JPH10259298A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition hardly causing deterioration of physical properties and change in color tone due to ionizing radiation irradiated for sterilization. SOLUTION: This polycarbonate resin composition is obtained by compounding 100 pts.wt. resin component comprising a halogenated polycarbonate or the halogenated polycarbonate and a non-halogenated polycarbonate with 0.01-5 pts.wt. aromatic compound having oxy group or carbonyl group and has 0.01-20wt.% halogen content derived from the halogenated polycarbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a halogenated polycarbonate resin composition containing an aromatic compound having an oxy group or a carbonyl group.

[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, JP-A-2-238049 discloses a method of blending a halogen-containing polycarbonate resin and polyalkylene glycol, and JP-A-2-265957 describes a method of blending a halogen-containing polycarbonate resin. And the method of compounding a carboxylic acid ester of polyalkylene glycol, respectively, are described, but the yellowing prevention effect is insufficient, or if the addition amount is increased as long as a sufficient effect is obtained, other physical properties are adversely affected. There were problems such as effects.

[0004]

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.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is that a resin component consisting of a halogenated polycarbonate or a halogenated polycarbonate and a non-halogenated polycarbonate has a weight of 100%. Of an aromatic compound having an oxy group or a carbonyl group in an amount of 0.01 to 5 parts by weight.
It is present in the polycarbonate resin composition in an amount of from 0.01 to 20% by weight.

Hereinafter, the present invention will be described in detail. The halogenated polycarbonate in the present invention is a polymer in which a halogen atom is bonded to a molecular chain. Examples of the halogen atom include a bromine atom, a chlorine atom, and an iodine atom. Atoms, and more preferably a bromine atom.

Examples of the halogenated polycarbonate include polymers and oligomers of a halogenated polycarbonate, and preferably, polymers and oligomers of a halogenated polycarbonate containing a structural unit derived from a halogenated aromatic dihydroxy compound in a molecular chain. No.

As a method for producing a halogenated polycarbonate, there is a method in which a halogenated aromatic dihydroxy compound is used as a part or all of the dihydric phenol compound when reacting the dihydric phenol compound with phosgene or a carbonic acid diester. Can be Examples of the halogenated polycarbonate include (1) a halogenated polycarbonate copolymer using a halogenated aromatic dihydroxy compound as a part of the aromatic dihydroxy compound,
(2) Halogenated polycarbonate homo-oligomer using only halogenated aromatic dihydroxy compounds as aromatic dihydroxy compound, (3) Halogenated polycarbonate resin using halogenated aromatic dihydroxy compounds as a part of aromatic dihydroxy compound Oligomers and the like.

The halogenated aromatic dihydroxy compound includes, for example, 2,2-bis (3,5-dibromo-4-
(Hydroxyphenyl) propane (= tetrabromobisphenol A), bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Methane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-
4-hydroxyphenyl) propane, bis (3-bromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 4, 4'-
And dihydroxy-3,3 ', 5,5'-tetrabromodiphenyl sulfide.
-Bis (3,5-dibromo-4-hydroxyphenyl)
And propane (= tetrabromobisphenol A). These halogenated aromatic dihydroxy compounds can be used alone or in combination of two or more.

When a halogenated polycarbonate is produced by the phosgene method, a terminal terminator or a molecular weight regulator can be used. Examples of the terminal terminator and the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Phenol, pt-butylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aromatic carboxylic acids, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, alkyl ether phenols, halogenated phenols , Halogenated aromatic carboxylic acids, halogenated aliphatic carboxylic acids, and the like. The terminator and molecular weight regulator are
One type or a mixture of two or more types can be used.

The viscosity average molecular weight of the halogenated polycarbonate in the present invention is a viscosity average molecular weight calculated from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and preferably from 1,000 to 100,0.
00. If the viscosity average molecular weight is less than 1,000, it tends to bleed out from the molded product at the time of molding.
If it exceeds 000, the fluidity and appearance characteristics are reduced. The viscosity average molecular weight of the halogenated polycarbonate is more preferably from 2,000 to 50,000, and most preferably from 3,000 to 40,000.

The non-halogenated polycarbonate resin in the present invention can be produced by reacting a non-halogen aromatic dihydroxy compound having no halogen atom bonded with phosgene or a carbonic acid diester.

The non-halogen aromatic dihydroxy compounds include, for example, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol 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-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3-cyclohexyl-
4-hydroxyphenyl) propane, 1,1-bis (4
Bis (hydroxyaryl) alkanes exemplified by -hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane; 1,1
-Bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,
Bis (hydroxyaryl) cycloalkanes exemplified by 3,5-trimethylcyclohexane and the like; 4,4 ′
Dihydroxydiaryl ethers exemplified by -dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; 4,4 '
Dihydroxydiaryl sulfides exemplified by -dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;
4,4′-dihydroxydiphenylsulfoxide, 4,
Dihydroxydiarylsulfoxides exemplified by 4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide and the like; exemplified by 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone and the like Dihydroxydiaryl sulfones: hydroquinone, resorcinol, 4,4′-
Dihydroxydiphenyl and the like, preferably,
2,2-bis (4-hydroxyphenyl) propane is exemplified. The non-halogenated aromatic dihydroxy compounds can be used alone or in combination of two or more.

When a non-halogenated polycarbonate resin is produced by the phosgene method, a terminal terminator and a molecular weight regulator can be used, and the terminal terminator and the molecular weight regulator are used for producing a halogenated polycarbonate. The above-mentioned terminal terminating agents and molecular weight regulators are used.

The non-halogenated aromatic polycarbonate resin may be branched. To obtain a branched non-halogenated aromatic polycarbonate resin, phloroglysine,
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) -1,3,5-triisopropylbenzene Polyhydroxy compounds exemplified, or 3,3-bis (4-hydroxyaryl)
Oxindole (= isatin bisphenol), 5-
Chlorisatin bisphenol, 5,7-dichlorisatin bisphenol, 5-bromoisatin bisphenol, or the like may be used.

The viscosity average molecular weight of the non-halogenated polycarbonate resin is determined by using methylene chloride as a solvent,
The viscosity average molecular weight calculated from the solution viscosity measured at a temperature of 25 ° C. is preferably 10,000 to 100,000, and more preferably 15,000 to 50,000.

Specific examples of the resin component in the polycarbonate resin composition of the present invention include (1) 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2, -bis (3,5 -Dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A), (2) a polycarbonate resin using bisphenol A and a composition of the copolymerized polycarbonate of (1), (3) Examples of polycarbonate resin using bisphenol A and polycarbonate oligomer using tetrabromobisphenol A, (4) compositions of polycarbonate resin using bisphenol A and copolymerized polycarbonate oligomer using tetrabromobisphenol A and bisphenol A, and the like. It is.

In the present invention, the compounding ratio of the halogenated polycarbonate to the non-halogenated polycarbonate is preferably 0.01 to 1%.
9% by weight and 9% non-halogenated polycarbonate
9.99 to 0% by weight.

The aromatic compound having an oxy group or a carbonyl group in the present invention is a compound represented by the following general formula (1) or (2).

[0020]

Embedded image

Wherein R ¹ , R ³ and R ⁵ are each C
1-10 alkyl group, alkoxy group, alkoxyalkyl group, arylalkoxy group, -CH ₂ OH
R ⁴ is a C1-15 alkylene group, alkenylene group, arylene group, alkylenedioxy group or arylene dialkyleneoxy group, and the arylene group and arylene dialkyleneoxy group are substituted with a nucleus. The group may have a C1-10 alkyl group or a halogen group, and X ¹ , X ² and X ³ are
^{Each, -O -, - CHR 6 -O} -, - CO -, - CH
R ⁷ -CO-, -CO-CO- or -CO-C (OR ⁸ ) ₂
And R ² , R ⁶ , R ⁷ and R ⁸ are each H, C
1 to 30 alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, arylalkyl groups, arylalkenyl groups, hydroxy groups, alkoxy groups, arylalkoxy groups, arylalkylalkoxy groups, acyl groups or arylacyl groups; The nucleus of the group, the arylalkyl group, the arylalkenyl group, the arylalkoxy group, the arylalkylalkoxy group and the arylacyl group may have a C1-10 alkyl group or a halogen group as a substituent. In the above case, the substituent may form another cyclic structure,
h, j, and k are each an integer of 0 to 5, i is an integer of 1 to 6, and the sum of h and i is 6. The compound having an aromatic compound having an oxy group or a carbonyl group may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (1) include diphenyl ether, allyl phenyl ether, dibenzyl ether, benzyl methyl ether, benzyl phenyl ether, benzyl naphthyl ether,
1,4-benzodioxane, 1,2-methylenedioxybenzene, piperonyl alcohol, benzophenone, dibenzyl ketone, benzyl methyl ketone, benzyl phenyl ketone, benzyl tolyl ketone, benzyl naphthyl ketone, dibenzoyl, benzoyl cyclobutane, benzoyl propane Benzoin, benzoin ethyl ether, 1,2-dibenzoylbenzene, 1,4-bismethoxymethylbenzene, phthalane, benzyl phenylacetate, benzyl benzoate, benzyl butyl phthalate, dicyclohexyl phthalate, benzyl dimethyl Ketal and the like.

Specific examples of the compound represented by the general formula (2) include dibenzoylmethane, dibenzoylpropane,
1,2 dibenzyloxyethane, hydroquinone dibenzyl ether, ethylene glycol dibenzoate and the like.

The amount of the aromatic compound having an oxy group or a carbonyl group in the present invention is 0.01 to 5 parts by weight based on 100 parts by weight of the halogenated polycarbonate or 100 parts by weight of the resin component composed of the halogenated polycarbonate and the non-halogenated polycarbonate. It is. If the compounding amount of the aromatic compound having an oxy group or a carbonyl group is less than 0.01 part by weight, the effect of improving the yellowing degree by irradiation with ionizing radiation tends to be insufficient, and if it exceeds 5 parts by weight, the mechanical properties deteriorate. Cheap. The amount of the aromatic compound having an oxy group or a carbonyl group is preferably 0.02 to 4 parts by weight of the polycarbonate resin composition, from the viewpoint of the balance between the effect of improving the yellowing degree and the mechanical properties. Preferably it is 0.05 to 3 parts by weight.

The polycarbonate resin composition of the present invention comprises:
A resin composition in which a specific amount of an aromatic compound having an oxy group or a carbonyl group is blended with a resin component composed of a halogenated polycarbonate or a resin component composed of a halogenated polycarbonate and a non-halogenated polycarbonate. Has a halogen content of 0.01 to 20% by weight. If the halogen content is less than 0.01% by weight, the effect of improving the degree of yellowing upon irradiation with ionizing radiation is insufficient, and if it exceeds 20% by weight, mechanical properties and heat resistance deteriorate. The halogen content derived from the halogenated polycarbonate in the polycarbonate resin composition is preferably 0.05 to 15% by weight, and more preferably 0.1 to 10% by weight. The halogen content can be measured by ashing the resin composition, collecting the generated gas, and measuring the content by ion chromatography.

In the present invention, the halogenated polycarbonate, or the halogenated polycarbonate and the non-halogen polycarbonate, may be mixed with an aromatic compound having an oxy group or a carbonyl group by an arbitrary step immediately before molding a final molded article. Then, it can be performed 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.

The resin composition of the present invention may further contain other additives for imparting desired properties within a range not impairing the object and effects of the present invention. For example, flame retardants such as halogen compounds, phosphorus compounds and metal sulfonic acid salts, flame retardant aids such as antimony compounds and zirconium compounds, anti-dripping agents at the time of ignition such as polytetrafluoroethylene and silicon compounds, 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, and other reinforcing agents, fillers, dyes and pigments, or one or more of them can be added and contained.

The resin 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. A blood centrifuge bowl, a surgical tool, an operating room tool, a tube for supplying oxygen to blood, a tube connector, a heart probe, a syringe, a surgical tool, an operating room instrument, a container for containing an intravenous injection solution, 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. The raw materials used are as follows.

(1) Halogenated polycarbonate-1:
3. Halogenated polycarbonate resin, N-3, manufactured by Mitsubishi Engineering-Plastics Corporation, bromine content
46% by weight, viscosity average molecular weight 25,000. (Hereinafter, referred to as halogenated PC-1) (2) Halogenated polycarbonate-2: halogenated polycarbonate oligomer, FR-53, manufactured by Mitsubishi Engineering-Plastics Corporation, bromine content 58.
8%, viscosity average molecular weight 7,300. (Hereinafter referred to as halogenated PC-2.) (3) Non-halogenated polycarbonate-1: polycarbonate resin containing no halogen, S-2000, manufactured by Mitsubishi Engineering-Plastics Corporation, having a viscosity average molecular weight of 25,000. (Hereinafter, referred to as PC-3)

The aromatic compounds having an oxy group or a carbonyl group (hereinafter, referred to as compound A) used in Examples and Comparative Examples are listed below. (4) dibenzyl ketone (hereinafter, referred to as compound A1) (5) dibenzyl ether (hereinafter, referred to as compound A2) (6) benzoin (hereinafter, referred to as compound A3) (7) xylylene oxide ( (Hereinafter, referred to as compound A4) (8) 1,2-dibenzyloxyethane (hereinafter, compound A)
No. 5. (9) 1,4-bismethoxymethylbenzene (hereinafter, referred to as compound A6) (10) Benzyl benzoate (hereinafter, referred to as compound A7) (11) Dicyclohexyl phthalate (hereinafter, referred to as compound A8)

[0032]

【Example】

[Examples 1 to 9 and Comparative Examples 1 to 3] A polycarbonate and an aromatic compound having an oxy group or a carbonyl group (compound A) shown in Table 1 were added to a tumbler at a compounding ratio shown in Table 1. The mixture was extruded at a barrel temperature of 270 ° C. using a φ40 mm uniaxial vent type extruder to obtain pellets. The pellets are placed in a hot air drier at 120 ° C.
After drying for 5 hours or more, a test piece having a thickness of 50 mmφ × 3 mm was injection molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. Using this molded piece, cobalt 60γ ray was irradiated with 25 kilogray (kGy), and the yellowness before and after the irradiation was measured by JI
According to SK7103, it was measured with a color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. to determine the degree of yellowing (ΔYI). The results are shown in Table 1.

[0033]

[Table 1]

[0034]

The polycarbonate resin composition of the present invention contains a specific amount of an aromatic compound having an oxy group or a carbonyl group, and contains a specific amount of a halogen derived from a halogenated polycarbonate. Outs are small, the appearance is excellent, the physical properties are hardly deteriorated, and the change in color tone due to ionizing radiation applied for sterilization is small. 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.

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[Procedure amendment]

[Submission date] April 24, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The halogenated aromatic dihydroxy compound includes, for example, 2,2-bis (3,5-dibromo-4-
Hydroxyphenyl) propane (= tetrabromobisphenol A), bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-bromo-4-
Hydroxyphenyl) propane, 2,2-bis (3,5
-Dichloro-4-hydroxyphenyl) propane, bis (3-bromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane , 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromodiphenyl sulfide, and the like, and preferably 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ( = Tetrabromobisphenol A). These halogenated aromatic dihydroxy compounds can be used alone or in combination of two or more.

Claims (5)

[Claims] 1. A resin component comprising a halogenated polycarbonate or a halogenated polycarbonate and a non-halogenated polycarbonate, wherein 100 parts by weight of the resin component is mixed with 0.01 to 5 parts by weight of an aromatic compound having an oxy group or a carbonyl group. A polycarbonate resin composition having a halogen content derived from a halogenated polycarbonate of 0.01 to 20% by weight. 2. The polycarbonate resin composition according to claim 1, wherein the halogenated polycarbonate is a halogenated polycarbonate containing a structural unit derived from a halogenated aromatic dihydroxy compound in a molecular chain. 3. The polycarbonate resin composition according to claim 1, wherein the halogenated polycarbonate has a viscosity average molecular weight of 1,000 to 100,000. 4. The polycarbonate resin composition according to claim 1, wherein the non-halogenated polycarbonate resin has a viscosity average molecular weight of 10,000 to 100,000. . 5. The polycarbonate according to claim 1, wherein the aromatic compound having an oxy group or a carbonyl group is a compound represented by the following general formula (1) or (2). Resin composition. Embedded image (Wherein, R ¹ , R ³ and R ⁵ are each a C1-10 alkyl group, an alkoxy group, an alkoxyalkyl group, an arylalkoxyalkyl group, a —CH ₂ OH group or a halogen group, and R ⁴ is A C1-15 alkylene group,
Alkenylene group, arylene group, alkylenedioxy group or arylenedialkyleneoxy group, the arylene group and arylenedialkyleneoxy group nucleus may have a C1-10 alkyl group or a halogen group as a substituent, X ¹ , X ² and X ³ are each
^{-O -, - CHR 6 -O -} , - CO -, - CHR 7 -CO
—, —CO—CO— or —CO—C (OR ⁸ ) ₂ —, wherein R ² , R ⁶ , R ⁷ and R ⁸ are each H, C 1-3
0 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, hydroxy group, alkoxy group, arylalkoxy group, arylalkylalkoxy group, acyl group or arylacyl group, aryl group, The nucleus of the arylalkyl group, the arylalkenyl group, the arylalkoxy group, the arylalkylalkoxy group, and the arylacyl group may have a C1-10 alkyl group or a halogen group as a substituent. If
The substituent may form another cyclic structure, and h, j
And k are each an integer of 0 to 5, and i is 1 to 6
And the sum of h and i is 6. )