JPH10324799A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition slight in deterioration of physical properties, extremely slight in yellowing in sterilization by ionizing irradiation, widely useful as medical products by compounding a resin component with a specific compound and specifying a halogen content. SOLUTION: This composition is obtained by compounding 100 pts.wt. of a resin component composed of (A) a halogenated polycarbonate or the component A and (B) a nonhalogenated polycarbonate with (C) 0.01-5 pts.wt. of (iii) a cyclic acetal group-containing compound, preferably a compound of formula I or formula II [R<1> to R<4> , R<6> and R<7> are H, a 1-10C alkyl, CH2 OH, etc.; R<5> is a 1-15C alkylene, alkenyl, etc.; R<8> is H, a 1-30C alkyl, cycloalkyl, etc.; X<1> to X<3> are each CHR<9> (R<9> is H, a 1-15C alkyl, etc.), O, etc.; (i), (j) and (r) are each 0 or 1; (h), (k) and (q) are each 1-10] and has 0.01-20 wt.% of a halogen content derived from the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a halogenated polycarbonate resin composition, and more particularly to an ionizing radiation-resistant halogenated 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. 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 discloses a method of blending a halogen-containing polycarbonate resin. And a method of compounding a carboxylic acid ester of polyalkylene glycol, respectively, are described, but the effect of preventing yellowing is insufficient, or increasing the amount of addition to obtain a sufficient effect adversely affects other physical properties. There was a problem such as the effect.

[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]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is to provide a resin component comprising a halogenated polycarbonate or a resin component comprising a halogenated polycarbonate and a non-halogenated polycarbonate. A compound having a cyclic acetal group in an amount of 0.01 to 5 parts by weight is added to 100 parts by weight of the component.
1 to 20% by weight of the polycarbonate resin composition.

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, 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.

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-halogen 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) Composition of polycarbonate resin using bisphenol A and polycarbonate oligomer using tetrabromobisphenol A, (4) polycarbonate resin using bisphenol A and tetrabromobisphenol A
And a composition of a copolymerized polycarbonate oligomer using phenol and bisphenol A.

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 compound having a cyclic acetal group in the present invention is a compound represented by the following general formula (1) or (2).

[0020]

Embedded image

Wherein R ¹ , R ² , R ³ , R ⁴ , R6 and R7
Are each, H, an alkyl group of C1-10, -CH ₂
An OH group, a —COOCH ₃ group, a phenyl group or a halogen group; R5 is a C1-15 alkylene group, alkenylene group or arylene group, and the nucleus of the arylene group is a C1-10 alkyl group as a substituent; Or a halogen group, and R ⁸ is H, a C1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, an alkoxyalkyl group, an acyl group, an arylacyl group. , A halogen group, a halogenated alkyl group, an amino group or an aminated alkyl group, and a nucleus of an aryl group, an arylalkyl group, an arylalkenyl group, and an arylacyl group is a C1-10 alkyl group or a halogen group as a substituent. may have, X ^1, X ² and X ³ are each, -CHR ⁹ - group -O- group, -NH- group or -PH
R ⁹ is H, a C1-15 alkyl group or an aryl group, i, j and r are each 0 or 1, h, k or q is 1-10
Where h, k or q is 2 or more,
R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R in the same compound
⁷ may be the same or different. The compound having a cyclic acetal group may be one kind or two or more.
More than one kind may be mixed and used.

Specific examples of the compound represented by the general formula (1) include 2,2'-ethylenebis-1,3-dioxolan, 2,2'-trimethylenebis-1,3-dioxolan, 2,2 '-Phenylenebis-1,3-dioxolane and the like.

Specific examples of the compound represented by the general formula (2) include 1,3-dioxolan, 2-methyl-1,3-
Dioxolan, 2-methyl-4-methyl-1,3-dioxolan, 2-pentyl-4-methyl-1,3-dioxolan, 2-n-hexyl-1,3-dioxolan, 2,
-Octyl-4-methyl-1,3-dioxolan, 2-
Methoxy-1,3-dioxolan, 2-chloromethyl-
1,3-dioxolan, 2-bromomethyl-1,3-dioxolan, 2- (2-bromoethyl) -1,3-dioxolan, 2-aminomethyl-1,3-dioxolan,
2- (2-aminoethyl) -1,3-dioxolan, 2
-Phenyl-1,3-dioxolan, 2-phenyl-4
-Methyl-1,3-dioxolan, 4-phenyl-1,
3-dioxolan, 2- (1-phenylethyl) -1,
3-dioxolan, 2- (1-phenylethyl) -4-
Methyl-1,3-dioxolan, 2-benzyl-1,3
-Dioxolan, 2-benzyl-4-methyl-1,3-
Dioxolan, 2-benzyl-4, 4-dimethyl-1,
3-dioxolan, 2-benzyl-4-hydroxymethyl-1,3-dioxolan, 2- {2- (2-methoxyethoxy) ethoxy} -1,3-dioxolan, 2-benzyl-4,4-dimethyl-1 , 3-dioxane, 4-
Phenyl-1,3-dioxane, 2-benzyl-5,5
-Dimethyl-1,3-dioxane and the like.

The amount of the compound having a cyclic acetal group in the present invention is 0.01 to 100 parts by weight of a halogenated polycarbonate or a resin component comprising a halogenated polycarbonate and a non-halogenated polycarbonate.
-5 parts by weight. If the compounding amount of the compound having a cyclic acetal 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 tend to deteriorate. The compounding amount of the compound having a cyclic acetal group is preferably from 0.02 to 4 parts by weight of the polycarbonate resin composition, more preferably from 0.1 to 4 parts by weight from the viewpoint of the balance between the effect of improving the yellowing degree and the mechanical properties. 05 to 3 parts by weight.

The polycarbonate resin composition of the present invention comprises:
A resin composition comprising a specific amount of a compound having a cyclic acetal group in a resin component composed of a halogenated polycarbonate or a resin component composed of a halogenated polycarbonate and a non-halogenated polycarbonate, and a halogen content derived from the halogenated polycarbonate. Is 0.01
-20% by weight. Halogen content is 0.01% by weight
If the amount is less than the above, the effect of improving the yellowing degree upon irradiation with ionizing radiation is insufficient, and if it exceeds 20% by weight, the mechanical properties and heat resistance decrease. The halogen content from the halogenated polycarbonate in the polycarbonate resin composition,
Preferably, it is 0.05 to 15% by weight, 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, as a method of blending a compound having a cyclic acetal group with a halogenated polycarbonate or a halogenated polycarbonate and a non-halogen polycarbonate, a method known to those skilled in the art can be used at any stage immediately before molding a final molded article. Can be performed by various methods well known 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 compounds having a cyclic acetal group (hereinafter referred to as compound A) used in Examples and Comparative Examples are listed below. (4) 2-benzyl-1,3-dioxolane (hereinafter, referred to as compound A1) (5) 2-benzyl-4-methyl-1,3-dioxolane (hereinafter, referred to as compound A2) (6) 2 , 2'-trimethylenebis-1,3-dioxolane (hereinafter, referred to as compound A3) (7) 2-methoxy-1,3-dioxolane (hereinafter, referred to as compound A4) (8) 4-phenyl- 1,3-dioxane (hereinafter, referred to as compound A5)

[0032]

【Example】

[Examples 1 to 6, Comparative Examples 1 to 3] Polycarbonate shown in Table 1 and a compound having a cyclic acetal group (compound A) were mixed in a tumbler at a mixing ratio shown in Table 1, Each was extruded at a barrel temperature of 270 ° C. using a φ40 mm uniaxial vent type extruder to obtain pellets. The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then dried at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. for 5 hours.
A test piece of 0 mmφ × 3 mm thickness was injection molded. Using this molded piece, a cobalt 60γ ray was irradiated with 25 kg gray (kG
y) Irradiation, and measure the yellowness before and after irradiation according to JIS K7103
According to the color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd.
And the degree of yellowing (ΔYI) was determined. Table 1 shows the results.
Shown in

[0033]

[Table 1]

[0034]

The polycarbonate resin composition of the present invention contains a specific amount of a compound having a cyclic acetal group and contains a specific amount of a halogen derived from a halogenated polycarbonate. It has excellent appearance characteristics, little deterioration in physical properties, and extremely 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 (5)

[Claims] 1. A resin component comprising a halogenated polycarbonate or 100 parts by weight of a resin component comprising a halogenated polycarbonate and a non-halogenated polycarbonate, wherein 0.01 to 5 parts by weight of a compound having a cyclic acetal group is blended. 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 resin composition according to claim 1, wherein the compound having a cyclic acetal group is a compound represented by the following general formula (1) or (2). Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R ⁷ are each H, a C1-10 alkyl group, a —CH ₂ OH group,
A COOCH ₃ group, a phenyl group or a halogen group,
R ⁵ is an alkylene group of C1～15, alkenylene or arylene group, as a substituent on the nucleus of the arylene group may have an alkyl group or a halogen group C1-10, R ⁸ is H, C1-30 alkyl, cycloalkyl, alkenyl, aryl, arylalkyl, arylalkenyl, alkoxyalkyl, acyl, arylacyl, halogen, halogenated alkyl, amino or aminated alkyl And a nucleus of an aryl group, an arylalkyl group, an arylalkenyl group or an arylacyl group may have a C1-10 alkyl group or a halogen group as a substituent, and X ¹ , X ² and X ³ are , Respectively,
A CHR ⁹ — group, a —O— group, a —NH— group, or a —PH— group, R 9 is H, a C1-15 alkyl group or an aryl group, and i, j and r are each 0 or 1
And h, k or q is an integer of 1 to 10, provided that when h, k or q is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R ⁷ may be the same or different, respectively. )