JPH0751371A - Injection needle and its production method - Google Patents

Abstract

PURPOSE:To obtain an injection needle made of a synthetic resin material with hygienic, physical and chemical properties substitutable for a metallic needle and friendly to environment in disposal, by forming an injection needle using a synthetic resin composition with a specific value of Rockwell hardness (M method). CONSTITUTION:This injection needle is formed from a synthetic resin composition with a Rockwell hardness (M method) of 65 or higher. Here, the synthetic resin shall have a modulus of bending elasticity of 20,000kg/cm<2> or higher. The synthetic resin composition shall contain one or more selected from a group consisting of polyethersulfone, polysulfone, polyamideimide, polyetherimide, polyimide, polycarbonate, polyester, polyamide, polypropylene, polyarylate, polymethylpentene, modified (polyphenylene oxide) and liquid crystal polyester. Thus, a thin and sharp needle substitutable for a stainless steel can be realized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is attached to a syringe, an infusion solution or a blood transfusion instrument used for medical purposes to inject a medicinal solution into the skin, subcutaneous, intramuscular, intravenous or internal organs of the human body. The present invention relates to a needle or an injection needle as a device for pressurizing and passing a drug solution through the skin.

[0002]

2. Description of the Related Art Regarding the injection needle, since it was indicated in Japanese Industrial Standard JIS T3101 in 1950, the Ministry of Health and Welfare Notification No. 443 has a disposable injection needle standard and the Ministry of Health and Welfare Notification No. 412 has an injection needle standard. These standards are based on the quality and test method when stainless steel or nickel chromium is used as the material. Therefore, in the prior art, there are many proposals regarding the shape of the needle as an examination item of the injection needle, for example, the shape of the cutting edge of the injection needle (Japanese Patent Publication No.
1-328878, 52-1158, etc.), a blade edge grinder (Japanese Patent Publication No. 61-28472), an injection needle and a manufacturing method (Japanese Patent Publication No. 1-27749). Further, a technique for manufacturing an injection needle using ceramics as a material (for example, Japanese Patent Laid-Open Nos. 3-284264 and 3-193).
No. 061), and further, there is a technique for manufacturing an injection needle (Japanese Patent Laid-Open No. 3-295566) in which a synthetic resin is used as an internal material of the injection needle and the resin surface of the needle blade is ceramic-coated. Many techniques have been proposed for injection needles made of synthetic resin (for example, Japanese Utility Model Publication No. 49-283).
No. 91, No. 55-15853, No. 57-50044, Jikken 3-42930, Japanese Examined Patent Publication No. 52-41584, and Japanese Unexamined Patent Publication No.
8-130052, JP-A-59-34265. A technique using a synthetic resin as a material for an introduction needle different from an injection needle is disclosed in, for example, Japanese Patent Laid-Open No. 59-905.
No. 64, No. 59-91968, No. 62-221368, No. 62-266077, and No. 63-288170. Further, as a method of manufacturing an injection needle made of a synthetic resin, there is a method proposed in Japanese Patent Publication No. 3-60511.

[0003]

In recent years, it has become difficult to dispose of used stainless steel injection needles in a sanitary and safe manner. Materials other than the above-mentioned metals,
In particular, an injection needle using a synthetic resin has attracted attention. However, all of the above technologies related to synthetic resin injection needles are aimed at manufacturing methods as industrial products, and the physical properties of the products, which have a great impact on hygiene, have passed various regulations as medical devices. It was not a problem in terms of producing what was obtained. INDUSTRIAL APPLICABILITY The present invention is an injection needle made of a synthetic resin, which has hygienic properties, physical properties, and chemical performance that can replace conventional metal injection needles, and is eco-friendly even when discarded. It is what

[0004]

The present invention which can solve the above problems relates to an injection needle made of a synthetic resin composition having a Rockwell hardness (M method) of 65 or more. In the injection needle of the present invention, the synthetic resin composition has a flexural modulus of 20,000 kg / c.
Particularly preferred is m ² or more, and preferred examples of the synthetic resin composition of the present invention include polyether sulfone, polysulfone, polyamide imide, polyether imide, polyimide, polycarbonate, polyester, polyamide, polypropylene, poly Examples thereof include those containing at least one selected from the group consisting of arylate, polymethylpentene, modified phenylene oxide, and liquid crystal polyester. The present invention also provides a method for manufacturing an injection needle, which has a Rockwell hardness (M
The method is characterized in that 65 or more synthetic resin compositions are kneaded and melted, and then the resin compositions are injection-molded into a needle mold. In the manufacturing method of the present invention, Rockwell hardness (M method) 65
The synthetic resin composition is kneaded and melted, and then the resin composition is injection-molded into a needle mold to obtain a molded product, and the needle tube portion of the molded article is stretched, and then the stretched portion is cut by a water jet method. By forming the injection needle tip blade by doing so, a sharp needle blade sharpness can be obtained.

[0005]

The present invention provides a thin tubular needle (hereinafter referred to as an injection needle) having a sharp tip blade suitable for use in intradermal, subcutaneous, intravenous, intraorganic, transfusion transfusion administration of drugs and the like to humans or animals. 2) to 6) or a needle having the shape shown in FIG. 6 for ejecting a drug solution and administering it into the skin. As an injection needle of such a shape, a prescribed amount of medicine,
Occasionally, when giving a large amount of liquid medicine or nutritional supplement to a patient, discomfort, pain, bleeding, occurrence of scratches, scars, etc. are minimized,
What can be promptly and hygienically administered is required. The injection needle of the present invention satisfying the above-mentioned essential requirements of the injection needle has a thin tube formed of a strong material even if it is made of synthetic resin,
It is an injection needle that has a sharp cutting edge and has good sharpness, and can be sanitarily sterilized by high-pressure steam sterilization, γ-ray (Co ₆₀ ) sterilization, gas (for example, ethylene oxide) sterilization. That is, in order to satisfy the above conditions, a synthetic resin composition that can form a thin, strong, and sharp blade is selected and molded, and the hardness of the synthetic resin composition is a Rockwell hardness (M method) as a guide at that time. The present inventors have found that a thin and strong tube and a sharp cutting edge can be formed as long as the condition (1) of 65) or more is satisfied, and the present invention has been achieved. Furthermore, the present inventors have developed a manufacturing method for obtaining a sharp cutting edge with extremely good sharpness by means of stretching a tube portion corresponding to an injection tube of a synthetic resin composition and then cutting it by a water jet method.

The hardness test method includes indentation hardness (Brinell hardness, Vickers hardness, Rockwell hardness H
R: Durometer hardness, JIS hardness, Barcol hardness), scratch hardness (Martens method, Beer Bam method),
There are many types such as scratch hardness (Mantels method, Biabum method), repulsion hardness, pendulum hardness (Shore hardness, Herbert hardness), but they are widely used in synthetic resin products and have relatively high measurement accuracy. Uses Rockwell hardness. In other words, with a JIS B7726 hardness tester, JISK69
11, JIS K7202, HRM hardness symbol (abbreviated as M method), standard load W ₁ 10 kg, test load W ₂ 10
It is a method in which the resin surface is pressed using 0 kg and the depth of the depression is used as a scale. (H _R = 130-500h, h
= The difference between the depression depths). The value of the Rockwell hardness M method referred to in the present invention is the test piece (thickness 6 m with the synthetic resin composition.
m, width 13 mm, area 25 mm ² ) was prepared, and the test piece was allowed to stand at room temperature (20 ± 3 ° C.) for 8 hours or more, and was an average value measured twice or more. Rockwell hardness is 1
When it is 30 or more, the measurement accuracy is deteriorated, and even if the kind, the composition and the amount of the synthetic resin are selected, the measurement value cannot be clearly reflected. This is because the indentation depth of the resin is measured by press-fitting a steel ball indenter and the indentation depth becomes smaller when the resin becomes harder, resulting in a decrease in accuracy. It was found that when the hardness measurement value is 65 or less, the bending elasticity value of the injection needle is small, the synthetic resin composition does not have heat resistance, and the sharpness of the blade edge disappears during high-pressure steam sterilization. That is, the Rockwell hardness of the injection needle of the present invention is particularly preferably 65 or more, particularly preferably 85 or more. However, it was found that the Rockwell hardness and the sharpness (sharpness) of the needle blade do not necessarily have a correlation. That is, although the hardness is limited to 65 or more in the present invention, the sharpness of the obtained needle tip may be unsatisfactory even if the hardness is 65 or more depending on the type of synthetic resin and the type of reinforcing agent. Further, the injection needle of the present invention preferably has a bending elastic modulus of 20,000 kg / cm ² or more, which is measured according to the bending elastic modulus test method for stainless steel needles of JIS T3101-1990.
It is more preferably 50,000 kg / cm ² or more, still more preferably 100,000 kg / cm ² . According to the present invention, JIS is a standard for stainless steel needles so that even synthetic resin needles have the same or higher performance as stainless steel needles.
It has strength and flexural modulus that fall within the specified values of T3101.

The synthetic resin composition according to the present invention will be specifically described below. Rockwell hardness of the present invention (M method)
The resin composition of 65 or more can be realized by blending a reinforcing agent and the like with a synthetic resin suitable for injection needle materials. Examples of the synthetic resin include polysulfone, polyether sulfone, polyamideimide, polyetherimide, liquid crystal polyester polyimide, polycarbonate, polyester, polyamide, polymethylpentene, polypropylene (abbreviated as PP), and polyacrylate (abbreviated as PAR). ,
One or more selected from the group consisting of modified phenylene oxide is preferred. These synthetic resins are excellent in high softening point, heat resistance, chemical resistance and physical properties,
Although known as engineering plastics, a high molecular weight synthetic resin produced using a catalyst having a high degree of activity and a synthetic resin having a high molecular orientation and high crystallinity are suitable for the use of the present invention. . Although various commercially available resins can be used, it should be noted that some commercially available products do not have the hardness applicable to needles such as PP and PAR. It goes without saying that these synthetic resins can be used in various forms such as powder and flakes.

The hardness of the synthetic resin composition of 65 or more can be easily achieved by adding a large amount of the reinforcing agent of about 80 parts by weight or more to 100 parts by weight of the synthetic resin. The amount of the agent is preferably 70 parts by weight or less. As a preferred reinforcing agent used in the synthetic resin composition according to the present invention, for example, glass fibers, carbon fibers, aramid fibers, alumina fibers, zirconia fibers, thin short fibers such as potassium titanate whiskers, white carbon, kaolin, mica, Inorganic compounds such as anhydrous mica, diatomaceous earth, magnesium oxide, talc, activated clay, and zinc white may be mentioned, and these reinforcing agents may be untreated, but silane coupling agents such as γ-glycidoxypropyltris Methoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, epoxyethyltriethoxysilane, isopropyltristearoyl titanate, tetraisopropylbis (dioctylphosphite) titanate, a Propyl trioctanoyl titanate it may be one which has been surface treated with isopropyl isostearoyl diacryl titanate. For the above-mentioned reason, the compounding amount is preferably 0 to 70 parts by weight based on 100 parts by weight of the synthetic resin.

The processing aids in the synthetic resin composition according to the present invention include waxes, ultra high molecular weight polyethylene,
Polypropylene wax, homologues with a large number of carbon atoms (for example, arachidic acid, behenic acid, etc.), metal soaps (for example, calcium stearate, etc.), fatty acid amides (for example, stearic acid amide, styrenebisstearylamide, etc.),
Fatty acid ester (for example, long-chain fatty acid ester), silicone oil, fluorine oil and the like are used as synthetic resin composition 100
0 to 4 parts by weight can be added to parts by weight. If it exceeds 4 parts by weight, hygiene will be deteriorated.

Examples of the nucleating agent of the synthetic resin according to the present invention include sorbitols (eg, di (benzylidene) sorbitol, di (p-methylbenzylidene) sorbitol, etc.), aluminum hydroxy-di-t-butylbenzoate, polyalkenylsilane, 2,2-methylenebis (2,6-di-t-butylphenyl) sodium phosphate, aluminum hydroxy-bis (t-butylphenyl) phosphate, etc. are added in an amount of 0 to 2 parts by weight per 100 parts by weight of the synthetic resin. be able to. If it is added in excess of 2 parts by weight, it bleeds to the surface of the product, resulting in poor hygiene.

The synthetic resin composition according to the present invention contains, for example, 2,6, di-t-butylhydroxytoluene (BHT), octadecyl-3- (4 ') as an antioxidant and a stabilizer.
-Hydroxy-3 ', 5'-di-t-butylphenyl)
Propionate (product name Irganox 1076, manufactured by Ciba Geigy), tetrakis [methylene (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name Irganox 1010, manufactured by Ciba-Geigy Co., Ltd.), 4,4′-thiobis (6-t-butyl-m-cresol), triethylene glycol -Bis-3 (2-t-butyl-4-hydroxy-5-methylphenyl) propionate, distearyl-thio-dipropionate, pentaerythritol tetrakis (β-lauryl-thio-propionate), 2,5-di-t -Butyl-hydroxybenzyl phosphonic acid monoethyl ester Ca salt (trade name: Irganox 1425, manufactured by Ciba Geigy Co., Ltd.) and the like were added in an amount of 0.
05 to 1 part by weight can be added.

A composition prepared by mixing the above-mentioned compounding agents with a powdery or flake-like synthetic resin material is kneaded and mixed at a temperature of 200 to 350 ° C. under a nitrogen atmosphere in a closed container, and then made into an injection needle type by a known technique. Injection molding. When injection molding is performed using the synthetic resin material of the present invention, by incorporating a needle tube stretching step in the molding step, the polymer array can be made long and regular, and therefore, an injection needle excellent in rigidity and hardness. Can be obtained. Further, in the present invention, the hardness of the needle surface can be increased by irradiating the needle surface with γ-rays and electron beams in the final step after injection needle molding. In addition, the effect of sterilizing the needle surface and polishing the needle blade (increasing the sharpness) can also be obtained by this treatment.

As a method of sharpening the blade, which is one of the features of the present invention, a so-called water jet method is used as the cutting means for molding the synthetic resin composition and then cutting the needle tube portion to form the blade tip. it can. And the water knife method, about 1000~6000kgf / cm ^2, preferably high pressure water 1000~5000kgf / cm ^2, an ultra high pressure water diameter 0.1~0.5mm preferably about 0.1~0.3mm It is a method of ejecting from an ultrafine nozzle and cutting by the impact action of this jet. According to this method, a needle tip type such as a so-called regular type shown in FIGS. 2 and 3 and a so-called short type shown in FIGS. 4 and 5, an intradermal injection needle type, a bubber type, or any other type of needle. The inventors have found that the angle of the cutting edge can be freely changed, and an injection needle with a thin needle tip and good sharpness can be manufactured even if it is made of a synthetic resin. As a concrete shape of the injection needle injection-molded using the synthetic resin of the present invention, not only the above-mentioned conventional shape but also two or more thin passages through the skin as shown in FIG. A preferable example is a spout device that penetrates into the body from above the skin.

[0014]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention should not be limited to these examples. [Example 1: Polyester resin (PET, PBT, etc.)] PBT (manufactured by Teijin Ltd., Teijin PBTC-7000)
N (trade name) intrinsic viscosity [η] 1.15) 100 parts by weight,
Polypropylene (J-209, manufactured by Tonen Petrochemical Co., Ltd.)
Trade name, MFR 3.5 g / 10 minutes, 230 ° C.) 10 parts by weight, p-t-butylaluminum benzoate 0.3 parts by weight, activated clay 10 parts by weight, glycerol monostearate ester 1 part by weight. , BHT (0.5 parts by weight) was dry blended with a Henschel mixer, and then kneaded with a twin-screw extruder at 240 ± 10 ° C. and 250 rpm to form the injection needle mold of FIG. Further, a part thereof was molded into a plate-shaped test piece for a hardness measurement test. The hardness of the molded test piece is JISK
7202, the result measured by scale M (abbreviated as hardness M method) is 82, and then the bending elastic modulus is determined by JISK6911 (AS
The result measured according to TMD790) is 32,000.
It was kg / cm ² . The injection needle was stretched to a specified value with an outer diameter of 0.7 mm, and a needle blade was formed at a water blade pressure of 4000 kg / cm ² , a nozzle diameter of 0.2 mm, and a water flow rate of 1.4 liters / minute at a needle blade angle of 12 °. Measure the sharpness of the needle tip according to JIST3101-19
It carried out according to 90 test methods. That is, 0.0
The load of gently contacting the surface of an aluminum foil having a thickness of 2 mm with a load applied gently and piercing and cutting was measured with an autograph (manufactured by Shimadzu Corporation). As a result of testing the three needles twice, the maximum load value was 12.3 g. As another test, an elasticity test based on the elasticity test of the injection needle of JIS T3101-1990, that is, the injection needle is fixed and held horizontally with one point A on the needle base side as a fulcrum, and a load is applied to the needle blade tip. 12 from the horizontal position downward
Bend to 0 °, hold for 1 minute, then let go, and visually inspect to return to original position. Furthermore, no abnormality was found in the inner and outer surface inspection, that is, by visually observing the coloring of the liquid by immersing the needle in the glycerin liquid. Similar results were obtained for the above composition in which glycerol monostearate was changed to glycerol distearate.

[Example 1-2: Polyethylene terephthalate resin (PET)] 100 parts by weight of PET (ESMO5030, trade name, manufactured by Kuraray Co., Ltd., containing 30% of glass fiber), Na salt of ethylene / methacrylic acid copolymer (Himilan 1707, trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 10 parts by weight, Hoechst wax E (trade name,
1 part by weight of Hoechst Co., Ltd., 2 parts by weight of polyethylene glycol diglycyl ether, and 0.3 parts by weight of an antioxidant (Irganox 1010, trade name), and the above raw materials were treated in the same manner as in Example 1-1. To form a test plate. The synthetic resin thus obtained has a hardness M105 and a flexural modulus of 110,0.
It was 00 kg / cm ² . Next, an injection needle was once molded in the same manner as in Example 1, the needle tube was stretched to a predetermined diameter, and the blade edge was cut by a water jet method to mold the shape as shown in FIG. As a result of measuring the sharpness of the needle in the same manner as in Example 1, a load of 1
It was 3.8 g.

[Example 1-3: Ester complex] 4,
187 g of 4'-diacetoxydiphenyl, 144 g of 4-acetoxybenzoic acid, 100 g of terephthalic acid and 0.4 g of sodium acetate were charged, and the mixture was evacuated with nitrogen and replaced with nitrogen under stirring at 240 ° C for 20 minutes at 260 ° C for 45 minutes at 290 ° C. The temperature is maintained at 320 ° C. for 35 minutes to distill off acetic acid, and the polymerization reaction is performed at a vacuum degree of about 10 Torr for 20 minutes. After cooling, wash with warm methanol solution, BHT 0.5
Parts by weight were added and dried. Based on 100 parts by weight of the synthetic resin, an ethylene / propylene copolymer resin (JISEPO
1, trade name, manufactured by Japan Synthetic Rubber Co., Ltd. 5 parts by weight, Riquemar S-900 (trade name, manufactured by Riken Vitamin Oil Co., Ltd.)
1.5 parts by weight were kneaded at a temperature of 250 to 270 ° C., a test plate and an injection needle were molded in the same manner as in Example 1-1, and the obtained product was similarly tested. As a result, hardness (M method)
Was 98 and the flexural modulus was 72,000 kg / cm ² . The sharpness of the tip of the injection needle was 11.3 g load.

[Examples 2-1 to 2-6: Polyamide Resin (PA)] PA is a crystalline linear polymer resin having an acid amide bond —CONH— as a main chain, such as ε-caprolactam. Ring-opening polymerization, hexamethylenediamine, metaxylenediamine, a condensation product of diaminobutane and adipic acid, sebacic acid, dicarboxylic acid, and a condensation polymerization product of 11-aminoundecanoic acid. Table 1 shows blending compositions in which various PAs and additives are combined. The compounding operation, processing, injection needle molding, and needle blade testing method were the same as in Example 1-1. The test results are also shown in Table 1. Unless otherwise noted, each of the following formulations means parts by weight.

[0018]

[Table 1]

The notes in Table 1 mean the following: 1) Condensation product of hexamethylenediamine and adipic acid, polyamide MXD6 (trade name), manufactured by Mitsubishi Gas Chemical Co., Inc. 2) PET, KS700YT (trade name), Kuraray Co., Ltd.
Made. 3) Modified grafted polyolefin, MODIPER A41
00 (trade name), manufactured by NOF CORPORATION. 4) Potassium titanate whiskers, diameter 0.3 μm, length 1
0 μm, Tismo D (trade name), manufactured by Otsuka Chemical Co., Ltd. 5) Ethylenebisstearylamide, Lubron E (trade name), manufactured by Nippon Kasei Co., Ltd. 6) Irganox 1010 (trade name), manufactured by Ciba Geigy. 7) Product treated with Polyamide 6 and 0.5% by weight of titanium coupling agent, Plascon 8203 (trade name) manufactured by Allied Chemical Co., Ltd. 8) PA, Ultramit A-3 (trade name), manufactured by Birdish Aniline Co., Ltd. 9) Glass fiber reinforced polyphthalamide resin, AMOD
EL (trade name), manufactured by Acomo Japan Co., Ltd. 10) Ultra-high molecular weight polyethylene powder, Hi-Zex Million (trade name), manufactured by Mitsui Petrochemical Industry Co., Ltd.

[Examples 3-1 to 3-3: Polyamideimide resin (PAI), polyimide resin (PI) and polyetherimide resin (PEI)] All of PAI and PI known as heat resistant resins Table 2 shows the compounding composition suitable for the injection needle of the present invention from PEI. An injection needle was molded in the same manner as in Example 1-1 with the blended composition,
The test was conducted similarly. The results are also shown in Table 2.

[0021]

[Table 2]

The notes in Table 2 mean the following: 6) is as described above. 6) Irganox 1010 (trade name). 11) PAI, Torlon 4203L (trade name), manufactured by Acomo Engineering Co., Ltd. 12) PI, AURUM450 (trade name), manufactured by Mitsui Toatsu Chemicals, Inc. 13) PEI, an amorphous homopolymer, Ultem 100
0 (trade name), manufactured by GE Plastics Co., Ltd. 14) γ-glycidoxypropyltrimethoxysilane, S
H6040 (trade name), manufactured by Toray Silicon Co., Ltd. 15) Silicon oil, TSF433 (trade name), manufactured by Toshiba Silicone Co., Ltd. 16) This is a product in which an injection needle was molded by the water jet method and then heat-treated at a temperature of 260 ° C for 24 hours.

[Examples 4-1 and 4-2: Polycarbonate] A polymer resin body is (--O--R--O--CO--).
A resin body made of bisphenol, diallyl carbonate, or the like as a raw material with a dioxy compound represented by _n , and having an average molecular weight of about 50,000 to 100,000. The resin body was molded into a resin composition suitable for the performance of an injection needle. Composition and Example 1-1
The results of the post-molding test conducted in the same manner as in Table 3 are shown in Table 3.

[0024]

[Table 3]

The notes in Table 3 mean the following: 6),
14) is the same as above. 6) Irganox 1010 14) γ-glycidoxypropyltrimethoxysilane 17) TAFRON SC-160 (trade name), manufactured by Idemitsu Petrochemical Co., Ltd. 18) Glass fiber, diameter 13 μm, length 3 mm, aminosilane treated product, 03MA409C (trade name), manufactured by Asahi Fiber Glass Co., Ltd. 19) Ethylene-ethylene acrylate resin, NUC65
70 (trade name), manufactured by Nippon Unica Co., Ltd.

[Examples 5-1 to 5-6: Polysulfone (PSF) Polyethersulfone (PES)] A polymer resin in which an aromatic ring is bonded with a —SO ₂ group, or an aromatic ring and Commercially available PSF and PES, which are polymer resin bodies having SO ₂ groups and an amount of ether bonds, were prepared by the formulation shown in Table 4 so as to obtain a composition suitable for the injection needle of the present invention. The compounded composition was kneaded at 300 to 320 ° C., injection-molded at a temperature of 250 to 330 ° C. in a closed nitrogen atmosphere, and tested by the same test method as in Example 1-1. The test results are also shown in Table 4.
Are shown together with.

[0027]

[Table 4]

The notes in Table 3 mean the following: 4) is the same as above. 4) Potassium titanate whiskers 20) PSF: Udel P-1700 (trade name), manufactured by Acomo Engineering Plastics Co., Ltd. 21) PES: VICTREX4800G (trade name), manufactured by Mitsui Toatsu Chemicals, Inc. 22) Zinhua: Zinhua S (trade name), manufactured by Sakai Chemical Co., Ltd. 23) Ethylenebisstearic acid amide. 24) Titanium oxide: manufactured by Sakai Chemical Co., Ltd. 25) Irganox 1425 (trade name), manufactured by Ciba Geigy. 26) Fluorine resin: Polyflon TEF (trade name), manufactured by Daikin Industries, Ltd.

[Example 6-1 and Example 6-2: Polymethylpentene (TPX)] Polymethylpentene: Melt flow rate TPX (trade name), Mitsui Toatsu Chemicals, Inc.
Example 1-1 was prepared by kneading a composition having an intrinsic viscosity [η] of 3.4 l / g and a melting point of 240 ° C) with the compounding agents shown in Table 5 added.
It was similarly injection-molded and similarly tested. The test results are summarized in Table 5.

[0030]

[Table 5]

The notes in Table 5 mean the following: Four),
6), 16), 18) are as described above. 4) Potassium titanate whiskers. 6) Irganox 1010 (trade name). 18) Glass fiber. 27) Polymethylpentene 28) PC: Panlite L-1250 (trade name), 4,4'-dioxydiphenylalkane-based resin manufactured by Teijin Chemicals Ltd. 29) Activated zinc flower: manufactured by Sakai Chemical Co., Ltd. 30) Zinc stearate.

[Example 7-1: Polyphenylene ether (PEE)] 100 parts by weight of poly (dimethylphenylene) ether (manufactured by Mitsubishi Yuka Co., Ltd., purified with acetone), styrene-maleic anhydride copolymer (commercial product) Name Diler 2
32, manufactured by Alcopolymer Co., Ltd., 20 parts by weight of maleic anhydride content 8% by weight, 30 parts by weight of graft PP (product containing 2.3% by weight of glycidyl methacrylate), Irga
0.5 parts by weight of phasPEPQ (trade name, anti-aging agent, manufactured by Ciba-Geigy Co., Ltd.) and 2 parts by weight of calcium stearate are mixed in a predetermined amount of the above, and the temperature is 250 to 250 in a Lapoplast mill kneader (manufactured by Toyo Seiki Seisakusho). The mixture was kneaded at 280 ° C, and injection-molded into a mold of an injection needle at 100 to 120 ° C. The hardness of the molded resin was measured according to JIS K6911, Rockwell hardness test method, and was 69 by M method.
The flexural modulus of JIS K6911 is 23,000 kg / c.
It was m ² . The needle tube of the injection needle was drawn to the prescribed size of JIST3101, and the needle blade was cut by the water jet method. Water pressure 3,800 kg / cm ² , jet nozzle diameter 0.2 mm
The injection needle blade was shaped into the shape shown in FIG. The sharpness test of the needle blade is based on JIST3101, and the load that the injection needle penetrates into 0.02 mm thick aluminum paper is determined by Autograph-10.
It was measured at 0 (manufactured by Shimadzu Corporation). The measurement was performed by averaging the highest measured values of three needles. The result was 15.3 g.

Example 7-2: PPE Poly (2,6-
Dimethyl phenylene) ether (manufactured by Mitsui Petrochemical Industry Co., Ltd., 100 parts by weight of intrinsic viscosity [η] 0.47 dl / g in chloroform at 30 ° C.), cyclic olefin resin (trade name ZEONEX 280, Nippon Zeon Co., Ltd.)
15 parts by weight, silane-treated clay (trade name Nuca)
p290, J. M. Huber) 30 parts by weight, calcium stearylate 1.5 parts by weight and Irgaph
0.3 part by weight of asPEPQ was kneaded in the same manner as in Example 7-1 to prepare a needle-shaped molded product and a test plate, and Example 7-1.
As a result of the same test as described above, the hardness of the synthetic resin is 70 by the M method,
The flexural modulus was 26,000 kg / cm ² . Next, the blade of the injection needle was cut by the water jet method in the same manner as in Example 7-1 and molded, and as a result, the sharpness of the needle blade was 16.2 g under a load.

Example 8-1: Polyarylate (Polymer Resin Having Ketone Group and Ether Group) A polymer resin body containing a ketone group and an ether group, in which the higher the content of the ketone group, the higher the heat resistance. PEK as having polyarylate
(Product name, manufactured by ICI, glass transition point 162 ° C to DSC
Method) 100 parts by weight of silicone oil (trade name T
After tri-blending 0.5 part by weight of SF433, manufactured by Toshiba Silicone Co., Ltd., melting and kneading at about 200 ° C.,
It was injected and molded into an injection needle mold and a test piece. Example 7-1
As a result of the same test, the hardness was 100 by the M method and the flexural modulus was 36,000 kg / cm ² . The injection needle was adjusted to a specified size and then the tip of the needle was molded by the water jet method. The sharpness of the needle blade was measured and the load was 12.3 g.

[Example 8-2: Polyarylate] When the triblending of Example 8-1 was performed, potassium titanate fibers (HT-manufactured by Titanium Industry Co., Ltd.) were added to the blend of Example 8-1.
200, fiber diameter 0.5 μm, length 20 μm) was mixed in an amount of 30 parts by weight, and the same operation as in Example 8-1 was performed.
The hardness of synthetic resin is 112 by M method, and the flexural modulus is 92,0.
It was 00 kg / cm ² . The sharpness of the tip of the molded injection needle was a load of 11.2 g.

[Example 8-3: Polyarylate] 100 parts by weight of PEK (same as in Example 8-1) as a polyarylate, an aromatic polyester resin (trade name Econol E1)
Example 7-1: 01-S, 10 parts by weight of Sumitomo Chemical Co., Ltd., 15 parts by weight of polyetherimide resin (trade name: Ultem 100, manufactured by General Electric Co., Ltd.) and 1.5 parts by weight of zinc stearate. The mixture was mixed in the same manner as described above, and the same operation as described below was performed to form an injection needle, and the blade sharpness of the needle was measured. Hardness (M method) 106, flexural modulus
87,000kg / cm ^2, of the needle tip sharpness load 12.1g.

[Examples 9-1 to 9-3: Polyarylate] Among engineering plastics, many kinds of synthetic resins having an ether group, a ketone group, and an ester group have been proposed. Using U polymer U-100 (trade name, manufactured by Unitika Ltd.) as a representative example, the resin compositions shown in Table 6 were prepared and molded and tested in the same manner as in Example 7-1. The results are also shown in Table 6.

[0038]

[Table 6]

The notes in Table 6 mean the following: a) White carpon: (Nipseal ER, manufactured by Taki Chemical Co., Ltd.). b) Activated zinc flower: manufactured by Honjo Chemical Industry Co., Ltd. c) Irganox 1010: trade name, manufactured by Ciba Geigy. d) Fatty acids and fatty acid esters having 24 to 34 carbon atoms. e) Aramid fiber: Kepler 49 (trade name, manufactured by DuPont). f) Vectra A130 (trade name), a liquid crystal polymer manufactured by Polyplastics Co., Ltd., mixed with 30 parts by weight of glass fiber.

[Example 10-1: Polypropylene resin (PP)] Propylene was added to an autoclave equipped with a stirrer in an amount of 0.
Adjust the pressure to 5 kg / cm ² , n-heptane, (C ₂ H ₅ ) ₂ Al
(OBu) _0.3 Cl _0.3 [OBu represents a butoxy group], di-n-butyl ether and TiCl ₄ were added as a solid catalyst, and propylene 6 was added at a temperature of 60 ° C.
The pressure is increased to kg / cm ^{2 and the} pressure is kept constant to carry out polymerization for 5 hours. Butyl alcohol is added to the polymer to terminate the polymerization, and the resin body is separated after washing with warm water. 0.3 parts by weight of Irganox 1010 (trade name, manufactured by Ciba-Geigy Co., Ltd.), 0.5 parts by weight of calcium stearate, and 0.5 parts by weight of di (benzylidene) sorbitol per 100 parts by weight of the dry resin.
5 parts by weight were added. Weight average molecular weight (Mw) of resin /
Ratio of number average molecular weight (Mn): 14, resin density (d): 0.911, hardness measurement of resin was 70 by M method in the same manner as in Example 7-1, flexural modulus of 23,000 kg / cm ^2.
Met. The sharpness of the molded injection needle was measured in the same manner as in Example 7-1 and the load was 15.2 g.

[Example 10-2: Polypropylene resin (PP)] The injection needle molded in Example 10-1 was subjected to electron irradiation in a nitrogen gas atmosphere with an electron beam irradiation device (manufactured by Nisshin High-Portage Co., Ltd.). 5 printing original lines for photolithography
After irradiation with Mrad, the sharpness of the injection needle was measured in the same manner as in Example 10-1, and as a result, the load was 13.5 g, which is an improvement of about 10%.

Example 10-3: Polypropylene Resin (PP) The synthetic resin composition of Example 10-1 was molded into a thick shape with an injection needle having a diameter of 7 mm. The needle tube of the injection needle was dipped in a triethylene glycol solution having a temperature of 110 ° C. to make a 0.1.
After the needle tube was stretched at a speed of 5 m / min, it was cut into a prescribed injection needle length by the water jet method and the needle blade (Fig.
Shape). The sharpness of the needle tip of the injection needle obtained in this example was 12.8 g, which was extremely improved.

[Example 10-4: Polypropylene resin (PP)] Modified polypropylene resin (grafted with 0.56% by weight of maleic anhydride, Tokuyama Soda Co., Ltd.)
Parts), a polymer resin in which propylene is blocked with ethylene (trade name BJ4H, manufactured by MFR3 /
10 minutes, 230 ° C (Measurement method: JISK6758)) 38
Parts by weight, glass fiber (made by Asahi Fiber Glass, diameter 3μ
m, length 15 μm) 16 parts by weight, anti-aging agent Irganox 1010 (trade name) 0.3 parts by weight, and γ-glycidoxypropyltrimethoxysilane 3 parts by weight are kneaded in a closed mixer to give about 180 It was melted to ˜200 ° C. and injection molded in a needle (FIG. 1) mold. The hardness, bending elastic modulus, and sharpness of the needle blade of the molded synthetic resin were measured in the same manner as in Example 7-1. As a result, the hardness M method 82, the bending elastic modulus 54,000.
It was kg / cm ² and needle blade sharpness load was 14.2 g.

[Examples 10-5 to 10-3: Polypropylene resin (PP)] Polypropylene (trade name, Nisseki Polypro J180Y, manufactured by Nippon Petrochemical Industry Co., Ltd., M
FR 50 g / 10 min) 100 parts by weight, carbon fiber (trade name Best Fight UM-68, diameter 4.7 μm, manufactured by Toho Rayon Co., Ltd.) and the like were kneaded in the composition shown in Table 7. The compounding operation, the molding of the test piece and the injection needle, and the tests of the molded injection needle were the same as in Example 7-1. The results are also shown in Table 7.

[0045]

[Table 7]

The notes in Table 7 mean the following: g) Irganox 1010: trade name, manufactured by Ciba Geigy. h) Pentaerythritol stearate: manufactured by Kao Yushi Co., Ltd. i) Talc: Mistron Vapor (trade name),
Made by Cyplus Ind.

[Comparative Example] A comparative test was carried out using a typical commercially available resin. [Comparative Example A: Polyvinyl chloride resin] Polyvinyl chloride resin (trade name: ZEON 103EP8, ZEON CORPORATION)
100 parts by weight, Stabilizer (Ca-Ba-Zn stearate mixed molten product) 4 parts by weight, calcium carbonate 60
Example 3 A mixture of 3 parts by weight of an epoxy plasticizer and 3 parts by weight of Example 7
An injection needle was molded in the same manner as -1. Hardness of molded product M method 6
4. The flexural modulus was 18,000 kg / cm ² . Example 7
Like -1, mold the needle blade by the water jet method,
As a result of measuring the sharpness of the needle blade, it was inferior to the products of Examples of the present invention having a load of 18.7 g. Such sharpness causes scratches when placed in the skin, and also causes discomfort to the recipient.

[Comparative Example B: Polyethylene resin (PE)]
PE (Brand name Hi-Zex 5100B, manufactured by Mitsui Petrochemical Co., Ltd., MFR 0.25 g / sufficient) 100 parts by weight, Irganox 1010 0.3 wt%, surface treated clay (Brand name, Nucap200L, manufactured by JM Huber) ) 60 parts by weight was blended, and an injection needle was molded in the same manner as in Example 7-1 to perform a test. As a result, the synthetic resin had a hardness of M 62 and a flexural modulus of 12,000 kg / cm ² . The sharpness of the product formed by cutting the injection needle by the water jet method had a load of 19 g, but the product cut with a rotating carbon steel blade had a load of 20.0 g or more. In addition, CO ₂ laser, output 500W, frequency 10
The sharpness of the needle tip formed by cutting with a laser of ~ 10,000 Hz had a load of 20.0 g or more.

[Comparative Example C: Other Resins] Resins such as ethylene / vinyl acetate resin, vinylidene chloride resin, butadiene resin polystyrene resin, polyvinyl alcohol, etc. are too soft as the material of the present invention and may be deformed by high-pressure steam sterilization. However, it was unsuitable for hygiene and characteristics as an injection needle, such as water absorbability and dimensional change.

[0050]

As described above, according to the present invention, the hardness of the resin composition is adjusted to Rockwell M by selecting the synthetic resin suitable for the characteristics of the injection needle and adding the reinforcing material and the processing aid to the synthetic resin. By adopting the method of 65 or more, it was possible to realize what can be practically used as a synthetic resin injection needle. In particular, according to the manufacturing method of the present invention in which the needle tip is formed by cutting the needle tube after drawing by a water jet method, a synthetic resin injection needle having a sharp cutting edge is manufactured with high productivity. be able to. Therefore, according to the present invention, it is possible to realize a thin, strong, yet sharp needle blade that can replace stainless steel. The injection needle of the present invention is made of synthetic resin and can be incinerated after use, so that it can be discarded. In addition, the method of manufacturing the injection needle of the present invention can be simplified and is highly productive and economically advantageous.

[Brief description of drawings]

FIG. 1 is a schematic sectional view illustrating an embodiment of the present invention.

FIG. 2 is a front view of a cutting edge regular of the injection needle of the present invention.

FIG. 3 is a side view of the cutting edge of FIG.

FIG. 4 is a front view of a cutting edge short circuit of the present invention.

5 is a side view of the cutting edge of FIG. 4. FIG.

FIG. 6 is a partial cross-sectional view showing a tubular main body injection head portion of the needleless hypodermic injection device of the present invention.

[Explanation of symbols]

 1 injection needle 2 cutting edge 3 needle tube 4 needle base 5 cutting surface 6 inclined surface 7 needle hole (liquid passage hole)

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Claims (5)

[Claims] 1. An injection needle made of a synthetic resin composition having a Rockwell hardness (M method) of 65 or more. 2. The flexural modulus of elasticity of the synthetic resin composition is 20,
The injection needle according to claim 1, which has a weight of 000 kg / cm ² or more. 3. The synthetic resin composition comprises polyethersulfone, polysulfone, polyamideimide, polyetherimide, polyimide, polycarbonate, polyester, polyamide, polypropylene, polyarylate, polymethylpentene, modified phenylene oxide and liquid crystal polyester. The injection needle according to claim 1 or 2, which comprises one or more selected from a group. 4. A method for producing an injection needle, which comprises kneading a synthetic resin composition having a Rockwell hardness (M method) of 65 or more, melting the resin composition, and injection-molding the resin composition into a needle mold. 5. A needle tube portion of a molded product obtained by kneading and melting a synthetic resin composition having a Rockwell hardness (M method) of 65 or more and then injection-molding the resin composition into a needle mold. The method for producing an injection needle according to claim 4, wherein the injection needle tip blade is formed by processing and then cutting the stretched portion by a water jet method.