Photosensitive resin, photosensitive resin composition using the same, cured product thereof, and color filter

Abstract

To provide a photosensitive resin composition giving a cured product which is good in alkaline developability, linearity and pattern shape, has good balance between surface curability and depth curability and suppresses generation of wrinkles on the surface and to provide a photosensitive resin using the same.SOLUTION: There are provided a resin represented by the following general formula (1) and a photosensitive resin composition using the same. R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group. E represents -CRxRy-, -CO-, -SO2-, -O-, -S-, -SS-, -SO-, -OCO-, -SiRxRy- or a direct bond. A represents a tetravalent tetracarboxylic acid residue. G1 represents an alkylene group having 1 or more carbon atoms. D represents a hydrogen atom or the like and n1 and n2 independently represent an integer of 0 or more. In addition, J represents a hydrogen atom or a substituent having a carboxy group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin that is cured by irradiation with light such as ultraviolet light or an electron beam and that can be patterned by performing an alkali development treatment; a photosensitive resin composition using this resin; and a cured product using the photosensitive resin composition and a color filter using the cured product. [Background technology]

[0002] In recent years, color liquid crystal displays (LCDs) and organic light-emitting diode (OLED) displays (OLEDs) have become commonplace in televisions, monitors, smartphones, and other displays. These LCDs, OLEDs, touch panels, and image sensors often incorporate components with patterns formed using photosensitive resin compositions. Among these components, color filters, for example, are used in almost all LCDs and, especially, in OLEDs, primarily in large-screen televisions, and are an important component that influences visibility. Color filters are typically manufactured by forming a black matrix on the surface of a transparent substrate, such as a glass or plastic sheet, followed by sequentially forming different hues of red, green, and blue (RGB) in a striped or mosaic pattern. While the pattern size varies depending on the application and color of the color filter, RGB pixels have been thinned from 100 μm to less than 50 μm, and black matrices have been thinned from 20 μm to less than 10 μm. Therefore, photosensitive resin compositions used to obtain color filters are required to form patterns with high dimensional precision. Furthermore, if the balance between the surface curability and deep curability of the photosensitive resin composition is lost, wrinkles will occur on the matrix surface during the baking process of the color filter. Depending on the application of the color filter, the unevenness of the filter surface can affect the visibility of displays such as LCDs, so the balance between the surface curability and deep curability is also an important property.

[0003] Furthermore, during the manufacture of LCDs, a transparent cured film (hereinafter referred to as the protective film) is formed on the surface of the color filter as a protective film. This film is formed for the purposes of smoothing out the irregularities on the color filter surface, improving the durability of the color filter against subsequent heat treatment and chemical treatment, and improving the reliability of the LCD. The protective film for color filters is required to have excellent transparency, chemical resistance, adhesion, hardness, flatness, heat resistance, and electrical reliability.

[0004] There are two methods for forming the protective film: heat curing and photolithography. The method to be used is determined by the color filter panel design and processing design, depending on the characteristics the protective film should have (the characteristics required of the protective film described above) and whether patterning is required. When forming a protective film using photolithography, in order to form an appropriate pattern, in addition to the characteristics described above, there is also an increasing demand for the photosensitive resin composition to have the ability to absorb short-wavelength ultraviolet light (high sensitivity) that does not affect the color display of the LCD.

[0005] Generally, photosensitive resin compositions for such applications, as well as resin compositions used in semiconductors, contain resins (including monomers and oligomers) that are polymerizable, alkali-soluble, or have both properties, or contain photopolymerization initiators, etc.

[0006] For example, Japanese Patent Laid-Open Publication No. 2017-219838 (Patent Document 1) discloses a photosensitive resin (copolymer) obtained by adding an epoxy group-containing (meth)acrylate to a reaction product of a fluorene compound and a tetracarboxylic dianhydride, and a photosensitive resin composition using the same. In this document, although the properties of the photosensitive resin composition are useful, the production method is such that the reaction that imparts polymerizability and the reaction that imparts alkali solubility are inseparable, and changing each property inevitably affects the other properties, so there is thought to be room for improvement.

[0007] Furthermore, Japanese Patent Laid-Open Publication No. 2008-156613 (Patent Document 2) and Japanese Patent Laid-Open Publication No. 2008-268854 (Patent Document 3) disclose photosensitive resin compositions using a carboxyl group-containing copolymer obtained by reacting a diol compound containing a polymerizable unsaturated group with a tetracarboxylic acid or its dianhydride, followed by reaction with an epoxy compound containing a polymerizable unsaturated bond group and further reaction with a dicarboxylic acid or its monoanhydride, resulting in a photosensitive resin with high sensitivity and a wide development adhesion margin. However, these publications do not address the balance between surface curability and deep curability. The inventions described in these publications contain a large amount of acrylic groups (acrylates), resulting in high sensitivity, which leads to an imbalance in curability between the surface and deep portions of the pattern, resulting in defects such as wrinkles on the surface and thick lines.

[0008] In other words, increasing the concentration of polymerizable unsaturated groups (acrylate concentration) is considered to increase sensitivity. However, simply increasing the acrylate concentration makes it more likely that a photocuring reaction will occur near the surface of the composition. When attempting to form a pattern according to a mask pattern, photocuring in the deeper portions is likely to be insufficient, resulting in dissolution of the deeper portions during development and a thinner pattern (a so-called undercut state). In this case, increasing the exposure dose can eliminate undercutting, but there is a risk that only a pattern thicker than the mask pattern can be formed. Therefore, simply increasing the acrylate concentration is not enough to increase sensitivity; this phenomenon is more pronounced when forming a black resist with a relatively low light transmittance. Therefore, achieving a balance between the surface curability and deep curability of a photosensitive resin composition is a very important technique for forming an appropriate pattern that matches the mask pattern, but no method has been proposed in the prior art to solve this problem. In addition, as another attempt to obtain a photosensitive resin composition that has a good balance between surface curability and deep curability, there is a method of designing a blend using an alkali-soluble resin that does not have a polymerizable unsaturated group and a photopolymerizable monomer. However, in this case, unless a certain amount of resin component is blended, there is another problem that it becomes difficult to form a pattern that has a small contact area with the substrate, particularly glass. For example, there is a concern that the composition may peel off during development or that sufficient adhesion may not be obtained during a reliability test. This phenomenon also becomes a problem when the resin component content is low, such as in black resist. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2017-219838 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-156613 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-268854 Summary of the Invention [Problem to be solved by the invention]

[0010] In view of the existence of such conventional techniques, the inventors of the present application conducted extensive research into the development of a photosensitive resin composition that combines a balance between sensitivity and alkaline developability. As a result, they found that this can be achieved by, in particular, performing an acrylic group introduction reaction using a specific component (C) described below and blocking the terminal structure using a specific component (D) so as to enable adjustment of the acid value and adjustment of the sensitivity to be performed separately.

[0011] Therefore, an object of the present invention is to provide a photosensitive resin composition using a photosensitive resin that has a good balance between sensitivity and alkaline developability.

[0012] Another object of the present invention is to provide a photosensitive resin composition using a photosensitive resin that has a good balance between surface curability and deep curability. [Means for solving the problem]

[0013] That is, the gist of the present invention is as follows. [1] A resin characterized by being represented by the following general formula (1): [ka] Here, R1, R2, R3, and R4 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. x R y -, -CO-, -SO2-, -O-, -S-, -SS-, -SO-, -OCO-, -SiR x R y - or indicates a direct bond, R x and R y represents hydrogen, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. x and R y may be bonded to each other to form a ring. A represents a tetravalent tetracarboxylic acid residue. G1 represents an alkylene group having one or more carbon atoms, D represents a hydrogen atom, a substituent having a polymerizable unsaturated group, or a substituent having a carboxy group and a polymerizable unsaturated group, and n1 and n2 independently represent an integer of 0 or more. J represents a hydrogen atom or a substituent having a carboxy group. However, at least one of the multiple Ds in general formula (1) represents a substituent having a carboxy group and a polymerizable unsaturated group. [2] The resin according to [1], characterized in that in general formula (1), D represents a hydrogen atom or a substituent represented by the following general formula (2), and J represents a hydrogen atom or a substituent represented by the following general formula (3): [ka] Here, G2 independently represents a single bond or an alkylene group having 1 or more carbon atoms, R5 represents a hydrogen atom or a methyl group, and Q represents a trivalent hydrocarbon group having 2 to 8 carbon atoms. Furthermore, n3 represents an integer of 1 or more, and when n3 is 2 or more, multiple G2 in the formula may be the same or different. [ka] Here, L represents a di- or tricarboxylic acid residue, and n4 represents 1 or 2. [3] A photosensitive resin composition containing the following (i) to (ii): (i) The resin described in [1] or [2] (ii) Photopolymerization initiator [4] The photosensitive resin composition according to [3], further comprising (iii) a photopolymerizable monomer having at least one ethylenically unsaturated bond. [5] The photosensitive resin composition according to [3] or [4], further comprising (iv) a dispersoid. [6] A cured product obtained by curing the photosensitive resin composition according to any one of [3] to [5]. [7] A color filter comprising the cured product according to [6]. [Effects of the Invention]

[0014] In the present invention, a carboxyl group- and photopolymerizable unsaturated group-containing copolymer (hereinafter referred to as photosensitive resin) suitable for use in photosensitive resin compositions is obtained by reacting a bis-hydroxy(alkoxy) group-containing compound with a tetracarboxylic acid or its dianhydride, reacting the resulting reaction product with an oxirane compound (epoxy compound) having a polymerizable unsaturated group, and then reacting the resulting product with a dicarboxylic acid or its monoanhydride. Furthermore, because this photosensitive resin has good alkaline developability, it also exhibits good linearity and pattern shape. Furthermore, because it has a good balance between surface curability and deep curability, it is possible to obtain a photosensitive resin composition that exhibits almost no wrinkling on the surface after heat treatment, even when used in a thick-film color filter. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below. To achieve the above-mentioned object, the present invention is characterized by using a resin represented by general formula (1). The photosensitive resin composition of the present invention is a photosensitive resin composition that contains such a resin represented by general formula (1) and a photopolymerization initiator as essential components, and depending on the application, exhibits its function by combining it with a photopolymerizable monomer having at least one ethylenically unsaturated bond, a dispersoid, etc. The resin represented by general formula (1) has radical polymerizability derived from the photopolymerizable unsaturated group, and also has alkali solubility due to the presence of an acidic group derived from a dicarboxylic acid or its acid monoanhydride used as a blocking agent.

[0016] The resin represented by general formula (1) is prepared by first reacting a bis-phenol compound or a bis-hydroxyalkoxy group-containing compound (hereinafter referred to as a bis-hydroxy(alkoxy) group-containing compound) with a tetracarboxylic acid or its dianhydride. Because the bis-hydroxy(alkoxy) group-containing compound does not contain a polymerizable unsaturated group, the sensitivity of the entire resin can be controlled solely through the subsequent reaction of imparting the polymerizable unsaturated group. Furthermore, the use of a tetracarboxylic acid or its dianhydride allows for control of the weight-average molecular weight of the entire resin. The resulting reaction product is then reacted with an oxirane compound (epoxy compound) having a polymerizable unsaturated group, followed by further reaction with a dicarboxylic acid or its monoanhydride, resulting in a copolymer containing a carboxy group and a photopolymerizable unsaturated group. This allows for separate control of the impartation of polymerizable unsaturated groups and alkali-soluble groups (carboxy groups), allowing for independent modification of each parameter when desired to alter the properties of the photosensitive resin composition. The resin in the present invention has both a polymerizable unsaturated group and an alkali-soluble group (carboxy group), and therefore provides the photosensitive resin composition with excellent photocurability and good developability in an alkaline developer, thereby imparting excellent patterning properties, thereby improving the properties of resists and the like used in the fields of semiconductors and displays.

[0017] The resin represented by general formula (1) in the present invention is a carboxyl group- and photopolymerizable unsaturated group-containing copolymer produced using at least four components: (A) component: a bis-hydroxy(alkoxy) group-containing compound; (B) component: a tetracarboxylic acid or its dianhydride; (C) component: an oxirane compound (epoxy compound) having a polymerizable unsaturated group; and (D) component: a dicarboxylic acid, a tricarboxylic acid, or its monoanhydride. Specifically, when the carboxyl group-containing compound produced by reacting the hydroxyl group of component (A) with the acidic group of component (B) is designated as compound (AB), and the compound having a polymerizable unsaturated group produced by reacting the acidic group of compound (AB) with the epoxy group of component (C) is designated as compound (ABC), the hydroxyl group of compound (ABC) reacts with the acidic group of component (D), thereby obtaining the desired copolymer, the resin of formula (1).

[0018] The synthesis method for compound (AB) is not particularly limited, but can be carried out at a reaction temperature of, for example, 90°C to 150°C, preferably 100°C to 140°C. It is preferable to quantitatively react components (A) and (B) so that the molar ratio (B / A) of components (A) to (B) is 50% or more and less than 100%. The weight-average molecular weight is not limited because it depends on the raw material species and compounding ratio of components (A) and (B), but is about 1000 to 12000, preferably about 1200 to 8000.

[0019] The photosensitive resin represented by general formula (1) can be obtained from the above compound (AB), which has a structure in which the D and J portions in general formula (1) remain hydrogen atoms, and the average value of n1 in the structural formula is preferably in the range of 0 to 20, more preferably in the range of 0 to 8. Furthermore, n2 is independently 0 or more, preferably 0 to 3, and more preferably 1 or 2. G1 represents an alkylene group having 1 or more carbon atoms, and preferably has 2 to 6 carbon atoms, and more preferably has 2 to 3 carbon atoms.

[0020] Next, the synthesis method of compound (ABC) is not particularly limited, and typical reaction conditions for the addition reaction of a carboxylic acid and an oxirane compound can be used. For example, the reaction temperature is preferably in the range of 40 to 120°C, more preferably about 50 to 100°C. The molar ratio of component (C) to compound (AB) [C / (AB)] is preferably 50% to 250%, more preferably 100% to 200%. Since component (C) is an oxirane compound having a polymerizable unsaturated group, the reaction of at least one component (C) with compound (AB) results in at least one D in general formula (1) becoming a substituent having a carboxyl group and a polymerizable unsaturated group, in combination with the subsequent reaction of component (D), which will be described later. In other words, the balance between the surface curability and deep curability of the resin composition can be controlled by the blending ratio of component (C) to be reacted. The weight average molecular weight is not limited because it depends on the type and blending ratio of the raw materials of component (C), but is about 1,000 to 15,000, preferably about 1,200 to 9,000.

[0021] The synthesis method for reacting compound (ABC) with component (D) is not particularly limited. For example, the reaction temperature is preferably in the range of 20 to 120°C, more preferably about 40 to 100°C. The molar ratio of component (D) to compound (ABC) [D / (ABC)] is preferably 10 to 500%, more preferably 30 to 400%. The molar ratio of component (D) can be freely changed to adjust the acid value of the resin represented by general formula (1). The weight-average molecular weight is not limited because it depends on the raw material type and blending ratio of component (D), but is approximately 1500 to 20,000, preferably approximately 2500 to 10,000. The acid value (solid acid value) of the resin represented by general formula (1) obtained by reacting component (D) is not limited because it depends on the raw material type and blending ratio of component (D), but is approximately 20 to 200 mgKOH / g, preferably approximately 20 to 150 mgKOH / g.

[0022] First, component (A) will be explained. The component (A) is a bis-hydroxy(alkoxy) group-containing compound having a structure in which an alkylene oxide according to the structure G1 is added to a bisphenol compound having the structures E and R1 to R4 in general formula (1). Specific examples of preferred E include -CR x R y -, -CO-, -SO2-, -O-, -S-, -SS-, -SO-, -OCO-, -SiR x R y - or a direct bond, etc. More preferably, -CR x R y -, -CO-, -SO2-, -O-, -SiR x R y - or a direct bond. R1 to R4 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. R x and R y Preferred examples of R include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, or a substituent combining these groups. More preferred examples include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 3 to 9 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, or a substituent combining these groups. x and R y may be bonded to each other to form a ring, and examples of the formed ring include a fluorenediyl group, an adamantanediyl group, and an indanediyl group.

[0023] Preferable specific examples of the bis-hydroxy(alkoxy) group-containing compound that can be considered from the preferable specific examples of E include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane ... dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,Examples of suitable bis(hydroxy(poly)C2-4 alkoxyphenyl)fluorenes include 9,9-bis(hydroxy(poly)C2-4 alkoxyphenyl)fluorene, such as 5-dibromophenyl)fluorene, 4,4'-biphenol, and 3,3'-biphenol. Among these, those using a 9,9-fluorenediyl group are more preferred. These bis-hydroxy(alkoxy) group-containing compounds can be used alone or in combination of two or more.

[0024] Next, as the tetracarboxylic acid or its dianhydride, which is the component (B) to be reacted with the bis-hydroxy(alkoxy) group-containing compound, it is preferable to use a tetracarboxylic acid or its dianhydride that can react with the hydroxyl groups in the bis-hydroxy(alkoxy) group-containing compound. Preferred examples include saturated linear hydrocarbon tetracarboxylic acids such as butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid; alicyclic tetracarboxylic acids such as cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid; and aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and diphenyl sulfone tetracarboxylic acid, as well as their dianhydrides. Biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and biphenyl ether tetracarboxylic acid or their dianhydrides are preferred, and biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and their dianhydrides are more preferred. These tetracarboxylic acids or their dianhydrides can be used alone or in combination. A in the general formula (1) represents a tetracarboxylic acid residue derived from the component (B).

[0025] Next, the oxirane compound (epoxy compound) (C), which is the component (A) to be reacted with the reaction product of the components (A) and (B) [compound (AB)], is one that can react with the epoxy group in component (C) and the carboxy group in compound (AB), and also contains one or more polymerizable unsaturated groups in the molecule. After reaction with compound (AB), component (C) becomes a substituent represented by general formula (2) (where J is a hydrogen atom at this stage), and has an epoxy group at the site that becomes Q after the reaction. In component (C) and general formula (1), G2 independently represents a single bond or an alkylene group having 1 or more carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms. R5 represents a hydrogen atom or a methyl group. n3 represents an integer of 1 or greater, preferably 1 to 3. When n3 is 2 or greater, multiple G2s may be the same or different. After the reaction, Q represents a trivalent hydrocarbon group having 2 to 8 carbon atoms, preferably a cycloalkane group. Specific examples of the cycloalkane group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.

[0026] Preferred specific examples of such component (C) include glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. These oxirane compounds can be used alone or in combination of two or more.

[0027] The dicarboxylic acids, tricarboxylic acids, or acid monoanhydrides of component (D), which are further reacted with compound (ABC), the reaction product of components (A), (B), and (C), are those capable of reacting the hydroxyl groups of compound (ABC) with the acidic groups of component (D). Specific preferred examples of component (D) include saturated linear hydrocarbon dicarboxylic acids such as succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid; saturated cyclic hydrocarbon dicarboxylic acids such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyl-endomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid; and acid monoanhydrides thereof. Preferably, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, trimellitic acid, or anhydrous compounds thereof, more preferably succinic acid, itaconic acid, tetrahydrophthalic acid, or an acid monoanhydride thereof, and these dicarboxylic acids or acid monoanhydrides can be used alone or in combination of two or more. J in general formula (1) is derived from component (D), and therefore, in the skeleton of general formula (1), L represents a divalent or trivalent carboxylic acid residue, and n4 represents 1 or 2.

[0028] In the synthesis of the resin of the present invention, which is represented by general formula (1) and characterized by having a carboxy group and a polymerizable unsaturated group in the molecule, the solvent to be used is not particularly limited. However, it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent. Specific examples of such solvents include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. The catalyst to be used is not particularly limited, and known catalysts such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine can be used. The above solvents and catalysts can be used alone or in combination of two or more.

[0029] In order to achieve the effect as a photosensitive resin composition, component (ii) a photopolymerization initiator is an essential component. In the present invention, the photopolymerization initiator is used to include a sensitizer. Specific examples of the photopolymerization initiator include acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(N,N-diethylamino)benzophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether; 2-methyl-1-[4-(methylsulfanyl)phenyl]-2-morpholino; α-aminoalkylphenone compounds such as 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide, biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole, and 2-trichloromethyl halomethylthiazole compounds such as 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; titanocene compounds such as bis(η5-cyclopentadienyl)bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]titanium; 2,4,6-tris(trichloromethyl)-1,3,5-triazine; 2-[3,4-(methylenedioxy)- triazine compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; (2,4,6-trimethylbenzoyl)diphenylphosphine oxide; bis(2,4,Acylphosphine oxide compounds such as 6-trimethylbenzoyl)phenylphosphine oxide, quinone compounds such as camphorquinone, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), captopropionate), thiol compounds such as 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, etc., tertiary amines such as triethanolamine and triethylamine, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione = 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone, o-acetyloxime, (2-methylphenyl)( Oxime ester compounds such as 7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyloxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(o-acetyloxime), ethanone,1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-o-acetyloxime, etc. can be used alone or in combination of two or more without particular limitation.

[0030] The amount of component (ii) photopolymerization initiator used is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on a total of 100 parts by weight of the resin of general formula (1) (component (i)), the epoxy acrylate or its acid-added compound (described below) as other resin components optionally contained, and the photopolymerizable monomer having at least one ethylenically unsaturated bond (component (iii) described below), which may be added depending on the application. If the amount of component (ii) photopolymerization initiator used is too small, the photopolymerization rate may decrease and the sensitivity of the photosensitive resin composition may also decrease. On the other hand, if the amount used is too large, the sensitivity of the photosensitive resin composition may become too high, resulting in problems such as pattern line widths being wider than desired and pattern edges not being sharp.

[0031] In addition, component (iii) photopolymerizable monomers having at least one ethylenically unsaturated bond, which are necessary depending on the application, include, for example, monomers having a hydroxyl group such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of the epoxy (meth)acrylate include (meth)acrylic acid esters such as acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, and caprolactone-modified dipentaerythritol hexa(meth)acrylate; compounds having an ethylenic double bond include dendritic polymers having a (meth)acrylic group; and cardo epoxy (meth)acrylates such as bisphenol A-type epoxy (meth)acrylate, bisphenol F-type epoxy (meth)acrylate, bisphenol fluorene-type epoxy (meth)acrylate, diphenyl fluorene-type epoxy (meth)acrylate, phenol novolac-type epoxy (meth)acrylate, cresol novolac-type epoxy (meth)acrylate, and phenol aralkyl-type epoxy (meth)acrylate, or acid adducts thereof. These compounds can be used alone or in combination of two or more.

[0032] These components (iii) can be added depending on the application. When added, it is preferable to adjust the blending ratio of the component (i) to the other resin components, such as the epoxy acrylate and its acid-added compound described below, which are optionally contained. The blending ratio of these components [(i) + α] / (iii)] is preferably 20 / 80 to 100 / 0, and more preferably 40 / 60 to 90 / 10. If the amount of component (iii) is too large, the cured product after photocuring may become brittle, and the acid value of the coating film in the unexposed areas may be low, resulting in reduced solubility in alkaline developers and dull pattern edges. Therefore, when using (iii), it is preferable to keep the blending ratio within the above range. The above α represents the other resin components, such as the epoxy acrylate and its acid-added compound described below.

[0033] Furthermore, in the photosensitive resin composition of the present invention, a dispersoid (component (iv)) can be added if necessary depending on the desired application or function. The dispersoid (component (iv)) is not particularly limited, and may be one or more of organic pigments selected from red, blue, green, purple, yellow, cyan, magenta, brown, black, white, etc.; inorganic pigments such as titanium oxide pigments and composite oxide pigments; organic fillers such as acrylic polymer particles and urethane polymer particles; inorganic fillers such as silica, talc, mica, glass fiber, carbon fiber, calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate; metal or metal oxide nanoparticles; dyes; light-shielding materials; extender pigments; and fillers. In particular, when a light-shielding material such as a black resist is used, examples thereof include carbon black, chromium oxide, iron oxide, titanium black, aniline black, perylene black, and cyanine black. Among these, carbon black is preferred due to its excellent light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. Examples of extender pigments or fillers include glass fiber, silica, mica, and alumina.

[0034] The dispersoid of component (iv) can be used together with a dispersant, if necessary. Examples of such dispersants include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Specific examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

[0035] When the dispersoid of component (iv) is used, it is preferably in the range of 10 to 400 parts by weight, and more preferably 50 to 230 parts by weight, per 100 parts by weight of the total amount of the resin represented by general formula (1) of component (i), the other resin components described below, and the optional component (iii). If the amount is too small, the function expected from the addition of (iv) is difficult to achieve. On the other hand, if the amount is too large, the dispersion stability of the photosensitive resin composition decreases, impairing development characteristics and film-forming ability, so the above range is desirable.

[0036] The photosensitive resin composition of the present invention can be dissolved in a solvent or mixed with various additives as needed. That is, a solvent can be used in addition to the above-mentioned essential and optional components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. Examples of the esters include glycol ethers such as diethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.

[0037] Furthermore, the photosensitive resin composition of the present invention may contain known additives, such as other resins, curing agents, curing accelerators, surfactants, silane coupling agents, viscosity modifiers, antifoaming agents, leveling agents, ultraviolet absorbers, thermal polymerization inhibitors, antioxidants, and plasticizers, as needed.

[0038] Examples of the other resin components include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, melamine resins, and epoxy resins. Examples of epoxy resins include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L, manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds (e.g., EPPN-501H, manufactured by Nippon Kayaku Co., Ltd.), tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having a (meth)acrylic group containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3', Examples of epoxy compounds include 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide 2021P, manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolead GT401, manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups (e.g., HiREM-1, manufactured by Shikoku Chemicals Corporation), multifunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series, manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB JP-100, manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton. Furthermore, compounds obtained by reacting these epoxy compounds with compounds having a polymerizable unsaturated group (for example, acrylic acid or methacrylic acid) to give epoxy acrylates, and compounds obtained by adding acids to these epoxy acrylates, can also be used.

[0039] Examples of curing agents include amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, and the like that contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, and the like. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants. Examples of silane coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like. Examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.

[0040] The photosensitive resin composition of the present invention preferably contains, based on the solid content excluding the solvent, the total solid content of the essential components (i) and (ii) (including (iii) and (iv) depending on the formulation), of 60% by weight or more, preferably 75% by weight or more, and more preferably 90% by weight or more. The amount of the solvent varies depending on the target viscosity, but is preferably 10 to 90% by weight based on the photosensitive resin composition.

[0041] The photosensitive resin of the present invention and the photosensitive resin composition using the same have good alkali developability, and can give a cured product (pattern) with good linearity and pattern shape. Moreover, the balance between surface curability and deep curability is good, so that, as will be confirmed in the examples described later, even when formulated as a thick film, the occurrence of wrinkles on the surface after heat treatment is extremely small.

[0042] The coating film (cured product) of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying the applied solution, and curing it by irradiating it with light (including ultraviolet light and radiation). By providing a portion that is irradiated with light (exposed portion) and a portion that is not irradiated with light (unexposed portion), curing only the exposed portion, and dissolving the unexposed portion (uncured portion) with an alkaline solution, a desired pattern can be formed.

[0043] Next, the method for manufacturing this pattern will be described. First, a photosensitive resin composition is applied to the surface of a substrate, and then a pre-bake is performed as a drying step to form a coating film. Next, this coating film is covered with a photomask and exposed to light, and the unexposed areas are dissolved and removed using an alkaline developer. This is followed by a post-bake as a baking step to obtain a pattern using the desired cured product. This pattern manufacturing method can be applied to the manufacture of color filters and touch panels, and semiconductor packaging.

[0044] When applying the photosensitive resin composition to a substrate, any method can be used, including known methods such as a spin coater, slit coater, or roller coater, as well as a solution immersion method or spray method. A coating film of the desired thickness is formed using these methods and then prebaked. Prebaking is carried out using a hot plate, oven, vacuum dryer, or a combination of these. The temperature and time for prebaking vary depending on the solvent used and the application of the photosensitive resin composition, but are typically carried out at 60 to 120°C for 1 to 10 minutes.

[0045] For example, visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays can be used for light irradiation during cured product formation, with radiation having a wavelength in the range of 250 to 450 nm being preferred. Examples of developers suitable for alkaline development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and diethanolamine. Development is particularly preferred using an alkaline aqueous solution containing 0.01 to 1% of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or lithium carbonate at a temperature of 20 to 30°C for 10 to 120 seconds. Fine patterns can be precisely formed using shower development, spray development, dip (immersion) development, puddle (liquid puddle) development, and other methods.

[0046] The conditions for post-baking after development vary depending on the formulation and application of the photosensitive resin composition, but are typically performed at 80 to 250°C for 10 to 120 minutes. This post-baking is performed for the purposes of increasing the adhesion between the patterned coating film and the substrate, improving linearity by thermal flow of the pattern, and reducing surface roughness, and is performed using a hot plate, oven, vacuum dryer, or a combination of these, just like pre-baking.

[0047] Examples of substrates used when forming a pattern include glass, silicon wafers, and resin films (e.g., polycarbonate, polyethylene terephthalate, polyethersulfone, etc.). If necessary, these substrates may be appropriately pretreated by forming a transparent electrode layer, chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, a gas-phase reaction method, vacuum deposition, or the like. [Example]

[0048] The present invention will be described in more detail below based on examples and comparative examples. However, the scope of the present invention is not limited to these examples and comparative examples. Furthermore, unless otherwise specified, evaluation of resins in the following examples was performed as follows.

[0049] [Solid content concentration] Approximately 1 g of the resin solution obtained in the examples (including comparative examples) was impregnated into a glass filter [W0(g)] placed in an aluminum cup, and weighed [W1(g)]. The weight after heating at 160°C for 2 hours [W2(g)] was calculated using the following formula. Solid content concentration (weight (%)) = 100 × (W2-W0) / (W1-W0)

[0050] [Acid value] The resin solution was dissolved in tetrahydrofuran and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-A19" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value per 1 g of the sample (synthetic resin solution).

[0051] [Molecular weight] Measurements were performed using gel permeation chromatography (GPC) "HLC-8320GPC" (manufactured by Tosoh Corporation, developing solvent: THF, columns: PL1110-6540 (1 tube) + PL1110-6530 (1 tube) + PL1110-6525 (1 tube) + PL1110-6520 (1 tube), column temperature: 40°C, flow rate: 1.0 mL / min), and the weight-average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by SAS Corporation, polystyrene kit).

[0052] The abbreviations used in the examples are as follows: BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride GMA: Glycidyl methacrylate ECHMMA: 3,4-epoxycyclohexylmethyl methacrylate 4HBAGE: 4-Hydroxybutyl acrylate glycidyl ether THPA: 1,2,3,6-tetrahydrophthalic anhydride PGMEA: Propylene glycol monomethyl ether acetate BHT: Dibutylhydroxytoluene TPP: Triphenylphosphine

[0053] [Example 1] A 300 mL three-neck flask equipped with a reflux condenser was charged with 74.9 g (170.1 mmol) of BPEF [component (A)], 25.1 g (85.1 mmol) of BPDA [component (B)], and 100 g of PGMEA. The mixture was stirred for 26 hours at 125-130°C to obtain reaction product (AB-1). Next, 14.9 g (104.6 mmol) of GMA [component (C)] was added to 115.1 g of this reaction product (AB-1), and 0.02 g (0.1 mmol) of BHT and 0.011 g (0.5 mmol) of TPP were added. The mixture was stirred for 18 hours at 85-90°C to obtain reaction product (ABC-1). The solids concentration of the resulting (ABC-1) was 55.9%. Next, 19.6 g (129.0 mmol) of THPA [component (D)] was added to 90.3 g of this reaction product (ABC-1), and the mixture was stirred for 8 hours while heating at 85 to 90° C., whereby Synthetic Resin 1 was obtained. The solid content of the obtained resin was 55.7%, the acid value of the solid content was 129 mgKOH / g, and the weight average molecular weight (Mw) was 3,400 as determined by GPC analysis. The names and blending ratios of components (A) to (D) in Example 1, as well as the acid value and weight average molecular weight of the obtained synthetic resin 1, are all shown in Table 1 (the same applies to the following Examples and Comparative Examples).

[0054] [Example 2] A 300 mL three-neck flask equipped with a reflux condenser was charged with 111.6 g (254.6 mmol) of BPEF [component (A)], 37.5 g (127.3 mmol) of BPDA [component (B)], and 60.1 g of PGMEA. The mixture was stirred for 20 hours at 135-140°C to obtain reaction product (AB-2). Next, 23.7 g (121.0 mmol) of ECHMMA [component (C)] was added to 97.4 g of this reaction product (AB-2), and 0.02 g (0.1 mmol) of BHT and 0.22 g (0.8 mmol) of TPP were added. The mixture was stirred for 16 hours at 85-90°C to obtain reaction product (ABC-2). The solids concentration of the resulting (ABC-2) was 65.0%. Next, 16.9 g (114.0 mmol) of THPA [component (D)] was added to 90.9 g of this reaction product (ABC-2), and the mixture was stirred for 8 hours while heating at 85 to 90° C., whereby Synthetic Resin 2 was obtained. The solid content of the obtained resin was 58.0%, the acid value of the solid content was 106 mgKOH / g, and the weight average molecular weight (Mw) was 3,600 as determined by GPC analysis.

[0055] [Examples 3 to 10] The reactions were carried out in the same manner as in Example 2, except that the raw materials and blending ratios shown in Table 1 were used instead of the components (A) to (D) used in Example 2, i.e., BPEF, BPDA, ECHMMA, and THPA, to obtain synthetic resins 3 to 10.

[0056] [Comparative Example 1] The reaction product (ABC-2) obtained in Example 2 above was used as Resin 11. The solid concentration of the synthesized Resin 11 was 65.5%, the solid acid value was 19 mgKOH / g, and the weight average molecular weight (Mw) determined by GPC analysis was 2700.

[0057] Comparative Example 2 The reaction product (ABC-2) of Example 2 was prepared by replacing ECHMMA (component (C)) with 4HBAGE, and this was used as Resin 12. The solid concentration of the synthesized Resin 12 was 66.0%, the solid acid value was 11 mgKOH / g, and the weight-average molecular weight (Mw) measured by GPC analysis was 2900.

[0058] [Table 1]

[0059] In Table 1 above, the raw materials used and their compounding ratios are listed. In the compounding ratios, "B / A" represents the molar ratio of component (B) to component (A), "C / (AB)" represents the molar ratio of component (C) to compound (AB) consisting of components (A) and (B), and "D / (ABC)" represents the molar ratio of component (D) to compound (ABC) consisting of compounds (AB) and component (C).

[0060] Next, photosensitive resin compositions were prepared using the resins (compounds) synthesized above based on the Examples and Comparative Examples. The components used in the compositions are as follows. Component 1: Resin (compound) solution synthesized in the above Examples or Comparative Examples Component 2: Ester oxime photopolymerization initiator (Irgacure OXE02 / BASF Japan Ltd.) Component 3: Photopolymerizable monomer (DPHA / Nippon Kayaku Co., Ltd.) Component 4: Carbon dispersion (pigment concentration 20.0%, dispersant 5.0%, total solids 25.0%, PGMEA 75%) Component 5: Other additives Component 6: Solvent (propylene glycol monomethyl ether acetate) Component 7: Solvent (cyclohexanone) Here, the other additives of component 5 are known additives exemplified in the above embodiment, but in this evaluation a silane coupling agent and a surfactant were added, and the total weight (%) thereof is shown in Table 2.

[0061] Components 1 to 7 shown above were mixed in the compounding ratios shown in Table 2 below to prepare photosensitive resin compositions using any of the resins (compounds) of Examples 1 to 10 and Comparative Examples 1 and 2.

[0062] [Table 2]

[0063] [Examples 11 to 14, Comparative Examples 3 to 4] Photosensitive resin compositions prepared using the resins obtained in Examples 2, 3, 6, and 10 and Comparative Examples 1 and 2 in the blending ratios shown in Table 2 were applied to glass substrates (125 mm x 125 mm) using a spin coater so that the film thickness after post-baking would be 1.1 μm (3.0 μm or more in the thick film wrinkle evaluation). Pre-baking was carried out at 90°C for 1 minute. Thereafter, the film was heated to 100°C for 1 minute under an I-ray irradiance of 20 mW / cm. 2 The substrate was exposed to ultraviolet light for 4 seconds through a pattern mask using an ultra-high pressure mercury lamp (UV light was irradiated for 10 seconds for the thick film wrinkle evaluation substrate) to allow for a photocuring reaction. The exposed coated substrate was then developed in a 0.05 wt % potassium hydroxide aqueous solution (24°C) for 1.5 times the number of seconds required to confirm the target pattern, followed by a water rinse to remove the unexposed areas. Subsequent post-baking was performed in an oven at 230°C for 30 minutes to obtain a test cured film pattern. The thick film wrinkle evaluation substrate was not subjected to a development process.

[0064] In the test cured film patterns obtained by the above method, the exposure sensitivity, taper shape, line shape, and thick film wrinkles were confirmed in addition to the difference in development time, and the confirmation method is described below.

[0065] [Exposure sensitivity] In the exposure process, a pattern mask having a pattern with a line width of 20 μm was placed on the substrate, and a test cured film pattern was prepared under the conditions of the above example. The exposure sensitivity was confirmed by comparing the line width of the 20 μm mask opening formed after post-baking. Note that in this evaluation method, the higher the sensitivity, the thicker the line width. ×: Peeling occurs -: Unexposed areas do not dissolve even after 180 seconds of development.

[0066] [Tapered shape] The cross-section of the 20 μm mask opening of the test cured film pattern was analyzed using a scanning electron microscope (SEM) (Keyence Corporation, product name: VE-7800) to confirm the cross-sectional shape (taper shape) of the pattern. A tapered shape from the glass substrate surface toward the coating surface was considered a forward taper and was evaluated according to the following ranks. ○: forward taper △: Reverse taper ×: Peeling occurs -: Unexposed areas do not dissolve even after 180 seconds of development.

[0067] Line Shape When the mask opening pattern of the test color filter with 20 μm was analyzed by SEM, it was evaluated according to the following ranks. Good linearity was confirmed. △: There was some rattling, but no fringes or other issues were observed. ×: Peeling occurs -: Unexposed areas do not dissolve even after 180 seconds of development.

[0068] [Observation of thick film wrinkles] The test was carried out using a substrate prepared so that the film thickness after post-baking would be 3.0 μm or more. Note that the substrate used in this evaluation was not subjected to a development process. The exposed areas of the prepared substrate were observed under a microscope at 200x magnification, and the results were evaluated according to the following rankings. ○: No wrinkles △: Wrinkles (low degree) ×: Wrinkles (high degree)

[0069] Table 3 shows the results obtained from the above-mentioned examples of photosensitive resin compositions and evaluation methods.

[0070] [Table 3]

[0071] From the above results, we have succeeded in finding a method for synthesizing a photosensitive resin that has a balance between sensitivity and alkaline developability, as well as a balance between surface curing and deep curing. [Industrial Applicability]

[0072] In the resin represented by general formula (1) of the present invention, the addition of polymerizable unsaturated groups and alkali-soluble groups (carboxy groups) can be controlled separately using the components (C) and (D), so that when the properties of the photosensitive resin composition are to be changed, each parameter can be changed independently. This allows for a wide range of applications depending on the intended use, such as adjusting the tapered shape and suppressing wrinkles on the pattern surface to flatten the color filter surface.

Claims

1. A resin represented by the following general formula (1) and characterized in that the acid value of the solid content is 20 to 200 mgKOH / g: 【Chemical 1】 Here, R １ , R ２ , R ３ , and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group. ｘ R ｙ -, -CO-, -SO ２ -, -O-, -S-, -SS-, -SO-, -OCO-, -SiR ｘ R ｙ - or a direct bond, R ｘ and R ｙ represents hydrogen, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. ｘ and R ｙ may be bonded to each other to form a ring. A represents a tetravalent tetracarboxylic acid residue. G １ represents an alkylene group having one or more carbon atoms, D represents a hydrogen atom or a substituent represented by the following general formula (2), and n １ The average value of is in the range of 1 to 8, and n ２ independently represent an integer of 0 or greater. J represents a hydrogen atom or a substituent represented by the following general formula (3). However, one or more of the multiple Ds in general formula (1) represent a substituent represented by the following general formula (2), and one or more of the Js in D represent a substituent represented by the following general formula (3). 【Chemistry 2】 Here, G ２ each independently represents a single bond or an alkylene group having one or more carbon atoms; R ５ represents a hydrogen atom or a methyl group, and Q represents a trivalent hydrocarbon group having 2 to 8 carbon atoms. ３ represents an integer of 1 or more, and n ３ If there are two or more G ２ may be the same or different. 【Chemistry 3】 Here, L represents a di- or tri-carboxylic acid residue, n ４ represents 1 or 2.

2. A photosensitive resin composition comprising the following (i) and (ii): (i) The resin according to claim 1 (ii) Photopolymerization initiator

3. 3. The photosensitive resin composition according to claim 2, further comprising (iii) a photopolymerizable monomer having at least one ethylenically unsaturated bond.

4. The photosensitive resin composition according to claim 2 or 3, further comprising (iv) a dispersoid.

5. A cured product obtained by curing the photosensitive resin composition according to any one of claims 2 to 4.

6. A color filter comprising the cured product according to claim 5 .

7. A method for producing the resin of claim 1, comprising: A bis-hydroxy(alkoxy) group-containing compound (A) is reacted with a tetracarboxylic acid or an acid dianhydride thereof (B) to produce a carboxy group-containing compound (AB); Next, the carboxy group-containing compound (AB) is reacted with an oxirane compound (epoxy compound) (C) having a polymerizable unsaturated group to produce a compound (ABC) having a polymerizable unsaturated group, Next, in the method of reacting the compound (ABC) having a polymerizable unsaturated group with a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride thereof (D), the molar ratio (B / A) of the component (A) to the component (B) is 50% or more and less than 100%, the molar ratio of the component (C) to the compound (AB) [C / (AB)] is 50% to 250%, and the component (C) is reacted with at least one compound (AB); The molar ratio [D / (ABC)] of the component (D) to the compound (ABC) is 10 to 500%, and at least one D in the general formula (1) is a substituent having a carboxy group and a polymerizable unsaturated group. A method for producing a resin, comprising:

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