WO2011062052A1 - Fluorene compound, stabilizer containing the fluorene compound, and composition - Google Patents

Abstract

Disclosed are: a novel fluorene compound which is capable of providing an organic material such as a polymer with high processing stability, high heat resistance and long life without using a secondary antioxidant; a stabilizer which contains the fluorene compound; and a composition which contains an organic material and the compound. Specifically disclosed is a fluorene compound which is characterized by being represented by formula (I). (In the formula, Y₁ represents -C(=O)-O-, -C(=O)-NH- or the like; X₁-X₈ each represents a hydrogen atom or the like; a represents 0 or 1, provided that a represents 0 when b or d is 0; A represents a group represented by formula (A1) or (A2) (wherein G₁ and G₂ each represents a divalent organic group having 1-20 carbon atoms, or the like; b represents 0 or 1; c represents an integer of 1-3; d represents 0 or 1; Y₂ and Y₃ each represents a chemical single bond or the like; and X₉-X₂₁ each represents a hydrogen atom or the like).)

Description

Fluorene Compound, Stabilizer and Composition Containing the Fluorene Compound

The present invention is a novel fluorene compound capable of imparting high processing stability, heat resistance and long life to organic materials such as polymers without using a phosphorus-based anti-aging agent which is a secondary anti-aging agent, The present invention relates to a stabilizer containing a fluorene compound, and an organic material and a composition containing the fluorene compound.

Organic materials such as polymers are susceptible to deterioration as they are due to heat, oxygen, or shear force during processing. Then, in order to improve those processing stability and heat resistance, and to aim at lifetime improvement, it is generally performed to add various anti-aging agents.
As an antiaging agent, a phenolic anti-aging agent, an amine anti-aging agent, etc. are known as a primary anti-aging agent (refer nonpatent literature 1 grade | etc.,).
As representative examples of primary anti-aging agents, the following compounds may be mentioned as commercial products.

Moreover, a high synergistic effect is acquired by using together with these anti-aging agents, and the secondary anti-aging agent which provides high processing stability, heat resistance, and long life to organic materials, such as a polymer, is also used widely.
As a representative example of a secondary antiaging agent, the phosphorus antiaging agent shown below as a commercial item is mentioned.

However, many of these phosphorus-based antioxidants are highly toxic, and when a thermoplastic resin containing a phosphorus-based antioxidant is used for food storage containers, etc., the amount of the antioxidant shifts to food although in a small amount. There is a risk of Therefore, when using phosphorus-based anti-aging agents, usable chemical structures and addition amounts are specified in detail by industry groups such as the Polyolefin Hygiene Council, etc., and it was necessary to pay close attention when using them. .

In addition, due to the increase in safety awareness in recent years, even in applications where the risk of direct human intake is low, such as automobile bumpers, only the approved materials mentioned above are being used, and their use in practical use There are many limitations on.
Furthermore, due to the recent increase in awareness of natural protection and environmental protection, the release of phosphorus anti-aging agents into the environment is becoming a problem.

On the other hand, in terms of characteristics as well, phosphorus-based antioxidants have poor compatibility with thermoplastic resins such as polyolefins, and there are many cases in which bleeding occurs, and there is a problem that their use and addition amount are limited .
From such many problems, there is a strong demand for a stabilizer having an antiaging effect equal to or greater than that without using a secondary antiaging agent such as a phosphorus antiaging agent.

The present invention has been made in view of the above-described prior art, and its object is to provide high processing stability and heat resistance to organic materials such as polymers without using secondary anti-aging agents such as phosphorus-based anti-aging agents. It is an object of the present invention to provide a novel fluorene compound capable of imparting properties and long life, a stabilizer containing the fluorene compound, and a composition containing an organic material and the fluorene compound.

As a result of intensive studies to achieve the above object, the present inventors have found that high processing stability and organic materials such as polymers can be obtained without using a phosphorus-based anti-aging agent which is a secondary anti-aging agent. The inventors have found a stabilizer having a novel chemical structure that can impart heat resistance and long life, and have completed the present invention.

Thus, according to the present invention, the following fluorene compounds of (1) to (4), stabilizers of (5), and compositions of (6) to (9) are provided.
(1) A fluorene compound represented by the following formula (I).

{In the above formula (I), Y ₁ is a single chemical bond, -O-, -S-, -C (= O) -O-, -C (= O) -NR ^1- , -C ( = O)-, -S (= O)-, -O-C (= O)-, -NR ¹ -C (= O)-, -SO _2- , -O-C (= O) -O- Or-(CH ₂ ) _n -O-. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6.
Each of X ₁ to X ₈ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ² , -O-C (= O) -R ² , -C (= O) -OR ² , -O-C (= O) -OR ² , -N ( R ³ ) R ⁴ , —NR ³ —C (= O) —R ² , —C (= O) —N (R ³ ) R ⁴ or —O—C (= O) —N (R ³ ) It represents the R ^4. Here, R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent,
a is 0 or 1; However, when the following b or d is 0, a is also 0.
A is the following formula (A1)

[In the above formula (A1), G ₁ represents a C1-C20 (c + 1) -valent organic group which may have a substituent,
b is 0 or 1;
c is an integer of 1 to 3;
Y ₂ is a single chemical bond, —O—, —S—, —O—C () O) —, —C (= O) —O—, —O—C (= O) —O—, ^{-NR 5 -C (= O) -} , - C (= O) -NR 5 -, - O-C (= O) -NR 5 -, - NR 5 -C (= O) -O -, - NR ^5- C (= O) -NR ^6- , -O-NR ^5- , or -NR ⁵ -O-. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.
Each of X ₉ to X ₁₂ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ⁷ , -O-C (= O) -R ⁷ , -C (= O) -OR ⁷ , -O-C (= O) -OR ⁷ , -N ( R ⁸ ) R ⁹ , -NR ⁸ -C (= O) -R ⁷ , -C (= O) -N (R ⁸ ) R ⁹ or -O-C (= O) -N (R ⁸ ) R ⁹ is shown. Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. Or the formula (A2)

Wherein G ₂ represents a divalent organic group having 1 to 20 carbon atoms, in the above formula (A2),
Y ₃ has the same meaning as Y ₂ above;
d is 0 or 1;
Each of X ₁₃ to X ₂₁ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -CF ₃ , -OR ¹⁰ , -O-C (= O) -R ¹⁰ , -C (= O) -OR ¹⁰ , -O-C (= O) -OR ¹⁰ , -N (R ¹¹ ) R ¹² , -NR ¹¹ -C (= O) -R ¹⁰ , -C (= O) -N (R ¹¹ ) R ¹² or -O-C (= O) -N (R ¹¹ ) represents R ¹²
Here, R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. Represents a group represented by }

₍₂₎ Y is 1, _{Y 2} and _{Y 3} are each independently a chemical single bond, -C (= O) -O - , - C (= O) -NR 13 - ( ^{wherein, R 13} is , A hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent), or -C (= O)-, and X ₁ to X ₂₁ each independently represent hydrogen The fluorene compound according to (1), which is an alkyl group having 1 to 12 carbon atoms which may have an atom or a substituent.

(3) The formula (A) is a formula (A11)

(In the above formula (A11), X ₉ to X ₁₂ have the same meaning as described above.) Or a group represented by the formula (A21)

The fluorene compound according to (1) or (2), which is represented by a group represented by (in the above formula (A21), X ₁₃ to X ₂₁ have the same meaning as described above).
(4) In the above (1) or (2), wherein Y ₁ is —C (= O) —O— or —C (= O) —NR ¹ — (R ¹ represents the same meaning as described above) The fluorene compound as described.
(5) A stabilizer containing the fluorene compound according to any one of the above (1) to (4).
(6) Component (a): A composition containing an organic material and the fluorene compound according to any one of components (b): (1) to (4).
(7) The composition according to (6), wherein the component (a) is a synthetic organic material.
(8) The composition according to (6) or (7), wherein the component (a) is a synthetic rubber.
(9) The composition according to (6) or (7), wherein the component (a) is a polyolefin.
(10) The composition according to any one of (6) to (9), which further contains other additives in addition to the component (a) and the component (b).

According to the present invention, novel fluorenes capable of imparting high processing stability, heat resistance and long life to organic materials such as polymers without using a phosphorus-based anti-aging agent which is a secondary anti-aging agent Provided are a compound, a stabilizer containing the fluorene compound, and an organic material and a composition containing the fluorene compound.

Hereinafter, the present invention will be described in detail in terms of 1) a fluorene compound, 2) a stabilizer containing a fluorene compound, and 3) a composition.

1) Fluorene Compound The fluorene compound of the present invention is a compound represented by the following formula (I).

In formula (I), Y ₁ represents a single chemical bond, -O-, -S-, -C (= O) -O-, -C (= O) -NR ^1- , -C (= O )-, -S (= O)-, -O-C (= O)-, -NR ¹ -C (= O)-, -SO _2- , -O-C (= O) -O-, or ,-(CH ₂ ) _n -O-.

Here, R ¹ is a hydrogen atom; or methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n -An alkyl group having 1 to 6 carbon atoms such as hexyl group;
n represents an integer of 1 to 6;

Further, a is 0 or 1, but when b or d described later is 0, a is also 0.

Each of X ₁ to X ₈ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ² , -O-C (= O) -R ² , -C (= O) -OR ² , -O-C (= O) -OR ² , -N ( R ³ ) R ⁴ , —NR ³ —C (= O) —R ² , —C (= O) —N (R ³ ) R ⁴ or —O—C (= O) —N (R ³ ) It represents the R ^4.

Examples of the halogen atom of X ₁ to X ₈ include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 12 carbon atoms in the alkyl group having 1 to 12 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and t And -butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

As a substituent of the alkyl group having 1 to 12 carbon atoms, halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group And alkoxy groups such as groups; nitro groups; cyano groups and the like.
Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, propenyl group and isopropenyl group.

Each of R ² , R ³ and R ⁴ independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Examples of the organic group having 1 to 20 carbon atoms of R ² , R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n- An alkyl group having 1 to 20 carbon atoms, such as pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group;
A cycloalkyl group having a carbon number of 3 to 20, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group;
An aryl group having 6 to 20 carbon atoms, such as phenyl, naphthyl and anthranyl;
And having 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy and the like 20 alkoxy groups; and the like.

Examples of the substituent of the organic group include a halogen atom, an alkoxy group, a nitro group, a cyano group and the like when the organic group is an alkyl group, and a halogen when the organic group is a cycloalkyl group and an aryl group. An atom, an alkoxy group, a nitro group, a cyano group, an alkyl group and the like can be mentioned. In the case of an alkoxy group, a halogen atom, a nitro group, a cyano group and the like can be mentioned.

Among these, as X ₁ to X ₈ , in view of availability and the like, each independently, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent is preferable.

A represents a group represented by the following formula (A1) or (A2).

In formula (A1), G ₁ represents a C ₁ to C 20 (b + 1) -valent organic group which may have a substituent. Here, b is 0 or 1, and c is an integer of 1 to 3.

That is, when b is 1 and c is 1, G ₁ is a divalent organic group having 1 to 20 carbon atoms which may have a substituent, and when b is 1 and c is 2, G ₁ is a trivalent organic group having 1 to 20 carbon atoms which may have a substituent, and when b is 1 and c is 3, G ₁ is a carbon which may have a substituent It is a tetravalent organic group of the number 1 to 20.
Specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₁ include, but are not limited to, the following.

(In the above formula, p represents an integer of 1 to 20 and q represents an integer of 1 to 6)
Specific examples of the trivalent organic group having 1 to 20 carbon atoms of G ₁ include, but are not limited to:

(In the above formula, r represents an integer of 0 to 19.)
Specific examples of the tetravalent organic group having 1 to 20 carbon atoms of G ₁ include, but are not limited to, the following.

(In the above formula, s represents an integer of 0 to 14.)
Examples of the substituent of the organic group having 1 to 20 carbon atoms of G ₁ include halogen atoms such as fluorine atom and chlorine atom; alkyl groups such as methyl group and ethyl group; alkoxy group such as methoxy group and ethoxy group; It can be mentioned.

Y ₂ is a single chemical bond, —O—, —S—, —O—C () O) —, —C (= O) —O—, —O—C (= O) —O—, ^{-NR 5 -C (= O) -} , - C (= O) -NR 5 -, - O-C (= O) -NR 5 -, - NR 5 -C (= O) -O -, - NR ^5- C (= O) -NR ^6- , -O-NR ^5- , or -NR ⁵ -O-.

Here, R ⁵ and R ⁶ each independently represent a hydrogen atom, or the same organic group having 1 to 20 carbon atoms which may have a substituent of R ² , R ³ and R ⁴ , It represents an organic group having 1 to 20 carbon atoms which may have a substituent.

Each of X ₉ to X ₁₂ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ⁷ , -O-C (= O) -R ⁷ , -C (= O) -OR ⁷ , -O-C (= O) -OR ⁷ , -N ( R ⁸ ) R ⁹ , -NR ⁸ -C (= O) -R ⁷ , -C (= O) -N (R ⁸ ) R ⁹ or -O-C (= O) -N (R ⁸ ) R ⁹ is shown.
Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Specific examples of X ₉ to X ₁₂ as a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkenyl group having 2 to 12 carbon atoms which may have a substituent are exemplified. And specific examples of the X ₁ to X ₈ halogen atoms, alkyl groups having 1 to 12 carbon atoms which may have a substituent, and alkenyl groups having 2 to 12 carbon atoms which may have a substituent And the same as those listed as

In addition, specific examples of the organic group having 1 to 20 carbon atoms which may have a substituent of R ⁷ , R ⁸ and R ⁹ include the substituents of the aforementioned R ² , R ³ and R ⁴ Specific examples of the organic group having 1 to 20 carbon atoms which may be mentioned include the same ones as listed above.
Preferred specific examples of the group represented by formula (A) include groups represented by the following formula (A11).

(In the above formula (A11), X ₉ to X ₁₂ have the same meanings as described above.)

In formula (A2), G ₂ represents a divalent organic group having 1 to 20 carbon atoms.
Specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₂ include the same ones listed as specific examples of the divalent organic group having 1 to 20 carbon atoms of G ₁ .

Y ₃ has the same meaning as Y _2, and d is 0 or 1.
Each of X ₁₃ to X ₂₁ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -CF ₃ , -OR ¹⁰ , -O-C (= O) -R ¹⁰ , -C (= O) -OR ¹⁰ , -O-C (= O) -OR ¹⁰ , -N (R ¹¹ ) R ¹² , -NR ¹¹ -C (= O) -R ¹⁰ , -C (= O) -N (R ¹¹ ) R ¹² or -O-C (= O) -N (R ¹¹ ) represents R ¹²
Here, R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.

Specific examples of X ₁₃ to X ₂₁ as a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkenyl group having 2 to 12 carbon atoms which may have a substituent are exemplified. And specific examples of the X ₁ to X ₈ halogen atoms, alkyl groups having 1 to 12 carbon atoms which may have a substituent, and alkenyl groups having 2 to 12 carbon atoms which may have a substituent And the same as those listed as

In addition, specific examples of the organic group having 1 to 20 carbon atoms which may have a substituent of R ¹⁰ , R ¹¹ and R ¹² include the substituents of the aforementioned R ² , R ³ and R ⁴ Specific examples of the organic group having 1 to 20 carbon atoms which may be mentioned include the same ones as listed above.

As a preferable specific example of group represented by Formula (A), group represented by a following formula (A21) is mentioned.

(In the above formula (A21), X ₁₃ to X ₂₁ have the same meanings as described above.)

In the present invention, among the compounds represented by the formula (I), in the formula (I), Y ₁ , Y ₂ and Y ₃ are each independently a chemical single bond, —C (= O ) -O -, - C (= O) -NR 13 -, or, -C (= O) - ^{(wherein, R 13} is a hydrogen atom or a carbon atoms which may have a substituent group to 20 And X ₁ to X ₂₁ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a substituent,
Further preferred is a compound wherein Y ₁ is —C (= O) —O— or —C (= O) —NR ^1- (wherein R ¹ is as defined above), and the following formula (I-1): And (I-2)

The compounds represented by (in the above formulas (I-1) and (I-2), A ₁₁ and A ₂₁ have the same meaning as described above) are particularly preferable.

Particularly preferred specific examples of the above formula (A11) are as follows.

Particularly preferred specific examples of the above formula (A21) are as follows.

(Method for producing fluorene compound)
The fluorolene compound represented by the formula (I) is represented by the following formula (II)

It can obtain by making the compound (Hereafter, it abbreviates as a "compound represented by a formula: QL ₁ "), and the compound represented by a formula: AL ₂ .

Here, X ₁ to X ₈ have the same meaning as described above, and each independently has a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a substituent Alkenyl group having 2 to 12 carbon atoms, cyano, nitro, -OR ² , -O-C (= O) -R ² , -C (= O) -OR ² , -O-C ( = O) -OR ² , -N (R ³ ) R ⁴ , -NR ³ -C (= O) -R ² , -C (= O) -N (R ³ ) R ⁴ or -O-C (= O) -N (R ³ ) R ⁴ is represented. L ₁ and _{L 2} has the formula: a compound represented by _{Q-L 1} the formula: with the compound reaction represented by _{A-L 2,} wherein: generating a compound represented by _Q-Y 1 -A Represents a group that
Examples of combinations of Y ₁ , L ₁ and L ₂ are shown below.

As a method of reacting a compound represented by the formula: QL ₁ with a compound represented by the formula: A-L ₂ , -O-, -S-, -NR ¹ -C (= O)- Form various chemical bonds such as -C (= O) NR ^1- , -NR ¹ C (= O) NR ^1- , -O-C (= O)-, -C (= O) -O-, etc. (See, for example, the method of synthesizing an organic compound according to Sandler and Caro functional group [I], [II] Kamogawa Shoten, published in 1976).

The fluorene compound of the present invention typically comprises an ether bond (-O-), an ester bond (-C (= O) -O-), an amide bond (-C (= O) -NR ^1- ), and It can manufacture by combining suitably the known compound which has a desired structure combining the formation reaction of an acid chloride (-COCl) arbitrarily.

The formation of an ether bond (—O—) can be carried out, for example, by the method of 1) to 5) shown below.
1) A compound represented by the formula: Q-OM (Q represents the same meaning as described above, M represents an alkali metal, and the same applies below) and a compound represented by the formula: AX (A represents the same meaning as described above, X represents a halogen atom, which is mixed with the compound represented by the following) and condensed. This reaction is generally referred to as Williamson synthesis.
2) The compound represented by the formula: Q-OH and the compound represented by the formula: AX are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
3) A compound represented by the formula: QE (E represents an epoxy group) and a compound represented by the formula: A-OH are mixed in the presence of a base such as sodium hydroxide or potassium hydroxide And condense.
4) A compound represented by the formula: Q-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: A-OM in the presence of a base such as sodium hydroxide or potassium hydroxide Mix, add and react.
5) The compound represented by the formula: QX and the compound represented by the formula: A-OM are mixed and condensed in the presence of copper or cuprous chloride. This reaction is generally referred to as Ullmann condensation.

The formation of an ester bond and an amide bond can be performed, for example, as follows.
1) A compound represented by the formula: Q-COOH and a compound represented by the formula: A-OH or A-NH ₂ are dehydrated and condensed in the presence of a dehydration condensation agent described later.

As the dehydration condensation agent used here, N, N-dicyclohexylcarbodiimide (DCC), 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide (WSC), 1,1-carbonyldiimidazole (CDI), N, N-disuccinimidyl carbonate (DSC), Bop reagent (Aldrich, USA), 2- (1H-benzotriazol-1-yl) -1,1,3,3-tetramethyluronium hexafluorophos Fert (HBTU), 2- (1H-benzotriazol-1-yl) -1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU), bromotrispyrrolidinophosphonium hexafluorophosphate (PyBroP ( Trademark: Novabiochem, Germany), diphenyl phosphorus Azide (DPPA), phosphorus oxychloride, phosphorus trichloride, triphenylphosphine / N- bromosuccinimide, and the like.
The amount of the dehydrating condensing agent to be used is generally 1 to 3 mol, per 1 mol of the compound represented by the formula: Q-COOH.

In this case, it is preferable to make a reaction system coexist a base such as pyridine, 4- (dimethylamino) pyridine, triethylamine, diisopropylethylamine, diazabicyclo [5.4.0] undec-7-ene (DBU) and the like. These bases can be used alone or in combination of two or more.
The amount of the base to be used is generally 0.0001 to 1 mol, per 1 mol of the compound represented by the formula: Q-COOH.

2) By acting a halogenating agent on a compound represented by the formula: Q-COOH, an acid halide represented by the formula: Q-COX is obtained, and the acid halide and the formula: A-OH or A-NH ₂ Are reacted in the presence of a base.

The formation of the acid halide can be performed, for example, as follows.
(I) A compound represented by the formula: Q-COOH is reacted with phosphorus trihalide or phosphorus pentahalide.
(Ii) A thionyl halide is allowed to act on a compound represented by the formula: Q-COOH.
(Iii) A compound represented by the formula: Q-COOH is allowed to act as a halogenated oxalyl.
(Iv) Chlorine or bromine is allowed to act on a compound represented by the formula: Q-COOAg.
(V) A compound represented by the formula: Q-COOH is allowed to act on a carbon tetrahalide solution of red mercuric oxide.

Organic bases such as triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, diazabicyclo [5.4.0] undec-7-ene (DBU) as the base used here; sodium hydroxide, potassium hydroxide And inorganic bases such as magnesium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases can be used alone or in combination of two or more.
The amount of the base to be used is generally 1 to 3 mol, per 1 mol of the compound represented by the formula: Q-COX.

3) After a mixed acid anhydride is obtained by reacting an acid anhydride with a compound represented by the formula: Q-COOH, the mixed acid anhydride is expressed by the formula: A-OH or A-NH ₂ The compounds represented are reacted.
It does not specifically limit as an acid anhydride to be used. For example, acetic anhydride, trifluoroacetic anhydride, anhydrous monochloroacetic acid and the like can be mentioned.
The amount of the acid anhydride to be used is generally 1 to 10 mol, per 1 mol of the compound represented by the formula: Q-COOH.

4) The compound represented by the formula: Q-COOH and the compound represented by the formula: A-OH or A-NH ₂ are dehydrated and condensed in the presence of an acid catalyst or a base catalyst.

In the synthesis of the fluorene compound of the present invention, the yield can be improved by protecting the hydroxyl group present in the intermediate. As a method of protecting a hydroxyl group, it can manufacture using a well-known method (For example, refer Greene's Protective Groups in Organic Synthesis 3rd edition publication: Wiley-Interscience, 1999 issue).

Deprotection of a hydroxyl-protecting group can be carried out using known methods depending on the structure and type of the protecting group.

Any reaction can be carried out in a suitable solvent.
The solvent to be used is not particularly limited as long as it is a solvent inert to the reaction. For example, ether solvents such as tetrahydrofuran, diethyl ether, diisopropyl ether, 1,3-dimethoxyethane, 1,4-dioxane; N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethylimidazolinone, Amide solvents such as N-methylpyrrolidone; halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene and xylene; pentane Aliphatic hydrocarbon solvents such as hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; acetonitrile; dimethyl sulfoxide; and mixed solvents of two or more of these solvents; .
The amount of the solvent to be used is generally 0.1 to 1000 g based on 1 g of the compound represented by the above formula: QL ₁ .

The reaction proceeds smoothly in the temperature range from −20 ° C. to the boiling point of the solvent used.
The reaction time depends on the reaction scale, but is usually several minutes to several hours.

In any of the reactions, after completion of the reaction, the usual post-treatment procedure in organic synthesis chemistry is carried out, and if desired, the objective is achieved by applying known separation / purification means such as column chromatography, recrystallization method, distillation method and the like. Can be isolated.
The structure of the target substance can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum or the like, elemental analysis or the like.

The fluorene compound obtained as described above can impart high processing stability, heat resistance, and long life to organic materials such as polymers.

The excellent anti-aging performance of the fluorene compound of the present invention can be confirmed, for example, as follows.
That is, a predetermined amount of a fluorene compound is added to a predetermined amount of polyolefin (polyethylene etc.) powder, and the obtained mixture is kneaded. During this time, the kneading resistance is continuously recorded as torque. During the kneading time, when the stabilizer (anti-aging agent) is consumed and the effect becomes weak, the polymer starts to be crosslinked, so the deterioration is measured as an increase in torque. The time it takes for the torque to begin to increase can be a measure of the stabilizing action (anti-aging performance).
In the fluorene compound of the present invention, the time taken for the increase with respect to torque to start is much longer than conventional anti-aging agents, and is excellent in the stabilizing action (anti-aging performance).

In addition, the rubber composition containing the fluorene compound of the present invention is significantly improved in heat resistance. For example, when the elongation is measured according to JIS K 6301 before and after leaving the rubber composition containing the fluorene compound of the present invention under an environment of 190 ° C. for 504 hours, the rate of change thereof is the conventional anti-aging agent. It is smaller than the rubber composition, and it can be seen that the rubber composition containing the fluorene compound of the present invention is excellent in heat resistance.

2) Stabilizer Containing Fluorene Compound The second of the present invention is a stabilizer containing the above fluorene compound.
The fluorene compounds of the present invention have the function of stabilizing organic materials against oxidative, thermal or light-induced degradation. In particular, the fluorene compound of the present invention can suppress deterioration due to natural oxidation and heat of an organic material used under high temperature, improve the heat resistance and processing stability of the organic material, and achieve long life. .

The applicable organic material is not particularly limited, and may be a natural organic material or a synthetic organic material. Among them, synthetic organic materials, in particular, synthetic polymer materials that have been used for applications where heat resistance is required, such as polyolefin, rubber, polystyrene resin, polyester, polycarbonate, polyamide, etc., are preferable, and higher heat resistance More preferred are polyolefins and rubbers that have come to be sought.

Examples of the polyolefin include polyethylene, polypropylene, polybutene, cycloolefin polymers and the like, which are used in the field where heat resistance is required, and are particularly known as heat resistant materials, mounting parts such as semiconductors, vehicle parts and civil engineering By applying to cycloolefin polymers used in the field of construction members and the like, they can be used in a higher temperature environment than ever before.

The cycloolefin polymer is obtained by polymerizing a cycloolefin monomer having a ring structure formed by carbon atoms in the molecule and having a carbon-carbon double bond in the ring.

As a cycloolefin monomer, a single ring cycloolefin monomer, a norbornene type monomer, etc. are mentioned, A norbornene type monomer is preferable. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted by a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group. The norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring.

Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene and the like.

Specific examples of norbornene-based monomers include dicyclopentadienes such as dicyclopentadiene and methyl dicyclopentadiene; tetracyclo [6.2.1.1 ^{3, 6} . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tetracyclododecenes such as dodec-9-ene-4,5-dicarboxylic acid anhydride; 2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl -2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2 , norbornenes such as 3-dicarboxylic anhydride; 7-oxa-2-norbornene, 5-ethylidene-7-oxa norbornenes oxa-2-norbornene and the like; tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), pentacyclo [6.5.1.1 ^{3 , 6} . 0 ^{2, 7} . 0 ^9,13] pentadeca-4,10-diene, pentacyclo ^{[9.2.1.0 2,10.} 0 ^3,8] pentadeca-5,12 tetracyclic or more cyclic olefins such as dienes; and the like.

Although the polymerization method may be bulk polymerization or solution polymerization, it is preferable to perform bulk ring-opening polymerization of a cycloolefin monomer using a metathesis catalyst.

The rubber is not particularly limited. For example, natural rubber, isoprene rubber, butadiene rubber, butyl rubber, chloroprene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber (nitrile rubber), styrene-butadiene-isoprene copolymer Rubbers containing conjugated diene units such as rubber, butadiene-isoprene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, acrylic rubber, hydrin rubber, ethylene propylene rubber, etc. may be mentioned. These rubbers may have a hydroxyl group, a carboxyl group, an alkoxysilyl group, an amino group, an epoxy group and the like. In addition, these rubbers may be hydrogenated, and examples thereof include acrylonitrile-butadiene copolymer rubber hydride (hydrogenated nitrile rubber). These rubbers may be used alone or in combination of two or more. Among these, in particular, application to acrylic rubber or hydrogenated nitrile rubber which is required to have high heat resistance is preferable from the viewpoint of the heat resistance improving effect.

When the fluorene compound of the present invention is used as a stabilizer of an organic material, the blending amount of the fluoreon compound of the present invention is 0.01 to 10 parts by mass of the fluorene compound of the present invention with respect to 100 parts by mass of the organic material. Preferably, it is 0.03 to 5 parts by mass, particularly preferably 0.05 to 3 parts by mass. When the compounding amount of the fluorene compound of the present invention is less than 0.01 parts by mass, the effect as a stabilizer is not exerted, while when it is more than 10 parts by mass, the effect as a stabilizer is not improved Also, it is not preferable because bleed out and discoloration of the molded product may occur.

The fluorene compounds of the present invention may be used alone or in combination of two or more. Moreover, in the range which does not impair the effect of invention, it can be used in combination with the other anti-aging agent etc. conventionally used.

3) Composition The third of the present invention is a composition containing a component (a): an organic material, and a component (b): the fluorene compound of the present invention.

The organic material of the component (a) is not particularly limited, and may be a natural organic material or a synthetic organic material. Among them, synthetic organic materials, in particular, synthetic polymer materials that have been used for applications where heat resistance is required, such as polyolefin, rubber, polystyrene resin, polyester, polycarbonate, polyamide, etc., are preferable, and higher heat resistance More preferred are polyolefins and rubbers which have come to be sought, with polyolefins being particularly preferred. These specific examples are similar to those described above.

The fluorene compound of component (b) is the fluorene compound of the present invention. The fluorene compounds of the present invention can be used singly or in combination of two or more.

The composition of the present invention may further contain other additives in addition to the components (a) and (b).
Other additives include those commonly used in the field of using synthetic polymeric materials. For example, reinforcing fillers such as carbon black and silica; non-reinforcing fillers such as calcium carbonate and clay; light stabilizers; anti-scorch agents; plasticizers; processing aids; lubricants; adhesives; Antifungal agents; antistatic agents; coloring agents; silane coupling agents; crosslinking agents (vulcanizing agents); crosslinking accelerators; crosslinking retarders; The amount of these additives to be added is not particularly limited as long as the purpose and effect of the present invention are not impaired, and an amount according to the purpose of the addition can be appropriately added.

(Method of preparing composition)
In the composition of the present invention, a predetermined amount of the component (a), the component (b) and optionally other additives are mixed and kneaded with a Banbury mixer or a kneader, and then further kneaded using a kneading roll. It can be prepared by
The order of blending of the components is not particularly limited. However, after sufficiently mixing the components that are difficult to react or decompose with heat, the crosslinking agent, which is a component that easily reacts or decomposes by heat, is short at a temperature that does not cause reaction or decomposition. It is preferred to mix on time.

EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to these production examples and examples.
Example 1 Synthesis of Compound 1

15 g (71.35 mmol) of fluorenecarboxylic acid, 16.86 g (71.35 mmol) of 2,6-ditert-butyl-4-hydroxymethylphenol in a nitrogen stream in a four-necked reactor equipped with a cooler and a thermometer 1.53 g (8.56 mmol) of 4- (dimethylamino) pyridine was dissolved in 500 mL of N-methylpyrrolidone (NMP). To this solution was added 16.41 g (85.62 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), and the whole volume was stirred at room temperature for 14 hours.
After completion of the reaction, the reaction solution was poured into 5 liters of water, and extraction operation was performed twice with 800 mL of ethyl acetate. The resulting ethyl acetate layer was washed with 500 mL of saturated brine. The ethyl acetate layer was dried over anhydrous magnesium sulfate and suction filtered. The filtrate was concentrated on a rotary evaporator to give 30 g of a yellow oil. The obtained oil was purified by silica gel column chromatography (n-hexane: toluene = 2: 1 (volume ratio)) to obtain 20.3 g (yield 66.4%) of compound 1 as a pale yellow solid.

The structure was identified by ¹ H-NMR.
¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.70 (d, 2 H, J = 4.0 Hz), 7.34-7.29 (m, 2 H), 7.22 (d, 4 H) , J = 4.0 Hz), 6.85 (s, 2 H), 5.03 (s, 1 H), 4. 15 (t, 1 H, J = 7.0 Hz), 3.06 (d, 2 H, J = 7.0 Hz), 1.36 (s, 18 H)

Example 2 Synthesis of Compound 2

In a four-necked reactor equipped with a condenser and a thermometer, in a nitrogen stream, 10 g (47.57 mmol) of fluorenecarboxylic acid, 7.89 g (42.81 mmol) of 4-aminodiphenylamine, 4- (dimethylamino) pyridine 0 .7 g (5.7 mmol) were dissolved in 300 mL of N-methyl pyrrolidone (NMP). To this solution was added 10.94 g (57.1 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WSC), and the whole volume was stirred at room temperature for 12 hours.
After completion of the reaction, the reaction solution was poured into 3 liters of water, and extraction operation was performed twice with 500 mL of ethyl acetate. The obtained ethyl acetate layer was washed with 300 mL of saturated brine. The ethyl acetate layer was dried over anhydrous magnesium sulfate and suction filtered. The filtrate was concentrated on a rotary evaporator to give 15 g of a yellow oil. The obtained oil was purified by silica gel column chromatography (toluene: ethyl acetate = 9: 1 (volume ratio)) to obtain 12.1 g of Compound 2 as a pale gray solid. (Yield 67.6%)

The structure was identified by ¹ H-NMR.
¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.83 (d, 2 H, J = 7.5 Hz), 7.77 (d, 2 H, J = 7.5 Hz), 7.48 (t , 2H, J = 7.5 Hz), 7.40 (t, 2H, J = 7.5 Hz), 7.23-7.20 (m, 4H), 6.97-6.94 (m, 4H) , 6.89 (t, 1 H, J = 7.5 Hz), 6.78 (s, 1 H), 5.60 (s, 1 H), 4.91 (s, 1 H)

(Evaluation of anti-aging performance)
The antiaging performance of the compounds 1 and 2 synthesized in Examples 1 and 2 was evaluated as follows.
As Comparative Examples, anti-aging agents A to J shown below were used.
The compounds (a) to (g) are the compounds shown below.

Antiaging agent A; composition containing compounds (a), (b) and (c) in a mass ratio of compound (a): compound (b): compound (c) = 15: 28.3: 56.7 (IRGANOX HP 2251, manufactured by Ciba Specials Chemicals)
Antiaging agent B; composition containing compounds (b) and (d) in a mass ratio of compound (b): compound (d) = 66.7: 33.3 (IRGANOX B 921 manufactured by Ciba Specials Chemicals Co., Ltd. )
Antiaging agent C; compound (e) (Sumilyzer GS, manufactured by Sumitomo Chemical Co., Ltd.)
Antiaging agent D; compound (c) (IRGANOX 1010, manufactured by Ciba Specials Chemicals Co., Ltd.)
Antiaging agent E; composition containing compounds (f) and (b) (IRGASTAB FS 301, manufactured by Ciba Specials Chemicals Inc.)
Antiaging agent F; composition containing compounds (e) and (b) in a weight ratio of compound (e): compound (b) = 50: 50 Antiaging agent G; compound (g)
Antiaging agent H; composition containing compounds (g) and (b) in a weight ratio of compound (g): compound (b) = 70: 30

(I) Evaluation test I
100 parts by mass of polyethylene powder (Sunfine UH900D, manufactured by Asahi Kasei Corp.), 0.1 parts by mass of each of Compound 1 and anti-aging agents A to F are mixed, and the resulting mixture is laboplast mill (type 20C200, Toyo The mixture is kneaded at 220 ° C. and 50 rpm in Seiki Seisakusho Co., Ltd.).
Kneading resistance is continuously recorded as torque during this time. During the kneading time, when the anti-aging agent (compound 1) is consumed and the effect becomes weak, the polymer starts to be crosslinked, so the deterioration is measured as an increase in torque. The time taken for the torque to begin to increase was measured as a measure of the stabilization effect. The results are shown in Table 1.

From Table 1, in the resin composition (Example 3) to which the fluorene compound of Example 1 was added, the time taken for the increase with respect to the torque to start was the anti-aging agent A ~ containing the conventional phosphorus-based anti-aging agent The F is longer than when F is used (Comparative Examples 1 to 6), and it can be seen that the fluorene compound of Example 1 is excellent in the stabilizing action (antiaging performance) of polyethylene.

(II) Evaluation test II
(II-1) Preparation of rubber composition 100 parts by mass of acrylic elastomer (Nipol AR22, manufactured by Nippon Zeon Co., Ltd.), 60 parts by mass of carbon black (Seat SO, manufactured by Tokai Carbon Co., Ltd.), 2 parts by mass of stearic acid, and compound 2 , 3 parts by weight of each of anti-aging agents G and H, and after kneading the whole volume at 50 ° C. using 0.8 liter Banbury, hexamethylene diamine carbamate (Diak No. 1, DuPont Dow Elastomer Japan) as a crosslinking agent A rubber composition was prepared by kneading 0.5 parts by mass of Co., Ltd. and 2 parts by mass of di-o-tolyl guanidine (Noxceler DT, manufactured by Ouchi Emerging Chemical Industry Co., Ltd.) as a crosslinking accelerator with an open roll.

(II-2) Preparation of Test Piece The rubber composition prepared in (II-1) was molded and crosslinked by pressing at 170 ° C. for 20 minutes, and then a sheet of 15 cm × 15 cm × 2 mm (thickness) was prepared. Furthermore, this sheet was heated at 170 ° C. for 4 hours for secondary crosslinking. The obtained sheet was used as a test piece.

(II-3) Evaluation of heat resistance Before and after leaving the test piece produced in (II-2) under an environment of 190 ° C. for 504 hours, the elongation is measured according to JIS K6301 and the change thereof according to the following formula The rate was calculated. It is judged that the heat resistance is higher as the rate of change is closer to zero, which is a preferable result. The heat resistance evaluation results are summarized in Table 2.

From Table 2, in the case of the rubber composition containing the fluorene compound of Example 2 (Example 4), the rate of change was compared to the rubber composition (Comparative Examples 7 to 9) to which the conventional anti-aging agent was added. The rubber composition containing the fluorene compound of Example 2 is found to be excellent in heat resistance.

Claims (10)

1. A fluorene compound represented by the following formula (I):
   

   

   {In the above formula (I), Y ₁ is a single chemical bond, -O-, -S-, -C (= O) -O-, -C (= O) -NR ^1- , -C ( = O)-, -S (= O)-, -O-C (= O)-, -NR ¹ -C (= O)-, -SO _2- , -O-C (= O) -O- Or-(CH ₂ ) _n -O-. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6.
   Each of X ₁ to X ₈ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ² , -O-C (= O) -R ² , -C (= O) -OR ² , -O-C (= O) -OR ² , -N ( R ³ ) R ⁴ , —NR ³ —C (= O) —R ² , —C (= O) —N (R ³ ) R ⁴ or —O—C (= O) —N (R ³ ) It represents the R ^4. Here, R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent,
   a is 0 or 1; However, when the following b or d is 0, a is also 0.
   A is the following formula (A1)
   

   

   [In the above formula (A1), G ₁ represents a C1-C20 (c + 1) -valent organic group which may have a substituent,
   b is 0 or 1;
   c is an integer of 1 to 3;
   Y ₂ is a single chemical bond, —O—, —S—, —O—C () O) —, —C (= O) —O—, —O—C (= O) —O—, ^{-NR 5 -C (= O) -} , - C (= O) -NR 5 -, - O-C (= O) -NR 5 -, - NR 5 -C (= O) -O -, - NR ^5- C (= O) -NR ^6- , -O-NR ^5- , or -NR ⁵ -O-. Here, R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent.
   Each of X ₉ to X ₁₂ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -OR ⁷ , -O-C (= O) -R ⁷ , -C (= O) -OR ⁷ , -O-C (= O) -OR ⁷ , -N ( R ⁸ ) R ⁹ , -NR ⁸ -C (= O) -R ⁷ , -C (= O) -N (R ⁸ ) R ⁹ or -O-C (= O) -N (R ⁸ ) R ⁹ is shown. Here, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. ]
   Or a group represented by the formula (A2)
   

   

   Wherein G ₂ represents a divalent organic group having 1 to 20 carbon atoms, in the above formula (A2),
   Y ₃ has the same meaning as Y ₂ above;
   d is 0 or 1;
   Each of X ₁₃ to X ₂₁ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a carbon number 2 to 12 which may have a substituent. Alkenyl group, cyano group, nitro group, -CF ₃ , -OR ¹⁰ , -O-C (= O) -R ¹⁰ , -C (= O) -OR ¹⁰ , -O-C (= O) -OR ¹⁰ , -N (R ¹¹ ) R ¹² , -NR ¹¹ -C (= O) -R ¹⁰ , -C (= O) -N (R ¹¹ ) R ¹² or -O-C (= O) -N (R ¹¹ ) represents R ¹² Here, R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. ]
   Represents a group represented by }
2. Y _{1, Y 2} and _{Y 3} are each independently a chemical single bond, -C (= O) -O - , - C (= O) -NR 13 - ( ^{wherein, R 13} is a hydrogen atom Or an organic group having 1 to 20 carbon atoms which may have a substituent) or -C (= O)-, and X ₁ to X ₂₁ each independently represent a hydrogen atom or a substituent The fluorene compound according to claim 1, which is an alkyl group having 1 to 12 carbon atoms which may have a group.
3. Said formula (A) is a following formula (A11)
   

   

   (In the above formula (A11), X ₉ to X ₁₂ have the same meaning as described above.) Or a group represented by the formula (A21)
   

   

   The fluorene compound according to claim 1 or 2, which is represented by a group represented by (in the above formula (A21), X ₁₃ to X ₂₁ have the same meaning as described above).
4. The fluorene compound according to claim 1 or 2, wherein Y ₁ is -C (= O) -O- or -C (= O) -NR ^1- (wherein R ¹ represents the same meaning as described above).
5. A stabilizer comprising the fluorene compound according to any one of claims 1 to 4.
6. Component (a): an organic material, and component (b): a composition containing the fluorene compound according to any one of claims 1 to 4.
7. The composition according to claim 6, wherein the component (a) is a synthetic organic material.
8. The composition according to claim 6 or 7, wherein the component (a) is a synthetic rubber.
9. The composition according to claim 6 or 7, wherein the component (a) is a polyolefin.
10. The composition according to any one of claims 6 to 9, further comprising other additives in addition to the component (a) and the component (b).