JPH05277187A - Piston sealing material for syringe - Google Patents

Abstract

PURPOSE:To provide the piston sealing material for a syringe having excellent sealability, low friction, wear resistant characteristic and heat resistance and the stability and reliability over a long period of time. CONSTITUTION:The syringe consists of a cylinder 1 and a piston 2 and a groove 4 is formed on the front end side of the piston 2. An O-ring 5 is inserted into this groove. This O-ring 5 is formed of a lubricative rubber compsn. consisting of a compd. compounded with a thermoplastic fluororesin as a first essential component, fluoro rubber as a second essential component and a low mol.wt. fluorine-contained polymer as a third essential component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a syringe piston seal material for injection syringes, and more particularly to improvements in syringe piston seal materials for industrial and medical use.

[0002]

2. Description of the Related Art Syringes for industrial and medical purposes discharge a liquid having a low viscosity to a high viscosity or a solid mixed liquid quantitatively from a small diameter portion at the tip. In this case, the liquid and the solid mixed liquid are loaded via a piston.
This piston is usually used for various purposes in order to stably and uniformly transmit a load, and various rubber materials are used depending on the application.

Conventionally, materials have been selected by focusing only on the sealing property, so that the shearing force generated in the sliding portion of the seal causes abrasion, and the replacement is performed in a short period of time.
In recent years, it has been required to reduce the friction of seals for the purpose of keeping the load constant and low pressure, suppressing wear and achieving more stable quantitativeness. For example, a typical example of an industrial syringe is a syringe for adhesives, but currently, diene rubber is mainly used. However, since the rubber is exposed to a high pressure by various organic solvents contained in the adhesive for a long period of time, problems such as deterioration of the rubber and abrasion of sliding parts have become problems. In addition, a sheet made of diene synthetic rubber or the like with a Teflon sheet attached to the surface is also used.

[0004]

However, similarly, since it is exposed to a high pressure for a long period of time, deterioration of rubber and peeling of an adhesive portion pose problems. Further, the sliding surface is not an elastic body, so that the sealing property is not sufficiently satisfied.

Therefore, in both industrial and medical syringe applications, piston seals are required to have excellent static friction characteristics and dynamic friction characteristics, and further have excellent wear resistance characteristics, long life, and excellent sealability. There is a demand for piston seals with. That is, there is a demand for a piston seal material having sufficient rubber elasticity and excellent sealability, low friction, and wear resistance.

Therefore, a main object of the present invention is to provide a syringe piston seal material which is excellent in sealability, low friction, abrasion resistance and heat resistance and which is stable and reliable for a long period of time.

[0007]

The invention according to claim 1 is
A syringe piston sealing material, wherein a part or the whole including a sliding surface of the syringe is formed from a lubricating rubber composition, and the lubricating rubber composition is a thermoplastic fluororesin which is a first essential component, and a second essential component. It is characterized by containing a fluororubber as a component and a low molecular weight fluoropolymer as a third essential component.

In the present invention, the fluororubber is a polymer or copolymer of unit monomers containing an average of one or more fluorine atoms, has a glass transition point of room temperature or lower, and has a rubber-like elasticity at room temperature. There is no particular limitation as long as it has the following, and a wide range can be exemplified.

Examples of the polymerization method of fluororubber include bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, catalyst polymerization, ionizing radiation polymerization, and redox polymerization. The molecular weight of fluororubber is usually 50,000.
A polymer having a molecular weight of 0 or more is desirable, and a polymer having a molecular weight as high as possible gives good results.
Above all, it is particularly preferable to use one having a size of about 100,000 to 250,000.

Typical examples corresponding to the above conditions are tetrafluoroethylene / propylene copolymer Aflas manufactured by Asahi Glass Co., Ltd., vinylidene fluoride / hexafluoropropylene copolymer DuPont / Showa Denko Viton, and fluorine. Fluorovinylidene / hexafluoropropylene / tetrafluoroethylene copolymer Technofluon made by Montefluos, fluorosilicone elastomer Dow Corning Silastic LS, perfluoroelastomer Daikin Industrial Co., Ltd. Can be mentioned.

In the present invention, the thermoplastic fluororesin which is the first essential component has a carbon chain in the main chain,
A polymer having a fluorine bond in its side chain, such as a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (hereinafter abbreviated as PFA) and a tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter referred to as FEP). Abbreviated) and tetrafluoroethylene / ethylene copolymer (hereinafter abbreviated as ETFE). Any of the above resins can be produced by various polymerization methods such as catalyst emulsion polymerization, suspension polymerization, catalyst solution polymerization, gas phase polymerization and ionizing radiation irradiation polymerization. The molecular weight is preferably 50,000 or less, more preferably more than 5,000 and almost 20,000 or less.

As a typical example corresponding to the above conditions, the above-mentioned PFA PFA manufactured by Mitsui DuPont Fluorochemical Co.
Examples include MP10 and FEP, Teflon FEP100 manufactured by Mitsui DuPont Fluorochemicals, and ETFE, Aflon COP manufactured by Asahi Glass.

The composition obtained by mixing the above-mentioned fluororubber and thermoplastic fluororesin has characteristics as an elastic body. In the present invention, the low molecular weight fluoropolymer, which is the third essential component, is blended in order to impart even more excellent sliding properties to such an elastic body.

In the present invention, the low molecular weight fluoropolymer means tetrafluoroethylene (TFE), a fluoropolyether having a main structural unit —C _n F _2n —O— (n is an integer of 1 to 4), Structural unit

[0015]

[Chemical 1]

Among the polyfluoroalkyl group-containing compounds (having 2 to 20 carbon atoms) having, for example, those having a molecular weight of 50,000 or less. In order to give excellent sliding properties,
It is particularly desirable that the low molecular weight fluoropolymer has a molecular weight of 5,000 or less. Among such low molecular weight fluorinated polymers, those having an average particle size of 5 μm or less of the tetrafluoroethylene polymer represented by the following formula are particularly preferable.

[0017]

[Chemical 2]

Examples of such materials include Bydax AR manufactured by DuPont and Furuon Lubricant L169 manufactured by Asahi Glass Co., Ltd.

Next, as a fluoropolyether having an average molecular weight of 50,000 or less and having a main structural unit of --C _n F _2n --O (n is an integer of 1 to 4),

[0020]

[Chemical 3]

And the like. Such polymers are those having a structural unit containing a functional group such as an isocyanate group, a hydroxyl group, a carboxyl group, and an ester group in order to improve the affinity (adhesion) with other compounding materials and additives. desirable.

Specific examples of such fluoropolyethers include the following.

[0023]

[Chemical 4]

These fluoropolyethers may be used alone or in combination. Further, a fluoropolyether having activated hydrogen as a functional group and an isocyanate compound having no polyfluoropolyether group may be used in combination. Further, a fluoropolyether having an isocyanate group, diamines not containing various fluoropolyether groups, triamines, or diols not containing various fluoropolyether groups,
A method of using triols together may be adopted.

In particular, it is desirable to use a combination of fluoropolyethers in which functional groups react with each other to increase the molecular weight. As such, it is likewise desirable to combine, for example, those having units containing isocyanate groups with those having units containing hydroxyl groups.

Examples of the polyfluoroalkyl group-containing compound include compounds having a polyfluoroalkyl group as shown below.

[0027]

[Chemical 5]

Those having the above polyfluoroalkyl group (having 2 to 20 carbon atoms) and having an average molecular weight of 50,000 or less include:

[0029]

[Chemical 6]

And the like, a polymer of a reaction product of a compound having a reactive group and a polyfluoroalkyl group with an ethylenically unsaturated compound having a group which reacts with the reactive group (for example, fluoroalkyl acrylate), and Examples thereof include a reaction product of a compound having a reactive group and a polyfluoroalkyl group with various polymers having a group that reacts with the reactive group, or a polycondensation product of the above compound.

Like the above-mentioned fluoropolyether, the polyfluoroalkyl group-containing compound is a functional group having a high affinity for improving the affinity (adhesion) with other compounding materials and additives, such as an isocyanate group, A compound having a unit containing a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an amino group, a sulfone group and the like is preferable.

These polyfluoroalkyl group-containing compounds may be used alone or in combination. In addition, a polyfluoroalkyl group-containing compound having a reactive group having activated hydrogen and an isocyanate compound not having a polyfluoroalkyl group may be used in combination. Also,
Adopting a method such as combining a polyfluoroalkyl group-containing compound having an isocyanate group with various polyfluoroalkyl group-free diamines, triamines or various polyfluoroalkyl group-free diol groups and triols. May be.

A combination of functional groups is preferable from the viewpoint of increasing the strength, and more specifically, it has a polyfluoroalkyl group having 2 to 20 carbon atoms and is selected from a hydroxyl group, a mercapto group, a carboxyl group and an amino group. A combination with a fluoropolymer containing at least one kind, or a fluoropolymer having a polyfluoroalkyl group having 2 to 20 carbon atoms and having a unit containing an isocyanate group, and polyfluoroalkyl having 2 to 20 carbon atoms Examples thereof include a combination with a fluorine-containing polymer having a group and a unit containing a reactive group having activated hydrogen.

Among these low molecular weight fluoropolymers,
It has been found that the use of fluoroolefin polymers or fluoropolyethers gives excellent results in lubricity, and the use of tetrafluoroethylene polymers having an average particle size of 5 μm or less gives the most desirable results.

In the present invention, the compounding ratio of fluororubber, thermoplastic fluororesin and low molecular weight fluoropolymer is such that the weight ratio of fluororubber to thermoplastic fluororesin is 5.
It is desirable that the ratio be 0:50 to 95: 5. If the blending weight ratio of the thermoplastic fluororesin exceeds 50/100,
The desired composition does not have sufficient elastic properties, and the ratio is 5/100.
This is because if it is less than this, sufficient abrasion resistance cannot be obtained.

The low molecular weight fluoropolymer is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the total of the fluororubber and the thermoplastic fluororesin. This is because if the compounding ratio of the low molecular weight fluoropolymer is less than 5 parts by weight, sufficient sliding properties cannot be obtained, and if it exceeds 50 parts by weight, the rubber-like elastic properties are impaired.

Further, with respect to the above-mentioned lubricating rubber composition, 3
Abrasion resistance can be improved by adding a cured powder of a thermosetting resin that does not melt at 00 ° C. or a heat-resistant resin powder having a glass transition point of 300 ° C. or higher.

The thermosetting resin powder is a fine powder of a phenol resin, an epoxy resin or the like after thermosetting, and the heat-resistant resin having a glass transition point of 300 ° C. or higher is a polyimide resin or an aromatic aramid resin. A powder is mentioned.

Among the commercially available resin powders, the hardened and ground product of phenol resin is manufactured by Kanebo Ltd .: Bell Pearl H30.
0, as a cured pulverized product of polyimide resin: PWA20 manufactured by Mikasa Sangyo Co., Ltd .; as a pulverized product of aromatic aramid resin: MP-P manufactured by Asahi Kasei Co., as a thermosetting resin powder having a glass transition point Tg of 300 ° C. or higher. Manufactured by Ube Industries, Ltd .: Upilex S (Tg> 500).

The particle size of such thermosetting resin powder is 1
A resin having a particle size of ˜15 μm is preferable from the viewpoint of maintaining rubber elasticity and easiness of kneading process. The thermosetting resin powder is preferably added in an amount of 5 to 20% by weight with respect to the first to third essential components. If it is less than 5% by weight, the effect of improving wear resistance is not obtained and 2
A large amount exceeding 0% by weight is not preferable because the rubber elasticity decreases.

In addition to the above components, various additives may be added within the range not impairing the object of the present invention. For example, as a vulcanizing material for fluororubber, isocyanurate, organic peroxide, etc., antioxidants such as sodium stearate, magnesium oxide, and calcium hydroxide, or acid acceptors, antistatic agents such as carbon, silica and alumina, etc. It goes without saying that the above-mentioned fillers, other metal oxides, colorants, flame retardants and the like may be appropriately added.

The method of mixing the various raw materials described above is not particularly limited, and the generally-used methods can be used for mixing. For example, the elastomer as the main raw material and the other raw materials may be individually mixed sequentially or simultaneously by a roll mixer or other mixer. At this time, it is desirable to provide a temperature controller to prevent heat generation due to friction.

When a roll mixer is used,
For finishing mixing, it is more preferable to tighten the roll interval to about 3 mm or less and perform thin threading.

The thrust washer material according to the present invention does not require a particularly limited means in the molding step, and the primary vulcanization (140 to 17) can be carried out by an ordinary press molding method.
After performing a pressure of 5 to 10 kgf / cm ² for 10 to 30 minutes at 0 ° C., secondary vulcanization (for example, 2 to 2 at 200 to 300 ° C.)
It may be molded into a seal by applying no pressure for 0 hours.

Further, only the lip-shaped portion or the portion of the lip-shaped portion, which is the seal portion of the thrust washer material, and which is in contact with the shaft is molded with the lubricating component composition containing the above-mentioned first to third essential components, Other parts may be composite-molded with general synthetic rubber, plastic or metal.

As the general synthetic rubber at this time, vulcanized rubber such as nitrile rubber, chloroprene rubber, butadiene rubber, urethane rubber, styrene rubber, butyl rubber, acrylic rubber, silicone rubber, ethylene rubber, and fluorine rubber, or urethane, polyester. , Thermoplastic elastomers such as polyamide, vinyl chloride, polybutadiene, and soft nylon, and liquid elastomers such as liquid urethane and liquid butadiene.

[0047]

In the syringe piston seal material according to the present invention, a part or the whole including the sliding surface thereof is a thermoplastic fluororesin as a first essential component, a fluororubber as a second essential component, and a third essential component. By forming it with a lubricious rubber composition consisting of a low molecular weight fluoropolymer, it has excellent wear resistance, low friction characteristics, heat resistance and sealability, and has excellent stability and reliability over a long period of time. Can be something. Therefore, since the initial piston movement, that is, the so-called static friction characteristic and dynamic friction characteristic, and the wear resistance characteristic are excellent, it is possible to obtain a piston seal material having a long life and excellent quantitativeness.

[0048]

1 is a sectional view of a syringe to which an embodiment of the present invention is applied.

In FIG. 1, the injector comprises a cylinder 1 and a piston 2, an extraction port 3 is formed at the tip of the cylinder 1, and the piston 2 is inserted from the other end side. A groove 4 is formed on the tip side of the piston 2 and an O-ring 5 is inserted therein. The O-ring 5 is formed of a lubricating rubber composed of a thermoplastic fluororesin as a first essential component, a fluororubber as a second essential component, and a low molecular weight fluoropolymer as a third essential component.

The raw materials used in Examples and Comparative Examples are collectively shown below. The mixing ratios of the respective components are all% by weight, but for the raw materials shown in (3) to (9), the total weight of the raw materials shown in (1) and (2) is 10
% By weight with respect to 0.

(1) Vinylidene fluoride / fluoropropylene copolymer (Technoflon FOR4 manufactured by Asahi Monte Corporation)
20) (2) Tetrafluoroethylene / ethylene copolymer
(Aflon COP manufactured by Asahi Glass Co., Ltd.) (3) Low molecular weight fluoropolymer (low molecular weight TFE)
(Lubricant L169 manufactured by Asahi Glass Co., Ltd.) (4) Low molecular weight fluoropolymer (low molecular weight PFPE)
(Japan Anymont Fomblin Z-DISO
C) (5) Carbon (MT carbon manufactured by Fadelbilt) (6) Sodium stearate (general industrial material) (7) Magnesium oxide (general reagent) (8) Calcium hydroxide (general reagent) (9) Phenolic resin (Kanebo) Belpearl H300) (10) Nitrile-butadiene copolymer (NBR)
(General industrial materials hardness JIS-A70) (11) Dimethyl silicone polymer (silicon rubber)
(General industrial material hardness JIS-A70) First, the fluororubber (1) was wound around a roll mixer having a roll interval of about 5 to 10 mm, and MT carbon, sodium stearate, and Mg were sequentially added at the ratios shown in Table 1.
O and Ca (OH) ₂ were added and kneaded. Then, the roll interval was adjusted to 1 mm, and mastication was performed about 10 times. For the purpose of preventing frictional heat at this time, cooling water was constantly passed through the roll to keep the roll temperature at 60 ° C or lower. Next, cooling water is stopped, steam is passed through the rolls, the rubber temperature is adjusted to 70 ° C or higher and 90 ° C or lower, and then the roll interval is returned to about 5 to 10 mm to obtain a low molecular weight fluoropolymer. Was added little by little and kneaded at the compounding ratio of each example shown in Table 1. After that, set the roll interval to 1 again.
It narrowed to mm and masticated 10 times.

[0052]

[Table 1]

In the compound obtained in the above steps, 150 × 150 × 1t sheet was subjected to primary vulcanization (170
It was manufactured by carrying out secondary vulcanization (230 ° C., 16 hours, free) at 10 ° C. for 10 minutes at a pressing pressure of 7 kgf / cm ² .
For each test piece, a friction test, an abrasion test, a non-stick property and an elastic body property were obtained. The method of each test is as follows.

Lubricating rubber compositions used in this invention were prepared and tested for friction and wear properties.

(1) Friction and wear test With respect to the obtained O-ring 5, the piston 2 as shown in FIG. 1 has a diameter of 12 mm, and the groove 4 is attached to an aluminum piston 2 having a diameter of 9.0 mm. The test was carried out against one cylinder of 12.5 mm aluminum cylinder. Measure the frictional force required to slide the cylinder 1, and reduce the speed to 5m.
The wear value was measured at the outer diameter of the O-ring 5 after reciprocating 1000 times at a stroke of 20 mm at m / sec. The results obtained are shown in Table 2.

(2) Non-adhesion In the obtained test piece, the contact angle to water was measured by a goniometer type contact angle measuring device, and it was judged that the larger the contact angle, the better the non-adhesiveness. The results are shown in Table 2.

(3) Elastic body property The obtained test piece is compliant with JIS-K6301,
The tensile strength, elongation, and hardness (JIS-A) were investigated. The results are shown in Table 2.

[0058]

[Table 2]

Comparative Example In the comparative example, the raw materials were blended in the proportions shown in Table 1, and kneading, molding and vulcanization were performed in the same manner as in the examples. In addition, the test pieces were adjusted and tested in exactly the same manner as in the examples. The results are shown in Table 2.

[Brief description of drawings]

FIG. 1 is a sectional view of a syringe to which an embodiment of the present invention is applied.

[Explanation of symbols]

 1 Cylinder 2 Piston 3 Extraction port 4 Groove 5 O-ring

Claims (7)

[Claims] 1. A syringe piston sealing material for industrial and medical use, wherein a part or the whole of a sliding portion is formed of a composition of a lubricating rubber, and the lubricating rubber composition is a first essential component. A certain thermoplastic fluororesin, a second essential component fluororubber, and a third essential component low molecular weight fluoropolymer,
Syringe piston seal material. 2. The syringe piston seal material according to claim 1, wherein a cured powder of a thermosetting resin or a heat resistant resin powder having a glass transition point of 300 ° C. or higher is added to the lubricating rubber composition. 3. The thermoplastic fluororesin as the first essential component is a tetrafluoroethylene / ethylene copolymer,
The syringe piston seal material according to claim 1, which is one or more selected from the group consisting of a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer. 4. The second essential component has a molecular weight of 100,0.
A fluororubber of from 00 to 250,000.
Syringe piston seal material. 5. The fluororubber which is the second essential component,
Group consisting of tetrafluoroethylene / propylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer, fluorosilicone copolymer and perfluoro-based copolymer The syringe piston seal material according to claim 1, which is one or more polymers selected from the group consisting of: 6. The low molecular weight fluoropolymer as the third essential component is selected from the group consisting of tetrafluoroethylene polymers having an average molecular weight of 50,000 or less, fluoropolyethers and polyfluoroalkyl group-containing compounds.
The syringe piston seal of claim 1 which is one or more polymers. 7. The syringe piston seal material according to claim 1, wherein the low molecular weight fluoropolymer which is the third essential component is a tetrafluoroethylene polymer having an average particle size of 5 μm or less.