JP3435843B2 - Polycarbonate polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate polymer having excellent light resistance, and more particularly to a polycarbonate polymer having a dibenzoylmethane structure in its main chain, which has a light resistance to long-wavelength ultraviolet light. Regarding coalescence.

[0002]

Polycarbonate has been widely used as an engineering plastic having excellent mechanical strength, heat resistance and transparency, for example, automobile parts and various precision machine parts. However, polycarbonate has insufficient light resistance, and has problems such as discoloration and deterioration of the product due to ultraviolet rays and a decrease in mechanical strength when used outdoors or under a fluorescent lamp. Therefore, conventionally, various ultraviolet absorbers have been used in polycarbonate singly or in combination (for example, JP-A-58-217548 and JP-A-63-10653). However, the ultraviolet absorbers used in these polycarbonate resin compositions have a maximum absorption wavelength.
Since it is in the vicinity of 295 nm, it mainly corresponds to ultraviolet rays of 290 to 320 nm (UV rays in the B region), and light resistance to ultraviolet rays in a wider region is not always sufficient. Recently, polycarbonate has also been used in various fields,
More severe light resistance is required, and polycarbonate having ultraviolet resistance in a wider range is required.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a polycarbonate polymer having excellent light resistance to long-wavelength ultraviolet light and light resistance to a wide range of ultraviolet light.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, a polycarbonate polymer having a dibenzoylmethane structure has a molecular weight of 320 to 400 n.
They have found that they are stable to m long-wavelength ultraviolet light (A region ultraviolet light), and have completed the present invention based on this finding.

That is, the present invention is a structural unit represented by the following general formula (A) having a dibenzoylmethane structure and a structural unit represented by the following general formula (B) derived from a bisphenol dihydric phenol. And the constitutional unit represented by the general formula (A) is 0.1 to 50.0 mo in all constitutional units.
It relates to a polycarbonate polymer having an intrinsic viscosity [η] of 0.15 to 2.00 dl / g.

[0006]

[Chemical 6]

(Wherein R _{1 to} R ₄ are halogen selected from hydrogen, fluorine, chlorine, bromine and iodine, an alkyl group having 1 to 5 carbon atoms which may have a substituent, and a carbon number of 6).
To 12 aryl groups, C2 to C5 alkenyl groups, C1 to C5 alkoxy groups, and C7 to C17 aralkyl groups, and the substituents which may be present on any of the carbons of these groups. Is an alkyl group or alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen selected from fluorine, chlorine, bromine or iodine, or a dimethylpolysiloxy group. )

[0008]

[Chemical 7]

(In the formula, each of R _{9 to} R ₁₂ is a halogen selected from hydrogen, fluorine, chlorine, bromine and iodine, an alkyl group having 1 to 5 carbon atoms which may have a substituent,
An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms, which may have any of these carbon atoms. A preferable substituent is an alkyl group or an alkenyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen selected from fluorine, chlorine, bromine or iodine, or a dimethylpolysiloxy group. X is one selected from the following.

[0010]

[Chemical 8]

Here, R ₁₃ and R ₁₄ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group or an aryl group having 6 to 12 carbon atoms, or R ₁₃
And R ₁₄ represent a group which forms a carbocycle or a heterocycle by being bonded to each other, and a substituent which may be present on the carbon atom of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms, or a carbon number of 1
Is a halogen selected from an alkoxy group of 5 to 5, fluorine, chlorine, bromine and iodine. a represents 0 or an integer of 1 to 20, b and c represent an integer of 1 to 100. )

The structure of the present invention will be described below. The polycarbonate composed of the constitutional unit represented by the general formula (A) and the constitutional unit represented by the general formula (B) of the present invention is an aromatic dihydroxy compound represented by the following general formula (C). ,

[0013]

[Chemical 9]

(In the formula, each of R _{5 to} R ₈ has the same meaning as in formula (A) above.)

It is obtained by reacting a bisphenol type dihydric phenol represented by the following general formula (D) with a carbonic acid ester forming compound.

[0016]

[Chemical 10]

(In the formula, each of R _{9 to} R ₁₂ has the same meaning as in the formula (B).)

Specific examples of typical compounds of the aromatic dihydroxy compound represented by the general formula (C) in the present invention are shown below. These compounds may be used alone or in combination of two or more.

The aromatic dihydroxy compound represented by the general formula (C) has been conventionally used as an ultraviolet protective agent for cosmetics. For example, Charles R. Hauser, e.
t al., J. Org. Chem., 22 , 909 (1957), S. Ayabe, et a
l., Phyto-chemistry, 19, 2179 (1980), or J.
Org. Chem., 36 , 1447 (1971) and the like methods known per se, for example, a substituted acetophenone compound can be produced by a reaction such as a substituted aromatic ester and Claisen condensation.

[0020]

[Chemical 11]

Specific examples of typical compounds of the dihydric phenol represented by the general formula (D) are shown below.

Biphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2, 2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α, ω
-Bis [3- (O-hydroxyphenyl) propyl] polydimethylsiloxane, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, 9,9-bis (4-hydroxyphenyl) fluorene, 2,2-bis (4-
Hydroxy-3-allylphenyl) propane and the like are exemplified. These may be used in combination of two or more. Among these, particularly, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, α, ω-bis [3- (O-hydroxyphenyl) propyl] polydimethyl Siloxane, α,
ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenyl It is preferably selected from ethane.

On the other hand, examples of the carbonic acid ester-forming compound include bisgene such as phosgene, oxalyl chloride or diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate. Examples include allyl carbonate.

The method for producing the polycarbonate polymer of the present invention is a known method used for producing a polycarbonate from ordinary bisphenols, for example, a direct reaction between a dihydric phenol and phosgene (phosgene method), or a two-step method. A method such as a transesterification reaction (transesterification method) between a dihydric phenol and a bisaryl carbonate can be adopted.

In the former phosgene method, dihydric phenol and phosgene are usually reacted in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene.

Further, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to accelerate the polycondensation reaction, and phenol or pt-butylphenol is used to adjust the degree of polymerization. It is desirable to carry out the reaction by adding a molecular weight regulator of, such as 4-hydroxydibenzoylmethane or 2- [2-hydroxy-3-
It is also possible to use a molecular weight modifier having an ultraviolet absorbing property such as (3,4,5,6-tetrahydrophthalimidomethyl) -5-tylphenyl] benzotriazole. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite or a branching agent such as phloroglucin or isatin bisphenol may be added.

The reaction is usually 0 to 150 ° C., preferably 5
Suitably it is carried out at a temperature in the range of -40 ° C. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to
It is 10 hours, preferably 1 minute to 2 hours. Further, it is desirable to keep the pH of the reaction system at 10 or more during the reaction.

On the other hand, in the latter transesterification method, dihydric phenol and bisaryl carbonate are mixed,
React at elevated temperature under reduced pressure. The reaction is usually 150-
It is carried out at a temperature in the range of 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is finally set to preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. It is done while letting go.

Although the reaction time depends on the reaction temperature and the degree of reduced pressure, it is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. Further, if desired, the reaction may be carried out by adding the above-mentioned molecular weight regulator, antioxidant or branching agent.

The polycarbonate polymer in the present invention can be molded by a known molding method such as extrusion molding, injection molding, blow molding, compression molding, and wet molding. The viscosity of the polymer suitable for molding has an intrinsic viscosity [η]. Is 0.15 to 2.0 (dl / g).

The constitutional unit represented by the general formula (A) in the polycarbonate polymer of the present invention is 0.1 to 50 mol in all constitutional units from the viewpoint of reactivity of the dihydroxy compound represented by the general formula (C). % Is preferable,
If it exceeds 50 mol%, the amount of unreacted monomer increases and it takes labor to remove it, and if it is less than 0.1 mol%, sufficient UV absorptivity cannot be exhibited.

In the polycarbonate polymer of the present invention, the constituent unit having a dibenzoylmethane structure represented by the general formula (A) present in the polymer structure acts as a long-wavelength ultraviolet absorber, and the polycarbonate polymer is It is incorporated into the main chain of and has extremely low volatility,
Further, it is compatible with other polymers and can be used for various polymers as a polymer ultraviolet absorber.

[0033]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 580 ml of 8.8% (w / v) aqueous sodium hydroxide solution was mixed with 25.6 g (denoted as DBM) of 4,4'-dihydroxydibenzoylmethane having the following structure (1).

[0035]

[Chemical 12]

2,2-bis (4-hydroxyphenyl) propane (referred to as BPA) 68.4 g and hydrosulfite 0.1 g
Was added and dissolved. To this, 360 ml of methylene chloride was added, 2.0 g of p-tert-butylphenol was added while stirring at 15 ° C, and then 51 g of phosgene was blown in over 50 minutes. After blowing, stir vigorously,
The reaction solution was emulsified, 0.2 ml of triethylamine was added after emulsification, and the mixture was stirred for about 1 hour for polymerization.

The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water was repeatedly washed with water until the pH of the washing liquid became neutral. Then, 470 ml of isopropanol was added to precipitate the polymer. Let The precipitate was filtered and dried to obtain a powdery polymer. This polymer has a concentration of 0.5 g in methylene chloride.
/ Dl solution has an intrinsic viscosity [η] of 0.52dl at a temperature of 20 ℃
It was / g.

The results of the obtained above polymer was analyzed from the infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, having a carbonate bond Was confirmed. Furthermore, absorption due to β-diketone was confirmed near 1600 cm ^-1 . In addition, absorption derived from hydroxyl groups was not observed at the position of 3650 to 3200 cm ^-1 . The infrared absorption spectrum of this polymer is shown in FIG. In addition, when the monomer in the polycarbonate is measured by GPC (gel permeation chromatography) analysis, DBM and BPA are both 20 ppm or less and hardly detected. As a result of the overall synthesis of these, it was confirmed that this polymer was a polycarbonate polymer having the structural units shown below.

[0039]

[Chemical 13]

Example 2 The procedure of Example 1 was repeated, except that DBM was changed to 51.2 g and BPA was changed to 45.6 g. The intrinsic viscosity [η] of the obtained polymer is
It was 0.50 dl / g, and it was confirmed from the infrared absorption spectrum analysis and the like as in Example 1 that this polymer was a polycarbonate polymer having the structural units shown below.

[0041]

[Chemical 14]

Example 3 The same procedure as in Example 1 was carried out except that 31.2 g of a dihydroxy compound represented by the following structural formula (2) (referred to as BDBM) was used in place of DBM.

[0043]

[Chemical 15]

The intrinsic viscosity [η] of the obtained polymer was 0.53 dl
/ G, and this polymer is recognized as a polycarbonate polymer having the structural units shown below from the infrared absorption spectrum analysis and the like.

[0045]

[Chemical 16]

Example 4 Instead of DBM, a dihydric phenol (S) represented by the following structural formula (3) was used.
iDBM) and 19.4 g of BPA and 89.4 g of BPA were used.

[0047]

[Chemical 17]

The intrinsic viscosity [η] of the obtained polymer was 0.53 dl
/ G, infrared absorption spectrum, etc. and Si by fluorescent X-ray
From the above confirmation, this polymer is recognized as a polycarbonate polymer having the structural units shown below.

[0049]

[Chemical 18]

Example 5 The same procedure as in Example 1 was carried out except that 28.6 g of a dihydroxy compound represented by the following structural formula (4) (referred to as MDBM) was used instead of DBM.

[0051]

[Chemical 19]

The intrinsic viscosity [η] of the obtained polymer was 0.52 dl
/ G, this polymer is recognized as a polycarbonate polymer having the structural units shown below by the infrared absorption spectrum and the like.

[0053]

[Chemical 20]

Example 6 Instead of BPA, 1,1-bis (4-hydroxyphenyl)
Example 1 was repeated except that 80.4 g of cyclohexane was used. The obtained polymer has an intrinsic viscosity [η] of 0.47 dl / g
From the infrared absorption spectrum, etc., this polymer is recognized as a polycarbonate polymer having the structural units shown below.

[0055]

[Chemical 21]

Example 7 The procedure of Example 1 was repeated except that 76.8 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane was used instead of BPA. The polymer obtained had an intrinsic viscosity [η] of 0.49 dl
/ G, this polymer is recognized as a polycarbonate polymer having the structural units shown below from the infrared absorption spectrum and the like.

[0057]

[Chemical formula 22]

Example 8 Using 25.6 g of DBM, 66.8 g of BPA and 18.1 g of the dihydroxy compound represented by the following structural formula (5), an aqueous solution of sodium hydroxide 6
The procedure of Example 1 was repeated except that the amount of phosgene was changed to 10 g and phosgene was changed to 52 g.

[0059]

[Chemical formula 23]

The intrinsic viscosity [η] of the obtained polymer was 0.53 dl
/ G, this polymer is recognized as a polycarbonate polymer having the structural units shown below from the infrared absorption spectrum and the like.

[0061]

[Chemical formula 24]

Example 9 Example 9 was repeated except that the amount of p-tert-butylphenol was changed to 0.27 g. The intrinsic viscosity [η] of the obtained polymer was 1.74 dl / g, and it was recognized from the infrared absorption spectrum and the like that this polymer was a polycarbonate polymer having the same constitutional unit as in Example 1.

Example 10 The procedure of Example 1 was repeated, except that p-tert-butylphenol was changed to 4.0 g. The intrinsic viscosity [η] of the obtained polymer was 0.28 dl / g, and it was recognized from the infrared absorption spectrum and the like that this polymer was a polycarbonate polymer having the same constitutional unit as in Example 1.

Example 11 The polycarbonate obtained in Example 1 was applied to a compression molding machine (25
A compression molded product of 160 mm × 160 mm × 3.2 mm was prepared at 0 ° C, 100 Kgf / cm ² ) and a light resistance test was conducted for 1000 hours using a sunshine weather meter.
I value) was determined.

Comparative Example 1 Example 1 was repeated except that 91.2 g of BPA alone was used without using DBM. The obtained polymer has an intrinsic viscosity [η] of 0.50.
At dl / g, this polymer was confirmed to be a polycarbonate polymer having the structural units shown below from the infrared absorption spectrum and the like. The obtained polycarbonate polymer was used in Example 11
Molded in the same manner as described above, and subjected to the light resistance test.

[0066]

[Chemical 25]

Comparative Example 2 DBM was added to the polycarbonate polymer obtained in Comparative Example 1.
Was blended in an amount of 27 wt% and molded in the same manner as in Example 11. As a result, the melted DBM was phase-separated during molding, and the molded product had many cracks and immediately cracked, and could not be subjected to the light resistance test.

Table 1 shows various measurement results of Examples 1 to 10 and Comparative Example 1, and Table 2 shows weather resistance test results of Example 11 and Comparative Example 1.

[0069]

[Table 1] Table 1 Examples and Comparative Examples 1 2 3 4 5 6 7 Diethyloxy compound (C) DBM DBM BDBM SiDBM MDBM DBM DBM (mol%) 25 50 25 2.5 25 25 25 Dihydric phenol (D) BPA BPA BPA BPA BPA BPZ DMBPA (mol%) 75 50 75 97.5 75 75 75 Intrinsic viscosity (dl / g) 0.52 0.50 0.53 0.53 0.52 0.47 0.49 IR (Carbonate bond) Yes Yes Yes Yes Yes IR (β-diketone bond) Yes Yes Yes Yes Yes Yes Yes Yes Residual monomer (ppm) ND ND ND ND ND ND ND

[0070]

[Table 2] Table 1 (continued) Examples and Comparative Examples 8 9 10 Comparative Example 1 Dihydroxyl compound (C) DBM DBM DBM --- (mol%) 24.4 25 25 --- Dihydric phenol (D) BPA BPA BPA BPA (mol%) 73.2 75 75 100 Dihydric phenol (D) SiDP --- --- --- (mol%) 2.4 --- --- --- Intrinsic viscosity (dl / g) 0.53 1.74 0.28 0.50 IR (Carbonate bond) Yes Yes Yes Yes Yes IR (β-diketone bond) Yes Yes Yes No No Residual monomer (ppm) ND ND ND ND

The items described in the table are specified below. BPA: 2,2-bis (4-hydroxyphenyl) propane BPZ: 1,1-bis (4-hydroxyphenyl) cyclohexane DMBPA: 2,2-bis (4-hydroxy-3-methylphenyl) propane SiDP: α, ω-bis [3- (O-hydroxyphenyl) propyl] polydimethylsiloxane DBM: 4,4'-dihydroxydibenzoylmethane BDBM: 2,4'-dihydroxy-4-tert-butyldibenzoylmethane SiDBM: 3- ( 3-dimethylpolysiloxy) propyl-
4,4'-Dihydroxybenzoylmethane MDBM: 2,4'-Dihydroxy-4-methoxydibenzoylmethane Intrinsic viscosity: 20 ° C, 0.5g / 100ml in dichloromethane solvent
The solution was used as a solution to determine the intrinsic viscosity. IR: infrared absorption spectrum, absorption by carbonyl in the vicinity of 1770 cm ^-1, absorption due to an ether bond at around 1240 cm ^-1, confirming absorption by β- diketone near 1600 cm ^-1. Residual monomer: GPC manufactured by Waters was used to separate and quantify the monomer components. ND indicates that it is below the detection limit and below 20 ppm. Fluorescent X-ray: Measured with a fluorescent X-ray manufactured by Shimadzu Corporation using a Cr tube

[0072]

[Table 3] Table 2 Examples and initial examples (0 hours) After 1000 hours (1000-0 hours) Comparative examples YI value YI value ΔYI value Example 11 3.2 7.7 4.5 Comparative example 1 2.8 14.9 12.1

Weather resistance test: Suga Test Instruments Co., Ltd. sunshine weather meter WEL-SH-2C (B region ultraviolet ray cut type) was used.

[0074]

INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a novel polycarbonate having a dibenzoylmethane structure in its repeating unit. In particular, it has long-wavelength UV absorption and therefore is required to have weather resistance, such as a street lamp. It is useful for covers, signal light lenses, vehicle light covers, and soundproof walls for highways. INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention can be used as various molding materials, raw materials for polymer alloys, and as a polymer ultraviolet absorbing additive.

[Brief description of drawings]

1 shows the IR spectrum of the polycarbonate polymer of Example 1. FIG.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A constitutional unit represented by the following general formula (A) having a dibenzoylmethane structure and a constitutional unit represented by the following general formula (B) derived from a bisphenol dihydric phenol. , The constitutional unit represented by the general formula (A) is 0.1 to 50.0 mol% in all constitutional units, and the intrinsic viscosity is
A polycarbonate polymer having an [η] of 0.15 to 2.00 dl / g. [Chemical 1] (In the formula, R _{1 to} R ₄ are hydrogen, fluorine, chlorine, bromine, and halogen selected from iodine, an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 12 carbon atoms, each of which may have a substituent. A group, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms,
Substituents which may be present on any of the carbons of these groups include an alkyl group or an alkenyl group having 1 to 5 carbon atoms and a carbon number of 1
To 5 alkoxy groups, halogens selected from fluorine, chlorine, bromine and iodine, and dimethylpolysiloxy groups. ) [Chemical 2] (In the formula, R _{9 to} R ₁₂ are each hydrogen, fluorine, chlorine,
Halogen selected from bromine and iodine, each of which may have a substituent, an alkyl group having 1 to 5 carbon atoms, and 6 to carbon atoms
A 12-aryl group, a C2-C5 alkenyl group, a C1-C5 alkoxy group, and a C7-C17 aralkyl group, and the substituents which may be present on any of the carbons of these groups are , A C1-5 alkyl or alkenyl group, a C1-5 alkoxy group, a halogen selected from fluorine, chlorine, bromine and iodine, and a dimethylpolysiloxy group. X is one selected from the following. [Chemical 3] Here, R ₁₃ and R ₁₄ each represent hydrogen, an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkoxy group or an aryl group having 6 to 12 carbon atoms, or R ₁₃ and R ₁₄ are A group which forms a carbocycle or a heterocycle by being bonded to each other, and a substituent which may be present on the carbon atom of these groups is an alkyl group or an alkenyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. It is a halogen selected from a group, fluorine, chlorine, bromine and iodine. a is 0 or an integer of 1 to 20, b and c
Represents an integer of 1 to 100. ) 2. An aromatic dihydroxy compound represented by the following general formula (C) and a dihydric phenol represented by the following general formula (D) are reacted with a carbonic acid ester forming compound. 1. The method for producing a polycarbonate polymer according to 1. [Chemical 4] (In the formula, each of R _{5 to} R ₈ has the same meaning as in the formula (A).) (In the formula, each of R _{9 to} R ₁₂ has the same meaning as in the formula (B).)