JP3339946B2 - Needle - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a needle whose surface is treated with silicone and which has improved piercing properties.

[0002]

2. Description of the Related Art There has been known a method of improving the sharpness of a metal knife such as a razor by coating the surface of the knife with a sliding film of silicone resin (Japanese Patent Publication No. 39-11423). No., JP-B-40-15710, JP-B-40-16111, JP-B-44-7193, JP-B-44-10707
No., JP-B-46-3627). Of these, Tokiko 46-36
No. 27 proposes a metal cutting blade which is treated by applying a silicone coating agent obtained by a reaction between polydimethylsiloxane containing a silanol group and aminosilane and curing by heating or leaving it at room temperature. , But also about injection needles. However, although this coating agent is excellent in adhesion and lubricity to the needle, the piercing property is improved, but it takes a long time to cure at room temperature, and 5% is required to obtain the required film strength. The above aminosilane is required. However, an increase in the amount of aminosilane causes a change with time due to a reaction with carbon dioxide gas in the air and the like, causing inconveniences such as clouding of the coating agent, generation of a precipitate, and change in piercing characteristics. In addition, if the amount of aminosilane is reduced with this coating agent, the curability becomes insufficient, and when left in blood, there is a problem in that the film may fall off and enter the living body, especially into the blood. Furthermore, there is a problem that it takes a long time to obtain a stable piercing property and adhesion after coating and hardening the injection needle, and improvement has been desired. In addition, in order to improve the deterioration of the piercing characteristics due to the temporal change during storage of the coating agent, a coating agent is prepared using a reactant of aminosilane and epoxysilane instead of aminosilane, and the injection needle is used. It is known that an injection needle having excellent piercing properties can be obtained by coating and air drying at room temperature (see JP-B-61-35870). However, the injection needle thus obtained has been desired to be improved so that a stable piercing property immediately after coating and even better piercing property can be obtained. In addition, even if the coating treatment of the injection needle, there is a problem that the piercing property is lowered before piercing the skin by piercing the sensation of the medicine bottle to aspirate the drug solution,
There has been a demand for durable and good piercing properties. An object of the present invention is to provide an injection needle having excellent piercing properties, particularly an injection needle showing good piercing properties immediately after being treated with a coating agent. .

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies to obtain an injection needle having excellent piercing properties, and as a result, have found that a coating containing a specific amino group-containing polyorganosiloxane and a specific polydiorganosiloxane is contained. Apply the agent,
The present inventors have found that an injection needle having good properties can be obtained by curing and surface-treating by a curing method including gamma-ray irradiation, and have accomplished the present invention. That is, the injection needle of the present invention has the following general formula (1)

[0004]

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[0005] (wherein, the field R ¹ is -OH, -OR ³ (where R ³ is that indicates a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ there are a plurality
In this case, they may be the same or different. ) And a monovalent hydrocarbon group .
R ¹ may be the same or different. R ² is a monovalent hydrocarbon group, a plurality of R ² is optionally substituted by one or more identical
You may. A represents a monovalent hydrocarbon group, a γ-aminopropyl group, an N- (β-aminoethyl) aminomethyl group,
A group selected from the group consisting of (N- (β-aminoethyl) amino) propyl groups, wherein a plurality of A
May also be different. m is an integer from 1 to 10,000, n is 0
An amino group-containing polyorganosiloxane containing at least one amino group per molecule in an amount of from 10 to 80% by weight. (2) The degree of polymerization is from 10 to 1,000, have a triorganosilyl group, an amino group in the molecule, a hydroxyl group and hydrolysis min
20-90 with polydiorganosiloxane containing no decomposable group
(1) A coating agent containing a silicone mixture composed by weight of 1% by weight and a surface treatment by a curing method including gamma ray irradiation.

The amino group-containing polyorganosiloxane of the component (1) of the present invention contains at least one amino group in one molecule. In the above formula, R ¹ is -OH,
—OR ³ and a group selected from the group consisting of monovalent hydrocarbon groups, wherein R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms. Examples of the monovalent hydrocarbon group as R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group; a tolyl group; And a cycloalkyl group such as an aryl group, a cyclohexyl group and a cyclooctyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom. As the monovalent hydrocarbon group as R ¹ , an alkyl group is preferable, and a methyl group is particularly preferable, since the properties of the obtained composition are good.
R ² is a monovalent hydrocarbon group, examples of which are the same as the monovalent hydrocarbon group as R ¹ , and an alkyl group, particularly a methyl group, is preferred. A is a monovalent hydrocarbon group and γ-aminopro
Pill group, N- (β-aminoethyl) aminomethyl group, γ
From-(N- (β-aminoethyl) amino) propyl group
A group selected from the group consisting of amino group-containing group selected, the monovalent hydrocarbon group include those similar to R ¹ are exemplified, Ru likewise der preferable. m is an integer of 1 to 10,000, and n is an integer of 0 to 10,000. As the amino group-containing polyorganosiloxane of the component (1), various polymerization degrees,
Those having an amino group content can be used, and two or more kinds can be used in combination. In the present invention, it is preferable to use one having a high degree of polymerization as a main component and further use one having a low degree of polymerization. M is 1,000 to 8,000 for high polymerization degree
Wherein n is from 0 to 100, and further preferably those having an amino group at both ends of the molecular chain and a side chain of a monovalent hydrocarbon group. By using such an amino group-containing polyorganosiloxane as a main component of the component (1), good piercing properties can be obtained in combination with the component (2). As described above, in the coating agent used in the present invention, it is preferable to use an amino group-containing polyorganosiloxane having a lower degree of polymerization in combination. As such a siloxane, m is 10 to 800, and n is 1 100100 are exemplified. In particular, those having a terminal trialkylsilyl group and having an amino group in the side chain are preferred. By using such a compound having a low degree of polymerization, the adhesion of the coating agent of the obtained injection needle becomes good. When a combination of a high polymerization degree and a low polymerization degree is used in the component (1), the high polymerization degree is preferably 50 to 80% by weight.

The amino group-containing polyorganosiloxane of the component (1) can be synthesized by a conventionally known method, for example, by hydrolyzing an amino group-containing alkoxysilane and a siloxane having a silanol group at both molecular chain terminals. Examples thereof include a method of performing a condensation reaction and a method of performing an addition reaction between an amino group-containing alkenyl compound and a polyorganohydrogensiloxane. In particular, in the case of synthesizing a polymer having a high degree of polymerization used in the present invention, a method in which an amino group-containing alkoxysilane and a siloxane having a silanol group at both molecular chain terminals are subjected to a hydrolysis / condensation reaction is preferable. The amino group-containing alkoxysilane has a general formula

[0008]

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Wherein Q is a hydrogen atom, —CH ₃ , —CH ₂ CH ₂ CH ₂
And -CH ₂ CH ₂ NHCH 1 monovalent group selected from ₂ CH ₂ group consisting of NH _2, R ⁴ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁵ is the
R ¹ and R ⁶ are the same substituents as those of R ³ described above, and q represents 0 or 1). Trialkoxysilane wherein q is 0 is preferably used. Examples of such amino group-containing alkoxysilanes include γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, γ- (N- (β- Aminoethyl) amino) propyltrimethoxysilane, γ- (N- (β-aminoethyl) amino) propylmethyldimethoxysilane, N- (β-aminoethyl) aminomethyltributoxysilane, γ- (N- (β- (N- (β-aminoethyl) amino) ethyl) amino) propyltrimethoxysilane and the like are exemplified. As the siloxane containing a silanol group at both ends of the molecular chain, the polymerization degree is preferably
1,000 to 8,000, particularly preferably used those 3,000 to 6,000, the substituent is exemplified the same groups as R ^1, preferably a methyl group or a phenyl group, particularly preferably those of only methyl groups.

The amino group-containing polyorganosiloxane of the component (1) of the present invention can be obtained by subjecting the above-mentioned amino group-containing alkoxysilane and silanol group-containing siloxane to hydrolysis and condensation by a known method. For example, these can be obtained by adding a hydrolysis catalyst such as an organic acid and an inorganic acid, and further, an organic solvent, and mixing and stirring them, if necessary, in the presence of water. Even if not, the reaction proceeds even if the amino group-containing alkoxysilane and the silanol group-containing siloxane are mixed and heated and stirred. When a polymer having a high degree of polymerization is synthesized as the component (1), the amino group-containing alkoxysilane is used in an amount of 1 to 100 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the siloxane having silanol groups at both molecular chain terminals. Partial reaction is preferred. The unreacted material can be used as it is mixed with the component (1). If necessary, the unreacted material can be used by removing the unreacted material by distillation under reduced pressure.

The component (2) of the present invention is a polydiorganosiloxane having a triorganosilyl group at the terminal of the molecular chain and containing no amino group in the molecule, and substantially having a hydroxyl group and a hydrolyzable group in the molecule. Is not contained. Examples of the substituent include a substituted or unsubstituted monovalent hydrocarbon group, and the same groups as those described for R ¹ include, for example, an alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a dodecyl group; And a fluoro-substituted alkyl group such as a 3,3,3-trifluoropropyl group is preferable, and among them, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
In addition, the polymerization degree is 10 to 1,000, and if it is less than 10, the coating of the formed coating agent becomes brittle and the adhesiveness becomes insufficient, and if it exceeds 1,000, the piercing characteristics of the obtained injection needle decrease. . The preferred degree of polymerization is from 20 to 100. Examples of the component (2) include polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and polymethyl (3,3,3-trifluoropropyl) siloxane. Dimethylsiloxane and polymethylphenylsiloxane are particularly preferred.

The coating composition used in the present invention comprises:
As a main component, it contains a silicone mixture of component (1) and component (2). This mixture has a composition in which component (2) is 90 to 20% by weight based on 10 to 80% by weight of component (1). Consisting of Preferably, the properties of the obtained injection needle are good,
Component (2) is blended in a composition of 50 to 30% by weight with respect to 50 to 70% by weight of (1). The coating agent composition used in the present invention is obtained by mixing and stirring the components (1) and (2), and if necessary, by using an organic solvent or by mixing and stirring in a heated state. The coating composition used in the present invention may contain various organic solvents, condensation reaction catalysts, various fillers, etc. in addition to the components (1) and (2). Organic solvents include 1,1,2-trichloro-1,2,2
-Chlorofluorocarbons such as trifluoroethane, methylene chloride, chlorine-containing hydrocarbons such as chloroform, hexane,
Examples thereof include hydrocarbons such as toluene, alcohols such as methanol and ethanol, and volatile siloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane. Among these, from the viewpoint of improving the stability of the coating agent composition, it is preferable to contain 1 to 20% by weight, particularly 2 to 10% by weight of alcohol, particularly ethanol. Examples of various fillers include inorganic fine powders such as silica, talc, titanium oxide, and zinc carbonate; polyethylene fine powders; fluororesin fine powders; polymethylsilsesquioxane fine powders; and organic fine powders such as silicone rubber fine powders; And those obtained by surface-treating these with silicone, silane, titanium compound and the like. When using an organic solvent, in the coating composition, component (1)
And the total amount of component (2) is 5 to 80% by weight, preferably
4040% by weight, and preservation may be performed in the form of this composition. When coating on an injection needle, the coating composition is further diluted with the organic solvent exemplified above. , The total amount of component (1) and component (2) is
It is preferable to prepare and use a coating agent so as to be 1 to 5% by weight.

The injection needle of the present invention is treated by applying the coating agent obtained above, volatilizing the solvent by air-drying or heating if necessary, and then irradiating with gamma rays. The application of the coating agent to the injection needle can be performed by a common application method such as dipping, brushing, and spraying. Further, if necessary, the solvent is volatilized by air drying, heating, or the like, and in some cases, the coating agent composition is simultaneously precured. Further, it is cured by irradiation with gamma rays. By performing the gamma ray irradiation, not only the curing of the coating agent composition is promoted, but also there is an advantage that the injection needle is sterilized. In the case of gamma-ray irradiation in the present invention, conditions such as dose and irradiation time are not particularly defined, but are usually 0.5 to 3 Mrad (γ dose), and sterilization time is 4 to 7 hours. The material of the injection needle to be subjected to the surface treatment of the present invention is SUS304, 304L, 321 which conforms to the Ministry of Health and Welfare Notification No. 443, disposable injection needle standard.

[0014]

The injection needle of the present invention has excellent piercing properties by applying a specific silicone coating agent and surface-treating it by a curing method including gamma ray irradiation. In particular, good piercing properties are obtained immediately after curing, and the durability is also good, which is useful for medical applications.

[0015]

The present invention will be described below with reference to examples. In addition, the part in an Example represents a weight part, and% represents weight%. The viscosity indicates a value at 25 ° C. Preparation Example 1 To 20 parts of polydimethylsiloxane containing silanol groups at both ends having an average degree of polymerization of 6000, 78 parts of toluene was added, and the mixture was stirred at 50 ° C. for 3 hours, and then γ- [N- (β-aminoethyl) amino] propylmethyldimethoxy 2 parts of silane was added and reacted at 80 ° C. for 12 hours to obtain an amino group-containing polyorganosiloxane (A
-1) was obtained. The siloxane obtained by the reaction was represented by the following average formula. The silicone content in the obtained reaction solution was about 20%.

[0016]

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Preparation Example 2 To 20 parts of polydimethylsiloxane containing silanol groups at both ends having an average degree of polymerization of 3000, 78 parts of toluene was added, and the mixture was stirred at 50 ° C. for 3 hours, and 3 parts of γ-aminopropyltrimethoxysilane was added. The mixture was reacted at 12 ° C. for 12 hours, and the volatile components such as the solvent and unreacted silane were distilled off to obtain amino group-containing polyorganosiloxane (A-2). The obtained siloxane was represented by the following average formula.

[0018]

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Further, in the examples, compounds represented by the following average formula were used.

[0020]

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Example 1 50 parts of amino group-containing polyorganosiloxane A-1, B
-1, 5 parts of polydiorganosiloxane C-1,
30 parts of toluene and 5 parts of ethanol were added and mixed and stirred to prepare a coating composition. Methylene chloride 4
The mixture was diluted by adding 00 parts to obtain a colorless and transparent coating agent. Two types of injection needles (16G and 22G) having different outer diameters were immersed in this coating agent and air-dried at room temperature for 1 hour.
Further, a hardening treatment was performed by irradiating γ-rays at 2 Mrad.
Then, into a cylindrical glass bottle with an outer diameter of 6 cm and a height of 10 cm,
A polyethylene sheet having a thickness of 50 μm was stretched, and the injection needle obtained as described above was vertically penetrated, and the penetration resistance was measured by an autograph. The piercing operation was performed three times, and the first and third measurements are shown in Table 1. In addition, the penetration resistance measured the resistance value at the time of passing after the injection needle penetrated the polyethylene film. Examples 2 to 7 In the same manner as in Example 1 with the composition shown in Table 1, a coating agent was prepared, and the injection needle was surface-treated. Next, the piercing resistance was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Examples 1 and 2 A coating agent was prepared with a composition not containing the component (2) of the present invention as shown in Table 2, and the surface of the injection needle was treated. Next, the piercing resistance was measured in the same manner as in Example 1. Table 2 shows the results. Comparative Example 3 In Example 1, γ-ray irradiation was not performed, and instead,
The surface of the injection needle was treated in the same manner as in Example 1 except that the heat treatment was performed for 1 hour. Next, the piercing resistance was measured in the same manner as in Example 1. Table 2 shows the results. Comparative Example 4 The injection needle was surface-treated in the same manner as in Example 1 except that γ-ray irradiation was not performed and curing was performed at room temperature for 20 hours instead. Next, the piercing resistance was measured in the same manner as in Example 1. Table 2 shows the results. Comparative Example 5 The puncture resistance of an untreated injection needle was measured in the same manner as in Example 1. Table 2 shows the results.

[0023]

[Table 1]

[0024]

[Table 2]

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinbo Takanashi 1727, Tsukiji Arai, Showa-machi, Nakakoma-gun, Yamanashi Prefecture Inside Terumo Corporation (56) References JP-A-56-119262 (JP, A) -242060 (JP, A) JP-B-46-3627 (JP, B1) Patent 2790972 (JP, B2) US Patent 5,258,013 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61L 24/00-33/18 A61M 5/32-5/34 C09D 183/00-183/16

Claims (5)

(57) [Claims] (1) The general formula: (In the formula, R ¹ is -OH, -OR ³ (where R ³ is shows a monovalent hydrocarbon group having 1 to 4 carbon atoms, if R ³ is present a plurality, equal der
Or different. ) And a monovalent hydrocarbon radical group selected from the group consisting of a plurality of R ¹ are the same der
Or different. R ² is a monovalent hydrocarbon group, and a plurality of R ² may be the same or different.
A represents a monovalent hydrocarbon group, a γ-aminopropyl group,
(Β-aminoethyl) aminomethyl group, γ- (N- (β
-Aminoethyl) amino) propyl group, wherein a plurality of A
May be. m is an integer of 1 to 10,000, n is an integer of 0 to 10,000), and an amino group-containing polyorganosiloxane containing at least one amino group in one molecule.
In 10 to 80 wt% (2) the degree of polymerization is 10 to 1,000, have a triorganosilyl group in the molecular chain terminal, amino groups in the molecule, a hydroxyl group and hydrolysis min
20-90 with polydiorganosiloxane containing no decomposable group
An injection needle, which is coated with a coating agent containing a silicone mixture consisting of 5% by weight and surface-treated by a curing method including gamma ray irradiation. 2. An amino group-containing polyorganosiloxane of the component (1) is different from an amino group-containing alkoxysilane in polymerization degree.
The injection needle according to claim 1, which is a reaction product with a polydiorganosiloxane having a silanol group at both molecular terminals at 1,000 to 8,000. 3. An amino group-containing polyorganosiloxane of the component (1) is different from the amino group-containing alkoxysilane in polymerization degree.
A mixture of a reaction product of 1,000 to 8,000 polydiorganosiloxane having silanol groups at both molecular chain terminals and an amino group-containing polyorganosiloxane containing an amino group in the side chain and having a degree of polymerization of 10 to 800. Claim 1
The injection needle as described. 4. The polydiorganosiloxane of component (2)
The injection needle according to claim 1, which is polydimethylsiloxane. 5. The polydiorganosiloxane of component (2)
The injection needle according to claim 1, which is polymethylphenylsiloxane.