JPH09143354A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin comsn. which is not yellowed by radiation sterilization by compounding a polycarbonate resin with an arom. oxy- or carbonyl-contg. compd. (e.g. dibenzyl ether) and a sulfoxide compd. (e.g. diphenyl sulfoxide). SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. polycarbonate resin with 0.01-5 pts.wt. arom. oxy- or carbonyl-contg. compd. and 0.01-5 pts.wt. sulfoxide compd. The resin is a thermoplastic polycarbonate resin obtd. from an arom. dihydroxy compd., suitable one being obtd. from disphenol A and having a viscosity average mol.wt. of 15,000-50,000. An example of the oxy- or carbonyl-contg. compd. is represented by formula I (wherein R<3> and R<5> are each a 1-10C alkyl, etc.; R<4> is a 1-15C alkylene, an arylene, etc.; X<2> and X<3> are each O, CO, or CHR<6> O; R<6> is H, an alkyl, etc.; and (j) and (k) are each 0-5) and an example of the sulfoxide compd., by formula II (wherein R<11> and R<13> are each a 1-30C alkyl, etc.; R<12> is a 1-15C alylene, an arylene, etc.; and (m) is 0-100). The compsn. is useful for medical goods.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing an aromatic compound having an oxy group or a carbonyl group and a sulfoxide compound. In particular, the present invention relates to a polycarbonate resin composition excellent in ionizing radiation resistance, with little change in color tone and deterioration in physical properties due to ionizing radiation irradiated for sterilization.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as medical products because of their excellent mechanical strength, impact strength, heat resistance, transparency and high safety. When used, these medical products are usually completely sterilized.
Specifically, there are a high-pressure steam sterilization method, an ethylene oxide gas (EOG) sterilization method, a sterilization method by irradiation with ionizing radiation such as gamma rays and electron beams. Among them, the high-pressure steam sterilization method has a high energy cost and requires a drying step after the sterilization treatment. In addition, EOG sterilization has toxicity of EOG itself and environmental problems related to disposal. Accordingly, recently, ionizing radiation (generally gamma rays) irradiation sterilization, which is relatively inexpensive and can be processed at a low temperature and in a dry manner, has been frequently used. However,
Polycarbonate resin has the drawback that it discolors yellow when exposed to ionizing radiation during sterilization, impairing the product value especially in medical applications.

As a method for solving such a disadvantage, for example, Japanese Patent Application Laid-Open No. 2-55062 discloses a method in which a halogen-containing polycarbonate resin is blended.
No. 9127 discloses a method of blending a nuclear brominated phthalic acid derivative, respectively.However, since metal is contained in the composition, metal corrosion is apt to occur, and metal of a special material is used for a molding machine or the like. Needed to use.

As a method of using a sulfur compound, a method of blending thioalcohols in JP-A-1-229052 and a method of blending thioethers in JP-A-2-115260 are disclosed in JP-A-2-115260. 490
No. 58, JP-A-4-36343, JP-A-6-1668
JP-A No. 07-93192 discloses a method of adding a compound having a mercapto group, and JP-A-6-93192 discloses a method of adding a compound having a sulfide group.
No. 209120 discloses a method of using a polyalkylene oxide and an aromatic compound having a sulfonic acid ester substituent in combination, but in any case, the effect of suppressing yellowing is insufficient, or a bad odor occurs during use. However, there is a problem that the environment during molding is deteriorated.

Further, Japanese Unexamined Patent Publication No. 62-135556 discloses a method of blending a polyether polyol or its alkyl ether, and Japanese Unexamined Patent Publication No. 2-232258 discloses a method of blending a benzyl alcohol derivative. , The effect of preventing yellowing is insufficient,
If the amount of addition is increased to obtain a sufficient effect, other physical properties are adversely affected.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition which has little deterioration in physical properties and very little yellowing upon sterilization by irradiation with ionizing radiation.

[0007]

The present invention has been made in order to solve the above-mentioned problems, and the gist of the present invention is to add 100 parts by weight of a polycarbonate resin to an aromatic compound having an oxy group or a carbonyl group. The present invention resides in a polycarbonate resin composition obtained by blending 01 to 5 parts by weight and 0.01 to 5 parts by weight of a sulfoxide compound.

The present invention will be described in detail below. The polycarbonate resin in the present invention is a polymer or copolymer of an optionally branched thermoplastic aromatic polycarbonate obtained by reacting an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with phosgene or a diester of carbonic acid. Is.

One example of the aromatic dihydroxy compound is 2,2.
2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, 2,2
-Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) ) Propane, 1,
Bis (hydroxyaryl) alkanes exemplified by 1-bis (4-hydroxyphenyl-1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, etc .; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; exemplified by 4,4'-dihydroxydiphenylether 4,4'-dihydroxy-3,3'-dimethyldiphenylether and the like Dihydroxy diaryl ethers; dihydroxy diaryl sulfides exemplified by 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4 ' Dihydroxy -3,
Dihydroxydiaryl sulfoxides exemplified by 3'-dimethyldiphenyl sulfoxide and the like; Dihydroxydiaryl sulfones exemplified by 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone and the like; Examples thereof include hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like. These aromatic dihydroxy compounds may be used alone or in combination of two or more. Among them, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used.

In order to obtain a branched aromatic polycarbonate resin, phloroglysin, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -2-heptene, 1,3,5-tri (2
-Hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2
Polyhydroxy compounds exemplified by -hydroxy-5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, or 3 , 3-Bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-
Bromoisatin bisphenol may be used.

In the case of the phosgene method polycarbonate, a terminal terminator or a molecular weight regulator may be used. Examples of the terminal terminator or the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group.
-In addition to butylphenol, tribromophenol and the like,
Examples include long-chain alkyl phenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, alkyl ether phenols and the like.
In the polycarbonate resin used in the present invention, one kind may be used, or two or more kinds may be mixed and used.

The molecular weight of the polycarbonate resin in the present invention is determined by using methylene chloride as a solvent at a temperature of 2
The viscosity average molecular weight converted from the solution viscosity measured at 5 ° C. is 10,000 to 100,000, preferably 15,000 to 50,000. The aromatic compound having an oxy group or a carbonyl group in the present invention is a compound represented by the following general formula (1) or (2).

[0013]

Embedded image

Where R¹, R^ThreeAnd R^FiveAre respectively C1
-10 alkyl group, alkoxy group, -CH_TwoOH group
Or a halogen group. R^FourIs C1-15 alkile
Group, alkenylene group, arylene group, alkylenedio
An oxy group or an arylenedialkyleneoxy group,
Nuclei of arylene and arylenedialkyleneoxy groups
Include as a substituent, a C1-10 alkyl group or halo.
It may have a gen group. X¹, X^TwoAnd X^ThreeIs it
-O- and -CHR respectively⁶-O-, -CO-, -CHR⁷-
CO-, -CO-CO- or -CO-C (OR⁸)_Two-so
Yes, R^Two, R⁶, R ⁷And R⁸Are H, C1-3, respectively.
0 alkyl group, cycloalkyl group, alkenyl group,
Reel group, arylalkyl group, arylalkenyl
Group, alkoxy group, arylalkoxy group, aryl group
Rukylkalkoxy group, acyl group or arylacyl group
And an aryl group, an arylalkyl group, an aryl group
Lucenyl group, arylalkoxy group, arylalkyl
As a substituent in the nucleus of the alkoxy group and arylacyl group
Having a C1-10 alkyl group or a halogen group
R which exists in the same nucleus^TwoA substituent having
When two or more are present, the substituents are the respective R^Two
It may be bound by a covalent bond via. h, j and k
Are integers of 0 to 5, respectively, and i is an integer of 1 to 6.
And the sum of h and i is 1 to 6. There is the oxy group
Or a compound having an aromatic compound having a carbonyl group
Can be used alone or in combination of two or more
good.

Specific examples of the compound represented by the general formula (1) include diphenyl ether, allyl phenyl ether, dibenzyl ether, benzyl methyl ether, benzyl phenyl ether, benzyl naphthyl ether,
1,4-benzodioxane, 1,2-methylenedioxybenzene, piperonyl alcohol, benzophenone, dibenzyl ketone, benzyl methyl ketone, benzyl phenyl ketone, benzyl tolyl ketone, benzyl naphthyl ketone, dibenzoyl, benzoyl cyclobutane, benzoyl propane , Benzoin ethyl ether, 1,2-dibenzoylbenzene, 1,4-bismethoxymethylbenzene, phenylacetic acid benzyl ester, benzoic acid benzyl ester, phthalic acid benzylbutyl ester, phthalic acid dicyclohexyl ester, benzyldimethylketal and the like. .

Specific examples of the compound represented by the general formula (2) include dibenzoylmethane, dibenzoylpropane,
1,2 dibenzyloxyethane, hydroquinone dibenzyl ether, ethylene glycol dibenzoate and the like.

The blending amount of the aromatic compound having an oxy group or a carbonyl group in the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the amount is less than 0.01 part by weight, the desired effect of improving the degree of yellowing due to irradiation with ionizing radiation is insufficient.
If it exceeds the weight part, mechanical properties are deteriorated, which is not preferable. From the viewpoint of improving the degree of yellowing and preventing the deterioration of mechanical properties, the preferable blending amount is 0.05 to 3 parts by weight. The sulfoxide compound in the present invention is a compound represented by the following general formula (3), (4) or (5).

[0018]

Embedded image

Where R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ and R
¹⁷ is a C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, acylalkyl group, alkoxyalkyl group, arylalkoxyalkyl group, arylalkoxyalkenyl group, alkoxy group, respectively. , An alkoxycarbonyl group, a polyethylene glycol ether group or a pyridyl group, and a C1-4 alkyl group as a substituent in the nucleus of the aryl group, arylalkyl group, arylalkenyl group, arylalkoxyalkenyl group and arylalkoxyalkyl group, Halogen group, -NO
₂ groups, -N (R ¹⁸⁾ ₂ group, -COOH group, -COOCH
₃ groups, —OH group, —CH ₂ OR ¹⁹ group or —OCH ₃ group, and the acylalkyl group, the alkoxyalkyl group, the arylalkoxyalkenyl group and the arylalkoxyalkyl group are an acyl group and an alkoxy group, respectively. Alternatively, it may have a plurality of arylalkoxy groups on the alkyl or alkenyl trunk, and R
⁹ and R ¹⁰ , R ¹¹ and R ^13, and R ¹⁴ and R ¹⁷ may be linked by a covalent bond. R ¹² , R ¹⁵ and R ¹⁶ are C1 to 1
5 alkylene group, alkenylene group, arylene group, arylene alkylene group or -O (CH ₂ CHR
²⁰ O) _t - is a group, as a substituent on the nucleus of the arylene group and the arylene alkylene group, an alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ¹⁸⁾ ₂ group, -CO
It may have an OH group, a —COOCH ₃ group, a —OH group, a —CH ₂ OR ¹⁹ group or a —OCH ₃ group, provided that R ¹⁵ and R ¹⁶ are different. R ¹⁸ , R ¹⁹ and R ²⁰ are respectively
H, C1-10 alkyl group, aryl group or arylalkyl group. m, n, and t are integers of 1 to 100. The sulfoxide compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (3) include dimethyl sulfoxide, dibutyl sulfoxide, diphenyl sulfoxide, dihydroxyphenyl sulfoxide, ditolyl sulfoxide, dibenzyl sulfoxide, divinyl sulfoxide, dixylyl sulfoxide, dimesityl sulfoxide. , Dinitrophenyl sulfoxide, diaminophenyl sulfoxide, dichlorophenyl sulfoxide, dimethoxyphenyl sulfoxide,
Dicyclohexylsulfoxide, 1-propenylmethylsulfoxide, methylcyclohexylsulfoxide, methylphenylsulfoxide, methyltolylsulfoxide, methylmethoxyphenylsulfoxide, methylchlorophenylsulfoxide, methylcarboxyphenylsulfoxide, methylallylsulfoxide, methylbenzylsulfoxide, phenylallylsulfoxide, phenyltolylsulfoxide , Phenylxylylsulfoxide, phenylmethoxyphenylsulfoxide, phenylvinylsulfoxide, phenylbenzylsulfoxide,
Phenylstyrylsulfoxide, phenylcinnamylsulfoxide, trimethyl-3- (phenylsulfinyl) orthopropionate, phenylmethoxymethylsulfoxide, phenylphenoxymethylsulfoxide,
Phenylacetonylsulfoxide, phenylphenacylsulfoxide, phenylcyclohexylsulfoxide,
Phenylmethylbenzylsulfoxide, phenylmethoxycarbonylsulfoxide, tolylbenzylsulfoxide, tolylbutylsulfoxide, tolylphenacylsulfoxide, tolybutoxysulfoxide, tolylsulfoxide, tolylaminophenylsulfoxide, tolylchlorobenzylsulfoxide, 4- (toluenesulfinyl) butane-2 -One, benzylallyl sulfoxide, 2-pyridylbenzyl sulfoxide, acetonyl nitrophenyl sulfoxide, trimethylene sulfoxide, tetramethylene sulfoxide, pentamethylene sulfoxide, benzothiophen-1-oxide, dibenzothiophen-1-oxide, thioxancene-9-oxide 2,2,5-dihydrothiophene-1-oxide, 4
-Butylthian-1-oxide and the like.

Specific examples of the compound represented by the general formula (4) include bis (methylsulfinyl) methane, 2,2-
Bis (methylsulfinyl) propane, bis (phenylsulfinyl) methane, 1,2-bis (phenylsulfinyl) ethane, 1,2-bis (phenylsulfinyl) ethylene, phenylsulfinylbenzylsulfinylphenylmethane, 1,4-dithiane-1 , 4-dioxide, polytetramethylene sulfoxide, polyhexamethylene sulfoxide and the like. Specific examples of the compound represented by the general formula (5) include poly (hexamethylene sulfoxide-co-octamethylene sulfoxide,
Poly (phenylene sulfoxide-co-hexamethylene sulfoxide, poly (hexamethylene sulfoxide-c
o-3,6,9,12,15,18-hexaoxyeicosanylene sulfoxide) and the like.

The content of the sulfoxide compound in the present invention is 100 parts by weight of the polycarbonate resin.
It is 0.01 to 5 parts by weight. If the blending amount is less than 0.01 part by weight, the desired effect of improving the yellowing degree by irradiation with ionizing radiation is insufficient, and if it exceeds 5 parts by weight, mechanical properties are deteriorated, which is not preferable. From the viewpoint of improving the yellowing degree and preventing the deterioration of mechanical properties, the preferable compounding amount is 0.05 to 3
Parts by weight.

The mixing ratio of the aromatic compound having an oxy group or a carbonyl group and the sulfoxide compound is not particularly limited, but is preferably 10/90 to 90/10 by weight. As described above, the polycarbonate resin composition containing a specific amount of an aromatic compound having a oxy group or a carbonyl group and a sulfoxide compound, respectively, by which the physical properties are not lowered, a polycarbonate resin composition with less yellowing degree Is obtained.

In the present invention, as a method for blending an aromatic compound having an oxy group or a carbonyl group and a sulfoxide compound with a polycarbonate resin, it is well known to those skilled in the art at any stage until just before the final molded article is molded. This can be done by various methods. For example, there are a method of mixing with a tumbler, a Henschel mixer, and the like, a method of quantitatively supplying the mixture to an extruder hopper by a feeder and mixing.

The composition of the present invention further has the following objects.
Other additives that impart desired properties may be added. For example, flame retardants such as halogen compounds, phosphorus compounds, metal sulfonic acid salts, flame retardant aids such as antimony compounds, zirconium compounds, etc., dripping inhibitors such as polytetrafluoroethylene, silicon compounds, etc., and impact resistance of elastomers and the like Improvers, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, plasticizers, release agents, lubricants, compatibilizers, foaming agents, glass fibers, glass beads, glass flakes, carbon fibers, fibrous magnesium , Potassium titanate whiskers, ceramic whiskers, mica, talc, etc.
It is also possible to add and contain one or more dyes and pigments.

The composition of the present invention can be formed into a desired molded article by a conventional molding method such as injection molding or blow molding. Medical molded articles for which it is desired to apply the ionizing radiation-resistant polycarbonate resin composition of the present invention include, specifically, artificial dialysers, artificial lungs, inhalation devices for anesthesia, intravenous connectors and accessories. Blood centrifuge bowls, surgical tools, operating room tools, tubing to supply oxygen to blood, tubing fittings, heart probes and syringes,
Examples include surgical tools, operating room instruments, containers for storing intravenous injections, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

[0028]

【Example】

[Examples 1 to 7, Comparative Examples 1 to 3] 100 parts by weight of a polycarbonate resin (Upilon S-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000), and an oxy group shown in Table 1 or An aromatic compound having a carbonyl group and a sulfoxide compound were mixed in a tumbler at a ratio shown in Table 1, and each was extruded at a barrel temperature of 270 ° C. using a φ40 mm uniaxial vent type extruder to obtain pellets. After drying the pellets in a hot air dryer at 120 ° C. for 5 hours or more, the resin temperature is 270 ° C., the mold temperature is 80 ° C., and the size is 50 mmφ × 3 m.
An m-thick test piece was injection molded. Using this molded piece, cobalt 60 γ-ray was irradiated with 25 kilogray (kGy), and the yellowness before and after the irradiation was measured with a color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS K7103. The degree of change (ΔYI) was determined. The results are shown in Table 1.

[0029]

[Table 1]

[0030]

EFFECT OF THE INVENTION The composition of the present invention has little deterioration in physical properties and little change in color tone due to ionizing radiation irradiated for sterilization. Therefore, it is useful for applications such as medical products, medical devices, and members of medical devices that are subjected to ionizing radiation irradiation sterilization.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08K 5/10 C08K 5/10 5/41 KKL 5/41 KKL

Claims (3)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
Aromatic compound having oxy group or carbonyl group 0.
01 to 5 parts by weight, and sulfoxide compound 0.01 to 5
A polycarbonate resin composition comprising parts by weight. 2. The polycarbonate resin composition according to claim 1, wherein the aromatic compound having an oxy group or a carbonyl group is a compound represented by the following general formula (1) or (2). Embedded image (In the formula, R ¹ , R ³ and R ⁵ are each a C 1-10 alkyl group, an alkoxy group, a —CH ₂ OH group or a halogen group, and R ⁴ is a C 1-15 alkylene group or an alkenylene group. , An arylene group, an alkylenedioxy group or an arylenedialkyleneoxy group, which may have a C1-10 alkyl group or a halogen group as a substituent in the nucleus of the arylene group and the arylenedialkyleneoxy group, and X ¹ , X ² and X ³ are each —O.
^{-, - CHR 6 -O -,} - CO -, - CHR 7 -CO -, -
CO-CO- or _{^{-CO-C (OR 8) 2}} - a and, R ^2,
R ⁶ , R ⁷ and R ⁸ are each H, a C1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group,
An arylalkyl group, an arylalkenyl group, an alkoxy group, an arylalkoxy group, an arylalkylalkoxy group, an acyl group or an arylacyl group, and an aryl group, an arylalkyl group, an arylalkenyl group,
The nucleus of the arylalkoxy group, the arylalkylalkoxy group and the arylacyl group has C1 to C1 as a substituent.
0 alkyl groups or halogen groups,
Further, when there are two or more substituents having R ² on the same nucleus, the substituents may be bonded by a covalent bond via each R ² , and h, j and k are respectively ,
Is an integer of 0 to 5, i is an integer of 1 to 6, and h and i
Is 1 to 6. ) 3. The polycarbonate resin composition according to claim 1, wherein the sulfoxide compound is a compound represented by the following general formula (3), (4) or (5). Embedded image (In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁷ are each a C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, An acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group, an arylalkoxyalkenyl group, an alkoxy group, an alkoxycarbonyl group, a polyethylene glycol ether group or a pyridyl group, which is an aryl group, an arylalkyl group, an arylalkenyl group, an arylalkoxyalkenyl group. And a substituent on the nucleus of the arylalkoxyalkyl group,
Alkyl C1 -4, halogen group, -NO ₂ group, -N
(R ¹⁸ ) ₂ group, —COOH group, —COOCH ₃ group, —OH
Group, a —CH ₂ OR ¹⁹ group or a —OCH ₃ group, and an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkenyl group and an arylalkoxyalkyl group respectively represent an acyl group, an alkoxy group or an arylalkoxy group. may have a plurality alkyl stem or alkenyl stem, also, R ⁹ and R ^10, R ¹¹
And R ¹³ and R ¹⁴ and R ¹⁷ may be bonded by a covalent bond, and R ¹² , R ¹⁵ and R ¹⁶ are C 1 to C ¹⁵ alkylene group, alkenylene group, arylene group, arylene dialkylene group or ^{_{O (CH 2 CHR 20 O)}} t - is a group, as a substituent on the nucleus of the arylene group and the arylene alkylene group, an alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ¹⁸⁾ ₂ groups, -COOH group, -C
OOCH ₃ group, -OH group, -CH ₂ OR ¹⁹ group or -OC
May have an H ₃ group, provided that R ¹⁸ , R ¹⁹ and R ²⁰ are different from R ¹⁵ and R ¹⁶ and are H, C 1 to 1, respectively.
0 is an alkyl group, an aryl group or an arylalkyl group, and m, n and t are integers of 1 to 100. )