JP2016155938A - Medical vinyl chloride resin composition containing trimellitic acid triester and medical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a medical vinyl chloride resin composition and a medical material less in reduction of flexibility and deterioration of coloring or the like after sterilization or germicidal treatment, further good in flexibility or cold resistance and having improved heat resistance.SOLUTION: By using trimellitic acid triester obtained by an esterification treatment of specific aliphatic acid saturated alcohol and trimellitic acid or an anhydride thereof as a plasticizer for vinyl chloride resin, coloring after a germicidal treatment or reduction of flexibility due to volatilization of the plasticizer is almost disappeared and heat resistance is enhanced without reducing flexibility or cold resistance at same time, whereby a medical vinyl chloride resin composition and a medical material less in deterioration after sterilization or germicidal treatment, usable stably, good in flexibility or cold resistance and having improved heat resistance are obtained.SELECTED DRAWING: None

Description

The present invention relates to a medical vinyl chloride resin composition and medical treatment that have little deterioration after sterilization or sterilization treatment, can be used stably, have good flexibility and cold resistance, and have improved heat resistance. More particularly, the present invention relates to a medical vinyl chloride resin composition and a medical material containing a plasticizer for vinyl chloride resin comprising a novel trimellitic acid triester.

The vinyl chloride resin composition has good processability, has excellent chemical resistance and durability, and can be adjusted to various hardnesses by blending a plasticizer. Vinyl chloride resin compositions are excellent in kink resistance compared to polyolefin and the like, and are widely used as medical materials such as medical tubes such as catheters and medical bags such as blood bags and infusion bags.

Soft vinyl chloride resin compositions used for medical materials require good flexibility, excellent heat resistance that can withstand heat treatment, and excellent cold resistance that can withstand low-temperature storage, as well as durability. From the standpoint of safety and safety, it is necessary that the elution and transferability of additives and the like be small, and selection of the plasticizer to be blended in the largest amount is very important.

So far, as the plasticizer, phthalate ester plasticizers typified by di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) have been used for a wide range of applications (Patent Document 1). . However, with phthalate ester plasticizers, it is difficult to obtain sufficient heat resistance during the above-described heat treatment, etc., and improvement in elution and migration is also demanded. Studies using trimellitic acid ester plasticizers and polyester plasticizers such as ethylhexyl (hereinafter referred to as “TOTM”) are underway (Patent Documents 2 to 5).

However, in the case of medical materials using trimellitic acid ester-based or polyester-based plasticizers, they are excellent in heat resistance, but plasticization efficiency and cold resistance are inferior, and in order to obtain sufficient flexibility and cold resistance, It is necessary to add a large amount of plasticizer. As a result, there is a concern that problems may occur in terms of safety, etc., and there is no one that has a well-balanced characteristic that satisfies all the above required characteristics by itself. It is. Accordingly, there is a need for medical materials with improved heat resistance without reducing flexibility and cold resistance, and the development of plasticizers and resin compositions that can provide such materials is awaited.

In the case of medical materials, it is necessary to sterilize and sterilize before use from the viewpoint of hygiene. The treatment methods include heat treatment such as dry heating and boiling, pressurized hot water treatment, a method of irradiating with ultraviolet rays and radiation, chemical treatment with ethylene oxide gas, etc. There is a concern that some ethylene oxide gas remains, and heat treatment or a method of irradiating ultraviolet rays or radiation is mainly used.

In recent years, due to an increase in medical accidents at hospitals and the like, thorough hygiene management at medical sites has become more severe, and the conditions for sterilization and sterilization treatment have become more severe. However, along with stricter conditions, for example, in the case of heat treatment, a decrease in flexibility due to volatilization of the plasticizer causes destruction of the material, and the above-mentioned TOTM can satisfy the requirement. It is gone. Further, even in the treatment by irradiation with ultraviolet rays or radiation, the deterioration of contents distinguishability due to coloring causes a medical accident, which is a big problem, and the improvement is strongly desired. In particular, it is known that coloring can be improved by blending a large amount of stabilizer (Patent Documents 6 to 9). However, blending a large amount of stabilizer is safety. The current situation is that there is a large problem in terms of the above, which is impossible in practice, and no effective improvement method has yet been found.

JP-A-10-176089 Japanese Patent Laid-Open No. 2003-165881 JP 2006-239026 A JP 2012-81247 A JP 60-115640 A JP-A-8-24329 JP-A-8-176383 JP 56-61448 A JP-A-2-222436

The object of the present invention is to solve the above-mentioned problems, that is, there is little deterioration in flexibility and coloration after sterilization and sterilization treatment, further flexibility and cold resistance are good, and heat resistance is improved. Another object is to provide a medical vinyl chloride resin composition and a medical material.

In view of the present situation, the present inventors have conducted intensive studies to solve the above problems, and as a result, trimellitic acid trimethyl ester obtained by esterifying a specific aliphatic saturated alcohol and trimellitic acid or its anhydride. A vinyl chloride resin composition for medical use with less flexibility after sterilization and sterilization treatment, stable use, good flexibility and cold resistance, and improved heat resistance. The medical material made from the resin composition is less deteriorated after sterilization or sterilization treatment, can be used stably, has good flexibility and cold resistance, and has improved heat resistance. As a result, the present invention has been found to be effective as a medical material.

That is, the present invention provides a medical vinyl chloride resin composition and a medical material containing the following novel vinyl chloride resin plasticizer.

[Item 1] A medical vinyl chloride resin composition containing a vinyl chloride resin and trimellitic acid or an anhydride thereof and a trimellitic acid triester obtained by esterification reaction with an aliphatic saturated alcohol, The aliphatic saturated alcohol is composed mainly of an aliphatic saturated alcohol having 9 carbon atoms, and the content of the aliphatic saturated alcohol in the aliphatic saturated alcohol is 60 wt% or more and a linear aliphatic saturated alcohol having 9 carbon atoms and 40 wt%. % Of a branched aliphatic saturated alcohol having 9 or less carbon atoms, and a linear rate of the aliphatic saturated alcohol is 60% or more.

[Item 2] The aliphatic saturated alcohol is a linear aliphatic having 9 carbon atoms, the main component of which is an aliphatic saturated alcohol having 9 carbon atoms, and the content in the aliphatic saturated alcohol is 60 to 95% by weight. The medical treatment according to [1], comprising a saturated alcohol and 5 to 40% by weight of a branched aliphatic saturated alcohol having 9 carbon atoms and a linearity ratio of the aliphatic saturated alcohol of 60 to 95%. Vinyl chloride resin composition for use.

[Item 3] The aliphatic saturated alcohol is mainly composed of an aliphatic saturated alcohol having 9 carbon atoms, and the content of the aliphatic saturated alcohol in the aliphatic saturated alcohol is 70 to 90% by weight. The medical use according to [Item 2], which contains alcohol and 10 to 30% by weight of a branched aliphatic saturated alcohol having 9 carbon atoms, and wherein the aliphatic saturated alcohol has a straight chain ratio of 70 to 90%. Vinyl chloride resin composition.

[Item 4] A medical vinyl chloride resin composition containing a trimellitic acid triester obtained by esterifying a vinyl chloride resin and trimellitic acid or an anhydride thereof with an aliphatic saturated alcohol, The aliphatic saturated alcohol comprises (1) 1-octene, a step of producing a aldehyde having 9 carbon atoms by a hydroformylation reaction of carbon monoxide and hydrogen, and (2) hydrogenation of the aldehyde having 9 carbon atoms into an alcohol. A medical vinyl chloride characterized by comprising an aliphatic saturated alcohol having a linear structure and a branched chain structure and having as a main component an aliphatic saturated alcohol having 9 carbon atoms and produced by a production method comprising a reduction step -Based resin composition.

[Item 5] The trimellitic acid triester according to any one of [Item 1] to [Item 3] or the trimellitic acid triester according to [Item 4] is used in an amount of 100 parts by weight of a vinyl chloride resin. The medical vinyl chloride resin composition according to any one of [Claim 1] to [Claim 4], which is 5 to 200 parts by weight based on the weight.

[Item 6] The amount of trimellitic acid triester according to any one of [Item 1] to [Item 3] or the trimellitic acid triester according to [Item 4] is 100 parts by weight of a vinyl chloride resin. The medical vinyl chloride resin composition according to any one of [Claim 1] to [Claim 4], which is 10 to 100 parts by weight based on the weight.

[Item 7] The medical vinyl chloride resin composition according to any one of [Item 1] to [Item 6], further comprising an epoxidized vegetable oil.

[Item 8] The medical vinyl chloride resin composition according to Item 7, wherein the amount of the epoxidized vegetable oil is 1 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

[Item 9] The medical vinyl chloride resin composition according to any one of [Item 1] to [Item 8], further comprising a fatty acid calcium salt and / or a fatty acid zinc salt.

[Item 10] The compounding amount of the fatty acid calcium salt and / or the fatty acid zinc salt (the amount used when either one is used or the total amount when both are used) is 100 wt. The medical vinyl chloride resin composition according to [Item 9], which is 0.1 to 10 parts by weight with respect to parts.

[Item 11] A medical material comprising the medical vinyl chloride resin composition according to any one of [Item 1] to [Item 10].

The vinyl chloride resin composition for medical use according to the present invention has good flexibility and cold resistance, and improved heat resistance, and is good even after heat sterilization treatment without lowering the plasticizer content due to volatilization. The medical material that retains flexibility and is hardly colored even in sterilization or sterilization treatment by irradiation with ultraviolet rays or radiation, the medical material obtained from the vinyl chloride resin composition has good flexibility and cold resistance, and The heat resistance is improved, and after the various sterilizations and sterilization treatments, there is little decrease in flexibility, and there is almost no coloring, and it can be used stably.

<Trimellitic acid triester>
The medical vinyl chloride resin composition of the present invention comprises trimellitic acid triester obtained by esterifying a specific aliphatic saturated alcohol (alcohol component) and trimellitic acid or its anhydride (acid component). The most characteristic feature is that it is contained as a plasticizing component (plasticizer) in the composition.
The trimellitic acid triester according to the present invention (hereinafter referred to as “the present ester”) comprises a predetermined acid component and an alcohol component according to a conventional method, preferably in an inert gas atmosphere such as nitrogen, without a catalyst or It can be easily obtained by esterification in the presence of a catalyst.

[Aliphatic saturated alcohol]
The aliphatic saturated alcohol used in the present invention is an aliphatic saturated alcohol mainly composed of an aliphatic saturated alcohol having 9 carbon atoms, and the ratio of the aliphatic saturated alcohol having 9 carbon atoms as the main component is used in the present invention. In the aliphatic saturated alcohol, preferably 60% or more (60 to 100%), more preferably 70% or more (70 to 100%), particularly preferably 80% or more (80 to 100%) is recommended.

In addition, it is recommended that the aliphatic saturated alcohol according to the present invention has a linear ratio of the aliphatic saturated alcohol of 60% or more, preferably 60 to 95%, more preferably 70 to 90%. .
The content of the linear saturated aliphatic alcohol having 9 carbon atoms is 60% by weight or more, preferably 60 to 95% by weight, more preferably 70 to 90% by weight in the aliphatic saturated alcohol used in the present invention. % Is recommended, and the content of the branched aliphatic saturated alcohol having 9 carbon atoms (such as 2-methyloctanol) is 40% by weight or less, preferably 5 to 40% by weight, more preferably A range of 10-30% by weight is recommended.

As the details of the embodiment of the aliphatic saturated alcohol used in the present invention, the aliphatic saturated alcohol is mainly composed of an aliphatic saturated alcohol having 9 carbon atoms (preferably 60% or more), and contained in the aliphatic saturated alcohol. A linear aliphatic saturated alcohol having 9 or more carbon atoms and a branched aliphatic saturated alcohol having 9 or less carbon atoms and not more than 40% by weight, and the linear chain of the aliphatic saturated alcohol The rate is 60% or more. In a more preferred embodiment, the aliphatic saturated alcohol is composed mainly of an aliphatic saturated alcohol having 9 carbon atoms (preferably 70% or more), and the content of the aliphatic saturated alcohol is 60 to 95% by weight. An embodiment comprising 9 linear aliphatic saturated alcohols and 5 to 40% by weight of branched aliphatic saturated alcohols having 9 carbon atoms, and the aliphatic acid saturated alcohol has a linear ratio of 60% or more As a particularly preferred embodiment, the aliphatic saturated alcohol is mainly composed of an aliphatic saturated alcohol having 9 carbon atoms (preferably 80% or more), and the content in the aliphatic saturated alcohol is 70 to 90% by weight. % Linear aliphatic saturated alcohol having 9 carbon atoms and 10-30 wt% branched aliphatic saturated alcohol having 9 carbon atoms, and the aliphatic saturated alcohol has a linear ratio of 70 to 9 % In a manner is recommended.

If the linear chain ratio is 60% or more and the content of the linear aliphatic saturated alcohol having 9 carbon atoms is 60% by weight or more, the present invention is sufficiently achieved without deteriorating flexibility and cold resistance. The improvement of heat resistance, which is the purpose of, is obtained. On the other hand, when the linearity ratio is less than 60% or the content of the linear aliphatic saturated alcohol having 9 carbon atoms is less than 60% by weight, the improvement in heat resistance, which is the object of the present invention, is insufficient. In addition, the flexibility and cold resistance tend to decrease, which is not preferable.

Further, even in the above range, sufficient performance can be obtained in the improvement of flexibility, cold resistance and heat resistance, which are the objects of the present invention, but the linearity ratio is in the range of 60 to 95% and the carbon number is 9%. By setting the content of the chain saturated alcohol in the range of 60 to 95% by weight, it becomes easier to mix with the vinyl chloride resin, and as a result, the process window at the time of molding is widened and the molding process is facilitated. In addition, it is effective in suppressing the generation of defective products during molding, and is more preferable.

In the present specification and claims, the straight chain ratio of the aliphatic saturated alcohol is the ratio (weight ratio) of the straight chain alcohol in the aliphatic saturated alcohol, and from the viewpoint of the effects of the present invention, Specifically, it can also be said to be the proportion of linear alcohol having 7 to 11 carbon atoms, and can be determined specifically by a method of analysis by gas chromatography.

Examples of the aliphatic saturated alcohol used in the present invention include (1) 1-octene, a step of producing an aldehyde having 9 carbon atoms by hydroformylation reaction of carbon monoxide and hydrogen, and (2) an aldehyde having 9 carbon atoms is hydrogenated. The aliphatic saturated alcohol obtained by the production method comprising the step of adding and reducing to an alcohol is an aliphatic saturated alcohol having 9 carbon atoms having a straight chain structure and a branched chain structure. It becomes an aliphatic saturated alcohol as the main component.

In the hydroformylation reaction which is the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms under hydrogen pressure in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst.

Specific examples (commercially available) of aliphatic saturated alcohols mainly composed of aliphatic saturated alcohols having 9 carbon atoms obtained in the above process include about 70% by weight or more of linear nonanol and about 30% by weight or less. Lineball 9 (trade name, manufactured by Shell Chemicals Co., Ltd.), which is a mixture of the branched chain nonanol.

[Esterification reaction]
In performing the esterification reaction of the alcohol component with trimellitic acid or an anhydride thereof, the alcohol component is preferably, for example, 3.05 mol to 4.00 mol per mol of trimellitic acid or anhydride thereof. It is recommended to use moles, more preferably 3.10 moles to 3.80 moles, especially 3.15 moles to 3.60 moles.

Examples of the catalyst used in the esterification reaction include mineral acids, organic acids, Lewis acids and the like. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid, and examples of the Lewis acid include aluminum derivatives, tin derivatives, Titanium derivatives, lead derivatives, zinc derivatives and the like are exemplified, and these can be used alone or in combination of two or more.

Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, Lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is, for example, preferably 0.01 wt% to 5.0 wt%, more preferably 0.02 wt% to 4.0 wt% with respect to the total weight of the acid component and alcohol component that are the ester synthesis raw materials. It is recommended to use% by weight, in particular 0.03% to 3.0% by weight.

Examples of the esterification temperature include 100 ° C to 230 ° C, and the reaction is usually completed in 3 hours to 30 hours.

There is no restriction | limiting in particular as trimellitic acid or its anhydride which is the acid component of the raw material of this ester, The commercially available thing normally used can be used. From the viewpoint of esterification reaction, it is most recommended to use the trimellitic anhydride.

In esterification, it is possible to use water entraining agents such as benzene, toluene, xylene and cyclohexane in order to promote distillation of water produced by the reaction.

Also, when oxygenated organic compounds such as oxides, peroxides, and carbonyl compounds are produced by oxidative degradation of raw materials, produced esters and organic solvents (water entraining agents) during the esterification reaction, the heat resistance, weather resistance, etc. are adversely affected. For this reason, it is desirable to carry out the reaction under normal or reduced pressure in an inert gas atmosphere such as nitrogen gas or in an inert gas stream. After completion of the esterification reaction, it is recommended that excess raw materials be distilled off under reduced pressure or normal pressure.

The present ester obtained by the above esterification method may be further purified by base treatment (neutralization treatment) → water washing treatment, liquid-liquid extraction, distillation (decompression, dehydration treatment), adsorption purification treatment, etc. as necessary. Good.

The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

Examples of the adsorbent used for the adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used alone or in combination of two or more.

Although the said process may be performed at normal temperature, it can also be performed by heating to about 40-90 degreeC.

<Medical vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention can be obtained by blending the above-described ester into a vinyl chloride resin as a plasticizer.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and its production method is carried out by a conventionally known polymerization method. In the case of a vinyl resin, a suspension polymerization method can be mentioned in the presence of an oil-soluble polymerization catalyst, and in the case of a vinyl chloride paste resin, an emulsion polymerization method can be mentioned in an aqueous medium in the presence of a water-soluble polymerization catalyst. The degree of polymerization of these vinyl chloride resins is usually 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.

In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- C2-C30 α-olefins such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Copolymers of vinyl compounds, polyfunctional monomers such as diallyl phthalate, and mixtures thereof with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylate esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyester Ren, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, poly Examples thereof include a graft copolymer obtained by grafting vinyl chloride monomer onto methyl methacrylate and a mixture thereof.

[Medical vinyl chloride resin composition]
The content of the present ester in the medical vinyl chloride resin composition of the present invention is appropriately selected according to its use, but is usually 5 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The amount is preferably 10 to 100 parts by weight. If it is less than 5 parts by weight, it is difficult to obtain a predetermined plasticizing effect, and if it exceeds 200 parts by weight, bleeding on the surface of the molded product is severe, which is not preferable in either case. However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer can be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate as a filler is blended with 100 parts by weight of a vinyl chloride resin, about 1 to 500 parts by weight of the plasticizer can be blended.

In the medical vinyl chloride resin composition, other known plasticizers can be used in combination with the ester. In addition, stabilizers, stabilization aids, antioxidants (anti-aging agents), UV absorbers, silane compound-based radiation-resistant materials, hindered amine-based light stabilizers, fillers, diluents, and thinning agents as necessary. Additives such as an agent, a thickener, a processing aid, a lubricant, an antistatic agent, a flame retardant, a foaming agent, an adhesive, and a colorant can be blended.

Other plasticizers and additives other than the present ester may be used alone or in combination of two or more kinds together with the present ester.

Known plasticizers that can be used in combination with this ester include, for example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), and diisononyl phthalate (DINP). ), Diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-ethylhexyl) terephthalate (DOTP), phthalic acid such as bis (2-ethylhexyl) isophthalate (DOIP) Esters, di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), diisononyl sebacate (DINS) Basic acid S , Trimellitic acid esters such as trimellitic acid tri-2-ethylhexyl (TOTM), trimellitic acid triisononyl (TINTM), trimellitic acid triisodecyl (TIDTM), pyromellitic acid tetra-2-ethylhexyl (TOPM), etc. Pyromellitic acid esters, phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), alkyl esters of polyhydric alcohols such as pentaerythritol, and dibasic acids such as adipic acid Polyesters having a molecular weight of 800 to 4000 synthesized by polyesterification with glycol, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and di-2-butyl 4,5-epoxy-1,2-cyclohexanedicarboxylate Ethyl hexyl ester Cycloesters, alicyclic dibasic acid esters such as 1,2-cyclohexanedicarboxylic acid diisononyl (DINCH), 4-cyclohexene-1,2-dicarboxylic acid di-2-ethylhexyl ester, dicapric acid 1.4-butane Fatty acid glycol esters such as diol, acetyl tributyl citrate (ATBC), citrate trihexyl acetyl citrate (ATHC), acetyl triethylhexyl citrate (ATEHC), butyryl citrate trihexyl (BTHC), etc., isosorbide diesters Examples thereof include chlorinated paraffins obtained by chlorinating paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearate, and higher fatty acid esters such as butyl oleate. When the plasticizer that can be used in combination is blended, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Among the known plasticizers that can be used in combination, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil can suppress coloring during sterilization due to ultraviolet irradiation or radiation irradiation. It is preferable to do. When the epoxidized vegetable oils are blended, the blending amount is recommended to be 1 to 50 parts by weight, preferably about 2 to 40 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid Examples include metal soap compounds such as zinc, organotin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. Moreover, when mix | blending a stabilizer, about 0.1-20 weight part is recommended for the compounding quantity of the stabilizer with respect to 100 weight part of vinyl chloride resin.

Of the stabilizers, a combination of calcium stearate and zinc stearate is most preferably used in terms of safety and the like. Further, the total amount is recommended to be 0.1 to 10 parts by weight, preferably 0.2 to 6 parts by weight, and the blending ratio is within the range showing the stabilizing effect. Although there is no particular limitation, it is often used in the range of 5: 1 to 1: 5.

Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol, etc. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. In addition, when the stabilizing aid is blended, the blending amount of the stabilizing aid with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 20 parts by weight.

Antioxidants include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, and the like. Sulfur compounds such as phenolic compounds, alkyl disulfides, thiodipropionic esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphinic compounds such as phosphites, organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. Moreover, when mix | blending antioxidant, about 0.2-20 weight part of the compounding quantity of antioxidant with respect to 100 weight part of vinyl chloride resin is recommended.

Examples of ultraviolet absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-methoxybenzophenone, 5- In addition to benzotriazole compounds such as methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. Moreover, when mix | blending a ultraviolet absorber, about 0.1-10 weight part is recommended as the compounding quantity of the ultraviolet absorber with respect to 100 weight part of vinyl chloride-type resin.

Examples of radiation-resistant materials for silane compounds include monoalkoxysilane compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldisilane. Dialkoxysilanes such as ethoxysilane, methylaminoethoxypropyl dialkoxysilane, N- (βaminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane Compound, methyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltrieth Sisilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (phenyl) -Γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- (polyethyleneamino) ) Propyltrimethoxysilane, γ-ureidopropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 Epoxycyclohexyl) trialkoxysilane compounds such as ethyltrimethoxysilane, tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, acetoxysilane compounds such as vinyltriacetoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyl Examples include chlorosilane compounds such as trichlorosilane and γ-chloropropylmethyldichlorosilane, and organosilane compounds such as triisopropylsilane, triisopropylsilyl acrylate, allyltrimethylsilane, and methyl trimethylsilylacetate. Moreover, when mix | blending a radiation resistant material, about 0.1-15 weight part of the compounding quantity of the radiation resistant material with respect to 100 weight part of vinyl chloride-type resin is recommended.

Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino And higher fatty acid ester mixtures, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, poly [ {(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}}, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6) -Tetramethyl- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ′, N ″, N ′ ″ − Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 In addition, when a light stabilizer is blended, the blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders of glass, carbon, metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide Examples thereof include magnesium carbonate, magnesium silicate, calcium silicate and the like. Moreover, when mix | blending a filler, about 1-100 weight part of the compounding quantity of the filler with respect to 100 weight part of vinyl chloride-type resin is recommended.

Examples of the diluent include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, low-boiling point aliphatic and aromatic hydrocarbons, and the like. Moreover, when mix | blending a diluent, about 1-50 weight part is recommended as the compounding quantity of the diluent with respect to 100 weight part of vinyl chloride-type resins.

As the viscosity reducer, various nonionic surfactants, sulfosuccinate anionic surfactants, silicone compounds with surface activity, soybean oil lecithin, monohydric alcohols, glycol ethers, polyethylene glycols, etc. Is exemplified. Moreover, when mix | blending a viscosity reducing agent, about 0.1-20 weight part is recommended as the compounding quantity of the viscosity reducing agent with respect to 100 weight part of vinyl chloride resin.

Thickeners include synthetic fine silica, bentonite, ultrafine precipitated calcium carbonate, metal soap, hydrogenated castor oil, polyamide wax, oxidized polyethylene, vegetable oil, granulated ester surfactant, nonionic interface An active agent etc. are illustrated. Moreover, when mix | blending a thickener, about 1-50 weight part is recommended for the compounding quantity of the thickener with respect to 100 weight part of vinyl chloride resin.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate and the like. Moreover, when mix | blending a processing aid, about 0.1-20 weight part is recommended as the compounding quantity of the processing aid with respect to 100 weight part of vinyl chloride-type resin.

Examples of the lubricant include silicone, liquid paraffin, baraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid wax, and higher fatty acid wax. When a lubricant is blended, the blending amount of the lubricant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Antistatic agents include alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agents, non-ionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, diethanolamine derivatives, alkylamidoamine type, alkyl Examples include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides, amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. In addition, when blending an antistatic agent, the blending amount of the antistatic agent with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, etc. Illustrative are halogen compounds such as phosphorus compounds and chlorinated paraffins. Moreover, when mix | blending a flame retardant, about 0.1-20 weight part is recommended as the compounding quantity of the flame retardant with respect to 100 weight part of vinyl chloride resin.

Examples of the foaming agent include organic foaming agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic foaming agents such as baking soda. Moreover, when mix | blending a foaming agent, about 0.1-30 weight part is recommended as the compounding quantity of the foaming agent with respect to 100 weight part of vinyl chloride-type resins.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chromium yellow, chromium green, phthalocyanine green, cobalt blue, phthalocyanine blue, molybdenum orange and the like. Moreover, when mix | blending a coloring agent, about 1-100 weight part of the compounding quantity of the coloring agent with respect to 100 weight part of vinyl chloride resin is recommended.

The medical vinyl chloride resin composition of the present invention comprises, for example, handling mixing, pony mixer, butterfly mixer, planetary mixer, dissolver, biaxial mixer, three-part mixing of the ester, vinyl chloride resin and various additives as required. Mixing machines such as roll mills, mortar mixers, Henschel mixers, Banbury mixers, ribbon blenders, etc., conical twin screw extruders, parallel twin screw extruders, single screw extruders, kneader type kneaders, roll kneaders, etc. By stirring and melting and mixing, a vinyl chloride resin composition in the form of powder, pellets or paste can be obtained.

[Medical materials]
The medical vinyl chloride resin composition according to the present invention includes vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting. It can be formed into a desired shape by molding using a conventionally known method such as extrusion coating, gravure printing, screen printing, slush molding, rotational molding, casting, dip molding, or welding.

The shape of the molded body is not particularly limited, and examples thereof include a rod shape, a sheet shape, a film shape, a plate shape, a cylindrical shape, a circular shape, an elliptical shape, or a special shape such as a star shape or a polygonal shape. Is done.

The molded body thus obtained is a tube such as a chest tube, a dialysis tube, an artificial respiration tube, an endotracheal tube, a respiratory tube, a nutrition tube, an extension tube, a urinary catheter, an aspiration catheter, an intravenous catheter, or a digestive tract catheter. Such as catheters, blood bags, infusion bags, drug solution bags, drain bags, etc., blood component separators, hemodialysis circuits, peritoneal dialysis circuits, cardiopulmonary circuits and other circuit equipment members, infusion sets, transfusion sets, veins It is very useful as medical materials such as injection sets, cardiopulmonary bypass, surgical gloves, pharmaceutical packaging materials, medical films, hygiene materials, and respiratory masks.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Linearity of the alcohol component of the raw material The linearity of the alcohol component of the raw material used in the examples and comparative examples of the present invention was measured by gas chromatography (hereinafter abbreviated as GC). The measuring method of the alcohol component of the raw material by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column DB-1 30m
Column temperature: raised from 60 ° C to 290 ° C. Temperature rising rate = 13 ° C./min Carrier gas: Helium sample: 50% acetone solution injection amount: 1 μL
Quantification: Quantification was performed using 1-hexanol as an internal standard substance.
In selecting an internal standard substance, it was confirmed in advance that 1-hexanol in the raw material alcohol component was below the detection limit by GC.

(2) Evaluation of physical properties of ester The ester obtained in the following production examples or the ester other than the present invention was analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Number of colors: measured in accordance with JIS K-0071 (1998).

(3) Production of vinyl chloride sheet (tensile properties, cold resistance, heat resistance, sheet for sheet color test)
Calcium stearate (manufactured by Nacalai Tesque) and zinc stearate (Nacalai) as stabilizers were added to 100 parts by weight of vinyl chloride resin (straight, polymerization degree 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi Vinyl Co., Ltd.). After mixing 0.3 and 0.2 parts by weight of Tesque Co., Ltd. and stirring and mixing with a mortar mixer, 50 parts by weight of a plasticizer and epoxidized soybean oil (Shin Nippon Rika Co., Ltd., Sunsoizer E) -2000H) 5 parts by weight was added and handled and mixed until uniform to prepare a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm. In addition, in the ultraviolet irradiation test, in order to clarify the difference in the effect of the plasticizer, a press sheet was prepared with a prescription not containing the epoxidized soybean oil, and used as a test sample.

[Evaluation of the physical properties]
(4) Tensile properties: Based on JIS K-6723 (1995), 100% modulus, breaking strength and breaking elongation of the press sheet were measured. The smaller the value of 100% modulus, the better the flexibility, and the breaking strength and breaking elongation are measures of practical strength of the material. Generally, the larger the value, the more practical the strength. It can be said that it is excellent.

(5) Cold resistance: Measured according to JIS K-6773 (1999) using a crashberg tester. The lower the softening temperature (° C), the better the cold resistance. The flexible temperature here refers to a temperature at a low temperature limit indicating a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ² ) in the measurement.

(6) Heat resistance: Based on evaluation of volatile loss and sheet coloring.
a) Volatilization loss: The change in weight of the sheet after heating the roll sheet for 60 minutes at 170 ° C. for 120 minutes in a gear oven was measured to calculate the weight loss rate (% by weight).
The smaller the value, the higher the heat resistance.
Volatilization loss (%) = ((weight before test−weight after test) / weight before test) × 100
b) Sheet coloring: The strength of the coloring degree after heating the roll sheet for 30 minutes at 170 ° C. for 60 minutes in a gear oven was visually evaluated in 6 stages.
◎: No coloring, ○: Slightly colored, ○ △: Slightly colored,
Δ: Coloring, ×: Strong coloring, XX: Remarkable coloring

(7) Ultraviolet ray irradiation test Measurement conditions (irradiation energy: 100 mW / m ² , irradiation conditions: black panel temperature 53 ° C./humidity 50% / 4 hours using a metal weather super accelerated weathering tester manufactured by Daipura Wintes Co., Ltd. Condensation condition: Black panel temperature 30 ° C./Humidity 98% / 2 hours, Shower condition: 10 seconds before and after condensation) is one cycle, and the degree of coloration of the press sheet after five cycles is visually evaluated in four stages did.
A: No coloring, B: Slight coloring, B: Coloring, X: Strong coloring

[Production Example 1]
In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade and reflux condenser, 96 g (0.5 mol) trimellitic anhydride (commercially available product for industry), linear aliphatic having 9 carbon atoms 259 g (1.8 mol) of an aliphatic saturated alcohol (Shell Chemicals: Lineball 9) containing 85.1% saturated alcohol and 11.7% branched aliphatic saturated alcohol having 9 carbon atoms, and ester 0.13 g of tetraisopropyl titanate was added as a oxidization catalyst, and the esterification reaction was performed at a reaction temperature of 190 ° C. The reaction was performed until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing the raw material alcohol under reduced pressure and removing the generated water out of the system. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 245 g of the desired trimellitic acid triester (hereinafter referred to as “ester 1”). Obtained.
The obtained ester 1 had an ester value of 284 mgKOH / g, an acid value of 0.02 mgKOH / g, and a color number of 20.

[Production Example 2]
In the same manner as in Production Example 1 except that 245 g (1.7 mol) of n-nonyl alcohol and 14 g (0.1 mol) of isononyl alcohol were added instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9). This was carried out to obtain 242 g of trimellitic acid triester (hereinafter referred to as “ester 2”).
The obtained ester 2 had an ester value of 283 mgKOH / g, an acid value of 0.04 mgKOH / g, and a color number of 20.

[Production Example 3]
Similar to Production Example 1 except that 173 g (1.2 mol) of n-nonyl alcohol and 87 g (0.6 mol) of isononyl alcohol were added instead of 259 g of the aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9). It implemented and obtained 240 g of trimellitic acid triester (henceforth "ester 3").
The obtained ester 3 had an ester value of 282 mgKOH / g, an acid value of 0.05 mgKOH / g, and a color number of 20.

[Production Example 4]
The same procedure as in Production Example 1 was conducted except that 259 g of isononyl alcohol was added instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9), and trimellitic acid triester (hereinafter referred to as “ester 4”). ) 238 g were obtained.
The obtained ester 4 had an ester value of 285 mgKOH / g, an acid value of 0.06 mgKOH / g, and a color number of 20.

[Production Example 5]
Similar to Production Example 1 except that 130 g (0.9 mol) of n-nonyl alcohol and 130 g (0.9 mol) of isononyl alcohol were added instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9). This was carried out to obtain 241 g of trimellitic acid triester (hereinafter referred to as “ester 5”).
The obtained ester 5 had an ester value of 283 mgKOH / g, an acid value of 0.05 mgKOH / g, and a color number of 20.

[Production Example 6]
Trimellitic acid triester (hereinafter referred to as “ester 6”) was carried out in the same manner as in Production Example 1 except that 234 g of 2-ethylhexyl alcohol was added instead of 259 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9). 219 g).
The obtained ester 6 had an ester value of 309 mgKOH / g, an acid value of 0.06 mgKOH / g, and a color number of 20.

[Production Example 7]
Except that 74 g (0.5 mol) of phthalic dianhydride was added instead of 96 g of trimellitic anhydride, and 173 g of isononyl alcohol was added instead of 259 g of aliphatic saturated alcohol (Shell Chemicals: Lineball 9) In the same manner as in Production Example 1, 168 g of diisononyl phthalate (hereinafter referred to as “ester 7”) was obtained.
The obtained ester 7 had an ester value of 266 mgKOH / g, an acid value of 0.04 mgKOH / g, and a color number of 10.

[Example 1]
As described in “(3) Production of vinyl chloride sheet”, the medical vinyl chloride resin composition of the present invention was prepared using the trimellitic acid triester (ester 1) obtained in Production Example 1 as a plasticizer. did. Subsequently, a vinyl chloride sheet (roll sheet and press sheet) was prepared from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test were performed. The obtained results are shown in Table 1.

[Example 2]
Except having used ester 2 instead of ester 1, it implemented like Example 1 and prepared the medical vinyl chloride resin composition of this invention, Then, a vinyl chloride sheet was obtained from the obtained vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test were carried out. The results obtained are summarized in Table 1.

[Example 3]
Except for using ester 3 instead of ester 1, the same procedure as in Example 1 was carried out to prepare a medical vinyl chloride resin composition of the present invention, and then a vinyl chloride sheet was obtained from the resulting vinyl chloride resin composition. A tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test were carried out. The results obtained are summarized in Table 1.

[Comparative Example 1]
Except that ester 4 was used instead of ester 1, the same procedure as in Example 1 was carried out to prepare a vinyl chloride resin composition, and then a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test. A cold resistance test, a heat resistance test, and an ultraviolet irradiation test were performed. The results obtained are summarized in Table 1.

[Comparative Example 2]
Except that ester 5 was used instead of ester 1, the same procedure as in Example 1 was carried out to prepare a vinyl chloride resin composition, and then a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test. A cold resistance test, a heat resistance test, and an ultraviolet irradiation test were performed. The results obtained are summarized in Table 1.

[Comparative Example 3]
Except that ester 6 was used instead of ester 1, the same procedure as in Example 1 was carried out to prepare a vinyl chloride resin composition, and then a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test. A cold resistance test, a heat resistance test, and an ultraviolet irradiation test were performed. The results obtained are summarized in Table 1.

[Comparative Example 4]
The same procedure as in Example 1 was conducted except that ester 7 was used instead of ester 1, and after preparing a vinyl chloride resin composition, a vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and a tensile test was conducted. A cold resistance test, a heat resistance test, and an ultraviolet irradiation test were performed. The results obtained are summarized in Table 1.

[Comparative Example 5]
After the vinyl chloride resin composition was prepared in the same manner as in Example 1 except that di-2-ethylhexyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sunsocizer DOP) was used instead of the ester 1, A vinyl chloride sheet was prepared from the obtained vinyl chloride resin composition and subjected to a tensile test, a cold resistance test, a heat resistance test, and an ultraviolet irradiation test. The results obtained are summarized in Table 1.

From the results of Table 1, it is apparent that the medical vinyl chloride resin compositions (Examples 1 to 3) containing the trimellitic acid triester of the present invention are the most commonly used phthalate ester plastics. It can be seen that the coloring after the ultraviolet irradiation test is very small compared to the resin composition containing the agent (Comparative Examples 4 and 5). In general, the cause of coloring of the molded product obtained from the vinyl chloride resin composition is that it is colored by the production of conjugated polyene by the dehydrochlorination reaction of the vinyl chloride resin, and the irradiation of ultraviolet rays and radiation promotes it. It is known to be colored at the time of sterilization and sterilization treatment. From the above results, it can be said that the same effect is exhibited not only in ultraviolet irradiation but also in sterilization and sterilization treatment by various radiation irradiation considered to be colored by the same mechanism. .

Similarly, a medical vinyl chloride resin composition (Examples 1 to 3) containing the trimellitic acid triester of the present invention is a resin containing a phthalate ester plasticizer that is currently most widely used. Compared with the composition (Comparative Examples 4 and 5), the loss of volatilization is small, and in sterilization and sterilization processes involving heating such as boiling and autoclave, there is less concern about deterioration such as reduced flexibility due to volatilization of the plasticizer. It turns out to be very useful.

Furthermore, by comparison with trimellitic acid triesters outside of the present invention (Comparative Examples 1 to 3), among the trimellitic acid triesters as a plasticizer, by selecting the trimellitic acid triester according to the present invention, Concerns of deterioration such as reduced flexibility due to volatilization of plasticizers during sterilization and sterilization with heating such as boiling and autoclave, etc. Is clearly reduced and is very useful.

By using the medical vinyl chloride resin composition of the present invention, heat resistance can be improved without lowering flexibility and cold resistance, and a plasticizer by volatilization after heat sterilization treatment. The medical material obtained from the vinyl chloride resin composition of the present invention has little decrease in amount, retains good flexibility, and is hardly colored even in sterilization or sterilization treatment by irradiation with ultraviolet rays or radiation. As a medical material that has little deterioration in flexibility and coloration after sterilization and sterilization treatment, has good flexibility and cold resistance, and improved heat resistance, sterilization and sterilization treatment are indispensable. Very useful in the medical field.

Claims (11)

  A vinyl chloride resin composition for medical use containing a trimellitic acid triester obtained by esterifying a vinyl chloride resin and trimellitic acid or an anhydride thereof and an aliphatic saturated alcohol, the aliphatic saturated resin The alcohol is composed mainly of an aliphatic saturated alcohol having 9 carbon atoms, and the content in the aliphatic saturated alcohol is a linear aliphatic saturated alcohol having 9 carbon atoms and 60% by weight or less carbon. A medical vinyl chloride resin composition comprising a branched aliphatic saturated alcohol of formula 9, and having a straight chain ratio of the aliphatic saturated alcohol of 60% or more.   The aliphatic saturated alcohol is mainly composed of an aliphatic saturated alcohol having 9 carbon atoms, and the content of the aliphatic saturated alcohol in the aliphatic saturated alcohol is from 60 to 95% by weight and a linear aliphatic saturated alcohol having 9 carbon atoms and 5 2. The medical vinyl chloride resin according to claim 1, comprising ˜40% by weight of a branched aliphatic saturated alcohol having 9 carbon atoms and a linearity ratio of the aliphatic saturated alcohol of 60 to 95%. Composition.   The aliphatic saturated alcohol is mainly composed of an aliphatic saturated alcohol having 9 carbon atoms, and the content of the aliphatic saturated alcohol in the aliphatic saturated alcohol is 70 to 90% by weight and a linear aliphatic saturated alcohol having 9 to 10 carbon atoms. 3. The medical vinyl chloride resin composition according to claim 2, comprising 30% by weight of a branched aliphatic saturated alcohol having 9 carbon atoms and a linearity ratio of the aliphatic saturated alcohol of 70 to 90%. object.   A vinyl chloride resin composition for medical use containing a trimellitic acid triester obtained by esterifying a vinyl chloride resin and trimellitic acid or an anhydride thereof and an aliphatic saturated alcohol, the aliphatic saturated resin (1) a step of producing a 9-carbon aldehyde by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen, and (2) a step of hydrogenating the 9-carbon aldehyde to reduce to alcohol. A medical vinyl chloride resin composition comprising an aliphatic saturated alcohol mainly composed of an aliphatic saturated alcohol having 9 carbon atoms and having a straight chain structure and a branched chain structure, which is produced by the production method comprising .   The amount of the trimellitic acid triester according to any one of claims 1 to 3 or the trimellitic acid triester according to claim 4 is 5 to 200 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. The medical vinyl chloride resin composition according to any one of claims 1 to 4.   The amount of trimellitic acid triester according to any one of claims 1 to 3 or trimellitic acid triester according to claim 4 is 10 to 100 parts by weight with respect to 100 parts by weight of vinyl chloride resin. The medical vinyl chloride resin composition according to any one of claims 1 to 4.   Furthermore, the medical vinyl chloride-type resin composition in any one of Claims 1-6 containing an epoxidized vegetable oil.   The medical vinyl chloride resin composition according to claim 7, wherein a blending amount of the epoxidized vegetable oil is 1 to 50 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.   The medical vinyl chloride resin composition according to any one of claims 1 to 8, further comprising a fatty acid calcium salt and / or a fatty acid zinc salt.   The blending amount of the fatty acid calcium salt and / or the fatty acid zinc salt (the blending amount when either one is used or the total amount when both are used) is 100 parts by weight of the vinyl chloride resin. The medical vinyl chloride resin composition according to claim 9, which is 0.1 to 10 parts by weight.   A medical material comprising the medical vinyl chloride resin composition according to any one of claims 1 to 10.