JPS61232161A - Sealing plug for vial - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sealing stopper for medicine bottles. More specifically, it has excellent corrosion resistance, stain resistance, visibility, and airtightness.
The present invention relates to a sealing stopper for medicine bottles provided with a coating layer having excellent non-stick properties.

[Conventional technology]

Sealing stoppers made of rubber or the like are used in medicine bottles for pharmaceuticals and general medicines. The sealing closure requires high corrosion resistance, sufficient airtightness, properties that do not contaminate the chemical, and non-adhesiveness that prevents the rubber closures from bonding together in order to ensure smooth closure during the automatic closure process. .

In order to provide non-adhesive properties, conventional sealing stoppers have been coated with fluororubber (for example, in Japanese Patent Application Laid-open No. 55-71268).
Methods such as laminating a plastic film were used.

[Problem that the invention seeks to solve]

Although conventional rubber plugs coated with fluororubber have non-adhesive properties, they have the problem of being gas permeable and not being sufficiently airtight. Furthermore, rubber stoppers covered with plastic films have problems such as peeling when bent (due to the difference in elastic modulus between rubber and plastic) and complicated molding processes.

The present invention has excellent adhesion to the base material of the sealing stopper such as rubber, and has flexibility, non-adhesiveness, and stain resistance, as well as high corrosion resistance, sufficient airtightness, and properties that do not contaminate chemicals. To provide an excellent sealing stopper for medicine bottles.

[Means for solving problems]

TECHNICAL FIELD The present invention relates to a sealing stopper for medicine bottles, which is provided with a coating layer mainly composed of a vinylidene fluoride copolymer having a functional group and/or a crosslinked product of a vinylidene fluoride copolymer having a functional group.

[Function and Examples]

The coating layer in the present invention is formed by applying a fluororesin paint consisting of a polymer composition mainly composed of a vinylidene fluoride copolymer having a functional group (hereinafter referred to as a fluorine-containing copolymer) and a crosslinking agent, and It is obtained by crosslinking and curing at room temperature and has a film thickness of about 1 to 100 μ-.

The fluorine-containing copolymer has properties not found in conventional fluororesins: it cures at room temperature to form a flexible film, and the formed coating has the corrosion resistance and airtightness of the fluoropolymer. , stain resistance, corrosion resistance 1, and non-adhesive properties. It also has good adhesion to rubber, cork, or glass. Regarding each component, composition, etc. of such a fluorine-containing copolymer, please refer to Japanese Patent Application No. 58-175.
It is explained in detail in the No. 123 specification.

In the present invention, the fluorine-containing copolymer usually contains 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, and 1 to 50 mol% vinyl monomer having a functional group, preferably 1 to 10 mol%. or vinylidene fluoride 50 to 99 mol%, preferably 65 to 85 mol%, vinyl monomer having a functional group 1 to 50 mol%, preferably 1 to 10 mol%, and preferably less than 30 mol% of fluoroolefins other than vinylidene fluoride. is comprised of 10 to 25 mol%.

The molecular weight of the fluorine-containing copolymer containing vinylidene fluoride as the main component and having a functional group measured by gel permeation chromatography (GPC, polyethylene standard) is usually in the range of 10,000 to 500,000. be.

The vinyl monomer having the above functional group usually has the formula:% formula% (wherein, X is a hydroxyl group, carboxyl group or glycidyl group, k is O or 1, m is an integer of 0 to 10, n
represents an integer of O to 4 [wherein, when X is a hydroxyl group, it is 1 to 4]. ) A compound represented by the formula: %Formula%) (wherein, X and n are as above, ~4 integer,
X is as defined above, or a compound represented by the formula: %Formula% (wherein, Y is as defined above).

Fluoroolefins other than vinylidene fluoride mentioned above are usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., and preferably tetrafluoroethylene or chlorotrifluoroethylene. .

As a method for producing the fluorine-containing copolymer used in the present invention, for example, each component is mixed with a polymerization catalyst in the presence of a solvent at a temperature of -20 to 150°C, preferably 5 to 95°C, and
~30+r/aJG, preferably 10+r/cd
Methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under pressure conditions of G or less may be employed.

Further, the fluorine-containing copolymer of the present invention has good compatibility with an acrylic resin and can be used in combination with an acrylic resin.

The above-mentioned acrylic resin refers to a single or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, single or copolymers of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, etc., copolymers of the above acrylates or methacrylates with hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, styrene, acrinitrile, etc., commercially available acrylic As resins, Hyfroid 3004 and Hyfroid 3
Examples include, but are not limited to, 018, Hyfroid 3046C (all manufactured by Hitachi Chemical Co., Ltd.), Acryzo Ink 8810-45, Acridic A314, and Acridic 47-540 (all manufactured by Dainippon Ink and Chemicals). Acrylic resin contains 5 methyl methacrylate.
Those containing 0% by weight or more and a molecular weight (GPC) of 5,000 to 300,000 are preferred from the viewpoint of compatibility with the fluorine-containing copolymer.

The blending ratio of the fluorine-containing copolymer and acrylic resin is usually 1 part by weight of the fluorine-containing copolymer to 1 part by weight of the acrylic resin.
The amount is 0 to 1900 parts by weight, preferably 25 to 400 parts by weight. When blended within this range, the weather resistance, translucency, and
Good pigment dispersibility etc.

The coating layer in the present invention is usually made of a coating composition made of rubber, cork, glass, etc., which is obtained by blending a crosslinking agent with a fluorine-containing copolymer as described above, and uniformly mixing and dissolving it in an appropriate solvent. It is formed by applying it to a transparent substrate, crosslinking and curing it at room temperature. Curing progresses quickly at room temperature, usually within 1
A hard coating can be obtained in ~10 days, but the time required for curing can be shortened by raising the temperature to a level that does not adversely affect the substrate.

The crosslinking agent is a functional group (
hydroxyl group, carboxyl group or glycidyl group)
It is a compound having two or more groups capable of crosslinking the fluorine-containing copolymer by reacting with the fluorine-containing copolymer. When the functional group is a hydroxyl group, the crosslinking is usually performed using isocyanates, acid anhydrides, or the like. When the functional group is a carboxyl group, it is usually an isocyanate, an amine, an amino resin, a compound containing a glycidyl group, etc. When the functional group is a glycidyl group, it is usually an amine. Examples of isocyanates include hexamethylene diisocyanate, tolylene diisocyanate,
Examples of amines include, but are not limited to, hydrogenated tolylene diisocyanate and their blocked isocyanates, such as diethylenetriamine, triethylenetetramine, xylenediamine, metaphenylenediamine, benzyldimethylamine, bisaminopropyltetraoxaspiro. Examples of acid anhydrides include, but are not limited to, undecane and the like, and include, but are not limited to, phthalic anhydride, pyromellitic anhydride, mellitic anhydride, and the like. Examples of amino resins include, but are not limited to, alkyl etherified methylol melamine, alkyl etherified methylol urea, alkyl etherified benzoylguanamine, and the like. An example of a compound containing a glycidyl group is the formula: %Formula% (wherein, Z represents a glycidyl group, and R1 represents an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group having 6 to 10 carbon atoms. ), aromatic triepoxides represented by the formula: % formula % (wherein R2 is a trivalent aromatic group, and Z is the same as above). Not limited to these.

The amount of the crosslinking agent is preferably adjusted to 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic resin.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran; amides such as N-dimethylformamide and N-dimethylacetamide; alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; aromatic carbonization such as toluene and xylene One or more types of hydrogens may be used.

The concentration of the fluorine-containing copolymer varies depending on the coating method, coating manufacturing method, etc., but is usually 1 to 70% by weight, preferably 20 to 60% by weight.

The fluorine-containing copolymer coating composition may optionally contain other polymers, curing accelerators, dyes, pigments, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, light stabilizers, Anti-scald agents, dispersants, antifoaming agents, etc. may be added.

The sealing stopper for medicine bottles of the present invention has a stopper base material usually made of rubber, cork, glass, etc., and a fluororesin containing a polymer composition whose main component is a vinylidene fluoride copolymer having a functional group and a crosslinking agent. It is obtained by applying a paint and crosslinking and curing it at room temperature to heating.

When painting, it may be applied directly to the plug base material, but if necessary, one or more layers of undercoating paint such as chlorinated rubber or urethane rubber may be provided on the plug base material, and the present invention A protective layer for use may be formed.

Application to the plug base material can be carried out by a conventional method such as a spray method, a dipping method, a dipping method, a roll coating method, or a knife coating method.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example I VdF70-E7Lz%, CTFE20-11. A fluorine-containing copolymer (parts by weight, the same shall apply hereinafter) consisting of % and M5FPIO mol% was added to 50 parts of methyl isobutyl ketone and mixed uniformly, and Coronate EH (
Polyisocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo) was added to Coronate E for OHHI3, a fluorine-containing copolymer.
Add 0.05 g of dibutitin dilaurate as a curing accelerator and an amount equivalent to 1.1 800 valence of H, and mix uniformly.
A coating composition was prepared.

On the other hand, a butyl rubber vulcanized plate of 100 cranes x 50 cranes x 2 cranes was roughened with sandpaper, degreased with ethyl alcohol,
A substrate was prepared.

On the substrate, 50 parts of n-butyl acetate was added to the coating composition.
It was diluted three times with a thinner consisting of 50 parts of methyl isobutyl ketone, applied by spray painting to form a coating film with a thickness of 5 μm, and cured at 25° C. for 7 days to obtain a test piece.

Example 2 A test piece was obtained in the same manner as in Example 1 using a fluororubber vulcanized plate.

Example 3 A test piece was obtained in the same manner as in Example 1 using a natural rubber vulcanized plate.

Example 4 VdF 70-1-le%, CTFE 20% moles and M5
Fluorine-containing copolymer consisting of FPIO mol% and MM
An acrylic resin consisting of A80 mol% EMAIO mol% and HEMAIO mol% was mixed with methyl isobutyl ketone at a ratio of To/30 (weight ratio) to prepare a 50% weight face, and Coronate E was added as a crosslinking agent.
OHHI3 of H-containing fluorine-containing copolymer and acrylic resin
On the other hand, an amount equivalent to 1.1 in 800 value of Coronate EH and a hardening accelerator dibutyltin dilaurate were added in an amount of 1X10-'g per 1g of solid content and mixed uniformly to prepare a coating composition.

A test piece was prepared in the same manner as in Example 1 using the above coating composition on a substrate in the same manner as in Example 1.

Example 5 A test piece was prepared using the coating composition of Example 4 on the same substrate as in Example 2 in the same manner as in Example 1.

Example 6 A test piece was prepared using the coating composition of Example 4 on the same substrate as in Example 3 in the same manner as in Example 1.

Comparative Examples 1 to 3 Butyl rubber vulcanized plate of Example 1 (Comparative Example 1)1. Example 2
A fluorine rubber vulcanized plate (Comparative Example 2) and a natural rubber vulcanized plate of Example 3 (Comparative Example 3) were used as comparative test pieces, respectively.

The following tests were conducted on the test pieces obtained in Examples 1 to 6 and Comparative Examples 1 to 3, respectively.

The results are shown in the first page.

[Adhesion]

Cut 1 square of 1 square meter into the obtained test piece using a cutter knife.
00 incisions were made and a peel test was performed 10 times using cellophane adhesive tape to measure the number remaining.

[Stain resistance]

After filling 1- on the surface of the test piece with Sakura Pentasochi (red) (@Sakura Crevasse) and leaving it for 24 hours, wipe it off with tissue paper impregnated with ethanol/methyl ethyl ketone (9 layers: 1 weight ratio) to judge the appearance. . In Table 1, ○ indicates that it can be completely removed, and × indicates that it remains in red.

[Non-adhesive]

Two samples of 1 cffl square were prepared from each of the test pieces of Examples 1 to 6 and Comparative Examples 1 to 3, and the samples were stacked on top of each other, a load of 100 g was applied, and after standing for 24 hours, one piece of the sample was Measure the time it takes for the other piece to fall. In Table 1, ○ means that the object falls under its own weight within 3 seconds, and ×
indicates that the object did not fall for more than 3 seconds.

Table 1 Examples 7 to 8 The coating compositions of Examples 1 and 4 were spray-coated onto a fluororesin film to form a coating film with a thickness of 25 μm.
After curing at 5°C for 7 days, it was peeled off to obtain a test piece in the form of a coating film.

The following tests were conducted for the tests obtained in Examples 7 to 8 and Comparative Examples 1 to 3, respectively. The results are shown in Table 2.

[Gas permeability]

For the obtained test piece, ASTM D 1434
Measure oxygen permeability according to ゜750GAS.

Table 2 Examples 9 to 25 A fluorine-containing copolymer or a fluorine-containing copolymer and an acrylic resin (the proportions are shown in Table 3) having the composition shown in Table 3 were dissolved in methyl isobutyl ketone, and a solid Min concentration is 30
The weight percentage was adjusted accordingly.

An amount equivalent to NC0 value 1.1 of Coronate EH and 10-3 g of dibutyltin dilaurate per 1 g of solid content were added to OHHI3 of the solid content of the solution, mixed thoroughly, and then coated on a butyl rubber vulcanized plate and left at room temperature. It was allowed to cure for 7 days. The resulting cured coatings each have a thickness of approximately 11~
It was a glossy coating of 18 μl.

The following tests were conducted for each sample.

The results are shown in Table 3.

[Non-adhesive]

Tests were conducted in the same manner as in Examples 1-6.

[Stain resistance]

lcl on the surface of the specimen! was filled with oil-based ink (Sakura Pen Touch red, manufactured by Sakura Crepas Co., Ltd.), left for 24 hours, and then wiped off with tissue paper soaked in ethanol/methyl ethyl ketone (9/1 weight ratio). ○ in Table 3 indicates complete removal.

In addition, each abbreviation representing a polymer in the examples represents the following compound.

VdF: vinylidene fluoride CTFE: chlorotrifluoroethylene TFE
: Tetrafluoroethylene M5FP: CFt-
CFCFtCH1OH3FHA: CFt-CFC
HtCHtOHHBVE: Hydroxybutyl vinyl ether GVE: Glycidyl vinyl ether 7 F HA: CF z = CF CF z
CF t CHzCH! OH MMA: Methyl methacrylate EMA:
Ethyl methacrylate HEMA: Hydroxyethyl methacrylate BMA: Butyl methacrylate MA: Methacrylic acid GMA: Glycidyl methacrylate 5FBA:
CFz=CFCFtCOOH [Effects of the Invention] As described above, the polymer composition containing the vinylidene fluoride copolymer having the functional group as a main component can be cured at room temperature, and has excellent adhesion, stain resistance, and non-contamination properties. Since a coating with excellent adhesiveness and airtightness can be formed on any type of closure base material, the sealing closure for medicine bottles of the present invention in which the coating film is provided as a coating layer is extremely excellent. It has adhesion, stain resistance, non-stick properties, airtightness, and excellent durability.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Alternatively, a sealing stopper for a medicine bottle is provided with a coating layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group.