JP6524768B2 - Oligofluor orange (meth) acrylate, (meth) acrylate resin composition, optical member and lens - Google Patents

Description

  The present invention relates to a novel oligofluorene (meth) acrylate, a (meth) acrylate resin composition, an optical member comprising the resin composition, and a lens.

  Compounds having a fluorene skeleton are known to have excellent functions in various properties such as heat resistance, and attempts to incorporate such compounds having a fluorene skeleton in order to improve the properties of resins and polymer materials. Is being done. For example, a fluorene compound having a 9,9-bis (aryl) fluorene skeleton is excellent in refractive index, heat resistance and the like, and various materials such as ink materials, light emitting materials, organic semiconductors, coating agents, lenses, liquid crystal displays etc. It is widely used (see Patent Document 1).

  On the other hand, in recent years, resins manufactured using acrylate compounds are excellent in transparency, weather resistance, chemical resistance, optical properties, and easy to be processed by heat and form, and optical materials such as lenses and displays, automobile members It is used for medical supplies etc., and injection molding is mentioned as the molding method. Injection molding is a method with a short molding time and high productivity, but when optical materials such as lenses and optical disks are obtained by injection molding, photoelasticity due to residual stress (internal strain) by rapid solidification under high pressure It is known that birefringence tends to remain and birefringence distribution exists in the molded body. Therefore, in order to eliminate the birefringence distribution, a material having a small photoelastic coefficient is required.

  As an acrylate compound having a fluorene skeleton, a fluorene-containing curable monomer having a 9,9-bisarylfluorene skeleton and having at least one (meth) acrylate group in hard coat applications used in optical laminates is known. (See Patent Document 2).

Unexamined-Japanese-Patent No. 2005-241962 JP, 2012-111931, A

Resin using 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF) described in Patent Document 2 by the present inventors as an example of an acrylate compound exhibiting high refractive index When the composition was examined, it was found that the photoelastic coefficient is not sufficient for practical use.
Then, this invention makes it a subject to show the high photorefractive index and a low photoelastic coefficient when manufacturing a resin composition, and to provide the fluorene (meth) acrylate compound suitably used for an optical use.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination, in order to solve the said subject, the present inventors show a high refractive index and a low photoelastic coefficient, when manufacturing a resin composition using specific oligofluor orange (meth) acrylate. The present invention has been achieved.
That is, the present invention provides the following.
[1] Carbons at position 9 of two or more fluorene units which may have a substituent may be a direct bond, or may have an alkylene group which may have a substituent, or a substituent Oligofluorene (meth) acrylate characterized in that it is linked onto a chain via an arylene group or an aralkylene group which may have a substituent.
[2] The oligofluor orange (meth) acrylate according to [1], which is represented by the following general formula (1).

(Wherein, R ¹ and R ² are each independently a direct bond, an alkylene group of 1 to 10 carbons which may be substituted, an arylene group of 4 to 10 carbons which may be substituted, or a substituent A C 6-10 aralkylene group which may be substituted,
Or an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, and an aralkylene group having 6 to 10 carbon atoms which may be substituted. Two or more of the groups are an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a group linked by a carbonyl group,
R ³ is a direct bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or 6 to 10 carbon atoms which may be substituted An aralkylene group,
R ^{4 to} R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 10 carbons which may be substituted, an aryl group of 4 to 10 carbons which may be substituted, or each of which may be substituted Acyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms which may be substituted, aryloxy group having 1 to 10 carbon atoms which may be substituted, 1 to 1 carbon atom which may be substituted Acyloxy group of 10, amino group which may be substituted, vinyl group having 1 to 10 carbon atoms which may be substituted, ethynyl group having 1 to 10 carbon atoms which may be substituted, silicon atom having a substituent And a substituted sulfur atom, a halogen atom, a nitro group or a cyano group.
However, at least two adjacent groups among R ^{4 to} R ⁹ may be bonded to each other to form a ring.
Each R ⁱ independently represents a hydrogen atom or a methyl group.
n shows the integer value of 1-5. )

[3] An oligofluorene (meth) acrylate composition comprising the oligofluorene (meth) acrylate according to [1] or [2] and a compound having a carbon-carbon double bond.
[4] A (meth) acrylate resin composition comprising the polymer obtained by polymerizing the oligofluorened orange (meth) acrylate according to [1] or [2] or containing the polymer.
[5] A (meth) acrylate resin composition comprising or containing a polymer obtained by polymerizing the oligofluorene (meth) acrylate composition according to [3]. [6] An optical member obtained by using the (meth) acrylate resin composition described in [4] or [5].
[7] A lens obtained by using the (meth) acrylate resin composition described in [4] or [5].
[8] An optical member having a hard coat layer composed of the (meth) acrylate resin composition according to [4] or [5].

  The oligofluorene (meth) acrylate compound of the present invention is useful as a resin raw material of an optical member because it exhibits a high refractive index and a low photoelastic coefficient when it is used to produce a resin composition.

The embodiment of the present invention will be described in detail below, but the description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following unless the gist is exceeded. It is not limited to the content of. In the present invention, "weight" is synonymous with "mass".
In the present invention, the repeating unit indicates a partial structure sandwiched between arbitrary linking groups in the polymer. It also includes a partial structure in which one of the terminal portions of the polymer is a linking group and the other is a polymerization reactive group. In the present invention, the structural unit is synonymous with the repeating unit.
In the present invention, "optionally substituted" is synonymous with "optionally substituted".

<1 oligofluor orange (meth) acrylate>
In the oligofluorene (meth) acrylate of the present invention, the carbon atoms at position 9 of two or more fluorene units which may have a substituent are directly bonded, or the carbon atoms at position 9 of the fluorene unit are They are linked in a chain form via an alkylene group which may have a substituent, an arylene group which may have a substituent, or an aralkylene group which may have a substituent.
Thus, the oligofluorened orange (meth) acrylate of the present invention has a high proportion of the fluorene ring in the compound, a strong π-π interaction between the fluorene rings, and a rigid structure, so it has a high refractive index and It is considered to exhibit a low photoelastic coefficient.

<1.1 alkylene group, arylene group, aralkylene group>
In the oligofluorene (meth) acrylate of the present invention, the alkylene group to which the fluorene unit is bonded is not particularly limited, but from the viewpoint of increasing the proportion of the fluorene ring, the carbon number is usually 1 or more. It is 10 or less, preferably 5 or less, more preferably 3 or less.

  Specific structures of the above-mentioned alkylene group are listed below and include, but are not limited to, methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene and the like A linear alkylene group; methyl methylene group, dimethyl methylene group, ethyl methylene group, propyl methylene group, butyl methylene group, (1-methylethyl) methylene group, 1-methyl ethylene group, 2-methyl ethylene group, 1- Alkylene containing a branched chain such as ethyl ethylene group, 2-ethyl ethylene group, 1-methyl propylene group, 2-methyl propylene group, 1,1-dimethyl ethylene group, 2, 2-dimethyl propylene group, 3-methyl propylene group Group (numerical value of substitution position is given from carbon on fluorene ring side); alicyclic ring as shown in the following [A] group Alicyclic alkylene group having a bond between any two points in a linear or branched alkylene group of Concrete

(The substitution position of two bonds in each ring structure shown in the above [A] group is arbitrary, and two bonds may be substituted on the same carbon.); It is shown in the following [B] group Heterocyclic alkylene group having a bond of a linear or branched alkylene group at any two positions of such a heterocyclic structure

(The substitution position of two bonds in each ring structure shown in the above [B] group is arbitrary, and two bonds may be substituted on the same carbon.).
Alicyclic structure as shown in the above-mentioned [A] group, and linkage of linear or branched alkylene group which heterocyclic structure as shown in the above-mentioned [B] group has at any two places Specific structures of the hand are listed below and include but are not limited to straight chains such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene and the like Alkylene groups; 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2 And alkylene groups containing a branched chain such as 2-dimethylpropylene group and 3-methylpropylene group (where the numerical value of the substitution position is given from the carbon bonded to the above ring structure).

  As a substituent which the said alkylene group may have, a halogen atom (Example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a C1-C10 alkoxy group (example, a methoxy group, an ethoxy group, etc.) Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); C1 to 10 acylamino group (eg, acetamide group, benzoyl amide group etc.); nitro group; cyano group; Examples: fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group etc.), alkoxy group having 1 to 10 carbon atoms (eg, methoxy group) , An ethoxy group, an acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.), Toromoto, aryl group having 1 to 3 substituents carbon atoms which may have from 6 to 10 selected from a cyano group (e.g., phenyl group, naphthyl group etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

Specific examples of the alkylene group which may be substituted include alkyl group-substituted alkylene groups such as cyclobutyl methylene group, cyclopentyl methylene group, cyclohexyl methylene group, 1-cyclohexyl propylene group, etc .; phenyl methylene group, 1-phenyl ethylene group, 1-
Aryl group-substituted alkylene groups such as phenylpropylene group; halogen atom-substituted alkylene groups such as 1,1,2,2-tetrafluoroethylene group, trichloromethylmethylene group, trifluoromethylmethylene group; 2-methoxymethyl-2-methyl group An alkoxy group-substituted alkylene group such as a propylene group may, for example, be mentioned (the numerical value of the substitution position is assigned from the carbon on the fluorene ring side).

Further, in the oligofluorene (meth) acrylate of the present invention, the arylene group to which the fluorene unit is bonded is not particularly limited, but from the viewpoint of increasing the proportion of the fluorene ring, the carbon number is usually 4 or more. Usually, it is 10 or less, preferably 8 or less, more preferably 6 or less.
The specific structure of the arylene group is given below and includes, but is not limited to, phenylene groups such as 1,2-phenylene group, 1,3-phenylene group, and 1,4-phenylene group; Naphthylene groups such as 5-naphthylene group and 2,6-naphthylene group; and heteroarylene groups such as 2,5-pyridylene group, 2,4-thienylene group and 2,4-furylene group.

  Examples of the substituent which the arylene group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, Isopropyl group etc .; C1-C10 alkoxy group (eg, methoxy group, ethoxy group etc.); C1-C10 acyl group (eg, acetyl group, benzoyl group etc.); C1-C10 acylamino Groups (eg, acetamide group, benzoyl amide group etc.); nitro group; cyano group etc. may be mentioned. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

  Specific examples of the arylene group which may be substituted include 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 3 -Methoxy-1,4-phenylene group, 3-trifluoromethyl-1,4-phenylene group, 2,5-dimethoxy-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4 -A phenylene group, a 2,3,5,6- tetrachloro 1, 4- phenylene group, a 3-nitro 1, 4- phenylene group, a 3-cyano 1, 4- phenylene group etc. are mentioned.

Furthermore, in the oligofluorene (meth) acrylate of the present invention, the aralkylene group to which the fluorene unit is bonded is not particularly limited, but from the viewpoint of increasing the proportion of the fluorene ring, its carbon number is usually 6 or more, Usually, it is 10 or less, preferably 9 or less, more preferably 8 or less.
The specific structure of the aralkylene group is given below, and is not limited thereto, but the aralkylene group as shown in the following [C] group

Can be mentioned.
Examples of the substituent which the aralkylene group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, Isopropyl group etc .; alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group etc.); acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group etc.);
To 10 acylamino groups (eg, acetamide, benzoylamide, etc.); nitro groups; cyano groups; halogen atoms (eg, fluorine, chlorine, bromine, iodine atoms), alkyl groups having 1 to 10 carbon atoms (eg, Examples: methyl, ethyl, isopropyl and the like), alkoxy having 1 to 10 carbons (eg, methoxy, ethoxy and the like), acyl having 1 to 10 carbons (eg, the acetyl, benzoyl and the like) And C 1 -C 10 optionally having 1 to 3 substituents selected from C 1 -C 10 acylamino (eg, acetamide, benzoylamide, etc.), nitro, cyano and the like And aryl groups (eg, phenyl group, naphthyl group etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

  Specific examples of the aralkylene group which may be substituted include 2-methyl-1,4-xylylene group, 2,5-dimethyl-1,4-xylylene group, 2-methoxy-1,4-xylylene group, 2 5-dimethoxy-1,4-xylylene group, 2,3,5,6-tetrafluoro-1,4-xylylene group, α, α-dimethyl-1,4-xylylene group, α, α, α ′, α′-tetramethyl-1,4-xylylene group and the like can be mentioned.

  Among them, an alkylene group is preferable, a methylene group, an ethylene group, a phenylene group, or a 1,4-xylylene group is more preferable, and a methylene group is more preferable, from the viewpoint of increasing the ratio of the fluorene ring and being rigid. In particular, when it is a methylene group, synthesis of an oligofluorene having one reactive functional group selectively is particularly preferable.

<1.2 Substituent which the fluorene unit may have>
In the oligofluorene (meth) acrylate of the present invention, the substituent which the fluorene unit may have includes a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); Alkyl group (eg, methyl group, ethyl group, isopropyl group etc.); alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group etc.); acyl group having 1 to 10 carbon atoms (eg, acetyl group, Benzoyl group etc .; C1-C10 acylamino group (eg, acetamide group, benzoylamide group etc.); C1-C10 acyloxy group (eg, acetoxy group, benzoyloxy group etc.); nitro group; cyano group Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group) ), An alkoxy group having 1 to 10 carbon atoms (eg, a methoxy group, an ethoxy group, etc.), an acyl group having 1 to 10 carbon atoms (eg, an acetyl group, a benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms Acetamido group, benzoylamide group etc., vinyl group having 1 to 10 carbon atoms (vinyl group, 2-methylvinyl group, 2,2-dimethylvinyl group, 2-phenylvinyl group, 2-acetylvinyl group etc.), C1-C10 ethynyl group (ethynyl group, methylethynyl group, tert-butylethynyl group, phenylethynyl group, acetylethynyl group, trimethylsilylethynyl group etc.), silicon atom having substituent (trimethylsilyl group, triethylsilyl group etc.) Trialkylsilyl groups of: trimethoxysilyl groups, trialkoxysilyl groups such as triethoxysilyl groups, etc.), nitro groups, 1-3 aryl group which may having 6 to 10 carbon atoms which may have a substituent selected from such anode group (e.g., phenyl group, naphthyl group etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

<1.3 (meth) acrylate group>
Oligo fluorene (meth) acrylates of the present invention, among the fluorene units linked at the 9-position, respectively to bind the substituent alpha ₁ and alpha ₂ carbon atoms at the 9-position of the fluorene units located at both ends, the substituent it can be assumed that the group alpha ₁ and alpha ₂ are (meth) acrylate groups bonded. In this case, α ₁ and α ₂ may be the same or different. In addition, the substituent α ₁
And α ₂ include a direct bond, that is, the (meth) acrylate group may be directly bonded to the carbon atom at position 9 of the fluorene unit.

  The (meth) acrylate group possessed by the oligofluorene (meth) acrylate of the present invention is an acrylate group or a methacrylate group, and is preferably an acrylate group from the viewpoint of reactivity, and of storage stability and easiness of synthesis From the viewpoint, methacrylate groups are preferred. In addition, although oligofluor orange (meth) acrylate of this invention has two (meth) acrylate groups, they may be same or different.

<1.4 Substituents α ₁ and α ₂ >
The substituents α ₁ and α ₂ are not particularly limited, but they may be a direct bond, an alkylene group having 1 to 10 carbons which may be substituted, an arylene group having 4 to 10 carbons which may be substituted, or Optionally substituted C 6-10 aralkylene group, optionally substituted C 1-10 alkylene group, optionally substituted C 4-10 arylene group, and optionally substituted A group in which two or more groups selected from the group consisting of an aralkylene group having 6 to 10 carbon atoms are connected by an oxygen atom, a sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a carbonyl group It can be mentioned.

  As the “optionally substituted alkylene group having 1 to 10 carbon atoms”, those exemplified as the alkylene group to which a fluorene unit is bonded can be preferably used. In this case, the number of carbon atoms is preferably less than 4, and more preferably 1 in view of high refractive index. On the other hand, from the viewpoint of imparting flexibility to the resin composition, the number of carbon atoms is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more.

As the “optionally substituted arylene group having 4 to 10 carbon atoms”, those exemplified as the arylene group to which a fluorene unit is bonded can be used. Similarly, as the “optionally substituted aralkyl group having 6 to 10 carbon atoms”, those exemplified as the aralkylene group to which fluorene is bonded can be used.
“Selected from the group consisting of“ optionally substituted alkylene group having 1 to 10 carbon atoms, optionally substituted arylene group having 4 to 10 carbon atoms and optionally substituted aralkyl group having 6 to 10 carbon atoms ” Specific examples of the “group in which two or more groups are connected by an oxygen atom, a sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a carbonyl group” are listed below, Although not limited, divalent groups as shown in the following [D] group

Can be mentioned. Among them, preferably, two or more groups selected from an alkylene group, an arylene group or an aralkylene group can be linked by an oxygen atom, which can impart flexibility while maintaining the transparency and the stability of the resin composition. And more preferably an alkylene group as shown in the following [E] group which can increase the glass transition temperature of the resin composition while imparting flexibility, and is a group linked by an oxygen atom.

Further, from the viewpoint of increasing the proportion of the fluorene ring, in the case of making such a linked group, the number of carbon atoms is preferably 2 or more, and 6 or less, preferably 4 or less. It is more preferable to
Among them, a direct bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or 1 carbon atom which may be substituted is preferable. Two or more groups selected from the group consisting of an alkylene group of 10, an arylene group of 4 to 10 carbon atoms which may be substituted, and an aralkylene group of 6 to 10 carbon atoms which may be substituted; And a group which is connected by a sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a carbonyl group.

  More preferably, it is a direct bond, a linear alkylene group, an alkylene group containing a branched chain, or a linear or branched alkylene group at any two points of the alicyclic structure as shown in the above [A] group. Alicyclic alkylene group having a bond, phenylene group, optionally substituted alkylene group of 1 to 10 carbon atoms, optionally substituted arylene group of 4 to 10 carbon atoms, and optionally substituted Two or more groups selected from the group consisting of an aralkylene group having 6 to 10 carbon atoms are a group in which they are linked by an oxygen atom.

  More preferably, direct bonds, methylene groups, ethylene groups, n-propylene groups, n-butylene groups, methyl methylene groups, tend to be able to achieve the low photoelastic coefficient required for lenses by not having an aromatic ring. 1-methylethylene group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group or an alicyclic alkylene group as shown in the following [F] group

(The substitution position of two bonds in each ring structure shown in the above-mentioned [F] group is arbitrary, and two bonds may be substituted on the same carbon).
Still more preferably, it is a direct bond, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a methylmethylene group, a 1-methylethylene group, a 2-methylethylene group or a 2,2-dimethylpropylene group . Particularly preferred is a methylene group, an ethylene group or an n-propylene group.

  Since a long chain length tends to lower the glass transition temperature, a short chain group, for example, a group having 2 or less carbon atoms is preferable. Furthermore, since the molecular structure becomes smaller and the proportion of the fluorene ring in the repeating unit tends to be increased, the desired optical properties can be expressed efficiently. In addition, a methylene group is preferable because it has an advantage of being able to be introduced at a short stage and industrially inexpensively.

On the other hand, in order to improve the mechanical strength and reliability at high temperature of the obtained polymer, an arylene group having 4 to 10 carbon atoms or a substituted one that can increase the glass transition temperature of the resin composition A group in which two or more groups selected from the group consisting of a good C1-C10 alkylene group and an optionally substituted C4-C10 arylene group are linked by an oxygen atom is preferable, 1,4 -A phenylene group, a 1, 5-naphthylene group, a 2, 6-naphthylene group, or a divalent group as shown in the following [D2] group is more preferable.

Further, the substituents α ¹ and α ² are preferably identical to facilitate production.
<1.5 Specific structure>
Specifically as an oligofluor orange (meth) acrylate of this invention, what is represented with following General formula (1) can be used preferably.

In the formula, R ¹ and R ² are each independently a direct bond, an alkylene group of 1 to 10 carbons which may be substituted, an arylene group of 4 to 10 carbons which may be substituted, or Optionally substituted C 6-10 aralkylene group, optionally substituted C 1-10 alkylene group, optionally substituted C 4-10 arylene group, and optionally substituted Two or more groups selected from the group consisting of an aralkylene group having 6 to 10 carbon atoms are an oxygen atom, a sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a group which is connected by a carbonyl group Yes,
R ³ is each independently an optionally substituted alkylene group of 1 to 10 carbon atoms, an optionally substituted arylene group of 4 to 10 carbon atoms, or an optionally substituted carbon number of 6 to 10 Is an aralkylene group of
R ^{4 to} R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 10 carbons which may be substituted, an aryl group of 4 to 10 carbons which may be substituted, or each of which may be substituted Acyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms which may be substituted, aryloxy group having 1 to 10 carbon atoms which may be substituted, 1 to 1 carbon atom which may be substituted Acyloxy group of 10, amino group which may be substituted, vinyl group having 1 to 10 carbon atoms which may be substituted, ethynyl group having 1 to 10 carbon atoms which may be substituted, silicon atom having a substituent And a substituted sulfur atom, a halogen atom, a nitro group or a cyano group. However, at least two adjacent groups among R ^{4 to} R ⁹ may be bonded to each other to form a ring.

Each R ⁱ is independently a hydrogen atom or a methyl group.
Further, R ^{4 to} R ⁹ in the general formula (1) may be the same or different. Similarly, two R ⁱ in the general formula (1) may be the same or different.
In the general formula (1), as R ¹ and R ² , those exemplified for <1.4 substituents α ₁ and α ₂ > can be preferably used.

Similarly, as R ³ , those exemplified for <1.1 alkylene group, arylene group, aralkylene group> can be preferably used.
Specific examples of the “optionally substituted alkyl group having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ are listed below, but are not limited thereto: methyl group, ethyl group, n -A straight alkyl group such as -propyl group, n-butyl group, n-pentyl group, n-hexyl and n-decyl; isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 2-ethylhexyl And alkyl groups containing branched chains such as groups; and cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl.

  As a substituent which the said alkyl group may have, a halogen atom (Example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a C1-C10 alkoxy group (example, a methoxy group, an ethoxy group, etc.) Acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.); C1 to 10 acylamino group (eg, acetamide group, benzoyl amide group etc.); nitro group; cyano group; Examples: fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group etc.), alkoxy group having 1 to 10 carbon atoms (eg, methoxy group) , An ethoxy group, an acyl group having 1 to 10 carbon atoms (eg, acetyl group, benzoyl group, etc.), an acylamino group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group, etc.), B group, an aryl group having 1 to 3 substituents carbon atoms which may have from 6 to 10 selected from a cyano group (e.g., phenyl group, naphthyl group etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

A trifluoromethyl group, a benzyl group, 4-methoxybenzyl group, a methoxymethyl group etc. are mentioned as a specific example of the alkyl group which may be substituted.
Specific structures of “optionally substituted aryl group having 4 to 10 carbon atoms” in R ^{4 to} R ⁹ are listed below, but are not limited thereto, but phenyl group, 1-naphthyl group And aryl groups such as 2-naphthyl group; and heteroaryl groups such as 2-pyridyl group, 2-thienyl group and 2-furyl group.

  Examples of the substituent which the aryl group may have include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, Isopropyl group etc .; C1-C10 alkoxy group (eg, methoxy group, ethoxy group etc.); C1-C10 acyl group (eg, acetyl group, benzoyl group etc.); C1-C10 acylamino Groups (eg, acetamide group, benzoyl amide group etc.); nitro group; cyano group etc. may be mentioned. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

  Specific examples of the aryl group which may be substituted include 2-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-benzoylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl group Group, 4-cyanophenyl group, 3-trifluoromethylphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4 -Methyl furyl group etc. are mentioned.

Specific structures of “optionally substituted acyl group having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ are listed below, and the structure is not limited thereto, but formyl group, acetyl group, propionyl Groups, aliphatic acyl groups such as 2-methylpropionyl group, 2,2-dimethylpropionyl group, 2-ethylhexanoyl group; benzoyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 2-furylcarbonyl group, etc. And an aromatic acyl group of

  As a substituent which the said acyl group may have, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, Isopropyl group etc .; C1-C10 alkoxy group (eg, methoxy group, ethoxy group etc.); C1-C10 acylamino group (eg, acetamide group, benzoylamide group etc.); nitro group; cyano group; Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), C 1-10 alkyl group (eg, methyl group, ethyl group, isopropyl group etc.), C 1-10 alkoxy group (example , Methoxy group, ethoxy group, etc.), C 1-10 acyl group (eg, acetyl group, benzoyl group, etc.), C 1-10 acylamino group (eg, acetamide group, benzoylamide) Etc.), a nitro group, an aryl group (e.g. 1 to 3 substituents carbon atoms which may have from 6 to 10 selected from a cyano group, a phenyl group, a naphthyl group, etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

Specific examples of the acyl group which may be substituted include chloroacetyl group, trifluoroacetyl group, methoxyacetyl group, phenoxyacetyl group, 4-methoxybenzoyl group, 4-nitrobenzoyl group, 4-cyanobenzoyl group, 4 -Trifluoromethyl benzyl group etc. are mentioned.
Specific structures of “optionally substituted alkoxy or aryloxy or aryloxy having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ are listed below, but are not limited thereto: Alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy and trifluoromethoxy; aryloxys such as phenoxy; and acyloxys such as acetoxy and benzoyloxy.

The number of carbon atoms in the optionally substituted alkoxy group having 1 to 10 carbon atoms, an aryloxy group or an acyloxy group is preferably 4 or less, more preferably 2 or less. Within this range, steric hindrance between the fluorene rings is less likely to occur, and the desired optical properties derived from the fluorene ring tend to be obtained.
As a substituent which the said alkoxy group or the aryloxy group or the acyloxy group may have, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); an alkyl group having 1 to 10 carbon atoms (for example Methyl group, ethyl group, isopropyl group etc .; alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group etc.); acylamino group having 1 to 10 carbon atoms (eg, acetamide group, benzoylamide group etc.) Nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group etc.), carbon number 1 To 10 alkoxy groups (eg, methoxy, ethoxy, etc.), C 1-10 acyl groups (eg, acetyl, benzoyl, etc.), C 1-10 acyl A C6-C10 aryl group optionally having 1 to 3 substituents selected from mino group (eg, acetamide, benzoylamide, etc.), nitro group, cyano group, etc. (eg, phenyl group And naphthyl group etc.). The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

Specific structures of “optionally substituted amino group” in R ^{4 to} R ⁹ are listed below, but are not limited thereto: amino group; N-methylamino group, N, N- Dimethylamino group, N-ethylamino group, N, N-diethylamino group, N, N-methylethylamino group, N-propylamino group, N, N-dipropylamino group, N-isopropylamino group, N, N Aliphatic amino groups such as diisopropylamino group; aromatic amino groups such as N-phenylamino group, N, N-diphenylamino group; formamide group, acetamide group, decanoylamide group, benzoylamide group, chloroacetamide group, etc. Of the following: alkoxyamino such as benzyloxycarbonylamino, tert-butyloxycarbonylamino and the like; It is.

Among these, since they do not have a proton with high acidity, have a small molecular weight, and tend to be able to increase the proportion of the fluorene ring, they can be N, N-dimethylamino, N-ethylamino, or N, N. -Diethylamino group is preferable, and N, N-dimethylamino group is more preferable.
As the substituent which the amino group may have, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, Isopropyl group etc .; C1-C10 alkoxy group (eg, methoxy group, ethoxy group etc.); C1-C10 acylamino group (eg, acetamide group, benzoylamide group etc.); nitro group; cyano group; Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), C 1-10 alkyl group (eg, methyl group, ethyl group, isopropyl group etc.), C 1-10 alkoxy group (example , Methoxy group, ethoxy group, etc.), C 1-10 acyl group (eg, acetyl group, benzoyl group, etc.), C 1-10 acylamino group (eg, acetamide group, benzoylamide) Etc.), a nitro group, an aryl group (e.g. 1 to 3 substituents carbon atoms which may have from 6 to 10 selected from a cyano group, a phenyl group, a naphthyl group, etc.) and the like. The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

The specific structure of “optionally substituted vinyl group having 1 to 10 carbon atoms” or “optionally substituted ethynyl group having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ includes a vinyl group, 2-methylvinyl group, 2,2-dimethylvinyl group, 2-phenylvinyl group, 2-acetylvinyl group, ethynyl group, methylethynyl group, tert-butylethynyl group, phenylethynyl group, acetylethynyl group, trimethylsilylethynyl group Etc.

It is preferable that carbon number in the C1-C10 vinyl group or ethynyl group which may be substituted is 4 or less. Within this range, steric hindrance between the fluorene rings is less likely to occur, and the desired optical properties derived from the fluorene ring tend to be obtained.
As a substituent which the said vinyl group or ethynyl group may have, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, Ethyl group, isopropyl group and the like); C1-C10 alkoxy group (eg, methoxy group, ethoxy group and the like); C1-C10 acylamino group (eg, acetamide group, benzoylamide group and the like); nitro group; Cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), alkoxy having 1 to 10 carbon atoms Group (eg, methoxy group, ethoxy group, etc.), C 1-10 acyl group (eg, acetyl group, benzoyl group, etc.), C 1-10 acylamino group (eg, acetamide group, Aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group etc.) optionally having 1 to 3 substituents selected from nzyl amide group etc., nitro group, cyano group etc. . The number of the substituents is not particularly limited, but is preferably 1 to 3. When two or more substituents are present, the types of substituents may be the same or different. Further, from the viewpoint of being able to be manufactured at low cost industrially, it is preferable that no substitution be made.

Specific examples of the “silicon atom having a substituent” as R ^{4 to} R ⁹ include trialkylsilyl groups such as trimethylsilyl and triethylsilyl; trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl Can be mentioned. Among these, a trialkylsilyl group which can be stably treated is preferable.
Specific structures of “a sulfur atom having a substituent” in R ^{4 to} R ⁹ are listed below, but are not limited thereto: sulfo group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, Alkyl sulfonyl groups such as isopropyl sulfonyl group; aryl sulfonyl groups such as phenyl sulfonyl group and p-tolyl sulfonyl group; alkyl sulfinyl groups such as methyl sulfinyl group, ethyl sulfinyl group, propyl sulfinyl group and isopropyl sulfinyl group; -Arylsulfinyl group such as tolylsulfinyl group; alkylthio group such as methylthio group, ethylthio group etc .; arylthio group such as phenylthio group, p-tolylthio group etc; alkoxysulfonyl group such as methoxysulfonyl group, ethoxysulfonyl group etc. Aryloxysulfonyl group such as phenoxysulfonyl group; aminosulfonyl group; N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N-tert-butylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N- Examples thereof include alkylsulfonyl groups such as diethylaminosulfonyl group; and arylaminosulfonyl groups such as N-phenylaminosulfonyl group and N, N-diphenylaminosulfonyl group. The sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium or the like.

Among these, a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group is preferable because a proton having a high acidity does not have a proton, a molecular weight is small, and a proportion of a fluorene ring tends to be increased. It is more preferable that
In R ^{4 to} R ⁹ , examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among these, fluorine atoms, chlorine atoms, or bromine atoms are preferable because they are relatively easy to introduce and have a tendency to increase the reactivity of the fluorene 9-position due to the electron-withdrawing substituent, and chlorine atoms or bromine atoms are preferable. It is more preferable that it is an atom.
Adjacent R ^{4 to} R ⁹ may be bonded to each other to form a ring. Specific examples thereof include substituted fluorene structures as shown in the following [G] group.

Among these R ^{4 to} R ⁹ , preferably, they are all hydrogen atoms or any one selected from the group consisting of R ⁴ and / or R ⁹ from a halogen atom, an acyl group, a nitro group, a cyano group and a sulfo group. And R ^{5 to} R ⁸ are hydrogen atoms. In the case of all hydrogen atoms, it can be derived from industrially inexpensive fluorene. In addition, when R ⁴ and / or R ⁹ is any one selected from the group consisting of a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfo group, and R ^{5 to} R ⁸ are hydrogen atoms, fluorene 9 Because the reactivity of the order is improved, various induction reactions tend to be adaptable. More preferably, all hydrogen atoms or R ⁴ and / or R ⁹ is selected from the group consisting of fluorine atom, chlorine atom, bromine atom and nitro group, and R ^{5 to} R ⁸ are hydrogen atoms. And particularly preferably all hydrogen atoms. Further, by adopting the above, there is also a tendency that the ratio of the fluorene ring can be increased and desired optical properties derived from the fluorene ring can be obtained.

Furthermore, in the above general formula (1), R ⁱ is a hydrogen atom or a methyl group, but is preferably a hydrogen atom from the viewpoint of reactivity, and a methyl group in terms of storage stability and easiness of synthesis Is preferred.
Moreover, in the said General formula (1), although n represents the integer value of 1-5, it is preferable from a viewpoint of synthetic | combination ease that it is 4 or less, and it is more preferable that it is 3 or less.

<1.6 Specific Example of Oligofluorinated Orange (Meth) Acrylate>
Specific examples of the oligofluorene (meth) acrylate of the present invention include structures as shown in the following [H] group.

<1.7 Physical Properties of Oligofluorinated Orange (Meth) Acrylate>
The physical properties of the oligofluorene (meth) acrylate of the present invention are not particularly limited, but it is preferable that the physical properties exemplified below be satisfied.
The melting point of the oligofluorene (meth) acrylate of the present invention is preferably 200 ° C. or less, more preferably 150 ° C. or less, and particularly preferably 120 ° C. or less. When the melting point is high and the crystallinity is high, when a coating film or the like is used, crystallization may occur and a uniform film may not be obtained. In addition, from the viewpoint of obtaining a high purity product, crystals are preferable at room temperature (20 ° C.), more preferably 40 ° C. or more, and particularly preferably 60 ° C. or more. If melting | fusing point is this temperature range, high purity goods can be obtained by crystallization. On the other hand, in order to use it without a solvent, it is preferable that melting | fusing point is below room temperature (20 degreeC).

  The refractive index at 589 nm of the oligofluorene (meth) acrylate of the present invention is preferably 1.58 or more, more preferably 1.60 or more. Furthermore, it is preferably 1.62 or more, and particularly preferably 1.63 or more. Besides being thin and lightweight when used for an optical material such as a lens due to its high refractive index, it can be mixed with other materials to obtain a material having a wide range of refractive index.

<2 Method for Producing Oligofluorinated Orange (Meth) Acrylate>
The method for producing the oligofluorene (meth) acrylate of the present invention is not particularly limited. For example, the step of obtaining the oligofluorene compound (II) by the crosslinking reaction of the starting fluorenes (I) (step (i)), substitution A step of obtaining oligofluorenediol (20) by performing a group introduction reaction (step (ii)), and then a step of introducing a (meth) acrylate group by transesterification with a compound having a (meth) acrylic acid skeleton It can be obtained through the step (iii)). As a process (i), the process (ia) and process (ib) shown below are mentioned, for example.

Wherein, R ¹ ~R ^9, R ⁱ and n, R ¹ ~R ^9, R ⁱ and n as defined in the formula (1).
Hereinafter, the step (i), the step (ii) and the step (iii) will be described separately.

<2.1 Step (ia): Method for Producing Oligofluorene Compound (II)>
The step (ia) is a step of obtaining the oligofluorene compound (II) by the crosslinking reaction of the raw material fluorenes (I).

Wherein, R ³ to R ⁹ and n have the same meanings as R ³ to R ⁹ and n in the formula (1). Hereinafter, the method for producing the oligofluorene compound (II) in the step (ia) will be described separately in the case of the numerical values of R ³ and n.

<2.1.1 Process (ia-1). When R ³ is a direct bond and n = 1: 9, 9'-
Method for producing bifluorenyl>
Several synthesis methods of 9,9'-bifluorenyl are known and can be synthesized from fluorenone and 9-bromofluorene (J. Chem. Res., 2004, 760; Tetrahedron Lett., 2007, 48, 6669.). 9,9'-bifluorenyl can be purchased as a reagent.

<2.1.2 Process (ia-2): Manufacturing method when R 3 is a methylene group and n = 1 to 5>
The oligofluorene compound having a methylene bridge represented by the following general formula (IIa) can be produced from the fluorenes (I) and formaldehydes in the presence of a base according to the reaction represented by the following formula.

In the above formulas, R ⁴ to R ⁹ and n have the same meanings as R ⁴ to R ⁹ and n in the formula (1).

<2.1.2.1 Formaldehydes>
The formaldehyde used in the step (ia-2) is not particularly limited as long as it is a substance capable of supplying formaldehyde into the reaction system, and examples include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized with formaldehyde, trioxane and the like. Be Paraformaldehyde is more preferable from the viewpoint that it is industrially inexpensive and powdery, so that operability is easy and accurate weighing is possible. On the other hand, formalin is more preferable in terms of being industrially inexpensive and having a low risk of exposure at the time of addition because it is liquid.

(Definition of theoretical quantity)
When producing the target oligofluorene compound (IIa), the theoretical amount (molar ratio) of formaldehyde with respect to the raw material fluorenes (I) is represented by n / (n + 1).

(Why not go beyond the theoretical amount)
When an excess of the theoretical amount of formaldehyde is used with respect to the fluorenes (I), it tends to form an oligofluorene compound in which fluorene is further crosslinked from the target oligofluorene compound (IIa). As the number of fluorene rings of the oligofluorene compound increases, the solubility decreases, so that the purification load tends to increase when there is an oligofluorene compound in which four or more fluorene rings are crosslinked in the target product I understand. Therefore, in general, the amount of formaldehyde used is preferably n / (n + 1) times or less of the target theoretical amount.

(The reason why it is better not to fall below the theoretical amount)
Also, if the amount of formaldehyde used is far below the theoretical n / (n + 1), whether the oligofluorene compound having a smaller number of crosslinks of the fluorene ring becomes a main product than the target oligofluorene compound (IIa), Alternatively, it is known that the yield tends to be greatly reduced because the raw material fluorenes (I) remain unreacted.

Therefore, the optimum amount of formaldehydes to be used is, specifically, n: 1, usually at least 0.1 times mol, preferably at least 0.3 times mol, more preferably with respect to fluorenes (I). It is 0.38 times mole or more, and usually 0.5 times mole or less, preferably 0.46 times mole or less, more preferably 0.42 times mole or less.
In the case of n = 2, it is usually 0.5 times mol or more, preferably 0.55 times mol or more, more preferably 0.6 times mol or more, and usually 0.66 times mol or less, preferably 0.65 It is preferably at most 2 moles, more preferably at most 0.63 moles. Thus, it is known that the structure of the main product and the ratio of the product largely change according to the amount of formaldehyde used, and by using the amount of formaldehyde used under limited conditions, the target n Several oligofluorene compounds (IIa) can be obtained in high yield.

<2.1.2.2 Base>
Examples of the base used in the step (ia-2) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, hydroxides of an alkaline earth metal such as calcium hydroxide and barium hydroxide, Carbonates of alkali metals such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogenphosphate and potassium phosphate, n -Organolithium salts such as butyllithium, tert-butyllithium, alkoxides of alkali metals such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, Triethylamine, diazabishi Tertiary amines such as Roundesen, tetramethylammonium hydroxide, as quaternary ammonium hydroxides such as tetrabutylammonium hydroxide is used. One of these may be used alone, or two or more may be used in combination.

  When the reaction is carried out in a homogeneous system, among these, preferred are alkali metal alkoxides having sufficient basicity in this reaction, more preferably industrially inexpensive sodium methoxide and sodium ethoxide. . Here, the alkoxide of the alkali metal may be in the form of powder, or may be in the form of liquid such as alcohol solution. Alternatively, it may be prepared by reacting an alkali metal and an alcohol.

On the other hand, when the reaction is carried out in a two-layer system, among these, preferably an aqueous solution of an alkali metal hydroxide having sufficient basicity in this reaction, more preferably industrially inexpensive sodium hydroxide, It is an aqueous solution of potassium hydroxide.
The concentration of the aqueous solution is usually 10 wt / wt% or more, preferably 25 wt / wt% or more, and more preferably 40 wt%, because the reaction rate is significantly reduced when the concentration is low when particularly preferred aqueous sodium hydroxide solution is used. It is particularly preferable to use an aqueous solution of at least 1 wt%.

  When the reaction is carried out in a homogeneous system, the amount of use of the base is not particularly limited with respect to the raw material fluorenes (I), but if the amount used is too large, the purification load after stirring and reaction increases. The molar amount is 10 times or less, preferably 5 times or less, more preferably 1 time or less, that of the fluorenes (I). On the other hand, when the amount of the base used is too small, the reaction proceeds slowly, so the lower limit is usually at least 0.01 times mol, preferably at least 0.1 times mol, of the starting fluorenes (I). More preferably, it is 0.2 times mole or more.

  On the other hand, when the reaction is carried out in a two-layer system, there is no particular upper limit to the amount of base used relative to the raw material fluorenes (I), but if the amount used is too large, the purification load after stirring and reaction becomes large Therefore, the molar amount is usually 10 times or less, preferably 5 times or less, more preferably 2 times or less that of the fluorenes (I). On the other hand, when the amount of the base used is too small, the reaction proceeds slowly, so the lower limit is usually at least 0.1 times mol, preferably at least 0.3 times mol, of the starting fluorenes (I). More preferably, it is 0.4 times mole or more.

<2.1.2.3 Solvent>
Step (ia-2) is desirably performed using a solvent. Specific examples of usable solvents include, as an alkyl nitrile solvent, acetonitrile, propionitrile and the like, and as an ether solvent, diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tertiary butyl methyl ether For example, as a halogen-based solvent, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc. As a halogen-based aromatic hydrocarbon, chlorobenzene, 1,2-dichlorobenzene, etc., an amide Examples of the solvent include N, N-dimethylformamide, N, N, -dimethylacetamide, and N-methylpyrrolidone. Examples of the sulfoxide solvent include dimethyl sulfoxide and sulfolane. Examples of the cyclic aliphatic hydrocarbon include cyclopentene. Monocyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane and 1,3-dimethylcyclohexane 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane etc .; Polycyclic aliphatic hydrocarbons; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Acyclic aliphatic hydrocarbons, and aromatic hydrocarbons such as toluene, p-xylene, o-xylene and m-xylene; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and tertiary butanol , Hexanol, octanol, cyclohexanol and the like.

  In a homogeneous reaction, the solubility of the anion generated from the fluorenes (I) is high, and the progress of the reaction tends to be good, so an amide solvent of a polar solvent or a sulfoxide solvent is preferable. Among them, N, N-dimethylformamide is particularly preferred. This is because the solubility of the oligofluorene compound (IIa) in N, N-dimethylformamide is low, and the target product is rapidly precipitated after formation, and the progress of the further reaction is suppressed to increase the selectivity of the target product. It is because there is a tendency.

  In a two-layer system reaction, a basic aqueous solution and two layers are formed, the solubility of the anion generated from fluorenes (I) tends to be high, and the progress of the reaction tends to be good. Or halogen solvents are preferred. Among them, tetrahydrofuran is particularly preferred. This is because the solubility of the oligofluorene compound (IIa) in tetrahydrofuran is low, and the target substance precipitates quickly after formation, and the progress of the reaction is suppressed, and the selectivity of the target substance tends to increase. is there.

One of these solvents may be used alone, or two or more thereof may be mixed and used.
The amount of the solvent used is usually such that the volume is 10 times, preferably 7 times, more preferably 4 times, the volume of the raw material fluorenes (I). On the other hand, if the amount of the solvent used is too small, the stirring becomes difficult and the reaction proceeds slowly. Therefore, the lower limit is usually 1 volume, preferably 2 volumes of the raw material fluorenes (I), More preferably, an amount is used that results in a 3-fold volume.

<2.1.2.4 Reaction format>
When the step (ia-2) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.

<2.1.2.5 Reaction conditions>
In order to suppress the formation of a compound in which the fluorene ring is crosslinked more than the oligofluorene compound (IIa), the step (ia-2) is preferably performed at a temperature as low as possible. On the other hand, if the temperature is too low, a sufficient reaction rate may not be obtained.
Therefore, as a specific reaction temperature, the upper limit is usually 40 ° C., preferably 30 ° C., more preferably 20 ° C. On the other hand, the lower limit is carried out at −50 ° C., preferably −20 ° C., more preferably 0 ° C. or more.
The general reaction time in the step (ia-2) is usually 30 minutes, preferably 60 minutes, more preferably 2 hours, and the upper limit is not particularly limited, but is usually 20 hours, preferably 10 hours, more preferably Is 5 hours.

<2.1.2.6 Separation and purification of target product>
After completion of the reaction, the desired product, the oligofluorene compound (IIa), may be isolated by adding the reaction solution to acidic water such as dilute hydrochloric acid or adding acidic water such as dilute hydrochloric acid to the reaction solution and depositing it. it can.
After completion of the reaction, a solvent in which the desired oligofluorene compound (IIa) is soluble and water may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent. However, since the solubility of the oligofluorene compound (IIa) in the solvent tends to be very low at room temperature, a method of precipitation by contacting with acidic water is usually preferable.

  The obtained oligofluorene compound (IIa) can be used as it is as a raw material of step (ii), but may be used for step (ii) after purification. As a purification method, a usual purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be adopted without limitation.

<2.1.3 Process (ia-3): Method for producing difluorene compound (IIb) when R ³ is other than direct bond and n = 1>
The difluorene compound represented by the following general formula (IIb) is produced from the fluorenes (I) as a raw material according to the reaction of the following step (ia-3) in the presence of the alkylating agent (III) and a base.

In the above formulae, R ³ is an optionally substituted C 1-10 alkylene group, an optionally substituted C 4-10 arylene group, or an optionally substituted carbon 6 10 Are aralkylene groups. R ⁴ to R ⁹ and n have the same meanings as R ⁴ to R ⁹ and n in the formula (1). X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine) or a mesyl group or a tosyl group.

It is widely known that the method for producing difluorene compound (IIb) uses n-butyllithium as a base, generates anion of fluorenes (I) and then couples it with alkylating agent (III). ^In the case where ³ is an ethylene group or a method for producing R ³ such as a propylene group (Organometallics, 2008, 27, 3924; J. Molec. Cat. A: Chem., 2004, 214, 187.). In addition to alkylene groups, there are reports of crosslinking with xylylene groups (J. Am. Chem. Soc., 2007, 129, 8458.). However, industrial production by these methods using n-butyllithium tends to be very difficult both in terms of safety and cost. Further, as a method for producing the difluorene compound (IIb), a method is known in which fluorene and ethylene glycol are dehydrated and condensed at a high temperature in the presence of a base (J. Org. Chem., 1965, 30, 2540.).

  Examples of the alkylating agent used in the step (ia-3) include diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-di Iodohexane, dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, dichloromethane, 1,2-dichloroethane, 1 And linear alkyl dihalides such as 1, 3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1-bromo-3-chloropropane and the like (excluding fluorine atoms) , Alkyl dihalides containing a branched chain such as 2,2-dimethyl-1,3-dichloropropane (excluding fluorine atoms), 1,4 Aralkyl dihalides such as bis (bromomethyl) benzene and 1,3-bis (bromomethyl) benzene (excluding fluorine atoms), ethylene glycol dimesylate, ethylene glycol ditosylate, propylene glycol dimesylate, tetramethylene glycol dimesylate And disulfonates of glycols such as lath.

<2.1.4 Step (ia-4): Method for Producing Oligofluorene Compound (IId) When R ³ is Other than Direct Bonding and n = 2 or More>
The oligofluorene compound represented by the following general formula (IId) is represented by the following formula (ia-4) in a solvent in the presence of an alkylating agent (III) and a base using the oligofluorene compound (IIc) as a raw material Manufactured according to the reaction.

In the above formulae, R ³ is an optionally substituted C 1-10 alkylene group, an optionally substituted C 4-10 arylene group, or an optionally substituted carbon 6 10 an aralkylene group, R ⁴ to R ⁹ and n have the same meanings as R ⁴ to R ⁹ and n in the formula (1). X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine) or a mesyl group or a tosyl group.
The oligofluorene compound (IId) can be produced under the same conditions by converting the fluorenes (I), which are raw materials of <2.1.3 step (ia-3)>, into the oligofluorene compound (IIc) .

<2.2 Process (ib): Method for Producing Oligofluorene Compound (II)>
Step (ib) is carried out by converting the fluorenes (I) as raw materials into 9-hydroxymethyl fluorenes (IV) and then reacting the olefin body (V) synthesized by dehydration with a fluorenyl anion, This is a method of producing an oligofluorene compound (II) in which R ³ is a methylene group. Unsubstituted 9-hydroxymethyl fluorene is commercially available as a reagent. For example, after converting 9-hydroxymethyl fluorene to dibenzofulvane, a method of synthesizing a mixture of oligofluorene (IIa) by anionic polymerization is known. (J. Am. Chem. Soc., 123, 2001, 9182-9183.). Oligofluorene (IIa) can be produced with reference to these.

<2.3 Process (ii): Method for Producing Oligofluorenediol (20)>
The step (ii) is a step for obtaining a oligofluorenediol (20) by carrying out a substituent introduction reaction to the oligofluorene compound (II). As a process (ii), the combination (following, process (iib-1) and process (iib-2) of the process (iia) shown below, the process (iib-1), and the process (iib-2) are carried out, for example Step (iib), and the like.

Wherein, R ¹ to R ⁹ and n are R ¹ to R ⁹ and n as defined in the formula (1). R ⁱⁱⁱ represents a hydrogen atom or a methyl group. R ^iv is an alkyl group of 1 to 10 carbons which may be substituted, an aryl group of 4 to 10 carbons which may be substituted, or an aralkyl group of 6 to 10 carbons which may be substituted Represent.

<2.3.1 Process (iia): Manufacturing method when R ¹ and R ² are methylene groups in the general formula (20)>
Oligofluorenedol (20a) in which R ¹ and R ² are methylene groups is produced from the oligofluorene compound (II) and formaldehydes in the presence of a base according to the reaction represented by the following formula.

Wherein, R ³ to R ⁹ and n have the same meanings as R ³ to R ⁹ and n in the formula (1).

<2.3.1.1 Formaldehyde>
The formaldehyde used in step (iia) is not particularly limited as long as it is a substance capable of supplying formaldehyde into the reaction system, and examples thereof include gaseous formaldehyde, aqueous formaldehyde solution, paraformaldehyde polymerized with formaldehyde, trioxane and the like. Among these, it is particularly preferable to use paraformaldehyde because it is industrially inexpensive and powdery, so that operability is easy and accurate weighing can be performed.

  The upper limit of the amount of formaldehyde used is not particularly limited with respect to the raw material oligofluorene compound (II), but if the amount used is too large, purification load after the reaction tends to increase, so It is 20 times mol or less, preferably 10 times mol or less, more preferably 5 times mol or less with respect to the fluorene compound (II). The lower limit is usually 2 times mole or more, since the theoretical amount is 2 times mole with respect to the raw material. There is no problem in using formaldehyde in a slight excess with respect to the starting oligofluorene compound (II) in order to accelerate the reaction and leave no starting materials or intermediates. The preferable amount of formaldehyde used at that time is at least 2.1 times mol, more preferably at least 2.2 times mol, with respect to the raw material oligofluorene compound (II).

<2.3.1.2 Base>
As the base, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide, sodium carbonate, sodium hydrogencarbonate and potassium carbonate Carbonates of alkali metals such as, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, sodium phosphate, sodium hydrogen phosphate, alkali metal salts of phosphoric acid such as potassium phosphate, n-butyllithium, tert-butyllithium, etc. Organolithium salts, alkoxide salts of alkali metals such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, triethylamine, diazabicycloundecene, etc. Tertiary Ami , Tetramethylammonium hydroxide, as quaternary ammonium hydroxides such as tetrabutylammonium hydroxide is used. One of these may be used alone, or two or more may be used in combination.

  Among these, preferred are alkali metal alkoxides having sufficient basicity in this reaction, and more preferred is industrially inexpensive sodium methoxide or sodium ethoxide. Here, the alkoxide of the alkali metal may be in the form of powder, or may be in the form of liquid such as alcohol solution. Alternatively, it may be prepared by reacting an alkali metal and an alcohol.

It has been found that when an excessive amount of the base is used relative to the raw material oligofluorene compound (II), the decomposition reaction of oligofluorenediol (20a) tends to proceed. Therefore, it is preferable that the molar amount is 1 times or less, preferably 0.5 times or less, more preferably 0.2 times or less with respect to the oligofluorene compound (II). On the other hand, when the amount of the base used is too small, the reaction proceeds slowly, so the lower limit is usually at least 0.01 times mol, preferably at least 0.05 times mol, of the starting material oligofluorene compound (II) It is.

<2.3.1.3 Solvent>
Step (iia) is preferably performed using a solvent.
Specifically, usable solvents include: alkyl nitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as methyl acetate and ethyl acetate; Linear esters such as propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl lactate and ethyl lactate; Cyclic esters such as γ-butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol -Ether esters such as monomethyl ether acetate, propylene glycol 1-monoethyl ether acetate, etc. As ether solvents, diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cyclopentyl ether, tertiary butyl methyl ether, etc., halogen As a solvent, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc. As a halogen-based aromatic hydrocarbon, chlorobenzene, 1,2-dichlorobenzene, etc. As an amide solvent And N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like; sulfoxide solvents such as dimethylsulfoxide and sulfolane; and cyclic aliphatic hydrocarbons such as Monocycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3- Dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane and the like; Polycyclic aliphatic hydrocarbons such as decaline; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-te Noncyclic aliphatic hydrocarbons such as ladecane, and aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, etc. Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, tasha Examples include libutanol, hexanol, octanol, cyclohexanol and the like.

Among them, amide solvents of polar solvents or sulfoxide solvents are preferable, and N, N-dimethylformamide is preferable because the solubility of the anion generated from the oligofluorene compound (II) is high and the progress of the reaction tends to be good. Particularly preferred.
One of these solvents may be used alone, or two or more thereof may be mixed and used. The upper limit of the amount of the solvent used is not particularly limited, but considering the production efficiency of the target substance per reactor, usually 10 volumes, preferably 7 volumes, of the starting material oligofluorene compound (II), More preferably, an amount is used that results in a 4-fold volume. On the other hand, when the amount of the solvent used is too small, stirring tends to be difficult and the progress of the reaction tends to be slow. Therefore, the lower limit is usually 1 volume of the starting material oligofluorene compound (II), preferably 2 An amount which is double volume, more preferably triple volume is used.

<2.3.1.4 Reaction format>
When the step (iia) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.
In the case of batch type reaction reagents, it is known that the decomposition reaction is likely to progress when the base is charged in a batch addition at the start of the reaction, so the starting material oligofluorene compound (II), It is preferable to add a small amount of base after adding the formaldehydes and the solvent.

<2.3.1.5 Reaction conditions>
In step (iia), it has been found that if the temperature is too low, a sufficient reaction rate can not be obtained, while if it is too high, the decomposition reaction tends to proceed, and temperature control is extremely important. Therefore, when N, N-dimethylformamide, which is the optimum solvent, and sodium ethoxide, which is the optimum base, are used, the lower limit is usually −50 ° C. and the upper limit is 30 ° C. Specifically, R ³
When is a methylene group and n = 1, the upper limit of the reaction temperature is preferably 20 ° C., more preferably 10 ° C. On the other hand, the lower limit is preferably carried out at -20 ° C, more preferably at 0 ° C or higher. When R ³ is an ethylene group and n = 1, the upper limit of the reaction temperature is preferably 2
It is carried out at 5 ° C., more preferably at 20 ° C. On the other hand, the lower limit is preferably carried out at 0 ° C., more preferably at 10 ° C. or more. When R ³ is a methylene group and n = 2, the upper limit of the reaction temperature is preferably 25 ° C., more preferably 20 ° C. On the other hand, the lower limit is preferably carried out at 0 ° C., more preferably at 10 ° C. or more.

<2.3.1.6 Separation and Purification of Target Substance>
After completion of the reaction, isolate the desired product oligofluorenzole (20a) by adding the reaction solution to acidic water such as dilute hydrochloric acid or adding acidic water such as dilute hydrochloric acid to the reaction solution and depositing it. Can.
In addition, after completion of the reaction, a solvent in which the desired product oligofluorandiol (20a) is soluble and water may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

  The presence of the metal component often causes a problem in the polymerization reaction, and the content ratio of the metal of the long period periodic table group 1 and group 2 in the monomer is 500 mass ppm or less, more preferably 200 mass ppm or less, More preferably, it can be 50 mass ppm or less, particularly preferably 10 mass ppm or less. Generally, liquid separation operation is very effective for removing metal components, but the target product oligofluorenedol (20a) is used only in highly polar solvents such as N, N-dimethylformamide and tetrahydrofuran. Because of dissolution, separation operation performed in a two-layer system is very difficult. On the other hand, it is difficult to sufficiently remove the incorporated metal components even if the precipitate after reaction termination is subjected to ordinary purification treatment such as washing with water or thermal suspension washing with an optional solvent. In some cases, metal components of several hundreds mass ppm order may remain. As a good purification method for removing metal components, a reaction precipitate containing impurities is dissolved in a relatively soluble solvent such as N, N-dimethylformamide, tetrahydrofuran or the like, and then added to water for precipitation. Is preferred as a simple and effective method for removing inorganic salts.

<2.3.2 Process (iib): Method for Producing Oligofluorenediol (20b) Using Michael Addition>
The oligofluorene derivative represented by the following general formula (19) is represented by the following step (iib-1) in the presence of a base from the oligofluorene compound (II) and the (meth) acrylic acid ester (V1-1) Are produced according to the reaction. By reducing the obtained oligofluorene derivative (19), it is possible to produce oligofluorenediol (20b).

Wherein, R ³ to R ⁹ and n have the same meanings as R ³ to R ⁹ and n in the formula (1). R ⁱⁱⁱ represents a hydrogen atom or a methyl group. R ^iv is an alkyl group of 1 to 10 carbons which may be substituted, an aryl group of 4 to 10 carbons which may be substituted, or an aralkyl group of 6 to 10 carbons which may be substituted Represent.

<2.3.2.1 (Meth) acrylic acid ester>
The (meth) acrylic acid ester as a reaction agent is represented by the general formula (VI-1) in the step (iib).
Specific examples of (meth) acrylic acid ester (VI-1) include methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate Acrylic esters such as 1,4-cyclohexanedimethanol monoacrylate, methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, methacrylic acid esters such as 2-hydroxyethyl methacrylate, Α-substituted unsaturated esters such as methyl 2-ethylacrylate and methyl 2-phenylacrylate, β-substituted unsaturated esters such as methyl cinnamate, ethyl cinnamate, methyl crotonate and ethyl crotonate, crotonaldehyde Such as α, β Unsaturated aldehydes and the like.

R ^iv is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate or phenyl methacrylate because methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate or phenyl methacrylate is smaller because the smaller one is industrially inexpensive and easily purified by distillation Particularly preferred.
Although two or more different (meth) acrylic acid esters (VI-1) may be used, it is preferable to use one kind of (meth) acrylic acid ester (VI-1) for the convenience of purification.

  Since the (meth) acrylic acid ester (VI-1) has high polymerization activity, when it is present at a high concentration, it tends to polymerize easily by external stimuli such as light, heat, acid and base. At that time, it may be very dangerous because it involves a large amount of heat. Therefore, it is better not to use too much the amount of (meth) acrylic acid ester (VI-1) used from the viewpoint of safety. Usually, it is 10 times mol or less, preferably 5 times mol or less, more preferably 3 times mol or less with respect to the starting material oligofluorene (II). The lower limit is usually 2 times mol or more because it is 2 times mol in theoretical amount with respect to the raw material. The amount of (meth) acrylic acid ester (VI-1) used is at least 2.2 times the molar amount of the starting material oligofluorene (II), in order to accelerate the progress of the reaction and to leave no starting materials or intermediates. Preferably it is 2.5 times mole or more.

<2.3.2.2 Base>
As the base, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and barium hydroxide, sodium carbonate, sodium hydrogencarbonate and potassium carbonate Carbonates of alkali metals such as, carbonates of alkaline earth metals such as magnesium carbonate and calcium carbonate, sodium phosphate, sodium hydrogen phosphate, alkali metal salts of phosphoric acid such as potassium phosphate, n-butyllithium, tert-butyllithium, etc. Organolithium salts, alkoxide salts of alkali metals such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, etc., alkali metal hydrides such as sodium hydride or potassium hydride, triethylamine, diazabicycloundecene, etc. Tertiary Ami , Tetramethylammonium hydroxide, tetrabutylammonium hydroxide, quaternary ammonium hydroxides such as benzyltrimethylammonium hydroxide used. One of these may be used alone, or two or more may be used in combination.

There is a large difference in the reactivity of the oligofluorene (II) when R ³ is a methylene group and otherwise. Therefore, the case where R ³ is a methylene group and the case other than that are described separately.
When R ³ is a methylene group, the decomposition reaction of oligofluorene (II) readily proceeds in the presence of a base in a solvent. Therefore, it is preferable to use a water-soluble inorganic base because side reactions such as decomposition reaction can be suppressed when the reaction is performed in a two-layer system of an organic layer and an aqueous layer. Among them, alkali metal hydroxides are preferable in terms of cost and reactivity, and sodium hydroxide or potassium hydroxide is more preferable.

The concentration of the aqueous solution is usually 5 wt / vol% or more, preferably 10 wt / vol% or more, and more preferably 25 wt%, since the reaction rate is significantly reduced when the concentration is low when particularly preferred aqueous sodium hydroxide solution is used. It is particularly preferable to use an aqueous solution of / vol% or more.
When R ³ is other than a methylene group, the reaction proceeds even in a two-layer system of an organic layer and an aqueous layer, but when the reaction is carried out using an organic base dissolved in the organic layer, the reaction proceeds rapidly. It is preferred to use an organic base. Among these, preferred are alkali metal alkoxides having sufficient basicity in this reaction, and more preferred is industrially inexpensive sodium methoxide or sodium ethoxide. Here, the alkoxide of the alkali metal may be in the form of powder, or may be in the form of liquid such as alcohol solution. Alternatively, it may be prepared by reacting an alkali metal and an alcohol.

When R ³ is a methylene group, the upper limit of the amount of use of the base is not particularly limited with respect to the raw material oligofluorene (II), but if the amount used is too large, the purification load after stirring or reaction increases In some cases, when using a 25 wt / vol% or more sodium hydroxide aqueous solution, which is a particularly preferable base, usually 20 volumes or less, preferably 10 volumes or less, relative to the oligofluorene (II), and further Preferably, it is 5 volumes or less. If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the amount of the base is usually 0.2 times or more that of the starting material oligofluorene (II). Preferably, it is 0.5 volume or more, more preferably 1 volume or more.

When R ³ is other than a methylene group, the amount of the base used is the raw material oligofluorene (II)
On the other hand, the upper limit is not particularly limited, but when the amount used is too large, the purification load after stirring or reaction may increase, so when sodium methoxide or sodium ethoxide which is a particularly preferable base is used, Usually, the amount is 5 times by mole or less, preferably 2 times by mole or less, more preferably 1 times by mole or less, particularly preferably 0.5 times by mole or less with respect to the oligofluorene (II). If the amount of the base is too small, the reaction rate is significantly reduced. Therefore, the amount of the base is usually at least 0.005 times the molar amount of the starting material oligofluorene (II). Preferably, it is 0.01 times mol or more, more preferably 0.05 times mol or more, and particularly preferably 0.1 times mol or more.

<2.3.2.3 Phase transfer catalyst>
In the step (iib-1), when the reaction is performed in a two-layer system of an organic layer and an aqueous layer, it is preferable to use a phase transfer catalyst in order to increase the reaction rate.
As a phase transfer catalyst, tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodide, acetyltrimethylammonium bromide, Halide (except fluorine) of quaternary ammonium salt such as benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidine C. quaternary pyrrolidinium salts such as sodium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide and the like (Excluding fluorine), N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide and other quaternary morpholinium salts Halide (excluding fluorine), N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpyridine Halide (except fluorine) of quaternary piperidinium salts such as peridinium acetate, N-methyl-N-ethylpiperidinium iodide and the like, crown ethers and the like. It is preferably a quaternary ammonium salt, more preferably benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

One of these may be used alone, or two or more may be used in combination.
If the amount of phase transfer catalyst used is too large relative to the raw material oligofluorene (II), the progress of side reactions such as hydrolysis of ester and sequential Michael reaction tends to be remarkable, and the cost is also a point of view Also, it is usually 5 times by mole or less, preferably 2 times by mole or less, more preferably 1 times by mole or less, with respect to the oligofluorene (II). When the amount of the phase transfer catalyst used is too small, the reaction rate tends to be significantly reduced. Therefore, the amount of the phase transfer catalyst used is usually at least 0.01 times the molar amount of the starting oligofluorene. Preferably, it is 0.1 times mole or more, more preferably 0.5 times mole or more.

<2.3.2.4 Solvent>
Step (iib-1) is desirably performed using a solvent.
Specifically, usable solvents include: alkyl nitrile solvents such as acetonitrile and propionitrile; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as methyl acetate and ethyl acetate; Linear esters such as propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl lactate and ethyl lactate; Cyclic esters such as γ-butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol -Ether esters such as monomethyl ether acetate, propylene glycol 1-monoethyl ether acetate, etc. As ether solvents, diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cyclopentyl ether, tertiary butyl methyl ether, etc., halogen As a solvent, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc. As a halogen-based aromatic hydrocarbon, chlorobenzene, 1,2-dichlorobenzene, etc. As an amide solvent Are, for example, N, N-dimethylformamide, N, N-dimethylacetamide, etc. As a sulfoxide solvent, dimethyl sulfoxide, sulfolane, etc. Cycloaliphatic hydrocarbons such as cyclopentane, cyclic Monocyclic aliphatic hydrocarbons such as rohexane, cycloheptane, cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1 2,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Cyclic aliphatic hydrocarbons; Non-cyclic such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, etc. As aromatic heterocycles such as pyridine, alcohol solvents such as methanol, ethanol, isopropanol, n -Butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

In the case where R ³ is a methylene group, oligofluorene (I
It has been found that there is a tendency to be able to suppress side reactions such as the decomposition reaction of I). Furthermore, when using a solvent that dissolves the raw material oligofluorene (II) well, the progress of the reaction tends to be good, so the solubility of the raw material oligofluorene (II) is 0.5 mass% or more It is preferable to use a solvent, more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more. Specifically, halogen-based aliphatic hydrocarbons, halogen-based aromatic hydrocarbons, aromatic hydrocarbons, or ether solvents are preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4-, Particularly preferred is dioxane or methylcyclopentyl ether.

One of these solvents may be used alone, or two or more thereof may be mixed and used.
The upper limit of the amount of the solvent used is not particularly limited, but in view of the production efficiency of the desired product per reactor, the volume of the raw material oligofluorene (II) is usually 20 times, preferably 15 times the volume, Preferably, an amount of 10 times the volume is used. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent will deteriorate and stirring will become difficult, and the progress of the reaction will slow, so the lower limit is usually 1 volume of the starting material oligofluorene (II), preferably Is used in such an amount as to be a 2-fold volume, more preferably a 4-fold volume.

It has been found that when R ³ is other than a methylene group, the solubility of the organic base and the oligofluorene (II) tends to greatly affect the reaction rate, and the dielectric constant of more than a certain value to secure its solubility. It is desirable to use a solvent with a rate. As a solvent which dissolves the organic base and the oligofluorene (II) well, aromatic heterocyclic ring, alkyl nitrile solvent, amide solvent, sulfoxide solvent are preferable, and pyridine, acetonitrile, N, N-dimethylformamide, N, N, Particularly preferred is N-dimethylacetamide, dimethylsulfoxide or sulfolane.

One of these solvents may be used alone, or two or more thereof may be mixed and used.
The upper limit of the amount of the solvent used is not particularly limited, but in view of the production efficiency of the desired product per reactor, the volume of the raw material oligofluorene (II) is usually 20 times, preferably 15 times the volume, Preferably, an amount of 10 times the volume is used. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent will be poor, the stirring will be difficult and the progress of the reaction will tend to be slow, so the lower limit is usually 1 volume of oligofluorene (II) as the raw material An amount is used, preferably 2 volumes, more preferably 4 volumes.

<2.3.2.5 Reaction format>
When the step (iib-1) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.
In the case of batch type reaction reagents, when (meth) acrylic acid ester (VI) is charged at once at the beginning of the reaction, (meth) acrylic acid ester (VI) is present at a high concentration. Therefore, the polymerization reaction of the side reaction is likely to proceed. Therefore, it is preferable to sequentially add (meth) acrylic acid ester (VI) little by little after adding the starting materials oligofluorene (II), phase transfer catalyst, solvent and base.

<2.3.2.6 Reaction conditions>
In the step (iib-1), if the temperature is too low, a sufficient reaction rate can not be obtained. On the contrary, if it is too high, the polymerization reaction of the (meth) acrylate (VI) tends to proceed, so temperature control It is desirable to Therefore, as the reaction temperature, specifically, the lower limit is usually 0 ° C., preferably 10 ° C., more preferably 15 ° C. On the other hand, the upper limit is usually 40 ° C., preferably 30 ° C., more preferably 20 ° C.
The general reaction time in the step (iib-1) is generally 2 hours, preferably 4 hours, more preferably 6 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, more preferably Is 10 hours.

<2.3.2.7 Separation / Purification of Target Substance>
After completion of the reaction, the target product oligofluorene derivative (19) is a method of concentrating the solvent after removing the by-produced metal halide and the remaining inorganic base from the reaction solution by filtration, or It is possible to isolate it by precipitating the target object oligofluorene derivative (19) by adopting a method of adding a solvent or the like.

Further, after completion of the reaction, acid water and a solvent in which the desired oligofluorene derivative (19) is soluble may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.
The solvent usable in the extraction is not particularly limited as long as it can dissolve the target object oligofluorene derivative (19), but is not particularly limited, but aromatic hydrocarbon compounds such as toluene and xylene, dichloromethane, chloroform And the like, or one or more kinds such as a halogen-based solvent are preferably used.

<2.3.2.8 Process (iib-2): Process for producing oligofluorenedol (20b) by reduction reaction of oligofluorene derivative (19)>
The oligofluorenediol represented by the following general formula (20b) is produced from the oligofluorene derivative (19) in the presence of a reducing agent according to the following step (iib-2).

Wherein, R ³ to R ⁹ and n have the same meanings as R ³ to R ⁹ and n in the formula (1). R ⁱⁱⁱ represents a hydrogen atom or a methyl group, and R ^iv is an alkyl group having 1 to 10 carbons which may be substituted, an aryl group having 4 to 10 carbons which may be substituted, or And optionally represent an aralkyl group having 6 to 10 carbon atoms.
The synthesis of diols by reduction of esters is well known in the synthesis and is produced in U.S. Patent Application Publication 2012/0170118 by a reduction reaction using lithium aluminum hydride as the reducing agent. Examples of methods using other metal hydrides include hydrogenated diisobutylaluminum, hydrogenated sodium bis (2-methoxyethoxy) aluminum and the like. Also, reduction of esters by catalytic hydrogenation reaction using ruthenium, rhodium, palladium and platinum as a catalyst is a widely known method.

<2.4 Production of Oligofluor Orange (Meth) Acrylate>
Step (iii) is a step of introducing a (meth) acrylate group into oligofluorenediol (20) using transesterification with a compound having a (meth) acrylic acid skeleton.
For example, as described below, a method (production method A, step (iii-1)) using acrylic acid halide as a compound having a (meth) acrylic acid skeleton, a method using acrylic anhydride (production method B, step (iii- 2)) A method using an acrylic acid or an acrylic ester (Production method C, step (iii-3)) is described separately.

Wherein, R ¹ to R ⁹ have the same meanings as R ¹ to R ⁹ in the formula (1). Each R ⁱ independently represents a hydrogen atom or a methyl group. R ^v represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms. Z
Represents a halogen atom.

<2.4.1 Production method A: Production method using (meth) acrylic acid halide>
Several methods for producing acrylic acid esters using (meth) acrylic acid halide and alcohol are known, and for example, methods using (meth) acrylic acid chloride, alcohol and a base are known (Japanese Patent Laid-Open No. 2003-128661) No. 2).
The oligofluorened orange (meth) acrylate represented by the general formula (1) is produced from oligofluorenedhol (20) and (meth) acrylic acid halide (VI-2) in the presence of a base according to the following steps Ru.

Wherein, R ¹ to R ⁹ is R ¹ to R ⁹ as defined in the formula (1). Each R ⁱ independently represents a hydrogen atom or a methyl group. Z represents a halogen atom.

<2.4.1.1 (Meth) acrylic acid halide>
The (meth) acrylic acid halide as a reagent is represented by the general formula (VI-2) in the step (iii-1), R ⁱ represents a hydrogen atom or a methyl group, and Z represents a halogen atom. Represent. Specifically, acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, methacrylic acid bromide and the like can be mentioned.

  There is no particular upper limit to the amount of (meth) acrylic acid halide (VI-2) used relative to the starting material oligofluorenedole (20), but if the amount used is too large, the purification load after the reaction will be large Therefore, the amount is usually 10 times or less, preferably 6 times or less, more preferably 4 times or less that of oligofluorenediol (20). On the other hand, since there are two reaction sites with respect to one molecule of oligofluorene compound (II), the lower limit is usually at least 2.0 times mol with respect to the starting material oligofluorene compound (II), preferably Is 2.2 times mol or more, more preferably 2.4 times mol or more.

<2.4.1.2 bases>
As the base used for the reaction, those commonly used in the ester production by the reaction of (meth) acrylic acid halide and alcohol can be used. For example, metal hydroxides such as sodium hydroxide and potassium hydroxide And aliphatic or aromatic amine compounds such as triethylamine, pyridine, 4-dimethylaminopyridine, benzyltrimethylammonium hydroxide and dimethylaniline, and tetramethylurea. One of these may be used alone, or two or more of these may be used in any combination. When a base is present, the amount used is not particularly limited, but if it is too large, the load upon purification after the reaction will increase, so usually 10 times mol or less of oligofluorenedole (20), The amount is preferably 5 times by mole or less, more preferably 4 times by mole or less, particularly preferably 3 times by mole or less. The base is usually at least twice the molar amount to the starting material oligofluorene (II), because there are two reaction sites for one molecule of oligofluorenedole (20). Preferably, it is 2.1 times mole or more, more preferably 2.2 times mole or more, and particularly preferably 2.3 times mole or more.

<2.4.1.3 Solvent>
A solvent can also be used for the reaction. Although the solvent used is not particularly limited, aromatic hydrocarbons such as benzene, toluene, xylene and the like; aliphatic hydrocarbons such as hexane, heptane, dodecane and the like; methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol and the like Alcohols; Halogenated solvents such as chloroform, dichloromethane, dichloroethane, etc .; Ethers such as tetrahydrofuran, dioxane, t-butyl methyl ether, cyclopentyl methyl ether etc .; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, anone etc. Acetonitrile, Nitriles such as butyronitrile; ester compounds such as ethyl acetate, butyl acetate and methyl formate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide; N, N ' Ureas such as dimethylimidazolidinone; water and mixtures of these solvents. Among these, the miscibility of aromatic hydrocarbons, aliphatic hydrocarbons, and triethylamine and pyridine is preferable, shows no nucleophilicity to (meth) acrylic acid halide, and is stable in the reaction and purification steps. Aromatic hydrocarbons, halogen solvents, ethers and ketones are more desirable.

<2.4.1.4 Reaction format>
When the step (iii-1) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.
In the case of the batch system, the method of charging the reaction agent into the reactor can be adopted without particular limitation. For example, in the case of batch type, when (meth) acrylic acid halide is charged at once at the start of the reaction, the (meth) acrylic acid halide is present at a high concentration, so that the polymerization reaction of side reaction tends to proceed. Therefore, it is preferable to add a small amount of (meth) acrylic acid halide successively after adding the starting material oligofluorenzole (20), the solvent and the base.

<2.4.1.5 Reaction conditions>
The reaction temperature is not particularly limited as long as the reaction is not inhibited.
As described above, the exchange reaction of (meth) acrylic acid halide with oligofluorenediol produces oligofluorinated (meth) acrylate. The order of addition of these compounds is not particularly limited, but usually, oligofluorenediol is dissolved or suspended in a reaction solvent, and the base and (meth) acrylic acid halide are added while paying attention to the temperature of the mixture.

<2.4.1.6 Separation and Purification of Target Substance>
After completion of the reaction, the target product oligofluor orange (meth) acrylate is a target product oligofluor oligofluorene (Meta) by adopting a method of concentrating a solvent or a method of adding a target poor solvent. ) It can be isolated by a method of precipitating acrylate.

In addition, after completion of the reaction, water and a solvent in which the desired product oligofluorene (meth) acrylate is soluble may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding an antisolvent.
The solvent which can be used in the extraction is not particularly limited as long as it can dissolve the objective oligofluorene (meth) acrylate, and there is no particular limitation, but an aromatic hydrocarbon compound such as toluene or xylene, dichloromethane, One or two or more kinds of solvents such as halogen solvents such as chloroform are suitably used.

  The oligofluorene (meth) acrylate obtained here can be used as it is as a component of the oligofluorene (meth) acrylate composition, etc., but may be used after purification. As a purification method, a usual purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be adopted without limitation. It is also possible to dissolve oligofluorene (meth) acrylate in a suitable solvent and treat with activated carbon. The solvents that can be used here are the same as the solvents that can be used in the extraction.

<2.4.2 Production Method B: Production Method Using (Meth) Acrylic Anhydride>
Several methods for producing (meth) acrylic acid esters using (meth) acrylic acid anhydride and alcohol are known, and in the example of US Patent No. 5,461,162, Li ₂ CO is used for acrylic acid ester and alcohol. A synthetic reaction of (meth) acrylic acid ester using ₃ as an acid catalyst has been studied.

  The oligofluorened orange (meth) acrylate represented by General formula (1) is manufactured according to the following process from oligofluorenedhol (20) and (meth) acrylic acid anhydride (VI-3).

Wherein, R ¹ to R ⁹ is R ¹ to R ⁹ as defined in the formula (1). Each R ⁱ independently represents a hydrogen atom or a methyl group.

<2.4.2.1 (meth) acrylic acid anhydride>
(Meth) acrylic acid anhydride as a reaction reagent is intended in the step (iii-2) represented by the general formula (VI-3), R ⁱ represents a hydrogen atom or a methyl group. Specifically, acrylic anhydride and methacrylic anhydride can be mentioned. The (meth) acrylic anhydride may use a reagent, but may be adjusted from (meth) acrylic acid and (meth) acrylic acid halide as needed. In particular, since acrylic anhydride is unstable, it is preferable to use it as needed.
The amount of (meth) acrylic acid anhydride used is usually 10 times or less by mole, preferably 5 times by mole or less, more preferably 10 times by mole or less based on the amount of oligofluorenediol (20), since the purification load increases when the amount is too large. It is 4 times mole or less, particularly preferably 3 times mole or less. (Meth) acrylic anhydride is usually 2 times the molar amount of the starting material oligofluorenzole (20), because there are two reaction sites for one molecule of oligofluorenzole (20). It is above. Preferably, it is 2.1 times mole or more, more preferably 2.2 times mole or more, and particularly preferably 2.3 times mole or more.

<2.4.2.2 Catalyst>
The reaction of (meth) acrylic anhydride with alcohols may be carried out without using a catalyst, but it is usually preferred to use a catalyst. As the catalyst, those used in conventional esterification reactions can be used. For example, alkali metal salts such as sodium and potassium of lower carboxylic acids such as sodium acetate, potassium propionate and sodium (meth) acrylate, amines such as pyridine, triethylamine and triethylenediamine, inorganic acids such as sulfuric acid and boric acid, methane Examples thereof include organic acids such as sulfonic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, zinc chloride, titanium chloride and lithium carbonate. The amount of the catalyst used may be an amount used in a normal esterification reaction, and the upper limit of the catalyst is usually 20 mol% or less, preferably 10 mol% or less, with respect to oligofluorenediol (20). More preferably, it is 5 mol% or less, particularly preferably 3 mol% or less. Usually, the lower limit value of the catalyst is 0.01 mol% or more with respect to the raw material oligofluorenediol (20). Preferably, it is 0.05 mol% or more, more preferably 0.1 mol% or more, and particularly preferably 0.5 mol% or more.

<2.4.2.3 Solvent>
The reaction can also use a solvent. Although the solvent used is not particularly limited, aromatic hydrocarbons such as benzene, toluene, xylene and the like; aliphatic hydrocarbons such as hexane, heptane, dodecane and the like; methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol and the like Alcohols; Halogenated solvents such as chloroform, dichloromethane, dichloroethane, etc .; Ethers such as tetrahydrofuran, dioxane, t-butyl methyl ether, cyclopentyl methyl ether etc .; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, anone etc. Acetonitrile, Nitriles such as butyronitrile; ester compounds such as ethyl acetate, butyl acetate and methyl formate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide; N, N ' Ureas such as dimethylimidazolidinone; water and mixtures of these solvents. Among these, the miscibility of aromatic hydrocarbons, aliphatic hydrocarbons and acids is preferred, and an aromatic which shows no nucleophilicity to (meth) acrylic acid halide and is stable in the reaction and post-treatment steps Group hydrocarbons, halogen solvents, ethers, and ketones are more desirable.

  If the amount of the solvent used is too large, productivity decreases and the load at the time of purification also increases. Therefore, the amount of the solvent is usually 20 volumes or less, preferably 15 volumes or less, with respect to oligofluorenediol (20) More preferably, it is 10 volumes or less, particularly preferably 8 volumes or less. If the amount of the solvent used is too small, the stirring becomes difficult, and therefore, the base is usually at least 1 volume of the starting material oligofluorenzole (20). Preferably, it is 2 volumes or more, more preferably 3 volumes or more, particularly preferably 4 volumes or more.

<2.4.2.4 Reaction format>
When the step (iii-2) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.
In the case of the batch system, the method of charging the reaction agent into the reactor can be adopted without particular limitation.

<2.4.2.5 Reaction conditions>
The reaction temperature is not limited as long as the reaction is not inhibited, but a range of 40 to 140 ° C. is preferable. If the reaction temperature is lower than 40 ° C., problems such as an increase in reaction time may occur. If the reaction temperature is higher than 140 ° C., problems such as distillation of (meth) acrylic anhydride and polymerization may occur. Can occur.
As described above, (meth) acrylic anhydride and oligofluorenediol, catalyzed transesterification to form oligofluorinated (meth) acrylate. The order of addition of these compounds is not particularly limited.

<2.4.2.6 Separation and purification of target product>
After completion of the reaction, the target product oligofluor orange (meth) acrylate is a target product oligofluor oligofluorene (Meta) by adopting a method of concentrating a solvent or a method of adding a target poor solvent. ) It can be isolated by a method of precipitating acrylate.

In addition, after completion of the reaction, water and a solvent in which the desired product oligofluorene (meth) acrylate is soluble may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding an antisolvent.
The solvent which can be used in the extraction is not particularly limited as long as it can dissolve the objective oligofluorene (meth) acrylate, and there is no particular limitation, but an aromatic hydrocarbon compound such as toluene or xylene, dichloromethane, One or two or more kinds of solvents such as halogen solvents such as chloroform are suitably used.

  The oligofluorene (meth) acrylate obtained here can be used as it is as a component of the oligofluorene (meth) acrylate composition, etc., but may be used after purification. As a purification method, a usual purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be adopted without limitation. It is also possible to dissolve oligofluorene (meth) acrylate in a suitable solvent and treat with activated carbon. The solvents that can be used here are the same as the solvents that can be used in the extraction.

<2.4.3 Process C: Process using (meth) acrylic acid>
The synthesis method of (meth) acrylic acid ester by transesterification with (meth) acrylic acid is well known, and its synthesis method is well known, and in JP-A 6-234699, acrylic acid and alcohol in the presence of paratoluenesulfonic acid catalyst It transesterifies to produce acrylic acid ester.
The oligofluorened orange (meth) acrylate represented by General formula (1) is manufactured from oligofluorenedol (20) and methacrylic acid (VI-4) according to the following process.

Wherein, R ¹ to R ⁹ is R ¹ to R ⁹ as defined in the formula (1). Each R ⁱ independently represents a hydrogen atom or a methyl group.

<2.4.3.1 (Meth) acrylic acids>
The (meth) acrylic acids in the step (iii-3) are unsaturated esters represented by the following general formula (VI-4).

Wherein, R ^v represents a hydrogen atom or an organic substituent having 1 to 10 carbon atoms, R ⁱ each independently represent a hydrogen atom or a methyl group.
As for R ^v , smaller ones are industrially inexpensive and easily purified by distillation, and have high reactivity, so acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate Or phenyl methacrylate is particularly preferred. Although two or more different (meth) acrylic acids (VI-4) may be used, it is preferable to use one (meth) acrylic acid (VI-4) in view of the ease of purification.

<2.4.3.2 Catalyst>
The reaction of (meth) acrylic acids with an alcohol can be carried out without using a catalyst, but it is usually preferred to use a catalyst. As the catalyst, those used in conventional esterification reactions can be used. Examples include acidic catalysts such as sulfuric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, strongly acidic cation exchange resins and the like.

  The use amount of the acidic catalyst is not particularly limited, but generally, the upper limit value of the acidic catalyst is 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less, with respect to oligofluorenediol (20). Preferably it is 3 mol% or less. If the amount of the acidic catalyst used is too small, the reaction may not proceed. Therefore, the lower limit of the catalyst is usually 0.01 mol% or more based on the starting material oligofluorenedole (20). Preferably, it is 0.05 mol% or more, more preferably 0.1 mol% or more, and particularly preferably 0.5 mol% or more.

<2.4.3.3 Solvent>
A solvent can also be used for the reaction. Although the solvent used is not particularly limited, aromatic hydrocarbons such as benzene, toluene, xylene and the like; aliphatic hydrocarbons such as hexane, heptane, dodecane and the like; methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol and the like Alcohols; Halogenated solvents such as chloroform, dichloromethane, dichloroethane, etc .; Ethers such as tetrahydrofuran, dioxane, t-butyl methyl ether, cyclopentyl methyl ether etc .; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, anone etc. Acetonitrile, Nitriles such as butyronitrile; ester compounds such as ethyl acetate, butyl acetate and methyl formate; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide; N, N ' Ureas such as dimethylimidazolidinone; water and mixtures of these solvents. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and mixtures of these solvents are preferable, and in this method, the reaction is usually carried out while removing by-produced water from the system. Since transesterification is an equilibrium reaction, the reaction can be cut off by removing water by-produced in the system, so that it can azeotrope with water and can remove water generated by the azeotrope. Toluene is more preferred.

  If the amount of the solvent used is too large, productivity decreases and the load at the time of purification also increases. Therefore, the amount of the solvent is usually 20 volumes or less, preferably 15 volumes or less, with respect to oligofluorenediol (20) More preferably, it is 10 volumes or less, particularly preferably 8 volumes or less. If the amount of the solvent used is too small, the stirring becomes difficult, and therefore, the base is usually at least 1 volume of the starting material oligofluorenzole (20). Preferably, it is 2 volumes or more, more preferably 3 volumes or more, particularly preferably 4 volumes or more.

<2.4.3.4 Reaction format>
When the step (iii-3) is carried out, the type of reaction may be a batch type reaction, a flow type reaction or a combination thereof, and the type can be adopted without particular limitation.
In the case of the batch system, the method of charging the reaction agent into the reactor can be adopted without particular limitation.

<2.4.3.5 Reaction conditions>
The reaction temperature is not limited as long as the reaction is not inhibited, but is usually 100 ° C to 140 ° C, preferably 110 ° C to 130 ° C, and more preferably 105 ° C to 120 ° C. In order to remove water by distillation, the reaction temperature is preferably higher than the temperature at which the water boils or azeotropes.
As described above, transfluorination reaction of (meth) acrylic acids with oligofluorenediol produces oligofluorinated (meth) acrylate. The order of addition of these compounds is not particularly limited, but in the usual range, firstly, oligofluorenediol is dissolved or suspended in the reaction solvent, and the acidic catalyst, (meth) acrylic acid is added while paying attention to the temperature of the mixture. .

<2.4.3.6 Separation and purification of target product>
After completion of the reaction, the target product oligofluor orange (meth) acrylate is a target product oligofluor oligofluorene (Meta) by adopting a method of concentrating a solvent or a method of adding a target poor solvent. ) It can be isolated by a method of precipitating acrylate.

In addition, after completion of the reaction, water and a solvent in which the desired product oligofluorene (meth) acrylate is soluble may be added to the reaction solution for extraction. The target substance extracted by the solvent can be isolated by a method of concentrating the solvent or a method of adding an antisolvent.
The solvent which can be used in the extraction is not particularly limited as long as it can dissolve the objective oligofluorene (meth) acrylate, and there is no particular limitation, but an aromatic hydrocarbon compound such as toluene or xylene, dichloromethane, One or two such as halogen solvents such as chloroform
More than species are preferably used.

  The oligofluorene (meth) acrylate obtained here can be used as it is as a component of the oligofluorene (meth) acrylate composition, etc., but may be used after purification. As a purification method, a usual purification method, for example, recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be adopted without limitation. It is also possible to dissolve oligofluorene (meth) acrylate in a suitable solvent and treat with activated carbon. The solvents that can be used here are the same as the solvents that can be used in the extraction.

<3 Oligofluor Orange (Meth) Acrylate Composition>
The oligofluorene (meth) acrylate composition of the present invention comprises oligofluorene (meth) acrylate and a compound having a carbon-carbon double bond. Thus, the oligofluorene (meth) acrylate composition of the present invention is desired to have heat resistance and optical properties by containing not only oligofluorene (meth) acrylate but a compound having a carbon-carbon double bond. There is a tendency to be able to easily adjust to

In addition, as oligofluorene (meth) acrylate, the thing as described in <1 oligofluorene (meth) acrylate> can be used.
<3.1 Compound Having Carbon-Carbon Double Bond>
The compound having a carbon-carbon double bond contained in the oligofluorene (meth) acrylate composition of the present invention is a compound having one or more carbon-carbon double bonds.

Examples of the carbon-carbon double bond include an alkenyl group such as a vinyl group and an allyl group, a (meth) acryloyl group and the like.
In the compound having a carbon-carbon double bond, the number of carbon-carbon double bonds may be one or more. For example, a compound having a carbon-carbon double bond may be composed of a monofunctional compound, and a compound having a monofunctional compound as a main component and having two or more carbon-carbon double bonds (polyfunctional compound ) May be included.

The compound having a carbon-carbon double bond may be a chain compound or may be a compound having a cyclic or cyclic skeleton.
Specific examples of the compound having a carbon-carbon double bond can be roughly classified into (meth) acrylic compounds and non- (meth) acrylic compounds. Although it does not specifically limit as a (meth) acrylic-type compound, For example, it can be divided roughly into a monofunctional (meth) acrylic-type compound and a polyfunctional (meth) acrylic-type compound.

<3.1.1 Monofunctional (Meth) Acrylic Compound>
Specific examples of monofunctional (meth) acrylic compounds include (meth) acrylic acid alkyls such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; (meth) acrylic acid (Meth) acrylic acid cycloalkyl such as cyclohexyl; (meth) acrylic acid polycyclic cycloalkyl such as bornyl (meth) acrylate and isobornyl (meth) acrylate; aryl (meth) acrylic acid such as phenyl (meth) acrylic acid; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Which (poly) oxyalkylene glycol mono (meth) acrylates; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetra Haloalkyl (meth) acrylates such as fluoropropyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; aminoalkyl such as N, N-dimethylaminoethyl acrylate (Meth) acrylates; (meth) acrylic acid esters such as glycidyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates; (meth) acrylic acids; (meth) acrylics Amide; N, N- dimethyl (meth) acrylamide such as N- substituted (meth) acrylamide; (meth) acrylamides such as N- methylol (meth) acrylamide. The monofunctional (meth) acrylic compounds may be used alone or in combination of two or more.
Among these, preferred (mono) functional (meth) acrylic compounds include (meth) acrylic acid alkyl esters. In particular, methyl (meth) acrylate and ethyl (meth) acrylate are more preferable because they are industrially available at low cost.

<3.1.2 Polyfunctional (Meth) acrylic Compound>
The multifunctional (meth) acrylic compounds are divided into difunctional (meth) acrylates and trifunctional or higher (meth) acrylates.

<3.1.2.1 Difunctional (meth) acrylic Compound>
Examples of difunctional (meth) acrylic compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neo Alkylene glycol di (meth) acrylates such as pentyl glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyoxyalkylene glycol di (meth) acrylates such as polytetramethylene glycol di (meth) acrylate; di (meth) acrylate of bisphenol A; glycerin di (meth) a Di (meth) acrylates of triols such as triacrylates, trimethylolpropane di (meth) acrylates, tris (hydroxyethy (le) isocyanurate di (meth) acrylates; di (meth) acrylates of tetraols such as pentaerythritol di (meth) acrylates Acrylate; bridged cyclic (meth) acrylates such as tricyclodecanedimethanol di (meth) acrylate; and the like.

<3.1.2.2 (Meth) acrylic Compound with Trifunctional or Higher>
Examples of trifunctional (meth) acrylic compounds include glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. Polyfunctional (meth) acrylates such as polyols tri to hexa (meth) acrylates such as meta) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate And so on.

The polyfunctional (meth) acrylic compounds may be used alone or in combination of two or more.
As the (meth) acrylic compound contained in the oligofluor orange (meth) acrylate composition of the present invention, a monofunctional (meth) acrylic compound and a multifunctional (meth) acrylic compound are mixed in any ratio. Can be used. Here, in order to obtain a film or sheet having flexibility, it is desirable to make the ratio of the monofunctional (meth) acrylic compound a majority. When a high hardness such as a hard coat is required, it is desirable to make the proportion of the polyfunctional (meth) acrylic compound a majority.

<3.1.3 Non- (meth) acrylic Compound>
Specific examples of the non- (meth) acrylic compounds include chain olefins such as ethylene, propylene, 1-butene, butadiene and isoprene; cyclic olefins such as norbornene, pinene, cyclopentadiene, cyclopentadiene and dicyclopentadiene; styrene Styrenic compounds such as α-methylstyrene, vinyltoluene, divinylbenzene and vinylnaphthalene; vinyl ester compounds such as vinyl acetate; nitrogen-containing compounds such as vinylpyrrolidone and triallylisocyanurate; halogens such as vinyl chloride and chloroprene Vinyl chloride; vinyl cyanide compounds such as (meth) acrylonitrile; alkyl vinyl ethers such as methyl vinyl ether; (anhydride) maleic acid, fumaric acid, itaconic acid, N-phenylmaleimide, 1,3 Phenylene bismaleimide, 1,4-phenylene bismaleimide, unsaturated carboxylic acid-based compounds such as 4,4'-diphenylmethane bismaleimide; and the like. These non- (meth) acrylic compounds may be used alone or in combination of two or more.

As a compound having a carbon-carbon double bond contained in the oligofluorene (meth) acrylate composition of the present invention, a homogeneous (meth) acrylate resin composition having reactivity close to that of oligofluorene (meth) acrylate and Preferred are (meth) acrylic compounds that can be expected to be obtained. Therefore, the compound having a carbon-carbon double bond may be composed of a (meth) acrylic acid compound alone, and the (meth) acrylic acid compound and the non- (meth) acrylic compound may be in any ratio. It may be mixed.
50 mol% or more is preferable, as for the ratio of the (meth) acrylic-type compound with respect to the whole compound which has a carbon-carbon double bond, 70 mol% or more is more preferable, and 80 mol% or more is more preferable.

<3.2 Other inclusions>
The oligofluorened orange (meth) acrylate composition of the present invention can be appropriately selected from polymerization initiators, catalysts (polymerization catalysts), emulsifiers, dispersants, chain transfer agents (thiols etc.), solvents etc. according to the polymerization method described later. May contain the components of

<3.2.1 Polymerization initiator>
A polymerization initiator may be contained in the oligofluorene (meth) acrylate composition of the present invention. When it is not contained, it may be added later before polymerization. Examples of the polymerization initiator (radical polymerization initiator) include a photopolymerization initiator and a thermal polymerization initiator. In general, a thermal polymerization initiator can be suitably used in general radical polymerization. As thermal polymerization initiators, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; dialkanoyl peroxides such as lauroyl peroxide; benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide and the like Diaroyl peroxide; peroxy esters such as percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxy octoate, t-butyl peroxy benzoate, etc. ketone peroxides, peroxy carbonates, peroxy carbonates Organic peroxides such as oxyketals; 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyl) Ronitrile), 2,2'-azobi Azonitrile compounds such as di (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide Azoamide compounds such as: 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc .; Azoalkane compounds such as 2'-azobis (2,4,4-trimethylpentane), 4,4'-azobis (4-cyanopentanoic acid); oxime frameworks such as 2,2'-azobis (2-methylpropionamidoxime) The thermal polymerization initiator may be used alone or in combination of two or more.

The proportion of the polymerization initiator is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, based on 100 parts by mass of the total of oligofluorene (meth) acrylate and the compound having a carbon-carbon double bond. More preferably, it is 0.2 parts by mass or more. On the other hand, the amount is usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

<3.2.2 Solvent>
A solvent may be contained in the oligofluorene (meth) acrylate composition of the present invention. When it is not contained, it may be added later before polymerization.
As the solvent (or dispersion medium), for example, alcohols such as ethanol, propanol, isopropanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as hexane, pentane and heptane; Alicyclic hydrocarbons such as pentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and chloroform; linear ethers such as dimethyl ether and diethyl ether; dioxane, tetrahydrofuran and the like Cyclic ethers of: methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate etc .; acetone, ethyl methyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone; methyl cellosolve, ethyl se Cellosolves such as Solve, butyl cellosolve; Carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether Glycol ether esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; N, N-dimethylformamide, N, N-dimethylacetamide etc., sulfoxides (amides such as dimethyl sulfoxide), acetonitrile, benzonitrile etc. Nitriles, organic solvents such as N-methyl pyrrolidone, etc. The solvents may be used alone or in combination. Can be used as a medium. Also, depending on the polymerization method (emulsion polymerization, suspension polymerization, etc.), it can also be polymerized in the presence of water.
The mass ratio of the oligofluorene (meth) acrylate and the compound having a carbon-carbon double bond to the total mass of the solvent (or dispersion medium) is, for example, preferably 0.01 to 90% by mass, and 0.05 to 70%. % By mass is more preferable, 0.1 to 50% by mass is further preferable, and 0.5 to 30% by mass is particularly preferable.

<3.3 Content of Compound Having Oligofluorene (Meth) Acrylate and Carbon-Carbon Double Bond>
The content ratio of the oligofluorene (meth) acrylate contained in the oligofluorene (meth) acrylate composition of the present invention is not particularly limited, but from the viewpoint of improving the refractive index and the photoelastic coefficient, The content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and still more preferably 30% by mass or more. It is particularly preferable that the content is 40% by mass or more.

  On the other hand, the content ratio of the compound having a monofunctional carbon-carbon double bond contained in the oligofluorene (meth) acrylate composition is not particularly limited, but from the viewpoint of adjustment of flexibility and optical properties, The content is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and further preferably 15% by mass or more based on the total mass of the composition. Still more preferably, it is particularly preferably 20% by mass or more, and from the viewpoint of reducing the heat resistance, it is preferably 90% by mass or less, more preferably 70% by mass or less, and 50% by mass It is further preferable that the content is less than or equal to%.

In addition, multifunctional carbon-contained in an oligofluorene (meth) acrylate composition
The content ratio of the compound having a carbon double bond is not particularly limited, but from the viewpoint of improving the glass transition temperature and hardness, the content is preferably 1% by mass or more based on the total mass of the composition, and 5% % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, and the resin tends to be brittle From the viewpoint of that, the content is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less.

  In addition, as oligo oligo orange (meth) acrylate composition which concerns on another aspect, using oligo oligo orange (meth) acrylate and what contains the polymerization initiator as described in <3.2.1 polymerization initiator> is used. It is also good. In this case, the compound may or may not contain a compound having a carbon-carbon double bond.

<4 (Meth) Acrylate Resin Composition>
The (meth) acrylate resin composition of the present invention consists of or contains a polymer obtained by polymerizing an oligofluorene (meth) acrylate or an oligofluorene (meth) acrylate composition.
When the oligofluorene (meth) acrylate composition is used, the polymer can be, for example, a copolymer obtained from oligofluorene (meth) acrylate and a compound having a polymerizable unsaturated bond.

The (meth) acrylate resin composition may be made of a polymer. The polymer may also contain the polymer, a polymerization initiator used in polymerization, a catalyst, an emulsifier, a dispersant, a chain transfer agent, and the like.
Hereinafter, the manufacturing method of the (meth) acrylate resin composition using an oligofluor orange (meth) acrylate composition is explained in full detail. In addition, when manufacturing (meth) acrylate using oligofluor orange (meth) acrylate, for example, oligofluor orange (meth) using the polymerization initiator as described in <3.2.1 polymerization initiator> The polymerization may be carried out in the same manner as the acrylate composition.

<4.1 Polymerization method of (meth) acrylate>
<4.1.1 Polymerization method>
The (meth) acrylate resin composition of the present invention is applied, for example, by applying the above-mentioned oligofluorene (meth) acrylate composition on a substrate to form a coating and then irradiating active energy rays, or heating Can be obtained by polymerization. Both irradiation and heating of active energy rays may be performed for curing.

<4.1.1.1 Application method>
As a method of applying the oligofull orange (meth) acrylate composition, for example, coating by a bar coater, an applicator, a die coater, a spin coater, a spray coater, a spray coater, a curtain coater, a roll coater etc., coating by screen printing etc., dipping etc. Application is mentioned.
The application amount of the oligofluor orange (meth) acrylate composition of the present invention on a substrate is not particularly limited, and can be appropriately adjusted according to the purpose, and after polymerization treatment by active energy ray irradiation after coating drying The amount of the film thickness of the obtained coating film is preferably 1 to 500 μm, and more preferably 5 to 300 μm.

<4.1.1.2 a: polymerization initiation method (active energy ray)>
As the active energy ray used for polymerization, an electron beam or light in the ultraviolet to infrared wavelength range is preferable. As the light source, for example, an ultra-high pressure mercury light source or metal halide light source can be used if the active energy ray is ultraviolet light, a metal halide light source or halogen light source can be used for visible light, and a halogen light source can be used for infrared light. A light source such as an LED can be used. The irradiation amount of the active energy ray is appropriately set according to the type of the light source, the film thickness of the coating film, and the like.

The irradiation dose of the active energy ray is appropriately set according to the type of light source, the film thickness of the coating film, etc. Preferably, the ethylenic non-conjugated compound having oligofluorene (meth) acrylate and a carbon-carbon double bond is preferably used. The reaction rate of the total amount of saturated groups can be appropriately set so as to be 80% or more, more preferably 90% or more. The reaction rate is calculated from the change in the absorption peak intensity of the ethylenically unsaturated group before and after the reaction from the infrared absorption spectrum.
After polymerization by irradiation with active energy rays, if necessary, heat treatment or annealing may be performed to further advance polymerization. It is preferable that the heating temperature in that case exists in the range of 80-200 degreeC. The heating time is preferably in the range of 10 to 60 minutes.

<4.1.1.2 b: polymerization initiation method (heating)>
When heat treatment is carried out for the polymerization of the oligofluor orange (meth) acrylate composition of the present invention, the heating temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 150 ° C. If the heating temperature is lower than 80 ° C., the heating time needs to be extended, which tends to be uneconomical, and if the heating temperature is higher than 200 ° C., energy costs are incurred and heating temperature rising time and temperature lowering time are required. And tend to be less economical.

<4.2 Physical Properties of (Meth) Acrylate Resin Composition>
<4.2.1 refractive index>
The (meth) acrylate resin composition of the present invention obtained by the above method preferably has a refractive index of 1.55 or more. Furthermore, it is more preferably 1.56 or more, still more preferably 1.57 or more, particularly preferably 1.58 or more, and most preferably 1.60 or more.

  When the refractive index of the (meth) acrylate resin composition is smaller than 1.55, the central part of the optical lens or the like may be thick, and the lightness characteristic of plastic may be impaired. The refractive index of the (meth) acrylate resin composition of the present invention is preferably 1.68 or less, more preferably 1.65 or less. When the refractive index of the (meth) acrylate resin composition is greater than 1.68, the transparency may be reduced due to surface reflection of light and scattering loss.

<4.2.2 Photoelastic coefficient>
The photoelastic coefficient of the (meth) acrylate resin composition of the present invention is preferably 45 × 10 ⁻¹² Pa ⁻¹ or less. More preferably, it is 40 × 10 ⁻¹² Pa ⁻¹ or less, particularly preferably 35 × 10 ⁻¹² Pa ⁻¹ or less, and usually 5 × 10 ⁻¹² Pa ⁻¹ or more. When the photoelastic coefficient is high, the birefringence of the material changes in the part where stress is generated when used for a large-sized molded product or when the molded product is bent, and the uniformity of optical physical properties may be impaired. There is sex.

<4.2.3 Glass transition temperature>
The glass transition temperature of the (meth) acrylate resin composition of the present invention is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher, and 120 ° C. or higher. Is particularly preferable, and 170 ° C. or less is preferable, 160 ° C. or less is more preferable, and 150 ° C. or less is more preferable. If it is less than this range, the optical physical properties may change from the designed values in the use environment, and the heat resistance which is practically necessary may not be satisfied. Moreover, when it exceeds this range, the melt-processability of a resin composition will fall, and a molded object with a favorable external appearance or a high dimensional accuracy may not be obtained. Furthermore, since the heat resistance is too high and the mechanical strength is lowered, the resin composition may become brittle and the processability and the handleability of the molded article may be deteriorated.

<4.3 Optical member>
The (meth) acrylate resin composition of the present invention described in detail above can be applied to various optical members since it has such properties as high refractive index and high heat resistance. As an optical member, for example, a lens, a filter, a diffraction grating, a prism, a light guide, a cover glass for a display device, a photo sensor, a photo switch, an LED, a light emitting element, an optical waveguide, a light splitter, an optical fiber adhesive, a display element Substrates, substrates for color filters, substrates for touch panels, display backlights, light guide plates, antireflection films, and the like. Moreover, it can also use as a hard-coat layer of these various optical members. For example, an optical overcoat, a hard coating agent, a display protective film, etc. can be mentioned.

4.3.1. Lens>
Among these, in particular, they can be preferably applied to plastic lenses because of their high refractive index and low photoelastic coefficient in the (meth) acrylate resin composition. Examples of the lens include an imaging lens for a camera (vehicle-mounted camera, digital camera, camera for PC, camera for mobile phone, surveillance camera, etc.), a spectacle lens, a light beam condensing lens, a light diffusing lens, and the like.

  Furthermore, in the lens using the (meth) acrylate resin composition of the present invention, if necessary, such as reflection prevention, high hardness addition, wear resistance improvement, chemical resistance improvement, antifogging addition, or fashion property addition, etc. In order to improve, physical or chemical treatments such as surface polishing, antistatic treatment, hard coating treatment, non-reflective coating treatment, dyeing treatment and the like can be applied.

  Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited by the following Examples as long as the gist thereof is not exceeded. The quality evaluation of the oligofluorene monomer of the present invention, and the characteristic evaluation of the resin composition and the film were conducted by the following methods. In addition, the characteristic evaluation method is not limited to the following method, and those skilled in the art can appropriately select it.

The abbreviations and the like of the compounds used in the following synthesis examples and examples are as follows.
THF: tetrahydrofuran (stabilizer-free, WAKO)
A-BPEF: 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Shin-Nakamura Kogyo Co., Ltd.)
PA-4A: pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
tBA: tert-butyl methacrylate (made by Tokyo Chemical Industry Co., Ltd.)

(1) Refractive index of the resin composition The refractive index of the resin composition is a reflection of a wavelength of 400 to 1000 nm, using a film obtained by the spin coating method as a measurement sample with a spectroscope thickness meter (FE-3000 manufactured by Otsuka Electronics) The rate was measured and the refractive index for the wavelength of 587.0 nm was calculated using the Fresnel equation.

(2) Photoelastic coefficient of resin composition The photoelastic coefficient of the resin composition was measured using a sample cut out from a 0.5 mm thick film to a width of 5 mm and a length of 20 mm as a measurement sample.
The measurement is performed using a device combining a birefringence measurement device consisting of a He-Ne laser, a polarizer, a compensator, an analyzer, and a light detector and a vibrating visco-elasticity measurement device ("DVE-3" manufactured by Rheology Co., Ltd.) I went. (For details, refer to Journal of The Rheological Society of Japan, Vol. 19, p 93-97 (1991).)

  The cut-out sample was fixed to a viscoelasticity measuring apparatus, and storage elastic modulus E 'was measured at a frequency of 96 Hz at room temperature of 25 ° C. At the same time, the emitted laser light is passed through the polarizer, sample, compensator, and analyzer in this order, picked up by the light detector (photodiode), and passed through the lock-in amplifier for the waveform of angular frequency ω or 2ω with respect to its amplitude and distortion The phase difference was determined, and the distortion optical coefficient O 'was determined. At this time, the directions of the polarizer and the analyzer were orthogonal to each other, and each was adjusted to form an angle of π / 4 with respect to the extension direction of the sample. The photoelastic coefficient C was determined from the following equation using the storage elastic modulus E 'and the strain optical coefficient O'.

C = O '/ E'
(3) Melting point measurement of oligofluor orange (meth) acrylate A small amount of oligofluor orange (meth) acrylate was packed in a capillary, and measurement was performed using a melting point measuring instrument SMP3 (manufactured by Stuart Scientific).
[Example of synthesis of monomer]
Synthesis Example 1

Synthesis Example 1A Synthesis of Bis (fluoren-9-yl) methane (Compound 1A) Fluorene (120 g, 722 mmol) and N, N-dimethylformamide (480 mL) were put in a 1 L four-necked flask, and after nitrogen substitution, 5 ° C. It cooled below. Sodium ethoxide (24.6 g, 361 mmol) was added and paraformaldehyde (8.7 g, 289 mmol) was added in small portions so as not to exceed 10 ° C. and stirred. After 2 hours, 1 mol / L hydrochloric acid (440 ml) was added dropwise to stop the reaction. The obtained suspension was suction filtered and washed with sprinkled water (240 mL). After that, the obtained crude product was dispersed in demineralized water (240 mL) and stirred for 1 hour. The suspension was suction filtered and then sprinkled and washed with demineralized water (120 mL). The resulting crude product was dispersed in toluene (480 mL) and then dehydrated under heating-refluxing conditions using a Dean-Stark apparatus. After returning to room temperature (20 ° C.), suction filtration and vacuum drying at 80 ° C. to constant weight give 84.0 g (yield) of bis (fluoren-9-yl) methane (compound 1A) as a white solid : 84.5%, HPLC purity: 94.0%) were obtained. The chemical shifts of ¹ H-NMR of Compound 1A are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.83 (d, J = 7.6 Hz, 4 H), 7.56 (dd, J1 = 7.6 Hz, J2 = 0.8 Hz, 4 H), 7.41 ( t, J = 7.3 Hz, 4 H), 7. 29 (dt, J1 = 7.3 Hz, J2 = 1.3 Hz, 4 H), 4.42 (t, J = 7.6 Hz, 2 H), 2.24 (D, J = 7.6 Hz, 2 H).

Synthesis Example 1B Synthesis of bis (9-hydroxymethylfluoren-9-yl) methane (Compound 1B) Bis (fluoren-9-yl) methane (100 g, 290 mmol) obtained in Synthesis Example 1A in a 500 mL four-necked flask Add N, N-dimethylformamide (400 mL),
After nitrogen substitution, paraformaldehyde (18.3 g, 610 mmol) was added. After cooling to 5 ° C. or less, sodium ethoxide (0.698 g, 13 mmol) was added and stirred so as not to exceed 10 ° C. After one and a half hours, 1 mol / L hydrochloric acid (32 mL) was added so as not to exceed 25 ° C. to stop the reaction. Further, water (300 mL) was added and stirred, and the obtained suspension was suction filtered and washed with sprinkled water (100 mL). The obtained crude product was dispersed in tetrahydrofuran (400 mL) and then heated under reflux for 1 hour. The temperature is returned to room temperature (20 ° C.), suction filtration is followed by vacuum drying at 80 ° C. to constant weight, and 108 g of a white solid (yield: 91%, HPLC purity: 99.1%). Thereafter, the white solid is dispersed in a mixture of toluene (800 mL) and water (200 mL), heated under reflux for 1 hour, filtered and dried, and then the obtained white solid is N, N-dimethylformamide ( The mixture was dispersed in 500 mL), warmed to a homogeneous solution, cooled to 40 ° C. or less, and slowly dropped into 0.03 mol / L hydrochloric acid (1500 mL). The obtained suspension was suction filtered, dispersed in demineralized water (200 mL) and stirred for 1 hour. The suspension was suction filtered and sprinkled with demineralized water (100 mL) for washing. The obtained product was dispersed in toluene (800 mL) and then subjected to azeotropic dehydration under heating to reflux. The temperature is returned to room temperature (20 ° C.), suction filtration is followed by vacuum drying at 100 ° C. to a constant weight to obtain 104 g (yield 87) of bis (9-hydroxymethylfluoren-9-yl) methane (compound 1B) as a white solid. %, HPLC purity: 99.8%). The contents of sodium and chlorine in the solid were each less than 10 ppm. The chemical shifts of ¹ H-NMR of compound 1B are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.12 (d, J = 7.3 Hz, 4 H), 7.01-6.93 (m, 8 H), 6.77 (dt, J1 = 7. 3 Hz, J2 = 1.0 Hz, 4 H), 4.97 (t, J = 4.6 Hz, 2 H), 3.31 (s, 2 H), 3.23 (d, J = 4.3 Hz, 4 H).
m. p. : 226 ° C
Synthesis Example 2

Synthesis Example 2A Synthesis of 1,2-bis (fluoren-9-yl) ethane (Compound 2A) A 100 mL four-necked flask is charged with fluorene (2.0 g, 12 mmol) and tetrahydrofuran (35 mL), and after substitution with nitrogen, ethanol -It cooled to -50 degrees C or less with a dry ice bath. A 1.6 mol / L n-butyllithium hexane solution (7.8 ml, 12.5 mmol) was added little by little so as not to exceed -40 ° C. and stirred. Thereafter, the temperature was raised to 10 ° C. and stirred for 1 hour, then 1,2-dibromoethane (0.55 ml, 6.4 mL) was added, and the mixture was further stirred for 2 hours. Thereafter, 1 mol / L hydrochloric acid (0.5 mL) is added dropwise, and the resulting suspension is suction filtered, washed with water and then dried under reduced pressure at 80 ° C. until constant weight to give 1,2-bis (white solid). 0.63 g (yield: 29.2%, HPLC purity: 98.0%) of fluoren-9-yl) ethane (compound 2A) was obtained. Further, the solvent of the filtrate was evaporated under reduced pressure, ethanol (25 mL) was added, and the mixture was stirred for 30 minutes. The suspension is suction filtered and vacuum dried to a constant weight at 80 ° C. to give 0.44 g (yield: 20) of 1,2-bis (fluoren-9-yl) ethane (compound 2A) as a white solid. .5%, HPLC purity: 84.0%) were obtained. The obtained white solids were combined to give 1.07 g (yield: 49.7%). The chemical shifts of ¹ H-NMR of compound 2A are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.75 (d, J = 7.6 Hz, 4 H), 7.37 (dt, J1 = 7.6 Hz, J2 = 0.5 Hz, 4 H), 7.27 7.34 (m, 8 H), 3.85 (s, 2 H), 1. 74 (t, J = 2.3 Hz, 4 H).

Synthesis Example 2B Synthesis of 1,2-bis (9-hydroxymethylfluoren-9-yl) ethane (Compound 2B) 1,2-bis (fluorene-9-) obtained in Synthesis Example 2A in a 1 L four-necked flask (E) (Compound 2A, 100 g, 278.9 mmol), paraformaldehyde (17.6 g, 585.8 mmol), N, N-dimethylformamide (400 mL), charged with nitrogen, and cooled to 10 ° C. or less. Sodium ethoxide (1.80 g, 27.9 mmol) was added and the temperature was raised to room temperature (20 ° C.) and stirred for 1 hour. After confirming the disappearance of the raw materials by HPLC, the reaction solution was dropped into 0.1 mol / L hydrochloric acid (440 mL) to stop the reaction. The obtained suspension was suction filtered and washed with sprinkled water (100 mL). Then, the obtained crude product was dispersed in N, N-dimethylformamide (300 mL) and stirred for 1 hour. This suspension was dropped into 0.005 mol / L hydrochloric acid (1000 mL), and after stirring for 30 minutes, suction filtration was performed. The obtained crude product was dispersed in demineralized water (500 mL) and stirred for 1 hour. The suspension was suction filtered and then sprinkled with demineralized water (200 mL) for washing. The obtained crude product was dispersed in toluene (500 mL) and then dehydrated under heating-refluxing conditions using a Dean-Stark apparatus. After returning to room temperature (20 ° C.), suction filtration and vacuum drying at 100 ° C. to constant weight give 1,2-bis (9-hydroxymethylfluoren-9-yl) ethane (compound 2B) as a white solid. ) (Yield: 96.3%, HPLC purity: 99.1%) were obtained. The chemical shifts of ¹ H-NMR of compound 2B are shown below.

¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.91 (d, J = 7.3 Hz, 4 H), 7.44 (dt, J1 = 7.6 Hz, J2 = 1.0 Hz, 4 H), 7. 35 (dt, J1 = 7.6 Hz, J2 = 1.0 Hz, 4 H), 7.18 (d, J = 7.3 Hz, 4 H), 4.79 (t, J = 5.3 Hz, 2 H), 3 18 (d, J = 5.3 Hz, 2 H), 1.40 (s, 4 H).
m. p. : 278 ° C

  <Example 1> Synthesis of 1,2-bis (9-acryloxymethylfluoren-9-yl) methane (compound 1C) using acrylic acid

Compound 1B (0.40 g, 1 mmol), acrylic acid (0.72 g, 10 mmol), p-toluenesulfonic acid monohydrate (19 mg, 0.1 mmol) are added to a 50 mL eggplant flask equipped with Dean Stark, and then an oil bath The temperature was set to 130 ° C., and reaction was performed under reflux conditions for 20 hours while distilling off toluene. During heating, acrylic acid (5.04 g, 70 mmol) was added as appropriate. The reaction solution was cooled to room temperature and washed successively twice with 10 mL of water and twice with 10 ml of saturated aqueous sodium bicarbonate solution. The solvent is distilled off with an evaporator, and the residue oil is purified by silica gel column chromatography to obtain 0.24 g of compound 1C as a white powder.
(Yield: 47%) was obtained. The chemical shifts of ¹ H-NMR of compound 1C are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.10-7.12 (m, 4 H), 7.03-7.07 (dt, 4 H, J = 1.3, 7.6 Hz), 6.92 -6.93 (m, 4H), 6.82-6.87 (dt, J = 1.3, 7.6 Hz), 6.34-6.39 (dd, 2H, J = 1.5, 17.4 Hz), 6.11-6.18 (dd, 2H, J = 10.4, 17.4 Hz), 5.85-5.88 (dd, 2H, J = 1.5, 10.4 Hz) , 4.02 (s, 4 H), 3.32 (s, 2 H)
m. p. : 103 ° C

Example 2 Synthesis of 1,2-bis (9-acryloxymethylfluoren-9-yl) methane (Compound 1C) Using Adjusted Acrylic Anhydride Acrylic acid (2.38 g in a 200 mL two-necked flask) 33 mmol) and toluene (60 ml) were added and ice cooled. Triethylamine (3.04 g, 30 mmol) was dropped here, and then acrylic acid chloride (2.72 g, 30 mmol) was dropped slowly so that the internal temperature was 10 ° C. or less, and an ammonium salt was precipitated. After stirring for 1 hour in the ice bath, the precipitated ammonium salt was separated by filtration to prepare an acrylic acid-toluene solution. P-Toluenesulfonic acid monohydrate (257 mg, 1.35 mmol), compound 1B (5.46 g, 13.5 mmol) and phenothiazine (5 mg) were added to the prepared acrylic anhydride-toluene solution, and the solution was added at 80 ° C. for 4 hours Heated and stirred. The reaction solution was cooled to room temperature and washed successively twice with 20 mL of water, once with 20 mL of saturated aqueous sodium bicarbonate solution and once with 10 mL of water. After distilling off the solvent using a rotary evaporator, methanol (30 mL) was added to the precipitated white solid and heated at 50 ° C. for 30 minutes to carry out a hot suspension wash. The reaction was stirred in an ice bath for 15 minutes and the slurry was filtered. The obtained white solid was dried under reduced pressure at 80 ° C. to obtain 5.77 g (yield: 83%) of compound 1C.

  <Example 3> Synthesis of 1,2-bis (9-acryloxymethylfluoren-9-yl) ethane (compound 2C) using acrylic acid

In a 50 mL four-necked flask, 1,2-bis (9-hydroxymethylfluoren-9-yl) ethane (compound 2B) (1.00 g, 2.34 mmol), toluene (5 mL), acrylic acid (0.55 g, 63 mmol), concentrated sulfuric acid (0.027 g, 0.26 mmol) was added, and heating was performed under reflux conditions for 10 hours using a Dean-Stark apparatus for dehydration. After cooling to room temperature (20 ° C.), 1 mol / L aqueous sodium carbonate solution (5 mL) and toluene (3 mL) were added to separate the layers. The product was extracted from the aqueous layer with toluene (5 mL × 3), and the organic layers were combined and washed with demineralized water (5 mL × 2) and saturated brine (5 mL). Magnesium sulfate was added and dried, and the desiccant was removed by filtration. After toluene was distilled off using a rotary evaporator, the residue was purified by a silica gel column to obtain 0.63 g of a compound 2C (yield: 51%, HPLC purity: 97.7%) as a white powder. The chemical shift of ¹ H-NMR of compound 2C is shown below.

¹ H-NMR (400 MHz, CDCl 3) δ 7.75 (m, 4 H), 7.39 (m,
4H), 7.29 (m, 4H), 7.13 (m, 4H), 6.14 (d, J = 15.9 Hz, 2 H), 5.86 (dd, J1 = 17.1 Hz, J2 = 10.3 Hz, 2 H), 5.65 (d, J = 10.4, 2 H), 4.00 (s, 4 H), 1. 44 (s, 4 H).
m. p. : 147 ° C

[Evaluation of refractive index]
<Examples 4, 5 and Comparative Example 1> Hardened film (thin film) on glass plate
Tetrahydrofuran was added thereto using fluo orange (meth) acrylate shown in Table 1 as a monomer to make a 2.5 mass% solution. Here, 5% by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Nippon Siber Hegner, Luna 200) as a polymerization initiator was added to the monomer and dissolved. The prepared solution was applied and dried on a glass substrate using a spin coater (manufactured by MIKASA) (rotational speed: 1000 rpm, time: 20 seconds) to form a thin film. Thereafter, using a high pressure mercury lamp (manufactured by Eye Graphics, Inc.), a cured film was produced by irradiating ultraviolet light with an illuminance of 100 mW / cm ² and an integrated light amount of 220 mJ / cm ² . Table 1 shows the measurement results of the refractive index of each cured film.

  From Table 1, the refractive index of the resin composition using the oligofluor orange (meth) acrylate of Example 1 and Example 2 is the same as that of the resin composition using the monofluor orange (meth) acrylate of Comparative Example 1 Was confirmed.

[Evaluation of photoelastic coefficient]
<Example 6, Comparative Examples 2 and 3> Resin composition having a thickness of 0.5 mm In the orange (meth) acrylate shown in Table 2, pentaerythritol tetraacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and tert-butyl methacrylate ( A 1: 1 mixed solution of monomers (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to prepare a solution adjusted at the ratio shown in Table 2. Here, 2% by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Nippon Siber Hegner, Luna 200) as a polymerization initiator was added and dissolved with respect to the total amount. This solution is poured into a mold formed of a silicone resin plate, and irradiated with ultraviolet light with an illuminance of 100 mW / cm ² and an integrated light quantity of 220 mJ / cm ² using a high pressure mercury lamp (manufactured by I-Graphics Co.) A thick resin composition test piece was obtained. Table 2 shows the measurement results of the photoelastic coefficient of each resin composition test piece.

  In general, a resin composition having an aromatic ring structure tends to exhibit a high photoelastic coefficient as compared to a resin composition having no aromatic ring structure. However, unlike Comparative Example 3 showing a high photoelastic coefficient, Example 6 showed a low photoelastic coefficient similar to Comparative Example 2 having no aromatic ring structure despite having an aromatic ring structure. That is, the resin composition obtained by using the oligofluorene (meth) acrylate of the present invention is as low as the resin composition having no aromatic ring structure while showing the refractive index derived from the aromatic ring structure. The photoelastic coefficient is shown.

Claims (7)

Characterized by being represented by the following general formula (1), oligo fluorene (meth) acrylate.

(Wherein, R ¹ and R ² each independently represent a direct bond or an optionally substituted carbon number of 1 to 1
An alkylene group of 0, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 6 to 10 carbon atoms,
Or an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, and an aralkylene group having 6 to 10 carbon atoms which may be substituted. Two or more of the groups are an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a group linked by a carbonyl group,
R ³ is a direct bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, or 6 to 10 carbon atoms which may be substituted An aralkylene group,
R ^{4 to} R ⁹ each independently represent a hydrogen atom, an alkyl group of 1 to 10 carbons which may be substituted, an aryl group of 4 to 10 carbons which may be substituted, or each of which may be substituted Acyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms which may be substituted, aryloxy group having 1 to 10 carbon atoms which may be substituted, 1 to 1 carbon atom which may be substituted 10
Acyloxy group, an optionally substituted amino group, an optionally substituted carbon number of 1 to 1
A vinyl group of 0, an ethynyl group having 1 to 10 carbon atoms which may be substituted, a silicon atom having a substituent, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group.
However, at least two adjacent groups among R ^{4 to} R ⁹ may be bonded to each other to form a ring.
Each R ⁱ independently represents a hydrogen atom or a methyl group.
n shows the integer value of 1-5. ) An oligofluorene (meth) acrylate composition comprising the oligofluorene (meth) acrylate according to claim 1 and a compound having a carbon-carbon double bond. Contain oligo fluorene (meth) acrylates is polymerized polymer of claim 1, characterized in (meth) acrylate resin composition. Oligo fluorene (meth) polymer obtained by polymerizing an acrylate composition according to claim 2
And (meth) acrylate resin composition characterized by containing. An optical member obtained by using the (meth) acrylate resin composition according to claim 3 or 4 . A lens obtained by using the (meth) acrylate resin composition according to claim 3 or 4 . An optical member comprising a hard coat layer composed of the (meth) acrylate resin composition according to claim 3 or 4 .