JPH04327858A - Container for enema - Google Patents

Abstract

PURPOSE:To provide a container in which the pH value of an enema does not change with time. CONSTITUTION:A container made of soft vinyl chrolide resin composed of 100 pts.wt of vinyl chrolide resin, 30-160 pts.wt of a copolymer of ethylene, carbon monoxide and vinyl acetate or a copolymer of ethylene, carbon monoxide and (meth)acrylic alkylester, or 10-60 pts.wt of a plasticizer, and 0.01-0.5 pts.wt of a hindered amine compound.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an enema container capable of adjusting the pH of an enema solution.

0002

2. Description of the Related Art Conventionally, plastic containers have been used as containers for glycerin enema liquid. As resins used in this plastic enema container, soft vinyl chloride resins plasticized with plasticizers and olefin resins such as polyethylene are known.

0003

[Problem to be solved by the invention] By the way, since soft vinyl chloride resin is highly flexible and has excellent transparency,
Although it is preferable as a resin for enema containers, enema containers made of soft vinyl chloride resin may elute liquid plasticizer and have an adverse effect on the glycerin enema solution, or may be contaminated with vinyl chloride resin compositions. There was a problem that acidic substances were eluted and the pH changed. Therefore, preservatives such as antioxidants were added to prevent the pH from changing.

[0004] In addition, enema containers made of olefin resin have problems in that the joints of the containers do not have sufficient strength, and as a result, the liquid content tends to leak, making it difficult to guarantee the quality of the container as a pharmaceutical product.

[0005] In view of the above points, the present invention uses a soft vinyl chloride resin as a material, which is highly flexible and has excellent transparency.
An object of the present invention is to provide an enema container in which the amount of acidic substances eluted from the container is reduced and the pH of a glycerin enema solution is controlled.

[0006]

[Means for Solving the Problems] In the present invention, an enema container contains 100 parts by weight of a vinyl chloride resin and an ethylene/carbon monoxide/vinyl acetate copolymer or an ethylene/carbon monoxide/(meth)acrylic copolymer. A soft vinyl chloride resin consisting of 30 to 160 parts by weight of an acid alkyl ester copolymer, or 10 to 60 parts by weight of a plasticizer, and 0.01 to 0.5 parts by weight of a hindered amine compound represented by the following formula (1) It is characterized by being made from a composition.

[0007]

[C3]

[0008] The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride, or a copolymer containing vinyl chloride as a main component and one or more other monomers copolymerizable therewith. Refers to copolymers. This vinyl chloride resin can be obtained by a conventional suspension polymerization method, emulsion polymerization method, or the like. Note that a vinyl chloride homopolymer and a vinyl chloride copolymer may be mixed and used.

Monomers copolymerizable with vinyl chloride include α-olefins such as ethylene and propylene;
Vinyl esters such as vinyl acetate, unsaturated carboxylic acid esters such as (meth)acrylic acid alkyl esters, vinyl ethers such as alkyl vinyl ethers, vinyl halides such as vinyl bromide and vinyl fluoride, other styrene, acrylonitrile, Vinyl monomers other than those mentioned above, such as vinylidene chloride, or vinylidene monomers may be mentioned.

Among the above-mentioned vinyl chloride resins, polyvinyl chloride having an average degree of polymerization of 800 to 1700, or polyvinyl chloride having an ethylene content of 2 to 8% by weight and an average degree of polymerization of 800 to 1,700, is particularly preferred.
2000 vinyl chloride-ethylene copolymer is preferably used. Further, this polyvinyl chloride and vinyl chloride-ethylene copolymer may be mixed and used in any ratio.

[0011] Furthermore, the ethylene/carbon monoxide/vinyl acetate copolymer or the ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer used in the present invention contains monomers of ethylene and carbon monoxide. , vinyl acetate or (meth)acrylic acid alkyl ester are supplied and mixed in a predetermined ratio into a high-speed stirring reactor together with t-butyl peroxide isobutyrate or azobutyl nitrile as a catalyst, and the mixture is heated at high temperature ( For example, 160-230℃), high pressure (for example, 24,000-270℃)
It can be produced by copolymerizing these monomers by stirring at high speed under 00 psi).

In this ethylene/carbon monoxide/vinyl acetate copolymer or ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer, the content of the ethylene component is 40 to 80% by weight, preferably 50 to 70% by weight. In weight%, the content of carbon monoxide is 5 to 30% by weight, preferably 10 to 40% by weight, and the content of vinyl acetate or alkyl (meth)acrylate ester is 10 to 60% by weight, preferably 10 to 40% by weight. % range is desirable. In addition, it is also possible to copolymerize other monomers as necessary.

Melt flow rate (MFR) of this ethylene/carbon monoxide/vinyl acetate copolymer or ethylene/carbon monoxide/acrylic acid alkyl ester copolymer
is 1 to 500 g/10 minutes, preferably 5 to 100 g/1
It is desirable that the time be 0 minutes. This MFR is ASTM
This is a value measured in accordance with D 1238 or JIS K 7210 at a temperature of 190° C. and a load of 2.16 kg.

[0014] The ethylene/carbon monoxide/vinyl acetate copolymer or the ethylene/carbon monoxide/acrylic acid alkyl ester copolymer is blended in an amount of 30 to 160 parts by weight per 100 parts by weight of the vinyl chloride resin. It is preferable that If the amount is less than 30 parts by weight, the transparency and flexibility of the resin will be poor, causing problems in practical use, while if it exceeds 160 parts by weight, stickiness tends to occur.

Generally, vinyl chloride resin and ethylene/carbon monoxide/vinyl acetate copolymer or ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer are mixed together. , one obtained as follows can also be used. (1) In the presence of an ethylene/carbon monoxide/vinyl acetate copolymer or an ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer, vinyl chloride alone or vinyl chloride and a monomer copolymerizable with it A vinyl chloride-based graft polymer of so-called ethylene/carbon monoxide/vinyl acetate or (meth)acrylic acid alkyl ester copolymer obtained by radical polymerization of・Contains a mixture of vinyl acetate copolymer or ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer and vinyl chloride homopolymer or vinyl chloride copolymer)
.

This polymer is produced according to the method described in Japanese Patent Publication No. 39-27876. (2) Add ethylene, carbon monoxide,
Vinyl acetate copolymer or ethylene/carbon monoxide/(
A mixture of meth)acrylic acid alkyl ester copolymers. (3) A mixture of the above graph and a polymer mixed with a vinyl chloride resin.

[0017] Furthermore, the hindered amine compound represented by the above formula (1) used in the present invention is, for example,
It is commercially available as Sanol ls-770 from Ciba Geigy. Such a hindered amine compound is used in an amount of 0.0 parts by weight based on 100 parts by weight of the vinyl chloride resin.
It is blended in an amount of 1 to 0.05 parts by weight. If the amount is less than 0.01 part by weight, it tends to stick to metal parts in the molding machine,
The effect of improving moldability is small. On the other hand, if the blending amount exceeds 0.5 part by weight, the overall composition tends to be colored and bleed.

As the plasticizer used in this invention, any plasticizer conventionally used for vinyl chloride resins can be used as long as it does not significantly impair transparency and hygiene safety. The blending amount is 10 to 60 parts by weight, preferably 3 parts by weight, per 100 parts by weight of the vinyl chloride resin.
The range is 0 to 50 parts by weight. Note that this plasticizer can also be used in combination with an ethylene/carbon monoxide/vinyl acetate copolymer or an ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer.

The soft vinyl chloride resin composition of the present invention is as described above, but when molding containers from this composition, vinyl chloride resin compositions such as stabilizers, lubricants, antistatic agents, colorants, and fillers are generally used. Compounding agents used in the resin may be blended as necessary within a range that does not impair the purpose of the present invention. In these formulations, particularly preferred stabilizers or lubricants include non-toxic additives such as Ca-Zn stabilizers, calcium stearate, zinc stearate, epoxidized soybean oil, and tris(nonylphenyl) phosphite. be.

[0020] The composition blended in this manner is supplied to a blended powder or once melt-kneaded and then fed to a molding machine such as an extruder and molded into a container shape using a mold. Note that this container is preferably used with a glycerin enema solution sealed therein.

[0021]

[Example] Next, an example of the present invention will be described. below,
Parts by weight are simply called parts.

Example 1 Vinyl chloride-ethylene copolymer (average degree of polymerization 1300,
100 parts of ethylene component (40% by weight), 70 parts of ethylene/carbon monoxide/vinyl acetate copolymer (Elvaloy 741: manufactured by DuPont), and a hindered amine compound (San
ol ls-770: manufactured by Ciba Geigy), 1.0 part of Ca-Zn composite stabilizer (Mark 37: manufactured by Adeka Argus), and epoxidized soybean oil (O-130).
P: manufactured by Adeka Argus Co., Ltd.) 10 parts and lubricant (Hiwax 4202E: manufactured by Mitsui Petrochemical Industries, Ltd.) 0.5 parts,
The mixture was kneaded for 5 minutes using rolls heated to 180° C. to form a sheet, which was then cut to obtain pellets.

The pellets were supplied to a 65 mm single screw extruder equipped with a T-die having a width of 650 mm, and the temperature was adjusted in the order of cylinder 1:
120℃, cylinder 2: 140℃, cylinder 3:1
The temperature was set at 50°C, and the T-die temperature was set at 160°C, and extrusion molding was carried out at an extrusion rate of 40 kg/Hr. A 0.4 mm sheet was continuously extruded for 20 hours, and its molding processability, transparency, and haze were evaluated. (Haze value), exudation properties, and changes in pH over time were measured. (1) Molding Processability Immediately after 20 hours of continuous extrusion molding, the molten resin in the T-die was sampled and observed for its color tone and the state of resin adhesion within the T-die. As a result, the T-die was found to be normal with no resin adhesion or coloring. (2) Transparency For sheets with a thickness of 0.4 mm, JIS K 7
When the light transmittance was measured in accordance with 105, it was 90.
It was 2%. (3) Haze (haze value) JIS K 7 for sheets with a thickness of 0.4 mm
When the haze was measured in accordance with 105, it was 4.0%. (4) Leakage A sheet with a thickness of 0.4 mm was left in a hot air constant temperature bath at 40° C. for one month and the degree of staining on the sheet surface was observed, and no staining was observed on the sheet surface. (5) Change in pH value over time A sheet with a thickness of 0.4 mm was processed into a bag shape, and the bag was filled with a solution of glycerin:water = 1:1, and kept at 40°C (in a dry constant temperature bath) for 10 days. Humidity 40℃ in constant temperature bath), 6
The pH values when stored at 0°C (in a dry constant temperature bath) and 80°C (in a dry constant temperature bath) were both 5.57. In addition,
The initial value of PH was 5.88.

Example 2 Hindered amine compound (Sanol ls-770
The same procedure as in Example 1 was carried out except that the amount of the compound (manufactured by Ciba Geigy) was changed to 0.01 part.

As a result, there was no resin adhesion inside the T-die,
The resin was colored slightly yellow, but the color was uniform as a whole. The light transmittance is 89.8% and the haze is 4.
．． 5%, no stains were observed on the sheet surface, and
The PH value was 6.00 in all cases.

Example 3 Hindered amine compound (Sanol ls-770
The same procedure as in Example 1 was carried out, except that the amount of the compound (manufactured by Ciba Geigy) was changed to 0.1 part.

As a result, there was no resin adhesion inside the T-die,
The resin was colored slightly yellow, but the color was uniform as a whole. The light transmittance is 89.8% and the haze is 4.
．． 5%, no stains were observed on the sheet surface, and
The PH value was 6.15 in all cases.

Example 4 100 parts of polyvinyl chloride (average degree of polymerization 1300), 50 parts of di-2-ethylhexyl phthalate (DOP),
Hindered amine compound (Sanol ls-770
: 0.05 part of Ciba Geigy), 1.0 part of Ca-Zn composite stabilizer (Mark 37: manufactured by Adeka Argus), and 10 parts of epoxidized soybean oil (O-130P: manufactured by Adeka Argus). and 0.5 part of a lubricant (Hiwax 4202E, manufactured by Mitsui Petrochemical Industries, Ltd.) were kneaded for 5 minutes using a roll heated to 180° C. to prepare a sheet, which was then cut to obtain pellets.

Using this pellet, the same procedure as in Example 1 was carried out. As a result, there was no adhesion of resin inside the T-die, and although the resin was colored slightly yellow, the color was uniform as a whole. In addition, the light transmittance is 89.7% and the haze is 4.6.
%, and no stains were observed on the sheet surface.

[0030] In addition, a container made from this resin composition was filled with a solution of glycerin:water = 1:1 with an initial pH of 5.88 in a 40°C dry constant temperature bath, and this was heated with hot air at a constant temperature of 40°C. When the pH values were measured when stored in the tank for 1 week, 2 weeks, 3 weeks, and 1 month, they were 6.23 and 5, respectively.
．． They were 90, 5.61, and 5.37. Note that the initial value of this liquid was 5.88.

Comparative Example 1 Hindered amine compound ((Sanol ls-77
The same procedure as in Example 1 was carried out except that 0: Ciba Geigy) was not used at all.

As a result, a portion of the resin was found to be strongly discolored to brown, and this portion remained attached to the mold. Further, a brown gel-like substance was observed in a part of the sheet. The light transmittance of this sheet is 90.0%, and the haze is 3.8
%, and no stains were observed on the sheet surface. Furthermore, the pH values after 10 days were all 5.68.

Comparative Example 2 Hindered amine compound ((Sanol ls-77
The same procedure as in Example 1 was conducted except that the amount of 0: Ciba Geigy Co., Ltd.) was changed to 1.0 part.

[0034] As a result, no resin was observed to adhere to the inside of the T-die, but the resin as a whole was strongly colored yellow. Further, the light transmittance of this sheet was 90.0%, the haze was 7.8%, and no stains were observed on the sheet surface. Furthermore, the pH values after 10 days were all 6.52.

Comparative Example 3 The same procedure as in Example 1 was carried out except that the amount of lubricant (Hiwax 4202E, manufactured by Mitsui Petrochemical Industries, Ltd.) was changed to 4.0 parts.

As a result, neither resin adhesion nor coloring was observed inside the T-die. In addition, the light transmittance of this sheet is 80
．． 2%, haze was 16.3%, and no stains were observed on the sheet surface. In addition, regarding the change in pH value over time, the same procedure as in Example 4 was carried out, and it was found that 1 week, 2 weeks,
The pH value when stored for 3 weeks and 1 month was 5, respectively.
．． They were 97, 5.64, 5.73, and 5.12.

[0037] As is clear from the results, it can be seen that in the case of the present invention, the change in pH value is small and well controlled.

[0038]

As described above, the enema container of the present invention has excellent transparency and flexibility, and there is no leaching of components from the resin composition, so that the pH of the enema liquid remains stable over a long period of time.

Claims (2)

[Claims] Claim 1: 100 parts by weight of a vinyl chloride resin, 30 to 160 parts by weight of an ethylene/carbon monoxide/vinyl acetate copolymer or an ethylene/carbon monoxide/(meth)acrylic acid alkyl ester copolymer, and the following: An enema container made from a soft vinyl chloride resin composition comprising 0.01 to 0.5 parts by weight of a hindered amine compound represented by formula (1). [Chemical formula 1] 2. A soft vinyl chloride resin comprising 100 parts by weight of a vinyl chloride resin, 10 to 60 parts by weight of a plasticizer, and 0.01 to 0.5 parts by weight of a hindered amine compound represented by the following formula (1). An enema container made from a resin composition. [Case 2]