JPH09296104A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition reducing a lowering of physical properties and a yellowing when sterilizing by irradiating an ionizing radiation by blending a polycarbonate resin with a specific compound and a sulfide compound, a sulfoxide compound or a sulfone compound. SOLUTION: This polycarbonate resin composition comprises (A) 100 pts.wt. polycarbonate resin (preferably having 15,000-50,000 viscosity-average molecular weight), (B) 0.01-5 pts.wt. compound having a (substituted) oxyacetylene unit or a substituted cyclic ether compound and (C) 0.01-5 pts.wt. sulfide compound (e.g. dimethyl sulfide), sulfide compound (e.g. dubiety sulfoxide) or sulfone compound (e.g. biphenyl sulfone). A compound of formula I or II [R<1> to R<4> are each H, a 1-30C alkyl, etc.; R<5> and R<6> are each H, an acyl etc.; (m) is >=3; (p) is >=1] is preferably used as the compound having the (substituted) oxymethylene unit of the component B. A compound of formula III (R<7> and R<8> are each H, hydroxyl, etc.; R<9> and R<10> are each H, an aryl, etc.) is preferably used as the substituted cyclic ether compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to an ionizing radiation resistant polycarbonate resin composition.

[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. Further, 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 known.
JP-A-4-36343, JP-A-6-166807.
In JP-A-5-209120, a method of blending a compound having a mercapto group is used, and in JP-A-5-209120, a method of using a polyalkylene oxide and an aromatic compound having a sulfonate ester substituent in combination is further disclosed.
JP-A No. 2 and JP-A No. 6-248170 describe a method of blending a compound having a sulfide group, but in any case, the effect of inhibiting yellowing is insufficient, or a bad odor is generated during use. There is a problem that the environment during molding is deteriorated.

Further, Japanese Patent Application Laid-Open No. Sho 61-215651 discloses a method of compounding a boron compound.
Japanese Patent Laid-Open No. 2-23222 discloses a method of blending a polyether polyol or its alkyl ether.
No. 58 describes a method of blending a benzyl alcohol derivative, and JP-A-2-132147 describes a method of blending itaconic acid, benzaldehyde dimethyl acetal, benzaldehyde propylene glycol acetal, and the like. There are problems that the effect is insufficient, or that if the added amount 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 to solve the above-mentioned problems, and its gist is to provide a compound having an oxymethylene unit and a substituted oxymethylene unit in 100 parts by weight of a polycarbonate resin. 0.01 to 5 parts by weight of a compound having or a substituted cyclic ether compound,
And 0.01 to 5 parts by weight of a sulfide compound, a sulfoxide compound or a sulfone 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; 1,1-bis (4-hydroxyphenyl) cyclopentane; Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-
Dihydroxydiaryl sulfides exemplified by dimethyldiphenyl sulfide and the like; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-
Dihydroxydiarylsulfoxides exemplified by 3,3′-dimethyldiphenylsulfoxide and the like; 4,4 ′
Dihydroxydiarylsulfones exemplified by -dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; hydroquinone, resorcinol, 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.

Further, 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) -1,3,3 A polyhydroxy compound exemplified by 5-triisopropylbenzene or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin bisphenol, 5,7-dichloroisatin bisphenol 5,
-Bromisatine bisphenol or the like 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 compound having an oxymethylene unit or the compound having a substituted oxymethylene unit in the present invention is a compound represented by the following general formula (1) or (2).

[0013]

[Chemical 6]

In the formula, R ¹ , R ² , R ³ and R ⁴ are respectively
H, C1 to C30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, hydroxy group, alkoxy group, acyl group or acyloxy group, and aryl group, arylalkyl group and arylalkenyl. The nucleus of the group may have a C1-10 alkyl group or a halogen group as a substituent, and R ⁵ and R ⁶ are H and C1-30, respectively.
Is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an acyl group, and C1 is a substituent at the nucleus of the aryl group, the arylalkyl group and the arylalkenyl group.
It may have an alkyl group or a halogen group of 10 and m is an integer of 3 or more, preferably an integer of 3 to 30, more preferably an integer of 3 to 15, and p is an integer of 1 or more, preferably 1 To an integer of 5000, more preferably 1
It is an integer of ~ 3000. The compound having an oxymethylene unit or the compound having a substituted oxymethylene unit may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (1) include trioxane, paraaldehyde, methacrolein, methaldehyde and the like. Specific examples of the compound represented by the general formula (2) include paraformaldehyde and polyacetal. The substituted cyclic ether compound in the present invention is a compound represented by the following general formula (3).

[0016]

Embedded image

In the formula, R ⁷ and R ⁸ are H and C 1, respectively.
To 30, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, a hydroxy group, an alkoxy group, an acyl group or an acyloxy group, and a nucleus of an aryl group, an arylalkyl group and an arylalkenyl group. Has C1 as a substituent
10 to 10 alkyl groups or halogen groups, and R ⁹ and R ¹⁰ are each H, a C 1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group or An acyl group, and a nucleus of an aryl group, an arylalkyl group, and an arylalkenyl group is a C1 to C1
0 alkyl groups or halogen groups,
n is an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 7. The substituted cyclic ether compound may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (3) include 2,5-dimethoxytetrahydrofuran, 2,
5-diethoxytetrahydrofuran, 2,5-diphenoxytetrahydrofuran, 2,5-dimethoxy-3-formyltetrahydrofuran, 2,5-dimethoxy-2,
5-dihydrofuran, 2,6-dimethoxytetrahydropyran, 2,6-diethoxytetrahydropyran and the like.

The compounding amount of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit or the substituted cyclic ether compound in the present invention is 0.01 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin. If the amount is less than 0.01 part by weight, the effect of improving the degree of yellowing by irradiation with ionizing radiation tends to be insufficient, and if it exceeds 5 parts by weight, the mechanical properties tend to deteriorate. The compounding amount of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit, or the substituted cyclic ether compound is preferably 100 parts by weight of the polycarbonate resin in terms of the balance between the effect of improving the yellowing degree and the mechanical properties. Is 0.
05 to 3 parts by weight. The sulfide compound in the present invention is a compound represented by the following general formula (4) or (5).

[0020]

Embedded image _{^{R 11 - (S) h -R}} 12 (4) R 13 - (S) i - {R 14 - (S) j} k -R 15 (5)

In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each a C1-30 alkyl group, cycloalkyl group,
An alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acyl group, an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group or an arylalkoxyalkenyl group, which is an aryl group, an arylalkyl group, an arylalkenyl group, an arylalkoxy as a substituent in the nucleus of the alkyl group and arylalkoxy alkenyl group, an alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ¹⁶⁾ ₂ group, -COO
R ¹⁷ group, —OR ¹⁸ group or —CH ₂ OR ¹⁹ group can be contained, and an acylalkyl group, an alkoxyalkyl group,
The arylalkoxyalkyl group and the arylalkoxyalkenyl group may each have a plurality of acyl groups, alkoxy groups or arylalkoxy groups on the alkyl or alkenyl trunk, and R ¹¹ and R ¹² and R ¹³ and R ¹⁵ May be linked by a covalent bond, R
¹⁴ is a C1-15 alkylene group, an alkenylene group, an arylene group, an alkylidene group, an arylalkylidene group or a dialkylenearylene group, and as a substituent in the nucleus of the arylene group, the arylalkylidene group and the dialkylenearylene group, C1 to 4 alkyl group, a halogen group, -NO ₂ group, -N (R ¹⁶⁾ ₂ group, -COOR
¹⁷ groups, —OR ¹⁸ groups or —CH ₂ OR ¹⁹ groups, wherein R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each H,
A C1-10 alkyl group, an aryl group, or an arylalkyl group, wherein h, i, and j are each 1 to 1
It is an integer of 0, and k is an integer of 1 to 1000, preferably 1 to 500. The sulfide compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (4) include dimethyl sulfide, dimethyl disulfide,
Dimethyl trisulfide, diethyl sulfide, divinyl sulfide, diphenyl sulfide, diphenyl disulfide, diphenyl trisulfide, bis (hydroxyphenyl) sulfide, ditolyl sulfide, ditolyl disulfide, bis (nitrophenyl) sulfide,
Bis (aminophenyl) sulfide, bis (chlorophenyl) sulfide, bis (methoxyphenyl) sulfide, dibenzoyl sulfide, dibenzoyl disulfide, dibenzyl sulfide, dibenzyl disulfide,
Dibenzyl trisulfide, dibenzyl tetrasulfide, dibenzyl pentasulfide, dibenzyl hexasulfide, dibenzyl heptasulfide, dibenzyl octasulfide, dicyclohexyl sulfide, dicyclohexyl disulfide, methyl cyclohexyl sulfide, methyl phenyl sulfide, methyl allyl sulfide, methyl benzyl Sulfide, phenylallyl sulfide, phenylvinyl sulfide, phenylbenzyl sulfide, phenylstyryl sulfide, phenylcinnamyl sulfide, phenylbenzoyl sulfide,
Phenylphenacyl sulfide, phenylcyclohexyl sulfide, tolyl benzyl sulfide, benzyl allyl sulfide, trimethylene sulfide, trimethylene disulfide, tetramethylene sulfide, tetramethylene disulfide, pentamethylene sulfide, thiophene, 4H-thiine, benzothiophene, dibenzothiophene, thiachroman , Thiaxanthene and the like.

Specific examples of the compound represented by the general formula (5) include diethylthioacetal, α-phenyl-diethylthioacetal, 1,1-bis (ethylthio) propane, 1,1-bis (ethylthio) propene. 1, 4-
Bis (methyldithio) cyclohexane, 1,3-dithiolane, 1,3-dithiane, 1,4-dithiane, 1,4-
Dithiene, 1,4-dithiadiene, thianthrene, 1,
3,5-trithiane, polyphenylene sulfide, and the like. The sulfoxide compound in the present invention is a compound represented by the following general formula (6), (7) or (8).

[0024]

Embedded image

Where R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty four}, R^{twenty five}And R
²⁸Are a C1-30 alkyl group and a cycloalkyl group, respectively.
Alkyl group, alkenyl group, aryl group, arylalkyl group
Group, arylalkenyl group, acylalkyl group, ar group
Coxyalkyl group, arylalkoxyalkyl group,
Reel alkoxyalkenyl group, alkoxy group, alco
Xycarbonyl group, polyethylene glycol ether group
Or a pyridyl group, an aryl group, an arylalkyl group
Group, arylalkenyl group, arylalkoxy group
It is placed at the nucleus of the kill group and arylalkoxyalkenyl group.
As a substituent, a C1-4 alkyl group, a halogen group, -N
O_TwoGroup, -N (R²⁹)_TwoGroup, -COOR³⁰Group, -OR³¹Base
Or -CH_TwoOR³²Can have a group, acylal
Kill group, alkoxyalkyl group, arylalkoxy group
Alkyl group and arylalkoxyalkenyl group are
Acyl group, alkoxy group or aryl alcohol
Having multiple xy groups on the alkyl or alkenyl trunk
R may²⁰And R^{twenty one}And R^{twenty two}And R^{twenty four}Shared
May be tied together, R^{twenty three}, R²⁶And R²⁷Is
A C1-15 alkylene group, an alkenylene group,
-O (CH_TwoCH_TwoO) _t-Group, arylene group or dialky
An arylene group, an arylene group and a dialkyrene
The nucleus of the arylene group has a C1-4 alkyl group as a substituent.
Kill group, halogen group, -NO_TwoGroup, -N (R²⁹)_TwoGroup, -C
OOR³⁰Group, -OR³¹Group or -CH _TwoOR³²Have a group
But R²⁶And R²⁷Is different, R²⁹, R
³⁰, R³¹And R³²Are H and C1-10 al, respectively.
A alkyl group, an aryl group, or an arylalkyl group
, U, v, and t are each an integer of 1 to 100.
It is preferably an integer of 1 to 50. The sulfoxy
One compound or a mixture of two or more compounds may be used.
You can use it.

Specific examples of the compound represented by the general formula (6) 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 (7) 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 (8) include poly (hexamethylene sulfoxide-co-octamethylene sulfoxide), poly (phenylene sulfoxide-co-hexamethylene sulfoxide), poly (hexamethylene sulfoxide-co-3, 6,9,12,15,18-hexaoxyeicosanylene sulfoxide). The sulfone compound in the present invention has the following general formulas (9) and (1
It is a compound represented by 0) or (11).

[0028]

Embedded image

In the formula, R ³³ , R ³⁴ , R ³⁵ and R ³⁷ are each a C1-30 alkyl group, cycloalkyl group,
An alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group or an arylalkoxyalkenyl group, which is an aryl group, an arylalkyl group, an arylalkenyl group, an arylalkoxyalkyl group and as nuclear substituent the arylalkoxy alkenyl group, an alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ⁴⁰⁾ ₂ group, -OR ⁴¹ group or -C
Can have an H ₂ OR ⁴² group, an acylalkyl group,
An alkoxyalkyl group, an arylalkoxyalkyl group and an arylalkoxyalkenyl group are, respectively,
The alkyl or alkenyl trunk may have a plurality of acyl groups, alkoxy groups or arylalkoxy groups, and R ³³ and R ³⁴ and R ³⁵ and R ³⁷ may be bonded by a covalent bond. ³⁶ , R ³⁸ and R ³⁹ are C1 to 1
5 is an alkylene group, an alkenylene group, or an arylene group, wherein the nucleus of the arylene group has C1 to C1 as a substituent.
4 alkyl group, halogen group, -NO ₂ group, -N (R ⁴⁰ ) ₂
Group, a —OR ⁴¹ group or a —CH ₂ OR ⁴² group, wherein R ⁴⁰ , R ⁴¹ and R ⁴² are each H, C1-1.
0 is an alkyl group, an aryl group, or an arylalkyl group, w is an integer of 1 to 100, and preferably
It is an integer of 1 to 50. The sulfone compounds may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (9) include dimethyl sulfone, dibutyl sulfone, diphenyl sulfone, dihydroxyphenyl sulfone, ditolyl sulfone, dixylyl sulfone, dimesityl sulfone, dinitrophenyl sulfone, diaminophenyl. Sulfone, dichlorophenyl sulfone, dimethoxyphenyl sulfone, divinyl sulfone, dicyclohexyl sulfone, dibenzyl sulfone, 1-propenylmethyl sulfone, methylphenyl sulfone, methyltolyl sulfone,
Methylcyclohexylsulfone, methylmethoxyphenylsulfone, methylchlorophenylsulfone, methylallylsulfone, methylbenzylsulfone, phenylallylsulfone, phenyltolylsulfone, phenylxylylsulfone, phenylmethoxyphenylsulfone, phenylvinylsulfone, phenylbenzylsulfone, phenylstyrylsulfone , Phenylcinnamyl sulfone,
Trimethyl-3- (phenylsulfonyl) orthopropionate, phenylmethoxymethylsulfone, phenylphenoxymethylsulfone, phenylacetonylsulfone, phenylphenacylsulfone, phenylcyclohexylsulfone, phenylmethylbenzenesulfone, phenylmethoxycarbonylsulfone, tolylylsulfone , Tolylbutylsulfone, tolylphenacylsulfone, tolylbenzylsulfone, tolylaminophenylsulfone, tolylchlorobenzylsulfone, 4- (toluenesulfonyl) butan-2-one, benzylallyl sulfone, trimethylene sulfone, tetramethylene sulfone, pentamethylene Sulfone, benzothiophene dioxide, dibenzothiophene dioxide, thioxancene-9,9-dioxide 2,5-dihydro-thiophene -
1,1-dioxide, 4-butylthiane-1,1-dioxide and the like.

Specific examples of the compound represented by the general formula (10) include bis (methylsulfonyl) methane, 2,2-
Examples thereof include bis (methylsulfonyl) propane, bis (phenylsulfonyl) methane, 1,2-bis (phenylsulfonyl) ethane, 1,2-bis (phenylsulfonyl) ethylene and phenylsulfonylbenzylsulfonylphenylmethane. Specific examples of the compound represented by the general formula (11) include 1,4-thioxane-1,1-dioxide and the like.

The compounding amount of the sulfide compound, the sulfoxide compound or the sulfone compound 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 effect of improving the degree of yellowing by irradiation with ionizing radiation tends to be insufficient, and if it exceeds 5 parts by weight, the mechanical properties tend to deteriorate. The amount of the sulfide compound, sulfoxide compound or sulfone compound is preferably 0.05 to 3 parts by weight based on 100 parts by weight of the polycarbonate resin from the viewpoint of the balance between the improvement effect of the yellowing degree and the mechanical properties.

The mixing ratio of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit or the substituted cyclic ether compound and the sulfide compound, the sulfoxide compound or the sulfone compound is not particularly limited,
The weight ratio is preferably 10/90 to 90/10. As described above, the polycarbonate resin, a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound and a sulfide compound, a sulfoxide compound or a sulfone compound,
By blending each in a specific amount, 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 of blending a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound, and a sulfide compound, a sulfoxide compound or a sulfone compound with a polycarbonate resin, a final molded article is used. Can be performed at any stage until just before molding by various methods well known to those skilled in the art. 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.

Further, the composition of the present invention 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. [Examples 1 to 5 and Comparative Examples 1 to 3] Polycarbonate resin (Upilon S-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000)
0. ) 100 parts by weight, a compound having an oxymethylene unit shown in Table-1, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound and a sulfide compound, a sulfoxide compound or a sulfone compound, and a ratio shown in Table-1. Then, mix with a tumbler, each φ4
Using a 0 mm uniaxial vented extruder, barrel temperature 270
Extruded at ℃ to obtain pellets. The pellets were dried in a hot air drier at 120 ° C. for 5 hours or more, and then 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 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.

[0038]

[Table 1]

[0039]

Industrial Applicability The polycarbonate resin composition of the present invention has little physical property deterioration 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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 71:02)

Claims (6)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
Polycarbonate resin containing 0.01 to 5 parts by weight of a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound, and 0.01 to 5 parts by weight of a sulfide compound, a sulfoxide compound or a sulfone compound. Composition. 2. The polycarbonate resin according to claim 1, wherein the compound having an oxymethylene unit or the compound having a substituted oxymethylene unit is a compound represented by the following general formula (1) or (2). Composition. Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are respectively H, C1 to
30, alkyl groups, cycloalkyl groups, alkenyl groups,
An aryl group, an arylalkyl group, an arylalkenyl group, a hydroxy group, an alkoxy group, an acyl group or an acyloxy group, wherein the aryl group, the arylalkyl group and the arylalkenyl group have a C1 to C1 substituent as a substituent.
0 alkyl groups or halogen groups,
R ⁵ and R ⁶ are H, a C1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an acyl group, respectively, and are an aryl group, an arylalkyl group and an arylalkenyl. The nucleus of the group may have a C1-10 alkyl group or a halogen group as a substituent, and m is 3
The above is an integer, and p is an integer of 1 or more. ) 3. The polycarbonate resin composition according to claim 1 or 2, wherein the substituted cyclic ether compound is a compound represented by the following general formula (3). Embedded image (Wherein, R ⁷ and R ⁸ are each an H, C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, hydroxy group, alkoxy group, acyl group or acyloxy group) And a nucleus of an aryl group, an arylalkyl group and an arylalkenyl group can have a C1-10 alkyl group or a halogen group as a substituent, and R ⁹ and R ¹⁰ are each H, C1 30 alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, arylalkyl groups, arylalkenyl groups or acyl groups, and the nuclei of the aryl group, the arylalkyl group and the arylalkenyl group each have C1-10 It can have an alkyl group or a halogen group, and n is an integer of 1 or more.) 4. The sulfide compound has the following general formula (4):
Or it is the compound shown by (5), The polycarbonate resin composition in any one of Claim 1 to 3 characterized by the above-mentioned. ## STR3 ## _{^{R 11 - (S) h -R}} 12 (4) R 13 - (S) i - {R 14 - (S) j} k -R 15 (5) ( wherein, R ^11, R ¹² , R ¹³ and R ¹⁵ are each C1
To 30 are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acyl group, an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group or an arylalkoxyalkenyl group, and an aryl group , arylalkyl group, arylalkenyl group, as a nucleus the substituents on the arylalkoxy group and an arylalkoxy group, arylalkenyl group, an alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ¹⁶⁾ ₂ group, -COOR ¹⁷ group, -O
R ¹⁸ group or —CH ₂ OR ¹⁹ group can be included, and an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group and an arylalkoxyalkenyl group can be an acyl group, an alkoxy group or an arylalkoxy group, respectively, and an alkyl group. Alternatively, a plurality of alkenyl groups may be contained, and R ¹¹ and R ¹² and R ¹³ and R
¹⁵ may be linked by a covalent bond, and R ¹⁴ is C1 to C1.
15 alkylene groups, alkenylene groups, arylene groups,
An alkylidene group, an arylalkylidene group or a dialkylenearylene group, wherein the arylene group, the arylalkylidene group and the dialkylenearylene group each have a C1-4 alkyl group, a halogen group or -N as a substituent in the nucleus thereof.
It may have an O ₂ group, —N (R ¹⁶ ) ₂ group, —COOR ¹⁷ group, —OR ¹⁸ group or —CH ₂ OR ¹⁹ group, and R ¹⁶ , R ¹⁷ ,
R ¹⁸ and R ¹⁹ are each H, a C1-10 alkyl group, an aryl group, or an arylalkyl group,
h, i, and j are each an integer of 1 to 10, and k
Is an integer of 1 to 1000. ) 5. The sulfoxide compound has the following general formula:
It is a compound represented by (6), (7) or (8).
The poly according to any one of claims 1 to 4, characterized in that
Carbonate resin composition. Embedded image(Where R²⁰, R^{twenty one}, R^{twenty two}, R^{twenty four}, R^{twenty five}And R²⁸Is it
Respectively, C1-30 alkyl group, cycloalkyl group,
Alkenyl group, aryl group, arylalkyl group, ant
Alkenyl group, acylalkyl group, alkoxyalkyl
Kill group, arylalkoxyalkyl group, arylalk
Coxyalkenyl group, alkoxy group, alkoxycarbo
Nyl group, polyethylene glycol ether group or pyri
A jyl group, an aryl group, an arylalkyl group, an ant
Alkenyl group, arylalkoxyalkyl group and
The nucleus of the arylalkoxyalkenyl group is a substituent.
C1-4 alkyl group, halogen group, -NO_TwoBase,
−N (R²⁹)_TwoGroup, -COOR³⁰Group, -OR³¹Group or-
CH_TwoOR³²An acylalkyl group
Group, alkoxyalkyl group, arylalkoxy
And arylalkoxyalkenyl groups, respectively.
And an acyl group, an alkoxy group or an arylalkoxy
Having a plurality of groups on the alkyl or alkenyl backbone.
May be R²⁰And R^{twenty one}And R^{twenty two}And R^{twenty four}Is a covalent bond
May be tied, R^{twenty three}, R²⁶And R²⁷Is that
And a C1-15 alkylene group, alkenylene group, -O
(CH_TwoCH_TwoO) _t-Group, arylene group or dialkylene
An arylene group, an arylene group and a dialkylene
The substituent of the nucleus of the arylene group may be a C1-4 alkyl.
Group, halogen group, -NO_TwoGroup, -N (R²⁹)_TwoGroup, -COO
R³⁰Group, -OR³¹Group or -CH _TwoOR³²Having a group
Where R²⁶And R²⁷Is different, R²⁹, R³⁰, R
³¹And R³²Is, respectively, H, C1-10 alkyl
A group, an aryl group, or an arylalkyl group,
u, v, and t are each an integer of 1 to 100.
You. ) 6. The sulfone compound has the following general formula (9):
The polycarbonate resin composition according to any one of claims 1 to 5, which is a compound represented by (10) or (11). Embedded image (In the formula, R ³³ , R ³⁴ , R ^35, and R ³⁷ are each C1
To 30, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group or an arylalkoxyalkenyl group; In the nucleus of the group, arylalkenyl group, arylalkoxyalkyl group and arylalkoxyalkenyl group, a C1-4 alkyl group, a halogen group, -NO
₂ group, -N (R ⁴⁰⁾ ₂ group, ⁴¹ group -OR or -CH ₂ OR ⁴²
Can have a group, an acylalkyl group, an alkoxyalkyl group, an arylalkoxyalkyl group and an arylalkoxyalkenyl group are each an acyl group,
R ³³ may have a plurality of alkoxy groups or arylalkoxy groups, and R ³³
And R ³⁴ and R ³⁵ and R ³⁷ may be bonded to each other by a covalent bond, and R ³⁶ , R ³⁸ and R ³⁹ are each a C1-15 alkylene group, an alkenylene group or an arylene group. as a substituent in the nucleus, the alkyl group of C1 -4, halogen group, -NO ₂ group, -N (R ⁴⁰⁾ ₂ group, -OR ⁴¹
Group or a —CH ₂ OR ⁴² group, R ⁴⁰ , R
⁴¹ and R ⁴² are each H, a C1-10 alkyl group, an aryl group, or an arylalkyl group, and w
Is an integer of 1 to 100. )