JPWO2009119622A1 - Photosensitive resin and photosensitive resin composition using the same - Google Patents

Abstract

Photosensitivity that can be easily manufactured at low cost, has easy cross-link density and acid value adjustment, and has excellent characteristics such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. The object is to provide a resin. The photosensitive resin is represented by the following general formula (2) to a polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with tetrabasic acid dianhydride. It is a photosensitive resin obtained by adding a carboxylic acid reactive (meth) acrylate compound. Wherein ring Z1 and ring Z2 represent an aromatic hydrocarbon group, R1a and R1b represent a hydrogen atom or a substituent, R2a and R2b represent a substituent other than a hydrogen atom, and R3a and R3b Represents a hydrogen atom or a methyl group, k1 and k2 are the same or different and represent an integer of 0 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3, and n1 and n2 are the same or different and represent 0 And p1 and p2 are the same or different and each represents an integer of 0 to 4. (In the formula, R4 represents a hydrogen atom or a methyl group, and R5 represents the following general formula (5). (Wherein q, r, and s each independently represent an integer of 0 to 9, provided that q, r, and s are not 0 at the same time.)

Description

  The present invention relates to a photosensitive resin having a fluorene skeleton and a photosensitive resin composition using the same. More specifically, the photosensitive resin has various excellent properties and can be easily produced at low cost. Resin and interlayer insulating films and protective films (for example, interlayer filters and protective films used for color filters, liquid crystal display elements, integrated circuit elements, solid-state image sensors, etc.) in liquid crystal displays and electronic parts, etc. The present invention relates to a photosensitive resin composition useful for preparation.

  It is known that a polymer compound having a fluorene skeleton has excellent physical properties such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. Utilizing this property, a polymer compound having a fluorene skeleton in which a radical polymerizable unsaturated bond structure (vinyl group) is introduced into the molecule is used as an optical overcoat agent, hard coat agent, antireflection film. In addition, studies on optical materials such as spectacle lenses, optical fibers, optical waveguides, and holograms are underway. For example, as a plastic lens material, a compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with (meth) acrylic acid chloride, or 9,9-bis (4-hydroxyphenyl) fluorene with ethylene oxide or propylene oxide A copolymer containing as a main component a compound obtained by adding (meth) acrylic acid after the addition of is disclosed (Patent Document 1).

  However, the compounds disclosed in this patent document have the disadvantages that the molecular weight is low, the structure is flexible, the refractive index is not sufficient, and the strength of the cured product is low because the crosslinking density is low. is there.

  In addition, polymer compounds having a fluorene skeleton are also applied to so-called photoresists such as liquid crystal color filters, black matrices, solder resists, etc., due to their excellent heat resistance and chemical resistance (Patent Documents). 2 and 3).

  Photosensitive resins based on these technologies can obtain a high crosslinking density and can obtain a cured product having excellent strength, heat resistance, and chemical resistance, but the synthesis takes a very long time. For this reason, the cost is high and it is difficult to say that it is widely used. Further, since coloring occurs due to the manufacturing method, it is difficult to apply to optical components that require transparency, and it cannot be said that the characteristics of the fluorene skeleton are fully utilized.

JP-A-4-325508 Japanese Patent No. 3673321 JP 2007-264433 A

  Therefore, it can be easily produced at a low cost, the crosslinking density and the acid value can be easily adjusted, and the fluorene skeleton originally has high heat resistance, high transparency, high refractive index, low linear expansion coefficient, etc. There is a demand for providing a photosensitive resin having excellent characteristics, and an object of the present invention is to provide such a photosensitive resin and a photosensitive resin composition using the photosensitive resin.

  In view of this situation, the present inventors have conducted extensive research to solve the above problems, and as a result, have obtained a polymer compound obtained by reacting a compound having a specific fluorene skeleton with tetrabasic dianhydride. A photosensitive resin obtained by adding a specific carboxylic acid-reactive (meth) acrylate compound can be easily produced at low cost, provides high strength at a high crosslinking density, and has high heat resistance and high transparency. The present inventors have found that it exhibits excellent characteristics such as a high refractive index and a low linear expansion coefficient, and has completed the present invention.

（式中、環Ｚ^１及び環Ｚ^２は単環式又は縮合多環式炭化水素環を示し、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ及びＲ^２ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示し、ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｍ１及びｍ２は同一又は異なって０〜３の整数を示し、ｎ１及びｎ２は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって０〜４の整数を示す。但し、環Ｚ^１及び環Ｚ^２が単環式炭化水素環の場合ｐ１及びｐ２は１〜３であり、環Ｚ^１及び環Ｚ^２が縮合多環式炭化水素環の場合、環Ｚ^１に含まれるｐ１の和及び環Ｚ^２に含まれるｐ２の和がそれぞれ１以上である。）

（式中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は下記一般式（５）で表される基を示す）

（式中、ｑ、ｒ、ｓはそれぞれ独立に０〜９の整数を示す。但し、ｑ、ｒ、ｓが同時に０となることはない。）That is, the present invention provides a polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride to a carboxylic acid represented by the following general formula (2). It is a photosensitive resin obtained by adding an acid-reactive (meth) acrylate compound.

(In the formula, ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or a substituent, and R ^2a and R ^2b represent other than a hydrogen atom. R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 are the same or different and represent an integer of 0 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3 , N1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 0 to 4, provided that the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings. If p1 and p2 is 1 to 3, when the ring ^{Z 1} and the ring ^{Z 2} is a condensed polycyclic hydrocarbon ring, the sum of p2 included in the sum and ring ^{Z 2} of p1 contained in the ring ^{Z 1} each 1 or more.)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group represented by the following general formula (5))

(In the formula, q, r, and s each independently represent an integer of 0 to 9. However, q, r, and s are not 0 simultaneously.)

  Moreover, this invention contains the said photosensitive resin, a photoinitiator, and / or a photosensitizer, The photosensitive resin composition characterized by the above-mentioned.

  The photosensitive resin of the present invention has high storage stability, can be easily produced at low cost, has excellent productivity, and has excellent characteristics such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. I have it. In addition, the photosensitive resin composition of the present invention using this photosensitive resin has high sensitivity and can provide a cured product having excellent strength and the like.

（式中、環Ｚ^１及び環Ｚ^２は単環式又は縮合多環式炭化水素環を示し、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ及びＲ^２ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示し、ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｍ１及びｍ２は同一又は異なって０〜３の整数を示し、ｎ１及びｎ２は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって０〜４の整数を示す。但し、環Ｚ^１及び環Ｚ^２が単環式炭化水素環の場合ｐ１及びｐ２は１〜３であり、環Ｚ^１及び環Ｚ^２が縮合多環式炭化水素環の場合、環Ｚ^１に含まれるｐ１の和及び環Ｚ^２に含まれるｐ２の和がそれぞれ１以上である。）The polymer compound constituting the photosensitive resin of the present invention is obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) and a tetrabasic acid dianhydride described later.

(In the formula, ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or a substituent, and R ^2a and R ^2b represent other than a hydrogen atom. R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 are the same or different and represent an integer of 0 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3 , N1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 0 to 4, provided that the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings. If p1 and p2 is 1 to 3, when the ring ^{Z 1} and the ring ^{Z 2} is a condensed polycyclic hydrocarbon ring, the sum of p2 included in the sum and ring ^{Z 2} of p1 contained in the ring ^{Z 1} each 1 or more.)

In the above formula (1), the hydrocarbon corresponding to the hydrocarbon ring represented by the ring Z ¹ and the ring Z ² is monocyclic or condensed polycyclic, for example, monocyclic carbonization such as benzene. Hydrogen, condensed bicyclic hydrocarbons (for example, C _8-20 condensed bicyclic hydrocarbons such as indene and naphthalene, preferably C _10-16 condensed bicyclic hydrocarbons), condensed tricyclic hydrocarbons (anthracene, And condensed 2- to 4-cyclic hydrocarbons such as phenanthrene. Examples of hydrocarbons that are particularly preferred in applications requiring high refractive index and heat resistance include condensed polycyclic aromatic hydrocarbons (such as naphthalene and anthracene), and naphthalene is particularly preferable. In addition, benzene is preferred in applications that require particularly high solubility, compatibility, and low solution viscosity. Ring Z ¹ and ring Z ² may be the same or different rings, and may usually be the same ring.

In the above formula (1), the substituent represented by R ^1a and R ^1b is not particularly limited, but is usually an alkyl group. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . The groups R ^1a and R ^1b may be different from each other or the same. When k1 (or k2) is 2 or more, the groups R ^1a (or R ^1b ) may be different or the same in the same benzene ring. Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

Examples of the substituents R ^2a and R ^2b substituted on the ring Z ¹ and the ring Z ² include alkyl groups (methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, t-butyl groups, and the like). _1-20 alkyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-10 cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), dimethylphenyl group (xylyl group) etc.), etc. C _6-10 aryl group, preferably C _6-8 aryl group, especially phenyl group), aralkyl group (C _6-10 aryl-C 1-4 alkyl group such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as alkoxy groups (C _1-4 alkoxy groups such as methoxy groups); acyl groups (C _1-6 acyl groups such as acetyl groups); alkoxycarbonyl groups (C _1- such as methoxycarbonyl groups) ₄ alkoxycarbonyl group etc.); halogen atom (fluorine atom, chlorine atom etc.); nitro group; cyano group etc.

Preferred substituents R ^2a (or R ^2b ) are an alkyl group (C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group), an aryl group (C _6-10 aryl group), an aralkyl group ( C _6-8 aryl-C _1-2 alkyl group), and C _1-4 alkyl group, C _1-4 alkoxy group, and C _6-8 aryl group are particularly preferable. The substituent R ^2a (or R ^2b ) may be substituted on the benzene ring alone or in combination of two or more. The groups R ^2a and R ^2b may be the same or different from each other, but are usually the same. When m1 (or m2) is 2 or more, the groups R ^2a (or R ^2b ) may be different or the same in the same hydrocarbon ring.

The substitution position of the substituent R ^2a (or R ^2b ) is not particularly limited, and depends on the substitution position of a hydroxyl group or a hydroxy (poly) alkyleneoxy group (hereinafter sometimes referred to as a hydroxyl group-containing group). Thus, the phenyl group constituting the phenol skeleton can be substituted at the 2-6 position (for example, the 2-position, 5-position, 2,5-position, etc.).

The substitution numbers m1 and m2 of the substituents R ^2a and R ^2b are preferably 0 to 2, more preferably 0 to 1 (particularly 0), although depending on the number of substitutions of the hydroxyl group-containing group. The substitution numbers m1 and m2 may be different but are usually the same in many cases.

The substituent represented by R ^3a and R ^3b of the hydroxyl group-containing group is hydrogen or a methyl group. R ^3a and R ^3b may be the same or different from each other, but are usually the same.

  The addition numbers n1 and n2 of the (poly) alkyleneoxy group are the same or different and can be selected from the range of 0 to 10, preferably 0 to 8 (for example, 1 to 8), more preferably 0 to 6 (for example, 1 to 6), particularly about 0 to 4 (for example, 1 to 4). Moreover, the sum (n1 + n2) of n1 and n2 can be selected from the range of 0-20, Preferably it is 0-16 (for example, 2-12), More preferably, it is 0-12 (for example, 2-12), Especially 0 About 8 (for example, 2-8) may be sufficient. When n1 (or n2) is 2 or more, the (poly) alkyleneoxy group may be composed of the same alkoxy group, and different types of alkoxy groups (for example, ethoxy group and propyleneoxy group) are mixed. Usually, it is often composed of the same alkoxy group.

The substitution numbers p1 and p2 of the hydroxyl group-containing group are in the range of 0 to 4, preferably 1 to 4, particularly preferably 1 to 2. However, when ring Z ¹ and ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are 1 to 3, and when ring Z ¹ and ring Z ² are condensed polycyclic hydrocarbon rings, ring Z ¹ p2 sum included in the sum and ring Z ² of p1 contained is 1 or more, respectively. Moreover, 2-8 are preferable and, as for the sum (p1 + p2) of p1 and p2, More preferably, it is 2-4. In particular, p1 and p2 are preferably 2 to 3 in applications in which the crosslink density of the cured product is required. The substitution numbers p1 and p2 may be different but are usually the same in many cases. The substitution position of the hydroxyl group-containing group is not particularly limited, and can be selected from the 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene according to the number of p1 (or p2), and p1 (or p2) is 2 In this case, for example, it may be 3,4-position, 3,5-position, and the like. One hydroxyl group-containing group may be generally substituted at the 4-position.

  In addition, the several hydroxyl group containing group which comprises the same phenol frame | skeleton may be the same, and may differ. For example, the plurality of hydroxyl group-containing groups may be composed of (i) a hydroxyl group alone where n1 = 0 (n2 = 0) (except when p1 and p2 are 2), and (ii) n1 = 0 (n2 = 0) and a hydroxyl (poly) alkoxy group (such as 2-hydroxyethoxy group) in which n1 ≠ 0 (n2 ≠ 0) may be formed, and (iii) n1 (Iv) different hydroxy (poly) alkoxy groups [n 2 ≠ 0 (n 2 ≠ 0)] [for example, 2 -Hydroxyethoxy group and 2- (2-hydroxyethoxy) ethoxy group].

（式中、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^６ｂ及びＲ^６ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示し、ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｍ１、ｍ２、ｍ３及びｍ４は同一又は異なって０〜３の整数を示し、ｎ１、ｎ２、ｎ３及びｎ４は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって１〜４の整数を示し、ｐ３及びｐ４は同一又は異なって０〜３の整数を示す。）Among the compounds having the fluorene skeleton of the general formula (1), those having a structure represented by the following general formula (3) are preferable in applications that require particularly high refractive index and heat resistance.

(Wherein, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^6b and R ^6b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, m1, m2, m3 and m4 are the same or different and represent an integer of 0 to 3, and n1, n2, n3 and n4 are the same or different And p1 and p2 are the same or different and represent an integer of 1 to 4, and p3 and p4 are the same or different and represent an integer of 0 to 3.)

R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. R ^6b and R ^6b correspond to R ^2a and R ^2b , m3 and m4 correspond to m1 and m2, n3 and n4 correspond to n1 and n2, respectively, and have the same meaning. Although p1 and p2 are the same as the above, 1-4 are preferable. p3 and p4 correspond to the above-mentioned p1 and p2, and 0-3 are preferable.

  Specifically, compounds in which p1 + p2 + p3 + p4 is 2 in the general formula (3) such as 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes; Examples thereof include compounds in which p1 + p2 + p3 + p4 is 2 or more in the general formula (3) such as -bis (polyhydroxyalkoxynaphthyl) fluorenes and 9,9-bis (polyhydroxypolyalkoxynaphthyl) fluorenes.

As 9,9-bis (hydroxyalkoxynaphthyl) fluorenes, for example, 9,9-bis (hydroxyalkoxynaphthyl) fluorene {for example, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] Fluorene, 9,9-bis [6- (2-hydroxypropoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [ And 9,9-bis (hydroxyC _2-4 alkoxynaphthyl) fluorene such as 5- (2-hydroxypropoxy) -1-naphthyl] fluorene} and the like.

Examples of 9,9-bis (hydroxypolyalkoxynaphthyl) fluorenes include, for example, 9,9-bis (hydroxydialkoxynaphthyl) fluorene [for example, 9,9-bis {6- [2- (2-hydroxy Ethoxy) ethoxy] -2-naphthyl} fluorene, 9,9-bis {6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl} fluorene, 9,9-bis {5- [2- (2 9,9-bis (hydroxydiC ₂ such as -hydroxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxypropoxy) propoxy] -1-naphthyl} fluorene _-4 alkoxy naphthyl) fluorene] 9,9-bis (hydroxymethyl dialkoxy naphthyl) fluorene such as; these compounds And in the general formula (3), n1, n2, n3, and n4 are 3 or more.

The 9,9-bis (polyhydroxyalkoxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyalkoxynaphthyl) fluorenes and have a compound in which p1 + p2 + p3 + p4 is 2 or more, for example, 9,9-bis (di or di) Trihydroxyalkoxynaphthyl) fluorene [eg, 9,9-bis [di (2-hydroxyethoxy) -2-naphthyl] fluorene, 9,9-bis [di (2-hydroxypropoxy) -2-naphthyl] fluorene, etc. 9,9-bis (polyhydroxyalkoxynaphthyl) fluorene such as 9,9-bis (di- or trihydroxyC _2-4 alkoxynaphthyl) fluorene and the like].

The 9,9-bis (polyhydroxypolyalkoxynaphthyl) fluorenes correspond to the 9,9-bis (hydroxyalkoxynaphthyl) fluorenes, n1, n2, n3, n4 are 2 or more and p1 + p2 + p3 + p4 is 2 or more. A compound such as 9,9-bis (di- or trihydroxydialkoxynaphthyl) fluorene [e.g. 9,9-bis {di [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl} fluorene, etc. 9 bis 9,9-bis (di or trihydroxy dialkoxy naphthyl) fluorene such as (di or trihydroxy-di C _2-4 alkoxy-naphthyl) fluorene, etc.]; corresponding to these compounds, the formula (formula 3 ) In which n1, n2, n3 and n4 are 3 or more.

  Of these, 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene and the like are preferable.

  Among the compounds having the fluorene skeleton of the general formula (1), those having a structure represented by the following general formula (4) are preferable in applications that require particularly high solubility, compatibility and low solution viscosity.

（式中、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^７ｂ及びＲ^７ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示す。ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｎ１及びｎ２は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって１〜３の整数を示す。）

(In the formula, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^7b and R ^7b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, n1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 1 to 3. .)

R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. R ^7b and R ^7b correspond to R ^3a and R ^3b and have the same meaning. Although p1 and p2 are the same as the above, 1-3 are preferable.

  Typical compounds represented by the formula (4) include 9,9-bis (hydroxyalkoxyphenyl) fluorenes (compounds in which n1 = n2 = 1 in the general formula (4)), 9,9- Bis (hydroxypolyalkoxydialkylphenyl) fluorenes (compounds wherein n1 and n2 are each 1 or more in the general formula (4)) are included.

9,9-bis (hydroxyalkoxyphenyl) fluorenes include, for example, 9,9-bis (hydroxyalkoxyphenyl) fluorenes {eg, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2 -Hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) Phenoxyethanol] fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenoxyethanol] fluorene 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4 -(2-hydroxyethoxy) -3,6-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -2,6-dimethylphenyl] fluorene, 9,9-bis [4- ( 2-hydroxyethoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [3- (2-hydroxypropoxy) -2,4-dimethylphenyl] fluorene 9,9-bis [4- (2-hydroxyethoxy) -3,4-dimethylphenyl] fluorene, 9,9-bis [2- (2-hydroxypropoxy) -3,4-dimethylphenyl] fluorene, etc. 9,9-bis (hydroxyalkoxyalkylphenyl) fluorene, preferably 9,9-bis (hydroxy-branched C _3-4 such as 9,9-bis (2-hydroxypropoxy-diC _1-4 alkylphenyl) fluorene Alkoxy-dialkylphenyl) fluorenes}.

  9,9-bis (hydroxypolyalkoxyphenyl) fluorenes include compounds in which n1 and n2 are 2 or more, such as 9,9-bis (hydroxydialkoxyphenyl) fluorenes {for example, 9,9-bis [ 4- (2-hydroxydiethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3- Methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,5-dimethylphenyl Fluorene, 9,9-bis [4- (2-hydroxydiethoxy) phenoxyethanol] fluorene, 9,9-bis [4- (2-H Roxydipropoxy) phenoxyethanol] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -3-methyl Phenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -2,5-dimethyl Phenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,6-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -2,6-dimethyl Phenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [ -(2-hydroxydipropoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy) -3,4-dimethylphenyl] fluorene, 9,9-bis [2 9,9-bis (hydroxydialkoxyphenyl) fluorene} such as-(2-hydroxydipropoxy) -3,4-dimethylphenyl] fluorene.

  Of these, 9,9-bis (hydroxyethoxyphenyl) fluorene, 9,9-bis (hydroxyethoxy-3-methylphenyl) fluorene, 9,9-bis (hydroxyethoxy-3,5dimethylphenyl) fluorene, 9 , 9-bis (hydroxyethoxy-2phenoxyethanol) fluorene is preferred.

Compounds having a fluorene skeleton represented by the above general formula (1) constituting the photosensitive resin of the present invention, particularly in a high refractive index and solubility, applications requiring compatibility and low solution viscosity, R ^2a And R ^2b is preferably a phenyl group.

Specifically, for example, the compound represented by the general formula (4) includes 9,9-bis (hydroxyalkoxyarylphenyl) fluorenes (in the general formula (4), n1 = n2 = 1, A compound in which R ^2a and R ^2b are phenyl groups), 9,9-bis (hydroxypolyalkoxyarylphenyl) fluorenes (in the general formula (4), n1 + n2 is 2 or more, and R ^2a and R ^2b are phenyl groups) Which is a compound).

  9,9-bis (hydroxyalkoxyarylphenyl) fluorenes include 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9-bis [4- (2-hydroxypropoxy) 9,9-bis (hydroxyalkoxyarylphenyl) fluorene such as -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-tolylphenyl] fluorene, preferably 9,9- Bis (2-hydroxyethoxyarylphenyl) fluorene} and the like.

  9,9-bis (hydroxypolyalkoxyarylphenyl) fluorenes include 9,9-bis (hydroxydialkoxyarylphenyl) fluorenes {eg, 9,9-bis {4- [2- (2-hydroxyethoxy 9,9-bis (hydroxydialkoxyarylphenyl) fluorene such as ethoxy] -3-phenylphenyl} fluorene, preferably 9,9-bis [2- (2-hydroxyethoxy) ethoxyarylphenyl] fluorene} included.

  Of these, 9,9-bis (hydroxyethoxyarylphenyl) fluorene is preferred.

  A tetrabasic acid dianhydride is used as a compound to be reacted with the compound having the fluorene skeleton.

  Specific examples of the tetrabasic dianhydride include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic Acid dianhydride, cyclohexane tetracarboxylic dianhydride, cycloheptane tetracarboxylic dianhydride, norbornane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid 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-tetra Dronaphthalene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and the like, and one or more of these are used. Among these, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, benzophenonetetracarboxylic dianhydride Biphenyltetracarboxylic dianhydride is preferred.

  A polymer compound constituting the photosensitive resin of the present invention can be obtained by subjecting the compound having a fluorene skeleton to an addition reaction with tetrabasic dianhydride. In this addition reaction, the ratio of tetrabasic dianhydride to 1 mol of the compound having a fluorene skeleton is preferably 0.5 mol to 1.5 mol, and more preferably 0.65 mol to 1.25 mol. When the ratio of tetrabasic acid dianhydride is less than 0.5 mol and exceeds 1.5 mol, sufficient molecular weight may not be obtained.

  A catalyst may be used in the addition reaction between the compound having a fluorene skeleton and tetrabasic acid dianhydride. The catalyst to be used is not particularly limited as long as it promotes the reaction. Examples thereof include pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N , N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, , 5-diazabicyclo [4,3,0] nonene-5, etc., quaternary ammonium compounds such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide, Fins, triphenylphosphine and the like and mixtures thereof. The amount of the catalyst to be used is not particularly limited, but a range of 0.1 to 2.0 parts by mass is preferable with respect to 100 parts by mass in total of the compound having a fluorene skeleton and the tetrabasic acid dianhydride. If the amount of the catalyst is more than 2.0 parts by mass, the electrical characteristics and storage stability of the photosensitive resin may be adversely affected.

  Further, in the addition reaction, a solvent may be used for the purpose of dissolving the reaction raw materials and reducing the viscosity. The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. Glycol ether acetates such as, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol ethers such as propylene glycol diethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ete Propylene glycol ether acetates such as acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, dimethyl Examples include sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  Although there is no restriction | limiting in particular also in the quantity of the solvent to be used, The range of 25-150 mass parts is preferable with respect to a total of 100 mass parts of the sum total of the compound which has a fluorene skeleton, and tetrabasic acid dianhydride. If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

  Addition of a solvent or catalyst to the compound having a fluorene skeleton and tetrabasic acid dianhydride, if necessary, is allowed to carry out an addition reaction. In the reaction, it is preferable to heat, the raw material is dissolved by heating, and the reaction rate is also accelerated. The The heating temperature can be appropriately set according to the type of the compound having a fluorene skeleton and the tetrabasic acid dianhydride and the apparatus to be used, but it is generally preferably in the range of 60 to 220 ° C. More preferably, it is the range of 90-160 degreeC. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, when the reaction temperature is higher than 220 ° C., side reactions such as coloring may occur, or the reaction rate may decrease due to an equilibrium in which the acid anhydride is closed.

  The photosensitive resin of the present invention can be obtained by adding a carboxylic acid reactive (meth) acrylate compound represented by the following general formula (2) to the polymer compound obtained as described above.

（式中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は下記一般式（５）で表される基を示す）

（式中、ｑ、ｒ、ｓはそれぞれ独立に０〜９の整数を示す。但し、ｑ、ｒ、ｓが同時に０となることはない。）

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group represented by the following general formula (5))

(In the formula, q, r, and s each independently represent an integer of 0 to 9. However, q, r, and s are not 0 simultaneously.)

  Specific examples of the carboxylic acid reactive (meth) acrylate represented by the general formula (2) include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3- Examples thereof include hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, and polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether.

  Such a carboxylic acid reactive (meth) acrylate compound is subjected to an addition reaction with the above polymer compound. The proportion of the carboxylic acid-reactive (meth) acrylate compound in the photosensitive resin of the present invention is not unclear because it varies depending on the application, but when used for a photocurable coating agent or an optical material, the acid value of the photosensitive resin It may be added until becomes zero. On the other hand, when applied to an alkali developable application, it is preferable to adjust the acid value of the resin solid content to be in the range of 30 to 150 mgKOH / g. If the acid value is lower than 30 KOH / g, the development speed may be reduced and a required pattern may not be obtained. On the other hand, when the acid value is higher than 150 mgKOH / g, the pattern is likely to be peeled off due to excessive development, and the electrical characteristics and the like may be deteriorated. In addition, in this specification, the acid value of resin solid content is a measured value based on JIS-K0070.

  In the reaction between the polymer compound and the carboxylic acid reactive (meth) acrylate compound, a catalyst may be used for the purpose of promoting the reaction. The type of the catalyst differs depending on the type of the carboxylic acid reactive (meth) acrylate compound, so it cannot be generally stated, but as an example, pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo [5,4 , 0] -7-undecene, 1,5-diazabicyclo [4,3,0] nonene-5, etc., tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, tetramethylammonium hydroxide Quaternary ammonium compounds, tributylphosphine, triphenylphosphine and the like and mixtures thereof.

  Moreover, there is no restriction | limiting in particular in the quantity of the catalyst to be used, However, The range of 0.1-2.0 mass parts is preferable with respect to 100 mass parts of compounds which have the said fluorene skeleton. If the amount of the catalyst is too large, the electrical properties and storage stability of the photosensitive resin may be adversely affected.

  Moreover, when making a carboxylic-acid reactive (meth) acrylate compound react, it is preferable to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited as long as it suppresses the reaction of unsaturated bond. Examples thereof include hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, t-butyl catechol, N-methyl-N-nitroso. Aniline or N-nitrosophenylhydroxylamine / ammonium salt (Wako Pure Chemical Industries, Ltd .: Q-1300), N-nitrosophenylhydroxylamine / aluminum salt (Wako Pure Chemical Industries, Ltd .: Q-1301), 2, Examples include 2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl. In particular, N-nitrosophenylhydroxylamine aluminum salt and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl are preferable. The amount of the polymerization inhibitor varies depending on the type and reaction conditions, and cannot be generally stated, but is preferably in the range of 5 to 2000 ppm with respect to the entire photosensitive resin. If it is less than this range, unsaturated bonds may react during production to cause gelation, and if it is more than this range, the sensitivity may decrease, which is not preferable.

  When adding the carboxylic acid reactive (meth) acrylate compound, it is preferable to heat for the purpose of improving the reaction rate. The heating temperature can be appropriately set depending on the type and apparatus of the carboxylic acid reactive (meth) acrylate compound, but is generally preferably in the range of 60 to 150 ° C. When the reaction temperature is lower than 60 ° C., it may take time to complete the reaction. On the other hand, if the reaction temperature is higher than 150 ° C., side reactions such as coloring may occur, or unsaturated bonds may react to cause gelation.

  The molecular weight of the photosensitive resin of the present invention thus obtained is not particularly limited, but is preferably 1,000 to 200,000 from the viewpoint of coating film strength, film forming property, or developability, and more preferably 2,500. ~ 50,000 is preferred. In the present specification, the molecular weight of the photosensitive resin is a weight average molecular weight in terms of styrene by GPC under the conditions described in the examples.

  The photosensitive resin composition of this invention contains the said photosensitive resin and a photoinitiator and / or a photosensitizer as an essential component. The photopolymerization initiator and / or photosensitizer may be mixed in a state dissolved or dispersed in a solvent, or chemically bonded to the photosensitive resin.

  The photopolymerization initiator and / or photosensitizer used in the present invention is not particularly limited, and examples thereof include benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, and bis-N. Benzophenones such as N, diethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and isopropoxychlorothioxanthone, ethyl anthraquinone, benzanthraquinone Anthraquinones such as aminoanthraquinone, chloroanthraquinone, anthraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, acetophenones, benzo Benzoin ethers such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, 2,4,6-trihalomethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole 2,4,5-triarylimidazole dimers such as dimer, benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], phenanthrenequinone, 9,10-phenanthrenequinone, benzoins such as methylbenzoin, ethylbenzoin, 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Heptane, etc., acridine derivatives, include bisacylphosphine oxide, can be used alone or in combination of two or more thereof.

  An accelerator may be further added to the photosensitive resin of the present invention. Examples of the accelerator include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine 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 sometimes simply referred to as “polymerizable monomer”) can be used. , Chemical resistance, heat resistance and mechanical strength can be improved. Moreover, it is also possible to add a polymerizable monomer for the purpose of adjusting flow characteristics. As the polymerizable monomer, any monomer having at least one unsaturated bond in the molecule can be used without particular limitation, and an appropriate monomer may be selected depending on the intended use and purpose. For example, polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, Trimethylolpropane propoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A polyoxyethylene di (meth) acrylate, bisphenol A dioxyethylene Di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A decaoxyethylene di (meth) acrylate, polyvalent carboxylic acid (such as phthalic anhydride), a compound having a hydroxyl group and an ethylenically unsaturated group ( β-hydroxyethyl (meth) acrylate, etc.), (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc. (Meth) acrylic acid alkyl ester, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycol Of epoxy compounds such as cidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, glycerin triglycidyl ether (Meth) acrylic acid adducts, unsaturated organic acids such as maleic acid and their anhydrides, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N- Ethyl methacrylamide, N-isopropyl methacrylamide, N-methylol methacrylamide, N, N-dimethyl acryl , Acrylamides such as N, N-diethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, styrenes such as styrene and hydroxystyrene, N-vinylpyrrolidone, N-vinylformamide, N- Examples thereof include vinylacetamide and N-vinylimidazole, and one or more of these can be used.

  A colorant can also be added to the photosensitive resin composition of the present invention for the purposes of design, visibility, and prevention of photoresist halation. The kind of colorant to be added can be appropriately selected depending on the purpose of coloring. For example, phthalocyanine dyes, anthraquinone dyes, azo dyes, indigo dyes, coumarin dyes, triphenylmethane dyes, phthalocyanine pigments Anthraquinone pigments, azo pigments, quinacridone pigments, coumarin pigments, triphenylmethane pigments and the like can be exemplified, and one or more of these can be used.

  The photosensitive resin composition of this invention can be made into the form of the paste which mixed the solution or the filler etc., For that purpose, it is also possible to contain a solvent. The type of solvent used is not particularly limited, but examples include water, ethylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, and diethylene glycol. Glycol ethers such as dimethyl ether, glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol, propylene glycol monomethyl ether Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers, propylene glycol monomethyl ether acetate , Propylene glycol ether acetates such as propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl lactate, lactate ester Lactate esters such as Le, ethyl acetate, acetic acid esters such as butyl acetate, dimethyl sulfoxide, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, and mixtures thereof.

  In the photosensitive resin composition of the present invention, conventionally known components such as a polymerization inhibitor, a plasticizer, an antifoaming agent, and a coupling agent can be further blended as necessary.

  The photosensitive resin composition of this invention can be obtained by mixing the said essential component and a solvent and other arbitrary components as needed according to a conventional method.

  When the photosensitive resin composition of the present invention obtained as described above is used as a photoresist, it is applied on a substrate as a solution or a paste. The coating method is not particularly limited, and screen printing, curtain coating, blade coating, spin coating, spray coating, dip coating, slit coating, and the like are applied. The applied solution or paste is exposed with UV or electron beam through a predetermined mask. When apply | coating using a solvent, you may pass through a drying process. A pattern can be formed by developing the exposed coating film wet. The developing method can be any of a spray method, a paddle method, an immersion method, and the like, but a spray method with few residues is preferable. Ultrasonic waves or the like can be irradiated as necessary. As the developer, weak alkaline water is preferably used. For the purpose of assisting developability, an organic solvent, a surfactant, an antifoaming agent, etc. can be added.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these.

Example 1
In a 1000 ml flask equipped with a stirrer and a condenser, pyromellitic dianhydride (Daicel product: PMDA) 64 g, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (produced by Osaka Gas Chemical Company) : BPEF) 136 g and propylene glycol monomethyl ether acetate 134 g were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 1 g of 4-dimethylaminopyridine, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: ADK STAB LA-7RD), 106 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) was added and stirred at 120 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A1) solution.

    The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 2900 mPa · s / 25 ° C., styrene-converted weight average molecular weight 12,523 by GPC, solid content acid value 2 0.2 mg KOH / g. In addition, Toki Sangyo Co., Ltd. BM type | mold viscosity meter was used for the viscosity measurement. Further, GPC was measured using TSKgel G7000HXL, TSKgel GMHXL 2 and TSKgel G2500HXL manufactured by Tosoh Corporation at a THF eluent of 40 ° C. and a flow rate of 0.5 ml / min. The acid value was measured according to the neutralization titration method described in JIS-K0070.

Example 2
In a 1000 ml flask equipped with a stirrer and a condenser tube, 72 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) (Product: BPEF) 128 g, 4-dimethylaminopyridine 1 g and propylene glycol monomethyl ether acetate 134 g were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: Adeka Stab LA-7RD) 0.04 g, 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) 84g was added, and it stirred at 120 degreeC for 4 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A2) solution. The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 4200 mPa · s / 25 ° C., styrene-converted weight average molecular weight 7,243 by GPC, solid content acid value 2 0.5 mg KOH / g.

Comparative Example 1
A photosensitive resin (A3) was obtained according to Synthesis Example 1 described in JP-A-4-325508.

Using the photosensitive resins of Examples 1 and 2 and Comparative Example 1, photosensitive compositions were prepared with the compositions shown in Table 1. This photosensitive composition was applied to a 1.1 mm thick soda lime glass substrate with a bar coater to a dry film thickness of 6 μm, dried for 10 minutes with a hot air dryer at 80 ° C., and then cooled to room temperature. Subsequently, ultraviolet rays with an integrated light amount of 300 mJ / cm ² were irradiated with an ultra-high pressure mercury lamp UV irradiator. The cured coating film was subjected to pencil hardness and crosscut-tape peel test in accordance with JIS-K5400 to evaluate the strength of the coating film.

  Since the photosensitive composition using the photosensitive resin of Comparative Example 1 had a low molecular weight, the film-forming ability was weak and could not be evaluated without adding other resin components. The photosensitive compositions using the photosensitive resins of Examples 1 and 2 gave smooth films, and both hardness and adhesion were good.

Example 7
In a 1000 ml flask equipped with a stirrer and a cooling tube, 76 g of pyromellitic dianhydride (Daicel product: PMDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Company) : BPEF) and propylene glycol monomethyl ether acetate (134 g) were added and heated in an oil bath at 155 ° C. for 4 hours with stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 1 g of 4-dimethylaminopyridine, 0.04 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: ADK STAB LA-7RD), 106 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) was added and stirred at 120 ° C. for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A4) solution.

  The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 4800 mPa · s / 25 ° C., styrene-converted weight average molecular weight by GPC was 23,169, and solid content acid value was 75. 0.2 mg KOH / g.

Example 8
In a 1000 ml flask equipped with a stirrer and a condenser, 90 g of biphenyltetracarboxylic dianhydride (Ube Industries, Ltd. product: BPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas Chemical) 110 g of BPEF, 134 g of propylene glycol monomethyl ether acetate, and 1 g of 4-dimethylaminopyridine were added and heated in an oil bath at 155 ° C. for 4 hours while stirring under a nitrogen stream. Subsequently, after cooling to 120 ° C., 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (ADEKA product: Adeka Stab LA-7RD) 0.04 g, 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) 80g was added, and it stirred at 120 degreeC for 2 hours. Next, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 50% by mass to obtain a light yellow transparent viscous photosensitive resin (A5) solution.

  The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 6600 mPa · s / 25 ° C., styrene-converted weight average molecular weight 18,230 by GPC, solid content acid value 71 0.6 mg KOH / g.

Comparative Example 4
A photosensitive resin (A6) was obtained according to Synthesis Example 1 and Example 1 described in Japanese Patent No. 3813244 using a bisphenolfluorene type epoxy resin having an epoxy equivalent of 257 (product of Osaka Gas Chemical Co., Ltd .: BPFG). The synthesis took 20 hours or more, and the productivity was remarkably low as compared with Examples 1 to 4 of the present invention.

Comparative Example 5
A photosensitive resin (A7) was obtained according to Synthesis Example 1 and Example 2 described in Japanese Patent No. 3813244 using a bisphenolfluorene type epoxy resin (Osaka Gas Chemical Co., Ltd. product: BPFG) having an epoxy equivalent of 257. The synthesis took 21 hours or more, and the productivity was remarkably low as compared with Examples 7 and 8 of the present invention.

Comparative Example 6
The same reaction was carried out except that 80 g of 4-hydroxybutyl acrylate glycidyl ether in Example 8 was changed to 60 g of glycidyl methacrylate (product of Mitsubishi Rayon Co .: GMA) to obtain a photosensitive resin solution (A8). The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight and solid content acid value by GPC, viscosity was 12,400 mPa · s / 25 ° C., GPC styrene-converted weight average molecular weight 16,100, solid content acid The value was 74.2 mgKOH / g.

Test example 1
About the photosensitive resin of Examples 7-8 and Comparative Examples 4-5, the polystyrene conversion weight average molecular weight by GPC immediately after manufacture and 1 month after room temperature preservation | save was measured, and the change rate was investigated. The results are shown in Table 2.

  The photosensitive resins of Examples 7 to 8 were hardly changed, but the photosensitive resins of Comparative Examples 2 to 3 were inferior in storage stability with an increase in molecular weight of about 25%.

Examples 9-12 and Comparative Examples 7-12
Using the photosensitive resins of Examples 7 to 8 and Comparative Examples 4 to 6, photosensitive compositions were prepared with the formulations shown in Table 3 below. This photosensitive composition was applied to a 1.1 mm thick soda lime glass substrate with a spin coater to a dry film thickness of 3 μm, dried on a hot plate at 100 ° C. for 90 seconds, and then cooled to room temperature. Subsequently, after performing soft contact exposure using an UGRA-OFFSET-TEST KAIL1982 as a mask at an ultraviolet illuminance of 15 mW / cm ² (365 nm) and an integrated light quantity of 20 mJ / cm ² with an ultrahigh pressure mercury lamp exposure machine, 1 at 25 ° C. A pattern was formed by immersing in 90% aqueous sodium carbonate for 90 seconds, and the sensitivity was evaluated by the number of remaining steps, and the resolution was evaluated by a microline. The results are also shown in Table 3.

  The photosensitive compositions using the photosensitive resins of Examples 7 to 8 (A4 to A5) have higher sensitivity than the photosensitive compositions using the photosensitive resins (A6 to A8) of Comparative Examples 4 to 6. Good resist properties were shown.

Example 13
In a 1000 ml flask equipped with a stirrer and a condenser tube, 71.8 g of 3,3′-4,4′biphenyltetracarboxylic anhydride (manufactured by Ube Industries: BPDA), 9,9-bis [4- (2-hydroxyethoxy) ) 3Phenylphenyl] fluorene (Osaka Gas Chemical Co., Ltd .: BOPPEF) 109.7g, propylene glycol monomethyl ether acetate 128g, 4-dimethylaminopyridine 0.25g was added and heated with a 120 ° C mantle heater for 4 hours with stirring. . Subsequently, 0.1 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry) and 13.7 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry) were added and heated at 120 ° C. for 4 hours. Furthermore, 34.68 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) was added, and the mixture was heated and stirred at 120 ° C. for 4 hours to obtain a light yellow transparent viscous photosensitive resin (A9) solution.
About the obtained resin solution, when the viscosity, the styrene conversion weight average molecular weight by GPC, solid content, and solid content acid value were measured, the viscosity was 187100 mPa · s / 25 ° C., the styrene conversion weight average molecular weight by GPC was 4,170, solid content It was 66.8%, and the solid content acid value was 85.4 mgKOH / g.

Example 14
In a 1000 ml flask equipped with a stirrer and a condenser, 61.22 g of 3,3′-4,4′biphenyltetracarboxylic anhydride (manufactured by Ube Industries: BPDA), 9,9-bis [6- (2-hydroxyethoxy) ) Naphtyl] Fluorene (Osaka Gas Chemical Co., Ltd .: BNFEO) 95.89 g, propylene glycol monomethyl ether acetate 125 g, 4-dimethylaminopyridine 0.25 g were added and heated with a mantle heater at 120 ° C. for 4 hours while stirring. Subsequently, 0.1 g of p-methoxyphenol (manufactured by Tokyo Chemical Industry) and 13.3 g of hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry) were added and heated at 120 ° C. for 4 hours. Furthermore, 56 g of 4-hydroxybutyl acrylate glycidyl ether (Nippon Kasei Co., Ltd. product: 4HBAGE) was added and heated and stirred at 120 ° C. for 4 hours to obtain a light yellow transparent viscous photosensitive resin (A10) solution.
The obtained resin solution was measured for viscosity, styrene-converted weight average molecular weight, solid content, and solid content acid value by GPC. Viscosity 586700 mPa · s / 25 ° C., styrene-converted weight average molecular weight 9,250 by GPC, solid content It was 59.0% and the solid content acid value was 60.4 mgKOH / g.

Examples 15-16
A photosensitive composition was prepared using the photosensitive resin of Example 13 and the formulation shown in Table 4. This photosensitive composition was evaluated in the same manner as in Examples 9-12.

  All the photosensitive compositions were highly sensitive and exhibited good resist characteristics.

  The photosensitive resin of the present invention can be easily produced at a low cost, the adjustment of the crosslinking density and the acid value is easy, and excellent heat resistance, high transparency, high refractive index, low linear expansion coefficient, etc. It has characteristics. Therefore, the resin composition using the photosensitive resin is used for interlayer insulating films and protective films (for example, color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc.) in liquid crystal displays and electronic components. It is useful for preparing a film or a protective film.

Examples of the substituents R ^2a and R ^2b substituted on the ring Z ¹ and the ring Z ² include alkyl groups (methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, s-butyl groups, t-butyl groups, and the like). _1-20 alkyl group, preferably C _1-8 alkyl group, more preferably C _1-6 alkyl group etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-10 cycloalkyl group, preferably C _5-8 cycloalkyl group, more preferably C _5-6 cycloalkyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), dimethylphenyl group (xylyl group), etc.), etc. C _6-10 aryl group, preferably a C _6-8 aryl group, especially phenyl group), an aralkyl group (benzyl group, C _6-10 aryl, such as phenethyl group - such as a C _1-4 alkyl group C, such as an alkoxycarbonyl group (methoxycarbonyl group _1; (such as C _1-4 alkoxy group such as methoxy group) alkoxy group; (C _1-6 acyl group such as acetyl group) an acyl group hydrocarbon group such as ₄ alkoxycarbonyl group etc.); halogen atom (fluorine atom, chlorine atom etc.); nitro group; cyano group etc.

（式中、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ、Ｒ^２ｂ、Ｒ ^６ａ 及びＲ^６ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示し、ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｍ１、ｍ２、ｍ３及びｍ４は同一又は異なって０〜３の整数を示し、ｎ１、ｎ２、ｎ３及びｎ４は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって１〜４の整数を示し、ｐ３及びｐ４は同一又は異なって０〜３の整数を示す。） Among the compounds having the fluorene skeleton of the general formula (1), those having a structure represented by the following general formula (3) are preferable in applications that require particularly high refractive index and heat resistance.

(In the formula, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^6a and R ^6b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, m1, m2, m3 and m4 are the same or different and represent an integer of 0 to 3, and n1, n2, n3 and n4 are the same or different And p1 and p2 are the same or different and represent an integer of 1 to 4, and p3 and p4 are the same or different and represent an integer of 0 to 3.)

R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. R ^6a and R ^6b correspond to R ^2a and R ^2b , m3 and m4 correspond to m1 and m2, n3 and n4 correspond to n1 and n2, respectively, and have the same meaning. Although p1 and p2 are the same as the above, 1-4 are preferable. p3 and p4 correspond to the above-mentioned p1 and p2, and 0-3 are preferable.

（式中、Ｒ^１ａ及びＲ^１ｂは水素原子又は置換基を示し、Ｒ^２ａ、Ｒ^２ｂ、Ｒ ^７ａ 及びＲ^７ｂは水素原子以外の置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示す。ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｎ１及びｎ２は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって１〜３の整数を示す。）

(In the formula, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^7a and R ^7b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, n1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 1 to 3. .)

R ^1a and R ^1b , R ^2a and R ^2b , R ^3a and R ^3b , k1 and k2, m1 and m2, n1 and n2 are the same as described above. R ^7a and R ^7b correspond to R ^3a and R ^3b and have the same meaning. Although p1 and p2 are the same as the above, 1-3 are preferable.

9,9-bis (hydroxyalkoxyarylphenyl) fluorenes include 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9 -bis [4- (2-hydroxy 9,9-bis (hydroxyalkoxyarylphenyl) fluorene such as propoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-tolylphenyl] fluorene, preferably 9, 9-bis (2-hydroxyethoxyarylphenyl) fluorene and the like are included.

There is no particular limitation on the amount of the solvent used, to a total 1 00 parts by weight of a compound having a fluorene skeleton and tetracarboxylic acid dianhydride is preferably in the range of 25 to 150 parts by weight. If it is less than 25 parts by mass, the viscosity may not be sufficiently reduced. On the other hand, when the amount exceeds 150 parts by mass, the reaction concentration may decrease too much and the reaction rate may decrease.

Such a carboxylic acid reactive (meth) acrylate compound is subjected to an addition reaction with the above polymer compound. The proportion of the carboxylic acid-reactive (meth) acrylate compound in the photosensitive resin of the present invention is not unclear because it varies depending on the application, but when used for a photocurable coating agent or an optical material, the acid value of the photosensitive resin It may be added until becomes zero. On the other hand, when applied to an alkali developable application, it is preferable to adjust the acid value of the resin solid content to be in the range of 30 to 150 mgKOH / g. If the acid value is too lower than 30 mgKOH / g, the development rate may decrease and a required pattern may not be obtained. On the other hand, when the acid value is higher than 150 mgKOH / g, the pattern is likely to be peeled off due to excessive development, and the electrical characteristics and the like may be deteriorated. In addition, in this specification, the acid value of resin solid content is a measured value based on JIS-K0070.

The photopolymerization initiator and / or photosensitizer used in the present invention is not particularly limited, and examples thereof include benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylaminobenzophenone, and bis-N. Benzophenones such as N, diethylaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, chlorothioxanthone and isopropoxychlorothioxanthone, ethyl anthraquinone, benzanthraquinone Anthraquinones such as aminoanthraquinone, chloroanthraquinone, anthraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, acetophenones, benzo Benzoin ethers such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, 2,4,6-trihalomethyltriazines, 1-hydroxycyclohexyl phenyl ketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole Dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole 2,4,5-triarylimidazole dimers such as dimer, benzyldimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], phenanthrenequinone, 9,10 Fenan DOO Renkinon, methyl benzoin, ethyl benzoin and benzoin ethers, 9-phenyl acridine, 1,7-bis (9,9'-acridinyl) Heptane, etc., acridine derivatives, include bisacylphosphine oxide, can be used alone or in combination of two or more thereof.

（式中、環Ｚ^１及び環Ｚ^２は単環式又は縮合多環式炭化水素環を示し、Ｒ^１ａ及びＲ^１ｂは水素原子又はアルキル基を示し、Ｒ^２ａ及びＲ^２ｂは炭化水素基、アルコキシ基、アシル基、アルコキシカルボニル基、ハロゲン原子、ニトロ基又はシアノ基から選ばれる置換基を示し、Ｒ^３ａ及びＲ^３ｂは水素原子又はメチル基を示し、ｋ１及びｋ２は同一又は異なって０〜４の整数を示し、ｍ１及びｍ２は同一又は異なって０〜３の整数を示し、ｎ１及びｎ２は同一又は異なって０〜１０の整数を示し、ｐ１及びｐ２は同一又は異なって０〜４の整数を示す。但し、環Ｚ^１及び環Ｚ^２が単環式炭化水素環の場合ｐ１及びｐ２は１〜３であり、環Ｚ^１及び環Ｚ^２が縮合多環式炭化水素環の場合、環Ｚ^１に含まれるｐ１の和及び環Ｚ^２に含まれるｐ２の和がそれぞれ１以上である。）

（式中、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５は下記一般式（５）で表される基を示す）

（式中、ｑ、ｒ、ｓはそれぞれ独立に０〜９の整数を示す。但し、ｑ、ｒ、ｓが同時に０となることはない。）
That is, the present invention provides a polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride to a carboxylic acid represented by the following general formula (2). It is a photosensitive resin obtained by adding an acid-reactive (meth) acrylate compound.

(Wherein, ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or an alkyl group, R ^2a and R ^2b represent a hydrocarbon group, A substituent selected from an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group ; R ^3a and R ^3b represent a hydrogen atom or a methyl group; and k1 and k2 are the same or different and 4 represents an integer of 4, m1 and m2 are the same or different and represent an integer of 0 to 3, n1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 0 to 4. Represents an integer, provided that when ring Z ¹ and ring Z ² are monocyclic hydrocarbon rings, p 1 and p 2 are 1 to 3, and when ring Z ¹ and ring Z ² are condensed polycyclic hydrocarbon rings, including the sum and ring ^{Z 2} of p1 contained in the ring ^{Z 1} The sum of p2 that is 1 or more, respectively.)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group represented by the following general formula (5))

(In the formula, q, r, and s each independently represent an integer of 0 to 9. However, q, r, and s are not 0 simultaneously.)

Claims (7)

A polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic acid dianhydride is reacted with a carboxylic acid reactivity (meta) represented by the following general formula (2). ) A photosensitive resin obtained by adding an acrylate compound.

(In the formula, ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or a substituent, and R ^2a and R ^2b represent other than a hydrogen atom. R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 are the same or different and represent an integer of 0 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3 , N1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 0 to 4, provided that the ring Z ¹ and the ring Z ² are monocyclic hydrocarbon rings. If p1 and p2 is 1 to 3, when the ring ^{Z 1} and the ring ^{Z 2} is a condensed polycyclic hydrocarbon ring, the sum of p2 included in the sum and ring ^{Z 2} of p1 contained in the ring ^{Z 1} each 1 or more.)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a group represented by the following general formula (5))

(In the formula, q, r, and s each independently represent an integer of 0 to 9. However, q, r, and s are not 0 simultaneously.) The photosensitive resin according to claim 1, wherein the compound having a fluorene skeleton represented by the general formula (1) is represented by the following general formula (3).

(In the formula, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^6a and R ^6b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, m1, m2, m3 and m4 are the same or different and represent an integer of 0 to 3, and n1, n2, n3 and n4 are the same or different And p1 and p2 are the same or different and represent an integer of 1 to 4, and p3 and p4 are the same or different and represent an integer of 0 to 3.) The photosensitive resin according to claim 1, wherein the compound having a fluorene skeleton represented by the general formula (1) is represented by the following general formula (4).

(In the formula, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a , R ^2b , R ^7b and R ^7b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b represent a hydrogen atom or a methyl group. K1 and k2 are the same or different and represent an integer of 0 to 4, n1 and n2 are the same or different and represent an integer of 0 to 10, and p1 and p2 are the same or different and represent an integer of 1 to 3. .) The photosensitive resin according to claim 1, wherein R ^2a and R ^2b in the general formula are phenyl groups.   The photosensitive resin according to any one of claims 1 to 4, which has an acid value of 30 to 150 mgKOH / g.   A photosensitive resin composition comprising the photosensitive resin according to claim 1, and a photopolymerization initiator and / or a photosensitizer.   Furthermore, the photosensitive resin composition of Claim 6 which contains the polymerizable monomer which has a 1 or more unsaturated group in a molecule | numerator.