JPS5887143A - Polyvinyl chloride composition - Google Patents

Abstract

PURPOSE:To provide a compsn. free from problems of bleeding, migration and toxicity of plasticizers, and with excellent mechanical characteristics such as flexibility, elongation, low-temp. bending and wear resistance, by blending PVC with a specific high-MW modified polyester as a plasticizer. CONSTITUTION:100pts.wt. PVC is blended with 10-150pts.wt. high-MW modified polyester obtained by the reaction of a polyester comprising an ester unit in which the sum of the number of carbon atoms in both diol and dicarboxylic acid components is 9-20 and having carboxyl groups at the both terminals, with a compd. having epoxy groups at the both terminals, yielding the titled compsn. The comspn. has sufficient flexibility in the absence of phthalate plasticizers such as dioctyl phthalate. Hence, the problems of bleeding, migration and toxicity due to low-molecular plasticizers are solved. Furthermore, the compsn. has excellent mechanical characteristics such as flexibility, elongation, low- temp. bending and wear resistance, and good workability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride composition comprising a special modified polyester and polyvinyl chloride (hereinafter abbreviated as vinyl chloride).

Currently, various compounds such as phthalate esters, aliphatic polyesters, and epoxy compounds are widely used as plasticizers for vinyl chloride. However, the most commonly used phthalate esters are dioctyl phthalate (DOP).While these phthalate esters have a large plasticizing effect, they have high migration and extractability. It is easily extracted by various organic solvents, and at the same time, when left in contact with other types of resins such as polyester, polyamide, and polyurethane, phthalate esters leached from the inside to the surface and migrated [7. , deterioration of mechanical properties such as decreased elongation often occurs.

Furthermore, as indicated in Ministry of Health and Welfare Notification No. 178, the amount of PVC compositions used for food packaging, etc. that can be extracted into n-hexane, etc. is regulated, and from the safety perspective of plastic containers, organic solvents The development of a plasticizer that will not be extracted or migrated to the surface by exposure is eagerly awaited.

The present invention relates to a PVC composition that is not easily extracted or migrated, and is non-extractable and non-extractable only when PVC is plasticized using a special modified polyester without using phthalate esters. A non-migration flexible, low-toxicity PVC composition is obtained Conventionally, as a plasticizer to replace DOP, a general polyester obtained from propylene glycol and adipic acid has been known as a PVC plasticizer. Since such polyesters have a larger molecular weight than dioctyl phthalate, they are said to have less extractability and migration. However, when such polyester was actually mixed with PVC and its extractability and migration properties were examined, it was found that a considerable amount of plasticizer was still extracted and migrated. This is thought to be due to oligomers in the polyester.

Furthermore, in Japanese Patent Publication No. 52-36896, 100 parts by weight of vinyl chloride is mixed with 4 to 1 aliphatic dicarboxylic acids having 6 to 12 carbon atoms without side chains and aliphatic diols having 4 to 12 carbon atoms without side chains.
A polyester glycol consisting of a mixed diol in which 5 mol % is replaced with an aliphatic diol having side buttons having 3 to 12 carbon atoms and hexamethylene diisocyanate are added in an amount of 0.98 to 1.
A low-toxicity soft vinyl chloride composition obtained by mixing 40 to 110 parts of polyester urethane obtained by reaction at a ratio of 0.6 mole is disclosed.

However, even in this case, although the extractability and migration of the plasticizer into the polymer have been improved, since incyanate is used, there is a concern about cytotoxicity due to residual incyanate groups, and at the same time, the introduction of urethane bonds , the plasticizing effect tends to be lower than that of polyester alone.

The present inventors have arrived at the present invention as a result of intensive research aimed at finding a PVC plasticizer that not only improves extractability and migration properties but also has an excellent plasticizing effect and is low in toxicity.

That is, the present invention is based on polyvinyl chloride ioo parts by weight, consisting of an ester unit in which the sum of the number of carbon atoms of the diol component and the dicarboxylic acid component is 9 to 20, and a polyester having carboxyl groups at both ends, and a polyester having carboxyl groups at both ends. This is a polyvinyl chloride composition prepared by blending 10 to 150 parts by weight of a high molecular weight modified polyester obtained by reacting a compound having an epoxy group with a compound having an epoxy group.

In the present invention, by using the above-mentioned high molecular weight modified polyester as a plasticizer, problems such as extraction, migration, and toxicity of the plasticizer are solved, and mechanical properties such as flexibility, strength and elongation, low temperature flexibility, and abrasion resistance are improved. A PVC composition with excellent physical properties can be obtained.

The PVC silk composition of the present invention is also excellent in antithrombotic properties.

The uninvented high molecular weight modified polyester is composed of an ester unit having a diol component and a dicarboxylic acid component having 9 to 20 carbon atoms, and a polyester having carboxyl groups at both ends, and (I3) an epoxy group at both ends. It is obtained by reacting a compound having a group.

A polyester having carboxyl groups at both ends (aluminum diol component and ethylene glycol).

Propylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, heptamethylene glycol, octamethylene glycol,
Nonamethylene glycol, Tecamethylene glycol, cyclohexanediol.

Aliphatic and/or aliphatic diols such as cyclohexanedimethanol are preferred. In addition, dicarboxylic acid components include glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, and sebacic acid.

Undecadionic acid, dodecadionic acid, etc. are commonly used.

The sum of the carbon elongation numbers of the ester units obtained from the diol component and the dicarboxylic acid component is 9 to 20. Good luck 10~
It is necessary to select diols and dicarbonate Fa+9 so that the total number of diols becomes 15. The sum of the number of carbon atoms in the ester unit is 9
If it is smaller, 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 (Al) uses conventional esterification conditions and equipment. The raw materials diol and dicarboxylic acid or its derivative are added to the esterification equipment, and the mixture is reacted with stirring at a temperature of 150 to 260°C.

In this case, suitable esterification catalysts are used, such as monophosphorous acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, Shu IVP stannous salts, alkyl lead oxides, tetrabutyl titanate,
0.01-0.5% by weight of zinc acetate, sodium carbonate, etc.
May be added. After carrying out the reaction at normal pressure of 150 to 260°C for 2 to 5 hours, the pressure was gradually reduced (7, the pressure was reduced to 0.1 to 50°C).
Preferably, it is reduced to smI (g) to completely remove any remaining water.

The number average molecular weight of the obtained polyester (A) is 500-
20,000. Preferably it is 1,000 to s, ooo. Also, the acid value is 14-110. Examples of the compound having an epoxy group at both ends (0, which is preferably 20 to 70) include those represented by the following general formula (I+, (I), (1)).

0 (In the formula, R1 is an alkylene group having 4 to 50 carbon atoms.

Aralkylene group or oxyalkylene group, -Q-X-
Q-.

←◎−X−◎−0−C)(2−CH−C)]]2+n0
-o-X-Q-■ Indicates H. X represents isopropylidene, methylene, sulfonyl or oxy group. n represents an integer of 1 to 10. ) (In the formula, horse represents an alkylene group, alkenylene group, aralkylene group, or aromatic group having 4 to 50 carbon atoms.) (In the formula, horse represents an alkylene group having 4 to 50 carbon atoms, an oxyalkylene group, Indicates an aralkylene group or an aromatic group.) General formula ((Compounds having an epoxy group represented by l include aliphatic diols having 4 to 50 carbon atoms, such as tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc. , or aromatic diols such as 4,4'-isopropylidenediphenol, 4
．． 4'-dihydroxyphenylmethane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxyphenyl sulfone, etc. or polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene with a molecular weight of 100 to 1000. Examples include copolymers with oxides in which the hydroxyl groups at both ends are diglycidyl etherified, and epoxy resins with a molecular weight of 400 to 2000 and having epoxy groups at both ends obtained from 4,4'-isopropylidene diphenol and epichlorohydrin. It will be done.

Examples of the compound having an epoxy group represented by n in general formula (I) include aliphatic saturated dicarboxylic acids having 4 to 50 carbon atoms, such as adipic acid, azelaic acid, sebacic acid, dimer acid, etc.; Dicarboxylic acids such as maleic acid, fusuric acid, etc., aromatic dicarboxylic acids such as tere-79-thalic acid, isophthalic acid, etc., or dicarboxylic acids having an aromatic nucleus in the side chain, such as 1,2-bis(ω-hydroxy). Examples include those obtained by converting both terminal carboxyl groups into diglycidyl esters, such as carbonylhexamethyl-phenyl)ethane.

Examples of compounds having an epoxy group represented by the general formula (, llD) include glycidyl ethers and glycidyl esters of oxycarboxylic acids such as ξ-caproic acid and benzoic acid.

In order to obtain the high molecular weight modified polyester of the present invention, 0.5 (of the compound having epoxy groups at both ends) per 1 mole of the above-mentioned polyester (5) having carboxyl groups at both ends.
The reaction is carried out in a proportion of ~1.5 mol, preferably 0.7-1.2 mol. The reaction conditions are 100 to 250°C, preferably 120 to 230°C, under a nitrogen stream, with stirring for 0.1 to 10 hours. At this time, catalysts generally used as ring-opening catalysts for epoxy groups may be used, but alkali metal salts of aliphatic monocarboxylic acids or dicarboxylic acids having 6 to 50 carbon atoms are particularly preferred. The amount of catalyst added is =10-0.05 to 0.5% by weight.

The resulting high molecular weight modified polyester has a reduced viscosity of 0.30 or more, preferably 0.50 or more, as measured at a concentration of 0.4 F/dt in a chloroform solvent at 30°C.

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. If it exceeds the limit, tackiness will increase and problems will arise 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 can be mixed using commonly used rolls, Henschel mixers, Banbury mixers, etc. When mixing, a solvent is used if necessary. As a solvent, tetrahydrofuran,
Examples include chloroform and tetrachloroethane.

Normally, when processing vinyl chloride, stabilizers and lubricants are essential, and the present invention is no exception. All commercially available stabilizers and lubricants can be used, but a combination of epoxy stabilizers, calcium stearate, and zinc stearate is particularly desirable when used for food packaging or medical purposes.

The PVC composition of the present invention has sufficient flexibility without using phthalate plasticizers such as DOP. Therefore, problems such as extraction, migration, and toxicity caused by low-molecular plasticizers are all solved. Moreover, it has excellent mechanical properties such as flexibility, strength and elongation, low-temperature flexibility, and abrasion resistance, and has good operability.

Furthermore, since the PVC composition of the present invention has extremely good anti-thrombotic properties, it is particularly suitable for blood circuits, flow control bags, catheters,
It is widely used in the field of materials that come into direct contact with blood, such as medical materials such as cannulae, and parts of artificial heart-lung machines, artificial hearts, and artificial kidneys. It is also used in traditional PVC applications such as food packaging, food hoses, belts, synthetic leather, and toys.

The present invention will be described in detail below with reference to Examples.

In addition, in the examples, all parts simply mean parts by weight. All viscous measurements were performed in chloroform solvent at 30°C.
, the value measured at a polymer concentration of 0.49/dt.

Synthesis Example 1 Adipic acid 1524 parts, 1,6-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 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 0.1 yatHg over 60 minutes. 0.1 more) 1
g, the reaction was carried out at 230°C for 60 minutes, and the acid value was 24.7. A polyester having a hydroxyl value of 0.50 and having carboxyl groups at both ends was obtained.

1500 parts of this polyester and epoxy resin YD-12
8 (manufactured by Tobu Kasei KK) (epoxy @ amount tc + 2.3V per unit) 88.9 parts and 3.0 parts of disodium dimerate were charged into an autoclave, and reacted for 4 hours with stirring at 180 ° C. under an air flow at room temperature. , ηs p/c O,75
Modified polyester A of No. 6 was obtained.

Synthesis Example 2 1524 parts of 13-adipic acid, 10 parts of 1,6-hexanediol
61 parts of neopentyl glycol, 104 parts of neopentyl glycol, 0.108 parts of tetrabutyl titanate and 0.089 parts of trimethyl phosphate were placed in an autoclave and the following Synthesis Example-1 was prepared.
The reaction was carried out in the same manner as above, and the acid value was 27.0 and the hydroxyl value was 0.
A polyester having 51 carboxyl groups at both ends was obtained. 1500 parts of this polyester and 1 epoxy resin YD
28.88,9 parts and 3.0 parts of disodium dimerate
The mixture was charged into an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain η sp/c O, 80 modified polyester B.

Synthesis Example 3 Adipic acid 1524 parts, 1,4-butanediol 899 parts
0.108 parts of tetrabutyl titanate and 0.089 parts of trimethyl phosphate were charged into an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain an acid value of 38.7,
A polyester having carboxyl groups at both ends and a hydroxyl value of 0.48 was obtained. 1,500 parts of this polyester, 153 parts of tucuricidyl sebacate, and 3.0 parts of disodium dimerate were charged into an autoclave-14=, and a reaction was carried out in the same manner as in Synthesis Example-1.
A modified polyester C having cO,78 was obtained.

Synthesis Example 4 1524 parts of sebacic acid, 76 parts of 1,6-hexanediol
2 parts, 75 parts of neopentyl glycol, 0.108 parts of tetrabutyl titanate, and 0.1 parts of trimethyl phosphate.
089 parts were charged into an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain a polyester having carboxyl groups at both ends and having an acid value of 26.8 and a hydroxyl value of 0.32. 1,500 parts of this polyester, 8 parts of tucuricidyl sebacate, and 3.0 parts of disodium dimerate were charged into an autoclave, and the reaction was carried out in the same manner as in Synthesis Example 1.
t)/CO, 83 modified polyester D was obtained.

Synthesis Example 5 1524 parts of sebacic acid, ethylene chloride: I-/l/4
60 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 an acid value of 26.
5. A polyester having a hydroxyl value of 0.350 and carboxyl groups at both ends was obtained. 1500 parts of this polyester, 9 parts of Evokin resin Y, [)-12888, and 3.0 parts of disodium dimerate were charged into an autoclave.
The reaction was carried out in the same manner as in Synthesis Example-1, and ηsp/c O,7
Modified polyester E of No. 7 was obtained.

Synthesis Example 6 3,629 parts of adipic acid and 3,545 parts of HD were charged into an autoclave, and 150 to 2
The temperature was raised in a 30°C trench for 2 hours, and the reaction was carried out while removing the produced water. Next, 0.36 parts of tetrabutyl titanate was added, and the temperature was maintained at 230° C. while the pressure was gradually reduced to 0.1 mmHg in 60 minutes. Furthermore, 230
The reaction was carried out at ℃-〇 for 3 hours at 1 Hg, and η5p/cO1
Polyester F of No. 33 was obtained.

Synthesis Example 7 A polyester glycol having a molecular weight of 2,000 and consisting of a mixed diol with a molar ratio of 6-hegysandiol and neopentyl glycol of 9-1 and adipic acid was synthesized. 1 mol of this polyester and 1.03 mol of hexamethylene diisocyanate were charged into an autoclave, and the reaction was carried out at 160°C for 2 hours with stirring under a stream of ♀ gas, and ηsp/
Polyurethane G with c O, 88 was obtained.

Examples 1 to 5 and Comparative Examples 1 to 3 Table 1 17 - Each component was first mixed in the formulation shown in Table 1 above. Next, this mixture was kneaded for 10 minutes using a steam-heated 8-inch mixing roll (roll salt [150-160°C)] to prepare a vinyl chloride composition.

At this time, the PVC silk composition was pulled out in a sheet form from the mixin roll to create a 2 ml thick sheet. Pressing conditions are press temperature 160-170℃, press time 3 minutes and pressure 100-120Kdd, cooling time 5 minutes and pressure 130
I went to grade 150.

Note that the physical property test was conducted according to the following method.

(1) 100% modulus (indicates the degree of plasticization)
-= Conforms to JIS K, 6301.

(2) Low-temperature bending fatigue test...Using a Demarsha bending fatigue tester, test specimens (21 m thick x 2.5 crn medium x 1 center of 15 sheets with center opening, width direction (with 21O1 cut gloss added)
Measure the number of times it takes to break.

(3) Extractability test...1 based on Ministry of Health and Welfare Notification 178
From the results shown in Table 8-2, it is clear that the vinyl chloride composition of the present invention has excellent flexibility, low-temperature properties, and extractability.

Synthesis Example 8) TOOCC34H,, 5898 parts of C0OH, 1.6-
Hexanediol 1182 parts, tetrabutyl titanate 0
．． 35 parts and 0.30 parts of trinotyl phosphate were placed in an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain an acid value of 20.3. A polyester dicarboxylic acid having a hydroxyl value of 0.22 was obtained. This polyester dicarboxylic acid 150
0 parts and Yl) -12858, 4 parts and Na00CC
34HasCOONa3, Og was charged into an autoclave, and the reaction was carried out in the same manner as in Example-1, and ηs
A modified polyester H having a p/c O, 78 was obtained.

Comparative Example 4 A blend of 100 parts of vinyl chloride (polymerization [1100) and 80 parts of modified polyester] and a composition sheet were prepared in the same manner as in the example.

Additional Examples 6 and 7 and Comparative Examples 5 to 7 Added to Section 2e PVC compositions were made 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 by the following method:
It is shown in Table 4.

Antithrombotic properties were evaluated using the column method developed by Sakurai et al.
omo! , Chem, 179.1121 (1978))
I did this with reference to.

That is, the polymer fM was applied to glass beads with a diameter of 200μ, and 0.5g of the beads were placed in a commercially available medical soft PVC tube 10cm21 with an inner diameter of 0.3m and cocks at both ends.
- Close-pack and fill with saline. 10 from Seiyawa vein
Collect 2 ml of fresh surface using a disposable syringe for mesocal with a capacity of 1 m, and immediately set it in a syringe pump that can extrude at a constant flow rate [7. Connect the previously prepared bead-packed column to the tip of the syringe from which the injection needle has been removed. death,
Flow the blood flow for 1 minute at a flow rate of 1.0 parts, collect the blood flow that has passed through the column into an EDTA-treated commercially available polydonor bottle 0110, and measure the number of platelets in the blood flow that has passed through the column using the Brecher Cr-onkite method. Calculate using. 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 is determined by the following formula, and the smaller this value is, the less the platelet stickiness is.

That is, it shows that the antithrombotic property is good.

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

Patent applicant: Toyobo Co., Ltd. =23- Voluntary writing of procedural amendments) ■Display of incident 1981 Patent Application No. 185914 2. Name of the invention polyvinyl chloride composition 3. Person who makes corrections Relationship to the case Patent applicant 2-2-8 Dojimahama, Kita-ku, Osaka 4. Subject of correction “Detailed description of the invention” column in the specification (1) Page 12, line 12 of the specification Correct "blood flow bag" to "blood bag".

(2) Bottom line of page 21 Correct r　O, 3 mml to rO, 3 cmJ.

Procedures Written amendment (spontaneous) November 24, 1980 1. Indication of s Patent Application No. 1859:14a Name of the invention Polyvinyl chloride composition 8 Relationship with the person making the amendment Patent Applicant 2-2-8-4 Dojimahama, Kita-ku, Osaka "Claims" column and "Detailed Description of the Invention" column (2) of the specification to be amended Page 4, line 16 of the specification Correct "both ends" to "end".

(8) On page 5, line 9 and line 13, "both ends" is corrected to "end".

(4) Page 7, line 9 - Correct "acid value 14-110" to "acid value 3-225."

(5) On page 7, line 9, “preferably 20-70” is changed to “preferably 7-110”
Correct.

(6)　Page 10, line 11 Correct "both ends" to "end".

(7) Insert the following sentence between the second and third lines of page 13.

[Acid value measurement method: Accurately weigh about 19 mm of polymer, dissolve it in 50 mm of methyl cellosolve-dioxane mixed solution (1:1 volume ratio), and use a potentiometric titration device (average) with N/1 O-KOH of known factor. Titrated using com1te-'y manufactured by Onsangyo Co., Ltd.
The end point (point of maximum potential change) was determined. A separate blank test was conducted.

A: 4 of N/1O-KOH required for titration of sample bath liquid
Number B: Number F of N/1O-KOH required for titration in blank test
: Factor S of N/1O-KOH: Sample weight (
9) OH value measurement method: Approximately 59% of HoIJmer was collected in a 1 ood Erlenmeyer flask and the %
Weigh this accurately, add acetylation reagent (pyridine: 1 part acetic anhydride)
5:1 volume ratio) 10- was added and the polymer was dissolved,
After attaching a cooling tube and reacting at 100° C. for 60 minutes, water was added and allowed to stand for 10 minutes, followed by titration using phenolphthalein as an indicator and a known factor of N/2=KOH. A blank test was conducted in which no sample was used.

2- A: Number of N/2-KOH strokes required for sample B: Number of N/2-KOH required for blank test F: N/2-KOH
7 Actor S: Sample weight (9) Av; Acid value (■KOH/Li)' (8)
On page 13, line 12, "both ends" is corrected to "end".

(9) “Both ends” on page 14, line 6 and line 17
is corrected to "end".

(10) Page 15, line 9 and the last line “both ends” are 1
Corrected to "terminus".

(11) The 7th line of page 16 is corrected to "HD J 16-hexanediol".

(12) Page 19, last line to page 20, lines 1 and 2
In the first line of page 0, "polyester dicarboxylic acid" is corrected to "polyester having a terminal carboxyl group."

α3) Page 20, lines 7-8 "Modified polyester" is "modified polyester H" 3- Correct to.

04) Page 20, line 1 O Correct "Add to Table 2" to "Table 3."

(15) Insert the following Synthesis Example 9.10 and Comparative Example 5.6 below Table 3 on page 20.

“Synthesis Example 9 1452 parts of acyhinic acid, 78 parts of 1,6-hexanediol
8 parts of tetrabutyl titanate, 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 a terminal carboxyl group and a hydroxyl value of 0.15 was obtained.

1500 parts of this polyester and epoxy resin YD-12
'7 103, 2 parts and disodium dimerate 3.
0 part was placed in an autoclave and reacted in the same manner as in Synthesis Example 1 to obtain polyester I with ηBp of 100.538.

Comparative Example 5 Table 4 shows the physical properties of a sheet obtained by blending 80 parts of this polyester 1 with vinyl chloride in the same composition as in Example 1.

Synthesis example 1α acipin ml + 52 parts, 1,6-hexanediol 11
82 parts of tetrabutyl titanate, 0.108 parts of tetrabutyl titanate, and 0.089 fW of trimethyl phosphate) were charged into 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. The reaction was carried out. Next, the temperature was maintained at 230°C, and the pressure was gradually reduced to 0. It was set as lmHg. The temperature was further increased to 250℃,
0. The reaction was carried out at ls+sHg for 3 hours to obtain a polyester having an S acid value of 2.7 and an S hydroxyl value of 1.8.

1500 parts of this polyester and epoxy resin YD-12
813.5 parts and 1.0 part of disodium dimerate were charged into an autoclave and reacted for 8 hours with stirring at 180°C under a nitrogen stream to obtain polyester J having an ηop/cO of 956.

Table 4 shows the physical properties of a sheet obtained by blending 580 parts of the polyester of Comparative Example with PVC with the same composition as in Example 1.

(16) 3rd line from the bottom of page 20 to the last line of page 21 [Examples 6, 7 and comparative examples 5 to 7... PVC tube 10 cll] was corrected as follows. do.

[Examples & Antithrombotic properties of the vinyl chloride compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were measured by the following method and are shown in Table 5.

Table 5 Antithrombotic properties are evaluated using the column method developed by Sakurai et al.
omol, Oh-am, 179, 1121 (1
This was done with reference to 9178)).

That is, each PVC composition sheet is bath-dissolved in tetrahydrofuran to prepare a 0.5% bath solution. This solution was used to coat the surface of glass beads with a diameter of 200μ and heated at 40℃ for 1 hour.
Surface-coated beads 1.09 dried for 2 hours at normal pressure and further dried for 12 hours at 0.5 to
+++J L17) Table 3 on page 23 of the same page is deleted.

(18) ``Table 4'' in the second line from the bottom of page 23 of the same page is changed to ``Table 4''.
Table 5 is corrected.

Attachment A Claims A polyester unit consisting of an ester unit in which the sum of the carbon atoms of one diol component and a dicarboxylic acid component is 9 to 2 o based on 100 parts by weight of polyvinyl chloride, and which has a carboxyl group at the terminal. High molecular weight modified polyester obtained by reacting a compound having an epoxy group at the end 10-1
A polyvinyl chloride composition containing 50 parts by weight.

10- 272-

Claims (1)

[Claims] A polyester consisting of an ester unit in which the sum of the carbon atoms of the diol component and dicarboxylic acid component is 9 to 20 based on 100 parts by weight of polyvinyl chloride, and having a carboxyl group at both ends and an epoxy group at both ends. High molecular weight modified polyester obtained by reacting compounds 10~
A polyvinyl chloride composition containing 150 parts by weight.