JP3370214B2 - 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 compound having a cyclic acetal group and a polyalkylene glycol 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.
No. 07, JP-A No. 5-209192 discloses a method of adding a compound having a mercapto group, and JP-A No. 6-93192 discloses a method of adding a compound having a sulfide group.
JP-A No. 120 discloses a method of using a polyalkylene oxide and an aromatic compound having a sulfonic acid ester substituent in combination, but in both cases, the yellowing-suppressing effect is insufficient or a malodor is generated during use. However, there is a problem that the environment during molding is deteriorated.

Further, in JP-A-62-135556, a method of blending a polyether polyol or an alkyl ether thereof is disclosed, and in JP-A-64-22959 and JP-A-1-161050, protection with a specific end group is carried out. The method of blending the above-mentioned polyether polyol is disclosed in Japanese Patent Laid-Open No.
-270869 and JP-A-2-13460, the method of blending polypropylene glycol is disclosed in JP-A-2 / 1990.
JP-A-132147 discloses a method of blending itaconic acid, rosin acid, benzaldehyde dimethyl acetal, benzaldehyde propylene glycol acetal, p-phthalaldehyde, etc., respectively, but the effect of suppressing yellowing is insufficient, or If the amount of addition is increased to obtain a sufficient effect, other physical properties are adversely affected.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polycarbonate resin composition which has little deterioration in physical properties and has 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 thereof is 0.01 to 5 parts by weight of a compound having a cyclic acetal group in 100 parts by weight of a polycarbonate resin. And a polyalkylene glycol, an ether of polyalkylene glycol, or an ester of polyalkylene glycol in an amount of 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.

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, α, α ', α "-tri (4-hydroxyphenyl)
Polyhydroxy compounds exemplified by -1,3,5-triisopropylbenzene and the like, or 3,3-bis (4-
Hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin bisphenol,
5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol, etc. 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 compound having a cyclic acetal group in the present invention is a compound represented by the following general formula (1) or (2).

[0014]

[Chemical 3] Where R¹, R², R^Four, R^Five, R⁶And R⁷Are H,
C1-10 alkyl group, -CH₂OH group, -COOC
H₃A group, a phenyl group or a halogen group, R ³Is C
1 to 15 alkylene group, alkenylene group or aryl
It is a len group, and C is a substituent on the core of the arylene group.
Having 1 to 10 alkyl groups or halogen groups
it can. R⁸Is H, a C1-30 alkyl group, cyclo
Alkyl group, alkenyl group, aryl group, aryl group
Kill group, arylalkenyl group, alkoxyalkyl
Group, acyl group, arylacyl group, halogen group, halogen
With an alkylated amino group, an amino group or an aminated alkyl group
Yes, aryl group, arylalkyl group, arylalkyl
As a substituent on the nucleus of the alkenyl group and the arylacyl group,
Having a C1-10 alkyl group or halogen group
You can X¹, X²And X³Is -CHR⁹-Group, -O-
Group, -NH- group, -S- group, -SS- group, or -P
H-group. R⁹Is an H, C1-15 alkyl group or
Or is an aryl group. j and k are 0 or
Is 1 and p, q and r are integers of 1 to 10 respectively.
Is a number. However, when p, q or r is 2 or more, they are the same.
R in the compound¹, R², R^Four, R^Five, R⁶Or R⁷Is that
They may be the same or different.

The compound having a cyclic acetal group may be used alone or in combination of two or more.
Specific examples of the compound represented by the general formula (1) include 2,
2'-ethylenebis-1,3-dioxolane, 2,2 '
-Trimethylenebis-1,3-dioxolane, 2,2 '
-Phenylenebis-1,3-dioxolane and the like. Specific examples of the compound represented by the general formula (2) include:
2-methyl-1,3-dioxolane, 2-methyl-4-
Methyl-1,3-dioxolane, 2-pentyl-4-methyl-1,3-dioxolane, 2-n-hexyl-1,
3-dioxolane, 2-octyl-4-methyl-1,3
-Dioxolane, 2-methoxy-1,3-dioxolane, 2-chloromethyl-1,3-dioxolane, 2-bromomethyl-1,3-dioxolane, 2- (2-bromoethyl) -1,3-dioxolane, 2- Aminomethyl-
1,3-dioxolane, 2- (2-aminoethyl)-
1,3-dioxolane, 2- (1-phenylethyl)-
1,3-dioxolane, 2- (1-phenylethyl)-
4-methyl-1,3-dioxolane, 2-benzyl-
1,3-dioxolane, 2-benzyl-4-methyl-
1,3-dioxolane, 2-benzyl-4,4-dimethyl-1,3-dioxolane, 2-benzyl-4-hydroxymethyl-1,3-dioxolane, 2- {2- (2-
Methoxyethoxy) ethoxy} -1,3-dioxolane, 2-benzyl-4,4-dimethyl-1,3-dioxane, 2-benzyl-5,5-dimethyl-1,3-dioxane and the like can be mentioned.

The compounding amount of the compound having a cyclic acetal group in the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Compounding amount 0.0
If it is less than 1 part by weight, the desired effect of improving the degree of yellowing 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 deterioration of mechanical properties, the compounding amount of the compound having a cyclic acetal group is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

The polyalkylene glycols, polyalkylene glycol ethers, and polyalkylene glycol esters that are the polyalkylene glycol compounds in the present invention are compounds represented by the following general formula (3) or (4).

[0018]

[Chemical 4] In the formula, R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ are respectively H and C1.
To 30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group or arylalkenyl group, wherein the aryl group, arylalkyl group and arylalkenyl group have a C1 to C1 substituent as a substituent.
It can have 10 alkyl or halogen groups. R ¹¹ and R ¹⁴ are each H or a C1-4 alkyl group. h and i are each an integer of 1 or more, preferably an integer of 1 to 1000. m and n are integers of 1 to 10, respectively.

The polyalkylene glycol, the ether of polyalkylene glycol or the 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-nonylphenyl. Ether, polypropylene glycol, polypropylene glycol methyl ether, polypropylene glycol dimethyl ether,
Examples thereof include polypropylene glycol dodecyl ether, polypropylene glycol benzyl ether, polypropylene glycol dibenzyl ether, polypropylene glycol-4-nonylphenyl ether, polytetramethylene glycol, and the like.

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-
Examples thereof include p-tert-butylbenzoic acid ester and polypropylene glycol dicaprylic acid ester.

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, preferably 0.05 to 3 parts by weight per 100 parts by weight of the polycarbonate resin. Parts by weight. If the 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.

The mixing ratio of the compound having a cyclic acetal group and polyalkylene glycol, ether of polyalkylene glycol or ester of polyalkylene glycol is not particularly limited, but preferably 10/9 by weight.
It is 0 to 90/10. As described above, the polycarbonate resin, the specific amount of each, by compounding a compound having a cyclic acetal group and a polyalkylene glycol, a polyalkylene glycol ether or a polyalkylene glycol ester polyalkylene glycol, the physical properties A polycarbonate resin composition having a low degree of yellowing can be obtained without any decrease.

In the present invention, as a method of blending the compound having a cyclic acetal group and the polyalkylene glycol with the polycarbonate resin, various methods well known to those skilled in the art can be used at any stage until just before the final molded article is molded. It can be done by a method. 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 comprises
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 made 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 it exceeds the gist.

[0027]

EXAMPLES The 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 1000) PPG2000 polypropylene glycol (molecular weight 2000) PPGST30 polypropylene glycol distearin Acid ester (molecular weight 3000)

[Examples 1 to 5 and Comparative Examples 1 to 3] 100 parts by weight of a polycarbonate resin, a compound having a cyclic acetal group shown in Table 1 and polyalkylene glycol, an ether of polyalkylene glycol or polyalkylene. The glycol esters were mixed in a tumbler in 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 drier for 120
After drying at 50 ° C. for 5 hours or more, a test piece of 50 mmφ × 3 mm thickness was injection molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. Using this molded piece, cobalt 60 gamma ray
Irradiate with kilogray (kGy) and measure the yellowness before and after irradiation.
According to IS K7103, the color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. was used to determine the degree of yellowing (ΔYI). The results are shown in Table-1.

[0029]

[Table 1]

[0030]

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.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-2-132147 (JP, A) US Pat. 4904710 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 69 / 00

Claims (3)

(57) [Claims] 1. To 100 parts by weight of a polycarbonate resin,
A polycarbonate resin composition comprising 0.01 to 5 parts by weight of a compound having a cyclic acetal group and 0.01 to 5 parts by weight of a polyalkylene glycol, a polyalkylene glycol ether or a polyalkylene glycol ester. 2. A compound having a cyclic acetal group is
A compound represented by the general formula (1) or (2)
The polycarbonate resin according to claim 1, wherein
Composition. [Chemical 1] (In the formula, R¹, R², R^Four, R^Five, R⁶And R⁷Respectively,
H, C1-10 alkyl group, -CH₂OH group, -CO
OCH₃A group, a phenyl group or a halogen group, R
³Is a C1-15 alkylene group, alkenylene group or
Is an arylene group, and in the nucleus of the arylene group is a substituent
Have a C1-10 alkyl group or halogen group
Can be R⁸Is H, a C1-30 alkyl group,
Cycloalkyl group, alkenyl group, aryl group, aryl
Alkyl group, aryl alkenyl group, alkoxy al
Kill group, acyl group, arylacyl group, halogen group, ha
Rogenated alkyl group, amino group or aminated alkyl
Group, aryl group, arylalkyl group, aryl
As a substituent in the nucleus of the alkenyl group and arylacyl group
Have a C1-10 alkyl group or halogen group
Can, X¹, X²And X³Is -CHR⁹-Group, -O-
Group, -NH- group, -S- group, -SS- group, or -P
H-group, R⁹Is an H, C1-15 alkyl group or
Or j is an aryl group, and j and k are 0 or
Is 1 and p, q and r are integers of 1 to 10 respectively.
Number, provided that if p, q, or r is 2 or more, they are the same
R in the compound ¹, R², R^Four, R^Five, R⁶Or R⁷Is that
They may be the same or different. ) 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. [Chemical 2] (In the formula, R ¹⁰ , R ¹² , R ¹³ and R ¹⁵ 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.
Can have an alkyl group of 10 or a halogen group, R ¹¹ and R ¹⁴ are each H or an alkyl group of C1 to 4, h and i are each an integer of 1 or more, and m and n is an integer of 1 to 10, respectively. )