JPS6366252A - Polyvinyl chloride composition - Google Patents

Abstract

PURPOSE:To obtain a polyvinyl chloride composition having excellent moldability and flexibility in addition to excellent blood compatibility and low dissolution property and suitable for medical use such as artificial blood vessel, etc., by compounding a polyvinyl chloride with a modified polyester having high molecular weight. CONSTITUTION:100pts.wt. of a polyvinyl chloride is compounded with 10-150pts. wt. of a high molecular weight modified polyester produced by charging (A) 1mol of a polyester composed of an ester unit wherein the sum of carbon numbers of the diol component and the dicarboxylic acid component is 9-20, preferably 10-15, having carboxyl group at the terminal and having a number-average molecular weight of 500-20,000, preferably 1,000-8,000 and (B) 0.5-1.5mol of a compound having epoxy group at the terminal, preferably the compound of formula I or formula II and reacting the components with each other in the presence of (C) a catalyst comprising a IIA or IIB metal salt, preferably Ca salt or Zn salt of a 2-50C aliphatic mono(or di)carboxylic acid or aromatic mono(or di)carboxylic acid.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to polyvinyl chloride compositions.

The polyvinyl chloride composition obtained by the present invention has excellent blood compatibility and low elution properties, as well as excellent moldability and flexibility, so it is suitable for medical applications, particularly blood handling equipment and blood contact medical equipment. suitable. As a specific example,
For example, blood circuits such as heart-lung and artificial kidneys, artificial blood vessels,
Artificial hearts, cardiac catheters, blood bags, blood bags for component transfusion, plasma storage bags, high-calorie infusion tubes, intravascular indwelling catheters, tubes/catheters for surgical procedures, cannillae, chimeap catheters for intravascular treatment diagnosis, and Used in the medical field, such as infusion bags and drug solution bags. In addition to medical applications, it also has low-temperature properties, secondary processability,
Utilizing properties such as gas barrier properties and low elution properties, it is suitable for packaging applications, particularly food packaging applications.

Maki (Conventional guest technique) Polyvinyl chloride (hereinafter abbreviated as PVC), which has been plasticized with phthalate esters, has excellent physical properties such as moldability, secondary processability, and flexibility, so it is used in medical applications. It is widely used in the industrial field, especially in disposable products and L7.

However, although gostylphthalates have a large plasticizing effect, they have poor migration and extraction properties, especially in applications that come into contact with blood and/or body fluids, such as blood circuits, various cannulae, catheters, blood bags, and blood transfusion bags. The toxicity of eluted phthalate esters is a problem.

Ru.

Although various attempts have been made to improve these drawbacks, no satisfactory solution has yet been found. Some examples are shown below.

Japanese Patent Publication No. 39-10545 KJj: "A free product which is one of the group consisting of a reaction product obtained by the reaction of a polyhydric alcohol and an organic acid containing 2 to 3 carboxyl groups and a natural resin. As a vinyl chloride-based town plastic agent characterized by reacting a carboxyl group-containing polyester type substance and an active oxirane ring-containing eboxide in the presence of a specific tertiary amine as well as a 1-〈d quaternary ammonium catalyst. A description of methods for making useful modifier compositions is included.

However, even if this modifier composition is used, the tertiary amine and/or quaternary ammonium salt used as a catalyst may be mixed into the plasticized PVC.
The product complies with the voluntary standard for medical plastics, medical vinyl chloride plum fat compound and ■ (Japan Medical Plastics Association, established in January 1980). do not have. In other words, it is certain that something is eluting from this plasticized PVC. For example, medical devices molded from leached resin,
Particularly when used in applications that come into contact with blood and body fluids, it is dangerous from a safety standpoint.

In addition to these problems, in the case of plasticized PVC,
Perhaps because it contains tertiary aban or quaternary ammonium salts, when used in applications that come into contact with blood, platelet adhesion and aggregation are significant and blood coagulation is rapid. That is, it cannot be said that this plasticized PVC composition satisfactorily solves the disadvantages of conventional PVC plasticized with phthalate esters (elubility, poor blood compatibility).

Furthermore, Japanese Patent Publication No. 52-36896 discloses that 100 parts by weight of vinyl chloride contains 4 to 15 moles of a 1-free aliphatic diol having a side chain of 4 to 2 carbon atoms. A polyester urethane obtained by reacting a polyester glycol consisting of a mixed diol replaced with an aliphatic diol with 1 mole of the hegizamethylene diinocyanate component at a ratio of 098 to 106 moles of the polyol component is 40%
A low non-toxic soft PVC composition obtained by mixing ~110 parts by weight is disclosed. However, even in this case, although the extractability and migration properties of the plasticizer polymer are improved,
Since isocyanate is used, there is a concern about toxicity due to residual isocyanate groups, and at the same time, the plasticizing effect tends to be lower than that of polyester alone due to the introduction of urethane bonds. The blood compatibility of this composition is plasticized with phthalate esters.Compared to vinyl chloride, the composition has not been improved in shatterability and is unsuitable for applications in which it comes into contact with blood.

The present inventors have already proposed PVC compositions with low toxicity, low dissolution, and excellent blood compatibility in Proposals 1 to 1 (Japanese Unexamined Patent Application Publication No. 1983-1973).
No. 87143). In this case, the vinyl chloride composition had low extractability, low toxicity, low dissolution, and was highly compatible with blood, particularly inhibiting platelet adhesion. However, 1-1 In the process of manufacturing high molecular weight modified polyester, which is a plasticizer polymer of PVC, the sum of the carbon numbers of the diol component and dicarboxylic acid component is 9 to 20.
As a catalyst for reacting a polyester consisting of an ester unit and having a terminal carboxyl group with a compound having an epoxy group at the terminal, a catalyst having 6 to 50 carbon atoms may be used.
Perhaps because of the use of alkali metal salts of aliphatic monocarboxylic acids or dicarboxylic acids, when the medical vinyl chloride resin compounds A and A were tested, compound E had no problems in the eluate test, but compound E If the test is carried out using 100% filtration, the appearance of bubbles during the eluate test will not meet the standards.

Another disadvantage is that when this plasticizer polymer is mixed with vinyl chloride and made into a compound, it becomes colored.

(Problems to be Solved by the Invention) As mentioned above, PVC plasticized with phthalate esters, which have been conventionally used for medical purposes, has excellent physical properties, but phthalate esters When used in applications that come into contact with blood, the toxicity of the eluted phthalate esters becomes a problem, and at the same time, the plasticizer elutes, resulting in a decline in physical properties. . Another disadvantage of PVC using phthalate esters is its poor blood compatibility.

In other words, when it comes into contact with blood, thrombus formation is likely to occur;
When using medical devices that come into contact with blood (such as various blood circuits) made of PVC plasticized with phthalate esters, the blood is usually heparinized to prevent blood from coagulating. . If a large amount of heparin is used during surgery, there are problems with bleeding tendency and side effects of heparin.

In order to solve these problems, attempts have been made to use high molecular weight modified polyesters as plasticizer polymers as described above, but the drawback of forming bubbles during dissolution tests has not been resolved. not present.

(Means for Solving the Problems) The inventors of the present invention have conducted various intensive studies aimed at solving the above-mentioned drawbacks, and as a result, have arrived at the present invention. That is, the present invention provides an ester unit consisting of an ester unit in which the sum of the carbon numbers of a diol component and a dicarboxylic acid component is 9 to 20, having a terminal carboxyl group, and having a number average molecular weight of 500, based on 100 parts by weight of polyvinyl chloride. This is a polyvinyl chloride composition formed by blending a polyester having a molecular weight of 20,000 to 10 to 150 parts by weight with an epoxy group-terminated ester.

In the present invention, polyvinyl chlorides include, for example, vinyl chloride, polyvinylidene chloride, or polyvinyl chloride copolymers (including terpolymers and graft copolymers),
Alternatively, it is mainly made of vinyl chloride and contains a blend of this and other polymers.

In the present invention, the high molecular weight modified polyester (A) is composed of ester units in which the sum of the carbon atoms of the diol component and dicarboxylic acid is 9 to 2 o, and has a number average molecular weight of 500 to 20,000 and has a carboxyl group at the terminal. It is obtained by reacting polyester with (B) a compound having an epoxy group at its terminal.

The diol component of the polyester (A) having a carboxyl group at the end includes ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, deca Aliphatic diols such as methylene glycol, 1,4-cyclohexanediol, 1,3-
Examples include alicyclic diols such as cyclohexanediol, 1,4-cyclohexanediol, and 1,3-cyclohexanediol.

In addition, dicarboxylic acid components include glutaric acid, adipic acid, pimelic acid, succinic acid, azelaic acid, sebacic acid,
Examples include aliphatic dicarboxylic acids such as undecadionic acid and dodecadionic acid. In addition, some aliphatic dicarboxylic acids (
50 molti) may be substituted with an aromatic dicarboxylic acid such as 7-talic acid, 0-7 talic acid and/or terephthalic acid.

The sum of the carbon numbers of the ester units obtained from the diol component and the dicarboxylic acid component is 9 to 20. Preferably 10-15
It is necessary to select diols and dicarboxylic acids so that If the sum of the carbon numbers of the ester units is less than 9, the compatibility of the modified polyester with vinyl chloride will deteriorate, making it impossible to obtain a uniform composition. Moreover, even if it exceeds 20, the compatibility is poor.

The production of polyester (A) uses conventional esterification conditions and equipment. A diol and a dicarboxylic acid or a derivative thereof as raw materials are added to an esterification apparatus, and the mixture is reacted with stirring at a temperature of 150 to 260°C. In this case, a suitable esterification catalyst, for example phosphoric acid,
Phosphous acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, stannous oxalate, argyl lead oxide, tetrabutyl titanate, zinc acetate, sodium carbonate, etc.
It may be added in an amount of about 1 to 0.5% by weight. Normal pressure reaction 4N
It is preferable to carry out the above at 150 to 260° C. for 2 to 5 hours, and then gradually reduce the pressure to 0.1 to 50 mmHg to completely remove the remaining monomers and produced water.

The number average molecular weight of the obtained polyester (A) is 500-
20,000, preferably 1,000 to 8,000. Further, the acid value is 3 to 225, preferably 7 to 110.

Examples of the compound (B) having an epoxy group at the terminal include those represented by general formulas (I) to (IV).

(■) (In the general formula (I) t or (I[), X represents a halogen atom. R1 and R2 have 2 to 3 carbon atoms and represent a sulfonyl or oxy group. t, m, n are 0 (Indicates an integer of ~10.) (I) (In the general formula (TII) or (TV), R3 and -]1- R4 represent an alkylene group, an aralkylene group, or an aromatic residue group having 4 to 50 carbon atoms.) Compounds having an epoxy group represented by the general formula (Y or (nXf) include aliphatic diols having 2 to 30 carbon atoms,
For example, ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol,
neopentyl glycol, hexamethylene glycol,
], ]4-cyclohexanediol 1,3-cycloheganediol, 1,4-cyclohexane dimetatool,
1,3-cyclohexane dimetatool, etc., or aromatic diols such as 4,4'-isopropylidenediphenol, 4,4'-dihydroxyphenyl ether,
4. 4'-dihydroxyphenylnulphonate, alkaline or polyalkylene glycol, e.g. molecular weight 100-1
000 polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, and a condensate of epichlorohydrin.

Examples of the compound having an epoxy group represented by the general formula (III) include aliphatic saturated dicarboxylic acids having 4 to 50 carbon atoms;
For example, adipic acid, azelaic acid, sebacic acid, dimer acid, etc., or aliphatic unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, etc., or aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, etc., or dicarboxylic acids in the chain, e.g. 1,2-
Examples include condensates of bis(-monohydroxycarbonylhexamethylphenyl)ethane and epichlorohydrin.

Examples of the compound having an epoxy group represented by the general formula (It7) include condensates of oxycarboxylic acids such as ε-caproic acid and benzoic acid and ebichloride.

It is preferable that R2 is a linear, branched, or Fi ring-forming alkylene group having 2 to 15 carbon atoms.

To obtain the high molecular weight modified polyester of the present invention, the compound (B) having an epoxy group at the end is 0.5 to 1 mol per mol of the polyester (A) having a carboxyl group at the end.
．． It is charged at a ratio of 5 mol, preferably 0.7 to 12 mol.

Examples of catalysts include salts of metals of Group IIA or Group IIB of the Periodic Table, such as aliphatic monocarboxylic acids having 2 to 50 carbon atoms, aromatic monocarboxylic acids, aliphatic dicarboxylic acids, or aromatic dicarboxylic acids of Group mA of the Periodic Table; / or salts of metals of group IIB, i.e. aliphatic monocarboxylic acids such as acetic acid, butyric acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, lauric acid, phosphoric acid, stearic acid, adipic acid, pimeline acids, succinic acid, azelaic acid, sebacic acid, undecadionic acid, dodecadionic acid,
Salts of metals belonging to Group IIA or Group IIB of the periodic table of aliphatic dicarboxylic acids such as dimer acid are used. Periodic Table IIA
Metals of the genus or 1I43 genus include Mg, C! a, Ba
%Zn etc. are exemplified. Among these, metal salts of aliphatic monocarboxylic acids having 8 to 15 carbon atoms, particularly calcium stearate and/or zinc stearate, are preferred. The amount of these metal salts added is 0.01 to 5.00% by weight,
It is preferable to add 005 to 2.00% by weight.

In the present invention, the polyester (A), the compound (B) having an epoxy group at the end, and the above-mentioned metal salt are charged, and the reaction temperature is 100 to 250°C, preferably 120 to 230°C, while stirring under a nitrogen stream. The reaction is carried out for 10 hours.

The resulting high molecular weight modified polyester has a molecular weight of 2.000.
~10,0000, preferably 5,000~7.0
000 and 0.4 at 30°C in chloroform solvent.
The reduced viscosity when measured at the concentration of g/dj is 0.2 to 2.
0, preferably 0.3 to 1.5.

In the present invention, 10 to 150 parts by weight of the above-mentioned high molecular weight modified polyester is mixed with 100 parts by weight of PVC, but when it is desired to obtain a soft PVC composition, it is preferable to mix 40 parts or more.
~stomach. If the amount exceeds 150 parts by weight, surface tackiness increases, causing problems in operability.

If the amount is less than 10 parts by weight, the object of the present invention will not be achieved.

The modified polyester may be mixed with vinyl chloride using a roll, Henschel mixer, Banbury mixer, or the like.

When mixing, if necessary, a low molecular plasticizer such as bis-2-ethylhexyl phthalate, dibutyl phthalate, didecyl phthalate, di-n-octyl phthalate,
Phthalate esters such as diisooctyl phthalate, didecyl phthalate, diisodecyl phthalate, linear dibasic acid esters such as dioctyl adipate, dioctyl azelate, dioctyl sebacate, tributyl citrate, trioctyl acetyl citrate It may be used in combination with butyl 7talylbutyl glycolate, etc.

When high molecular weight modified polyester is used in combination with these low molecular plasticizers, the amount of these low molecular plasticizers added is 10% of PVC.
1 to 40 parts by weight, preferably 3 to 3 parts by weight
0 parts by weight, and the weight ratio is 0.05 to 0.50, preferably 0.1 to 0.3 with respect to the amount of high molecular weight modifier added.
It is.

During mixing, it is also possible to use small amounts of volatile solvents, such as chloroform, tetrachloroethane, acetone, tetrahydrofuran, cyclohexanol, etc., to facilitate impregnation of the high molecular weight modified polyester into the vinyl chloride.

Normally, stabilizers and lubricants are essential when processing PVC, and the present invention is no exception.

All commercially available stabilizers and lubricants can be used, and stabilizers that will be developed in the future can also be used, but when used for medical purposes, food packaging, etc., epoxy stabilizers,
A combination of calcium stearate and zinc stearate is desirable.

(Function) The vinyl chloride composition of the present invention has sufficient flexibility without using a phthalate plasticizer.

Therefore, there are no problems such as extraction, migration, or toxicity caused by low molecular weight plasticizers. In particular, the periodic table IIA is used as a reaction catalyst for polyester (A) and a compound (B) having an epoxy group at the end.
Because a salt of a metal of Group 2 or Group IIB is used, unlike the case where a tertiary N amine or a quaternary ammonium salt or an alkali metal salt is used as a catalyst,
Conforms to medical vinyl chloride resin compound test law,
The obtained vinyl chloride compound acid has little coloration and is highly thermally stable. Moreover, it has excellent mechanical properties such as flexibility, strength and elongation, low-temperature flexibility, oil resistance, and abrasion resistance, and has good operability.

Furthermore, since the PVC composition of the present invention has extremely good antithrombotic properties, it can be used particularly in blood circuits, blood bags, catheters, cannulae, infusion tubes, and bypass tubes. It is widely used in the field of materials that come into contact with blood, such as artificial heart-lung machines, artificial hearts, and artificial kidneys. It is also used in conventional PVC applications such as food packaging, hoses, belts, synthetic leather, and rice cakes.

(Example 1) The present invention will be explained in detail with reference to Examples below.

In addition, in the examples, all parts simply mean parts by weight. All viscosity measurements were made in chloroform solvent at 30"
'C, 0.4g/dj Novolimer thick f Te? lIJ is a fixed value.

In addition, in the examples, physical property tests were performed according to the following method.

0,) 100 Timozylus (indicating the degree of plasticization)・-
...Conforms to JIS K6301.

C21 Low-temperature bending fatigue test...Test I using a Dayma-Sha bending fatigue tester! JA temperature = 10±1
At ℃, the number of times a test piece (2 mm thick x 25 m wide x 15 side length sheet with a Caputo cloth inserted in the center and width direction of 2 m1']'1) outside the cut was measured.

Based on C31 medical vinyl chloride resin compound test method eluate test (Japan Medical Plastics Association Voluntary Standard for Medical Plastics established in January 1981).

Specifically, test item 15. (The 1st section is a glass container press-fitting bar,
Add 300 mg of real fish, seal L'#:, then heat at 121℃ for an hour using a high-pressure steam sterilizer, leave it to reach room temperature, add water to this liquid, and make exactly 4tC300ml.
5. Meanwhile, the blank test solution 'fc
Tests for appearance, foaming, pH, tin, zinc 1, potassium permanganate reducing substance, vapor residue, and ultraviolet absorption spectra are conducted for products manufactured by X.

(4) Coloring: Hunter scale b value was measured using a color difference meter. The smaller the b value, the less yellowish coloration, and the more deterioration is suppressed.

6) Extractability test: Based on Ministry of Health and Welfare Notification No. 178.

Test piece 1. Put axxoo pieces into an Erlenmeyer flask, and
Add 200mz of hebutane, stopper, and shake at 25°C for 60 minutes. After shaking for 60 minutes, n-hebutane was horizontally striped under reduced pressure, and the concentrated solution was taken into a quartz evaporating dish, evaporated to dryness on a water bath, and then dried at 105 °C for 2 hours. After that, let it cool in a desiccator. After cooling, it is weighed to determine the weight difference a(-g) between the front and rear of the evaporating dish, and the amount of evaporation residue is determined using the following formula.

b: Blank test value obtained for the same amount of leaching liquid (n-hebutane) as the test solution Standard: 150 ppm or less is considered to be a pass.

6) Antithrombotic properties were evaluated using the 7-pzeta column method developed by Sakurai et al. (Makromol Ohem, 179,112
This was done with reference to H1978)). That is, if diameter 2
00μ glass beads coated with polymer L and 1.0g of the beads were mixed into a commercially available medical soft PVC cheese with an inner diameter of 3.0mm and cocks at both ends. Closely pack ynK and fill with physiological saline. From the jugular vein of an adult dog, use a 7-dical disposable syringe with a capacity of 10 m x 2.
Collect the fresh side of mt! -1 Immediate extraction at constant flow rate 1.
Set 1 to a compatible syringe pump, connect the tip of the syringe with the needle removed to the bead-packed column prepared in advance, and let blood flow for 1 minute at a flow rate of 1.0 + nz 7 minutes.
The blood that has passed through the column is collected into an EDTA-treated commercially available Polydna bottle 0110.The number of platelets in the blood that has passed through the column is determined by
Calculated using the t8 method. The platelet adhesion number is the value obtained by subtracting the number of platelets after passing through the column from the number of platelets in the bloodstream before passing through the column.

A relative comparison of platelet adhesion between materials was determined using the following formula, and the smaller the value, the less the adhesion of the platelets and the better the antithrombotic properties.

Platelet relative adhesion ratio = Number of platelets adhesion to beads coated with each composition Number of platelets adhesion to beads coated with each composition Synthesis Example 1 1524 parts of adipic acid, 11 parts of 1,6-hexanediol
82 parts of tetrabutyl titanate, 0.108 parts of tetrabutyl titanate, and 0.089 parts of trimethyl phosphate were placed in an autoclave, and the temperature was raised to 150 to 230°C over 2 hours under a nitrogen stream, and the water produced was removed while stirring to allow the reaction to proceed. went.

Next, the temperature was maintained at 230°C, and the pressure was gradually reduced to Q, lmmHg over 60 minutes. Furthermore, Q, l mm
Hg, the reaction was carried out at 230°C for 60 minutes, and the acid value was 37.4.
A polyester having a terminal carboxyl group and a hydroxyl value of 0.3 was obtained.

1500 parts of this polyester and an epoxy compound represented by general formula (1), Bunacol 211 (manufactured by Nagase Chemical Industries, Ltd., epoxy equivalent: 138.0 g/equivalent) 151.
8 parts and 6.0 parts of calcium stearate were charged into an autoclave, and reacted for 1 hour with stirring at 200° C. under a nitrogen stream to obtain a high molecular weight modified polyester of ηSP/C0567.

Synthesis Example 2 1524 parts of adipic acid, 10 parts of 1,6-hexanediol
61 parts, neopentyl glycol 104 parts, tetrabutyl titanate 0.108 parts and trimethylphos 7-ether)
0.089 part was charged into an autoclave, and the following Synthesis Example 1
The reaction was carried out in the same manner as above, and the acid value was 44.9 and the hydroxyl value was 05.
A polyester having terminal lupogyl groups was obtained.

1500 parts of this polyester and an epoxy compound represented by the general formula (I[), Bunacol 210 (manufactured by Nagase Chemical Industries, Ltd., epoxy equivalent: 141.2 g/equivalent) 18
6.5 parts and 4.0 parts of zinc stearate were charged into an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1. +ysp/
A high molecular weight modified polyester B having a cO of 45 was obtained.

Synthesis Example 3 2153 parts of sebacic acid, 900 parts of 1,4-butanediol
1.0 parts, 0.108 parts of tetrabutyl titanate, and 0.089 parts of trimethyl phosphate) were charged into an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1. A polyester having carboxyl groups at both ends and a hydroxyl value of 0.48 was obtained. This polyester 15
00 parts, 296.4 parts of diglycidyl sebacate, and 4.5 parts of magnesium laurate were charged into an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1. '7SP/C0
, 63 modified polyester C was obtained.

Synthesis Example 4 2005 parts of azelaic acid, 7 parts of 1,6-hexanediol
62 parts of neopentyl glycol, 377 parts of neopentyl glycol, 0.108 parts of tetrabutyl titanate, and 0.089 parts of trimethyl phosphate were placed in an autoclave and reacted in the same manner as in Synthesis Example 1 to form a terminal carboxyl group with an acid value of 351 and a hydroxyl value of 0.21. A polyester having the following properties was obtained. 1,500 parts of this polyester, an epoxy compound represented by general formula (IV), 145.4 parts of a condensate of benzoic acid and epichlorohydrin (epoxy equivalent: 141 g/equivalent), and 0.40 part of cadmium stearate were charged into an autoclave, and Example React the same way as in 1? A high molecular weight modified polyester D having an sr/c of 0.46 was obtained.

Synthesis Example 5 2153 parts of sebacic acid, 621 parts of ethylene glycol,
0.108 part of tetrabutyl titanate and 0.089 part of trimethyl phosphate were charged into autoclave 4 [phase] and reacted in the same manner as in Synthesis Example 1 to obtain a polyester having a terminal carboxyl group with a 411 oxidation hydroxyl value of 0.35. 1500 parts of this polyester and general formula (1
), an epoxy compound shown by Bunacol EX-920
(Manufactured by Nagase Chemical Industries, Ltd., epoxy equivalent: 180g/
220 parts (equivalent) and 4.0 parts of calcium stearate were charged into an autoclave, and the reaction was carried out in the same manner as in Example 1 to obtain a high molecular weight modified polyester E having v5p/(0.63).

Synthesis Example 6 Adipic acid 1555 parts, l,6-hexanediol 11
82 parts of tetrabutyl titanate, 0.108 parts of tetrabutyl titanate, and 0.089 parts of trimethyl phosphate were placed in an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain a polyester having terminal carboxyl groups with an acid value of 37.4 and a hydroxyl value of 0.3. Obtained.

1,500 parts of this polyester, 211.5 parts of an epoxy compound represented by the general formula (TI), YD-127 (manufactured by Tobu Kasei Co., Ltd., epoxy equivalent: 192.3 g/drawing weight), and 0.35 g of calcium laurate were placed in an autoclave. Reaction 1~te'? in the same manner as Synthesis Example 1. sp/C'
A high molecular weight modified polyester F having a molecular weight of 0.58 was obtained.

Synthesis Example 7 1555 parts of adipic acid, 441 parts of 1,4-cyclohexane dimethal, 0108 parts of tetrabutyl titanate and 0.089 parts of trimethyl phosphate were charged into an autoclave, and the acid value was determined by reaction I2 in the same manner as in Synthesis Example 1. 29.5
A polyester having a terminal carboxyl group and a % hydroxyl value of 0.27 was obtained.

1500 parts of this polyester and an epoxy compound represented by general formula (1), Bunacol 212 (Nagase Kasei Kogyo Co., Ltd., epoxy equivalent: 150 g/equivalent) 130
3 parts and 030 parts of calcium sebacate were placed in an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain ηS.
A polymer bond-modified polyester G having a P/C of 0.55 was obtained.

Synthesis Example 8 3629 parts of adipic acid, 1,6-to, Gizafudiol 3
545 parts were charged into an autoclave, and the reaction was carried out at 150-230''C-4 for 2 hours under stirring in a nitrogen stream at 150 to 230''C-4 while removing produced water.

Next, 0.36 part of tetrabutyl titanate was added to the mixture at 230°C.
The temperature was maintained at -L-&i, and the vacuum was removed to [2,60 min O,], mmHg. Further 230℃-0
, 1 mm'Hg for 3 hours, ηsp/cO, 3
Polynisdel H of No. 3 was obtained.

Synthesis Example 9 A polyester glycol having a molecular weight of 2000 was synthesized from adipic acid and a mixed diol in which the molar ratio of 1.6-hegysandiyl to neopentyl glycol was 9=1. 103 mol of xamethylene diisocyanate was added to 1 mol of this polyester in an autoclave at 160°.
The reaction was carried out at C for 2 hours with stirring under a nitrogen stream, and vs.
A polyurethane ratio of p/(:0.88 was obtained.

Synthesis Example 1 () 1500 parts of the polyester having a terminal carboxyl group with an acid value of 37.4 and a hydroxyl value of 0.3 obtained in Synthesis Example 1 and the epoxy compound represented by general formula (II), YD-127 (
Manufactured by Tobu Kasei Co., Ltd., epoxy equivalent: 192.3 g / 211.5 parts 1τ dodecyl-dimethyl-β-hydroxyethylammonium bromide 200 parts, 15
After melting at 0'G for 15 minutes, the melt was cooled to obtain Polyester J, described in Japanese Patent Publication No. 10545/1988, having MA SP/C0.40.

Synthesis Example 11 1500 parts of the polyester having a terminal carboxyl group with an acid value of 37.4 and a hydroxyl value of 03 obtained in Synthesis Example 1 and the general formula (
The epoxy compound shown in 1), Bunacol 211 (
Manufactured by Nagase Chemical Industries, Ltd., epoxy equivalent: 138.0g
/ equivalent) 151.8 parts and sodium stearate 3
, 0 parts were charged into an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain polyester K having v3p/c of 0.55.

Synthesis Example 12 HOOCC! 34) I68 C0OH6028 part,]
1182 parts of -26-hexanediol, 0.35 parts of tetrabutyl titanate and trimethyl phosphate) 0.
30 parts were charged into an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain a polyester having an acid value of 20□3, a hydroxyl value of 022, and a terminal carboxyl group.

This polyester'! 00 parts of YD 128 (epoxy equivalent: 192.3 g/Japanese leaf) and 6.0 parts of calcium stearate were placed in an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain η5p7c0.6.
Polyester L of No. 2 was obtained.

Examples 1 to 7 and Comparative Examples 1 to 6 Each component was first mixed in the formulation shown in Table 1 below. Next, this mixture was melt-mixed using a twin-screw extruder (cylinder temperature: 150 to 175°C) [7] and pelletized to produce a vinyl chloride composition. The pellets were pulverized and the vinyl chloride composition was drawn out into a sheet using a mixing roll to create a 2 mm thick sheet. The pressing conditions were a press temperature of 160 to 170°C, a press time of 3 minutes and a pressure of 100 to 120/d, a cooling time of 5 minutes and a pressure of 13
It was carried out at 0 to 150&y/CJ. Using the obtained sheet, 100% modulus measurement, low temperature flex fatigue test, compound test, b value measurement and extractability test were conducted. The results are shown in Table 2.

Table 1 Table 2 Table (*2) KMHO4 consumption, pH, foaming, distillation residue fail (*3) Foaming fails (*4) KMnO4 consumption, foaming, UVi yield fail Table 2 shows that the PVC composition of the present invention has excellent flexibility and low-temperature properties, has little coloring after compounding, and suppresses thermal deterioration, and also passes the compound test Pope's extractables test and extractability test. It is clear that the composition has low toxicity, low extractability, and high thermal stability.

Examples 8 to 10 and Comparative Examples 7 to 10 PVC compositions were prepared in the same manner as in Example 1 with the formulations shown in Table 3.

Table 3 The antithrombotic properties of the resulting compositions were measured and the results are shown in Table 4.

As is clear from Table 4, the PVC composition of the present invention had significantly improved blood compatibility.

Claims (2)

[Claims] (1) Based on 100 parts by weight of polyvinyl chloride, the diol component and the dicarboxylic acid component are composed of ester units having a total carbon number of 9 to 20, have a terminal carboxyl group, and have a number average molecular weight of 500 to 20; 000 and a compound having an epoxy group at the end of the periodic table II_
A polyvinyl chloride composition containing 10 to 150 parts by weight of a high molecular weight modified polyester obtained by reaction in the presence of a metal salt of group A or group II_B. (2) The salt of a metal in Group II_A or Group II_B of the Periodic Table is a calcium salt of an aliphatic monocarboxylic acid, an aromatic monocarboxylic acid, an aliphatic dicarboxylic acid, and/or an aromatic dicarboxylic acid having 2 to 50 carbon atoms, or The polyvinyl chloride composition described in Patent No. 1, which is a zinc salt.