TW201003310A - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents

Abstract

Disclosed is a photosensitive resin which can be produced readily at a low cost, is easy to adjust its cross-linking density and acid value, and has excellent properties including high heat resistance, high transparency, a high refractive index and a low linear expansion coefficient. The photosensitive resin is produced by adding a (meth)acrylate compound having reactivity to a carboxylic acid and represented by general formula (2) to a polymeric compound, wherein the polymeric compound is produced by reacting a compound having a fluorene skeleton and represented by general formula (1) with a tetrabasic acid dianhydride. [In general formula (1), the rings Z1 and Z2 independently represent an aromatic hydrocarbon group; R1a and R1b independently represent a hydrogen atom or a substituent; R2a and R2b independently represent a substituent other than a hydrogen atom; R3a and R3b independently represent a hydrogen atom or a methyl group; k1 and k2 independently represent an integer of 0 to 4; m1 and m2 independently represent an integer of 0 to 3; n1 and n2 independently represent an integer of 0 to 10; and p1 and p2 independently represent an integer of 0 to 4.] [In general formula (2), R4 represents ahydrogen atom or a methyl group; and R5 represents a group represented by general formula (5).] [In general formula (5), q, r and s independently represent an integer of 0 to 9, provided that it is impossible that all of q, r and s represent 0 simultaneously.]

Description

[Technical Field] The present invention relates to a photosensitive resin having an anthracene skeleton and a photosensitive resin composition using the same, and more particularly, to a photosensitive resin composition, It is a photosensitive resin which can be easily manufactured at low cost, and an interlayer insulating film or a protective film (for example, a color filter, a liquid crystal display element, or a product) for modulating a liquid crystal display or an electronic component or the like. An interlayer insulating film or a protective film used for a bulk circuit element, a solid state imaging device, or the like). [Prior Art] A polymer compound having an anthracene skeleton is known to have excellent physical properties such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. By using this property, a polymer compound having an anthracene skeleton having a radical polymerizable unsaturated bond structure (vinyl group) introduced into a molecule is used as an optical coating agent, a hard coating agent, an antireflection film, a spectacle lens, an optical fiber, and a light guide. The use of optical materials such as wave tubes and holograms has been studied. For example, plastic lens materials have disclosed a compound which reacts chlorinated (meth)acrylic acid on 9,9-bis(4-hydroxyphenyl)fluorene or 9,9-bis(4-hydroxyphenyl)fluorene. A copolymer obtained by adding a compound reacted with (meth)acrylic acid as a main component after addition of ethylene oxide or propylene oxide (Patent Document 1). However, the compound disclosed in this patent document has a low molecular weight and a soft structure, and it is difficult to provide a sufficient refractive index and a low crosslinking density, so that the strength of the cured product is low. -5-201003310 The polymer compound having a ruthenium skeleton is also suitable for use as a so-called photoresist for liquid crystal color filters, black matrices, solder resists, etc., because of its excellent heat resistance and chemical resistance (Patent Document 2) And 3). The photosensitive resin obtained by such a technique can obtain a high crosslinking density, and can obtain a cured product excellent in strength, heat resistance, and chemical resistance. However, since it takes a long time to synthesize it, the cost is high and it is difficult. It is said that it is widely used as the current situation. Further, since the coloring is caused by the manufacturing method, it is difficult to apply it to an optical component requiring transparency, and it is difficult to fully utilize the characteristics of the skeleton. (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2007-264433 (Patent Document 3) (Invention) (Invention) Problem to be Solved Therefore, it is sought to provide a photosensitive resin which can be easily produced at low cost, and it is easy to adjust the crosslinking density or the acid value, and the skeleton has high heat resistance, high transparency, and high refractive index. An object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the same, which are excellent in characteristics such as a low linear expansion ratio. (Means for Solving the Problem) In view of the facts, the inventors of the present invention have solved the above-mentioned problems, and the results of the intensive investigation of -6-201003310 have been found in specific compounds having an anthracene skeleton and tetrabasic acid dianhydride. The photosensitive resin obtained by adding a specific carboxylic acid-reactive (meth) acrylate compound to the polymer compound obtained by the reaction can be easily produced at a low cost, and can have high strength at a high crosslinking density. The present invention has been completed by exhibiting excellent characteristics such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. In other words, the photosensitive resin of the present invention is a compound obtained by reacting a compound having an anthracene skeleton represented by the following formula (丨) with a tetrabasic acid dianhydride, and is added to the following formula. (2) A carboxylic acid-reactive (meth) acrylate compound as shown; (Chemical 6)

(wherein ring Z1 and ring Z2 represent a monocyclic or condensed polycyclic hydrocarbon ring, Rh and Rlb represent a hydrogen atom or a substituent, and feet 23 and R2b represent a substituent other than a hydrogen atom, and 1133 and R3b represent a hydrogen atom or Methyl, kl and k2 represent integers of the same or different 〇~4, and ml and m2 represent the same-or different 整数~3 integers 'nl and n2 represent integers of the same or different 〇~1〇, Pi and p2 are different from each other or from 0 to 4 integers. However, when ring z1 and ring Z2 are monocyclic hydrocarbon rings, 'pi and P2 are 1 to 3'. Ring Z1 and ring Z2 are condensed polycyclic hydrocarbons. In the ring, the sum of p 1 contained in the ring Z1 and the sum p2 contained in the ring Z2 are 1 or more of 201003310 respectively (base in the formula) C 7]

(2) R5 is represented by the following general formula (5): -C2H4〇j~^C3H6〇-C4H8i (5) (wherein q, r, and s independently represent integers of 〇~9, respectively, q, r, s are not 0) at the same time. The photosensitive resin of the present invention contains the photosensitive resin, a photopolymerization initiator, and/or a photosensitizer. [Effects of the Invention] The photosensitive resin of the present invention has high storage stability, can be easily produced at low cost, and has excellent productivity, and has excellent properties such as high heat resistance, high transparency, high refractive index, and low linear expansion ratio. By. Further, the photosensitive resin composition of the present invention using the photosensitive resin can obtain a cured product having high sensitivity and strong g-stomach. -8-201003310 [Best Mode for Carrying Out the Invention] The polymer compound constituting the photosensitive resin of the present invention is a compound having an anthracene skeleton represented by the following formula (1) and a quaternary compound described later. The acid dianhydride reaction is obtained. 【化9】

(wherein, ring Z1 and ring Z2 represent a monocyclic or condensed polycyclic hydrocarbon ring, Rla and ruler 115 represent a hydrogen atom or a substituent, 1123 and R2b represent a substituent other than a hydrogen atom, and R3a and R3b represent a hydrogen atom or Methyl, kl and k2 represent the same or different integers of 0 to 4 'ml and m2 represent integers of the same or different 〇~3, nl and n2 represent integers of the same or different 〇~10, pi and P2 is a different or different integer of 0 to 4'. However, when ring z1 and ring Z2 are monocyclic hydrocarbon rings, 'pi and p2 are 1 to 3' ring Z1 and ring Z2 is a condensed polycyclic hydrocarbon ring. The sum of p丨 contained in the ring Z1 and the sum p2 contained in the ring z2 are respectively 1 or more) In the above formula (1), 'the hydrocarbon corresponding to the hydrocarbon ring represented by the ring Z1 and the ring Z2' is a single The cyclic or condensed polycyclic type may be, for example, a monocyclic hydrocarbon such as benzene or a condensed bicyclic hydrocarbon (for example, a cs~u condensed bicyclic hydrocarbon such as anthracene or naphthalene, preferably a C^-!6 condensation II) A condensation 2 or a 4-ring hydrocarbon such as a cyclic hydrocarbon or a condensed tricyclic hydrocarbon (fluorene, phenanthrene or the like). Particularly preferred hydrocarbons for use in applications requiring high refractive index and heat resistance -9-201003310 include, for example, condensed polycyclic aromatic hydrocarbons (naphthalene, and the like), and particularly preferably naphthalene. Further, it is preferable to use benzene in applications where high solubility, compatibility, and low solution viscosity are required. Further, the ring Z1 and the ring Z2 are the same or different rings, and generally may be the same ring. Further, in the above formula (1), the substituents represented by Rla and Rlb are not particularly limited, but are generally a hospital base. The group may be a Cl-6 alkyl group (C丨-4 alkyl group, especially methyl group) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a tert-butyl group. The bases 1113 and Rlb may also be different or may be the same. Further, when k1 (or k2) is 2 or more, the radicals Rla (or Rlb) may be different in the same benzene ring, or may be the same. Further, the bonding position (substitution position) of the group Rla (or Rbb) constituting the benzene ring of the anthracene skeleton is not particularly limited. Preferably, the substitution numbers kl and k2 or 0 or 1, especially 0. Further, the substitution numbers kl and k2 may be different, but are generally the same. The substituents R2a and R2b substituted with the ring Z1 and the ring Z2 may, for example, be a Cbn alkyl group such as an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group or tert-butyl group). Preferably, it is a Cl_8 alkyl group, more preferably a Cl-6 alkyl group, etc., a cycloalkyl group (cyclopentyl group, cyclohexyl group or the like, c5_1C) cycloalkyl group, preferably a C5.8 ring courtyard group, more preferably c5.6. a Cm aryl group such as a cycloalkyl group or the like, an aryl group (phenyl group, alkylphenyl group (methylphenyl (tolyl), dimethylphenyl (xylyl), etc.), preferably C6.9 aryl a hydrocarbon group such as a aryl group (such as a C6_1()aryl-Cl4 alkyl group such as a benzyl group or a phenethyl group; or an alkoxy group (such as a methoxy group; Alkoxy group, etc.; fluorenyl group (such as a sulfonyl group or the like); an alkoxy group (such as a C14 alkoxycarbonyl group such as a methoxycarbonyl group); a halogen atom (a gas atom, a chlorine atom, etc.) Nitro; cyano group. -10-201003310 Preferred substituents R2a (or R2») are alkyl (Ci.6 alkyl), cycloalkyl (C5-8 cycloalkyl), aryl (C6-1G aryl), aralkyl (c6-8_Ci_2 alkyl), in particular, is preferably Cm alkyl, Cl. 4 alkoxy, C6_8 aryl. The substituent R2a (or R2b) may be substituted with two or more kinds alone or in combination of a benzene ring. Further, the radicals R2a and R2b may be the same or different from each other, but are generally the same. Further, when ml (or m2) is 2 or more, the base R2a (or R2b) may be different or may be the same in the same hydrocarbon ring. Further, the position of substitution of the substituent R2a (or R2b) is not particularly limited, and may be in accordance with a substitution position of a thiol group or a thiol group (hereinafter, collectively referred to as a group having a radical group). It is substituted at positions 2 to 6 (for example, 2-position, 5-position, 2, 5-position, etc.) of the phenyl group constituting the phenol skeleton. The number of substitutions ml and m2 of the substituents R2a and R2b are also preferably 0 to 2 (especially 0) depending on the number of substitutions of the hydroxyl group-containing group. Also, algebras ml and m2 may be different, but are generally the same. The substituent represented by 1133 and R3b having a hydroxyl group is hydrogen or a methyl group. Moreover, R3a and R3b may be the same or different from each other, but generally the same - the number of additions of 〇 (poly) siloxanes nl and n2 are the same or different, and may be selected from the range of 0 to 10, preferably It is 0 to 8 (for example, 1 to 8), more preferably 〇~6 (for example, 1 to 6), and particularly preferably 〇~4 (for example, 1 to 4). Moreover, the sum of nl and n2 (nl+n2) can be selected from the range of 0 to 20, preferably 〇~16 (for example, 2M2), more preferably 0~12 (for example, 2~12), especially 〇~ 8 (for example, 2 to 8) or so. Further, when nl (or n2) is 2 or more, the '(poly)alkyleneoxy group may be composed of the same alkoxy group, or a different alkoxy group (for example, ethoxy group and epoxidized propen-11). 201003310 Alkyl) is a mixture of the same, but generally consists of the same oxy group. The number of substitutions pi and P2 of the hydroxyl group are in the range of 0 to 4, preferably 1 to 4, and particularly preferably 1 to 2. . However, when ring Z1 and ring Z2 are monocyclic hydrocarbon rings, Pi and ? 2 is 1 to 3, and when ring Z1 and ring Z2 are condensed polycyclic hydrocarbons, the sum of p 1 contained in ring Z1 and p2 contained in ring Z2 are 1 or more, respectively. Further, the sum of pi and ρ2 (pl + p2) is preferably 2 to 8', more preferably 2 to 4. In particular, in the use of the crosslink density of the cured product, Pi and P2 are preferably 2 or 3° and the algebras pl and p2 may be different but generally the same. The position of substitution containing a radical group is not particularly limited, and according to the number of pl (or P2), when 'Pi (or P2) is 2 from the 2 to 6 positions of the phenyl group substituted at the 9-position of the oxime, for example, It can also be 3, 4 - bit, 3, 5 - bit, etc. A group containing a hydroxyl group can also be substituted at the 4-position. Further, the plurality of hydroxyl group-containing groups constituting the same phenol skeleton may be the same or different. For example, a complex group containing a radical group (i) may have a hydroxyl group of nl=0 (n2 = 0) alone (except when pl and P2 are 2), and (ii) nl = 0 (n2 = 0). The hydroxyl group of nl # 〇(n2 尹0) hydroxy (poly) alkoxy (2-hydroxyethoxy group, etc.) constitutes '(1)) hydroxy (poly) which can be the same as nl矣〇(n2fu0) The alkoxy group alone constitutes '(iv) may also be a different hydroxy (poly)alkoxy group of nl#0(n2# 0) [eg '2-hydroxyethoxy group and 2-(2-hydroxyethoxy group) Ethoxylated]. In the use of the compound having an anthracene skeleton of the above formula (1), which is required to have a particularly high refractive index and heat resistance, it is preferred to be a structure represented by the following formula (3). -12- 201003310 【化1 0】

(wherein Rla and Rlb represent a hydrogen atom or a substituent, R2a, R2b R6b represent a substituent other than a hydrogen atom, R3a and R3b represent a hydrogen H group, and kl and k2 represent the same or different integers of 〇~4' m M3 and m4 represent integers of the same or different 〇~3, nl, n2 n4 represent integers of the same or different 〇~i〇, pi and p2 are different from each other by an integer of 1 to 4, and P3 and P4 represent The same or different (number). Rule 13 and Rlb, 1123 and R2b, 1132 and R3b, kl and k2 m2, nl and n2 are the same as above. Further, 1163 and R6b are double R2a and R2b, m3 and m4. Corresponding to the above ml and m2, corresponding to the above nl and n2, have the same meaning. Pi is the same as above, but preferably is 1 to 4. The p3 and P4 systems and the above P1 and 'are preferably 0 to 3. For example, 9,9-bis(hydroxyl-oxynaphthyl 9,9-bis(hydroxypolyalkoxynaphthyl) anthracene or the like can be used as the above-mentioned 1+卩2 + ?3+?4 is 2 a compound; 9,9-bis (polyhydroxy alkoxypurine, 9,9-bis(polyhydroxy polyalkoxynaphthyl) anthracene, etc., R6a and Minzi or A1, m2, 丨, n3 and the people The same or >~3 of the whole, ml and Ϊ should be before N3 and n4 p2 correspond to p2) anthracene, phenylnaphthyl in formula (3), and pl+p2 + p3+p4 are compounds of 2, etc. 9,9 - double (in the formula (3) -13- 201003310 The hydroxyalkoxynaphthyl) oxime may, for example, be 9,9-bis(hydroxyalkoxynaphthyl)anthracene [e.g., 9,9-bis[6-(2-hydroxyethoxy)-2-naphthalene] ,芴,9,9-bis[6-(2-hydroxypropoxy)-2-naphthyl]anthracene, 9,9-bis[5-(2-hydroxyethoxy)-buphthyl]anthracene, 9 9,9-bis[5-(2-hydroxypropoxy)-1-naphthyl]anthracene, etc. 9,9-bis(hydroxy C2_4alkoxynaphthyl)anthracene, etc. 9,9_bis(hydroxyl The polyalkoxynaphthyl) oxime may, for example, be 9,9-bis(hydroxydialkoxynaphthyl)anthracene [e.g., 9,9 bis[6-(2-(2-hydroxyethoxy))] Ethoxy)-2-naphthyl]anthracene, 9,9-bis[6-(2-(2-hydroxypropoxy)propoxy)-2-naphthyl]anthracene, 9,9-bis[5 -(2-(2-hydroxyethoxy)ethoxy)-1_naphthyl]anthracene, 9,9-bis[5-(2-(2-hydroxypropoxy)propoxy)-1_ 9,9-bis(hydroxydialkyloxychalyl), such as naphthyl]anthracene, etc., 9,9-bis(hydroxydialkoxy-based), ίέί 'In the general term II In the case of (3), η 1 , η 2 , η 3 , and η 4 are compounds of 3 or more. Examples of the 9,9-bis (polyhydroxyalkoxynaphthyl) anthracene include, for example, the aforementioned 9,9-bis ( a hydroxyalkoxynaphthyl)anthracene, 1)1+1)243+?4 is a compound of 2 or more, and examples thereof include 9,9-bis(di or trihydroxyalkoxynaphthyl)anthracene [for example, 9 9,9-bis[bis(2-hydroxyethoxy)-2-naphthyl]anthracene, 9,9-bis[bis(2-hydroxypropoxy)-2-naphthyl]anthracene 9,9- 9,9-bis(polyhydroxyalkoxynaphthyl)anthracene such as bis(di or trihydroxy C2_4 alkoxynaphthyl) anthracene or the like. Examples of the 9,9-bis(polyhydroxy polyalkoxynaphthyl) anthracene include, for example, the above-mentioned 9,9-bis(hydroxyalkoxynaphthalenyl) anthracene, and 111, 112, 113, and 114 are 2 The above compound in which pl+p2 + p3+p4 is 2 or more may, for example, be 9,9-bis(di or trihydroxydialkoxynaphthyl)anthracene [e.g., 9,9-bis[di[2- -14] - 201003310 9,2-bis(di- or tri-based di-C2_4 alkoxynaphthyl) anthracene, etc., of 2-(transethylethoxy)ethoxy]-2-naphthyl]anthracene, etc. In the above formula (Chemical Formula 3), ni, n2, n3, and n4 are compounds of 3 or more, etc., in the above formula (Chemical Formula 3). Among these, '9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]anthracene or the like is preferable. Among the compounds having an anthracene skeleton of the above formula (1), those having a particularly high solubility, compatibility, and low solution viscosity are preferably those having the structure shown by the following formula (4). [1 1]

(wherein Rla and Rlb represent a hydrogen atom or a substituent, and R2a, R2b, R7a and R7b represent a substituent other than a hydrogen atom; R3a and R3b represent a hydrogen atom or a methyl group, and kl and k2 represent the same or different 〇~ An integer of 4, nl and n2 represent the same or different 〇~1〇 integer 'P1 and P2 represent the same or different integers from 1 to 3). 1113 and Rlb, 112!1 and R2b, R3a& R3b, kl and k2, ml and m2, nl and n2 are the same as described above. Further, R7a and R7b have the same meanings as those of R3a and R3b described above. The Pi and P2 systems are the same as described above, and are preferably 1 to 3. -15- 201003310 The compound represented by the above formula (4) contains a 9,9-bis(hydroxyalkoxyphenyl)anthracene (in the above formula (4), a compound of nl=n2 = l And 9,9-bis(hydroxypolyalkoxydialkylphenyl)anthracene (a compound in which n1 and n2 are each 1 or more in the above formula (4)). 9.9-bis(hydroxyalkoxyphenyl)anthracene, for example, 9,9-bis(base oxyphenyl)anthracene {e.g., 9,9-bis[4-(2-hydroxyethoxy) Phenyl]anthracene, 9.9-bis[4-(2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[4_(2-hydroxyethoxy)-3-methylphenyl]anthracene, 9 ,9-bis[4-(2-hydroxypropoxy)_3_methylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl ,9,9-bis[4-(2-hydroxyethoxy)phenoxyethane]anthracene, 9,9-bis[4_(2-pyridylpropoxy)phenoxyethane]芴9,9-bis[4-(2-hydroxyethoxy)_3_methylphenyl]indole, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]芴, 9,9·bis[4-(2-hydroxyethoxy)-2,5-dimethylphenyl]anthracene, 9,9-bis[4·(2·hydroxypropyloxy)-2, 5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-3,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyl Propyl)-2,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxyethoxy)-2,4-dimethylphenyl]anthracene, 9,9· Bis[3-(2-hydroxypropoxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[4-(2-carbylethoxy)-3,4-dimethyl Phenyl]anthracene, 9,9-double [ 9,9-bis(hydroxyalkoxyalkylphenyl)anthracene of 2-(2.hydroxypropoxy)- 3,4-dimethylphenyl]anthracene, preferably contains 9,9-double 9.9-bis (hydroxyl branch (: 3-4 alkoxy-dialkylphenyl) oxime) of 2-hydroxypropyloxy-bis(^_4-alkylphenyl)anthracene etc. 9.9- double ( In the hydroxypolyalkoxyphenyl) oxime, a compound in which η 1 and n 2 are 2 or more, for example, 9,9-bis(hydroxydialkoxyphenyl)anthracene {e.g. 9, 9, 9 bis [4-(2) -hydroxydiethoxy)phenyl]anthracene, 9,9-bis[4-(2-diaminodipropoxy-16-201003310-yl)phenyl]anthracene, 9,9-bis[4-(2- Hydroxydiethoxy)-3-methylphenyl]anthracene, 9.9-bis[4-(2-hydroxydipropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-( 2-hydroxydiethoxy)-3,5-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)phenoxyethanol]anthracene, 9,9-double [4-(2-Hydroxydipropoxy)phenoxyethanol]indole, 9,9-bis[4-(2-hydroxydiethoxy)-3-methylphenyl]anthracene, 9.9-double [ 4-(2-hydroxydipropoxy)-3-methylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-2,5-dimethylphenyl]anthracene 9,9-bis[4-(2-hydroxydipropoxy) -2,5-Dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-3,6-dimethylphenyl]anthracene, 9,9-double [ 4-(2-hydroxydipropoxy)-2,6-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxy)-2,4-dimethylbenzene ], 9,9-bis[3-(2-hydroxydipropoxy)-2,4-dimethylphenyl]anthracene, 9,9-bis[4-(2-hydroxydiethoxyl) , 9,9-double of -3,4-dimethylphenyl]anthracene, 9,9-bis[2-(2-hydroxydipropoxy)-3,4-dimethylphenyl]anthracene (Hydroxydialkoxyphenyl) fluorene}. Among these, 9,9-bis(hydroxyethoxyphenyl)anthracene 9,9-bis(hydroxyethoxy-3-methylphenyl)anthracene, 9,9-bis(hydroxyethoxyl) Alkyl-3,5-dimethylphenyl)anthracene, 9,9-bis(hydroxyethoxy-2-phenoxyethanol)anthracene or the like. In the use of the compound having an anthracene skeleton represented by the above formula (1) which constitutes the photosensitive resin of the present invention, it is preferable to use R2a and R2b as a benzene in a particularly high refractive index, solubility, compatibility, and low solution viscosity. base. Specifically, for example, a 9,9-bis(hydroxyalkoxyarylphenyl)anthracene is contained in the compound represented by the above formula (4) (in the above formula (4), nl=n2 = l, R2a, R2b are compounds of phenyl), 9,9-bis(hydroxypolyalkoxyarylphenyl)anthracene (in the above formula (4), nl+n2 is 2 or more, R2a-17-201003310, R2b is a compound of phenyl). 9,9-bis(hydroxyalkoxyarylphenyl)indoles contain 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]anthracene, 9-bis[4 9,9-(2-hydroxypropoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl]anthracene Bis(hydroxyalkoxyarylphenyl)anthracene, preferably contains 9,9-bis(2-hydroxyethoxyphenylphenyl)anthracene or the like. 9,9-bis(hydroxypolyalkoxyarylphenyl)indoles contain 9,9-bis(hydroxydialkoxyarylphenyl)anthracenes [eg 9,9-double {4-[2 9,9-bis(hydroxydialkoxyarylphenyl)anthracene, such as -(2-hydroxyethoxy)ethoxy]-3-phenylphenyl}anthracene, preferably contains 9,9- Bis[2-(2-hydroxyethoxy)ethoxyarylphenyl]anthracene]. Among these, it is preferably 9,9-bis(hydroxyethoxyarylphenyl)anthracene or the like. For the compound which reacts with the above compound having an anthracene skeleton, a tetrabasic acid dianhydride can be used. Specific examples of the tetrabasic acid dianhydride include butane tetracarboxylic dianhydride, pentylene tetracarboxylic dianhydride, hexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid II. Anhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetra Carboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid Dihydride, 4,4,-(hexafluoroisopropylidene)diphthalic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3'-4,4'-diphenylfluorene One or two or more of these may be used as the carboxylic acid dianhydride or the like. Among these, it is preferably pyromelliyl-18-201003310 acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2 - a dicarboxylic acid anhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride hydrazine, can be obtained by adding a tetrabasic acid dianhydride to the above compound having an anthracene skeleton to form the photosensitivity of the present invention. A polymer compound of a resin. The ratio of the tetrabasic acid dianhydride in the addition reaction to the compound 1 molar having an anthracene skeleton is preferably from 0.5 mol to 1.5 mol, more preferably from 65 mol to 1.25 mol. When the ratio of the tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, sometimes a sufficient molecular weight cannot be obtained. A catalyst may also be used when the compound having an anthracene skeleton is reacted with a tetrabasic acid dianhydride. The catalyst to be used is not particularly limited as long as it can promote the reaction, and examples thereof include pyridine, quinoline, imidazole, indole, indole-dimethylcyclohexylamine, triethylamine, and anthracene. Methylmorpholine, Ν-ethylmorpholine, triethylenediamine, hydrazine, hydrazine-dimethylaniline, hydrazine, hydrazine-dimethylbenzylamine, tris(Ν,Ν-dimethylaminocarbamate Phenol, 4-dimethylaminopyridine, 1,8-diazobicyclo[5.4.0]-7-undecene, 1,5-diazobicyclo[4.3.0]nonene Grade 4 ammonium compound, tributylphosphine, three a mixture of phenylphosphine and the like and the like. In addition, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass based on 100 parts by mass of the total of the compound having an anthracene skeleton and the tetrabasic acid dianhydride. If the amount of the catalyst exceeds 2.0 parts by mass, the electrical properties or storage stability of the photosensitive resin may be adversely affected. Further, in the case of the addition reaction, the dissolution of the reaction material is carried out, and the viscosity is lowered, etc. -19-201003310, and a solvent can also be used. The type of the solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include glycol ethers such as ethylene glycol diethyl acid and diethylene glycol dimethyl ether, and ethylene glycol singles. Glycol ether acetate such as ethyl ether acetate vinegar, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether, propylene glycol dimethyl charm , propylene glycol ethers such as dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether Acetate, propylene glycol ether acetate such as dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid, butyl acetate, etc. a mixture of esters, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like. The amount of the solvent to be used is not particularly limited, but is preferably in the range of 25 to 150 parts by mass based on 100 parts by mass of the total of the compound having a skeleton and the tetrabasic acid dianhydride. When the amount is less than 25 parts by mass, the viscosity is sufficiently lowered. Further, when it exceeds 150 parts by mass, the concentration of the reactant is too low, and sometimes the reaction rate is lowered. In the case of a compound having an anthracene skeleton and a tetrabasic acid dianhydride, a solvent or a catalyst is added to carry out an addition reaction, but when the reaction is carried out, heating is carried out, and the raw material is dissolved by heating, and the reaction rate is also accelerated. The heating temperature may be appropriately set depending on the type of the ruthenium skeleton compound and the tetrabasic acid dianhydride or the apparatus used, but it is preferably in the range of 60 to 220 °C. More preferably, it is in the range of 90 to 160 °C. If the reaction temperature is lower than 60 ° C, it sometimes takes time until the end of the reaction. Further, when the reaction temperature is higher than 220 °C, a side reaction such as coloring occurs, or the acid anhydride is subjected to a ring closure or the like in an equilibrium of -20-201003310, and the reaction rate may be lowered. The carboxylic acid-reactive (meth) acrylate compound represented by the following formula (2) is obtained from the polymer compound obtained by the above method to obtain the photosensitive resin of the present invention. (base in the formula) [Chemical 1 2] R4

(2) R5 is represented by the following formula (5) [Chemical Formula 1]

C2H4〇f- /q 〇3^β〇

-c4h8o-^— (5) (where q, r, and s independently represent integers from 0 to 9, respectively, but q, r, and s are not equal to each other). The carboxylic acid-reactive (meth) acrylate represented by the above formula (2) may specifically be, for example, 2-hydroxyethyl (meth) acrylate glycidyl ether or 2-hydroxypropyl (methyl) Acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (methyl ) Acrylate glycidyl ether and the like. The carboxylic acid-reactive (meth) acrylate compound is subjected to an addition reaction of the above-mentioned high -21 - 201003310 molecular compound. The ratio of the residual acid-reactive (meth) acrylate compound in the photosensitive resin of the present invention varies depending on the application, and it is difficult to use it in the case of a photocurable coating agent or an optical material. The acid value of the photosensitive resin is added to the limit. Further, when it is suitable for use in alkali development, the acid value of the resin solid content is adjusted to be in the range of 30 to 150 mgKOH/g. If the acid value is lower than 30 Κ Ο H / g ', the development speed may be lowered and the necessary pattern may not be obtained. Further, when the acid value is higher than 150 mgKOH/g, the image is sometimes excessively developed, the pattern is easily peeled off, and electrical characteristics are also lowered. Further, in the present invention, the acid value of the resin solid content is measured in accordance with JIS-K 0 0 7 0. In the reaction between the above polymer compound and a carboxylic acid-reactive (meth) acrylate compound, a catalyst may be used for the purpose of promoting the reaction. The type of the catalyst varies depending on the type of the carboxylic acid reactive (meth) acrylate compound, so that it is difficult to cite, for example, pyridine, quinoline, imidazole, hydrazine, hydrazine Methylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine 'triethylenediamine, hydrazine, hydrazine-dimethylaniline, hydrazine, hydrazine-dimethylbenzylamine, Tris(Ν,Ν-dimethylaminomethyl)phenol, 4-dimethylaminopyridine, 1,8-diazobicyclo[5·4_0]-7·undecene, anthracene, 5- Amines such as diazobiscyclo[4.3.0]oxime-5, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, etc. A fourth-order ammonium compound, tributylphosphine, triphenylphosphine, etc., and the like. Further, the amount of the catalyst to be used is not particularly limited, but is preferably in the range of 0.1 to 2.0 parts by mass based on 100 parts by mass of the compound having an anthracene skeleton. If the amount of the catalyst is too large, it may adversely affect the electrical properties of the photosensitive resin or the preservation of -22-201003310. Further, when a carboxylic acid reactive (meth) acrylate compound is reacted, a polymerization inhibitor is preferably added. The type of the polymerization inhibitor is not particularly limited as long as it is a reaction for suppressing the unsaturated bond, but examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, and t-butyl group. Tea, N-methyl-N-nitrosoaniline or N-nitrosophenylhydroxylamine/ammonium salt (made by Wako Pure Chemical Industries, Ltd.: Q-1300), N-nitrosophenylhydroxylamine /Aluminium salt (made by Wako Pure Chemical Industries Co., Ltd.: Q-1301), 2,2,6,6-tetramethylhexahydropyridin-1-oxygen, 4-hydroxy-2,2,6,6-tetra Hexahydropyridin-1-oxygen and the like. Particularly preferred is N-nitrosophenylhydroxylamine/aluminum salt, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo. The amount of the polymerization inhibitor varies depending on the type and the reaction conditions, so that it is difficult to be used in the same manner, but it is preferably in the range of 5 to 2000 Ppm with respect to the entire photosensitive resin. If it is less than this range, the unsaturated bond may react during production to cause gelation, and if it is more than this range, the sensitivity may be lowered, which is not preferable. When a carboxylic acid-reactive (meth) acrylate compound is added, it is preferred to heat it for the purpose of improving the reaction rate. The heating temperature can be appropriately set depending on the type or device of the carboxylic acid reactive (meth) acrylate compound, but it is preferably in the range of about 60 to 150 °C. If the reaction temperature is lower than 60 ° C, it sometimes takes time until the end of the reaction. Further, when the reaction temperature is higher than 150 °C, a side reaction such as coloring or the like is caused, or a reaction is caused by a non-saturated bond to cause gelation. The molecular weight of the photosensitive resin of the present invention obtained in this manner is not particularly limited, but is preferably from 1,000 to 200,000, more preferably from 2,500 to 50,000, from the viewpoints of coating film strength, coating property, and development. Further, in the present specification, the molecular weight of the optical resin of -23-201003310 is a styrene-equivalent weight average molecular weight obtained by GPC under the conditions described in the examples. The photosensitive resin of the present invention contains the above-mentioned photosensitive resin, photopolymerization initiator and/or photosensitizer as essential components. The photopolymerization initiator and/or the photosensitizer are mixed in a state of being dissolved or dispersed in a solvent, or may be chemically bonded to a photosensitive resin. The photopolymerization initiator and/or photosensitizer used in the present invention are not particularly limited, but may, for example, be benzophenone, 4 hydroxybenzophenone, or bis-N,N-dimethylamino group. Benzophenone, bis-N,N-diethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. a thioxanthone such as a ketone, 2,4-diethylthianone, isopropyl thioxanthone, chlorothiazinone or isopropoxychlorothiazide, ethyl hydrazine, Benzoquinones, amidoxime, chloranil, hydrazine-2-sulfate, guanidene-2,6-disulfonate, oxime, acetophenone methyl ether a benzoin ether such as benzoin ethyl ether or benzoin phenyl ether, 2,4,6-trihalomethyltriazine, 1-hydroxycyclohexyl phenyl ketone, 2-(o- Chlorophenyl)-4,5-diphenylimidazolium, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole, 2-(o-fluoro Phenyl)-4,5-diphenylimidazolium, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium, 2-(p-methoxyphenyl)- 4,5-diphenylimidazolium, 2,4-di(p-methoxy) 2,4,5-triarylimidazolium, such as phenyl)-5-phenylimidazolium, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolium , benzyl dimethyl ketal, 2-benzyl-2- dimethylamino-1-(4-morpholinylphenyl)-butane-i-ketone, 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholin-1-propanone, 2-hydroxy--24-201003310 2-methyl-1-phenyl-propan-1-one, l-[ 4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1,2-octanedione, ^[4-(phenylthio)- , 2-(o-benzylidene fluorenyl)], phenanthrenequinone, 9,1 fluorene, phenanthrene, ethyl benzoin, etc. Benzene, 9-phenylpyridazine, ι In the case of 7-bis(9,9,-pyridazinyl)heptane, etc., a pyridazine derivative or a bis-indenylphosphine oxide, one type or two or more types may be used. Further, an accelerator may be added to the photosensitive resin of the present invention. Examples of the accelerator include ethyl p-dimethylamino benzoate, isoamyl p-dimethylamino benzoate, N, N-dimethylethanolamine, hydrazine methyl diethanolamine, and the like. Ethanolamine and the like. In the photosensitive resin composition of the present invention, a polymerizable monomer having one or more unsaturated groups in the molecule (hereinafter, simply referred to as "polymerizable monomer") can be further used. Sensitivity, chemical resistance, heat resistance and mechanical strength. Further, a polymerizable monomer may be added for the purpose of adjusting the flow characteristics and the like. When the polymerizable monomer has one or more unsaturated bonds in the molecule, it can be used without particular limitation, and may be appropriately selected according to the intended use and purpose. For example, polyethylene glycol di(methyl)propionic acid ester (the number of vinyl groups is 2 to 14), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylic acid Ester, trimethylolpropane ethoxy di(methyl)propanic acid vinegar's trimethyl methacrylate propoxy tri(meth) acrylate, tetramethylol methane tri(meth) acrylate, Tetramethylol methane tetra(meth) acrylate, polypropylene glycol di(meth) acrylate (the number of propylene groups is 2 to 14), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, bisphenol A polyoxyethylene di(methyl)-25- 201003310 acrylate, bisphenol A dioxyethylene di(meth) acrylate, bisphenol A trioxyethylene di(meth) acrylate , bisphenol A decaoxyethylene di (meth) acrylate, polycarboxylic acid (phthalic anhydride, etc.) and a hydroxyl group and a compound having an ethylenically unsaturated group (/3-hydroxyethyl (meth) acrylate, etc.) Esterified product, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid An alkyl (meth)acrylate such as an ester or 2-ethylhexyl (meth)acrylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, or triethylene glycol diglycidyl group Ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl A (meth)acrylic acid addition product of an epoxy compound such as a group ether, a polypropylene glycol diglycidyl ether, a sorbitol triglycidyl ether or a glycerol triglycidyl ether, or an unsaturated organic compound such as maleic acid Acids and their anhydrides, N-methyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-methylol acrylamide, N-methyl methacrylamide , N-ethylmethacrylamide, N-isopropylmethacrylamide, hydroxymethylmethacrylamide, N,N-dimethylpropenamide, ν,Ν-diethyl Propylene oxime such as acrylamide, N,N-dimethyl methacrylamide, hydrazine, hydrazine-diethyl methacrylamide A styrene type such as styrene or hydroxystyrene, Ν-vinylpyrrolidone, Ν-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc. can be used. Or two or more. In the photosensitive resin composition of the present invention, a coloring agent may be added for the purpose of preventing halo or the like in terms of design, visibility, and photoresist. The type of the coloring agent to be added may be appropriately selected depending on the purpose of coloring, and examples thereof include -26-201003310 phthalocyanine dyes, anthraquinone dyes, azo dyes, indigo dyes, coumarin dyes, and the like. a phenylmethane dye, a phthalocyanine pigment dye, an anthraquinone pigment dye, an azo pigment, a quinacridone pigment, a coumarin pigment, a triphenylmethine pigment, and the like. One or two or more of these may be used. The photosensitive resin composition of the present invention can form a paste in which a solution or a chelating agent is mixed, and therefore may contain a solvent. The type of the solvent to be used is not particularly limited, and examples thereof include ethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like. Glycol ethers such as ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetate such as monoethyl ether acetate or diethylene glycol monobutyl ether acetate; propylene glycol such as propylene glycol, dipropylene glycol or tripropylene glycol; propylene glycol monomethyl ether; propylene glycol monoethyl Ethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol ether, propylene glycol monomethyl Propylene glycol ether acetates such as phenyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl Ketones such as ketones and cyclohexanone, lactates such as methyl lactate and ethyl lactate, and ethyl acetate , Butyl acetate, acetates, etc., dimethyl sulfoxide Sa, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, etc. and mixtures thereof. In the photosensitive resin composition of the present invention, a conventionally known component such as a polymerization inhibitor, a plasticizer, an antifoaming agent, or a coupling agent can be further added as needed. -27-201003310 The photosensitive resin composition of the present invention can be used as usual The above-mentioned essential components and optional solvents or other optional components are mixed by the method. When the photosensitive resin composition of the present invention obtained as described above is used as a photoresist, it is applied onto a substrate by a solution or a paste. The coating method is not particularly limited, but screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, die coating, and the like can be applied. The applied solution or paste is exposed to UV or electron beam via a specific mask'. It can also be passed through a drying step when coated with a solvent. The exposed coating film is developed in a wet manner to form a pattern. The development method may be any of a spray type, a paddle type, a dipping type, etc., but it is preferably a spray type with few residues. Ultrasonic waves, etc. can also be irradiated as needed. It is advisable to use weakly alkaline water for the developer. An organic solvent, a surfactant, an antifoaming agent, or the like may be added for the purpose of the developmental subsidy. [Embodiment] [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Example 1 In a 1 000 ml flask equipped with a stirrer and a cooling tube, pyromellitic dianhydride (product of Daicel: PMDA) 64 g, 9,9-bis[4-(2-hydroxyethoxy) was placed. )phenyl]anthracene (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) 136 g, propylene glycol monomethyl ether acetate I34g, under a nitrogen stream -28- 201003310

It was heated in an oil bath at 155 ° C for 4 hours while stirring. Then, after cooling to 120 ° C, 1 g of 4-dimethylaminopyridine, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-:!-oxygen (ADEKA 7 RD ) 0.04 was added. g, 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) 106 g, and stirring was continued at 120 ° C for 4 hours. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 50% by mass to obtain a pale yellow transparent viscous photosensitive resin (A1) solution. The obtained resin solution was measured for viscosity, GPC styrene-equivalent weight average molecular weight, and solid acid value, and the viscosity was 2,900 mP^S/25 ° C, and the weight average molecular weight of styrene in terms of GPC was 1,2523. The solid acid value was 2.2 mgKOH/g. Further, a BM type viscometer manufactured by Toki Sangyo Co., Ltd. was used for the viscosity measurement. Further, the measurement of GPC was carried out by using TSKgel G7000HXL, TSKgel GMHXL 2, TSKgel G25 00HXL manufactured by Tosoh Co., Ltd. in a column, and measured at a flow rate of 0-5 ml/min in a THF solution at 40 °C. The acid value was measured in accordance with JIS-K0070 and titration. Example 2 Phenyltetracarboxylic dianhydride (product of Ube Industries, Ltd.: BPDA) was placed in a 1 000 ml flask equipped with a stirrer and a cooling tube. 72 g, 9, 9-bis [4- ( 2- Hydroxyethoxy)phenyl]indole (manufactured by Osaka Gas Chemical Co., Ltd.: BPEF) 128 g, 4-dimethylaminopyridine lg, propylene glycol monomethyl ether acetate 134 g, stirred at 155 ° under a nitrogen stream C in the oil bath plus -29- 201003310

Heat for 4 hours. Then, after cooling to 120 ° C, 4-hydroxy-2,2,6,6-tetramethylhexahydropyridine-1-oxo (Adekastab LA-7RD, manufactured by Adeka Co., Ltd.) was added to 0.04 g, 4-hydroxybutyl group. Acrylate glycidyl ether (product of Nippon Kasei Co., Ltd.: 4 Η BAGE) 8 4 g, and stirred at 120 ° C for 4 hours. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so as to have a nonvolatile content of 50% by mass to obtain a pale yellow transparent viscous photosensitive resin (A2) solution. The obtained resin solution was measured for viscosity, GPC styrene-equivalent weight average molecular weight, and solid acid value, and the viscosity was 4200 mPa_s/25 ° C, and the weight average molecular weight obtained by GPC was 7243, and the solid acid value was determined. It is 2.5 mgKOH/g. Comparative Example 1 A photosensitive resin (A 3 ) was obtained in accordance with Synthesis Example 1 described in JP-A-9-3 2 00 8 . Using the photosensitive resins of Examples 1 and 2 and Comparative Example 1, a photosensitive composition was produced in the composition shown in Table 1. The photosensitive composition was coated on a 1.1 mm thick soda glass substrate by a bar coater to a dry film thickness of 6 μm, dried in a 80 ° C warm air dryer for 1 minute, and then cooled to room temperature. . Then, an ultraviolet light having an integrated light amount of 300 mJ/cm2 was irradiated with an ultrahigh pressure mercury lamp UV irradiator. For this hardened coating film, the pencil hardness and the hundred-bar peeling test were carried out in accordance with JIS-K5400, and the strength of the coating film was evaluated. -30-201003310 [Table 1] Example 3 Example 4 Comparative Example 2 Example 5 Example 6 Comparative Example 3 Photosensitive resin A1 2.00 2.00 Photosensitive resin A2 2.00 2.00 Photosensitive resin A3 1.00 1.00 Photopolymerization initiator w 0.05 0.05 0.05 0.05 0.05 0.05 DPHA*2 0.50 0.50 0.50 PGMEA*3 1.45 1.45 2.45 2.62 2.62 3.62 Pencil hardness 4H 4H 5H 5H 3H 100 peel 100/100 100/100 Not film 100/100 100/100 50/100 Special note Matte/eyelet* 1 Irgacurel 84 (manufactured by Ciba Specialty Chemicals Co., Ltd.) *2 Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) *3 Photosensitive composition of the photosensitive resin of Comparative Example 1 using propylene glycol monomethyl ether acetate Since the system has a low molecular weight and a weak film forming ability, it cannot be evaluated unless other resin components are applied. Using the photosensitive composition of the photosensitive resin of Examples 1 and 2, a smooth film was obtained, and both hardness and adhesion were good. Example 7 In a 1000 ml flask equipped with a stirrer and a cooling tube, pyromellitic dianhydride (product of Daicel Co., Ltd.: PMDA) 76 g, 9,9-bis[4-(2-hydroxyethoxy) was placed. Phenyl]anthracene (manufactured by Osaka Gas Chemical Co., Ltd., BPEF) 124 g, propylene glycol monomethyl ether acetate 134 g' was heated in an oil bath of 1 5 51 for 4 hours while stirring under a nitrogen stream. Then, after cooling-31 - 201003310 to 1 20 °c, 1 g of 4-dimethylaminopyridine was added, and 4-hydroxy-2,2 tetramethylhexahydropyridine-1-oxo (made by Adeka: Adekastab 7RD) 0·04 g, 4-hydroxybutyl acrylate glycidyl ether (product of Nisshin Co., Ltd.: 4HBAGE) 106g, stirred at 120 ° C for 2 hours, then cooled to room temperature, 50% by weight of non-volatile components A solution of a light yellow transparent viscous resin (A4) was obtained by adding propylene glycol monomethyl ether acetate. The obtained resin solution was measured for viscosity, GPC benzene, weight average molecular weight, and solid acid value, and the viscosity was 4,800 mPa ° C, and the weight average molecular weight of styrene converted by GPC was 231. The solid acid value was 75.2 mgKOH. /g. Example 8 In a 1000 ml flask equipped with a stirrer and a cooling tube, phenyltetracarboxylic dianhydride (product of Ube Industries Co., Ltd.: BPDA) 90 g, bis[4-(2-hydroxyethoxy)phenyl]芴(Osaka Gas Chemical Co., Ltd. BPEF) 1 1 〇g '134g of propylene glycol monomethyl ether acetate and 1 g of 4-dimethylpyridine were heated in an oil bath of 155 t for 4 hours while stirring under a nitrogen stream. Then, after cooling to 120 ° C, 4-hydroxy-2,2 tetramethylhexahydropyridine-1-oxo (Adekastab 7RD, manufactured by ADEKA) was added, 0.04 g, 4-hydroxybutyl acrylate glycidyl group. Ether (product of Nisshin Co., Ltd.: 4 HBAGE) 80 g, stirred at 120 ° C for 2 hours. After cooling to room temperature, propylene glycol monomethyl ether acetate was obtained so that the nonvolatile content was 50% by mass, and a yellowish transparent viscous feeling was obtained, and 6,6-L A- was normalized. However, the addition of sensitizers to s/25 69, incorporation 9,9- system: amide addition, 6,6- LA- localization and then adding photo-32-201003310 resin (A 5 ) solution. The obtained resin solution was measured for viscosity, GPC styrene-equivalent weight average molecular weight, and solid acid value, and the viscosity was 66 〇〇mPa.s/25t, and the weight average molecular weight obtained by GPC was 1,823 〇. The solid acid value was 71.6 mg K 〇 H / g. Comparative Example 4 A bisphenol quinone type epoxy resin (BPFG, manufactured by Osaka Gas Chemical Co., Ltd.) of 110 g of epoxy group equivalent: 257 was used. According to Synthesis Example 1 and Example 1 described in Japanese Patent No. 3813244, a photosensitive resin (A6) was obtained. ). It takes more than 20 hours to synthesize the system, and the productivity is significantly lower than that of the embodiment 丨~4 of the present invention. Comparative Example 5 A bisphenol quinone type epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., _ BPFG) having an epoxy group equivalent of 257 was used. According to Synthesis Example 1 and Example 2 described in Japanese Patent No. 3813244, a photosensitive resin was obtained. a 7). The synthesis system requires more than 21 hours, and the productivity is significantly lower than that of the embodiment 7 and the embodiment 8 of the present invention. Comparative Example 6 The same procedure was carried out except that 8 〇g of 4-hydroxybutyl acrylate glycidyl ether of Example 8 was changed to glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.: G Μ A) of 60 g. The reaction was carried out to obtain a photosensitive tree-33-201003310 fat solution (A8). The obtained resin solution was measured for viscosity, GPC styrene-equivalent weight average molecular weight, and solid acid value, and was a viscosity of 12400 mPa, s/25 ° C, and a weight average molecular weight of 16100 obtained by GPC. The acid value was 74.2 mgKOH/g. Test Example 1 The photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 5 were measured for the polystyrene-equivalent weight average molecular weight obtained by GPC after storage for one month after the production and at room temperature, and the rate of change was examined. The results are shown in Table 2. [Table 2]_ styrene-converted weight average molecular weight obtained by GPC Change rate after one month after manufacture Example 7 23169 23681 102.2% Example 8 18230 18558 101.8% Comparative Example 4 5840 7180 122.9% Comparative Example 5 6340 7930 125.1% The photosensitive resin of Examples 7 to 8 showed almost no change. However, in the photosensitive resin of Comparative Examples 2 to 3, an increase in molecular weight of about 25% was observed, which was poor in storage stability. Examples 9 to 12 and Comparative Examples 7 to 1 2

Using the photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 6, a photosensitive composition was prepared by the following Table 3. The photosensitive composition was applied to a dry glass film having a thickness of 3 μm on a spinner of a 1.1 m m thick glass substrate, dried on a hot plate at 100 ° C -34 to 201003310 for 90 seconds, and then cooled to room temperature. Then, with an ultra-high pressure mercury lamp exposure machine, ultraviolet light is irradiated with 15 mW/cm2 (3 6 5 nm), the integrated light amount is 20 mJ/cm2, and U GR A - Ο FFSET - TE ST KAIL 1 982 is used as a mask for soft contact exposure. Thereafter, the image was immersed in 1% sodium carbonate water at 25 ° C for 90 seconds to form a pattern, and the sensitivity was evaluated by the order of the remaining steps, and the resolution was evaluated by a fine line. The results are shown in Table 3. [Table 3] Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 (A 戚 A4 2.00 2.00 A5 2.00 2.00 A6 2.00 2.00 A7 2.00 2.00 A8 2.00 2.00 Photopolymerization initiator μ 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 DPHA*2 0.50 0.50 0.50 0.50 0.50 PGMEA^3 1.70 2.99 1.70 2.99 1.70 2.99 1.70 2.99 1.70 2.99 Step sensitivity 5 7 5 11 shedding 0 3 4 1 3 Resolution [μιη] Line 4 4 4 4 25 6 6 6 6 Line spacing 8 8 6 6 12 8 8 8 8 * 4 Irgacure OXE-01 (manufactured by Ciba Specialty Chemical Co., Ltd.) Compared with Comparative Examples 4 to 6 In the photosensitive composition of the photosensitive resin (A6 to A8), the photosensitive composition using the photosensitive resin of Examples 7 to 8 (A4 to A5) has high sensitivity and exhibits excellent photoresist characteristics. -35 - 201003310 Example 1 3 In a 1000 ml flask equipped with a stirrer and a cooling tube, 3,3'-4,4'-biphenyltetracarboxylic anhydride (manufactured by Ube Industries, Ltd.: BPDA) was placed. 71.8 g, 9, 9 -double [4-(2-hydroxyethoxy) ) 3 phenylphenyl] fluorene (obtained by Osaka Gas Chemical Co., Ltd.: BOPPEF) 109.7 g, propylene glycol monomethyl ether acetate 128 g, 4-dimethylaminopyridine 0.25 g, and electric heating at 120 ° C while stirring The package was heated for 4 hours. Then, 0.1 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 13.7 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 1200 ° C for 4 hours. Further, 4-hydroxyl was added. Butyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) 34_68g' was heated and stirred at 120 ° C for 4 hours to obtain a pale yellow transparent viscous photosensitive resin (A 9 ) solution. The viscosity, GPC styrene-converted weight average molecular weight, solid content and solid acid value were determined as 'viscosity 1 87 1 00 mPa.s/25 〇C, styrene equivalent weight average molecular weight 4170 obtained by GPC, solid fraction 66.8 %, solid acid value of 85.4 mgKOH / g Example 14 4 Place 3,3,-4,4,-biphenyltetracarboxylic anhydride in a 1000 ml flask equipped with a stirrer and a cooling tube (Ube Industries Company system:]31>£)eight) 61.22g, 9,9-bis[6-(2-hydroxyl Oxy)naphthyl]anthracene (BNFEO, manufactured by Osaka Gas Chemical Co., Ltd.) 95.89 g, propylene glycol monomethyl acetate vinegar 125 g, 4-dimethylaminopyridine pyridine 0_25§' while stirring, at 120 ° C -36- 201003310 The electric heating bag is heated for 4 hours. Then, 13.3 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 120 T: for 4 hours. Further, 4 g of hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4HBAGE) was added to 56 g to 1,200. (: Heating and stirring for 4 hours to obtain a pale yellow transparent viscous photosensitive resin (A 1 〇) solution. For the obtained resin solution, the viscosity, GPC styrene-converted weight average molecular weight, solid content, and solid acid value were measured. Thereafter, the viscosity was 5 86700 mPa·s / 25 ° C, the weight average molecular weight of styrene in terms of GPC was 925 0, the solid content was 59.0%, and the solid acid value was 60.4 mg KOH / g. Examples 15 to 16 Using Example 1 The photosensitive resin of 3 was prepared into a photosensitive composition by the formulation of Table 4. The photosensitive composition was evaluated in the same manner as in Examples 9 to 12. [Table 4] Example 15 Example 16 (A) Ingredients A9 1.50 1.50 Photopolymerization initiator μ 0.05 0.05 DPHA*2 0.50 PGMEA*3 2.20 3.49 Step sensitivity 7 10 Resolution [μηι] Line 4 4 Line spacing 6 6 -37- 201003310 Photosensitive composition sensitivity of either It is also high and exhibits good photoresist characteristics. [Industrial Applicability] The photosensitive resin of the present invention can be easily produced at low cost, and it is easy to adjust the crosslinking density or the acid value, and has high heat resistance and high transparency. High refractive index and The resin composition using the photosensitive resin can be used for preparing an interlayer insulating film or a protective film (for example, a color filter or a liquid crystal display element) such as a liquid crystal display or an electronic component. Interlayer insulating film or protective film used for integrated circuit components, solid-state imaging devices, etc. -38-

Claims (1)

201003310 VII. Patent application range: 1. A photosensitive resin which is obtained by reacting a compound having an anthracene skeleton represented by the following formula (1) with a tetrabasic acid dianhydride, and adding the following a carboxylic acid-reactive (meth) acrylate compound represented by the above formula (2); (wherein ring Z1 and ring Z2 represent a monocyclic or condensed polycyclic hydrocarbon ring, Rli and Rlb represent a hydrogen atom or a substituent, R2a and R2b represent a substituent other than a hydrogen atom, and feet 33 and R3b represent a hydrogen atom or Methyl, kl and k2 represent the same or different integers from 0 to 4, (iv) m2 represents the same or different integers of 3 'nl and n2 represent the same- or different integers 〇10, and Pi and p2 represent the same Or a different integer of 0 to 4, but when the ring z1 and the ring Z2 are monocyclic hydrocarbon rings, P1 and P2 are 1 to 3, and when the ring and ring Z2 are condensed polycyclic hydrocarbon rings, they are contained in the ring Z1. The sum of P1 and the sum of p2 contained in ring Z2 are respectively 1 or more) -39- 201003310 [Chemical 2] R4 (wherein R4 represents a hydrogen atom or a methyl group, and R5 represents a group represented by the following formula (5)) [ί匕3] C2n 〇3Ηβ〇 C4h8o (5) (wherein q, r, and s each independently represent an integer of 0 to 9, but q, r, and s are not equal to each other). (2) The photosensitive resin according to the first aspect of the invention, wherein the compound having an anthracene skeleton represented by the above formula (1) is represented by the following formula (3); (wherein Rla& Rlb represents a hydrogen atom or a substituent; R2a, R2b, 63 and R6b represent a substituent other than a hydrogen atom, and R3a and R3b represent a hydrogen atom or a -40 - 201003310 group, and k1 and k2 represent the same or Indiguments of ~4, mi, m2, m3, and m4 represent integers of the same or different 〇~3, nl, n2, n3, and n4 represent integers of the same or different 〇~ι〇, pi and P2 denotes an integer of 1 to 4 which is the same or different, and p3 and p4 represent the same or different integers of 3~3). (3) The photosensitive resin according to the first aspect of the invention, wherein the compound having an anthracene skeleton represented by the above formula (1) is represented by the following formula (4); (wherein 'Rla& ruler' denotes a hydrogen atom or a substituent, R2a, R2b, 1173 and R7b represent a substituent other than a hydrogen atom, R3a and R3b represent a hydrogen atom or a methyl group, and kl and k2 represent the same or different An integer of ～4, nl and π2 represent integers of the same or different 〇10, and pi and ρ2 represent the same or different integers of 1 to 3.) 4. As in any of claims 1 to 3 of the patent application. The photosensitive resin according to any one of the above-mentioned formulas, wherein the acid value is 30 to 150 mgKOH/g. 6. A photosensitive resin composition comprising a photosensitive resin according to any one of items 1 to 5 of the above-mentioned application, and a photopolymerization initiator and/or a photosensitizer 7. The photosensitive resin composition of claim 6, wherein the polymerizable monomer having one or more unsaturated groups is further contained in the molecule. -42 - 201003310 Four designated representative figures: (1) The representative representative figure of this case is: no (2) A brief description of the symbol of the representative figure No Fifth, if the case of formula, please reveal features that best shows the chemical formula of the present invention. None