JP3370219B2 - Polycarbonate resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing a cinnamyl 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 they have excellent mechanical strength, impact resistance, heat resistance, transparency and high safety. When used, these medical products are usually completely sterilized.
Specifically, it is 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 or electron beams. Of these, the high-pressure steam sterilization method has a high energy cost, and further requires a drying step after the sterilization treatment. In addition, EOG sterilization has toxicity of EOG itself and environmental problems related to disposal. Therefore, recently, the ionizing radiation (generally gamma ray) irradiation sterilization method, which is relatively inexpensive and can be processed at low temperature and dry type, has been widely used. However,
Polycarbonate resin has a drawback that it discolors yellow when irradiated with ionizing radiation during sterilization, which impairs the product value particularly in medical applications.

As a method of solving such a drawback, for example, in JP-A-2-55062, a method of blending a halogen-containing polycarbonate resin is disclosed in JP-A-5-17.
In Japanese Patent No. 9127, a method of blending a nuclear brominated phthalic acid derivative is described, but since a composition contains halogen, metal corrosion is likely to occur, and a metal of a special material is used for a molding machine or the like. Had to use.

Further, 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 known. 490
58, JP-A-4-36343, and 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, in JP-A-61-215651, a method of blending a boron compound is disclosed in JP-A-62-13.
Japanese Patent Laid-Open No. 2-23222 discloses a method of blending a polyether polyol or its alkyl ether.
In JP-A 58-58, each method of blending a benzyl alcohol derivative is described, 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 were problems such as.

[0006]

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

[0007]

The present invention has been made to solve the above-mentioned problems, and the gist thereof is to add 100 parts by weight of a polycarbonate resin to a cinnamyl compound represented by the general formula (1). It exists in a polycarbonate resin composition containing 0.01 to 5 parts by weight.

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

An example of an aromatic dihydroxy compound is 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 , 1-bis (4-hydroxyphenyl) cyclohexane and the like, bis (hydroxyaryl) cycloalkanes; 4,4′-dihydroxydiphenyl ether 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, etc. Dihydroxy diaryl ethers; 4,4'-dihydroxydiphenyl sulfide, dihydroxy diaryl sulfides exemplified by 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 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. You may use these aromatic dihydroxy compounds individually or in mixture of 2 or more types. Of these, 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
-Hydroxy-5-methylbenzyl) -4-methylphenol, polyhydroxy compound exemplified by 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-
Bromisatin bisphenol or the like may be used.

In the case of the phosgene-based polycarbonate, a terminal stopper or a molecular weight modifier may be used. Examples of the terminal terminator or the molecular weight modifier include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol and pt
-Butylphenol, tribromophenol, etc.,
Examples include long-chain alkylphenols, 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 2 at a temperature of methylene chloride as a solvent.
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 cinnamyl compound in the present invention is a compound represented by the following general formula (1).

[0013]

[Chemical 2]

In the formula, each R ¹ is a C1-10 alkyl group, an alkoxy group, a —OH group, a —CH ₂ OH group or a halogen group. X is -CO-, -COO-,
_{-CH 2 -O -, - CH 2} -CO-, or -CH ₂ -O
-COO-, preferably -CO-, -COO
-, or -CH ₂ -O-. R ² is H, C1 to 3
0 is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acyl group, or an arylacyl group, and is preferably an H, C1-30 alkyl group, an alkenyl group, or an aryl group. , An arylalkyl group or an acyl group,
The nucleus of the aryl group, the arylalkyl group, the arylalkenyl group, and the arylacyl group has C as a substituent.
1-10 alkyl groups, alkoxy groups, -OH groups, -C
It can have H ₂ OH groups or halogen groups. m
Is an integer of 0-5.

The cinnamyl compounds may be used alone or in combination of two or more. Specific examples of the compound represented by the general formula (1) include cinnamyl alcohol, cinnamaldehyde, methoxycinnamaldehyde, cinnamyl methyl ether, cinnamyl ethyl ether, cinnamyl allyl ether, cinnamyl phenyl ether, cinnamyl benzyl ether. , Cinnamyl methyl ketone, cinnamyl ethyl ketone, cinnamyl allyl ketone, cinnamyl phenyl ketone, cinnamyl benzyl ketone, acetic acid cinnamyl ester, propionic acid cinnamyl ester, butyric acid cinnamyl ester, benzoic acid cinnamyl ester, cinnamon bark Acid methyl ester, methyl cinnamic acid methyl ester, cinnamic acid ethyl ester, cinnamic acid vinyl ester, cinnamic acid allyl ester, cinnamic acid phenyl ester, cinnamic acid benzyl ester, cinnamic acid Cinnamyl ester, carbonate Shin'namirumechiru, cinnamyl phenyl and the like carbonates.

The amount of the cinnamyl compound used 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 degree of yellowing and preventing deterioration of mechanical properties, the amount of the cinnamyl compound added is
The amount is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

In the present invention, the method of blending the cinnamyl compound with the polycarbonate resin can be carried out by various methods well known to those skilled in the art at any stage immediately before the molding of the final molded product. For example, there are a method of mixing with a tumbler, a Henschel mixer, and the like, a method of quantitatively supplying to an extruder hopper with a feeder, and mixing.

The composition of the present invention further has the following objects.
Other additives that give desired properties may be added. For example, halogen compounds, phosphorus compounds, flame retardants such as sulfonic acid metal salts, antimony compounds, flame retardant aids such as zirconium compounds, anti-dripping agents during ignition of polytetrafluoroethylene, silicon compounds, impact resistance of elastomers, etc. Improver, antioxidant, heat stabilizer, ultraviolet absorber, antistatic agent, plasticizer, mold release agent, lubricant, compatibilizer, foaming agent, glass fiber, glass beads, glass flake, carbon fiber, fibrous magnesium , Potassium titanate whiskers, ceramic whiskers, mica, talc and other reinforcing agents, fillers,
It is also possible to add one or more kinds of 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. Examples of medical molded articles for which it is desired to apply the ionizing radiation resistant polycarbonate resin composition of the present invention, specifically, artificial dialyzer, artificial lung, inhalation device for anesthesia, vein connector and accessories , Blood centrifuge bowls, surgical tools, operating room tools, tubes supplying oxygen to blood, tube connections, heart probes and syringes,
Examples thereof include surgical tools, operating room instruments, and containers for containing 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 the gist thereof is exceeded.

Examples [ Examples 1 to 5 and Comparative Example 1 ] 100 parts by weight of a polycarbonate resin (Iupilon S-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000.), And described in Table 1. The cinnamyl compounds were mixed in a tumbler at the ratios 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. The pellets are heated in a hot air dryer at 120 ° C for 5
After drying for more than an hour, resin temperature 270 ° C, mold temperature 80
℃ at the test piece 50 mm φ × 3 mm thickness was injection molded. Using this molded piece, cobalt 60γ rays were irradiated with 25 kilogray (kGy), and the yellowness before and after irradiation was measured by JIS.
Color difference meter SM manufactured by Suga Test Instruments Co., Ltd. according to K7103
The measurement was carried out at -3-CH to obtain the degree of yellowing (ΔYI). The results are shown in Table-1.

[0021]

[Table 1]

[0022]

EFFECTS 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, members of medical devices, and the like in which ionizing radiation irradiation sterilization is performed.

Front page continued (72) Inventor Ken Shimomai 5-6-2 Higashi-Hachiman, Hiratsuka City, Kanagawa Mitsubishi Engineering Plastics Co., Ltd. Technical Center (56) Reference US Patent 5021478 (US, A) US Patent 3954839 ( (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (4)

(57) [Claims] 1. To 100 parts by weight of a polycarbonate resin,
Cinnamyl compound 0.0 represented by the following general formula (1)
A polycarbonate resin composition containing 1 to 5 parts by weight. [Chemical 1] (In the formula, each R ¹ is a C 1-10 alkyl group,
Alkoxy group, -OH group, a -CH ₂ OH group or a halogen group, X is, -CO -, - COO -, - CH 2 -
O -, - CH ₂ -CO-, or -CH ₂ -O-COO-
And R ² is H, a C1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acyl group, or an arylacyl group, and an aryl group, an arylalkyl group , The arylalkenyl group, and the arylacyl group may have a C1-10 alkyl group, an alkoxy group, a —OH group, a —CH ₂ OH group or a halogen group as a substituent, and m is 0 to 5 Is an integer. ) 2. X in the cinnamyl compound represented by the general formula (1) is —CO—, —COO—, or —CH.
₂ —O—, R ² is H, a C1-30 alkyl group,
The polycarbonate resin composition according to claim 1, which is an alkenyl group, an aryl group, an arylalkyl group, or an acyl group. 3. The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin is 10,000 to 100,000. 4. The polycarbonate resin composition according to claim 1, wherein the compounding amount of the cinnamyl compound represented by the general formula (1) is 0.05 to 3 parts by weight. object.