JPH09255861A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition, hardly deteriorating physical properties and yellowing when sterilized by exposure to ionizing radiation by blending a polycarbonate resin with a (substituted)oxymethylene unit- containing compound or a substituted cyclic ether compound and a sulfonic ester group-containing compound. SOLUTION: This polycarbonate resin composition is obtained by blending (A) 100 pts.wt. of a polycarbonate resin with (B) 0.01-5 pts.wt. of (i) a compound having a (substituted)oxymethylene unit or (ii) a substituted cyclic ether compound and (C) 0.01-5 pts.wt. of a compound having sulfonic ester group. The component (i) is preferably a compound, etc., of formula I [R<1> and R<2> are each H, a 1-30C alkyl, an alkenyl, an aryl, etc.; (m) is an integer of >=3]. The component (ii) is preferably a compound of formula II [R<7> and R<8> are each H, a 1-30C alkyl, an acyl, etc.; R<9> and R<10> are each H, a 1-30C alkyl, an aryl, etc.; (n) is an integer of >=1]. The component C is preferably a compound, etc., of formula III R<11> and R<12> are each a 1-30C alkyl, an aryl, etc.; (h) is an integer of 0-5; (j) is an integer of 1-6 and [(h)+(j)] is <=6}.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound and a compound having a sulfonic acid ester 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. 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
No. 07, the method of compounding a compound having a mercapto group is disclosed. In Japanese Patent Application Laid-Open No. 5-209120, a method of using a polyalkylene oxide and an aromatic compound having a sulfonic acid ester substituent in combination is disclosed. 93
No. 192 and JP-A No. 6-248170 describe a method of blending a compound having a sulfide group, but in any case, the effect of suppressing yellowing is insufficient, or a bad odor occurs during use, There is a problem that the environment during molding is deteriorated.

Further, Japanese Patent Application Laid-Open No. Sho 61-215651 discloses a method of compounding a boron compound.
Japanese Patent Laid-Open No. 2-23222 discloses a method of blending a polyether polyol or its alkyl ether.
No. 58 describes a method of blending a benzyl alcohol derivative, and JP-A-2-132147 describes a method of blending itaconic acid, benzaldehyde dimethyl acetal, benzaldehyde propylene glycol acetal, and the like. There are problems that the effect is insufficient, or that if the added amount is increased to obtain a sufficient effect, other physical properties are adversely affected.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition which has little deterioration in physical properties and very little yellowing upon sterilization by irradiation with ionizing radiation.

[0007]

The present invention has been made to solve the above-mentioned problems, and its gist is to provide a compound having an oxymethylene unit and a substituted oxymethylene unit in 100 parts by weight of a polycarbonate resin. 0.01 to 5 parts by weight of a compound having or a substituted cyclic ether compound,
And compounds having a sulfonate group 0.01 to 5
It exists in a polycarbonate resin composition prepared by blending parts by weight.

The present invention will be described in detail below. The polycarbonate resin in the present invention is a polymer or copolymer of an optionally branched thermoplastic aromatic polycarbonate obtained by reacting an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with phosgene or a diester of carbonic acid. Is.

One example of the aromatic dihydroxy compound is 2,2.
2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, 2,2
-Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) ) Propane, 1,
Bis (hydroxyaryl) alkanes exemplified by 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane; 1,1-bis (4-hydroxyphenyl) cyclopentane; Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-
Dihydroxydiaryl sulfides exemplified by dimethyldiphenyl sulfide and the like; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-
Dihydroxydiarylsulfoxides exemplified by 3,3′-dimethyldiphenylsulfoxide and the like; 4,4 ′
Dihydroxydiarylsulfones exemplified by -dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl and the like. These aromatic dihydroxy compounds may be used alone or in combination of two or more. Among them, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used.

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 determined by using methylene chloride as a solvent at a temperature of 2
The viscosity-average molecular weight calculated from the solution viscosity measured at 5 ° C. is 10,000 to 100,000, and preferably 15,000 to 50,000. The compound having an oxymethylene unit or the compound having a substituted oxymethylene unit in the present invention is a compound represented by the following general formula (1) or (2).

[0013]

Embedded image

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

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

[0016]

Embedded image

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

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

The compounding amount of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit or the substituted cyclic ether compound in the present invention is 0.01 to 5 parts by weight based on 100 parts by weight of the polycarbonate resin. If the amount is less than 0.01 part by weight, the effect of improving the degree of yellowing by irradiation with ionizing radiation tends to be insufficient, and if it exceeds 5 parts by weight, the mechanical properties tend to deteriorate. The compounding amount of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit, or the substituted cyclic ether compound is preferably 100 parts by weight of the polycarbonate resin in terms of the balance between the effect of improving the yellowing degree and the mechanical properties. Is 0.
05 to 3 parts by weight. The compound having a sulfonate group in the present invention is a compound represented by the following general formula (4), (5) or (6).

[0020]

[Chemical 6]

In the formula, R ¹¹ , R ¹³ , R ¹⁶ and R ¹⁸ are each a C1-30 alkyl group, an aryl group, an aryl sulfone group or a halogen group, and R ¹² and R ¹⁵ 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, which can have a C1-10 alkyl group or a halogen group as a substituent in the nucleus of the aryl group, arylalkyl group or arylalkenyl group, and R ¹⁴ and R ¹⁷ are each , A C1-15 alkylene group, an alkenylene group, or an arylene group, and the nucleus of the arylene group may have a C1-10 alkyl group or a halogen group as a substituent, and h, k, v, and q are: Each is an integer of 0 to 5, j is an integer of 1 to 6, the sum of h and j is 6 or less, and u and w are each an integer of 1 or more, preferably 1 to It is an integer of 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 (4) include benzenesulfonic acid methyl ester, benzenesulfonic acid phenyl ester, toluenesulfonic acid methyl ester, toluenesulfonic acid ethyl ester, toluenesulfonic acid butyl ester, and toluenesulfone. 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, naphthalene sulfonic acid methyl ester, naphthalene disulfonic acid dimethyl ester , Diphenylsulfone-3-sulfonic acid methyl ester, such as diphenyl sulfone-3-sulfonic acid phenyl ester.

Specific examples of the compound represented by the general formula (5) 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 (6) 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 sulfonic acid ester 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 effect of improving the degree of yellowing by irradiation with the intended 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 sulfonate ester group is such that polycarbonate resin 1 is used in terms of the balance between the effect of improving the yellowing degree and the mechanical properties.
It is preferably 0.05 to 3 parts by weight with respect to 00 parts by weight.

The mixing ratio of the compound having an oxymethylene unit, the compound having a substituted oxymethylene unit or the substituted cyclic ether compound and the compound having a sulfonic acid ester group is not particularly limited, but is preferably 10 / by weight.
90 to 90/10. As described above, the physical properties are deteriorated by blending the polycarbonate resin with a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound, and a compound having a sulfonic acid ester group, respectively in specific amounts. And a polycarbonate resin composition having a low degree of yellowing can be obtained.

In the present invention, as a method of blending a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound and a compound having a sulfonic acid ester group with a polycarbonate resin, a final molded article is molded. It can be performed by various methods known to those skilled in the art at any stage until just before. 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 further has the following objects.
Other additives that impart desired properties may be added. For example, flame retardants such as halogen compounds, phosphorus compounds, metal sulfonic acid salts, flame retardant aids such as antimony compounds, zirconium compounds, etc., dripping inhibitors such as polytetrafluoroethylene, silicon compounds, etc., and impact resistance of elastomers and the like Improvers, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, plasticizers, release agents, lubricants, compatibilizers, foaming agents, glass fibers, glass beads, glass flakes, carbon fibers, fibrous magnesium , Potassium titanate whiskers, ceramic whiskers, mica, talc, etc.
It is also possible to add and contain one or more dyes and pigments.

The composition of the present invention can be formed into a desired molded article by a conventional molding method such as injection molding or blow molding. Medical molded articles for which it is desired to apply the ionizing radiation-resistant polycarbonate resin composition of the present invention include, specifically, artificial dialysers, artificial lungs, inhalation devices for anesthesia, intravenous connectors and accessories. Blood centrifuge bowls, surgical tools, operating room tools, tubing to supply oxygen to blood, tubing fittings, heart probes and syringes,
Examples include surgical tools, operating room instruments, containers for storing intravenous injections, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

【Example】

[Examples 1 to 5 and Comparative Examples 1 to 3] Polycarbonate resin (Upilon S-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000)
0. ) 100 parts by weight, a compound having an oxymethylene unit shown in Table-1, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound and a compound having a sulfonate group, in the ratio shown in Table-1, The mixture was mixed with a tumbler and extruded at a barrel temperature of 270 ° C. using a φ40 mm uniaxial vent type extruder to obtain pellets. The pellets are heated in a hot air dryer at 120 ° C for 5
After drying for more than an hour, resin temperature 270 ° C, mold temperature 80
A test piece having a thickness of 50 mmφ × 3 mm was injection-molded at 0 ° C. Using this molded piece, cobalt 60γ rays were irradiated with 25 kilogray (kGy), and the yellowness before and after irradiation was measured by JIS.
Color difference meter SM manufactured by Suga Test Instruments Co., Ltd. according to K7103
The measurement was carried out at -3-CH to obtain the degree of yellowing (ΔYI). The results are shown in Table 1.

[0030]

[Table 1]

[0031]

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 (4)

[Claims] 1. 100 parts by weight of a polycarbonate resin,
Polycarbonate resin composition containing 0.01 to 5 parts by weight of a compound having an oxymethylene unit, a compound having a substituted oxymethylene unit or a substituted cyclic ether compound, and 0.01 to 5 parts by weight of a compound having a sulfonate ester group. . 2. The polycarbonate resin according to claim 1, wherein the compound having an oxymethylene unit or the compound having a substituted oxymethylene unit is a compound represented by the following general formula (1) or (2). Composition. Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ are respectively H, C1 to
30, alkyl groups, cycloalkyl groups, alkenyl groups,
An aryl group, an arylalkyl group, an arylalkenyl group, a hydroxy group, an alkoxy group, an acyl group or an acyloxy group, wherein the aryl group, the arylalkyl group and the arylalkenyl group have a C1 to C1 substituent as a substituent.
0 alkyl groups or halogen groups,
R ⁵ and R ⁶ are H, a C1-30 alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an acyl group, respectively, and are an aryl group, an arylalkyl group and an arylalkenyl. The nucleus of the group may have a C1-10 alkyl group or a halogen group as a substituent, and m is 3
The above is an integer, and p is an integer of 1 or more. ) 3. The polycarbonate resin composition according to claim 1, wherein the substituted cyclic ether compound is a compound represented by the following general formula (3). Embedded image (Wherein, R ⁷ and R ⁸ are each an H, C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, hydroxy group, alkoxy group, acyl group or acyloxy group) And a nucleus of an aryl group, an arylalkyl group and an arylalkenyl group can have a C1-10 alkyl group or a halogen group as a substituent, and R ⁹ and R ¹⁰ are each H, C1 30 alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, arylalkyl groups, arylalkenyl groups or acyl groups, and the nuclei of the aryl group, the arylalkyl group and the arylalkenyl group each have C1-10 It can have an alkyl group or a halogen group, and n is an integer of 1 or more.) 4. The resin according to claim 1, wherein the compound having a sulfonate group is a compound represented by the following general formula (4), (5) or (6). Composition. Embedded image (In the formula, R ¹¹ , R ¹³ , R ¹⁶ and R ¹⁸ are respectively C1 to
30 is an alkyl group, an aryl group, an aryl sulfone group or a halogen group, and R ¹² and R ¹⁵ 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, and a substituent in the nucleus of the aryl group, the arylalkyl group and the arylalkenyl group, It may have an alkyl group or a halogen group C1-10, R ¹⁴ and R ^17, respectively, C1 to
15 is an alkylene group, an alkenylene group or an arylene group, and the nucleus of the arylene group has C1 to C1 as a substituent.
It may have 10 alkyl groups or halogen groups, h, k, v and q are each an integer of 0 to 5, j is an integer of 1 to 6, and the sum of h and j is 6 Below, u and w are each an integer of 1 or more. )