula (I-2) In the formula (I-2): D' represents a hydrogen atom, a glycidyl group or a structure represented by the following formula (I-2-1), wherein at least one D' represents a formula (I-2) -1) the structure shown, and at least two D' represent a glycidyl group; AO represents an alkylene group having a carbon number of 2 to 6; f represents an integer of 4 to 10; g represents an integer of 0 to 10; Represents an integer from 0 to 10; and i represents an integer from 0 to 10: In the formula (I-2-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer of from 3; and d represents an integer from 1 to 10; and the compound (E) is selected from the group consisting of a thermal acid generator and a thermal base generator.

The present invention further provides a method of producing a color filter, which comprises forming a pixel layer using the photosensitive resin composition described above.

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

The present invention further provides a liquid crystal display device comprising the aforementioned color filter.

The present invention provides a photosensitive resin composition comprising: a pigment (A); an alkali-soluble resin (B); an ethylenically unsaturated group-containing compound (C); a photoinitiator (D); a compound (E); And a solvent (F); wherein: the alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1) having a formula (I-1) Structure and / or structure shown in formula (I-2): Formula (I-1) In the formula (I-1): D represents a hydrogen atom, a glycidyl group or a structure as shown in the formula (I-1-1), wherein at least one D represents a formula (I-1-). 1) the structure shown, and at least two D represent glycidyl groups; a represents an integer from 1 to 100; In the formula (I-1-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer up to 3; and d represents an integer from 1 to 10; Formula (I-2) In the formula (I-2): D' represents a hydrogen atom, a glycidyl group or a structure represented by the following formula (I-2-1), wherein at least one D' represents a formula (I-2) -1) the structure shown, and at least two D' represent a glycidyl group; AO represents an alkylene group having a carbon number of 2 to 6; f represents an integer of 4 to 10; g represents an integer of 0 to 10; Represents an integer from 0 to 10; and i represents an integer from 0 to 10: In the formula (I-2-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer of from 3; and d represents an integer from 1 to 10; and the compound (E) is selected from the group consisting of a thermal acid generator and a thermal base generator.

The pigment (A) of the present invention may be an inorganic pigment, an organic pigment or a combination thereof.

The inorganic pigment may be a metal compound such as a metal oxide or a metal salt, which may be selected from the group consisting of oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, and antimony, and the foregoing. A composite oxide of a metal and a metal salt.

The organic pigment may be selected from CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81 , 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139 , 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI pigment red 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48:2, 48:3, 48:4, 49:1, 49:2 , 50:1, 52:l, 53:l, 57, 57:l, 57:2, 58:2, 58:4, 60:l, 63:l, 63:2, 64:l, 81:l , 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170 , 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 1 93,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; CI Pigment Violet 1, 14, 19, 23, 29 , 32, 33, 36, 37, 38, 39, 40, 50; CI pigment blue l, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1, 7. The above organic pigments may be used singly or in combination of plural kinds.

In one embodiment, the pigment (A) preferably has an average particle diameter of 10 nm to 200 nm, more preferably 20 nm to 150 nm, still more preferably 30 nm to 130 nm.

The pigment (A) is used in an amount of 30 parts by weight to 500 parts by weight, preferably 40 parts by weight to 450 parts by weight, based on the amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 50 parts by weight. Parts by weight to 400 parts by weight.

If necessary, the pigment (A) can also optionally use a dispersing agent such as a cationic, anionic, nonionic, amphoteric, polyoxyalkylene or fluorine surfactant.

The aforementioned surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ether surfactants such as polyethylene oxide octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate and polyethylene glycol Polyethylene glycol diester surfactant such as fatty acid ester; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant; tertiary amine modified polyurethane interface Active agent; manufactured by Shin-Etsu Chemical Co., Ltd. and model KP; manufactured by Toray Dow Corning Silicon and model SF-8427; manufactured by Kyoritsu Oil & Fat Chemical Industry, model of Polyflow; Dekm Corporation Produced by Tochem Products Co., Ltd., and model F-Top; manufactured by Dainippon Ink Chemical Industry, and model of Megafac; manufactured by Sumitomo 3M and modeled by Fluorad; manufactured by Asahi Glass, and model number It is a product of Asahi Guard and Surflon. The surfactants may be used singly or in combination of plural kinds.

The alkali-soluble resin (B) of the present invention may comprise a first alkali-soluble resin (B-1).

The first alkali-soluble resin (B-1) is an organic ruthenium compound containing a polyfunctional epoxy group, and may contain a compound represented by the formula (I-1) and/or a compound represented by the formula (I-2): In the formula (I-1), D may represent a hydrogen atom, a glycidyl group, or a structure represented by the following formula (I-1-1), wherein at least one D represents the following formula (I- 1-1) The structure shown, and at least two D represent glycidyl groups; a represents an integer from 1 to 100: In the formula (I-1-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents An integer from 1 to 3; and d represents an integer from 1 to 10; In the formula (I-2), D' represents a hydrogen atom, a glycidyl group or a structure represented by the formula (I-2-1), wherein at least one D' represents a formula (I- 2-1) The structure shown, and at least two D' represent a glycidyl group; AO represents an alkylene oxide group having a carbon number of 2 to 6; f represents an integer of 4 to 10; An integer up to 10; h represents an integer from 0 to 10; and i represents an integer from 0 to 10: In the formula (I-2-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents An integer from 1 to 3; and d represents an integer from 1 to 10.

In one embodiment, a, f, g, h, and i of the above formula (I-1) and formula (I-2) may independently represent different integers, respectively. Preferably, a represents an integer from 1 to 40, f represents an integer from 4 to 8, g represents an integer from 0 to 8, h represents an integer from 0 to 8, and i represents an integer from 0 to 8. More preferably, a represents an integer from 1 to 30, f represents an integer from 4 to 5, g represents an integer from 0 to 5, h represents an integer from 0 to 5, and i represents an integer from 0 to 5.

In the formula (I-1), a may represent an integer of 1 or more as described above. When a is 1, the compound represented by the formula (I-1) is a glycerol derivative. From the viewpoint of increasing the reactive group, the compound represented by the formula (I-1) may be a 2 bis glycerol derivative or a 3 1,3-triglycerol derivative or the like. Here, a may be an integer of 2 or more, preferably an integer of 3 or more, and more preferably an integer of 4 or more (that is, a polyglycerol derivative). Further, although g, h, and i each represent an integer of 0 or more, g, h, and i preferably each independently represent an integer of 1 or more. The sum of g, h and i may be an integer from 0 to 24, preferably an integer from 3 to 24, and more preferably an integer from 3 to 21.

In the formula (I-1-1), a specific example of D ₁ may be a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group or a hexyl group. When D ₂ represents an alkyl group having 1 to 4 carbon atoms, D ₂ may be a methyl group, an ethyl group, a propyl group or a butyl group or the like.

The AO in the formula (I-2) may represent an alkoxy group having a carbon number of 2 to 6. In one embodiment, AO may represent an Ethylene Oxide (EO) group, a Propylene Oxide (PO) group or a Butylene Oxide (BO) group. Further, when g, h and i each represent an integer of 2 or more, the alkoxy group may be a linking chain, wherein each of EO, PO and BO may be a structure of a single alkoxy group, or two or more The structure formed by the combination of alkoxy groups. Furthermore, when g, h and i respectively represent an integer of 3 or more, and the AO segment is composed of two or more alkyleneoxy groups, the AO segment may be a random polymer or a block polymerization. Things.

In the formula (I-2-1), a specific example of D ₁ may be a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group or a hexyl group. When D ₂ represents an alkyl group having 1 to 4 carbon atoms, D ₂ may be a methyl group, an ethyl group, a propyl group or a butyl group or the like.

In the formula (I-1), the content of the glycidyl group (hereinafter abbreviated as (i)) and the content of a functional group such as an alkoxyalkyl group or a stanol group (hereinafter abbreviated as (ii)] are molar ratios [hereinafter]. (i)/(ii)] may be from 0.02 to 100, preferably from 0.05 to 50, and more preferably from 0.1 to 10. If the aforementioned molar ratio is less than 0.02, the content of a functional group such as an alkoxyalkyl group or a stanol group is too large, and the synthesis is difficult based on the designed structure, and the obtained product has a defect of poor stability. When the aforementioned molar ratio is more than 100, the content of a functional group such as an alkoxyalkyl group or a stanol group is extremely small, and the effect of a functional group such as an alkoxyalkyl group or a stanol to be introduced is eliminated.

In the above formula (I-2), the content of the glycidyl group (hereinafter abbreviated as (iii)] and the content of a functional group such as an alkoxyalkyl group or a stanol group (hereinafter abbreviated as (iv)] is a molar amount. The ratio [(iii)/(iv)] may be from 0.1 to 9, and preferably from 0.2 to 5.

The organogermanium compound containing a polyfunctional epoxy group is formed by reacting a part of a hydroxyl group and a decane coupling agent to form a bond in the structure of the polyfunctional epoxy group-containing polyglycidyl ether compound. In a specific example, a decane coupling agent having an isocyanate group (hereinafter simply referred to as an isocyanate group) can be used as a decane coupling agent. Among them, a hydroxyl group may form a urethane bond with an isocyanate group.

In one embodiment, the polyfunctional epoxy group-containing organogermanium compound may be a polyfunctional epoxy group-containing compound having at least two epoxy groups and at least one alkoxyalkyl group and a stanol group. The polyfunctional epoxy group-containing compound having at least two epoxy groups and at least one alkoxyalkyl group and a stanol group may be a polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group. The hydroxy group is prepared by reacting an isocyanate group of a decane coupling agent having an isocyanate group and at least one alkoxy or stanol group.

In this specific example, when (poly)glycerol polyglycidyl ether is used as the polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group, the formula (I-1) can be obtained. The first alkali-soluble resin (B-1). When the sorbitol polyglycidyl ether is used as the polyglycidyl ether compound having at least two epoxy groups and at least one hydroxyl group, the first alkali-soluble resin represented by the above formula (I-2) can be obtained ( B-1).

The aforementioned (poly)glycerol polyglycidyl ether may have a structure represented by the following formula (I-1-2): In the formula (I-1-2), D ₃ represents a hydrogen atom or a glycidyl group, wherein at least one D ₃ represents a hydrogen atom, and at least two D ₃ represent a glycidyl group. The definition of a is as described above.

As shown in the formula (I-1-2), the content of the glycidyl group [hereinafter abbreviated as (v)] and the content of the hydroxyl group [hereinafter referred to as (vi)] are molar ratio [(v)/(vi)] It may be from 0.01 to 100, preferably from 0.02 to 50, and more preferably from 0.1 to 40. Further, the epoxy equivalent thereof may be from 100 to 500, preferably from 100 to 400, and more preferably from 100 to 300. When the epoxy equivalent is less than 100, the (poly)glycerol polyglycidyl ether represented by the formula (I-3) is not easily synthesized, and if the epoxy equivalent is more than 500, the epoxy group content is too low, and the obtained is obtained. The compound containing a polyfunctional epoxy group is added to the photosensitive resin composition, and after the lithography process, the formed pixel colored layer is less likely to achieve the effect of improving the splash resistance.

The aforementioned sorbitol polyglycidyl ether may have a structure represented by the following formula (I-2-2): Formula (I-2-2)

In the formula (I-2-2), D ₄ represents a hydrogen atom or a glycidyl group, wherein at least one D ₄ represents a hydrogen atom, and at least two D ₄ represent a glycidyl group. AO represents an alkoxy group having a carbon number of 2 to 6. f represents an integer of 4 to 10, g represents an integer of 0 to 10, h represents an integer of 0 to 10, and i represents an integer of 0 to 10.

As shown in the formula (I-2-2), the content of the glycidyl group (hereinafter abbreviated as (vii)] and the content of the hydroxyl group (hereinafter referred to as (viii)] are molar ratio [(vii)/(viii)] It may be from 0.1 to 9, and preferably from 0.2 to 5. Second, the epoxy equivalent may be from 100 to 500, preferably from 100 to 400, and more preferably from 100 to 300. When the epoxy equivalent is less than 100, the sorbitol polyglycidyl ether represented by the formula (I-4) is not easily synthesized. When the epoxy equivalent is more than 500, the content of the epoxy group is too low, and the obtained compound containing a polyfunctional epoxy group is added to the negative photosensitive resin composition, which is formed after the lithography process. The pixel coloring layer is not easy to achieve the effect of improving the splash resistance.

The (poly)glycerol polyglycidyl ether and the sorbitol polyglycidyl ether of the polyglycidyl ether compound may be commercially available products, for example, manufactured by Sakamoto Pharmaceutical Co., Ltd., and model number SR-4GL. It is manufactured by Nagase Industrial Co., Ltd. and is modeled after Denacol Ex-1310, Denacol EX-1410, Denacol E-1610 or Denacol EX-610U.

Next, in the reaction with the polyglycidyl ether, a decane coupling agent having a hydrolyzable alkylene group is introduced, which does not react with an epoxy group, and has a functional group which selectively reacts with a hydroxyl group. Among them, the decane coupling agent is preferably an isocyanate decane.

Specific examples of the isocyanate decane may be 3-isocyanate propyl trimethoxy decane, 3-isocyanate propyl methyl dimethoxy decane, 3-isocyanate propyl dimethyl methoxy decane, 3-isocyanate propyl trisole Ethoxy decane, 3-isocyanate propyl methyl diethoxy decane, 3-isocyanate propyl dimethyl ethoxy decane, isocyanate methyl trimethoxy decane, isocyanate methyl methyl dimethoxy decane, Isocyanate methyl dimethyl methoxy decane, isocyanate methyl triethoxy decane, isocyanate methyl methyl diethoxy decane, isocyanate methyl dimethyl ethoxy decane, and the like. Among them, the isocyanate decane may preferably be 3-isocyanate propyl triethoxy decane or 3-isocyanate propyl trimethoxy decane.

In the reaction of the polyglycidyl ether compound and the isocyanate decane, the content of the hydroxyl group in the polyglycidyl ether compound is 1 mol, and the content of the isocyanate group in the isocyanate decane may be 0.01 mol to 1 mol. And preferably from 0.1 mole to 1 mole.

The organofluorene compound having a polyfunctional epoxy group of the present invention can be obtained by reacting a polyglycidyl ether compound with an isocyanate decane. The reaction temperature may be from 25 ° C to 90 ° C, and preferably from 40 ° C to 80 ° C. When the reaction temperature is not within the above range, the reaction rate becomes lower when the reaction temperature is lower than 25 ° C, and the hydroxyl group of the polyglycidyl ether compound and the alkoxyalkyl group of the isocyanate decane are esterified when the reaction temperature is higher than 90 ° C. When the reaction is exchanged, side reactions may occur. Secondly, the reaction time of the aforementioned reaction is not particularly limited and may generally be from 10 minutes to 24 hours.

In the reaction of the polyglycidyl ether compound and the isocyanate-based decane, the solvent to be used is not particularly limited as long as the solvent does not react with the isocyanate-based decane. Specific examples of the solvent include a hydrocarbon solvent, an aromatic solvent, a ketone solvent, a guanamine solvent, an ester solvent, or an ether solvent. Specific examples of the solvent may be a hydrocarbon solvent such as pentane, hexane, heptane, octane, decane or cyclohexane; an aromatic solvent such as benzene, toluene or xylene; acetone or methyl ethyl ketone; a ketone solvent such as methyl isobutyl ketone or cyclohexanone; a guanamine solvent such as formamide, dimethylformamide, pyrrolidone or N-methylpyrrolidone; ethyl acetate, butyl acetate or An ester solvent such as a lactone; an ether solvent such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran or 1,4-dioxane.

In the reaction of the aforementioned polyglycidyl ether compound with isocyanate decane, a catalyst may be added to the reaction to increase the reaction rate. The catalyst can be the catalyst used in the general polyurethane reaction. Specific examples of the catalyst may be a tertiary amine compound, dibutyltin oxide, dioctyltin oxide or tin(II) bis(2-ethylhexanoate).

The total amount of the polyglycidyl ether compound and the isocyanate decane used is 100% by weight, and the catalyst may be included in an amount of 0.001% by weight to 1% by weight.

The organic ruthenium compound containing the polyfunctional epoxy group can be obtained by a colloidal permeation chromatography method, and the polyvalent epoxy group-containing organic ruthenium compound can have a weight average molecular weight of 200. Up to 10,000, and preferably from 300 to 8,000. When the weight average molecular weight of the organofluorene compound containing a polyfunctional epoxy group is less than 200, the organofluorene compound containing a polyfunctional epoxy group is not easily synthesized. If the organofluorene compound containing a polyfunctional epoxy group has a weight average molecular weight of more than 10,000, it has a defect of being inferior in handleability.

Specific examples of the compound of the present invention can be listed as follows: in the formula (I-1), b is 3, d is 3, the average value of a is 9, and the content of the glycidyl group and the content of the ethoxylated alkyl group are The molar ratio is 3; in the formula (I-1), b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 6; in the formula (I-1), b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 0.3; In I-1), b is 3, d is 3, the average value of a is 7, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3; in the formula (I-2) , b is 3, d is 3, f is 4, g, h and i are 2, AO is an extended ethoxy group, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3; In the formula (I-2), b is 3, d is 3, f is 4, g, h and i are both 2, AO is a propoxyl group, and the content of the glycidyl group and the ethoxylated alkyl group are The molar ratio of the content is 3; in the formula (I-2), b is 3, d is 3, f is 4, g, h and i are 2, AO is a buttoxy group, and a glycidyl group Content and ethoxylate The molar ratio of the alkyl group is 3; in the formula (I-2), b is 3, d is 3, f is 4, g, h and i are both 2, and AO is an extended ethoxy group and a propylene group. The mixing of the oxy groups, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated decyl group is 3; in the formula (I-2), b is 3, d is 3, and f is 4, g, h. And i are both 4, AO is a mixture of ethoxylated and propoxylated oxy groups, each AO group is formed as a random polymer, and the molar ratio of the content of glycidyl group to the content of ethoxylated decyl group is 3; and in the formula (I-2), b is 3, d is 3, f is 4, g, h and i are 4, and AO is a mixture of an extended ethoxy group and a propenyloxy group, each AO The group is formed as a block polymer, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is 3.

The first alkali-soluble resin (B-1) may be used in an amount of from 0.1 part by weight to 30 parts by weight, based on the total amount of the alkali-soluble resin (B), and is preferably from 0.5 part by weight to 20 parts by weight. Parts, and more preferably 1 part by weight to 10 parts by weight.

When the photosensitive resin composition of the present invention does not contain the first alkali-soluble resin (B-1), the obtained photosensitive resin composition has a splash-resistant layer formed by the lithographic process after the lithographic process. Defects in poor plating.

In a preferred embodiment of the present invention, the alkali-soluble resin (B) may further comprise a second alkali-soluble resin (B-2).

The second alkali-soluble resin (B-2) can be obtained by a polymerization reaction of a mixture, and the mixture contains an epoxy compound (b-2-1) having at least two epoxy groups and having at least one carboxylic acid group. And at least one ethylenically unsaturated group compound (b-2-2). Next, the mixture may optionally further comprise a carboxylic anhydride compound (b-2-3) and/or a compound having an epoxy group (b-2-4).

The epoxy compound (b-2-1) having at least two epoxy groups may have a structure represented by the following formula (II-1) or the following formula (II-2). Here, the description that the epoxy compound (b-2-1) may have a structure represented by the following formula (II-1) or the following formula (II-2) also encompasses the following formula (II-1) The compound having the structure shown and the compound having the structure represented by the following formula (II-2) exist simultaneously as the epoxy compound (b-2-1). Specifically, the epoxy compound (b-2-1) having at least two epoxy groups as described above has, for example, a structure represented by the following formula (II-1): In the formula (II-1), Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different, respectively, and Y ₁ , Y ₂ , Y ₃ and Y ₄ may represent a hydrogen atom or a halogen atom. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.

The epoxy compound (b-2-1) having at least two epoxy groups as shown in the above formula (II-1) may comprise a reaction of a bisphenol fluorene with an epihalohydrin. The epoxy group-containing bisphenol quinone type compound is obtained, but is not limited thereto.

Specific examples of the above bisphenol quinone type compound may include, but are not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis (4) -9-9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)indole [9,9 -bis(4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene[9,9-bis(4-hydroxy-3-fluorophenyl)fluorene], 9,9-bis(4-hydroxy-3-methoxy 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-hydroxy-3,5-dichlorophenyl) a compound such as fluorene], 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

The above-mentioned epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin (epibromohydrin).

The epoxy group-containing bisphenol quinoid compound obtained by reacting the bisphenol quinoid compound with the halogenated propylene oxide may include, but is not limited to: (1) manufactured by Nippon Steel Chemical Co., Ltd. Products such as ESF-300, etc.; (2) Products manufactured by Osaka Gas Co., Ltd.: PG-100, EG-210, etc.; (3) SMS Technology Co., Ltd. .) manufactured goods: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

Next, the epoxy compound (b-2-1) having at least two epoxy groups may have a structure represented by the following formula (II-2): In the formula (II-2), Y ₅ to Y ₁₈ 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; An integer representing 0 to 10.

The epoxy compound (b-2-1) having at least two epoxy groups as shown in the above formula (II-2) is, for example, by the following formula (II-2- in the presence of an alkali metal hydroxide) 1) The compound shown is reacted with a halogenated propylene oxide to obtain: In formula (II-2-1) of formula (II-2-1), Y ₅ and Y ₁₈ to define the lines were ₅ g to Y ₁₈ g of the same as defined in the formula Y (II-2) in the, in This will not be repeated.

Further, the epoxy compound (b-2-1) having at least two epoxy groups represented by the above formula (II-2) is, for example, in the presence of an acid catalyst, and the following formula (II-2-2) is used. After the condensation reaction of the compound shown with a phenol, a compound represented by the formula (II-2-1) is formed. Next, dehydrohalogenation is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy compound (b-2-1) having at least two epoxy groups as shown in the formula (II-2). : In the formula (II-2-2), Y ₁₉ and Y ₂₀ may each be the same or different hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 An aromatic group to 15; Y ₂₁ and Y ₂₂ are the same or different halogen atoms, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, and the aforementioned alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the aforementioned alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the above phenols may include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butanol. (t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol (vinylphenol), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The above phenols may be used singly or in combination of plural kinds.

The compound may be used in an amount of from 1 mol to 1 mol based on the above formula (II-2-2), and the phenol may be used in an amount of from 0.5 mol to 20 mol, and preferably from 2 mol to 15 mol.

Specific examples of the above acid catalyst may include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminium chloride. Chloride), zinc chloride, etc., of which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The above acid catalysts may be used singly or in combination of plural kinds.

Further, the amount of the acid catalyst to be used is not particularly limited, but the amount of the compound represented by the above formula (II-2-2) is 100% by weight, and the amount of the acid catalyst used is preferably 0.1% by weight. Percentage to 30 weight percent.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Next, specific examples of the above organic solvent may include, but are not limited to, toluene, xylene, or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

The organic solvent is used in an amount of 50% by weight to 300% by weight based on the total amount of the compound and the phenol used as shown in the formula (II-2-2), and preferably 100% by weight to 100% by weight 250 weight percent. Further, the above condensation reaction may be carried out at a temperature of from 40 ° C to 180 ° C, and the operation time of the condensation reaction may be from 1 hour to 8 hours.

After completion of the above condensation reaction, a neutralization treatment or a water washing treatment may be carried out. The above neutralization treatment adjusts the pH of the solution after the reaction to 3 to 7, and preferably 5 to 7. The water washing treatment may be carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof may include an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylene tetramine, aniline, phenylenediamine (diethyl trimine) Organic amines such as phenylene diamine; and ammonia, sodium dihydrogen phosphate, and the like. The above washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off by heat treatment under reduced pressure, and concentrated to obtain a compound represented by the formula (II-2-1).

Specific examples of the above halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane (3). -bromo-1, 2-epoxypropane) or any combination of the above. 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 may be carried out at a temperature of from 20 ° C to 120 ° C and may be operated for a period of from 1 hour to 10 hours.

In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added to the dehydrohalogenation reaction may be used. In this specific example, while the 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 dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The ammonium salt is used as a catalyst, and reacted at 50 ° C to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour. 10 hours for the dehydrohalogenation reaction.

The 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 compound represented by the above formula (II-2-1). . The alkali metal hydroxide added in the above dehydrohalogenation reaction may be used in an amount of from 0.8 to 15 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the above formula (II-2-1) being 1 equivalent. It is preferably from 0.9 equivalents to 11 equivalents.

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. A polar solvent or the like is used to carry out the reaction. In the case of using an alcohol, the total amount of the halogenated propylene oxide used is 100% by weight, and the alcohol may be used in an amount of 2 to 20% by weight, preferably 4 to 15% by weight. In the case of using an aprotic polar solvent, the aprotic polar solvent may be used in an amount of 5 to 100% by weight based on the total amount of the halogenated propylene oxide, and preferably 10 Weight percentage to 90 weight percent.

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 decompression. The above heating and decompression is carried out, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (about 10 mm - Hg) or less.

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

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, a solvent such as toluene or methyl isobutyl ketone may be distilled off by heating and decompression to obtain an epoxy compound having at least two epoxy groups as shown in the formula (II-2). (b-2-1). The epoxy compound (b-2-1) having at least two epoxy groups represented by the above formula (II-2) may include, but is not limited to, trade names NC-3000, NC-3000H, NC-3000S, and A product manufactured by Nippon Kayaku Co., Ltd., such as NC-3000P.

The aforementioned compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group may, for example, be selected from the group consisting of (1) to (3): (1) acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2 -Methacrylic acid oxiranium adipic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl Maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Propyl tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate or 2-methyl propylene oxybutyl phthalate Formic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound may include, but is not limited to, adipic acid, succinic acid, maleic acid or Phthalic acid; (3) by a half ester compound obtained by reacting a (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes, but not limited to, 2-hydroxyethyl acrylate; 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate], 2-hydroxypropyl acrylate, 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 carboxylic anhydride compound (b-2-3) contained in the mixture of the second alkali-soluble resin (B-2) described below, and thus will not be described herein.

The aforementioned mixture may also optionally contain a carboxylic anhydride compound (b-2-3).

The above carboxylic anhydride compound (b-2-3) may be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, and clothing. Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or trimellitic acid a dicarboxylic anhydride compound such as 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether A tetracarboxylic anhydride compound such as tetracarboxylic acid dianhydride.

The above epoxy group-containing compound (b-2-4) may, for example, be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and a glycidyl ether compound having an unsaturated group. A group consisting of an epoxy group-containing unsaturated compound or any combination of the above. The glycidyl ether compound having an unsaturated group may include, but is not limited to, manufactured by Nagase Chemical Co., Ltd., and its model numbers are Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, and Denacol EX- 146, Denacol EX-171 or Denacol EX-192 and other products.

The second alkali-soluble resin (B-2) may be an epoxy compound (b-2-1) having at least two epoxy groups as shown in the formula (II-1) and having at least one carboxylic acid group and at least one The ethylenically unsaturated group compound (b-2-2) is subjected to a polymerization reaction to form a reaction product having a hydroxyl group. Next, the carboxylic anhydride compound (b-2-3) is 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 amount of the acid anhydride group contained in the carboxylic anhydride compound (b-2-3) may preferably be 0.4 equivalent to 1 equivalent, and more preferably 0.75 equivalent to 1 equivalent. When a plurality of carboxylic anhydride compounds (b-2-3) are used, such carboxylic anhydride compounds (b-2-3) may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (b-2-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably from 1/99 to 90/ 10, and more preferably 5/95 to 80/20. Further, the above reaction may be operated at a temperature ranging from 50 ° C to 130 ° C.

The second alkali-soluble resin (B-2) may be an epoxy compound (b-2-1) having at least two epoxy groups as shown in the formula (II-2) and having at least one carboxylic acid group and at least one The ethylenically unsaturated group compound (b-2-2) is reacted to form a reaction product having a hydroxyl group. Next, a carboxylic anhydride compound (b-2-3) and/or a compound (b-1-4) having an epoxy group are added, and a polymerization reaction is carried out. The epoxy group-containing epoxy compound (b-2-1) having at least two epoxy groups represented by the formula (II-2) has a total equivalent weight of 1 equivalent, and the above has at least one carboxylic acid group and at least one The acid equivalent of the ethylenically unsaturated group compound (b-2-2) may preferably be from 0.8 equivalents to 1.5 equivalents, and more preferably from 0.9 equivalents to 1.1 equivalents. The carboxylic anhydride compound (b-2-3) may be used in an amount of from 10 moles to 100 moles, preferably from 20 moles to 100 moles, based on the total amount of hydroxyl groups of the above-mentioned reaction product having a hydroxyl group of 100 moles. And more preferably from 30 to 100.

In the preparation of the second alkali-soluble resin (B-2), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The above reaction catalyst may be used singly or in combination, and the above reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. (triethanolamine), tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, and the like. The total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenic unsaturated group is 100. The amount of the reaction catalyst used may preferably be from 0.01 part by weight to 10 parts by weight, and more preferably from 0.3 part by weight to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di- T-butyl-p-cresol) or phenothiazine. In general, the above polymerization inhibitors may be used singly or in combination of plural kinds. The total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenic unsaturated group is 100. The polymerization inhibitor may preferably be used in an amount of from 0.01 part by weight to 10 parts by weight, and more preferably from 0.1 part by weight to 5 parts by weight, per part by weight.

In the preparation of the second alkali-soluble resin (B-2), a polymerization solvent can be used as necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; and ketones such as methyl ethyl ketone or cyclohexanone. a compound; an aromatic hydrocarbon compound such as toluene or xylene; a celecin compound such as cellosolve or butyl cellosolve; carbitol or butyl carbitol (butyl) Carbitol); propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di(propylene glycol) methyl ether [poly(poly(propylene glycol) methyl ether] Propylene glycol) alkyl ether] compound; acetate compound such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; lactic acid An alkyl lactate compound such as ethyl lactate or butyl lactate; or a dialkyl glycol ether; or ethyl 3-ethoxypropionate. The above polymerization solvent can be generally used singly or in combination of plural kinds. Further, the acid value of the above second alkali-soluble resin (B-2) is preferably from 50 mg-KOH/g to 200 mg-KOH/g, and more preferably from 60 mg-KOH/g to 150 mg-KOH/ g.

Further, the second alkali-soluble resin (B-2) is measured by a gel permeation chromatography (GPC), and the number average molecular weight in terms of polystyrene is generally from 500 to 10,000, preferably 800. To 8,000, and more preferably 1,000 to 6,000.

In a specific example of the present invention, the total amount of the alkali-soluble resin (B) used is 100 parts by weight, and the second alkali-soluble resin (B-2) is used in an amount of 70 parts by weight to 99.9 parts by weight, preferably 80 parts by weight to 99.5 parts by weight, and more preferably 90 parts by weight to 99 parts by weight.

The alkali-soluble resin (B) of the present invention may further include, but not limited to, a resin containing a carboxylic acid group or a hydroxyl group, and specific examples of the other alkali-soluble resin may be an acrylic resin, a urethane resin, or a novolac ( Novolac) alkali-soluble resin such as resin

The ethylenically unsaturated group-containing compound (C) according to the present invention may comprise an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

Specific examples of the above unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, propylene morpholine, methacryl morpholine, acetyl 7-amino-3,7-dimethyl Octyl ester, 7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobornyl acrylate , isobornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyl diglycol acrylate , ethyl diglycol methacrylate, third octyl acrylamide, third octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethyl urethane, A Dimethylamino acrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentene oxyethyl acrylate, dicyclopentene oxyethyl methacrylate, dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, N,N-dimethyl decylamine, N,N-dimethyl methacrylamide, C Tetrachlorophenyl ester, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, methacrylic acid Hydroquinone ester, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichloroacrylate Phenoxyethyl ester, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, methacrylic acid - 2-tribromophenoxyethyl ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl Indoleamine, nitrogen-vinyl tyrosinone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, methyl Pentabromophenyl acrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, poly propylene glycol monoacrylate, poly propylene glycol monomethacrylate, acrylic borneol Isobornyl acrylate or methacrylate and the like. The above unsaturated compound having at least one ethylenically unsaturated group may be used singly or in combination of plural kinds.

Specific examples of the above unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, tris(2-hydroxyethyl) Isocyanate dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate Triacrylate (caprolactone modified) tris(2-hydroxyethyl)isocyanate trimethacrylate, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, ethylene oxide ( Hereinafter referred to as EO) modified trimethylol propyl triacrylate, EO modified trimethylol propyl trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate PO modified trimethylol propyl trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethyl Ethyl ester, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, Polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol pentamethyl acrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethacrylate, Caprolactone modified dipentaerythritol pentaacrylate, caprolactone modified dipentaerythritol pentamethacrylate, ditrimethylolpropyl tetraacrylate, tetramethyl acrylate Methyl propyl ester, EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethyl Acrylate, EO modified hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A II Methacrylate, PO modified triglyceride, EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polycondensation Glycerol ether methacrylate, manufactured by Japan East Asia Synthetic Co., Ltd. and model number TO-1382, or manufactured by Nippon Kayaku Co., Ltd. and model number KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD Goods such as DPCA-60, KAYARAD DPCA-120 or KAYARAD DPEA-12. The above unsaturated compound having at least two ethylenically unsaturated groups may be used singly or in combination of plural kinds.

Preferably, the ethylenically unsaturated group-containing compound (C) is selected from trimethylol propyl triacrylate, EO modified trimethylol propyl triacrylate, and PO modified trisuccinic acid trihydroxyl. Methyl propyl ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrihydroxy hydroxytetraacrylate Methyl propyl ester, PO modified triglyceride, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 or any combination of the above.

The above ethylenically unsaturated group-containing compound (C) may be used singly or in combination of plural kinds.

The ethylenically unsaturated group-containing compound (C) may be used in an amount of 20 parts by weight to 200 parts by weight, preferably 30 parts by weight to 180%, based on 100 parts by weight of the total amount of the alkali-soluble resin (B). Parts by weight, and more preferably 50 parts by weight to 150 parts by weight.

The photoinitiator (D) of the present invention may be selected from the group consisting of an acetophenone compound, a biimidazol compound, an acyl oxime or a combination thereof.

The above acetophenone-based compound is selected from the group consisting of p-dimethylamino-acetophenone, α,α'-dimethoxyoxo acetophenone (α,α'-dimethoxyazoxy-acetophenone). , 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone [2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone], 2- Benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)- 1-butanone].

The above diimidazole compound is selected from 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 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'-double (o- Ethylphenyl)-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' -tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2 '-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2- Phenyl)-4,4',5,5'-tetraphenyl-biimidazole [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].

The above lanthanide compound is selected from the group consisting of ethane ketone, 1-[9-ethyl-6-(2-methylbenzomethyl)-9-hydro-oxazol-3- substituent]-, 1 -(oxy-acetonitrile) {Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), for example, Ciba Specialty Chemicals A product of the type CGI-242 manufactured by the following formula (III-1)}, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2- (1-(4-(benzoyl)phenyl)-heptane-1,2-dione-2-(O-benzoyloxime), for example, manufactured by Ciba Specialty Chemicals, Inc., model CGI-124 , the structure of which is represented by the following formula (III-2)}, ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzhydryl)-9- Hydrogen-carbazole-3-substituent]-,1-(oxy-acetamidine){Ethanone,1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole -3-yl]-, 1-(O-acetyl oxime), for example, a product manufactured by Asahi Chemical Co., Ltd., whose structure is as shown in the following formula (III-3)}: Formula (III-1) Formula (III-2) Formula (III-3)

Preferably, the photoinitiator (D) is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N , N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole, ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9-hydro-oxazol-3-substituted]-, 1-(oxy-acetamidine)肟) or a combination of these.

The photoinitiator (D) of the present invention may optionally be added with the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone -4-碸 (thioxanthone-4-sulfone), benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4, Benzophenone compound such as 4'-bis(diethylamino)benzophenone; benzil, acetyl, etc. Alpha-diketone compound; acyloin compound such as benzoin; benzoin methylether, benzoin ethylether, A acyloin ether compound such as benzoin isopropyl ether; 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide (2,4,6-trimethyl-benzoyl- Diphenyl-phosphineoxide, bis-(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4 , acylphosphine oxide, etc., 4-trimethyl-benzyl-phosp hineoxide] Quin(anthraquinone), quinone compound such as 1,4-naphthoquinone; phenacyl chloride, tribromomethyl-phenylsulfone a halide such as tris(trichloromethyl)-s-triazine or a peroxide such as di-tertbutylperoxide. The above compound is preferably a benzophenone compound, and more preferably 4,4'-bis(diethylamine)benzophenone.

The photoinitiator (D) may be used in an amount of 5 parts by weight to 100 parts by weight, preferably 10 parts by weight to 90 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B), and More preferably, it is 15 parts by weight to 80 parts by weight.

The compound (E) according to the present invention is selected from the group consisting of a thermal acid generator and a thermal base generator, and the above thermal acid generator or thermal base generator may be used singly or in combination of two or more.

The thermal acid generator according to the present invention comprises an ionic thermal acid generator and a nonionic thermal acid generator.

The ionic thermal acid generator preferably does not contain heavy metals or halogen ions.

Specific examples of the ionic thermal acid generator are sulfonium salts such as triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, and 1-dimethylthio-4,7. -dihydroxynaphthalene, 4-hydroxyphenyldimethylhydrazine, benzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl-4-hydroxyphenylmethylhydrazine, 2-methylbenzyl- Methanesulfonate, trifluoromethanesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, 4-ethylmercaptophenylmethylhydrazine, 2-methylbenzyl-4-benzylidylphenylmethylhydrazine , hexafluorophosphonate, commercially available benzyl sulfonium salts such as SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L , SI-145L, SI-150L, SI-160L, SI-180L (all manufactured by Sanxin Chemical Industry Co., Ltd.).

The nonionic thermal acid generator is, for example, a halogen-containing compound, a diazomethane compound, a hydrazine compound, a sulfonate compound, a carboxylic acid ester compound, a phosphate compound, a sulfonimide compound, a sulfonated benzotriazole compound, or the like. .

The halogen-containing compound such as a halogenated hydrocarbon compound, a halogenated heterocyclic compound, and the like are preferably 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane. Alkyl, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine.

The diazomethane compound such as bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolyl) Diazomethane, bis(2,4-xylsulfonyl)diazomethane, bis(p-chlorophenyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonium (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl (benzhydryl)diazomethane .

The hydrazine compound such as a β-ketoxime compound, a β-sulfonyl compound, a diaryl sulfonium compound or the like; preferably 4-trityl hydrazine methyl hydrazine, trimethylphenyl benzhydryl methyl hydrazine, bis (benzene) Methanesulfonyl)methane, 4-chlorophenyl-4-methylphenylhydrazine.

The sulfonate compound, such as an alkyl sulfonate, a haloalkyl sulfonate, an aryl sulfonate, an imide sulfonate; preferably a benzoin tosylate, pyrogallol Mesylate, nitrobenzyl-9,10-diethoxyindole-2-sulfonate, sodium 2,6-dinitrobenzenesulfonate and commercially available imidosulfonates such as PAI- 101, PAI-106 (manufactured by Green Chemical Co., Ltd.), CGI-1311 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

The carboxylic acid ester compound is o-nitrobenzyl carboxylic acid ester and the like.

The sulfonimide compound such as N-(trifluoromethylsulfonyloxy) succinimide (trade name: SI-105, manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonyloxy) succinimide (trade name: SI-106, manufactured by Green Chemical Co., Ltd.), N-(4-methylbenzenesulfonyloxy) amber ylide (trade name: SI-101, manufactured by Green Chemical Co., Ltd.), N-(2- Trifluoromethylbenzenesulfonyloxy) succinimide, N-(4-fluorophenylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy)phthalic acid Imine, N-(camphorsulfonyl) phthalimide, N-(2-trifluoromethylbenzenesulfonyloxy) phthalimide, N-(2-fluorophenyl) Sulfomethoxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide (trade name: PI-105, manufactured by Green Chemical Co., Ltd.), N-( Camphorsulfonyloxy)diphenylmaleimide, 4-(methylbenzenesulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylbenzenesulfonyloxy) Diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmale Imine, N-(phenylsulfonyloxy)bicyclo[2. 2.2.1] hept-5-ene-2,3-dicarboxylimine (trade name: NDI-100, manufactured by Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2. 1] G--5-ene-2,3-dicarboxylimine (trade name: NDI-101, manufactured by Green Chemical Co., Ltd.), N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]g- 5-ene-2,3-dicarboxylimine (trade name: NDI-105, manufactured by Green Chemical Co., Ltd.), N-(nonafluorobutsulfonyloxy)bicyclo[2.2.1]hept-5-ene- Diimine (trade name: NDI-109, manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-diimine (trade name NDI-106, Manufactured by Green Chemical Co., Ltd.), N-(camphorsulfonyl)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(trifluoromethyl Sulfomethoxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2. 1]hept-5-ene-2,3-dicarboxylimenine, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxylimine imine, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(2 -trifluoromethylbenzenesulfonyloxy)-7-oxabicyclo[2.2.2.1]hept-5-ene-2,3- Dicarboxylated imine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(4-fluorophenylsulfonate Mercapto)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]g Alkane-5,6-oxy-2,3-dicarboxylimenide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyl N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenide, N-(2-trifluoromethyl) Benzosulfonyloxy)bicyclo[2.2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2 .1] heptane-5,6-oxy-2,3-dicarboxylic acid quinone imine, N-(trifluoromethylsulfonyloxy)naphthyl dicarboxy quinone imine (trade name NAI-105, N-(camphorsulfonyloxy)naphthalene diimine (trade name: NAI-106, manufactured by Green Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthyl Dicarboxy quinone imine (trade name: NAI-101, manufactured by Green Chemical Co., Ltd.), N-(phenylsulfonyloxy)naphthyl dicarboxy quinone imine (trade name: NAI-100, manufactured by Green Chemical Co., Ltd.), N-(2-trifluoromethylbenzenesulfonyloxy)naphthyl dicarboxyl Imine, N-(4-fluorophenylsulfonyloxy)naphthyldicarbenium imine, N-(pentafluoroethylsulfonyloxy)naphthyldicarbenium imine, N-(sevoflurane N-sulfonyloxy)naphthyldicarboxylimineimine, N-(nonafluoropentasulfonyloxy)naphthyldicarboxylimineimine (trade name NAI-109, manufactured by Green Chemical Co., Ltd.), N-( Ethylsulfonyloxy)naphthyldicarboxylimineimine, N-(propylsulfonyloxy)naphthyldicarboxylimenide, N-(butylsulfonyloxy)naphthyldicarboximine (trade name: NAI-1004, manufactured by Green Chemical Co., Ltd.), N-(pentylsulfonyloxy)naphthyldicarbenium imine, N-(hexylsulfonyloxy)naphthyldicarbenium imine, N -(heptylsulfonyloxy)naphthyldicarbenium imine, N-(octylsulfonyloxy)naphthyldicarbenium imine, N-(decylsulfonyloxy)naphthalene diimine .

Other thermal acid generators such as 1-(4-n-butoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4,7-Di-n-butoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate tetrahydrothiophene salt.

Specific examples of the thermal base generator according to the present invention are transition metal complexes and fluorenyl hydrazines. The transition metal complexes such as bromopentadecyl ammonium cobalt perchlorate, bromopentadecane methylamine cobalt perchlorate, bromopentadecane propylamine perchlorate, hexaammonium perchlorate, and hexa Amine cobalt perchlorate, hexabromopropylamine cobalt perchlorate and the like.

The sulfhydryl group is, for example, acetophenone acetophenone, acetophenone benzophenone oxime, acetophenone oxime, acetophenone acetophenone oxime, butyl benzophenone oxime, butyl ketone oxime, hexamethylene oxime Acetophenone oxime, hexamethylene benzophenone oxime, hexanyl acetonide oxime, propylene acetophenone oxime, propylene fluorenyl benzophenone oxime, propylene fluorenyl acetonide oxime, and the like.

On the other hand, the hot base generator according to the present invention preferably comprises a compound represented by the following formula (IV-1) or a salt derivative thereof and/or a compound represented by the following formula (IV-2) and/or Or a compound represented by the following formula (IV-3): Wherein: r represents an integer of 2 to 6; and R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a hydroxyalkane having a substituent of 1 to 6 carbon atoms; a base or a dialkylamino group having 2 to 12 carbon atoms. Preferably, r represents an integer from 3 to 5.

In a specific example of the present invention, R ³¹ and R ³² are independently represented by a hydrogen atom; and an alkyl group having 1 to 8 carbon atoms may be, for example but not limited to, methyl, ethyl, isopropyl, n-butyl, a tert-butyl or n-hexyl group; a hydroxyalkyl group having a carbon number of 1 to 6 which may have a substituent, such as, but not limited to, a hydrocarbon methyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxyisopropyl group. a 3-hydroxy-tert-butyl or 6-hydroxyhexyl group; or a dialkylamino group having 2 to 12 carbon atoms, such as, but not limited to, dimethylamino, methylethylamino, and diethyl Amino group, diisopropylamino group, tert-butylmethylamino group or di-n-hexylamino group, and the like.

Preferred specific examples of the compound represented by the formula (IV-1) or a salt derivative thereof are 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5-di. Azabicyclo[4.4.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 5-hydroxypropyl-1,8-diaza Heterobicyclo[5.4.0]undec-7-ene or 5-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene, or a product of Aporo: U-CAT® SA810, U-CAT® SA831, U-CAT® SA841, U-CAT® SA851, U-CAT® 5002; more preferably DBN, U-CAT® SA851 or U-CAT® 5002. Wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 8 which may have a substituent, and a carbon number of 3 to 8 may have a substituent. a cycloalkyl group, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, may have a substitution a aryl group or a heterocyclic group which may have a substituent; R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 8 which may have a substituent, and a carbon number of 3 to 8 which may have a substituent. a cycloalkyl group, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alkynyl group having 2 to 8 carbon atoms which may have a substituent, may have a substitution a aryl group or a heterocyclic group which may have a substituent, or a single ring which may have a substituent, or a combination of each other to form a polycyclic ring which may have a substituent; R ³⁹ represents a carbon number of 1 to 12 which may have a substituent An alkyl group, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an alkenyl group having 2 to 12 carbon atoms which may have a substituent, an alkynyl group having 2 to 12 carbon atoms which may have a substituent, or The carbon number of an alkyl group with 1 to 3 substituents of the aryl group having a carbon number of an alkyl group with 1 to 3 substituents of the aralkyl group or the substituted heterocyclic group, but the total number of carbon atoms of R ³⁹ 12 or less. Formula (IV-3) wherein: R ³³ , R ³⁴ , R ³⁵ and R ³⁶ , R ³⁷ and R ^{38 are} as defined in formula (IV-2); R ⁴⁰ represents a carbon number of 1 to 12 which may have a substituent An alkylene group, a cycloalkylene group having 3 to 12 carbon atoms which may have a substituent, an alkenylene group having 2 to 12 carbon atoms which may have a substituent, and an alkynylene group having 2 to 12 carbon atoms which may have a substituent An arylene group having an alkyl substituent of 1 to 3 carbon atoms, an aralkylene group which may have an alkyl substituent of 1 to 3 carbon atoms or a heterocyclic group which may have a substituent, but R ⁴⁰ The total number of carbon atoms is 12 or less.

Preferred specific examples of the compounds represented by the formulae (IV-2) and (IV-3) are, for example, {[(2-nitrobenzyl)oxy]carbonyl}methylamine, {[(2-nitro) Benzyl)oxy]carbonyl}propylamine, {[(2-nitrobenzyl)oxy]carbonyl}hexylamine, {[(2-nitrobenzyl)oxy]carbonyl}cyclohexylamine, { [(2-Nitrobenzyl)oxy]carbonyl}aniline, {[(2-nitrobenzyl)oxy]carbonyl}piperidine, bis{[(2-nitrobenzyl)oxy]carbonyl} Hexamethylenediamine, bis{[(2-nitrobenzyl)oxy]carbonyl}phenylenediamine, bis{[(2-nitrobenzyl)oxy]carbonyl}toluenediamine, double {[(2- Nitrobenzyl)oxy]carbonyl}-diaminodiphenylmethane, bis{[(2-nitrobenzyl)oxy]carbonyl}piperazine, {[(2,6-dinitrobenzyl) )oxy]carbonyl}-methylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}propylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl} Hexylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, {[(2,6-dinitrobenzyl)oxy]carbonyl}aniline, {[(2, 6-Dinitrobenzyl)oxy]carbonyl}piperidine, bis{[(2,6-dinitrobenzyl)oxy]carbonyl}hexanediamine, bis{[(2,6-dinitro) Benzyl)oxy]carbonyl}phenylenediamine, bis{[(2,6-dinitrobenzyl)oxy] Toluene diamine, bis{[(2,6-dinitrobenzyl)oxy]carbonyl}diaminodiphenylmethane, bis-{[(2,6-dinitrobenzyl)oxy O-nitrobenzyl carbazates such as carbonyl}piperazine; such as {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}methylamine, {[(α,α-Dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}propylamine, {[(α,α-dimethyl-3,5-dimethoxy) Benzyl)oxy]carbonyl}hexylamine, {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}cyclohexylamine, {[(α,α-二Methyl-3,5-dimethoxybenzyl)oxy]carbonyl}aniline, {[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}piperidine , bis{[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}hexanediamine, bis{[(α,α-dimethyl-3,5-di Methoxybenzyl)oxy]carbonyl}phenylenediamine, bis{[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}toluenediamine, double {[ (α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl}diaminodiphenylmethane, bis{[(α,α-dimethyl-3,5-di α,α-dimethyl-3,5-dimethoxybenzylamine such as methoxybenzyl)oxy]carbonyl}piperazine Formates; and such as N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(isopropoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethylpyrrolidine, N-( Isopropoxycarbonyl)azetidine, N-(1-ethylpropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethylpropoxycarbonyl)-2, 2,6,6-tetramethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine, N-(1-ethylpropoxycarbonyl)pyrrolidine, N-(1-ethyl Propyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-ethylpropoxycarbonyl)-azetidine, N-(1-propylbutoxycarbonyl)-2, 6-Dimethyl piperidine, N-(1-propylbutoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(1-propylbutoxycarbonyl)diisopropyl Base amine, N-(1-propylbutoxycarbonyl)pyrrolidine, N-(1-propylbutoxycarbonyl)-2,5-dimethylpyrrolidine, N-(1-propylbutoxylate Alkylcarbonyl)-azetidine, N-(cyclopentyloxycarbonyl)-2,6-dimethylpiperidine, N-(cyclopentyloxycarbonyl)-2,2,6,6-tetramethyl Piperidine, N-(cyclopentyloxycarbonyl)diisopropylamine, N-(cyclopentyloxycarbonyl) Pyrrolidine, N-(cyclopentyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(cyclopentyloxycarbonyl)-azetidine, N-(cyclohexylcarbonyl)-2, 6-Dimethyl piperidine, N-(cyclohexylcarbonyl)-2,2,6,6-tetramethylpiperidine, N-(cyclohexylcarbonyl)diisopropylamine, N-(cyclohexylcarbonyl)pyrrolidine , N-(cyclohexylcarbonyl)-2,5-dimethylpyrrolidine, N-(cyclohexylcarbonyl)-azetidine, N-(tert-butoxycarbonyl)-2,6-dimethyl Piperidine, N-(tert-butoxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(tert-butoxycarbonyl)diisopropylamine, N-(tert-butoxycarbonyl)pyrrole Alkane, N-(tert-butoxycarbonyl)-2,5-dimethylpyrrolidine, N-(tert-butoxycarbonyl)-azetidine, N-(benzyloxycarbonyl)-2,6 - dimethyl piperidine, N-(benzyloxycarbonyl)-2,2,6,6-tetramethylpiperidine, N-(benzyloxycarbonyl)diisopropylamine, N-(benzyloxycarbonyl) Pyrrolidine, N-(benzyloxycarbonyl)-2,5-dimethylpyrrolidine, N-(benzyloxycarbonyl)-azetidine or 1,4-bis(N,N'-diiso) Propylaminocarbonyloxy)cyclohexane; more preferably N-(isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(1-ethylpropoxycarbonyl)diisopropylamine N-(cyclopentyloxy) -2,6-dimethylpiperidine, N-(benzyloxycarbonyl)pyrrolidine or 1,4-bis(N,N'-diisopropylaminocarbonyloxy)cyclohexane Other compounds.

Other thermal base generators such as 2-nitrobenzyl cyclohexylcarbamate or O-carbamoylhydroxyamines amide.

In a specific example of the present invention, the compound (E) may be used in an amount of from 0.1 part by weight to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B), preferably from 0.5 part by weight to 9 parts by weight. Part by weight, and more preferably from 1 part by weight to 8 parts by weight. When the photosensitive resin composition of the present invention does not use the compound (E), the obtained photosensitive resin composition has a defect of poor sputtering resistance after the lithographic process.

Further, the compound (E) is preferably a thermal acid generator, more preferably an ionic thermal acid generator.

The solvent (F) is selected from a soluble pigment (A), an alkali-soluble resin (B), an ethylenically unsaturated group-containing compound (C), a photoinitiator (D), and a compound (E), and The components that react with each other and have appropriate volatility.

The solvent (F) may be the same as the solvent used to prepare the alkali-soluble resin (B), and will not be described herein. Preferably, the solvent (F) is selected from the group consisting of propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.

The solvent (F) may be used in an amount of from 400 parts by weight to 5,000 parts by weight, preferably from 700 parts by weight to 4,500 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 1000 parts by weight to 4000 parts by weight.

The photosensitive resin composition of the present invention may optionally contain a dye (G). According to the use with the aforementioned pigment (A), the dye (G) can select a dye (G) of a specific spectrum. In a specific example of the present invention, the dye (G) may be an azo dye, an azo metal complex dye, an anthraquinone dye, an indigo dye, a sulfonium dye, a phthalocyanine dye, a diphenylmethane dye, or a triphenylmethane. Dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes or oxazine dyes, and the like.

In a preferred embodiment of the present invention, the dye (G) may be CI solvent red 2, CI solvent red 24, CI solvent red 27, CI solvent red 49, CI solvent red 52, CI solvent red 57, CI solvent red. 89, CI solvent red 111, CI solvent red 114, CI solvent red 119, CI solvent red 124, CI solvent red 135, CI solvent red 136, CI solvent red 137, CI solvent red 138, CI solvent red 139, CI solvent red 143, CI solvent red 144, CI solvent red 145, CI solvent red 146, CI solvent red 147, CI solvent red 148, CI solvent red 149, CI solvent red 150, CI solvent red 151, CI solvent red 152, CI solvent red 155, CI solvent red 156, CI solvent red 162, CI solvent red 168, CI solvent red 169, CI solvent red 170, CI solvent red 171, CI solvent red 172, CI solvent red 177, CI solvent red 178, CI solvent red 179, CI Solvent Red 181, CI Solvent Red 190, CI Solvent Red 191, CI Solvent Red 194, CI Solvent Red 199, CI Solvent Red 200, CI Solvent Red 201, CI Solvent Red 299, CI Direct Red 2, CI Direct Red 81, CI acid red 1, CI acid red 14, CI acid red 27, CI acid 52, CI acid red 87, CI acid red 88, CI acid red 289, CI alkaline red 1, CI medium red 3, CI ice dyed red 21, CI red reduction 1, CI reduction red 2, CI reduction red 15, CI Red reduction 23, CI reduction red 41, CI reduction red 47, CI dispersion red 1, CI dispersion red 11, CI dispersion red 15, CI dispersion red 22, CI dispersion red 60, CI dispersion red 92, CI dispersion red 146, CI Disperse red 191, CI disperse red 283, CI disperse red 288, CI active red 12. The aforementioned dyes (G) may be used singly or in combination of plural kinds.

The dye (G) is used in an amount of from 0 part by weight to 50 parts by weight, preferably from 0 part by weight to 40 parts by weight, based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight, and more preferably 0 parts by weight to 30 parts by weight.

The photosensitive resin composition of the present invention may optionally include an additive (H), for example, a filler, a polymer compound other than the alkali-soluble resin (B), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like. .

The additive (H) may be used singly or in combination, and the additive (H) includes, but is not limited to, a filler such as glass or aluminum; an alkali-soluble resin such as polyvinyl alcohol, polyethylene glycol monoalkyl ether or polyfluoroalkyl acrylate. Polymer compound other than (B); vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, nitrogen-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidylpropyl Trimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy a adhesion promoter such as decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane; 2,2-thio Antioxidant such as bis(4-methyl-6-tert-butylphenol) or 2,6-di-tert-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxybenzene Ultraviolet absorber such as 5-chlorophenyl azide or alkoxyphenone; and sodium polyacrylate Anti-agglomerating agent.

The additive (H) is used in an amount of from 0.1 part by weight to 10 parts by weight, based on the total amount of the alkali-soluble resin (B), and is preferably from 0.3 part by weight to 7 parts by weight, and more preferably 0.5 parts by weight to 4 parts by weight.

The present invention also provides a method of producing a color filter comprising the steps of forming a pixel colored layer on a substrate by using the above-mentioned photosensitive resin composition, thereby producing and providing a color filter.

In other words, the method for manufacturing the color filter of the present invention is mainly mixed into a solution by a coating method such as rotary coating, cast coating, ink-jet coating or roll coating. The aforementioned photosensitive composition in the state is coated on the substrate. After coating, most of the solvent is removed by drying under reduced pressure, and the solvent is removed by pre-bake to form a pre-baked coating film. Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. The drying under reduced pressure is usually carried out at a pressure of from 0 to 200 mm-Hg for from 1 second to 60 seconds, and the pre-baking is carried out at a temperature of from 70 ° C to 110 ° C for from 1 minute to 15 minutes. After prebaking, the prebaked film was exposed to a designated mask and immersed in a developing solution at a temperature of 23 ± 2 ° C for development. After 15 seconds to 5 minutes, the unexposed portions are removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, and i-line, and the ultraviolet device may be a (super) high-pressure mercury lamp or a metal halide lamp.

The substrate may be, for example, an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, a soda glass, or a glass having a transparent conductive film attached thereto for a liquid crystal display device; or A photoelectric conversion device substrate (for example, a germanium substrate) such as a solid-state imaging device. These substrates generally form a black matrix that separates the colored layers of each pixel.

Further, specific examples of the developer may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, and diethyl ether. Amine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine, 1,8-diazabicyclo-(5,4,0)-7-undecene An alkaline aqueous solution composed of a basic compound. The concentration of the developer may generally be 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.

When the developer composed of the alkaline aqueous solution is used, it is usually washed with water after development, and then air-dried with compressed air or compressed nitrogen.

After drying, the substrate having the photo-curing coating layer is heated by a heating device such as a hot plate or an oven at a temperature of 100 ° C to 280 ° C for 1 to 15 minutes to remove volatile components in the coating film and to make the coating film The unreacted ethylenically unsaturated double bond undergoes a thermosetting reaction. A photosensitive resin composition of each color (mainly including red, green, and blue colors) is repeatedly operated in the same step three times on a predetermined pixel to obtain a pixel coloring layer of three colors of red, green, and blue.

Next, on the pixel colored layer, an ITO (indium tin oxide) deposited film is formed under vacuum at a temperature of 220 ° C to 250 ° C, and if necessary, after etching and wiring the ITO deposited film, the liquid crystal alignment film is coated. The quinone imine can be used as a color filter for a liquid crystal display device.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

The liquid crystal display device of the present invention mainly comprises a color filter (CF) substrate obtained by the above method for producing a color filter, and a drive substrate provided with a thin film transistor (TFT). First, a gap (cell gap) is interposed between the two substrates. After the peripheral portions of the two substrates are bonded together with a sealing agent, the liquid crystal is filled in the gap between the surface of the substrate and the sealing agent. Then, the injection hole is sealed to constitute a liquid crystal cell. Next, a liquid crystal display device can be obtained by laminating a polarizing plate on the outer surface of the liquid crystal cell (that is, on the other side faces of the respective substrates constituting the liquid crystal cell).

The liquid crystal used in the above, 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.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention. Synthesis of First Alkali Soluble Resin (B-1) <Synthesis Example B-1-1>

A stirrer, a condenser, a dropping funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 49.0 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, the absorption peak of the isocyanate group of the raw material was measured by infrared spectroscopy (IR spectroscopy), and it was confirmed that it disappeared, and it was confirmed by the absorption peak of the formed urethane bond, and it was confirmed. Completed for the reaction. The obtained product is the first alkali-soluble resin (B-1-1) of Synthesis Example B-1-1, which is a pale yellow liquid having a weight average molecular weight of 1800 and a viscosity of 1074 mPa. S, and the epoxy equivalent is 265. The obtained product has a structure represented by the formula (I-1), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is Is 3. <Synthesis Example B-1-2>

A stirrer, a condenser, a dropping funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 24.5 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, the absorption peak of the isocyanate group of the starting material was measured by infrared spectroscopy, and it was confirmed that it had disappeared, and was replaced by the absorption peak of the formed urethane bond, and it was confirmed that the reaction was completed. The obtained product is the first alkali-soluble resin (B-1-2) of Synthesis Example B-1-2, which is a pale yellow liquid having a weight average molecular weight of 1,700 and a viscosity of 1,184 mPa. S, and the epoxy equivalent is 219. The obtained product has a structure represented by the formula (I-1), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is Is 6. <Synthesis Example B-1-3>

A stirrer, a condenser, a dropping funnel, and a thermometer were placed in a 1 liter reaction bottle. 100 g of polyglycerol polyglycidyl ether (epoxy equivalent: 168; manufactured by Sakamoto Pharmaceutical Co., Ltd. and model SR-4GL) was placed in a reaction flask. After heating to 80 ° C, 441.0 g of 3-isocyanate propyl triethoxy decane was added to the dropping funnel and added dropwise to the reaction flask. After stirring at 80 ° C for 4 hours, the absorption peak of the isocyanate group of the starting material was measured by infrared spectroscopy, and it was confirmed that it had disappeared, and was replaced by the absorption peak of the formed urethane bond, and it was confirmed that the reaction was completed. The obtained product is the first alkali-soluble resin (B-1-3) of Synthesis Example B-1-3, which is a pale yellow liquid having a weight average molecular weight of 2,500 and a viscosity of 1374 mPa. S, and the epoxy equivalent is 910. The obtained product has a structure represented by the formula (I-1), wherein b is 3, d is 3, the average value of a is 9, and the molar ratio of the content of the glycidyl group to the content of the ethoxylated alkyl group is Is 0.3. Synthesis of Second Alkali Soluble Resin (B-2) <Synthesis Example B-2-1>

100 parts by weight of an antimony 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 parts by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at In the range of 100 ° C to 110 ° C, after 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heating to 110 ° C to 115 ° C, after 2 hours of reaction, a second alkali-soluble resin of the synthetic example B-2-1 having an acid value of 98.0 mg-KOH/g and a number average molecular weight of 1,623 was obtained (B -2-1). <Synthesis Example B-2-2>

100 parts by weight of an antimony 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 parts by weight 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min, and the temperature was maintained at In the range of 100 ° C to 110 ° C, after 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, while 13 parts by weight of benzophenone tetracarboxylic dianhydride was added, and the reaction was carried out at 90 ° C to 95 ° C for 2 hours. Next, 6 parts by weight of tetrahydrophthalic anhydride was added and reacted at 90 ° C to 95 ° C for 4 hours to obtain Synthesis Example B having an acid value of 99.0 mg-KOH/g and a number average molecular weight of 2,162. a second alkali-soluble resin of -2-2 (B-2-2). <Synthesis Example B-2-3>

400 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent: 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight The triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mg-KOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain Synthesis Example B having an acid value of 102 mg-KOH/g and a number average molecular weight of 2,589. -2-3 of a second alkali soluble resin (B-2-3). <Synthesis Example B-2-4>

200 parts by weight of an epoxy compound (Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent: 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol, and 2.5 parts by weight The triphenylphosphine and 200 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.5 mg-KOH/g was obtained. Next, 85 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain Synthesis Example B having an acid value of 105 mg-KOH/g and a number average molecular weight of 3,410. a second alkali soluble resin (B-2-4) of -2-4. Synthesis of Acrylic Resin <Synthesis Example B'-1>

A stirrer, thermometer, condenser, and nitrogen inlet were placed on a four-necked flask and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 100 °C. Next, 18 parts by weight of methacrylic acid (abbreviated as MAA), 18 parts by weight of 2-hydrocarbyl methacrylate (abbreviated as HEMA), 64 parts by weight of benzyl methacrylate (abbreviated as BzMA) and 4.5 parts by weight of 2,2'-azobis-2-methylbutyronitrile (abbreviated as AMBN) was dissolved in 100 parts by weight of propylene glycol methyl ether acetate, and the mixed solution was dropwise added within 2 hours. In a four-necked flask. After reacting at 100 ° C for 6.5 hours, 20 parts by weight of 2-methylglycidyl methacrylate (abbreviated as MGMA) was added to a four-necked flask filled with nitrogen, and the temperature was raised to 110 °C. After reacting for 6 hours, the acrylic resin (B'-1) of Synthesis Example B'-1 was obtained. Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 6 were prepared according to Table 1. <Example 1>

30 parts by weight of CI Pigment Red 254 (abbreviated as A-1), 1 part by weight of the first alkali-soluble resin (abbreviated as B-1-1) obtained by the above Synthesis Example B-1-1, 99 parts by weight The second alkali-soluble resin (abbreviated as B-2-1) prepared in the above Synthesis Example B-2-1, 20 parts by weight of EO-modified trimethylolpropyl trimethacrylate (referred to as C- 1), 5 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinyl) (abbreviated as D-1) and 0.1 parts by weight A part by weight of propylene benzophenone oxime (abbreviated as E-1) is added to 400 parts by weight of ethyl 3-ethoxypropionate (abbreviated as F-1), and a shaking type is used. The stirrer) was uniformly stirred to obtain the photosensitive resin composition of Example 1. The obtained photosensitive resin composition was evaluated by the following evaluation method of the sputtering resistance, and the obtained result is shown in Table 1. <Example 2 to Example 20>

In the second to the ninth embodiments, the preparation method is the same as the method for producing the photosensitive resin composition of the first embodiment, except that the examples 2 to 20 change the types of the raw materials in the photosensitive resin composition and The usage amount, the formulation and the evaluation results are shown in Table 1, and are not described here. <Comparative Example 1 to Comparative Example 6>

In Comparative Example 1 to Comparative Example 6, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Comparative Examples 1 to 6 changed the types of raw materials in the photosensitive resin composition and The usage amount, the formulation and the evaluation results are shown in Table 1, and are not described here. Table 1: Splash resistance evaluation method

The photosensitive resin compositions obtained in Examples 1 to 20 and Comparative Examples 1 to 6 were changed in chromaticity before and after sputtering, whereby the sputtering resistance was evaluated. Briefly, the photosensitive resin compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 6 were applied by spin coating to a glass substrate having a size of 100 mm × 100 mm. . Then, drying under reduced pressure was carried out at a pressure of 100 mm-Hg for 30 seconds. Next, a prebaking process was carried out at a temperature of 80 ° C for 2 minutes to form a prebaked film having a film thickness of 2.5 μm. After the pre-baking process, the pre-baked coating film was irradiated with ultraviolet light having an energy of 60 mJ/cm ² (exposure machine model: Canon PLA-501F), and the exposed pre-baked coating film was immersed in a developing solution at 23 ° C. in. After 1 minute, the coating film was washed with pure water and baked at 230 ° C for 30 minutes to form a pixel colored layer on the glass substrate.

Next, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model number MCPD), and then a film resistance was formed by sputtering on the pixel colored layer. An ITO film of 14.6 Ω/sq and a film thickness of 2040 Å was used to prepare the color filter, wherein the sputtering temperature was 220 °C.

Thereafter, the chromaticity of the color filter is measured again, and the chromaticity change (ΔEab*) is calculated by the following formula (V), and the smaller the chromaticity change (ΔEab*) is, the better the sputter resistance is. Evaluated according to the following evaluation criteria: Formula (V) ◎: ΔEab*<1; ○: 1≦ΔEab*<2; Δ: 2≦ΔEab*<3; ╳: 3≦ΔEab*.

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

Claims (10)

A photosensitive resin composition comprising: a pigment (A); an alkali-soluble resin (B); an ethylenically unsaturated group-containing compound (C); a photoinitiator (D); a compound (E); and a solvent (F) Wherein: the alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1) having a structure as shown in formula (I-1) and/or The structure shown by the formula (I-2): Formula (I-1) In the formula (I-1): D represents a hydrogen atom, a glycidyl group or a structure as shown in the formula (I-1-1), wherein at least one D represents a formula (I-1-). 1) the structure shown, and at least two D represent glycidyl groups; a represents an integer from 1 to 100; In the formula (I-1-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer up to 3; and d represents an integer from 1 to 10; Formula (I-2) In the formula (I-2): D' represents a hydrogen atom, a glycidyl group or a structure represented by the following formula (I-2-1), wherein at least one D' represents a formula (I-2) -1) the structure shown, and at least two D' represent a glycidyl group; AO represents an alkylene group having a carbon number of 2 to 6; f represents an integer of 4 to 10; g represents an integer of 0 to 10; Represents an integer from 0 to 10; and i represents an integer from 0 to 10: In the formula (I-2-1), D ₁ represents an alkyl group having 1 to 6 carbon atoms; D ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; b represents 1 An integer of from 3; and d represents an integer from 1 to 10; and the compound (E) is selected from the group consisting of a thermal acid generator and a thermal base generator. The photosensitive resin composition of claim 1, wherein the alkali-soluble resin (B) further comprises a second alkali-soluble resin (B-2) which is polymerized by a mixture The reaction is prepared, and the mixture comprises an epoxy compound (b-2-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2) -2). The photosensitive resin composition of claim 2, wherein the epoxy compound (b-2-1) having at least two epoxy groups has a structure represented by formula (II-1) or formula (II-2) ; In the formula (II-1), Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and carbon. An alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms; In the formula (II-2), Y ₅ to Y ₁₈ 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; An integer representing 0 to 10. The photosensitive resin composition according to claim 1, wherein the compound (E) is a thermal acid generator. The photosensitive resin composition of claim 1, wherein the pigment (A) is used in an amount ranging from 30 to 500 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (B); The unsaturated group compound (C) is used in an amount ranging from 20 to 200 parts by weight; the photoinitiator (D) is used in an amount ranging from 5 to 100 parts by weight; and the compound (E) is used in an amount ranging from 0.1 to 0.1. 10 parts by weight; and the solvent (F) is used in an amount ranging from 400 to 5000 parts by weight. The photosensitive resin composition of claim 1, wherein the first alkali-soluble resin (B-1) is used in an amount ranging from 0.1 to 30% by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (B). Share. The photosensitive resin composition of claim 2, wherein the second alkali-soluble resin (B-2) is used in an amount ranging from 70 to 99.9 by weight based on the total amount of the alkali-soluble resin (B) used in an amount of 100 parts by weight. Share. A method of producing a color filter, which comprises forming a pixel layer using the photosensitive resin composition according to any one of claims 1 to 7. A color filter produced by the method of producing a color filter according to claim 8. A liquid crystal display device comprising the color filter according to claim 9.