JPH10279787A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, showing little yellowing by ionizing radiation when irradiated with ultraviolet or visible ray, by including a compound generating active radicals or ions in a polycarbonate resin at a specific content. SOLUTION: This composition is obtained by including 0.01 to 5 pts.wt. of a compound generating active radicals or ions, when irradiated with ultraviolet or visible ray, in 100 pts.wt. of a polycarbonate resin. Such a compound is preferably an acetophenone-, benzophenone-, thioxanthone- or phosphorus- based one, or the like. This composition is resistant to deterioration of properties and suffers little discoloration when irradiated with ionizing radiation for sterilization, and hence is useful, e.g. for products for medical purposes and medical equipment members.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition which is less yellowed by ionizing radiation.

[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. These medical products are usually completely sterilized when used.
Specific examples include high-pressure steam sterilization, ethylene oxide gas (EOG) sterilization, and sterilization by irradiation with ionizing radiation such as gamma rays or 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 resins have a disadvantage that when irradiated with ionizing radiation during sterilization, they discolor yellow and impair 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 07-93120 discloses a method of compounding a compound having a mercapto group, and JP-A 5-209120 discloses a method of using a polyalkylene oxide and an aromatic compound having a sulfonic ester substituent in combination. JP-A-6-248170 discloses a method of compounding a compound having a sulfide group.
-302179 describes a method of blending a saccharin compound, but in any case, the yellowing inhibiting effect is insufficient, and there is a problem that an odor is generated during use and the environment during molding is deteriorated. I do.

Further, Japanese Patent Application Laid-Open No. Sho 61-215651 discloses a method of compounding a boron compound.
No. 5,556, 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]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the gist of the present invention is to generate active radicals or active ions in 100 parts by weight of a polycarbonate resin by ultraviolet light or visible light. In a polycarbonate resin composition containing 0.01 to 5 parts by weight of a compound.

As the polycarbonate resin in the present invention, an aromatic dihydroxy compound or a polymer of a thermoplastic aromatic polycarbonate which may be branched and obtained by reacting an aromatic dihydroxy compound with a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester is used. Or it is a copolymer.

As the aromatic dihydroxy compound, for example, 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,
Bis (hydroxyaryl) alkanes exemplified by 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane; 1,1-bis (4-hydroxyphenyl) cyclo Pentane, 1,1-bis (4-hydroxyphenyl)
Bis (hydroxyaryl) cycloalkanes exemplified by cyclohexane, 1,1, -bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 4,4′-dihydroxydiphenyl ether;
Dihydroxydiaryl ethers exemplified by 4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like; 4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides exemplified by 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulphoxide; 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulphoxide; 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-
Dihydroxydiarylsulfones exemplified by dimethyldiphenylsulfone and the like; hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl and the like;
Particularly preferred is 2,2-bis (4-hydroxyphenyl) propane. The aromatic dihydroxy compounds may be used alone or as a mixture of two or more.

In order to obtain a branched aromatic polycarbonate resin, phloroglysin, 2,6-dimethyl-2,4,4
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 or 3,3-bis (4-
Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol,
5,7-Dichloroisatin bisphenol, 5-bromoisatin 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, such as phenol, pt-butylphenol, pt-octylphenol,
(1-methyl-1-phenylethyl) phenol, tribromophenol, and the like, and a long-chain alkylphenol,
Aliphatic carboxylic acid chloride, aliphatic carboxylic acid, aromatic carboxylic acid, hydroxybenzoic acid alkyl ester,
Alkyl ether phenol and the like. One type of terminal terminator or molecular weight regulator may be used alone, or two or more types may be used in combination.

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 capable of generating active radicals or active ions by ultraviolet light or visible light in the present invention is, specifically, a compound capable of absorbing light having a wavelength of 100 to 600 nm to generate active radical species or active ion species. , A compound generally used as an initiator in photopolymerization. The wavelength of the light is preferably 200 to 5
00 nm, more preferably 250 to 450 nm. As the compound that generates an active radical or an active ion by ultraviolet light or visible light, preferably, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a phosphorus-based compound, an acridone-based compound, and a dicarbonyl-based compound are exemplified. The compounds that generate active radicals or active ions by ultraviolet light or visible light may be used alone or in combination of two or more.

As the acetophenone-based compound, preferably, a compound represented by the following general formula (1) is exemplified.

[0015]

Embedded image

In the formula (1), R ¹ is a hydroxy group, an alkoxy group or an amino group, preferably a hydroxy group, an alkoxy group having 1 to 30 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
0 is a secondary amino group. R ² and R ³ are each
A hydrogen atom, a halogen group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an arylalkyl group or an arylalkoxyalkyl group, preferably a hydrogen atom, a halogen group, an alkyl group having 1 to 30 carbon atoms, and 1 carbon atom; An alkoxy group having from 30 to 30, an alkoxyalkyl group having from 2 to 60 carbon atoms, an aryl group having from 6 to 30 carbon atoms,
An arylalkyl group having 7 to 60 carbon atoms or 8 to 8 carbon atoms
60 arylalkoxyalkyl groups, more preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 60 carbon atoms An aryl group, an arylalkyl group and an arylalkoxyalkyl group, the aromatic ring of which is an alkyl group, an alkoxy group or a halogen group, preferably having 1 to 2 carbon atoms.
It may have an alkyl group of 0, an alkoxy group having 1 to 20 carbon atoms or a halogen group, and R ² and R ³ may combine with each other to form a cyclic structure.

R ⁴ is a hydroxy group, hydroxyalkyl group, hydroxyalkoxy group, acyl group, acyloxy group, alkyloxycarbonyl group, amino group, alkyl group, alkoxy group, alkoxyalkyl group, aryl group, arylalkyl group, An arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group, preferably a hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, and an acyl having 1 to 30 carbon atoms Group, an acyloxy group having 1 to 30 carbon atoms, an alkyloxycarbonyl group having 2 to 30 carbon atoms, a secondary amino group having 1 to 30 carbon atoms,
An alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 60 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and 8 carbon atoms An arylalkoxyalkyl group having 1 to 30 carbon atoms, an alkylsulfide group having 1 to 30 carbon atoms, an arylsulfide group having 6 to 30 carbon atoms or a halogen group, more preferably a hydroxy group, a hydroxyalkoxy group having 1 to 30 carbon atoms, A secondary amino group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms or an alkyl sulfide group having 1 to 30 carbon atoms, and an aryl group, an arylalkyl group, an arylalkoxyalkyl In the aromatic ring of the aryl group and the aryl sulfide group, an alkyl group or a halogen group as a substituent, preferably having 1 carbon atom May have an alkyl group or a halogen group 20, a is an integer from 0 to 5, when a is 2 or more, R ⁴ may be different from each other,
They may combine with each other to form a ring structure.

Specific examples of the acetophenone compound include, for example, 2,2-diethoxyacetophenone,
Hydroxy-2-methyl-1-phenylpropane-1-
On, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1- (4- (2-hydroxyethoxy) phenyl) propan-1-one,
-Hydroxycyclohexyl phenyl ketone, 2-
Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-hydroxy-2-phenylacetophenone , Anisoin, 4,4'-dimethylbenzoin, 2-methoxy-2-phenylacetophenone, 2-ethoxy-2-
Examples include phenylacetophenone, 2-propoxy-2-phenylacetophenone, 2-isobutoxy-2-phenylacetophenone, and the like.

The benzophenone-based compound preferably includes a compound represented by the following general formula (2).

[0020]

Embedded image

In the formula (2), R ⁵ and R ⁶ are each
Hydroxy group, hydroxyalkyl group, hydroxyalkoxy group, acyl group, acyloxy group, alkyloxycarbonyl group, amino group, alkyl group, alkoxy group, alkoxyalkyl group, aryl group, arylalkyl group, arylalkoxyalkyl group, alkyl sulfide A hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and a 1 to 30 carbon atoms. An acyloxy group, an alkyloxycarbonyl group having 2 to 30 carbon atoms, a secondary amino group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 2 carbon atoms
~ 60 alkoxyalkyl group, 6 ~ 30 carbon atom aryl group, 7 ~ 60 carbon atom arylalkyl group, 8 ~ 60 carbon atom arylalkoxyalkyl group, 1 ~ carbon atom
An alkyl sulfide group having 30 carbon atoms, an aryl sulfide group having 6 to 30 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl having 7 to 60 carbon atoms Group, an alkyloxycarbonyl group having 2 to 30 carbon atoms or 6 to 6 carbon atoms
30 arylsulfide groups, wherein the aryl, arylalkyl, arylalkoxyalkyl, and arylsulfide groups have an aromatic ring as a substituent, preferably an alkyl or halogen group having 1 to 20 carbon atoms. And b and c are integers of 0 to 5, and when b is 2 or more,
R ⁵ may be different from each other, may be bonded to each other to form a cyclic structure, and when c is 2 or more, R 5
⁶ may be different from each other or may be bonded to each other to form a cyclic structure.

Specific examples of the benzophenone compound include, for example, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2,5-dimethylbenzophenone,
Examples include 3,4-dimethylbenzophenone, 4,4'-dimethylbenzophenone, 2,4,6-trimethylbenzophenone, methyl 2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and the like.

The thioxanthone compound preferably includes a compound represented by the following general formula (3).

[0024]

Embedded image

In the formula (3), R ⁷ and R ⁸ are each
Hydroxy group, hydroxyalkyl group, hydroxyalkoxy group, acyl group, acyloxy group, alkyloxycarbonyl group, amino group, alkyl group, alkoxy group, alkoxyalkyl group, aryl group, arylalkyl group, arylalkoxyalkyl group, alkyl sulfide A hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxyalkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and a 1 to 30 carbon atoms. An acyloxy group, an alkyloxycarbonyl group having 2 to 30 carbon atoms, a secondary amino group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 2 carbon atoms
~ 60 alkoxyalkyl group, 6 ~ 30 carbon atom aryl group, 7 ~ 60 carbon atom arylalkyl group, 8 ~ 60 carbon atom arylalkoxyalkyl group, 1 ~ carbon atom
An alkyl sulfide group having 30 carbon atoms, an aryl sulfide group having 6 to 30 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 60 carbon atoms And the aromatic ring of the aryl group, arylalkyl group, arylalkoxyalkyl group and arylsulfide group may have an alkyl group or a halogen group as a substituent, preferably an alkyl group or a halogen group having 1 to 20 carbon atoms. D and e are integers from 0 to 5;
When R is 2 or more, R ⁷ may be different from each other, or may be bonded to each other to form a cyclic structure;
When R is 2 or more, R ⁸ may be different from each other, or may be bonded to each other to form a cyclic structure.

Specific examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-diethylthioxanthone. As the phosphorus-based compound, preferably, a compound represented by the following general formula (4) is exemplified.

[0027]

Embedded image

In the formula (4), R ⁹ , R ¹⁰ and R ¹¹ each represent a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an amino group, an alkyl group, Group, alkoxyalkyl group, aryl group, arylalkyl group, arylalkoxyalkyl group, alkylsulfide group, arylsulfide group or halogen group, preferably a hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, A hydroxyalkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an acyloxy group having 1 to 30 carbon atoms, an alkyloxycarbonyl group having 2 to 30 carbon atoms, a secondary amino group having 1 to 30 carbon atoms, and 1 carbon atom ~ 30
Alkyl group having 1 to 30 carbon atoms, alkoxyalkyl group having 2 to 60 carbon atoms, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 60 carbon atoms, arylalkoxy having 8 to 60 carbon atoms Alkyl group, carbon number 1
An alkyl sulfide group having from 30 to 30 carbon atoms, an aryl sulfide group having from 6 to 30 carbon atoms or a halogen group, more preferably an alkyl group having from 1 to 30 carbon atoms, an aryl group having from 6 to 30 carbon atoms, or an aryl having from 7 to 60 carbon atoms An alkyl group, and the aromatic ring of the aryl group, the arylalkyl group, the arylalkoxyalkyl group and the arylsulfide group has an alkyl group or a halogen group as a substituent, preferably an alkyl group or a halogen group having 1 to 20 carbon atoms. Wherein f, g and h are integers of 0 to 5, and when f is 2 or more, R ⁹ may be different from each other, or may be bonded to each other to form a cyclic structure; If g is 2 or more, R ¹⁰ may be different from each other, may form a ring structure by bonding with each other, is h is 2 or more If, R ¹¹ may be different from each other, they may form a ring structure bonded to each other.

Specific examples of the phosphorus compound include 2, 4,
6-trimethylbenzoyldiphenylphosphine oxide and the like. As the acridone-based compound, preferably, a compound represented by the following general formula (5) is used.

[0030]

Embedded image

In the formula (5), R ¹² and R ¹³ each represent a hydroxy group, hydroxyalkyl group, hydroxyalkoxy group, acyl group, acyloxy group, alkyloxycarbonyl group, amino group, alkyl group, alkoxy group,
An alkoxyalkyl group, an aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group, preferably a hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, and a 1 to 30 carbon atom. Hydroxyalkoxy group, C1-30 acyl group, C1-30 acyloxy group, C2-30 alkyloxycarbonyl group, C1-30 secondary amino group, C1-30 An alkyl group, an alkoxy group having 1 to 30 carbon atoms, and 2 carbon atoms
~ 60 alkoxyalkyl group, 6 ~ 30 carbon atom aryl group, 7 ~ 60 carbon atom arylalkyl group, 8 ~ 60 carbon atom arylalkoxyalkyl group, 1 ~ carbon atom
An alkyl sulfide group having 30 carbon atoms, an aryl sulfide group having 6 to 30 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 60 carbon atoms And the aromatic ring of the aryl group, arylalkyl group, arylalkoxyalkyl group and arylsulfide group may have an alkyl group or a halogen group as a substituent, preferably an alkyl group or a halogen group having 1 to 20 carbon atoms. I and j are integers from 0 to 5;
When R is 2 or more, R ¹² may be different from each other, and may be bonded to each other to form a cyclic structure;
When R is 2 or more, R ¹³ may be different from each other or may be bonded to each other to form a cyclic structure. R
¹⁴ is a hydrogen atom, an alkyl group or an alkoxyalkyl group, preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an alkoxyalkyl group having 2 to 30 carbon atoms.

As the acridone compound, 9 (10
H) -acridone and the like. As the dicarbonyl compound, a compound represented by the following general formula (6) is preferably mentioned.

[0033]

Embedded image

In the formula (6), R ¹⁵ and R ¹⁶ are each a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an amino group, an alkyl group, an alkoxy group,
An alkoxyalkyl group, an aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group, preferably a hydroxy group, a hydroxyalkyl group having 1 to 30 carbon atoms, and a 1 to 30 carbon atom. Hydroxyalkoxy group, C1-30 acyl group, C1-30 acyloxy group, C2-30 alkyloxycarbonyl group, C1-30 secondary amino group, C1-30 An alkyl group, an alkoxy group having 1 to 30 carbon atoms, and 2 carbon atoms
~ 60 alkoxyalkyl group, 6 ~ 30 carbon atom aryl group, 7 ~ 60 carbon atom arylalkyl group, 8 ~ 60 carbon atom arylalkoxyalkyl group, 1 ~ carbon atom
An alkyl sulfide group having 30 carbon atoms, an aryl sulfide group having 6 to 30 carbon atoms or a halogen group, more preferably an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 60 carbon atoms And the aromatic ring of the aryl group, arylalkyl group, arylalkoxyalkyl group and arylsulfide group may have an alkyl group or a halogen group as a substituent, preferably an alkyl group or a halogen group having 1 to 20 carbon atoms. K and l are integers from 0 to 5;
When R is 2 or more, R ¹⁵ may be different from each other, or may be bonded to each other to form a cyclic structure;
When R is 2 or more, R ¹⁶ may be different from each other, or may be bonded to each other to form a cyclic structure.

In the formula (7), R ¹⁷ and R ¹⁸ are a hydrogen atom, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an aryloxy group, an arylalkyl group or an arylalkoxyalkyl group, respectively.
Preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkoxyalkyl group having 2 to 60 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms , An arylalkyl group having 7 to 60 carbon atoms or an arylalkoxyalkyl group having 8 to 60 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 6 to 6 carbon atoms.
An aryloxy group of 30 or an aryl group having 6 to 30 carbon atoms, and the aromatic ring of the aryl group, the aryloxy group, the arylalkyl group and the arylalkoxyalkyl group has an alkyl group or a halogen group as a substituent, preferably 1 to 30 carbon atoms. It can have 20 alkyl groups or halogen groups, and R ¹⁹ is a single bond, an alkylene group or an arylene group, preferably a single bond, having 1 to 15 carbon atoms.
An alkylene group or an arylene group having 6 to 30 carbon atoms, more preferably a single bond or an arylene group having 6 to 30 carbon atoms, and an alkyl or halogen group as a substituent on the aromatic ring of the arylene group, preferably Carbon number 1
May have an alkyl group or a halogen group to 20, R ^17, R ¹⁸ and R ¹⁹ may form a ring structure by bonding with each other.

Specific examples of the dicarbonyl compound include:
Methyl benzoyl formate, ethyl benzoyl formate, benzyl, anthraquinone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

The amount of the compound that generates active radicals or active ions by ultraviolet light or visible light 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 amount of the photopolymerization initiator is preferably 0.02 to 3 parts by weight, more preferably 0.02 to 3 parts by weight, from the viewpoint of the balance between the effect of improving the yellowing degree and the mechanical properties, based on 100 parts by weight of the polycarbonate resin. It is 0.05 to 2 parts by weight. As described above, a polycarbonate resin composition having a low yellowing degree can be obtained without reducing physical properties by blending a polycarbonate resin with a compound that generates an active radical or an active ion by a specific amount of ultraviolet light or visible light. Can be

The compound which generates an active radical or an active ion by ultraviolet light or visible light, together with a sensitizer,
It can also be blended with a polycarbonate resin. Examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, N, N
-Dimethylaniline, N, N-dimethylparatoluidine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-
Dimethylaminobenzoate, 2-ethylhexyl 4
-Dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-butoxyethyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 4-dimethylaminobenzoin, 4-dimethylaminoacetophenone, 4-dimethylaminobenzophenone, 4,4 '-Bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-dimethylamino-9-fluorenone and the like. The amount of the sensitizer is 10
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and most preferably 0.05 to 2 parts by weight with respect to 0 parts by weight.

In the present invention, as a method of compounding a compound capable of generating active radicals or active ions with ultraviolet light or visible light with a polycarbonate resin, a person skilled in the art can provide the compound at any stage immediately before molding a final molded product. Can be performed by various methods. For example,
Mixing with a tumbler, Henschel mixer, etc.,
There is 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, blow molding and the like. 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 of the present invention.

【Example】

[Examples 1 to 12, Comparative Example 1] Polycarbonate resin (Iupilon S-2000, manufactured by Mitsubishi Engineering-Plastics Corporation, viscosity average molecular weight 25,000)
0. ) 100 parts by weight and a compound that generates an active radical or an active ion by ultraviolet light or visible light shown in Table 1 were mixed in a tumbler in an addition amount (parts by weight) shown in Table 1, and each was 40 mm in diameter. The pellet was extruded at a barrel temperature of 270 ° C. using a single-screw vented extruder. After drying the pellets at 120 ° C. for 5 hours or more in a hot air drier, the resin temperature was 270 ° C. and the mold temperature was 80 ° C.
A test piece having a thickness of 50 mmφ × 3 mm was injection molded.
Using this molded piece, cobalt 60γ ray was irradiated with 25 kilogray (kGy), and the yellowness before and after the irradiation was measured according to JIS K7
According to 103, color difference meter SM-3 manufactured by Suga Test Instruments Co., Ltd.
The measurement was carried out with -CH to determine the yellowing degree (ΔYI). The results are shown in Table 1.

[0043]

[Table 1]

[0044]

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.

Claims (8)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
A polycarbonate resin composition comprising 0.01 to 5 parts by weight of a compound capable of generating active radicals or active ions by ultraviolet light or visible light. 2. The compound that generates an active radical or an active ion by ultraviolet light or visible light is an acetophenone compound, a benzophenone compound, a thioxanthone compound, a phosphorus compound, an acridone compound or a dicarbonyl compound. The polycarbonate resin composition according to claim 1, wherein 3. The polycarbonate resin composition according to claim 2, wherein the acetophenone compound is a compound represented by the general formula (1). Embedded image (In the formula (1), R ¹ is a hydroxy group, an alkoxy group or an amino group, and R ² and R ³ are each a hydrogen atom, a halogen group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, An arylalkyl group or an arylalkoxyalkyl group, an aryl group,
The aromatic ring of the arylalkyl group and arylalkoxy group may have an alkyl group or a halogen group as a substituent, they may form a ring structure bonded with each other and R ² and R ^3, R ⁴ Is a hydroxy group,
Hydroxyalkyl group, hydroxyalkoxy group, acyl group, acyloxy group, alkyloxycarbonyl group, amino group, alkyl group, alkoxy group, alkoxyalkyl group, aryl group, arylalkyl group, arylalkoxyalkyl group, alkylsulfide group, aryl An aryl group, an arylalkyl group, an arylalkoxyalkyl group or an arylsulfide group, which may have an alkyl group or a halogen group as a substituent;
When a is 2 or more, R ⁴ may be different from each other, or may be bonded to each other to form a cyclic structure. ) 4. The polycarbonate resin composition according to claim 2, wherein the benzophenone-based compound is a compound represented by the general formula (2). Embedded image (In the formula (2), R ⁵ and R ⁶ are each a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group,
Acyl group, acyloxy group, alkyloxycarbonyl group,
An amino group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group,
The aromatic ring of the arylalkyl group, arylalkoxyalkyl group and arylsulfide group can have an alkyl group or a halogen group as a substituent, b and c are integers of 0 to 5, and b is 2 or more. If
R ⁵ may be different from each other, may be bonded to each other to form a cyclic structure, and when c is 2 or more, R 5
⁶ may be different from each other or may be bonded to each other to form a cyclic structure. ) 5. The polycarbonate resin composition according to claim 2, wherein the thioxanthone compound is a compound represented by the general formula (3). Embedded image (In the formula (3), R ⁷ and R ⁸ are each a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group,
Acyl group, acyloxy group, alkyloxycarbonyl group,
An amino group, an alkyl group, an alkoxy group, an alkoxyalkyl group, an aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group,
The aromatic ring of the arylalkyl group, arylalkoxyalkyl group and arylsulfide group may have an alkyl group or a halogen group as a substituent, d and e are integers of 0 to 5, and d is 2 or more If
R ⁷ may be different from each other, may be bonded to each other to form a cyclic structure, and when e is 2 or more,
⁸ may be different from each other or may be bonded to each other to form a cyclic structure. ) 6. The polycarbonate resin composition according to claim 2, wherein the phosphorus compound is a compound represented by the general formula (4). Embedded image (In the formula (4), R ⁹ , R ¹⁰ and R ¹¹ each represent a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an amino group, an alkyl group, an alkoxy group, Alkoxyalkyl group, aryl group, arylalkyl group, arylalkoxyalkyl group, alkylsulfide group,
An aryl sulfide group or a halogen group, and the aromatic ring of the aryl group, the arylalkyl group, the arylalkoxyalkyl group and the aryl sulfide group can have an alkyl group or a halogen group as a substituent,
f, g and h are integers from 0 to 5, and when f is 2 or more, R ⁹ may be different from each other, or may be bonded to each other to form a cyclic structure; In the above, R ¹⁰ may be different from each other, and may be bonded to each other to form a cyclic structure. When h is 2 or more, R ¹¹ may be different from each other, and To form a ring structure. ) 7. The polycarbonate resin composition according to claim 2, wherein the acridone compound is a compound represented by the general formula (5). Embedded image (In the formula (5), R ¹² and R ¹³ each represent a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an amino group, an alkyl group, an alkoxy group, an alkoxyalkyl group , An aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group, and a substituent on the aromatic ring of the aryl group, the arylalkyl group, the arylalkoxyalkyl group and the arylsulfide group. Can have an alkyl group or a halogen group, and i
And j are integers of 0 to 5, and when i is 2 or more, R ¹² may be different from each other, may be bonded to each other to form a cyclic structure, and j is 2 or more. In this case, R ¹³ may be different from each other or may be bonded to each other to form a cyclic structure, and R ¹⁴ is a hydrogen atom, an alkyl group or an alkoxyalkyl group. ) 8. The dicarbonyl compound represented by the general formula (6)
Or the compound represented by (7), wherein the polycarbonate resin composition according to any one of claims 2 to 7. Embedded image (In the formula (6), R ¹⁵ and R ¹⁶ each represent a hydroxy group, a hydroxyalkyl group, a hydroxyalkoxy group, an acyl group, an acyloxy group, an alkyloxycarbonyl group, an amino group, an alkyl group, an alkoxy group, an alkoxyalkyl group , An aryl group, an arylalkyl group, an arylalkoxyalkyl group, an alkylsulfide group, an arylsulfide group or a halogen group, and a substituent on the aromatic ring of the aryl group, the arylalkyl group, the arylalkoxyalkyl group and the arylsulfide group. Can have an alkyl group or a halogen group;
And l are integers from 0 to 5, and when k is 2 or more, R ¹⁵ may be different from each other, may be mutually bonded to form a cyclic structure, and 1 is 2 or more. In this case, R ¹⁶ may be different from each other or may be bonded to each other to form a cyclic structure. In the formula (7), R ¹⁷ and R ¹⁸ are each a hydrogen atom, an alkyl group, an alkoxy group, An alkoxyalkyl group, an aryl group, an aryloxy group, an arylalkyl group or an arylalkoxyalkyl group, and the aromatic ring of the aryl group, the arylalkyl group and the arylalkoxyalkyl group may have an alkyl group or a halogen group as a substituent. ,
R ¹⁹ is a single bond, an alkylene group or an arylene group, and the aromatic ring of the arylene group can have an alkyl group or a halogen group as a substituent, and R ¹⁷ , R ¹⁸ and R ¹⁹ are bonded to each other. An annular structure may be formed. )