JPH09310010A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polycarbonate resin composition for medical purposes which contains a cinnamyl compound and a sulfonate group-containing compound with reduced deterioration in physical properties and causes no change in color tone by ionizing radiation for sterilization. SOLUTION: This polycarbonate resin composition comprises (A) 100 pts.wt. of a polycarbonate resin, (B) 0.01-5 pts.wt. of a cinnamyl compound and (C) 0.01-5 pts.wt. of a sulfonate ester group-bearing compound. In a preferred embodiment, the component (B) is a compound of formula I (R<1> is a 1-10C alkyl, alkoxy, OH, CH2 OH, a halogen; X is CO, COO, CH2 -O; R<2> is H, a 1-30C alkyl, a cycloalkyl, an alkenyl, an aryl; m is 0-5), typically cinnamyl alcohol and the component (C) is a compound of formula II (R<3> is a 1-30C alkyl, an aryl, an arylsulfone; R<4> is H, a 1-30C alkyl, a cycloalkyl; h is 0-5; j is 1-6 where h+j=6), typically methyl benzenesulfonate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing a cinnamyl 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 the gist thereof is that 100 parts by weight of a polycarbonate resin, 0.01 to 5 parts by weight of a cinnamyl compound, and A polycarbonate resin composition comprising 0.01 to 5 parts by weight of a compound having a sulfonate group is present.

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 cinnamyl-based compound in the present invention is a compound represented by the following general formula (1).

[0013]

Embedded image

In the formula, R ¹ is a C1-10 alkyl group, an alkoxy group, a --OH group, a --CH ₂ OH group or a halogen group, and X is --CO--, --COO--,
_{-CH 2 -O -, - CH 2} -CO -, - CH 2 -O-CO
O—, R ² is H, C1-30 alkyl group, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl group, acyl group or arylacyl group, and aryl group, arylalkyl The nucleus of the group, the arylalkenyl group and the arylacyl group can have a C1-10 alkyl group, an alkoxy group, a —OH group, a —CH ₂ OH group or a halogen group as a substituent, and m is 0 to It is an integer of 5.

The cinnamyl compounds may be used alone or in combination of two or more. Specific examples of the compound represented by the general formula (1) include cinnamyl alcohol, cinnamaldehyde, methoxycinnamaldehyde, cinnamyl methyl ether, cinnamyl ethyl ether, cinnamyl allyl ether, cinnamyl phenyl ether, cinnamyl benzyl ether. , Cinnamyl methyl ketone, cinnamyl ethyl ketone, cinnamyl allyl ketone, cinnamyl phenyl ketone, cinnamyl benzyl ketone, acetic acid cinnamyl ester, propionic acid cinnamyl ester, butyric acid cinnamyl ester, benzoic acid cinnamyl ester, cinnamon bark Acid methyl ester, methyl cinnamic acid methyl ester, cinnamic acid ethyl ester, cinnamic acid vinyl ester, cinnamic acid allyl ester, cinnamic acid phenyl ester, cinnamic acid benzyl ester, cinnamic acid Cinnamyl ester, carbonate Shin'namirumechiru, cinnamyl phenyl and the like carbonates.

The amount of the cinnamyl compound in the present invention is based on 100 parts by weight of the polycarbonate resin.
It is 0.01 to 5 parts by weight. 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 cinnamyl compound is preferably 0.05 to 3 based on 100 parts by weight of the polycarbonate resin from the viewpoint of the balance between the effect of improving the yellowing degree and the mechanical properties.
Parts by weight. The compound having a sulfonate group in the present invention is a compound represented by the following general formula (2), (3) or (4).

[0017]

Embedded image

In the formula, R ³ , R ⁵ , R ⁸ and R ¹⁰ are each a C1-30 alkyl group, aryl group, arylsulfone group or halogen group, and R ⁴ and R ⁷ 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 ⁶ and R ⁹ are each ,
A C1-15 alkylene group, an alkenylene group or an arylene group, wherein the nucleus of the arylene group is a substituent,
It may have a C1-10 alkyl group or a halogen group, 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
And u and w are each an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70.
Is an integer. 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 (2) 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 (3) 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 (4) 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 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 cinnamyl compound and the compound having a sulfonic acid ester group is not particularly limited, but is preferably 10/90 to 90/10 by weight. As described above, by blending the cinnamyl compound and the compound having a sulfonic acid ester group in specific amounts in the polycarbonate resin, a polycarbonate resin composition having a low degree of yellowing can be obtained without deteriorating the physical properties.

In the present invention, as a method of blending a cinnamyl compound and a compound having a sulfonic acid ester group with a polycarbonate resin, various methods well known to those skilled in the art can be used at any stage until just before the final molded article is molded. It can be done by a method. 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 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 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.

[0026]

EXAMPLES 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. [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 and a cinnamyl compound and a compound having a sulfonate group shown in Table 1 are shown in Table-
Mix in a tumbler at the ratio described in 1, and each is φ40.
mm uniaxial vent type extruder, barrel temperature 270 ℃
Was extruded to obtain pellets. After drying the pellets at 120 ° C. for 5 hours or more in a hot air drier, the resin temperature 2
A test piece of 50 mmφ × 3 mm thickness was injection molded at 70 ° C. and a mold temperature of 80 ° C. Using this molded piece, cobalt 6
Irradiation with 0 γ-rays at 25 kilogray (kGy), yellowness before and after irradiation is measured by a color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. according to JIS K7103 to obtain yellowing degree (ΔYI). It was 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,
A polycarbonate resin composition comprising 0.01 to 5 parts by weight of a cinnamyl compound and 0.01 to 5 parts by weight of a compound having a sulfonate group. 2. The polycarbonate resin composition according to claim 1, wherein the cinnamyl compound is a compound represented by the following general formula (1). Embedded image (In the formula, each R ¹ is a C 1-10 alkyl group,
Alkoxy group, -OH group, a -CH ₂ OH group or a halogen group, X is, -CO -, - COO -, - CH 2 -
_{O -, - CH 2 -CO -} , - CH is ^₂ -O-COO-, R ₂ is, H, an alkyl group of C1-30, cycloalkyl group, alkenyl group, aryl group, arylalkyl group, arylalkenyl Group, an acyl group or an arylacyl group, and the nucleus of the aryl group, the arylalkyl group, the arylalkenyl group and the arylacyl group has, as a substituent, a C1-10 alkyl group, an alkoxy group,-
OH group can have a -CH ₂ OH group or a halogen group, m is an integer from 0 to 5. ) 3. The resin according to claim 1, wherein the compound having a sulfonate group is a compound represented by the following general formula (2), (3) or (4). Composition. Embedded image (In the formula, R ³ , R ⁵ , R ⁸ and R ¹⁰ are respectively C1 to C3.
An alkyl group, an aryl group, an aryl sulfone group or a halogen group of 0, and R ⁴ and R ⁷ are H and C, respectively.
1 to 30 are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an acyl group, and the aryl group, the arylalkyl group and the arylalkenyl group have a C1 to It may have 10 alkyl groups or halogen groups, and R ⁶ and R ⁹ are each a C 1-15 alkylene group, an alkenylene group or an arylene group, and C 1-10 as a substituent in the nucleus of the arylene group. An alkyl group or a halogen group of
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 or less,
u and w are each an integer of 1 or more. )