Polyvinyl chloride resin composition

Abstract

PURPOSE: The present invention provides a polyvinyl chloride resin composition which is superior in heat stability and processability and has less elution from the composition. CONSTITUTION: a polyvinyl chloride resin composition comprising 100 parts by weight of a polyvinyl chloride resin, 10 to 120 parts by weight of di(2-ethylhexyl)terephthalate, and 0.5 to 20 parts by weight of epoxidized vegetable oil having a peroxide number of 5 or less.

Claims

1. A method for producing a medical instrument by forming a polyvinyl chloride resin composition which comprises 100 parts by weight of a polyvinyl chloride resin, 10 to 120 parts by weight of a plasticizer consisting essentially of di(2-ethylhexyl)terephthalate, and 0.5 to 20 parts by weight of epoxidized vegetable oil having a peroxide number of 5 or less; wherein plasticizers other than di(2-ethylhexyl) terephthalate are either not present in the composition or are present in the composition only in trace amounts.

2. The method according to claim 1, wherein the composition further comprises 0.05 to 10 parts by weight of silicone oil.

3. The method according to claim 1, wherein the instrument is a medical tube or a medical bag.

Description

EXAMPLES

Examples 1 to 7 and Comparative Examples 1 to 14

(1) The components in the amounts (part by weight) as shown in Table 1 were melt kneaded in a press kneader approximately at 160 degrees C. to prepare a polyvinyl chloride resin composition. The composition was put through rolls into a sheet. The sheet was formed into a predetermined size by a press machine to obtain a specimen. The specimen was subjected to the following tests (1) and (2). Besides, the polyvinyl chloride resin composition obtained above was subjected to the following test (3). The results are as shown in Table 1.

(2) The abbreviations in the Tables are as follows. PUC: polyvinyl Chloride resin (average degree of polymerization: 1300) DOTP: di(2-ethylhexyl)terephthalate DOP: di(2-ethylhexyl)phthalate TOTM: tri(2-ethylhexyl)trimellitate DINCH: diisononylcyclchexane-1,2-dicarboxylate DOA: di(2-ethylhexyl)adipate
Tests
(1) Tests on Eluted Materials

(3) The following tests were carried out according to the Japanese Pharmacopoeia. 15.00 Grams of the specimen with a thickness of 1 mm were washed with water and then dried at room temperature. This specimen was put into a 500 ml-volume conical flask, followed by addition, of 300 ml of distilled water. The flask was sealed with a silicone rubber stopper and then heated in a high-pressure steam sterilizer at 121 degrees C. for 60 minutes. After decompression, the conical flask containing the specimen therein was removed from the high-pressure steam sterilizer and allowed to stand until the temperature of the flask decreased to room temperature. The specimen was transferred together with the distilled water in to a 300 ml-volume volumetric flask, to which distilled water was supplemented to a total volume of just 300 ml to obtain a test solution. Separately, the same procedures were repeated to prepare a blank, test solution containing no specimen. The test solution and the blank test solution were subjected to the following tests (i) to (v).

(4) (i) pH Test

(5) To each 20 ml of the test solution and the blank test solution, added was 1 ml of a solution which had been prepared by adding water to 1.0 g of potassium chloride to a total amount of 1000 ml. Then, pH values of the resulting solutions were measured and a difference between these pH values was calculated. A larger difference means that a more amount of materials which affect pH elute.

(6) (ii) Tin Test

(7) Preparation of a Test Solution for the Tin Test

(8) 10.0 Ml of the test solution was put in a 25 ml volumetric flask, to which a potassium permanganate solution was added dropwise until the color of the solution turned pale red, and then a small amount of L-ascorbic acid was added to cause decoloration. To the solution, added sequentially were 1.5 ml of 1N hydrogen chloride, 5.0 ml of citric acid diluted with water by 10 times, and 2.5 ml of polyvinyl alcohol having a degree of polymerization of 2000, followed by addition of 5.0 ml of a solution of phenylfluoron in ethanol, and water was further added to a total amount of 25.0 ml. The resulting solution was shaken well and then allowed to stand for approximately 20 minutes to obtain a test solution for the tin test.

(9) Preparation of an Aqueous Dilute Nitric Acid Solution

(10) Dilute nitric acid was prepared according to the Japanese Phamacopoeia, Sixteenth Edition. That is, water was added to 10.5 ml of nitric acid to a total amount of 100 ml, which was a 10% dilute nitric acid. The 10% dilute nitric acid was further diluted by three times to obtain an aqueous dilute nitric acid solution (A).

(11) Standard Solution for the Tin Test

(12) A tin standard solution (1000 ppm, ex. Kanto Chemical Co., Inc.) was diluted to a concentration of 1.0 μg/ml. 5.0 Ml of this was put in a 20 ml stoppered volumetric flask instead of the test solution. A potassium permanganate solution was added dropwise until the color of the solution turned pale red. Then the same procedures as in the aforesaid preparation of a test solution for the tin test were repeated to obtain a standard solution for the tin test (0.25 μg/ml), except that the aqueous dilute nitric acid solution (A) in place of water was added to a total amount of 20 ml. Similarly, standard solutions for the tin test of concentrations of 0.01 μg/ml, 0.05 μg/ml and 0.1 μg/ml were prepared.

(13) Quantitative Analysis of Tin

(14) The standard solutions for the tin test were subjected to measurement of an absorbance at a wavelength of 510 nm with a water reference to prepare a calibration curve. Similarly, the test solutions for the tin test were subjected to measurement of absorbances at the same wavelength with a water reference. Concentrations of tin were found from the absorbances on the calibration curve. A polyvinyl chloride resin composition may contain tin derived from a catalyst in the preparation of vinyl chloride or contaminants.

(15) (iii) Tests on Potassium Permanganate-Reducing Materials

(16) 20.0 Ml of the test solution was put in a stoppered conical flask, to which 20.0 ml of a 0.002 mol/L potassium permanganate solution and 1 ml of the 10% dilute nitric acid were added, boiled for 3 minutes and cooled. After 0.1 g of potassium iodide was added, the flask was tightly stopped, snaked and allowed to stand for ten minutes, to which five drops of a starch solution were added as an indicator. Titration with a 0.01 mol/L sodium thiosulfate solution was carried out to determine an amount of potassium permanganate solution consumed (X). The same procedures as described above were repeated on the blank test solution to determine an amount of potassium permanganate solution consumed (Y). The value, X−Y, is indicated as ΔKMnO.sub.4. A higher value means that a more amount of potassium permanganate-reducing materials, mainly organic substances, eluted.

(17) (iv) Evaporation Residue Test

(18) Twenty ml of the test solution was evaporated to dryness on a water bath. The resulting residue was dried at 105 degrees C. for an hour and then weighed.

(19) (v) Ultraviolet Absorption Spectrum Test

(20) The blank test solution was put in a quartz cell having a liquid thickness of 10 mm and used for correction of a ultraviolet and visible spectrophotometer, U-3010 (ex. Hitachi, Ltd.). Similarly, the test solutions were put in the quartz cell and subjected to measurement of absorbance in the wavelength range of 220 to 350 nm with the same spectrophotometer to determine a maximum absorbance. The results are as shown in Table 1.

(21) (2) Heat Stability Test

(22) The heat stability test was carried out according to the Japanese Industrial Standards (JIS) K6723 to determine a period of time (in minute) for which the specimen remained stable at 170±3 degrees C. This test was carried out as follows. The specimen was put in a test tube together with a test paper, congo red paper. The tube was sealed and then put in an oil bath at 170±3 degrees C. to measure a period of time which was necessary for the specimen to change, A time when a color of the congo red paper changed was regarded as the time when the specimen changed.

(23) (3) Processability Test

(24) Thirty grams of the polyvinyl chloride resin composition were kneaded in LABO PLASTOMILL 30C 150 type, ex Toyo Seiki Seisaku-Sho, Ltd., under the conditions of a cell temperature or 160 degrees C., a rotation speed of 50 rpm and a preheating time of 5 minutes to measure a period of time which is necessary for the composition to reach a maximum torque value. This is referred to as a gelation time. A shorter gelation time means that the processability is better.

(25) TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Comp. Comp. Comp. Comp. ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 Ex. 1 Ex. 2 Ex. 3 Ex. 4 PVC 100 100 100 100 100 100 100 100 100 100 100 DOTP (molecular weight: 391) 50 10 50 100 50 50 50 50 50 50 50 DOP (molecular weight: 391) 0 0 0 0 0 0 0 0 0 0 0 TOTM (molecular weight: 547) 0 0 0 0 0 0 0 0 0 0 0 DINCH (molecular weight: 424) 0 0 0 0 0 0 0 0 0 0 0 DOA (molecular weight: 371) 0 0 0 0 0 0 0 0 0 0 0 Epoxidized soybean oil 1 5 5 5 10 20 5 0 30 0 0 (peroxide number: 3) Epoxidized soybean oil 0 0 0 0 0 0 0 0 0 1 5 (peroxide number: 8) Ca—Zn type composite stabilizer 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Silicone oil* 0 0 0 0 0 0 0.1 0 0 0 0 ΔpH 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Tin, μg/ml 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 ΔKMnO.sub.4, ml 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Evaporation residue, mg 0.2 0.3 0.3 0.3 0.4 0.4 0.1 0.1 0.4 0.3 0.4 Ultraviolet absorption spectrum 0.03 0.04 0.04 0.03 0.04 0.05 0.01 0.02 0.05 0.03 0.06 (absorbance) Heat stability, min. 95 140 115 95 120 130 115 75 130 95 115 Processability (gelation time), 3′12″ 2′42″ 3′00″ 3′46″ 3′12″ 3′23″ 3′02″ 4′20″ 3′24″ 3′17″ 3′06″ minute(′) and second(″) Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 PVC 100 100 100 100 100 100 100 100 100 100 DOTP (molecular weight: 391) 50 50 0 0 0 0 0 0 0 0 DOP (molecular weight: 391) 0 0 50 50 0 0 0 0 0 0 TOTM (molecular weight: 547) 0 0 0 0 50 50 0 0 0 0 DINCH (molecular weight: 424) 0 0 0 0 0 0 50 50 0 0 DOA (molecular weight: 371) 0 0 0 0 0 0 0 0 50 50 Epoxidized soybean oil 0 0 5 5 5 5 5 5 5 5 (peroxide number: 3) Epoxidized soybean oil 10 20 0 0 0 0 0 0 0 0 (peroxide number: 8) Ca—Zn type composite stabilizer 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Silicone oil* 0 0 0 0.1 0 0.1 0 0.1 0 0.1 ΔpH 0.2 0.2 0.7 0.5 0.6 0.5 0.6 0.5 0.6 0.5 Tin, μg/ml 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.01 0.02 0.01 ΔKMnO.sub.4, ml 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Evaporation residue, mg 0.5 0.6 0.4 0.3 0.2 0.2 0.2 0.2 0.2 0.2 Ultraviolet absorption spectrum 0.06 0.06 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (absorbance) Heat stability, min. 120 130 155 155 125 125 85 85 85 85 Processability (gelation time), 3″17″ 3′28″ 1′10″ 1′10″ 5′26″ 5′26″ 4′38″ 4′38″ 1′02″ 1′03″ minute(′) and second(″) *KF-96 100cs (trade name, dimethyl silicone oil, ex Shin-Etsu Chemical Co., Ltd.)

(26) As apparent from Table 1, the present polyvinyl chloride resin compositions comprising di(2-ethylhexyl)terephthalate (DOTP) as a plasticizer and epoxidized soybean oil having the peroxide number of 5 or less were superior in heat, stability and processability, and showed the less elution and the less pH change. On the other hand, the composition of Comparative Example 1 comprising the epoxidized soybean oil in an amount less than the present lower limit was inferior in heat stability and processability. The compositions of Comparative Examples 3 to 6 where the peroxide number of epoxidized soybean oil was more than 5 showed the larger evaporation residues and the larger ultraviolet absorbences, compared to those in the compositions of Examples 1, 3, 5 and 6. This means that the former compositions had higher tendency to elution. Among these Examples and Comparative Examples, Example 3 and Comparative Example 3 showed the comparable levels of the evaporation resides and the ultraviolet absorbances, but the composition of Example 3 was superior in heat stability than that of Comparative Example 3. The compositions of Comparative Examples 7 to 14 comprising a plasticizer other than DOTP showed the larger pH change.

Example 8 and Comparative Examples 15 to 23

(27) The components in the amounts (parts by weight) as shown in Table 2 were melt kneaded in a press kneader at approximately 160 degrees C. to prepare a polyvinyl chloride resin composition. The composition was put through rolls into a sheet. The sheet was formed into a predetermined size by a press machine to obtain a specimen. The specimen was subjected to the following GS-MS test. The results are as shown in Table 2.

(28) GS-MS Test

(29) (i) Extraction Test with Distilled Water

(30) The specimen having a size of 65 mm×65 mm×2 mm and weight of approximately 10.00 g was washed with distilled water and dried at room temperature. This specimen was put in a 500 ml-volume glass container and closed, to which 300 ml of distilled water was then added, followed by shaking at 37 degrees C. for 5 hours. The distilled water was transferred to a 300 ml-volume volumetric flask, to which distilled water was further added to a total of just 300 ml to obtain a test solution. The sane procedures as described above were repeated without the specimen to obtain a blank test solution.

(31) Each of the test solution and the blank test solution obtained above was evaporated to dryness using an evaporator to obtain a dried residue. The residue was dissolved in acetone and a total was adjusted to 10 ml in a volumetric flask. The solution was analyzed by a gas chromatography mass spectrometer (GC-MS apparatus) to determine an amount of the plasticizer (mg/ml) extracted into distilled water. Operation conditions areas fellows. A calibration curve was prepared using standard materials for DOTP, DOP, TOTM and DOA, ex Kanto Chemical Co., Inc., and a standard material for DINCH, ex BASF.

(32) Operation Conditions:

(33) Apparatus: GCMS-QP2010Plus (ex Shimadzu Corporation); Column: DB-1 MS (ex Agilent Technologies, Inc.), 0.25 mm Φ×30 m with a membrane thickness of 0.25 μm; Inlet temperature: 280 degrees C.; Interface temperature: 280 degrees C.; Carrier gas: helium (2 mL/min.) Injected amount of a solution to be analyzed: 1 μL (using an auto-sampler); Column temperature: 100 degrees C. (1 minute)-20 degrees C./min.-230 degrees C. (0 minute)-10 degrees C./min.-300 degrees C. (15 minutes).
(ii) Extraction Test with a 40 vol/vol % Ethanol Solution in Water

(34) The same procedures as in test (i) above were repeated to determine an amount of a plasticizer (mg/ml) extracted into a 40 vol/vol % ethanol solution in water, except that the distilled water was replaced with the 40 vol/vol % ethanol solution in water. The ethanol solution was prepared from special grade ethanol, ex Kanto Chemical Co., and distilled water.

(35) TABLE-US-00002 TABLE 2 Exam- Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. Comp. ple 8 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Composition PVC 100 100 100 100 100 100 100 100 100 100 DOTP (molecular weight: 391) 50 50 0 0 0 0 0 0 0 0 DOP (molecular weight: 391) 0 0 50 50 0 0 0 0 0 0 TOTM (molecular weight: 547) 0 0 0 0 50 50 0 0 0 0 DINCH (molecular weight: 424) 0 0 0 0 0 0 50 50 0 0 DOA (molecular weight: 371) 0 0 0 0 0 0 0 0 50 50 Epoxidized soybean oil 10 0 10 0 10 0 10 0 10 0 (peroxide number: 3) Epoxidized soybean oil 0 10 0 10 0 10 0 10 0 10 (peroxide number: 8) Ca—Zn type composite stabilizer 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Results of Distilled water, mg/ml ND ND 1.20 × 3.00 × 9.60 × 5.80 × ND ND 9.40 × 3.30 × extraction 10.sup.−5 10.sup.−5 10.sup.−5 10.sup.−7 10.sup.−5 10.sup.−6 tests 40 vol/vol % Ethanol solution 7.40 × 3.20 × 5.40 × 9.60 × 7.50 × 2.10 × 8.30 × 2.10 × 1.60 × 5.60 × in water, mg/ml 10.sup.−7 10.sup.−5 10.sup.−3 10.sup.−3 10.sup.−5 10.sup.−8 10.sup.−5 10.sup.−4 10.sup.−2 10.sup.−2 ND = Not detected

(36) As apparent from Table 2, the composition of Example 8 comprising DOTP as a plasticizer and epoxidized soybean oil having the peroxide number of 5 or less showed the less elutions of the plasticizer into distilled water and into the aqueous ethanol solution, compared to those in the compositions of Comparative Examples 15 to 23 which met only one or neither of the aforesaid two requirements.