JPH0987506A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a polycarbonate compsn. which is less likely to cause a change in color tone or a deterioration in properties upon exposure to an ionizing radiation for sterilization by incorporating predetermined amts. of a particular arom. compd. and a particular glycol into a polycarbonate resin. SOLUTION: An arom. compd. having an oxy or carbonyl group (e.g. dibenzyl ether, dibenzyl ketone, or 1,4-bismethoxymethylbenzene) in an amt. of 0.01 to 5 pts.wt. and a polyalkylene glycol and an ether of polyalkylene glycol or an ester of polyalkylene glycol (e.g. polyethylene glycol, polypropylene glycol, or polypropylene glycol distearate) in an amt. of 0.01 to 5 pts.wt. are incorporated into 100 pts.wt. polycarbonate resin.

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 polyalkylene glycol, a polyalkylene glycol ether or a polyalkylene glycol ester. 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, JP-A-62-135556 discloses a method of blending a polyether polyol or an alkyl ether thereof, and JP-A-64-22959 and JP-A-1-161050 protects with a specific end group. The method of blending the above-mentioned polyether polyol is disclosed in Japanese Patent Laid-Open No.
No. 2,270,869 and Japanese Patent Laid-Open No. 2-13460 disclose a method of blending polypropylene glycol.
No. 232258 discloses a method of blending a benzyl alcohol derivative, but the effect of suppressing yellowing is insufficient, and if the addition amount is increased enough to obtain a sufficient effect, other physical properties are adversely affected. There was a problem such as exerting it.

[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. A polycarbonate resin composition comprising 01 to 5 parts by weight and 0.01 to 5 parts by weight of a polyalkylene glycol, an ether of polyalkylene glycol or an ester of polyalkylene glycol.

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 calculated from the solution viscosity measured at 5 ° C. is 10,000 to 100,000, and 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).

[0014]

Embedded image In the formulas (1) and (2), R ¹ , R ³ and R ⁵ are respectively
Alkyl C1-10, a -CH ₂ OH group or a halogen group, R ⁴ is an alkylene group of C1～15, alkenylene group, an arylene group or alkylenedioxy group, the substituents on the nucleus of the arylene group As C1 to 1
0 alkyl groups or halogen groups,
X ¹ , X ² and X ³ are respectively —O— and —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 H, C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, alkoxy group, arylalkoxy group, arylalkylalkoxy group, acyl group or arylacyl group, respectively. And an aryl group, an arylalkyl group, an arylalkenyl group, an arylalkoxy group, an arylalkylalkoxy group, and an arylacyl group can have a C1-10 alkyl group or a halogen group as a substituent in the nucleus. When there are two or more substituents having R ² on the same nucleus, the substituents may be bonded to each other via a covalent bond via each R ² , and h, j and k are each 0 Is an integer from 1 to 5, i is an integer from 1 to 6, and the sum of h and i is 1
It is 6. The compound having an aromatic compound having an oxy group or a carbonyl group may be used alone or in combination of two or more.

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, and ethylene glycol dibenzoate.

The compounding 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 polyalkylene glycol, ether of polyalkylene glycol or ester of polyalkylene glycol in the present invention is a compound represented by the following general formula (3) or (4).

[0018]

Embedded image In formulas (3) and (4), R ⁹ , R ¹¹ , R ¹² and R ¹⁴ are each H, C1-30 alkyl, cycloalkyl, alkenyl, aryl, arylalkyl or arylalkenyl. Group, which can have a C1-10 alkyl group or a halogen group as a substituent in the nucleus of the aryl group, the arylalkyl group and the arylalkenyl group, and R ¹⁰ and R ¹³ are H and C 1, respectively.
To 4 alkyl groups, and n and q are each an integer of 1 or more, preferably an integer of 1 to 1000. m and p are integers of 1 to 10, respectively. The polyalkylene glycol, ether of polyalkylene glycol or ester of polyalkylene glycol may be used alone or in combination of two or more kinds.

Specific examples of the compound represented by the general formula (3) include polyethylene glycol, polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol dodecyl ether,
Polyethylene glycol benzyl ether, polyethylene glycol dibenzyl ether, polyethylene glycol-4-nonyl phenyl ether, polypropylene glycol, polypropylene glycol methyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dodecyl ether, polypropylene glycol benzyl ether, Polypropylene glycol dibenzyl ether, polypropylene glycol-
4-nonyl phenyl ether, polytetramethylene glycol, etc. are mentioned.

Specific examples of the compound represented by the general formula (4) include polyethylene glycol diacetate ester, polyethylene glycol acetic acid propionate ester, polyethylene glycol dibutyrate ester, polyethylene glycol distearate ester, polyethylene glycol dibenzoate ester, Polyethylene glycol di-2,
6-dimethyl benzoate, polyethylene glycol di-p-tert-butyl benzoate, polyethylene glycol dicaprylate, polypropylene glycol diacetate, polypropylene glycol acetate propionate, polypropylene glycol dibutyrate, polypropylene glycol distearate , Polypropylene glycol dibenzoate, polypropylene glycol di-2,6-dimethylbenzoate, polypropylene glycol di-
p-tert-butyl benzoate, polypropylene glycol dicaprylate and the like.

The amount of polyalkylene glycol, polyalkylene glycol ether or polyalkylene glycol ester used in the present invention is 0.01 to 5 parts by weight per 100 parts by weight of the polycarbonate resin. 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 degree of yellowing 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 carbonyl group and the polyalkylene glycol, the ether of polyalkylene glycol or the ester of polyalkylene glycol is not particularly limited, but is preferably 10/90 to 90 by weight. It is / 10. As described above, the polycarbonate resin is blended with a polyalkylene glycol, a polyalkylene glycol, a polyalkylene glycol ether or a polyalkylene glycol ester, respectively, and an aromatic compound having a specific amount of an oxy group or a carbonyl group. As a result, a polycarbonate resin composition having a low degree of yellowing can be obtained without deteriorating the physical properties.

In the present invention, as a method for blending an aromatic compound having an oxy group or a carbonyl group and a polyalkylene glycol with a polycarbonate resin, a person skilled in the art can carry out at any stage until just before the final molded article is molded. This can be performed by various known 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 may further comprise,
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 product according to 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.

[0027]

EXAMPLES Raw materials used in each example are as follows. Polycarbonate resin: Iupilon S-2000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000) Polyalkylene glycol compound: PEG1000 Polyethylene glycol (molecular weight 1,000) PPG2000 Polypropylene glycol (molecular weight 2,000) PPGST30 polypropylene Glycol distearate ester (molecular weight 3,000)

[Examples-1 to 7, Comparative Examples-1 to 3] 100 parts by weight of a polycarbonate resin, and an aromatic compound and a polyalkylene glycol compound having an oxy group or a carbonyl group shown in Table 1 are shown in Table 1. The mixture was mixed in a tumbler at a ratio of -1 and extruded at a barrel temperature of 270 ° C. using a φ40 mm uniaxial vent type extruder to obtain pellets. The pellets are placed in a hot air drier at 120 ° C.
After drying for 5 hours or more, a test piece having a thickness of 50 mmφ × 3 mm was injection molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. Using this molded piece, cobalt 60γ ray was irradiated with 25 kilogray (kGy), and the yellowness before and after the irradiation was measured by JI
According to SK7103, it was measured with a color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. to determine the degree of yellowing (ΔYI). 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.

Claims (3)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
Aromatic compound having oxy group or carbonyl group 0.
A polycarbonate resin composition obtained by blending 01 to 5 parts by weight and 0.01 to 5 parts by weight of a polyalkylene glycol, a polyalkylene glycol ether or a polyalkylene glycol ester. 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 (Wherein, R ^1, R ³ and R ⁵ are each an alkyl group, -CH ₂ OH or halogen group of C1-10, R ⁴
Is a C1-15 alkylene group, an alkenylene group, an arylene group or an alkylenedioxy group, and the nucleus of the arylene group may have a C1-10 alkyl group or a halogen group as a substituent, and X ¹ , X ² and X ³ are
^{Each, -O -, - CHR 6 -O} -, - CO -, - CH
^{R 7 -CO -, - CO-} CO- or -CO-C (OR ⁸⁾ ₂
And R ² , R ⁶ , R ⁷ and R ⁸ are H, C 1 respectively.
To 30 alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, arylalkyl groups, arylalkenyl groups, alkoxy groups, arylalkoxy groups, arylalkylalkoxy groups, acyl groups or arylacyl groups, aryl groups, arylalkyl The nucleus of the group, the arylalkenyl group, the arylalkoxy group, the arylalkylalkoxy group and the arylacyl group can have a C1-10 alkyl group or a halogen group as a substituent, and R ^{2 in the} same nucleus can be substituted. When there are two or more substituents, the substituents are the respective R
² may be covalently bonded via ² , h, j and k are each an integer of 0 to 5, i is an integer of 1 to 6, and the sum of h and i is 1 to 6 Is. ) 3. The polyalkylene glycol, the ether of polyalkylene glycol or the ester of polyalkylene glycol is a compound represented by the following general formula (3) or (4), wherein: Polycarbonate resin composition. Embedded image (In the formula, R ⁹ , R ¹¹ , R ¹² and R ¹⁴ are H and C, respectively.
1 to 30 are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group or an arylalkenyl group, wherein the nucleus of the aryl group, the arylalkyl group and the arylalkenyl group has a substituent of C1 to C1.
It may have 10 alkyl groups or halogen groups, R ¹⁰ and R ¹³ are each an H, C 1-4 alkyl group, n and q are each an integer of 1 or more, and m and p Are integers of 1 to 10, respectively. )