KR101254054B1 - Photosensitive resin and photosensitive resin composition comprising the same - Google Patents

Abstract

(식에서 고리 Z¹ 및 고리 Z²는 방향족탄화수소기를 나타내고, R^1a 및 R^1b는 수소원자 또는 치환기를 나타내고, R^2a 및 R^2b는 수소원자 이외의 치환기를 나타내고, R^3a 및 R^3b는 수소원자 또는 메틸기를 나타내고, k1 및 k2는 동일하거나 또는 서로 다른 0∼4의 정수를 나타내고, m1 및 m2는 동일하거나 또는 서로 다른 0∼3의 정수를 나타내고, n1 및 n2는 동일하거나 또는 서로 다른 0∼10의 정수를 나타내고, p1 및 p2는 동일하거나 또는 서로 다른 0∼4의 정수를 나타낸다)
[식 2]

(식에서 R⁴는 수소원자 또는 메틸기를 나타내고, R⁵는 하기 일반식(5)로 나타내어지는 기를 나타낸다)
[식 5]

(식에서 q, r, s는 각각 독립적으로 0∼9의 정수를 나타낸다. 단, q, r, s가 동시에 0이 되는 경우는 없다)An object of the present invention is to provide a photosensitive resin which can be easily manufactured at low cost, easy to adjust the crosslinking density and acid value, and has excellent properties such as high heat resistance, high transparency, high refractive index and low linear expansion coefficient.
The photosensitive resin is a carboxylic acid reactive (meth) acryl represented by the following general formula (2) to a high molecular compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic dianhydride. It is the photosensitive resin obtained by adding a rate compound.
[Formula 1]

(Ring Z ^{1 in the} formula And ring Z ² represents an aromatic hydrocarbon group, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a and R ^2b represent a substituent other than a hydrogen atom, R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 represent the same or different integers from 0 to 4, m1 and m2 represent the same or different integers from 0 to 3, n1 and n2 represent the same or different integers from 0 to 10 , p1 and p2 represent the same or different integers from 0 to 4)
[Formula 2]

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

(Wherein q, r and s each independently represent an integer of 0 to 9, except that q, r and s do not become 0 at the same time)

Description

Photosensitive resin and photosensitive resin composition using the same {PHOTOSENSITIVE RESIN AND PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME}

The present invention relates to a photosensitive resin having a fluorene skeleton and a photosensitive resin composition using the same, and more particularly, to various and excellent properties. And a low-cost photosensitive resin and an interlayer insulating film or protective film in a liquid crystal display, an electronic component, or the like using the same. For example, to prepare a color filter, a liquid crystal display device, an integrated circuit device, an interlayer insulating film or a protective film used for a solid state imaging device, or the like. It relates to useful photosensitive resin compositions.

It is known that a high molecular compound having a fluorene skeleton has excellent physical properties such as high heat resistance, high transparency, high refractive index, and low linear expansion coefficient. Using this property, a polymer compound having a fluorene skeleton in which a radical polymerizable unsaturated bond structure (vinyl group) is introduced into a molecule is used as an optical overcoat agent. In recent years, studies have been made on optical materials such as hard-coating agents, anti-reflection films, spectacle lenses, optical fibers, optical waveguides, holograms, and the like. For example, as a plastic lens material, (meth) acrylic chloride is added to 9,9-bis (4-hydroxyphenyl) fluorene. Ethylene oxide or propylene oxide is added to the reacted compound or 9,9-bis (4-hydroxyphenyl) fluorene, followed by reaction of (meth) acrylic acid. The copolymer which has the compound made into the main component is disclosed (patent document 1).

However, the compound disclosed in this patent document is low in molecular weight, flexible in structure, and can not be said to have sufficient refractive index. Moreover, since the crosslinking density is low, there exists a fault that hardened | cured material strength is low.

In addition, a polymer compound having a fluorene skeleton is used in the form of a liquid crystal color filter, a black matrix, a solder resist, or the like, by using properties of excellent heat resistance and chemical resistance. It is applied also to what is called photoresist (patent documents 2 and 3).

It is said that the photosensitive resin by these techniques can obtain the high crosslinking density, and can obtain the hardened | cured material excellent in intensity | strength, heat resistance, and chemical-resistance, but since it requires very long time for the synthesis | combination, it is said that it is widely spread and widely spread. Difficult was the situation. In addition, since the coloration occurs due to the production method, application to optical parts requiring transparency is difficult, and it cannot be said that the characteristics of the fluorene skeleton are sufficiently utilized.

Japanese Patent Laid-Open No. 4-325508 Japanese Patent No. 3673321 Japanese Patent Laid-Open No. 2007-264433

Therefore, it is easy to manufacture at low cost, and it is easy to adjust the crosslinking density and acid value, and also has the photosensitivity which has excellent characteristics, such as the high heat resistance, high transparency, high refractive index, and low linear expansion coefficient which the fluorene frame | skeleton originally has, etc. The provision of resin is calculated | required, and this invention makes it a subject to provide such a photosensitive resin and the photosensitive resin composition using the same.

In view of these circumstances, the present inventors have made intensive studies to solve the above problems, and as a result, specific carboxylic acid reactive (meth) acrylates are applied to a high molecular compound obtained by reacting a compound having a specific fluorene skeleton with tetrabasic dianhydride. A photosensitive resin obtained by adding a carboxylic acid methacrylate compound can be easily manufactured at low cost, has high strength at high crosslinking density, and has excellent heat resistance, high transparency, high refractive index, and low linear expansion coefficient. The present invention has been found to complete the present invention.

That is, this invention is the carboxylic acid reactive (meth) acryl represented by following General formula (2) to the high molecular compound obtained by making the compound which has a fluorene skeleton represented by following General formula (1), and tetrabasic dianhydride react. It is the photosensitive resin obtained by adding a rate compound.

[Formula 1]

(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 a substituent, R ^2a and R ^2b represent a substituent other than a hydrogen atom, and R ^3a And R ^3b represents a hydrogen atom or a methyl group, k1 and k2 represent the same or different integers from 0 to 4, m1 and m2 represent the same or different integers from 0 to 3, and n1 and n2 are the same Or a different integer from 0 to 10, and p1 and p2 represent the same or different integers from 0 to 4. However, when ring Z ¹ and ring Z ² are a monocyclic hydrocarbon ring, p1 and p2 are 1 to 3, and when the ring Z ¹ and the ring Z ² are condensed polycyclic hydrocarbon rings, the sum of X1 included in the ring Z ¹ and the sum of X2 contained in the ring Z ² are each one or more)

[Formula 2]

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

[Equation 5]

(Wherein q, r and s each independently represent an integer of 0 to 9, except that q, r and s do not become 0 at the same time)

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

The photosensitive resin of the present invention has high storage stability, can be easily manufactured 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. Moreover, the photosensitive resin composition of this invention using this photosensitive resin can obtain hardened | cured material which is high in sensitivity, and excellent in intensity | strength.

The high molecular compound which comprises the photosensitive resin of this invention is obtained by making the compound which has a fluorene skeleton represented by following General formula (1), and tetrabasic dianhydride mentioned later react.

[Formula 1]

(Ring Z ^{1 in the} formula And ring Z ² represents a monocyclic or condensed polycyclic hydrocarbon ring, R ^1a and R ^1b represent a hydrogen atom or a substituent, R ^2a and R ^2b represent a substituent other than a hydrogen atom, and R ^3a and R ^3b are hydrogen An atom or a methyl group, k1 and k2 represent the same or different integers from 0 to 4, m1 and m2 represent the same or different integers from 0 to 3, and n1 and n2 represent the same or different zeros The integer of -10 is shown, p1 and p2 represent the same or different integer of 0-4. Provided that when ring Z ¹ and ring Z ² are monocyclic hydrocarbon rings, p1 and p2 are 1 to 3, and when ring Z ¹ and ring Z ² are condensed polycyclic hydrocarbon rings, ｐ1 included in ring Z ¹ And the sum of ｐ2 included in the ring Z ² is 1 or more, respectively.)

In the 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 hydrocarbons such as benzene and condensed 2 cyclic hydrocarbon (e.g. indene (indene), naphthalene (naphthalene), etc. of C _{8- 20} 2 condensation polycyclic hydrocarbon, preferably a C _{10 - 16} 2 condensed polycyclic hydrocarbon, a condensed tricyclic hydrocarbons (anthracene (anthracene), phenanthrene and condensed 2 to 4 cyclic hydrocarbons such as (phenanthrene), etc. Condensed polycyclic aromatic hydrocarbons (naphthalene, anthracene, etc.) may be mentioned as preferred hydrocarbons particularly in applications requiring high refractive index and heat resistance. Naphthalene is particularly preferred, and benzene is particularly preferred for applications in which high solubility, compatibility and low solution viscosity are required, and ring Z ¹ and ring Z ² are the same ring or ring; May be another ring or may be the same ring.

In the formula (1), the substituents represented by R ^1a and R ^1b are not particularly limited, but are usually alkyl groups. Examples of the alkyl group include C _1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (for example, C _{1). -4} alkyl group, especially methyl group) etc. can be illustrated. The groups R ^1a and R ^1b may be different from each other or may be 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. In addition, the bonding position (substitution position) of group R <^1a> (or R < ^1b ) with respect to the benzene ring which comprises a fluorene skeleton is not specifically limited. Preferred substitutions k1 and k2 are zero or one, in particular zero. The number of substitutions k1 and k2 may be different from each other, but they are usually the same.

The substituent R ^2a and R ^2b is substituted on the ring Z ¹ and Z ² ring, an alkyl group (methyl group, such as an ethyl group, a propyl group, an isopropyl group, a butyl group, a s- butyl group, a t- butyl group C _{1- 20} alkyl group , preferably C _{1 - 8} alkyl, more preferably C _{1 - 6} alkyl group such as and the like), a cycloalkyl group (cycloalkyl group), (a cyclopentyl group (cyclopentyl group), cyclohexyl group (cyclohexyl group), C _{5- 10} cycloalkyl, preferably C _{5 - 8} cycloalkyl group, more preferably a C _{5 - 6} cycloalkyl group and the like), aryl group (aryl group) [a phenyl group (phenyl group), alkyl phenyl (alkylphenyl group), (phenyl group (methylphenyl group) (group-SAT (tolyl group)), dimethylphenyl group (dimethylphenyl group) (xylyl group (xylyl group) etc.) and the like of the C _{6- 10} aryl group, preferably a C _{6 - 8} aryl group, especially phenyl group) , an aralkyl group (aralkyl group) _- hydrocarbon groups such as (a benzyl group (benzyl group), phenethyl group (phenethyl), C _{6- 10} aryl such as ₁ -C ₄ alkyl group, and the like); Alkoxy group (alkoxy group) (C _{1- 4} alkoxy group such as methoxy group (methoxy group), and the like); Acyl group (acyl group) (acetyl group (acetyl group), such as a C _{1- 6} acyl group and the like); Alkoxycarbonyl group (alkoxycarbonyl group) (methoxy-carbonyl group (C _{1- 4} alkoxycarbonyl group such as methoxycarbonyl group)); Halogen atoms (fluorine atoms, chlorine atoms, etc.); Nitro group; Cyano group etc. are mentioned.

Preferred substituents R ^2a (or R ^2b) is an alkyl (C _{1 - 6} alkyl group), a cycloalkyl group (C _{5 - 8} cycloalkyl group), aryl group (C _{6 - 10} aryl group), aralkyl group (aryl C _6-8 and -C _1-2 alkyl), especially C _{1 - 4} alkyl, C _{1 -} is preferably an _8-aryl-4 alkoxy group, C _6. The substituent R ^2a (or R ^2b ) may be used alone or in combination of two or more thereof to be substituted with a benzene ring. The groups R ^2a and R ^2b may be the same as or different from each other, but are usually the same. When m1 (or m2) is 2 or more, R ^2a (or R ^2b ) in the same hydrocarbon ring may be different from each other or may be the same.

The substitution position of the substituent R ^2a (or R ^2b ) is not particularly limited and is a hydroxyl group or a hydroxylpoly (alkyleneoxy) group (hereinafter referred to as a hydroxyl group-containing group). Depending on the substitution position of the compound), the substitution may be carried out at the 2nd to 6th positions (for example, 2nd, 5th, 2, 5th, etc.) of the phenyl group constituting the phenol skeleton. have.

The number of substitutions m1 and m2 of the substituents R ^2a and R ^2b is preferably 0 to 2, more preferably 0 to 1 (particularly 0), depending on the number of substitutions of the hydroxyl group-containing group. The number of substitutions m1 and m2 may be different from each other, but usually the same.

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

Addition number n1 and n2 of a (poly) alkyleneoxy group are the same or different, and can be selected in the range of 0-10, Preferably it is 0-8 (for example, 1-8), More preferably, it is 0- 6 (for example, 1 to 6), in particular, 0 to 4 (for example, 1 to 4) may be sufficient. In addition, the sum (n1 + n2) of n1 and n2 can be selected in 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 0-8 (for example, 2-8) may be sufficient. Moreover, when n1 (or n2) is two or more, the (poly) alkyleneoxy group may be comprised by the same alkoxy group, and a heterogeneous alkoxy group (for example, an ethoxy group and a propyleneoxy group (propyleneoxy group) Although group)) may be mixed and comprised, they are usually comprised by the same alkoxy group.

As for the substitution numbers p1 and p2 of a hydroxyl-group containing group, 1-4 are preferable as a range of 0-4, and 1-2 are especially preferable. Provided that when ring Z ¹ and ring Z ² are monocyclic hydrocarbon rings, p1 and p2 are 1 to 3, and when ring Z ¹ and ring Z ² are condensed polycyclic hydrocarbon rings, ｐ1 included in ring Z ¹ And the sum of X2 contained in the ring Z ² 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. Especially in the use which crosslinking density of hardened | cured material is calculated | required, p1 and p2 have preferable 2-3. In addition, although the substitution numbers p1 and p2 may be different, they are usually the same. The substitution position of the hydroxyl group-containing group is not particularly limited and may be selected from the 2-6th positions of the phenyl group substituted at the 9th position of fluorene according to the number of p1 (or p2), and p1 (or p2) In the case of 2, for example, the third, fourth, third, and fifth digits may be used. One hydroxyl group containing group may replace the 4th position normally.

The plurality of hydroxyl group-containing groups constituting the same phenol skeleton may be the same or different from each other. For example, a plurality of hydroxyl group-containing groups may be composed of a hydroxyl group alone (except when p1 and p2 are 2) in which (i) n1 = 0 (n2 = 0), and (ii) hydroxyl group with n1 = 0 (n2 = 0) and hydroxypoly (alkoxy) group with n1 ≠ 0 (n2 ≠ 0) (2-hydroxyethoxy group) Etc.), (iii) may be composed of the same hydroxy (poly) alkoxy group alone, where n1 ≠ 0 (n2 ≠ 0), and (iv) different hydroxides of n1 ≠ 0 (n2 ≠ 0). It may be comprised with a hydroxy (poly) alkoxy group (for example, 2-hydroxyethoxy group and 2- (2-hydroxyethoxy) ethoxy group (2- (2-hydroxyethoxy) ethoxy group)).

Among the compounds having the fluorene skeleton of the general formula (1), a structure represented by the following general formula (3) is particularly preferable in applications in which high refractive index and heat resistance are required.

[Equation 3]

(Wherein 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, R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 represents the same or different integers from 0 to 4, m1, m2, m3 and m4 represent the same or different integers from 0 to 3, and n1, n2, n3 and n4 represent the same or different zeros An integer of -10, p1 and p2 represent the same or different integers of 1 to 4, p3 and p4 represent the same or different integers 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 above. In addition, R ^6a and R ^6b are R ^2a and R ^2b , m3 and m4 correspond to the m1 and m2, n3 and n4 correspond to the n1 and n2, respectively, and have the same meaning. p1 and p2 are as above-mentioned, but 1-4 are preferable. p3 and p4 correspond to said p1 and p2, and 0-3 are preferable.

Specifically, 9,9-bis (hydroxyalkoxy naphthyl) fluorenes (9,9-bis (hydroxy alkoxy naphthyl) fluorenes), 9,9-bis (hydroxypolyalkoxy naphthyl) fluorene ( Compounds in which p1 + p2 + p3 + p4 is 2 in General Formula (3) such as 9,9-bis (hydroxy poly alkoxy naphthyl) fluorenes); 9,9-bis (polyhydroxyalkoxy naphthyl) fluorenes (9,9-bis (polyhydroxy alkoxy naphthyl) fluorenes), 9,9-bis (polyhydroxypolyalkoxy naphthyl) fluorenes (9, In the said General formula (3), such as 9-bis (polyhydroxy poly alkoxy naphthyl) fluorees, the compound whose p1 + p2 + p3 + p4 is 2 or more is mentioned.

As 9, 9-bis (hydroxyalkoxy naphthyl) fluorene, for example, 9, 9-bis (hydroxyalkoxy naphthyl) fluorene {For example, 9, 9-bis [6- (2- hydride) Hydroxyethoxy) -2-naphthyl] fluorene (9,9-bis [6- (2-hydroxyethoxy) 2-naphthyl] fluorene), 9,9-bis [6- (2-hydroxypropoxy)- 2-naphthyl] fluorene (9,9-bis [6- (2-hydroxypropoxy) 2-naphthyl] fluorene), 9,9-bis [5- (2-hydroxyethoxy) -1-naphthyl] fluorene, 9,9-bis [5- (2-hydroxypropoxy) -1-naphthyl] 9,9-bis such as fluorene (hydroxy-C _{2 - 4} alkoxy-naphthyl) fluorene} etc., etc. Can be mentioned.

As 9, 9-bis (hydroxy polyalkoxy naphthyl) fluorene, for example, 9, 9-bis (hydroxy dialkoxy naphthyl) fluorene [for example 9, 9-bis {6- [2] -(2-hydroxyethoxy) ethoxy] -2-naphthyl} fluorene (9,9-bis {6- [2- (2-hydroxyethoxy) ethoxy] -2-naphthyl} fluorene), 9,9 -Bis {6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl} fluorene (9,9-bis {6- [2- (2-hydroxypropoxy) propoxy] -2-naphthyl } fluorene), 9,9-bis {5- [2- (2-hydroxyethoxy) ethoxy] -1-naphthyl} fluorene, 9,9-bis {5- [2- (2-hydroxy hydroxy-propoxy) propoxy] -1-naphthyl} fluorene 9,9-bis such as fluorene (hydroxydiphenyl C _{2 - 4} alkoxy-naphthyl) fluorene, etc.] such as 9,9-bis (hydroxydiphenyl alkoxy Naphthyl) fluorenes (9,9-bis (hydroxy dialkoxy naphthyl) fluorenes); The compound etc. which correspond to these compounds and whose n1, n2, n3, n4 are three or more in the said General formula (3) are mentioned.

As 9,9-bis (polyhydroxyalkoxy naphthyl) fluorene, the compound corresponding to said 9,9-bis (hydroxyalkoxy naphthyl) fluorene and p1 + p2 + p3 + p4 is two or more, an example For example 9,9-bis (di or trihydroxyalkoxynaphthyl) fluorene (9,9-bis (di- or tri-hydroxy alkoxy naphthyl) fluorene) [for example 9,9-bis [di (2 -Hydroxyethoxy) -2-naphthyl] fluorene (9,9-bis [di (2-hydroxyethoxy) -2-naphthyl] fluorene), 9,9-bis [di (2-hydroxypropoxy) 2-naphthyl] fluorene 9,9-bis such as (9,9-bis [di (2 -hydroxy propoxy) -2- naphthyl] fluorene) ( di or tri-hydroxy-C _{2 - 4} alkoxy-naphthyl) 9,9-bis (polyhydroxyalkoxy naphthyl) fluorene, such as fluorene].

As 9, 9-bis (polyhydroxy polyalkoxy naphthyl) fluorene, it respond | corresponds to said 9, 9-bis (hydroxyalkoxy naphthyl) fluorene, n1, n2, n3, n4 are two or more, and A compound in which X1 + p2 + p3 + p4 is 2 or more, for example 9,9-bis (di or trihydroxydialkoxynaphthyl) fluorene [for example 9,9-bis {di [2- (2- 9,9-bis (di or such as hydroxyethoxy) ethoxy] -2-naphthyl} fluorene (9,9-bis {di [2- (2-hydroxyethoxy) ethoxyl-2-naphthyl} fluorene) 9,9-bis (di or trihydroxy dialkoxy naphthyl) fluorene, such as trihydroxy di C _2-4 alkoxy naphthyl) fluorene; The compound etc. which correspond to these compounds and whose n1, n2, n3, n4 are three or more in said Formula (3) are mentioned.

Among 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), a structure represented by the following general formula (4) is particularly preferable for applications in which high solubility, compatibility, and low solution viscosity are required.

[Formula 4]

(Wherein 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 represents the same or different integers from 0 to 4, n1 and n2 represent the same or different integers from 0 to 10, and p1 and p2 represent the same or different integers from 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 above. In addition, R ^7a and R ^7b correspond to the above R ^3a and R ^3b and have the same meaning. p1 and p2 are as above-mentioned, but 1-3 are preferable.

Representative compounds represented by the formula (4) include 9,9-bis (hydroxyalkoxyphenyl) fluorenes (9,9-bis (hydroxy alkoxyphenyl) fluorene) (n1 = n2 in the general formula (4). = 1), 9,9-bis (hydroxy polyalkoxy dialkyl phenyl) fluorenes (n1, n2 in the general formula (4) is 9,9-bis (hydroxy polyalkoxy dialkyl phenyl) fluorenes) Compound, each of which is one or more).

Examples of the 9,9-bis (hydroxyalkoxyphenyl) fluorenes include 9,9-bis (hydroxyalkoxyphenyl) fluorenes {for example, 9,9-bis [4- (2-hydroxy Ethoxy) phenyl] fluorene (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene), 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene (9,9 -bis [4- (2-hydroxy propoxy) phenyl] fluorene), 9,9-bis [4- (2-hydroxyethoxy) -3-methylphenyl] fluorene (9,9-bis [4- (2 -hydroxyethoxy) -3-methylphenyl] fluorene), 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene (9,9-bis [4- (2-hydroxy propoxy)- 3-methylphenyl] fluorene), 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] fluorene (9,9-bis [4- (2-hydroxyethoxy) -3, 5-dimethylphenyl] fluorene), 9,9-bis [4- (2-hydroxyethoxy) phenoxyethanol] fluorene (9,9-bis [4- (2-hydroxyethoxy) phenoxyethanol] fluorene), 9, 9-bis [4- (2-hydroxypropoxy) phenoxyethanol] fluorene (9,9-bis [4- (2-hydroxy propoxy) 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-hydroxy propoxy) -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] flu 9,9-bis (hydroxyalkoxyalkylphenyl) fluorene (9,9-bis, such as orene and 9,9-bis [2- (2-hydroxypropoxy) -3,4-dimethylphenyl] fluorene (hydroxy alkoxy alkyl phenyl) fluorene), preferably 9,9-bis (2-hydroxy-propoxy-di-C _{1 - 4} alkylphenyl) fluorene such as 9,9 ratio It includes (hydroxy-C branch _{3-dialkyl phenyl-4} alkoxy)} fluorene acids.

9,9-bis (hydroxypolyalkoxyphenyl) fluorenes include compounds in which n1 and n2 are two or more, for example, 9,9-bis (hydroxydialkoxy Phenyl) fluorenes (9,9-bis (hydroxy dialkoxyphenyl) fluorenes) {for example 9,9-bis [4- (2-hydroxydiethoxy) phenyl] fluorene (9,9-bis [4- (2-hydroxydiethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) phenyl] fluorene (9,9-bis [4- (2-hydroxy dipropoxy) phenyl] fluorene), 9,9-bis [4- (2-hydroxydiethoxy) -3-methylphenyl] fluorene (9,9-bis [4- (2-hydroxydiethoxy) -3-methylphenyl] fluorene), 9,9-bis [4- (2-hydroxydipropoxy) -3-methylphenyl] fluorene (9,9-bis [4- (2-hydroxy dipropoxy) -3-methylphenyl] fluorene), 9,9-bis [4- (2-hydroxydiethoxy) -3,5-dimethylphenyl] fluorene (9,9-bis [4- (2-hydroxydiethoxy) -3,5-dimethylphenyl] fluorene), 9,9-bis [4- (2-hydroxydiethoxy) phenoxyethanol] fluorene (9,9-bis [4- (2-hydroxydiethox y) phenoxyethanol] fluorene), 9,9-bis [4- (2-hydroxydipropoxy) phenoxyethanol] fluorene (9,9-bis [4- (2-hydroxyl dipropoxy) phenoxyethanol] 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) -2,5-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -2,5-dimethylphenyl ] Fluorene (9,9-bis [4- (2-hydroxyl dipropoxy) -2,5-dimethylphenyl] fluorene), 9,9-bis [4- (2-hydroxydiethoxy) -3,6-dimethyl Phenyl] fluorene, 9,9-bis [4- (2-hydroxydipropoxy) -2,6-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxydiethoxy)- 2,4-dimethylphenyl] fluorene, 9,9-bis [3- (2-hydroxydipropoxy) -2,4-dimethylphenyl] fluorene, 9,9-bis [4- (2-hydroxy Oxydiethoxy) -3,4-dimethylphenyl] fluorene, 9,9-bis [2- (2-hydroxydipropoxy) -3,4-dimethylphenyl] fluorene And 9,9-bis (hydroxydialkoxyphenyl) fluorene}.

Among them, 9,9-bis (hydroxyethoxyphenyl) fluorene, 9,9-bis (hydroxyethoxy-3-methylphenyl) fluorene, 9,9-bis (hydroxyethoxy-3,5 Dimethylphenyl) fluorene, 9, 9-bis (hydroxyethoxy-2 phenoxy ethanol) fluorene, etc. are preferable.

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

Specifically, for example, the compound represented by the general formula (4) includes 9,9-bis (hydroxyalkoxy aryl phenyl) fluorenes (the above-mentioned). In general formula (4), n1 = n2 = 1, and R <^2a> , R <^2b> is a phenyl group), 9,9-bis (hydroxypolyalkoxy arylphenyl) fluorene (9,9-bis (hydroxy polyalkoxy) aryl phenyl) fluorenes (compounds in which n1 + n2 is 2 or more and R ^2a and R ^2b in the general formula (4) are phenyl groups).

9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (9,9-bis [4-) for 9,9-bis (hydroxyalkoxy arylphenyl) fluorenes (2-hydroxyethoxy) -3-phenyl phenyl] fluorene), 9,9-bis [4- (2-hydroxypropoxy) -3-phenylphenyl] fluorene (9,9-bis [4- (2- hydroxy propoxy) -3-phenyl phenyl] fluorene), 9,9-bis [4- (2-hydroxypropoxy) -3-torylphenyl] fluorene (9,9-bis [4- (2-hydroxy propoxy 9,9-bis (hydroxyalkoxyarylphenyl) fluorene, such as) -3-tolylphenyl] fluorene), preferably 9,9-bis (2-hydroxyethoxyarylphenyl) fluorene (9,9- bis (2-hydroxyethoxy aryl phenyl) fluorene).

Examples of the 9,9-bis (hydroxypolyalkoxyarylphenyl) fluorene include 9,9-bis (hydroxydialkoxyarylphenyl) fluorenes (examples). For example, 9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] -3-phenylphenyl} fluorene (9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy 9,9-bis (hydroxydialkoxyarylphenyl) fluorene, such as] -3-phenyl phenyl} fluorene), preferably 9,9-bis [2- (2-hydroxyethoxy) ethoxyarylphenyl ], Fluorene (9,9-bis [2- (2-hydroxyethoxy) ethoxy aryl phenyl] fluorene)}.

Among these, 9, 9-bis (hydroxyethoxy arylphenyl) fluorene etc. are preferable.

As the compound to be reacted with the compound having the fluorene skeleton, tetrabasic dianhydride is used.

Specific examples of the tetrabasic dianhydride include butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride. ), Cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, cycloheptantetracarboxylic dianhydride, norbornene tetracarboxylic dianhydride, nordianhydrane tetracarboxylic acid Anhydrous (pyromellitic acid dianhydride), benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, bipe Biphenylethertetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (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 (4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride), naphthalene-1,4 , 5,8-tetracarboxylic acid dianhydride (naphthalene-1,4,5,8-tetracarboxylic dianhydride), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride), 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride), 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (3, 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride) and the like, 1 type, or 2 or more types of is used. Among them, pyromellitic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride And biphenyl tetracarboxylic dianhydride are preferred.

The high molecular compound which comprises the photosensitive resin of this invention is obtained by addition-reacting tetrabasic dianhydride to the compound which has the said fluorene skeleton. In this addition reaction, the ratio of the tetrabasic acid 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 dianhydride is less than 0.5 mol and more than 1.5 mol, sufficient molecular weight may not be obtained.

You may use a catalyst for addition reaction of the compound which has a fluorene skeleton, and tetrabasic dianhydride. The catalyst to be used is not particularly limited as long as it promotes the reaction. For example, pyridine, quinoline, imidazole, N, N-dimethylcyclohexylamine, and triethyl Amine (triethylamine), N-methylmorpholine, N-ethylmorpholine, N-ethylmorpholine, triethylenediamine, N, N-dimethylaniline, N, N-N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1,8 Diazabicyclo [5,4,0] -7-undecene (1,8-diazabicyclo [5,4,0] -7-undecene), 1,5-diazabicyclo [4,3,0] nonene Amines such as -5 (1,5-diazabicyclo [4,3,0] -5-nonene), tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl Quaternary ammonium compounds such as trimethyl benzyl ammonium chloride, tetramethyl ammonium hydroxyde, tributylphosphine, triphenylphosphine, etc. And mixtures thereof. Moreover, although there is no restriction | limiting in particular also in the quantity of the catalyst to be used, The range of 0.1-2.0 mass parts is preferable with respect to a total of 100 mass parts of a compound which has a fluorene skeleton and tetrabasic dianhydride. When the amount of the catalyst is too large than 2.0 parts by mass, adverse effects may occur on the electrical properties and storage stability of the photosensitive resin.

In addition, in addition reaction, you may use a solvent for the purpose of melt | dissolution of a reaction raw material, viscosity reduction, etc. The type of solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent include glycol ethers such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether. Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate (glycol ether acetates), dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether diethyl ether), Propylene glycol ethers such as propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol ether acetates, acetone, methyl, such as dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate Acetate esters, such as ketones, such as ethyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, and butyl acetate ( ester acetate), dimethylsulfoxide, 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 dianhydride. If it is less than 25 mass parts, a viscosity may not fully reduce. On the other hand, when it exceeds 150 parts by mass, the concentration of the reactant may be excessively lowered so that the reaction rate may decrease.

Although a solvent or a catalyst is added to the compound having a fluorene skeleton and tetrabasic dianhydride as necessary for addition reaction, it is preferable to heat the reaction, and the raw material is dissolved by heating and the reaction rate is accelerated. The heating temperature can be appropriately set depending on the kind of the compound having a fluorene skeleton, tetrabasic dianhydride and the apparatus to be used, but the range of 60 to 220 ° C is generally preferable. More preferably, it is the range of 90-160 degreeC. If the reaction temperature is lower than 60 ℃ may take a long time to complete the reaction. On the other hand, when reaction temperature is higher than 220 degreeC, side reactions, such as coloring, may generate | occur | produce, or reaction rate may fall by equilibrium which an acid anhydride ring-closes.

The photosensitive resin of this invention is obtained by adding the carboxylic acid reactive (meth) acrylate compound represented by following General formula (2) to the high molecular compound obtained as mentioned above.

[Formula 2]

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

[Equation 5]

(Wherein q, r and s each independently represent an integer of 0 to 9, except that q, r and s do not become 0 at the same time)

Specifically as carboxylic acid reactive (meth) acrylate represented by the said General formula (2), 2-hydroxyethyl (meth) acrylate glycidyl ether and 2-hydroxypropyl ( 2-hydroxypropyl methacrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether (4-hydroxybutyl methacrylate glycidyl ether), polyethylene glycol-polypropylene glycol (meth) acrylate glycidyl ether (polyethylene glycol-polypropylene glycol methacrylate glycidylether).

This carboxylic acid reactive (meth) acrylate compound is added to the polymer compound. Although the ratio of the carboxylic acid reactive (meth) acrylate compound in the photosensitive resin of this invention differs according to a use, it cannot say uniformly, but when used for a photocurable coating agent or an optical material, the acid value of the photosensitive resin You may add until (iii) becomes zero. On the other hand, when applying to alkali developability use, it is preferable to adjust so that the acid value of resin solid content may be in the range of 30-150 mggOH / g. When the acid value is too low than 30 mggOH / g, the developing speed may decrease, and a required pattern may not be obtained. On the other hand, when an acid value is higher than 150 mggOH / g, it may become overdevelopment, and a pattern will peel easily, and electrical characteristics etc. may fall. In addition, in this specification, the acid value of resin solid content is a measured value based on JIS-K0070.

In reaction of the said high molecular compound and a carboxylic acid reactive (meth) acrylate compound, you may use a catalyst for the purpose of reaction promotion. Since the kind of catalyst differs according to the kind of carboxylic acid reactive (meth) acrylate compound, it cannot be said uniformly, but as an example, pyridine, quinoline, imidazole, N, N- dimethylcyclohexylamine, triethylamine, N Methyl morpholine, N-ethyl morpholine, triethylenediamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, tris (N, N-dimethylaminomethyl) phenol, 4-dimethylaminopyridine, 1, Amines such as 8-diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [4,3,0] nonene-5, tetramethylammonium chloride, tetramethylammonium bromide, trimethyl Quaternary ammonium compounds such as benzyl ammonium chloride and tetramethylammonium hydroxide, tributylphosphine, triphenylphosphine and the like and mixtures thereof.

Although there is no restriction | limiting in particular also in the quantity of the catalyst to be used, 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. When the amount of the catalyst is too large, it may adversely affect the electrical characteristics and storage stability of the photosensitive resin.

Moreover, when making a carboxylic acid reactive (meth) acrylate compound react, it is preferable to add a polymerization inhibitor. There is no restriction | limiting in particular in the kind of polymerization inhibitor as long as it suppresses reaction of an unsaturated bond, For example, hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butyl T-butylcatechol, N-methyl-N-nitrosoaniline or N-nitrosophenylhydroxylamine (ammonium salt of N-nitrosophenyl hydroxylamine) High School Co., Ltd. product: Q-1300), N-nitrosophenyl hydroxylamine aluminum salt (Wakkoyaku Kogyo Co., Ltd. product: Q-1301), 2,2,6,6-tetramethylpi Ferridine-1-oxyl (2,2,6,6-tetramethylpiperidine-1-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-2 , 2,6,6-tetramethylpiperidine-1-oxyl) and the like. In particular, N-nitrosophenyl hydroxylamine aluminum salt and 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl are preferable. Although the quantity of a polymerization inhibitor differs according to the kind and reaction conditions, although it cannot speak uniformly, the range of 5-2000 mm is preferable with respect to the whole photosensitive resin. If less than this range, unsaturation may react during manufacture and gelation may occur, and if more than this range, sensitivity may fall and it is unpreferable.

When adding a carboxylic acid reactive (meth) acrylate compound, it is preferable to heat for the purpose of the improvement of reaction rate. Although heating temperature can be set suitably according to the kind and apparatus of a carboxylic acid reactive (meth) acrylate compound, the range of 60-150 degreeC is generally preferable. If the reaction temperature is lower than 60 ° C, it may take a long time to complete the reaction. On the other hand, when reaction temperature is higher than 150 degreeC, side reactions, such as coloring, may occur, or an unsaturated bond may react and gelatinization may occur.

Although the molecular weight of the photosensitive resin of this invention obtained in this way is not specifically limited, From a viewpoint of coating film strength, film forming property, or developability, 1,000-200,000 are preferable and 2,500-50,000 are more preferable. In addition, in this specification, the molecular weight of photosensitive resin is a styrene conversion weight average molecular weight by GP of the conditions described in the Example.

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

As a photoinitiator and / or a photosensitizer used for this invention, although it does not restrict | limit especially, For example, benzophenone, 4-hydroxybenzophenone, bis-N, N-dimethylamino Bis-N, N-dimethylamino benzophenone, bis-N, N-diethylamino benzophenone, 4-methoxy-4'-dimethylaminobenzophenone Benzophenones such as methoxy-4'-dimethylamino benzophenone, thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone and chlorothiooxane Thioxanthones such as chlorothioxanthone and isopropoxychlorothioxanthone, ethylanthraquinone, benzanthraquinone, aminoanthraquinone, chloroanthraquinone and chloroanthraquinone Quinone-2-sulfonate (ant anthraquinones such as hraquinone-2-sulfonate, anthraquinone-2,6-disulfonate, anthraquinones, acetophenones, and benzoin methyl ether ), Benzoin ethers such as benzoin ethyl ether and benzoin phenyl ether, 2,4,6-trihalomethyltriazines (2,4,6) -trihalomethyl triazines), 1-hydroxycyclohexylphenylketone, 2- (o-chlorophenyl) -4,5-diphenylimidazole duplex (2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer), 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazoledimer (2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimmer), 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer (2- (o-fluorophenyl) -4,5-diphenylimidazole dimer), 2- (o-methoxyphenyl ) -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, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2 2,4,5-triaryl such as-(2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer (2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimmer) Imidazole dimers (2,4,5-triarylimidazole dimer), benzyl dimethyl ketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one ( 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone (2 -methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (2-hydroxy-2-methyl- 1-phenyl-propan-1-one), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one), 1,2-octanedione (1,2-octanedione), 1- [4- (phenylthio)- , 2- (O-benzoyloxime)] (1- [4- (phenylthio)-, 2- (o-benz oyloxime)]), phenanthrenequinone, 9,10-phenanthrenequinone, 9,10-phenanthrenequinone, methylbenzoin, ethylbenzoin and other benzoins, 9-phenyl Acridine derivatives such as acridine (9-phenylacridine), 1,7-bis (9,9′-acridinyl) heptane (1,7-bis (9,9′-acridinyl) heptane) ) And bisacylphosphine oxide ((bis) acylphosphine oxide), and one or two or more thereof can be used.

An accelerator may be further added to the photosensitive resin of the present invention. Examples of accelerators include p-dimethylamino ethyl, p-dimethylamino isoamyl, N, N-dimethylethanolamine, and N-. Methyl diethanolamine (N-methyldiethanolamine), triethanolamine, etc. are mentioned.

In the photosensitive resin composition of the present invention, a polymerizable monomer having one or more unsaturated groups in a molecule (hereinafter may be simply referred to as a "polymerizable monomer") can be further used. It can improve chemical resistance, heat resistance and mechanical strength. Moreover, a polymerizable monomer can also be added for the purpose of adjusting a flow characteristic. As this polymerizable monomer, as long as it has one or more unsaturated bonds in a molecule | numerator, it can use without a restriction | limiting especially, What is necessary is just to select a suitable thing according to the use and the objective to apply. For example, polyethylene glycol di (meth) acrylate (the number of ethylene groups is 2-14), trimethylolpropanedi (meth) acrylate (trimethylolpropane di (meth) acrylate), Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy tri (meth) acrylate, trimethylolpropane propoxytrimethyl (meth) acrylate (trimethylolpropane propoxy trimethacrylate), tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) Acrylate (polypropylene glycol di (meth) acrylate) (the number of propylene groups is 2-14), dipentaerythritol penta (meth) acrylate (dipentaeryth ritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A polyoxyethylene di (meth) acrylate, bisphenol A Bisphenol A trioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, bisphenol A deoxyoxy di (meth) acrylate Compounds having a hydroxyl group and an ethylenically unsaturated group, such as acrylate (bisphenol A decaoxyethylene di (meth) acrylate), multivalent carboxylic acid (phthalic anhydride, etc.) Esterified compounds with hydroxyethyl (meth) acrylate (ß-hydroxyethyl (meth) acrylate, etc.), (meth) acrylic acid methyl ester, and (meth) acrylic acid (Meth) acrylic acid alkyl esters such as ester (methacrylic acid ethyl ester), (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester ester, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol Diglycidyl ether (tetraethylene glycol diglycidyl ether), polyethylene glycol diglycidyl ether (propylene glycol diglycidyl ether), dipropylene glycol diglycidyl ether (dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene Tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol triglycidyl ether, glycerin triglycidyl ether, etc. (Meth) acrylic acid adducts of epoxy compounds, unsaturated organic acids such as maleic acid and their anhydrides, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-methylolacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N- N-isopropylmethacrylamide, N-methylolmethacrylamide, N, N-dimethylacrylamide, N, N-diethyl arc Acrylamides such as amide (N, N-diethylacrylamide), N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, Styrenes such as styrene and hydroxystyrene, N-vinylpyrrolidone, N-vinyl formamide, N-vinyl acetamide, N -N-vinyl imidazole etc. can be illustrated, and 1 type, or 2 or more types of these can be used.

A coloring agent can also be added to the photosensitive resin composition of this invention for the purpose of designability, visibility, antihalation of a photoresist, etc. The kind of coloring agent to be added can be appropriately selected according to the purpose of coloring, for example, phthalocyanine dyes, anthraquinone dyes, azo dyes, indigo dyes ( indigo dyes, coumarin dyes, triphenylmethane dyes, phthalocyanine pigments, anthraquinone pigments, azo pigments, quinacridone pigments, coumarin pigments , Triphenylmethane pigments, and the like, and one or two or more thereof can be used.

The photosensitive resin composition of this invention can be made into the form of the paste which mixed the solution, the filler, etc., and can also contain a solvent for this. Although there is no restriction | limiting in particular in the kind of solvent used, As an example, Ethylene glycol, such as water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc. Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and diethylene glycol dimethyl ether, and ethylene glycol monoethyl ether acetate Glycol ether acetates such as diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycols such as propylene glycol, dipropylene glycol and tripropylene glycol , Propylene Glycol Monome Ether (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 ethers such as propylene glycol diethyl ether and dipropylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and the like. Propylene glycol ether acetates, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactic acid esters such as methyl lactate, ethyl lactate, ethyl acetate, butyl acetate Of acetic acid esters, dimethyl sulfoxide, N- methylpyrrolidone can be given money, dimethylformamide, dimethylacetamide, and mixtures thereof.

In the photosensitive resin composition of this invention, conventionally well-known components, such as a polymerization inhibitor, a plasticizer, an antifoamer, and a coupling agent, can be further mix | blended as needed.

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

When using the photosensitive resin composition of this invention obtained as mentioned above as a photoresist, it is apply | coated on a board | substrate as 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, Slit coating or the like is applied. The applied solution or paste is exposed to light by an electron beam or an electron beam with a predetermined mask therebetween. When apply | coating using a solvent, you may go through a drying process. A pattern can be formed by developing the exposed coating film in a wet manner. The developing method can be any of spray method, paddle method, immersion method, etc., but a spray method with less residue is preferable. Ultrasonic waves etc. can also be irradiated as needed. As the developing solution, it is preferable to use alkaline water. An organic solvent, a surfactant, an antifoaming agent, etc. may be added for the purpose of developing assistance.

(Example)

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

Example 1

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 64 g of pyromellitic dianhydride (manufactured by Daicel Chemical Industries., Ltd .: PDMA), 9,9-bis [4- (2-hydric) Oxyethoxy) phenyl] fluorene (Osaka Gas Chemicals Co., Ltd.): 136 g of JPPE, 134 g of propylene glycol monomethyl ether acetate are added, and the mixture is stirred under a nitrogen stream for 4 hours in an oil bath at 155 ° C. Heated. Subsequently, after cooling to 120 degreeC, 1-g of 4-dimethylamino pyridine, 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl (made by ADEGA Corporation: ADEGASLA LA-7RD ( ADK STAB LA-7RD)) 0.04g, 106g of 4-hydroxybutyl acrylate glycidyl ether (product made from Nihon Kasei Co., Ltd .: 4HWAHAE) were added c, and it stirred at 120 degreeC for 4 hours. . Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A1) solution was obtained.

About the obtained resin solution, the viscosity, the styrene conversion weight average molecular weight by WPC, and solid content acid value were measured, and the viscosity was 2900 mPas / 25 degreeC, the styrene conversion weight average molecular weight by BPC is 12,523, and solid content acid value 2.2 mg gOH / g. In addition, the viscosity type | mold VMS type | mold manufactured by KK was used for the viscosity measurement. In addition, the measurement of GPC was carried out by THF eluent 40 degreeC and 0.5 ml / mI flow rate using the TOSGELEL G7000HVL and TSGELGEL G2500HBL made by Tosoh Corporation, and TGGELG2500HLL on the column. . The acid value was measured in accordance with the neutralization titration method described in JIS-K0070.

Example 2

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 72 g of biphenyl tetracarboxylic dianhydride (manufactured by Ubuheungsan Co., Ltd .: JPDA), 9,9-bis [4- (2-hydroxy) 128 g of methoxy) phenyl] fluorene (made by Osaka Chemical Co., Ltd .: PEPF), 1 g of 4-dimethylaminopyridine, and 134 g of propylene glycol monomethyl ether acetate were added, and it heated in 155 degreeC oil bath for 4 hours, stirring under nitrogen stream. Subsequently, after cooling to 120 degreeC, 4-hydroxy-2,2,6,6- tetramethyl piperidine- 1-oxyl (made by ADEGA: Adegas Tab LA-7RD) 0.04g, 4-hydroxy 84 g of butyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HWAA) were added, and the mixture was stirred at 120 ° C for 4 hours. Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A2) solution was obtained. About the obtained resin solution, the viscosity, the styrene conversion weight average molecular weight by XPC, and solid content acid value were measured, and it was 4200 mPas / 25 degreeC and styrene conversion weight average molecular weight 7,243 by BPC, and solid content acid value 2.5 mg gOH / g.

Comparative Example 1

Photosensitive resin (A3) was obtained according to the synthesis example 1 of Unexamined-Japanese-Patent No. 4-325508.

Using the photosensitive resin of Examples 1-2 and the comparative example 1, the photosensitive composition was created with the composition of Table 1. The photosensitive composition was applied on a 1.1 mm thick soda-lime glass plate with a bar coater to have a dry film thickness of 6 μm, dried for 10 minutes with a warm air dryer at 80 ° C., and then cooled to room temperature. I was. Subsequently, ultraviolet rays with an integrated light quantity of 300 mPa / cm ² were irradiated with an ultra-high pressure mercury lamp irradiator. About this cured coating film, the pencil hardness and the crosscut tape peel test were implemented along with JIS-K5400, and the strength of the coating film was evaluated.

The photosensitive composition using the photosensitive resin of the comparative example 1 was weak in coating film formation ability because of low molecular weight, and it could not be evaluated unless another resin component was added. As for the photosensitive composition using the photosensitive resin of Examples 1-2, the smooth film | membrane was obtained and both hardness and adhesiveness were favorable.

Example 7

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 76 g of pyromellitic dianhydride (manufactured by Daicera Co., Ltd .: PMDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka Gas 124 g of PFPE) and 134 g of propylene glycol monomethyl ether acetate were added, and it heated in 155 degreeC oil bath for 4 hours, stirring under nitrogen stream. Subsequently, after cooling to 120 degreeC, 1-g of 4-dimethylamino pyridine, 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl (made by ADEVA: AdecastabLA-7RD) 0.04 g and 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HBAE) were added and stirred at 120 ° C for 2 hours. Next, to room temperature, propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A4) solution was obtained.

About the obtained resin solution, the viscosity, the styrene conversion weight average molecular weight by WPC, and solid content acid value were measured, and the viscosity was 4800 mPas / 25 degreeC, the styrene conversion weight average molecular weight 23,169 by WPC and solid content acid value 75.2 mggOHH / g.

Example 8

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 90 g of biphenyltetracarboxylic acid dianhydride (manufactured by Ubo Chemical Co., Ltd .: JPDA), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (Osaka 110 g of Chemical Chemicals Co., Ltd. (PP), 134 g of propylene glycol monomethyl ether acetate, and 1 g of 4-dimethylaminopyridine were added, and it heated in 155 degreeC oil bath for 4 hours, stirring under nitrogen stream. Subsequently, after cooling to 120 degreeC, 4-hydroxy-2,2,6,6- tetramethyl piperidine- 1-oxyl (made by ADEGA: Adecastabr-7-7D) 0.04g, 4-hydroxy 80 g of butyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd .: 4HBAE) was added, and the mixture was stirred at 120 ° C for 2 hours. Next, it cooled to room temperature and propylene glycol monomethyl ether acetate was added so that a non volatile matter might be 50 mass%, and the pale yellow transparent viscous photosensitive resin (A5) solution was obtained.

About the obtained resin solution, when the viscosity, the styrene conversion weight average molecular weight by WPC, and solid content acid value were measured, the viscosity was 6600 mPas / 25 degreeC, the styrene conversion weight average molecular weight by BPC is 18,230, and solid content acid value 71.6 mggOHH / g.

Comparative Example 4

Synthesis Example 1 and the practice described in Japanese Patent No. 3813244, using a bisphenol fluorene type epoxy resin (product of Osaka Chemical Co., Ltd .: PFF) having a weight per epoxide equivalent of 257 Photosensitive resin (A6) was obtained in accordance with Example 1. Synthesis required 20 hours or more, and productivity was remarkably low compared with Examples 1-4 of this invention.

Comparative Example 5

The photosensitive resin (A7) was obtained according to the synthesis example 1 and Example 2 of Unexamined-Japanese-Patent No. 3813244 using bisphenol fluorene type | mold epoxy resin (made by Osaka Chemical Co., Ltd .: PFF) of epoxy equivalent 257. The synthesis required more than 21 hours and the productivity was significantly lower compared to Examples 7 and 8 of the present invention.

Comparative Example 6

80 g of 4-hydroxybutyl acrylate glycidyl ether of Example 8 was changed to 60 g of glycidyl methacrylate (Mitsubishi Rayon Co., Ltd. product: XMA). The same reaction was performed and the photosensitive resin solution (A8) was obtained. About the obtained resin solution, the viscosity, the styrene conversion weight average molecular weight by PCC, and solid content acid value were measured, and the viscosity was 12,400 mPas / 25 degreeC, the styrene conversion weight average molecular weight by BPC is 16,100, and solid content acid value 74.2 mggOHH / 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 PPC immediately after manufacture and 1 month after room temperature storage was measured, and the change rate was investigated. The results are shown in Table 2. Indicates.

The photosensitive resins of Examples 7 to 8 show little change, but the photosensitive resins of Comparative Examples 2 to 3 exhibited an increase in molecular weight of about 25%, resulting in inferior storage stability.

Examples 9-12 and Comparative Examples 7-12

Using the photosensitive resin of Examples 7-8 and Comparative Examples 4-6, the photosensitive composition was created by the combination of following Table 3. The photosensitive composition was applied to a 1.1 mm thick soda lime glass substrate with a spin coater to have a dry film thickness of 3 μm, dried for 90 seconds on a 100 degree hot plate, and then cooled to room temperature. Subsequently after the UV light intensity 15mW / cm ² (365nm), cumulative dose 20mJ / cm ² to super-high pressure mercury lamp exposure machine, and a UGRA-OFFSET-TEST KAIL1982 as a mask soft contact exposure (soft contact exposure), the 25 ℃ 1 The pattern was formed by immersion for 90 seconds in% sodium carbonate water, and the sensitivity was evaluated by the microline with the remaining number of steps. The results are shown in Table 3 together.

Compared with the photosensitive compositions using the photosensitive resins (A6 to A8) of Comparative Examples 4 to 6, the photosensitive compositions using the photosensitive resins of Examples 7 to 8 (A4 to A5) exhibited high sensitivity and good resist characteristics. .

Example 13

Into a 1000 ml flask equipped with a stirrer and a cooling tube, 71.8 g of 3,3'-4,4 'biphenyltetracarboxylic anhydride (manufactured by UBU), 9,9-bis [4- (2-hydroxy) 109.7 g of methoxy) 3phenylphenyl] fluorene (manufactured by OSAKA Chemical Co., Ltd.), 128 g of propylene glycol monomethyl ether acetate, and 0.25 g of 4-dimethylaminopyridine were added, followed by stirring in a mantle heater at 120 ° C. Heated for hours. Subsequently, 0.1 g of p-methoxyphenol (manufactured by Tokyo Kasei) and 13.7 g of hydroxyethyl acrylate (manufactured by Tokyo Kasei) were added thereto, followed by heating at 120 ° C. for 4 hours. Further, 34.68 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HWAHAE) was added thereto, and the mixture was heated at 120 ° C for 4 hours while stirring to obtain a pale yellow transparent viscous photosensitive resin (A9) solution.

About the obtained resin solution, viscosity, the styrene conversion weight average molecular weight by solid state, solid content, and solid content acid value were measured, and the viscosity 187100 mPas / 25 degreeC, styrene conversion weight average molecular weight 4,170 by solid content, 66.8% of solid content acid value, solid content acid value were measured. 85.4 mg gOH / g.

Example 14

In a 1000 ml flask equipped with a stirrer and a cooling tube, 61.22 g of 3,3'-4,4 'biphenyltetracarboxylic anhydride (manufactured by UBH): 9,9-bis [6- (2-hydroxye 95.89 g of methoxy) naphthyl] fluorene (the Osaka Chemical Co., Ltd. make: NOFEO), 125 g of propylene glycol monomethyl ether acetates, and 0.25 g of 4-dimethylaminopyridine were added, and it heated at 120 degreeC mantle heater for 4 hours. Subsequently, 0.1 g of p-methoxyphenol (manufactured by Tokyo Kasei) and 13.3 g of hydroxyethyl acrylate (manufactured by Tokyo Kasei) were added thereto, and the mixture was heated to 120 ° C. for 4 hours. In addition, 56 g of 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nihon Kasei Co., Ltd .: 4HBAE) was added thereto, and the mixture was heated with stirring at 120 ° C for 4 hours to obtain a pale yellow transparent viscous photosensitive resin (A10) solution.

The viscosity and styrene conversion weight average molecular weight, solid content, and solid acid value of the obtained resin solution were measured, and the viscosity was 586700 mPas / 25 ° C, styrene conversion weight average molecular weight 9,250, solid content 59.0%, and solid content acid value of BPC. 60.4 mggOH / g.

Examples 15-16

The photosensitive composition was created by the combination of Table 4 using the photosensitive resin of Example 13. This photosensitive composition was evaluated similar to Examples 9-12.

Both photosensitive compositions were highly sensitive and exhibited good resist characteristics.

The photosensitive resin of the present invention can be easily manufactured at low cost, easy to adjust the crosslinking density and acid value, and has excellent properties such as high heat resistance, high transparency, high refractive index and low linear expansion coefficient. Therefore, the resin composition using this photosensitive resin is used for interlayer insulating films and protective films (e.g., interlayer insulating films and protective films used for color filters, liquid crystal display devices, integrated circuit devices, solid-state imaging devices, etc.) in liquid crystal displays and electronic components. It is useful when preparing.

Claims (14)

A polymer compound obtained by reacting a compound having a fluorene skeleton represented by the following general formula (1) with a tetrabasic dianhydride (4). A photosensitive resin obtained by adding a carboxylic acid reactive (meth) acrylate compound (carboxylic acid anti methacrylate compound) represented by following General formula (2) to a compound.
[Formula 1]

(Wherein, ring Z ¹ and ring Z ² represent a monocyclic or condensed polycyclic hydrocarbon ring, and R ^1a and R ^1b represent a hydrogen atom or An alkyl group , and R ^2a and R ^2b represent a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, and a nitro group ) Or a substituent selected from a cyano group , R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 represent the same or different integers from 0 to 4, m1 And m2 represents the same or different integers from 0 to 3, n1 and n2 represent the same or different integers from 0 to 10, and p1 and p2 represent the same or different integers from 0 to 4; However, the ring Z ¹ and the ring Z ² is a monocyclic hydrocarbon ring If the p1 and p2 is 1 to 3, and the ring Z ¹ and Z ² ring is condensed is at least 1, the sum of each sum and p1 p2 included in the ring Z ² contained in the ring Z ¹ when the cyclic hydrocarbon ring to be)

[Formula 2]

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

[Formula 5]

(Wherein q, r and s each independently represent an integer of 0 to 9, except that q, r and s do not become 0 at the same time)
The method of claim 1,
The compound which has a fluorene skeleton represented by the said General formula (1) is represented by following General formula (3), Photosensitive resin characterized by the above-mentioned.
[Equation 3]

Wherein R ^1a and R ^1b represent a hydrogen atom or an alkyl group , and R ^2a , R ^2b , R ^6a and R ^6b are selected from a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group A substituent, R ^3a and R ^3b represent a hydrogen atom or a methyl group, k 1 and k 2 represent the same or different integers from 0 to 4, and m 1, m 2, m 3 and m 4 are the same or different from 0 to 3 N1, n2, n3 and n4 represent the same or different integers from 0 to 10, p1 and p2 represent the same or different integers from 1 to 4, and p3 and p4 are the same or Different integers from 0 to 3)
The method of claim 1,
The compound which has a fluorene skeleton represented by the said General formula (1) is represented by following General formula (4), Photosensitive resin characterized by the above-mentioned.
[Formula 4]

Wherein R ^1a and R ^1b represent a hydrogen atom or an alkyl group , and R ^2a , R ^2b , R ^7a and R ^7b are selected from a hydrocarbon group, an alkoxy group, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group or a cyano group A substituent, R ^3a and R ^3b represent a hydrogen atom or a methyl group, k1 and k2 represent the same or different integers from 0 to 4, n1 and n2 represent the same or different integers from 0 to 10; , p1 and p2 represent the same or different integers of 1 to 3)
4. The method according to any one of claims 1 to 3,
R ^2a and R ^2b of the general formula is a phenyl group (photosensitive resin), characterized in that.
The method according to any one of claims 1 to 3 ,
The acid value is 30-150 mggOH / g, The photosensitive resin characterized by the above-mentioned.
5. The method of claim 4 ,
The acid value is 30-150 mggOH / g, The photosensitive resin characterized by the above-mentioned.
The photosensitive resin of any one of Claims 1-3 and a photoinitiator and / or a photosensitizer are included, The photosensitive resin composition characterized by the above-mentioned.
The photosensitive resin of Claim 4, a photoinitiator, and / or a photosensitizer are included, The photosensitive resin composition characterized by the above-mentioned.
The photosensitive resin of Claim 5, a photoinitiator, and / or a photosensitizer are included, The photosensitive resin composition characterized by the above-mentioned.
The photosensitive resin of Claim 6 and a photoinitiator and / or a photosensitizer are included, The photosensitive resin composition characterized by the above-mentioned.
8. The method of claim 7 ,
The photosensitive resin composition containing the polymerizable monomer which has one or more unsaturated groups in a molecule | numerator further.
9. The method of claim 8 ,
The photosensitive resin composition containing the polymerizable monomer which has one or more unsaturated groups in a molecule | numerator further.
10. The method of claim 9 ,
The photosensitive resin composition containing the polymerizable monomer which has one or more unsaturated groups in a molecule | numerator further.
The method of claim 10 ,
The photosensitive resin composition containing the polymerizable monomer which has one or more unsaturated groups in a molecule | numerator further.