JPS5835537B2 - Vinyl chloride resin composition and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention applies to vinyl chloride resins (hereinafter simply referred to as vinyl chloride resins) other than paste resins.

The present invention relates to a vinyl chloride resin composition which has little elution of additives, particularly plasticizers, and which has little adverse effect on blood, and a method for producing the same.

Conventionally, various additives have been used for vinyl chloride resins.

In particular, plasticizers are used in large amounts to soften vinyl chloride resins.

When such vinyl chloride resin is used in food containers, medical equipment, etc., additives are selected to be as harmless to the human body as possible, but later research has shown that some additives are harmful. It is possible that it may become clear.

Therefore, it is desirable to prevent additives from eluting as much as possible in the usage environment.

For example, phthalic acid ester is used as a plasticizer, but it is known that when a vinyl chloride resin product containing this ester is brought into contact with a solvent such as water, the plasticizer gradually dissolves out.

Although there is still no clear proof that this eluted fuculate ester affects health when introduced into living organisms, it is important from a medical standpoint to prevent its elution as much as possible. .

In addition, although there are conventional non-migratory plasticizers, they have low processability due to high viscosity, large molecular weight,
Generally, since it is polyester-based, it is easily saponified and difficult to soften, so it is not suitable as a plasticizer for medical or food applications.

Therefore, the purpose of this invention is to be able to prevent the elution of additives, especially plasticizers, to vinyl chloride resins, and to have little adverse effect on blood, such as foods, beverage containers, medical instruments, etc. It is an object of the present invention to provide a vinyl chloride-based resin composite acid that can be safely used in applications such as medical devices made from the resin composition, and a method for producing the resin composition.

The present inventors have discovered that by incorporating silicone oil into a vinyl chloride resin together with conventional additives, the elution of additives can be significantly prevented, and the present invention has been achieved.

That is, the present invention includes a vinyl chloride resin other than a paste resin, and 20 to 80% by weight of the resin.
In a vinyl chloride resin composition consisting of an added plasticizer and other additives, at least one silicone oil selected from polymethylphenylsiloxane, polydimethylsiloxane, and polymethylhydrogen siloxane is chlorinated. It contains 0.2 to 7% by weight based on the vinyl resin, and a molded product obtained from the composition is added to a 15% by weight aqueous sodium lauryl sulfate solution at 60°C for 90 minutes.
The elution ratio of the eluate to the total plasticizer after 6 hours of immersion is 40
% or less, and furthermore, the potassium permanganate consumption in the water after immersing 20 g of the above composition in 200 ml of water and heating it at 121 ° C. for 20 minutes is 0.50 (17100 mol potassium permanganate consumption) or less. This is a vinyl chloride resin composition useful for medical purposes.

In the method for producing vinyl chloride resin according to this invention, silicone oil is emulsified with a portion of a plasticizer in advance, and then added to the vinyl chloride resin to which a plasticizer has also been added, and then mixed and heated. do.

In this specification tζ, vinyl chloride resin refers to vinyl chloride resin, polyvinyritine chloride, copolymers (including terpolymers) of polyvinyl chloride, or polyvinyl chloride as a main component, and The concept also includes blends with other polymers.

Comonomers that can form copolymers of polyvinyl chloride include vinyl esters, vinyl ethers, vinylitine compounds such as vinylidene chloride, lower olefins, vinyl acetate, vinyl bromide, vinyl fluoride, aromatic compounds (such as styrene), These include cyclic unsaturated compounds (for example, vinylpyridine), acrylic acid and its derivatives, and conjugated unsaturated compounds such as butadiene.

Examples of other polymers that may be blended with polyvinyl chloride include styrene-acrylonitrile copolymer, styrene-methyl meccrylate copolymer, and the like.

As for the silicone oil added to the vinyl chloride resin, at least one selected from polymethylphenylsiloxane, polydimethylsiloxane, and polymethylhydrogensiloxane is used.

When adding silicone oil to vinyl chloride resin,
Since silicone oil has poor affinity with vinyl chloride resin, sufficient dispersion cannot be obtained if it is directly mixed.
By mixing the resin with a plasticizer with relatively good affinity before adding it, the resin can be well dispersed in the resin and the resin surface can be coated.

The amount of the silicone oil added is 0.2 to 7% by weight, preferably 1 to 4% by weight, based on the vinyl chloride resin.

If the amount of silicone added is less than 0.2% by weight, the effect of preventing the elution of additives such as plasticizers will not be sufficient, and if it is more than 7% by weight, it will not only be difficult to mold, but also be difficult to prevent from vinyl chloride resin. Mixing becomes poor, making it impossible to obtain a homogeneous vinyl chloride resin product.

The plasticizer is usually added in an amount of 20 to 80 parts by weight per 1ζ of 100 parts by weight of polyvinyl chloride, but it is preferable that as the amount of plasticizer increases, the amount of silicone added also increases.

The types and amounts of additives such as plasticizers that have been used in the past may be used as usual.

As for the lubricant, since silicone oil itself has a lubricant effect, addition of other lubricants such as %l can be omitted.

Example: Polyvinyl chloride pellets having the formulations shown in Table 1 below were made, and then these were made to a thickness of **0.4 mm.
It was formed into a sheet.

In the table, the numerical values for the amounts added indicate parts by weight.

Moreover, in Examples 1 to 8, the silicone oil was mixed in advance with 20 parts by weight of a plasticizer, and then added to the vinyl chloride resin.

Next, 20 g of each sheet-like sample of each Example and Reference Example was immersed in 200 ml of water, heated in an autoclave at 121° C. for 20 minutes, and then allowed to cool.

Using these as test solutions, the amount of potassium permanganate consumed was measured based on a predetermined test method.

The results are shown in Table 2. Next, Examples 1 to 8, Reference Example 1
A test piece was cut from the sample, immersed in a sodium lauryl sulfate aqueous solution (15% by weight), and heated at 60°C for 24 hours.
The samples were left to stand for 96 hours, and the weight changes were measured.

The results are shown in Table 3. Furthermore, regarding the sheets of each example, regarding the effects of toxicity tests, eluate tests, and sterilization treatment,
Each test was conducted based on a prescribed test method.

The results are shown in Table 4 below for Examples 1 to 3.

In addition, as shown in this Table 4, almost the same results were obtained for Examples 4 to 8, which were omitted.

Note that (c) in the personal statement means that no toxicity is recognized.

Further, in shrinkage percentage, "horizontal" means the direction of stretching, and "vertical" means the direction perpendicular to the stretching direction.

(Note 2) Based on the test method announced by the Ministry of Health and Welfare shown in (Note 1) in Table 2.

Next, the sheets of Examples 5 and 7 were also tested for 100% modulus, tensile strength, and seal strength by high frequency sealing.

The results are shown in Table 5.

High-frequency seal conditions for seal strength: Constant electrical input, seal area 20 x 8 (distance) Water vapor transmission: Temperature 20°C, humidity 65%, left for 14 days (Note 3)
(JIS-ni-6723 soft vinyl chloride compound)
The standards were applied mutatis mutandis.

Furthermore, the functional tests shown in Table 6 below were conducted for Examples 5 and 7, and the results are shown in Table 6.

Table 6 (Functional test results) (Test according to the Ministry of Health and Welfare notification shown in Table 2 Note 1) Serra
tiamar TGC131T, 7 days Cladosporium Candida.

Curvalaria.

Medium, PDA, 3 scolding, ■2 target Two bacteria used in microbial penetration test.

Culture medium.

Mold resistance test: Use mold.

(Out of specification) Furthermore, a plasticizer elution test using bovine plasma was conducted for Example 5 and Reference Example 4, and the results are shown in Table 7.

Others include red blood cell survival test, triglyceride quantitative test,
U ■ Absorption test, platelet survival test (Ries Elaker method),
As a result of blood coagulation test and serum preservation test,
There was nothing abnormal at all.

As is clear from all of these test results, the vinyl chloride resins according to each example significantly suppress the elution of additives such as plasticizers compared to the reference example that does not contain silicone oil. In addition, it has little adverse effect on blood, and is suitable for medical equipment, such as artificial kidney blood circuits, artificial heart-lung machines, catheters, blood bags, etc.

In addition, in the above-mentioned example, an example was shown in which vinyl chloride resin was used as the vinyl chloride resin, but similar effects were obtained in the case of other vinyl chloride resins.

As explained above, according to the present invention, it is possible to obtain a vinyl chloride resin that can significantly suppress the elution of additives such as plasticizers.

Therefore, it is particularly suitable for food containers, medical instruments used for collecting, storing, and administering physiological solutions, etc., and is also suitable for covering electric wires, etc. due to its excellent weather resistance, hydrophobicity, and oil resistance. do.

Claims (1)

[Scope of Claims] 1. A vinyl chloride resin other than a paste resin, a plasticizer added to the resin in an amount of 20 to 80% by weight,
In a vinyl chloride-based resin composition comprising other additives, at least one silicone oil selected from polymethylphenylresiloxane, polydimethylsiloxane, and polymethylhydrodiene siskisane is added in an amount of 0.2 to 0.2% based on the vinyl chloride resin. 7% by weight, and after immersing a molded product obtained from the composition in a 15% by weight sodium lauryl sulfate aqueous solution at 60°C for 96 hours, the elution rate of the eluate based on the total plasticizer is 40% or less, and It is characterized in that after immersing 20 g of the above composition in 200 ml of water and heating it at 121° C. for 20 minutes, the amount of potassium permanganate consumed in the water is 0.50 (17,100 mol potassium permanganate consumed) or less. A vinyl chloride resin composition useful for medical purposes. 2 0.2 to 7% by weight of at least one silicone oil selected from polymethylphenylsiloxane, polydimethylsiloxane, and polyhydrogensiloxane, based on the vinyl chloride resin excluding the paste resin, and one part of the plasticizer. 15% by weight lauryl sulfate at 60° C. )I
The elution rate of the eluate based on the total plasticizer after immersion in the Jum aqueous solution for 96 hours is 40% or less, and the molded product 20
g in 200ml of water and heated at 121°C for 20 minutes, the consumption of potassium permanganate in the water is 0.50.
(1/100 mole potassium permanganate consumption) or less, a method for producing a vinyl chloride resin composition useful for medical use.