JPH0931315A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition which can give an article which, when sterilized by irradiation with an ionizing radiation, undergoes less deterioration in properties and is reduced in yellowing by mixing a polycar bonate resin with a sulfonic-ester-group-containing compound and a cyclic-acetal- group-containing compound. SOLUTION: This resin composition is obtained by mixing 100 pts.wt. polycarbonate resin having a viscosity-average molecular weight of 10,000-100,000 and being a polymer or copolymer of a thermoplastic aromatic polycarbonate obtained by reacting an aromatic dihydroxy compound [e.g. 2,2-bis(4- hydroxyphenyl)propane] with phosgene or a carbonic diester with 0.01-5 pts.wt. sulfonic-ester-group-containing compound (e.g. methyl benzenesulfonate) and 0.01-5 pts.wt. cyclic-acetal-group-containing compound (e.g. 2,2'-ethylenebis-1,3- dioxolane).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing a compound having a sulfonic acid ester group and a compound having a cyclic acetal group. In particular, the present invention relates to a polycarbonate resin composition excellent in ionizing radiation resistance, with little change in color tone and deterioration in physical properties due to ionizing radiation irradiated for sterilization.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as medical products because 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. 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 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 disclosed in JP-A-2-115260. 490
No. 58, JP-A-4-36343, JP-A-6-1668
JP-A No. 07-93192 discloses a method of adding a compound having a mercapto group, and JP-A-6-93192 discloses a method of adding a compound having a sulfide group.
No. 209120 discloses a method of using a polyalkylene oxide and an aromatic compound having a sulfonic acid ester substituent in combination, but in any case, the effect of suppressing yellowing is insufficient, or a bad odor occurs during use. However, there is a problem that the environment during molding is deteriorated.

Further, in JP-A-61-215651, a method of blending a boron compound is disclosed in JP-A-62-13.
Japanese Patent Laid-Open No. 2-23222 discloses a method of blending a polyether polyol or its alkyl ether.
In Japanese Patent Laid-Open No. 58-132147, itaconic acid, rosin acid, benzaldehyde dimethyl acetal,
Benzaldehyde propylene glycol acetal, p
-Each method of adding phthalaldehyde, etc. is described, but there are problems such as insufficient yellowing suppression effect or adversely affecting other physical properties if the addition amount is increased enough to obtain a sufficient effect. There was a point.

[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 compounds 0.01 to 5 having a sulfonic acid ester group in 100 parts by weight of a polycarbonate resin. It exists in the polycarbonate resin composition which mix | blends 0.01-5 weight part of compounds which have a weight part, and the compound which has a cyclic acetal group.

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, etc .; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; exemplified by 4,4'-dihydroxydiphenylether 4,4'-dihydroxy-3,3'-dimethyldiphenylether and the like Dihydroxy diaryl ethers; dihydroxy diaryl sulfides exemplified by 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4 ' Dihydroxy -3,
Dihydroxydiaryl sulfoxides exemplified by 3'-dimethyldiphenyl sulfoxide and the like; Dihydroxydiaryl sulfones exemplified by 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone and the like; Examples thereof include hydroquinone, resorcin, 4,4′-dihydroxydiphenyl and the like. 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.

In order 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
Polyhydroxy compounds exemplified by -hydroxy-5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, or 3 , 3-Bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-
Bromoisatin bisphenol 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
Using methylene chloride as a solvent, the viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. is 1
000 to 100,000, preferably 15,
It is 000 to 50,000. The compound having a sulfonate group in the present invention has the following general formula (1),
It is a compound represented by (2) or (3).

[0012]

Embedded image

In the formula, R ¹ , R ³ , R ⁶ and R ⁸ are respectively
It is a C1-30 alkyl group, an aryl group, an aryl sulfone group or a halogen group. R ² and R ⁵ are each 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, an aryl group,
The nucleus of the arylalkyl group and the arylalkenyl group may have a C1-4 alkyl group or a halogen group as a substituent. R ⁴ and R ⁷ are each C1
To 15 alkylene group, alkenylene group or arylene group, wherein the nucleus of the arylene group has C1 as a substituent.
~ 4 alkyl groups or halogen groups. h, j, l, and n 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 or less. k and m are each an integer of 1 or more,
It is preferably an integer of 1 to 100. The compound having a sulfonate group may be used alone or in combination of two or more.

Specific examples of the compound represented by the general formula (1) include benzenesulfonic acid methyl ester, benzenesulfonic acid phenyl ester, toluenesulfonic acid methyl ester, toluenesulfonic acid ethyl ester, toluenesulfonic acid butyl ester and toluene sulfone. Acid phenyl ester, toluenesulfonic acid benzyl ester, toluenesulfonic acid phenethyl ester, toluenesulfonic acid naphthyl ester, xylenesulfonic acid methyl ester, xylenesulfonic acid phenyl ester, mesitylenesulfonic acid methyl ester, mesitylenesulfonic acid phenyl ester, benzenedisulfonic acid methyl ester Ester, benzenedisulfonic acid phenyl ester, diphenylsulfone-3-sulfonic acid methyl ester, diphenylsulfone-3 Acid phenyl ester, and the like. Specific examples of the compound represented by the general formula (2) include benzenesulfonic acid methoxyethyl ester,
Toluenesulfonic acid methoxymethyl ester, toluenesulfonic acid methoxyethyl ester, toluenesulfonic acid ethoxyethyl ester, toluenesulfonic acid butoxyethyl ester, toluenesulfonic acid phenoxyethyl ester, toluenesulfonic acid benzyloxyethyl ester, xylenesulfonic acid methoxyethyl ester,
Mesitylenesulfonic acid methoxyethyl ester, toluenesulfonic acid butoxyethoxyethyl ester, toluenesulfonic acid phenoxyethoxyethyl ester, toluenesulfonic acid benzyloxyethoxyethyl ester and the like can be mentioned. Specific examples of the compound represented by the general formula (3) include bistosyloxymethane, 1,2-bistosyloxyethane, diethylene glycol di-para-tosylate and tetraethylene glycol di-para-tosylate.
And the like.

The compounding amount of the compound having a sulfonate group 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 desired effect of improving the yellowing degree by irradiation with ionizing radiation is insufficient, and if it exceeds 5 parts by weight, mechanical properties are deteriorated, which is not preferable. From the viewpoint of improving the degree of yellowing and preventing deterioration of mechanical properties, the compounding amount of the compound having a sulfonic acid ester group is set to that of the polycarbonate resin 1
It is preferably 0.05 to 3 parts by weight with respect to 00 parts by weight. The compound having a cyclic acetal group in the present invention is a compound represented by the following general formula (4) or (5).

[0016]

Embedded image

Wherein R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵
Are each, H, an alkyl group of C1-10, -CH ₂
OH group, -COOCH ₃ group, a phenyl group or a halogen group. R ¹¹ is a C 1-15 alkylene group, an alkenylene group or an arylene group, and the nucleus of the arylene group may have a C 1-10 alkyl group or a halogen group as a substituent. R ¹⁶ is H, C1-30
Alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group,
Alkoxyalkyl group, acyl group, arylacyl group,
It is a halogen group, a halogenated alkyl group, an amino group or an aminated alkyl group, and has a C1-10 alkyl group or a halogen group as a substituent in the nucleus of the aryl group, the arylalkyl group, the arylalkenyl group and the arylacyl group. Can have. X ^1, X ² and X ^3, respectively, -CHR ¹⁷ - group, -O- group, -NH- group, -S-
A group, a —S—S— group or a —PH— group, and R ¹⁷ is
H, a C1-15 alkyl group or an aryl group.
y and z are 0 or 1, respectively. p, q and r are each an integer of 1 to 10, provided that p, q
When q or r is 2 or more, R ⁹ , R ¹⁰ in the same compound,
R ¹² , R ¹³ , R ^{14 and} R ¹⁵ may be the same or different.

The compound having the cyclic acetal group is 1
You may use it by a kind or in mixture of 2 or more types.
Specific examples of the compound represented by the general formula (4) include 2,
2'-ethylenebis-1,3-dioxolane, 2,2 '
-Trimethylenebis-1,3-dioxolane, 2,2 '
-Phenylenebis-1,3-dioxolane and the like.

Specific examples of the compound represented by the general formula (5) include 2-methyl-1,3-dioxolane, 2-methyl-4-methyl-1,3-dioxolane and 2-pentyl-4-methyl-. 1,3-dioxolane, 2-n-hexyl-1,3-dioxolane, 2-octyl-4-methyl-1,3-dioxolane, 2-methoxy-1,3-dioxolane, 2-chloromethyl-1,3 -Dioxolane,
2-bromomethyl-1,3-dioxolane, 2- (2-
Bromoethyl) -1,3-dioxolane, 2-aminomethyl-1,3-dioxolane, 2- (2-aminoethyl) -1,3-dioxolane, 2- (1-phenylethyl) -1,3-dioxolane, 2- (1-phenylethyl) -4-methyl-1,3-dioxolane, 2-benzyl-1,3-dioxolane, 2-benzyl-4-methyl-1,3-dioxolane, 2-benzyl-4,4 -Dimethyl-1,3-dioxolane, 2-benzyl-4-hydroxymethyl-1,3-dioxolane, 2- {2- (2
-Methoxyethoxy) ethoxy} -1,3-dioxolane, 2-benzyl-4,4-dimethyl-1,3-dioxane, 2-benzyl-5,5-dimethyl-1,3-dioxane and the like.

The compounding amount of the compound having a cyclic acetal group in the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Compounding amount 0.0
If the amount is less than 1 part by weight, the effect of improving the yellowing degree by the target irradiation of ionizing radiation is insufficient, and if it exceeds 5 parts by weight,
It is not preferable because mechanical properties are deteriorated. From the viewpoint of improving the degree of yellowing and preventing deterioration of mechanical properties, the compounding amount of the compound having a cyclic acetal group is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

The mixing ratio of the compound having a sulfonic acid ester group and the compound having a cyclic acetal group is not particularly limited, but is preferably 10/90 to 90/10 by weight.

In the present invention, a method for blending a compound having a sulfonic acid ester group and a compound having a cyclic acetal group into a polycarbonate resin is well known to those skilled in the art at any stage until just before the final molded article is molded. Can be carried out by various methods. 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 composition of the present invention may further include,
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 made 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 of the present invention.

[0026]

【Example】

[Examples-1 to 7, Comparative Examples-1 to 3] Polycarbonate resin (Upilon S-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,0)
00. ) 100 parts by weight, the compound having a sulfonic acid ester group shown in Table-1 and the compound having a cyclic acetal group are mixed in a tumbler at a ratio shown in Table-1, and each is a 40 mm uniaxial vent extruder. Was extruded at a barrel temperature of 270 ° C. to obtain pellets. After drying the pellets at 120 ° C. for 5 hours or more in a hot air drier, the resin temperature was 270 ° C., the mold temperature was 80 ° C., and the diameter was 50 mmφ.
A test piece having a thickness of 3 mm was injection molded. 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.

[0027]

[Table 1]

[0028]

EFFECT OF THE INVENTION The composition of the present invention has little deterioration in physical properties and little change in color tone due to ionizing radiation irradiated for sterilization. Therefore, it is useful for applications such as medical products, medical devices, and members of medical devices that are subjected to ionizing radiation irradiation sterilization.

Claims (3)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
0.01 to 5 parts by weight of a compound having a sulfonic acid ester group and 0.01 to 5 parts of a compound having a cyclic acetal group
A polycarbonate resin composition comprising parts by weight. 2. The polycarbonate resin composition according to claim 1, wherein the compound having a sulfonate group is a compound represented by the following general formula (1), (2) or (3). Embedded image (In the formula, R ¹ , R ³ , R ⁶ and R ⁸ are each C1-30.
Is an alkyl group, an aryl group, an aryl sulfone group or a halogen group, and R ² and R ⁵ are H and C 1 respectively.
To 30 alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, arylalkyl groups, arylalkenyl groups or acyl groups, wherein the aryl group, the arylalkyl group and the arylalkenyl group have a C1-4 substituent as a substituent. may have an alkyl group or a halogen group, R ⁴ and R ⁷ are each an alkylene group, alkenylene group or arylene group C1～15,
The nucleus of the arylene group may have a C1-4 alkyl group or a halogen group as a substituent, and h, j, l
And n are integers of 0 to 5, respectively, and i is 1 to 6.
Is an integer, the sum of h and i is 6 or less, and k and m are integers of 1 or more, respectively. ) 3. The polycarbonate resin composition according to claim 1 or 2, wherein the compound having a cyclic acetal group is a compound represented by the following general formula (4) or (5). Embedded image ^{(Wherein, R 9, R 10, R} 12, R 13, R 14 and R ¹⁵ are each, H, an alkyl group of C1-10, -CH ₂ OH group, -
A COOCH ₃ group, a phenyl group or a halogen group,
R ¹¹ is a C 1-15 alkylene group, an alkenylene group or an arylene group, and the nucleus of the arylene group can have a C 1-10 alkyl group or a halogen group as a substituent, and R ¹⁶ is H, C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, alkoxyalkyl group, acyl group, arylacyl group, halogen group, halogenated alkyl group, amino group or aminated alkyl. The aryl group, the arylalkyl group, the arylalkenyl group and the arylacyl group may have a C1-10 alkyl group or a halogen group as a substituent in the nucleus, and X ¹ , X ² and X ³ are , -C
HR ¹⁷ - group, -O- group, -NH- group, -S- group, -S-
S-group or -PH- group, R ¹⁷ is H, C1 to 1
5 is an alkyl group or an aryl group, and y and z are
Each is 0 or 1, p, q and r are each an integer of 1 to 10, provided that p, q or r is 2
In the above case, R ⁹ , R ¹⁰ , R ¹² , R ¹³ and R in the same compound
¹⁴ or R ¹⁵ may be the same or different. )