WO2016013528A1 - Coating agent and needle having surface treated with said coating agent - Google Patents

Abstract

[Problem] The present invention provides: a coating agent having improved durability; and a needle coated with the coating agent. The coating agent according to the present invention comprises (1) 10 to 60% by mass of an amino-group-containing polyorganosiloxane (A) which contains at least one amino group per molecule, (2) 0.1 to 30% by mass of a condensation product (B) of a compound (B-1) represented by general formula (B) with a compound (B-2) having a group represented by general formula (B'), and (3) 10 to 89.9% by mass of a polydiorganosiloxane (C) (wherein the total amount of the amino-group-containing polyorganosiloxane (A), the condensation product (B) and the polydiorganosiloxane (C) is 100% by mass).

Description

Coating agent and needle formed by surface treatment with the coating agent

The present invention relates to a coating agent and a needle formed by surface treatment with the coating agent.

Injection is used by patients suffering from illness for the purpose of injecting medicinal solutions for treatment and anesthesia during surgery. Even healthy people often experience injections such as blood donation and vaccination. However, due to pain at the time of puncture and a sense of incongruity at the time of injecting a chemical solution, the injection gives a lot of pain to patients and healthy people. For this reason, various studies have been made for the purpose of alleviating pain, such as the shape of the tip of the injection needle and the coating agent on the surface of the injection needle. Among these, silicone has been mainly used as a coating agent on the injection needle surface. This silicone coating agent imparts lubricity to the injection needle and reduces friction during puncture. Therefore, the injection needle coated with the silicone coating agent relieves pain during injection. For example, Patent Document 1 reported a silicone coating agent containing an amino group-containing polyorganosiloxane and polydiorganosiloxane at a specific mixing ratio. The injection needle coated with the coating agent exhibits excellent piercing properties.

JP 7-178159 A

However, even if it has an injection needle coated with the coating agent described in Patent Document 1, it does not mean that patients do not give pain to the subject completely, and improvement in piercing characteristics is required. Yes.

Also, a needle coated with a silicone coating agent may be used for multiple punctures. For example, a silicone-coated needle may be used when a medicine is sucked through a stopper of a medicine bottle and then injected into a patient. In addition, the bottle needle subjected to the silicone coating treatment may be inserted into a different infusion bag when the infusion bag is replaced. In such a case, there has been a problem that the coating agent peels off from the needle surface, and friction (puncture resistance) increases during use, causing pain to the patient. For this reason, it is also required to further improve durability (suppression / prevention of coating peeling).

Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a coating agent with improved durability and a needle that is surface-treated (applied) with the coating agent.

Another object of the present invention is to provide a coating agent with improved piercing properties and a needle that is surface-treated (applied) with the coating agent.

As a result of intensive studies to solve the above problems, the present inventors have used the above-mentioned problems by using a specific amount of a specific isocyanurate compound in addition to the amino group-containing polyorganosiloxane and polydiorganosiloxane. The present invention has been completed.

That is, the above-mentioned purposes are as follows: (1)

Provided that each R ¹ independently represents a monovalent hydrocarbon group or —OR ⁵ group. In this case, each R ⁵ independently represents a monovalent monovalent hydrocarbon group having 1 to 4 carbon atoms, which is substituted or unsubstituted. Represents a hydrocarbon group of
Each R ² independently represents a monovalent hydrocarbon group;
Each A independently represents an amino group-containing group;
m: n = 1: 5 to 100, and m is an integer from 1 to 100.
An amino group-containing polyorganosiloxane (A) containing at least one amino group in one molecule, represented by the formula:
(2) The following general formula B:

However, R ³ and R ^{3 ′} each independently represents a monovalent hydrocarbon group or a hydroxyl group (—OH), and at least one of R ³ and at least one of R ^{3 ′} are a hydroxyl group (—OH). ) And
Each R ⁴ independently represents a monovalent hydrocarbon group;
p is an integer of 1 to 10,000,
And a compound represented by the following general formula B ′:

Provided that each R ⁷ independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein at least one of R ⁷ is an alkoxy group. ,
r is an integer from 1 to 6;
* Represents a bond position,
A condensate (B) of the compound (B-2) having a group represented by the formula: 0.1 to 30% by mass; and (3) the following general formula C:

However, R ⁹ and R ¹⁰ each independently represent a monovalent hydrocarbon group,
q is an integer of 8 to 1000,
The polydiorganosiloxane (C) is represented by 10 to 89.9% by mass (the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) is 100% by mass. is there)
It can be achieved by a coating agent containing

It is a graph which shows the puncture resistance of the needle | hook surface-treated with the coating agent of Example 1 and Comparative Example 1 by heating. It is a graph which shows the puncture resistance of the needle | hook surface-treated with the coating agent of Example 1 and the comparative example 1 by the gamma ray. It is a graph which shows the trunk | drum puncture resistance of the needle | hook surface-treated with the coating agent of Example 1 and the comparative example 1 by the gamma ray.

The coating agent of the present invention is
(1) The following general formula A:

Provided that each R ¹ independently represents a monovalent hydrocarbon group or —OR ⁵ group. In this case, each R ⁵ independently represents a monovalent monovalent hydrocarbon group having 1 to 4 carbon atoms, which is substituted or unsubstituted. Represents a hydrocarbon group of
Each R ² independently represents a monovalent hydrocarbon group;
Each A independently represents an amino group-containing group;
m: n = 1: 5 to 100, and m is an integer from 1 to 100.
An amino group-containing polyorganosiloxane (A) containing at least one amino group in one molecule, represented by the formula:
(2) The following general formula B:

However, R ³ and R ^{3 ′} each independently represents a monovalent hydrocarbon group or a hydroxyl group (—OH), and at least one of R ³ and at least one of R ^{3 ′} are a hydroxyl group (—OH). ) And
Each R ⁴ is independently a monovalent hydrocarbon group;
p is an integer of 1 to 10,000,
And a compound represented by the following general formula B ′:

Provided that each R ⁷ independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein at least one of R ⁷ is an alkoxy group. , R is an integer from 1 to 6,
* Represents a bond position,
A condensate (B) of the compound (B-2) having a group represented by the formula: 0.1 to 30% by mass; and (3) the following general formula C:

However, R ⁹ and R ¹⁰ each independently represent a monovalent hydrocarbon group,
q is an integer of 8 to 1000,
The polydiorganosiloxane (C) is represented by 10 to 89.9% by mass (the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) is 100% by mass. is there)
including. Since the coating agent of the present invention has excellent adhesion to the surface of a substrate (for example, a needle), peeling of the coating from the substrate can be suppressed / prevented, and the durability is excellent. Moreover, since the coating agent of this invention is excellent in lubricity, it can reduce the friction (puncture resistance) at the time of puncture, and can improve the piercing property.

In the present specification, an amino group-containing polyorganosiloxane (A) containing at least one amino group in one molecule represented by the general formula A is referred to as “amino group-containing polyorganosiloxane (A)”, Compound (B-1) represented by formula B is “compound (B-1)”, compound (B-2) having a group represented by general formula B ′ is “compound (B-2)”, and compound The condensate (B) of (B-1) and the compound (B-2) is designated as “condensate (B)” or “isocyanurate compound”, and the polydiorganosiloxane (C) represented by the general formula C is designated as “ They are referred to as “polydiorganosiloxane (C)”, respectively.

As described above, the coating agent of the present invention comprises 10 to 60% by mass of the amino group-containing polyorganosiloxane (A), 0.1 to 30% by mass of the condensate (B), and 10 to 89.9% by mass. It is characterized by containing polydiorganosiloxane (C) (total amount of amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) = 100 mass%). By the said composition, the coating agent of this invention can reduce friction with a base material, and is excellent in the piercing property. In addition, since the coating agent of the present invention has excellent adhesion to the surface of a substrate (for example, a needle), it can suppress / prevent peeling of the surface treatment product (film) from the substrate by the coating agent, and is excellent in durability. . The reason why the above effect can be achieved is unknown, but is estimated as follows. In addition, this invention is not limited by the following estimation.

That is, the present inventors diligently studied to further improve the adhesion and durability of the coating agent described in Patent Document 1 to the substrate. As a result, it has been found that it is effective to increase the number of crosslinking points at which amino group-containing polyorganosiloxanes or amino group-containing polyorganosiloxane and polyorganosiloxane can react (bond). Specifically, the coating agent described in Patent Document 1 includes an amino group-containing polyorganosiloxane having an amino group at a terminal or a structural unit, and polydiorganosiloxane. Here, the polydiorganosiloxane imparts lubricity to the coating film by the organosiloxane portion. In addition, in the amino group-containing polyorganosiloxane, the polyorganosiloxane portion imparts lubricity, and the amino group is bonded to a substrate (for example, a hydroxyl group on the surface of a metal substrate) to form a film. For this reason, the amino group-containing polyorganosiloxane contributes to lubricity, adhesion to the substrate, and film-forming properties. However, although the amino group-containing polyorganosiloxane has bonding properties with the base material, there is no cross-linking point where amino group-containing polyorganosiloxanes or amino group-containing polyorganosiloxane and polyorganosiloxane can react (bond). As a result of intensive studies by the present inventors on the method for increasing the crosslinking point, the network formation on the substrate of the film formed using the coating agent is further improved, and the adhesion and durability to the substrate are improved. We found a means to further improve the performance. Specifically, the adhesion and durability of the coating agent can be further improved by including the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) in a specific composition. found. Here, the amino group-containing polyorganosiloxane (A) is an amino group-containing polyorganosiloxane having an amino group in the structural unit of Patent Document 1, and the polydiorganosiloxane (C) is a polydiorganosiloxane of Patent Document 1. Each corresponds. That is, the present invention is characterized by further including the condensate (B) in the coating agent described in Patent Document 1. The condensate (B) has an amide group (—N (R) —C (═O) —) in its structure. Since this amide group interacts with the surface of the substrate, particularly the hydroxyl group on the surface of the substrate, it has excellent adhesion to the substrate. In the coating agent of the present invention, the amino group-containing polyorganosiloxane (A) can also be bonded to the substrate via the amino group. Therefore, since the film formed using the coating agent of the present invention has higher adhesion to the substrate as compared with the case where the coating agent described in Patent Document 1 is used, Peeling can be suppressed and prevented more effectively, and durability can be improved. In addition, the condensate (B) includes a hydroxyl group (R ³ , R ^{3 ′} ) present in the compound (B-1) and an alkoxy group (substituent R ⁷ ) present in the compound (B-2). Condensed. That is, the compound (B-2) has a large number of crosslinking points that condense with the compound (B-1), up to three per group of the general formula B ′. For this reason, in the condensate (B), many hydroxyl groups derived from the compound (B-1) can be bonded via the crosslinking point of the compound (B-2) (alkoxy group as the substituent R ⁷ ). The condensate (B) is also condensed with a hydroxyl group derived from the compound (B-1) of another condensate (B) via a crosslinking point (an alkoxy group as the substituent R ⁷ ) of the compound (B-2). can do. For this reason, when the coating agent of the present invention is used, a three-dimensional wide and strong network can be formed. Therefore, the film formed using the coating agent of the present invention is superior in film-forming property (becomes a stronger film) than the case where the coating agent described in Patent Document 1 is used. Can be improved. For this reason, if the needle surface-treated with the coating agent of the present invention is used, the film (coating agent) will not peel off from the needle surface or less even when used multiple times. Therefore, since high lubricity can be maintained, friction during use (puncture resistance), and hence pain given to the patient can be effectively reduced. Furthermore, if it is the coating agent of this invention, it can suppress and prevent that a film peels from the needle | hook (base material) surface. Therefore, even if the needle surface-treated with the coating agent of the present invention is stuck in the infusion bag, foreign matter (coating strip) is prevented / prevented from being mixed into the infusion bag, from the viewpoint of safety. preferable.

Further, the coating agent of the present invention provides an organosiloxane portion in the condensate (B) in addition to imparting lubricity by the organosiloxane portion of the amino group-containing polyorganosiloxane (A) and polydiorganosiloxane (C). Can also provide lubricity. Therefore, the film formed using the coating agent of the present invention has improved lubricity and can reduce friction (puncture resistance) with the substrate. For this reason, if the needle surface-treated with the coating agent of the present invention is used, the pain caused by the puncture on the patient can be further reduced.

Therefore, the coating agent of the present invention can improve durability and lubricity (puncture characteristics) when applied to a substrate. Therefore, the coating agent of the present invention can be particularly suitably used for needles that are strongly required to have the characteristics described above, particularly injection needles.

Hereinafter, embodiments of the present invention will be described. In this specification, “X to Y” indicating a range includes X and Y, and means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

[Amino group-containing polyorganosiloxane (A)]
The amino group-containing polyorganosiloxane (A) according to the present invention has the following general formula A:

Indicated by The amino group-containing polyorganosiloxane (A) according to the present invention interacts with a substrate, particularly a hydroxyl group present on the substrate surface via an amino group (substituent “A” in the general formula A), Can be bonded (adhered) to the substrate. Further, the organosiloxane moiety (—Si (R ² ) ₂ O—) present in the amino group-containing polyorganosiloxane (A) according to the present invention imparts lubricity (easy to pierce). When there are two or more structural units of the formula: —Si (R ² ) ₂ O— (n is 2 or more), each structural unit may be the same or different. . Similarly, when there are two or more structural units of the formula: —Si (R ² ) (A) O— (m is 2 or more), each structural unit may be the same or different. There may be. Furthermore, the coating agent of this invention may contain amino group containing polyorganosiloxane (A) individually by 1 type, or may contain 2 or more types of amino group containing polyorganosiloxane (A).

In the above general formula A, R ¹ is a monovalent hydrocarbon group or —OR ⁵ group. Here, the plurality of R ¹ may be the same or different. The monovalent hydrocarbon group is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkenyl group having 2 to 24 carbon atoms, and 3 to 9 carbon atoms. And an aryl group having 6 to 30 carbon atoms. Here, the linear or branched alkyl group having 1 to 24 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl Group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl 1-t-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group N-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group , N-tricosyl group, n-tetracosyl group and the like. The linear or branched alkenyl group having 2 to 24 carbon atoms is not particularly limited, and examples thereof include a vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, and 1-butenyl group. 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group 5-heptenyl group, 1-octenyl group, 3-octenyl group, 5-octenyl group, dodecenyl group, octadecenyl group and the like. The cycloalkyl group having 3 to 9 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The aryl group having 6 to 30 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a terphenyl group, a pentarenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group, a fluorenyl group, Examples include acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aseantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. It is done. Of these, a linear or branched alkyl group having 1 to 16 carbon atoms is preferred from the standpoint of improving lubricity and compatibility with a solvent, and a linear or branched alkyl group having 1 to 8 carbon atoms. An alkyl group is more preferable, a linear or branched alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group is particularly preferable. The “compatibility” refers to mutual solubility between different kinds of molecules, and means easy mixing at the molecular level. R ⁵ independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms. Here, when a plurality of R ¹ are —OR ⁵ groups, the plurality of —OR ⁵ groups may be the same or different from each other. Here, the monovalent hydrocarbon group is not particularly limited, but for example, a linear or branched alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group). Group, isobutyl group, sec-butyl group, tert-butyl group), linear or branched alkenyl group having 2 to 4 carbon atoms (vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl Group, 1-butenyl group, 2-butenyl group, 3-butenyl group) and a cycloalkyl group having 3 or 4 carbon atoms (cyclopropyl group, cyclobutyl group). Among these, a methyl group and an ethyl group are preferable from the viewpoint of more improving lubricity and adhesion to a substrate.

In the above general formula A, R ² represents a monovalent hydrocarbon group. Here, the plurality of R ² may be the same or different. Here, the monovalent hydrocarbon group is not particularly limited, but has the same definition as the substituent “R ¹ ”. Of these, a linear alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable, from the viewpoints of improving lubricity and availability.

In the above general formula A, A represents an amino group-containing group. Here, when there are a plurality of A (m is 2 or more), each A may be the same or different. The amino group-containing group is not particularly limited, but for example, β-aminoethyl group, γ-aminopropyl group, N- (β-aminoethyl) aminomethyl group, γ- (N- (β-aminoethyl) amino) A propyl group etc. are mentioned. Of these, γ-aminopropyl group, N- (β-aminoethyl) aminomethyl group or γ- (N- (β-aminoethyl) is preferred from the viewpoints of improving lubricity and adhesion to the substrate. ) Amino) propyl group is preferable, and γ- (N- (β-aminoethyl) amino) propyl group and γ-aminopropyl group are more preferable.

In the above general formula A, m is an integer of 1 to 100, preferably an integer of 3 to 20. N is an integer that satisfies m and the relationship m: n = 1: 5 to 100. Preferably, m: n = 1: 10 to 100. If m and n are as described above, a sufficient number of amino groups are present in the amino group-containing polyorganosiloxane (A), so that sufficient adhesion to the substrate can be achieved. In addition, with such m and n, since a sufficient number of organosiloxane moieties are present in the amino group-containing polyorganosiloxane (A), the coating agent exhibits sufficient lubricity, Friction (puncture resistance) can be further reduced. n is not particularly limited as long as the above relationship is satisfied, but is preferably 10 to 800.

The molecular weight of the amino group-containing polyorganosiloxane (A) is not particularly limited, but the weight average molecular weight is preferably 5000 to 50000, and more preferably 7500 to 30000. In this specification, a weight average molecular weight means the value calculated | required by the calibration curve method from the measurement result by a gel filtration chromatography (GPC) analysis using polystyrene as a reference material.

The amino group-containing polyorganosiloxane (A) is contained in an amount of 10 to 60% by mass based on the total amount of the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C). . Here, when the content of the amino group-containing polyorganosiloxane (A) is less than 10% by mass, the coating agent is easily peeled off, which is not preferable. Conversely, when the content of the amino group-containing polyorganosiloxane (A) exceeds 60% by mass, the contents of the other essential components of the condensate (B) and the polydiorganosiloxane (C) are too small. The effects of these components cannot be fully demonstrated. The amino group-containing polyorganosiloxane (A) is preferably used in an amount of 15 to 55% by mass with respect to the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C). Included, more preferably in an amount of 20-50% by weight. If it is such quantity, adhesiveness with a base material and lubricity (Easy piercing, reduction effect of piercing resistance) can be improved more effectively. In addition, the safety of the coating agent can be further improved, which is particularly preferable when used for medical applications such as needles. In addition, when amino group containing polyorganosiloxane (A) is contained in 2 or more types of mixtures, content of the said amino group containing polyorganosiloxane (A) is a total amount.

The method for producing the amino group-containing polyorganosiloxane (A) according to the present invention is not particularly limited. For example, the amino group-containing polyorganosiloxane (A) according to the present invention can be produced in the same manner as described in known literatures such as JP-A-7-178159 or appropriately modified.

[Condensate (B)]
The condensate (B) according to the present invention has the following general formula B:

And a compound represented by the following general formula B ′:

And a compound (B-2) having a group represented by the following formula: The condensate (B) according to the present invention has an amide group (—N (R) —C (═O) —). Since this amide group interacts with a base material, particularly a hydroxyl group of the base material, it has excellent adhesion to the base material. Therefore, adhesion with the base material is promoted together with the amino group present in the amino group-containing polyorganosiloxane (A). Further, the condensate (B) is formed by condensing a hydroxyl group (R ³ , R ^{3 ′} ) present in the compound (B-1) with an alkoxy group (substituent R ⁷ ) present in the compound (B-2). It is a thing. That is, the compound (B-2) has a large number of crosslinking points that condense with the compound (B-1), up to three per group of the general formula B ′. For this reason, in the condensate (B), many hydroxyl groups derived from the compound (B-1) can be bonded via the crosslinking point of the compound (B-2) (alkoxy group as the substituent R ⁷ ). Further, the condensate (B) also condenses with the hydroxyl group derived from the compound (B-1) of another condensate (B) through the crosslinking point of the compound (B-2). Furthermore, the condensate (B) also condenses with R ¹ (particularly, —OR ⁵ group) in the compound (A) via the crosslinking point (alkoxy group as the substituent R ⁷ ) of the compound (B-2). . Therefore, when the coating agent of the present invention is used, a three-dimensional wide and strong network can be formed. Therefore, since the film formed using the coating agent of this invention is strong, durability can be improved. For this reason, when the needle surface-treated with the coating agent of the present invention is used, even when the rubber plug is punctured a plurality of times, the coating (coating agent) does not peel off from the needle surface. Therefore, since the needle surface-treated with the coating agent of the present invention can maintain high lubricity, friction during use (puncture resistance) is small, and pain to the patient can be effectively reduced. For example, even if the needle surface-treated with the coating agent of the present invention is inserted into an infusion bag, the film (coating agent) is peeled off from the needle surface, and foreign matter (film peeling material) is mixed into the infusion bag. It is preferable from the viewpoint of safety. In addition, since the condensate (B) has an organosiloxane moiety (—Si (R ⁴ ) ₂ O—), lubricity (easy piercing) can be imparted. In addition, the coating agent of this invention may contain the condensate (B) individually by 1 type, or may contain 2 or more types of condensates (B).

Further, as described above, the condensate (B) according to the present invention is a condensate of the compound (B-1) and the compound (B-2). Here, the structure of the condensate (B) according to the present invention (condensation form of the compounds (B-1) and (B-2)) is unknown, but is considered to be the following mixture form . That is, the condensation is performed by reacting the hydroxyl group (R ³ , R ^{3 ′} ) present in the compound (B-1) with R ⁷ (hydrocarbon group or alkoxy group) present in the compound (B-2). . Therefore, for example, the compound (B-2) has the following structure:

In this case, the condensate (B) of the compound (B-1) and the compound (B-2) is converted into one R ⁷ existing in the compound (B-2) and the compound (B-1). The following structure obtained by reacting with one hydroxyl group of R ³ and R ^{3 ′} present:

A plurality of R ⁷ present in the compound (B-2) and one of the hydroxyl groups of R ³ and R ^{3 ′} present in the compound (B-1) react with each other to give the following structure (the following structure This is an example in which two R ⁷ present in B-2) and a hydroxyl group present in compound (B-1) have reacted, but the following is merely an example, and the same form can be applied to a plurality of cases ):

The following structure obtained by reacting one R ⁷ present in the compound (B-2) with hydroxyl groups present at both ends of the compound (B-1):

And compounds in which a plurality of the above condensations occur, and combinations of any two or more of the above. The compound (B-1) reacts with each other by hydrolysis to form a three-dimensional network. Therefore, the presence of the condensate (B) according to the present invention makes it possible to form a strong film and significantly improve the durability.

Compound (B-1) is represented by the following general formula B:

Indicated by When there are two or more structural units of the formula: —Si (R ⁴ ) ₂ O— (p is 2 or more), each structural unit may be the same or different. . In addition, the compound (B) may be produced using one kind of compound (B-1) or may be produced using two or more kinds of compounds (B-1).

In the general formula B, R ³ and R ^{3 ′} represent a monovalent hydrocarbon group or a hydroxyl group (—OH). Here, R ³ and R ^{3 ′} may be the same or different. Provided that at least one and R ³ of ^{R 3 'at} least one is a hydroxyl group (-OH), a least one and R ³ of ^{R 3'} is preferably at least one is a hydroxyl group, ^{R 3 'more} preferably 1 or 2 is a hydroxyl group, R ³ and R ^3' 1 or 2 and / or R ³ in it is particularly preferred is a hydroxyl group one by one. Since the monovalent hydrocarbon group as R ³ and R ^{3 is the same} as the definition in General A above, description thereof is omitted here. Of these, from the viewpoints of improving lubricity, durability, improving compatibility with solvents, etc., a linear or branched alkyl group having 1 to 16 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. A branched alkyl group is more preferable, a linear or branched alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group is particularly preferable.

In the general formula B, R ⁴ represents a monovalent hydrocarbon group. Here, each R ⁴ present in one structural unit may be the same or different. Further, when there are a plurality of structural units (n is 2 or more), each structural unit may be the same or different. Since the monovalent hydrocarbon group as R ^{4 is the same} as the definition in General A above, the description thereof is omitted here. A linear or branched alkyl group having 1 to 16 carbon atoms is preferred from the viewpoints of improving lubricity, improving durability, compatibility with solvents, etc., and a linear or branched alkyl group having 1 to 8 carbon atoms. Group is more preferable, a linear or branched alkyl group having 1 to 4 carbon atoms is still more preferable, and a methyl group is particularly preferable.

P is an integer of 1 to 10000, preferably an integer of 2000 to 5000. Within the above range, the compound (B-1), and therefore the condensate (B), has a sufficient amount of organosiloxane moiety, so that it exhibits sufficient lubricity and friction (puncture) with the substrate. Resistance) can be further reduced. The molecular weight of the compound (B-1) is not particularly limited, but the weight average molecular weight is preferably 10,000 to 1,500,000, and more preferably 50,000 to 1,000,000.

Compound (B-2) has the following general formula B ′:

It has the group shown by. Compound (B) may be produced using one kind of compound (B-2) or may be produced using two or more kinds of compounds (B-2).

In the general formula B ′, R ⁷ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Here, R ⁷ may be the same or different. However, at least one of R ⁷ is an alkoxy group, more preferably 2 or 3 of R ⁷ is an alkoxy group, and particularly preferably all three of R ⁷ are alkoxy groups. When compound B is composed of a plurality of compounds of general formula B ′ (B-2), each compound (B-2) may be the same or different, It is preferable that they are the same. The monovalent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The alkoxy group having 1 to 4 carbon atoms is not particularly limited, and includes a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, and the like. In view of ease of condensation with the compound (B-1), an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable. R is an integer of 1 to 6. From the viewpoints of improving the ease of condensation with the compound (B-1), adhesion and durability, r is preferably an integer of 2 to 4.

The compound (B-2) may have another group (constituent site) as long as it has a group represented by the above general formula B ′, but is composed of a group represented by the above general formula B ′. It is preferable. Here, the number of the group represented by the general formula B ′ constituting the compound (B-2) is not particularly limited, but is preferably 2 or more from the viewpoint of improving the adhesion and durability. . That is, the compound (B-2) preferably has at least two groups represented by the general formula B ′. As described above, when the compound (B-2) has two or more groups (silane) represented by the general formula B ′, a network (knitting structure) is easily formed, so that the resulting film becomes stronger and durable. Can be improved. Considering the effect of further improving the adhesion and durability, the number of groups represented by the general formula B ′ constituting the compound (B-2) is more preferably 2 to 5, particularly preferably 3 It is a piece. That is, the compound (B-2) has the following formula:

It is particularly preferred that In the above structure, R ⁷ and r are the same as those in the general formula B ′, and thus the description thereof is omitted here.

More specifically, tris (3- (trimethoxysilyl) methyl) isocyanurate, tris (3- (triethoxysilyl) methyl) isocyanurate, tris (3- (tripropoxysilyl) methyl) isocyanurate, tris ( 3- (triisopropoxysilyl) methyl) isocyanurate, tris (3- (trimethoxysilyl) ethyl) isocyanurate, tris (3- (triethoxysilyl) ethyl) isocyanurate, tris (3- (tripropoxysilyl) Ethyl) isocyanurate, tris (3- (triisopropoxysilyl) ethyl) isocyanurate, tris (3- (trimethoxysilyl) propyl) isocyanurate, tris (3- (triethoxysilyl) propyl) isocyanurate, tris ( 3- (Tripropoxy Ril) propyl) isocyanurate, tris (3- (triisopropoxysilyl) propyl) isocyanurate, tris (3- (dimethoxyethoxysilyl) methyl) isocyanurate, tris (3- (methoxydiethoxysilyl) methyl) isocyanurate , Tris (3- (dimethoxypropoxysilyl) methyl) isocyanurate, tris (3- (methoxydipropoxysilyl) methyl) isocyanurate, tris (3- (dimethoxyisopropoxysilyl) methyl) isocyanurate, tris (3- ( Methoxydiisopropoxysilyl) methyl) isocyanurate, tris (3- (dimethoxyethoxysilyl) ethyl) isocyanurate, tris (3- (methoxydiethoxysilyl) ethyl) isocyanurate, tris (3- (dimethyl) Xypropoxysilyl) ethyl) isocyanurate, tris (3- (methoxydipropoxysilyl) ethyl) isocyanurate, tris (3- (dimethoxyisopropoxysilyl) ethyl) isocyanurate, tris (3- (methoxydiisopropoxysilyl) Ethyl) isocyanurate, tris (3- (dimethoxyethoxysilyl) propyl) isocyanurate, tris (3- (methoxydiethoxysilyl) propyl) isocyanurate, tris (3- (dimethoxypropoxysilyl) propyl) isocyanurate, tris ( 3- (methoxydipropoxysilyl) propyl) isocyanurate, tris (3- (dimethoxyisopropoxysilyl) propyl) isocyanurate, tris (3- (methoxydiisopropoxysilyl) propyl) Examples include isocyanurate. Of these, tris (3- (trimethoxysilyl) propyl) isocyanurate and tris (3- (triethoxysilyl) propyl) isocyanurate are preferable, and tris (3- (trimethoxysilyl) propyl) isocyanurate is more preferable. . The condensate (B) obtained by using such a compound (B-2) strongly interacts with the base material (excellent adhesion) and has a large number of crosslinking points, thus forming a strong film. can do. For this reason, the film formed using the coating agent containing the said condensate (B) can provide the more outstanding piercing characteristic (lubricity) and durability.

As described above, the condensate (B) is obtained by the condensation of the compound (B-1) and the compound (B-2). Here, the condensation method of the compound (B-1) and the compound (B-2) is not particularly limited, and a known condensation method can be applied similarly or appropriately modified. Specifically, a method in which compound (B-1) and compound (B-2) are reacted in an appropriate solvent in the presence of a catalyst, if necessary, is preferable. Here, the applicable solvent is not particularly limited, but can dissolve the compounds (B-1) and (B-2) and has low reactivity with the compounds (B-1) and (B-2). preferable. Specifically, use of an organic solvent having no active proton is preferable, and benzene, toluene, xylene, cumene, dioxane, tetrahydrofuran, hexane, pentane, heptane and the like can be more preferably used. The said solvent may be used independently or may be used with the form of a 2 or more types of liquid mixture. The solvent is preferably dehydrated in advance. Here, the amount of the solvent used is not particularly limited, but the total concentration of the compounds (B-1) and (B-2) is preferably about 5 to 30% by mass.

In the above method, the mixing ratio of the compounds (B-1) and (B-2) is not particularly limited as long as the condensation of the compound (B-1) and the compound (B-2) can proceed. Specifically, the compound (B-2) is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the compound (B-1). With such an amount, the compound (B-1) and the compound (B-2) can be efficiently condensed. The condensation conditions of the compound (B-1) and the compound (B-2) are not particularly limited as long as the condensation of the compound (B-1) and the compound (B-2) can proceed. Specifically, the condensation temperature is preferably 50 to 100 ° C., more preferably 70 to 90 ° C. Further, the condensation time is preferably 7 to 20 hours, more preferably 8 to 12 hours. Under such conditions, the condensation of compound (B-1) and compound (B-2) proceeds efficiently, and the desired condensate (B) can be produced in high yield. When the compound (B-1) is a mixture of two or more, it is understood that the amount of the compound (B-1) is a total amount. Similarly, when the compound (B-2) is a mixture of two or more, it is understood that the amount of the compound (B-2) is a total amount.

As described above, the condensation of the compound (B-1) and the compound (B-2) may be performed in the presence of a suitable catalyst. The catalyst which can be used in this case is not particularly limited, and a known catalyst can be used. Specifically, platinum complexes such as chloroplatinic acid, platinum-olefin complexes and platinum-vinylsiloxane complexes, platinum catalysts in which platinum black and platinum are supported on a carrier, rhodium catalysts such as chlorotris (triphenylphosphine) rhodium, Examples thereof include nickel catalysts such as dichlorobis (triphenylphosphine) nickel and cobalt catalysts such as dicobalt octacarbonyl.

Further, the reaction product obtained by the above condensation reaction may be further purified by a known means such as silica gel column chromatography if necessary. The condensate (B) may be prepared in advance and then mixed with the amino group-containing polyorganosiloxane (A) or polydiorganosiloxane (C), or the amino group-containing polyorganosiloxane ( A) and polydiorganosiloxane (C) may be mixed. In the latter case, from the viewpoint of achieving an accurate composition, the amino group-containing polyorganosiloxane (A) is preferably added after the condensation reaction. This is because polydiorganosiloxane (C) does not participate in the condensation reaction and may be present simultaneously during the condensation reaction, but amino group-containing polyorganosiloxane (A) may contribute to the condensation reaction. Because.

The condensate (B) is contained in an amount of 0.1 to 30% by mass with respect to the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C). Here, when the content of the condensate (B) is less than 0.1% by mass, the strength of the formed film cannot be sufficiently achieved and the durability is inferior. On the contrary, when the content of the condensate (B) exceeds 30% by mass, the content of the other essential component amino group-containing polyorganosiloxane (A) and polydiorganosiloxane (C) is too small. The effects of these components cannot be fully demonstrated. The condensate (B) is preferably contained in an amount of 1 to 20% by mass with respect to the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C), and more It is preferably contained in an amount of 5 to 15% by mass. With such an amount, the durability can be further improved. Moreover, adhesiveness with a base material and lubricity (the piercing ease, the reduction effect of piercing resistance) can be improved more effectively. In addition, the safety of the coating agent can be further improved, which is particularly preferable when used for medical applications such as needles. In addition, when a condensate (B) is contained with 2 or more types of mixtures, content of the said condensate (B) is a total amount.

It was also found that the condensate (B) is preferably mixed with the amino group-containing polyorganosiloxane (A) at an appropriate ratio. That is, the condensate (B) is preferably contained in an amount of more than 1 part by weight and 50 parts by weight or less with respect to 100 parts by weight of the amino group-containing polyorganosiloxane (A). More preferably. When the mixing ratio of the amino group-containing polyorganosiloxane (A) and the condensate (B) is such that the effects of the condensate (B) and the amino group-containing polyorganosiloxane (A) are more remarkably exhibited. A firmer film can be formed, and lubricity (ease of piercing, reduction effect of piercing resistance) can be further improved. In addition, when the condensate (B) is a mixture of two or more, it is understood that the amount of the condensate (B) is a total amount. Similarly, when the amino group-containing polyorganosiloxane (A) is a mixture of two or more, it is understood that the amount of the amino group-containing polyorganosiloxane (A) is a total amount.

[Polydiorganosiloxane (C)]
The polydiorganosiloxane (C) according to the present invention has the following general formula C:

Indicated by The polydiorganosiloxane (C) is a polydiorganosiloxane having a triorganosilyl group at the end of the molecular chain and containing no amino group in the molecule as shown in the above structure. And does not contain hydrolyzable groups.

Polydiorganosiloxane (C) imparts lubricity to the coating film by the organosiloxane portion. For this reason, due to the presence of the polydiorganosiloxane (C), the formed film can exhibit high lubricity (the ease of piercing and the effect of reducing piercing resistance). When two or more structural units of the formula: —Si (R ¹⁰ ) ₂ O— are present (q is 2 or more), each structural unit may be the same or different. Furthermore, the coating agent of this invention may contain polydiorganosiloxane (C) individually by 1 type, or may contain 2 or more types of polydiorganosiloxane (C).

In the above general formula C, R ⁹ and R ¹⁰ represent a monovalent hydrocarbon group. Here, the plurality of R ⁹ may be the same or different. Similarly, the plurality of R ¹⁰ may be the same or different. Since the monovalent hydrocarbon group as R ⁹ and R ^{10 is the same} as defined in the general formula A, description thereof is omitted here. Of these, from the viewpoint of improving lubricity, a linear or branched alkyl group having 1 to 16 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable. A linear or branched alkyl group having 1 to 4 carbon atoms is even more preferable, and a methyl group is particularly preferable.

In the above general formula C, q is an integer of 8 to 1000, preferably an integer of 10 to 200. If it is q as described above, the polydiorganosiloxane (C) can exhibit sufficient lubricity and can further reduce friction (puncture resistance) with the substrate. Therefore, the molecular weight of the polydiorganosiloxane (C) is not particularly limited, but the weight average molecular weight is preferably 500 to 7000, more preferably 1500 to 5000.

Specifically, preferred examples of the polydiorganosiloxane (C) include polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydiisopropylsiloxane, polymethylethylsiloxane, polymethylpropylsiloxane, polymethylisopropylsiloxane, polyethyl Examples include propylsiloxane and polyethylisopropylsiloxane. Of these, polydimethylsiloxane is preferred in consideration of lubricity (piercing characteristics) and the like.

The polydiorganosiloxane (C) is contained in an amount of 10 to 89.9% by mass with respect to the total amount of the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C). Here, when the content of the amino group-containing polyorganosiloxane (A) is less than 10% by mass, the lubricity (easy to pierce and the effect of reducing piercing resistance) is inferior, which is not preferable. On the contrary, when the content of polydiorganosiloxane (C) exceeds 90% by mass, the content of the other essential component amino group-containing polyorganosiloxane (A) and condensate (B) is too small. The effects of these components cannot be fully demonstrated. The polydiorganosiloxane (C) is preferably contained in an amount of 20 to 70% by mass based on the total amount of the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C). More preferably, it is contained in an amount of 30 to 60% by mass. If it is such quantity, lubricity (Easy piercing, reduction effect of piercing resistance) can be improved more effectively. In addition, when polydiorganosiloxane (C) is contained in 2 or more types of mixtures, content of the said polydiorganosiloxane (C) is a total amount.

The coating agent of the present invention essentially contains the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C). Here, the coating agent of the present invention may be composed of only the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C), or may further contain other components in addition to the above. May be included. In the latter case, other components that can be used are not particularly limited, and include components that are usually added to known coating agents, in particular, needle coating agents. More specifically, an organic solvent, a condensation reaction catalyst, an antioxidant, a dye, a surfactant, a slip agent, a primer, and the like can be mentioned. Further, the content of other components is not particularly limited as long as the effects of the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C) are not impaired, but the amino group-containing polyorganosiloxane ( A), about 0.1 to 5% by mass with respect to the total amount of the condensate (B) and the polydiorganosiloxane (C). When the amino group-containing polyorganosiloxane (A), condensate (B) or polydiorganosiloxane (C) is contained in a mixture of two or more, it is understood that these contents are the total amount. To do.

Of these, organic solvents are particularly preferably used. Here, it does not restrict | limit especially as an organic solvent, The solvent similar to what is used for a well-known coating agent can be used. Specifically, chlorofluorocarbon solvents such as 1,1,2-trichloro-1,2,2-trifluoroethane, chlorine-containing hydrocarbons such as methylene chloride (dichloromethane) and chloroform, fats such as butane, pentane, and hexane Aromatic hydrocarbons such as aromatic hydrocarbons, benzene, toluene, xylene, esters such as ethyl acetate and butyl acetate, water-insoluble ketones such as methyl isobutyl ketone, ethers such as tetrahydrofuran (THF), butyl ether, dioxane, Examples thereof include aliphatic alcohols such as methanol, ethanol and isopropanol, volatile siloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane, acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and carbon disulfide. These organic solvents may be used alone or as a mixed solvent in which two or more of these solvents are combined. The amount of the organic solvent used is not particularly limited, but considering the ease of coating, the total concentration of amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) is 5 to It is preferably about 80% by mass, preferably about 10 to 60% by mass. In addition, when coating the needle with the coating agent of the present invention, the coating agent may be further diluted with the organic solvent. In this case, the total concentration of amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) is 1 to 10% by mass, more preferably 3 to 7% by mass. It is preferable to dilute with an organic solvent.

The production method of the coating agent of the present invention is not particularly limited, and the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C), and, if necessary, the other components described above, A method of mixing with the above-described composition and stirring and mixing can be used. In the above method, it is preferable to add an organic solvent. This makes it possible to actually easily coat needles and the like. Here, it does not restrict | limit especially as an organic solvent, The organic solvent described as said other component is used preferably. Here, the stirring and mixing conditions are not particularly limited. Specifically, the stirring / mixing temperature is preferably 10 to 40 ° C., more preferably 20 to 30 ° C. The stirring / mixing time is preferably 1 to 5 hours, more preferably 1 to 3 hours. Under such conditions, the amino group-containing polyorganosiloxane (A), the condensate (B) and the polydiorganosiloxane (C) and, if necessary, the other components do not cause an undesirable reaction. And evenly mixed.

The coating agent of the present invention can improve the lubricity and durability of the object. For this reason, the coating agent of this invention can be used especially suitably in the field | area of the needle | hook with a high request | requirement of the said characteristic. Therefore, this invention also provides the needle | hook formed by surface-treating a needle | hook by the hardening process of the coating agent of this invention.

The needle may be formed of any material, and materials similar to those normally used for needles, particularly medical needles (for example, injection needles), such as metal materials and polymer materials, can be used. The metal material is not limited to the following, but various stainless steels (SUS) such as SUS304, SUS316L, SUS420J2, and SUS630, gold, platinum, silver, copper, nickel, cobalt, titanium, iron, aluminum, tin, or nickel- Various alloys such as titanium (Ni-Ti) alloy, nickel-cobalt (Ni-Co) alloy, cobalt-chromium (Co-Cr) alloy, zinc-tungsten (Zn-W) alloy, metal-ceramic composites, etc. Is mentioned. The said metal material may be used independently or may use 2 or more types together. The metal material is bonded to the hydroxyl group on the surface and the nitrogen atom of the amide group (—N (R) —C (═O) —) of the condensate (B) constituting the coating agent. For this reason, the needle | hook formed with the said material is excellent in adhesiveness with the film by the coating agent of this invention. Examples of the polymer material include, but are not limited to, polyamide resins such as nylon 6, nylon 11, nylon 12, nylon 66 (all are registered trademarks), linear low density polyethylene (LLDPE), and low density polyethylene (LDPE). ), Polyolefin resins such as polyethylene resins such as high density polyethylene (HDPE) and polypropylene resins, modified polyolefin resins, epoxy resins, urethane resins, diallyl phthalate resins (allyl resins), polycarbonate resins, fluororesins, amino resins (urea resins, (Melamine resin, benzoguanamine resin), polyester resin, styrene resin, acrylic resin, polyacetal resin, vinyl acetate resin, phenol resin, vinyl chloride resin, silicone resin (silicon resin), polyether resin, polyethylene Such as de resin and the like. The above polymer materials may be used alone or in combination of two or more.

Moreover, the base material surface-treated with the coating agent of the present invention has a functional group such as a hydroxyl group or a carboxyl group from the viewpoint of easily interacting with a functional group such as an amino group or an amide group of the coating agent of the present invention. The base material which has is preferable. In particular, when the base material is a metal material, the metal material is preferable because of its high adhesion to the coating agent of the present invention because its surface is covered with an oxide film and has a hydroxyl group and the like. In addition, in the case of a substrate that has little interaction with functional groups such as amino groups and amide groups that the coating agent of the present invention has, the coating of the present invention can be performed by imparting functional groups such as hydroxyl groups to the substrate by plasma treatment or the like. Adhesiveness between the agent and the substrate can be enhanced.

The surface treatment method using the coating agent of the present invention is not particularly limited, but it is preferable that the curing treatment is performed by heating or irradiating a coating film containing the coating agent.

The formation method of the coating film containing a coating agent is not restrict | limited, A well-known coating method is applicable. Specifically, the dipping method (dipping method), coating / printing method, spraying method (spray method), brush coating, spin coating method, coating agent-impregnated sponge coating method, etc. are applied as coating (coating) methods. can do. In addition, when coating a coating agent on the needle surface, the penetration of the coating agent into the needle may be prevented by sending a gas such as air into the needle. Thereby, needle clogging due to the coating agent can be prevented. Moreover, the coating agent coated on the base material may be volatilized by air drying, heating or the like, if necessary, and in some cases, the coating agent may be precured at the same time.

When a coating film is formed only on a part of the needle surface, only a part of the needle surface is immersed in the coating agent, and the coating agent (coating solution) is coated on a part of the needle surface. The film may be formed on a desired surface portion of the needle surface by reacting by heating, radiation irradiation, or the like. If it is difficult to immerse only a part of the needle surface in the coating agent, the surface of the needle that does not need to be formed in advance must be protected (covered) with an appropriate removable member or material. Etc.), the needle is immersed in a coating agent, and the coating agent is coated on the surface of the needle, and then the protective member (material) on the surface of the needle that does not need to form a coating film is removed and then heated. The film can be formed on a desired surface portion of the needle surface by reacting by irradiation with radiation or the like. However, the present invention is not limited to these forming methods, and a coating film can be formed by appropriately using conventionally known methods. For example, when it is difficult to immerse only a part of the needle surface in the coating agent, another coating method (for example, an application method or a spray method) may be applied instead of the dipping method. If both the outer and inner surfaces of the needle surface need to have lubricity and durability, the dipping method (dipping method) can be used because both the outer surface and the inner surface can be coated at once. ) Is preferably used.

Among the surface treatments (curing treatments), the heat treatment conditions (reaction conditions) in the case of heat treatment are the reaction between the amino group-containing polyorganosiloxane (A) and the condensate (B) or the condensate (B). Thus, there is no particular limitation as long as it is a condition capable of forming a strong film. The heating temperature is preferably 50 to 150 ° C, more preferably 60 to 130 ° C. The heating time is preferably 2 to 48 hours, more preferably 15 to 30 hours. Under such reaction conditions, the amino group-containing polyorganosiloxane (A) and the condensate (B) can react with the substrate surface to form a strong film. In addition, the amino group-containing polyorganosiloxane (A) (amino group) and the condensate (B) (amide group) can be firmly bonded to the substrate. The pressure condition during the heat treatment is not limited at all, and it can be performed under normal pressure (atmospheric pressure), or under pressure or reduced pressure. Moreover, as a heating means (apparatus), an oven, a dryer, a microwave heating apparatus etc. can be utilized, for example.

In addition, when the surface treatment (curing treatment) is performed by radiation irradiation, the radiation is not particularly limited, and may be gamma rays (γ rays), electron beams, neutron rays, or X-rays. Of these, gamma rays or electron beams are preferred. By irradiating with radiation, not only the curing treatment of the coating agent is accelerated, but also sterilization of the needle can be performed. Radiation irradiation conditions (reaction conditions) are not particularly limited as long as the amino group-containing polyorganosiloxane (A) and the condensate (B) or the condensate (B) can react with each other to form a strong film. It is not something. For example, in the case of gamma irradiation, conditions such as the dose and irradiation time are not particularly limited, but usually the γ dose is 10 to 50 kGy, preferably 15 to 25 kGy. Under such irradiation conditions, the amino group-containing polyorganosiloxane (A) and the condensate (B), or the condensate (B) can react to form a strong film. In addition, the amino group-containing polyorganosiloxane (A) (amino group) and the condensate (B) (amide group) can be firmly bonded to the substrate.

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. In the following examples, the operation was performed at room temperature (25 ° C.) unless otherwise specified. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”, respectively.

Synthesis Example 1: Synthesis of condensate (B1) A condensate (B1) was synthesized as follows. That is, 10 parts by mass of a polydimethylsiloxane having both ends silanol groups having the following structure (weight average molecular weight = about 884,000), 2 parts by mass of tris (3- (trimethoxysilyl) propyl) isocyanurate having the following structure and dehydrated toluene 109 A part by mass was added and stirred at 85 ° C. for 8 hours. After reacting for a predetermined time, the reaction solution was purified by a gel filtration column to synthesize a condensate (B1).

Example 1
Amino group-containing polyorganosiloxane (A) (weight average molecular weight = about 15000) 66 parts by mass, condensate (B1) synthesized in Synthesis Example 1 10 parts by mass, polydimethylsiloxane (weight average molecular weight = about 3000, general formula Q = 38 in C) 73 parts by mass and 20 parts by mass of ethanol were added and stirred at 85 ° C. for 2 hours to obtain Coating Agent 1. In this example, amino group-containing polyorganosiloxane (A) having the following structure was used.

Comparative Example 1
In Example 1, except that N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (average molecular weight 250,000, polymerization degree 4000) having the following structure was used instead of the condensate (B1). Reaction similar to Example 1 was performed and the coating agent 2 was obtained. N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane was prepared in the same manner as Preparation Example 1 of JP-A-7-178159.

For the coating agents 1 and 2 obtained in Example 1 and Comparative Example 1, the penetration resistance was measured according to the following method.

[Measurement of piercing resistance]
(Coating on injection needle 1)
Each coating agent is diluted with dichloromethane so that the concentration of the silicone component (the total amount of the amino group-containing polyorganosiloxane (A), condensate (B1) and polydimethylsiloxane) is about 5% by mass, and is colorless. A transparent coating solution was obtained. Using a tensile tester (Autograph AG-1kNIS Shimadzu Corporation), an 18G injection needle (needle part made of SUS304) was immersed in this coating solution, and the injection needle was pulled up at a speed of 1000 mm / min. It was naturally dried at room temperature for 2 hours. Further, the injection needle was heated in an oven at 105 ° C. for 24 hours for curing. The injection needle whose surface is coated with the coating agent 1 is referred to as an injection needle 1, and the injection needle whose surface is coated with the coating agent 2 is referred to as a comparative injection needle 1.

(Coating on injection needle 2)
Each coating agent is diluted with dichloromethane so that the concentration of the silicone component (the total amount of the amino group-containing polyorganosiloxane (A), condensate (B1) and polydimethylsiloxane) is about 5% by mass, and is colorless. A transparent coating solution was obtained. Using a tensile tester (Autograph AG-1kNIS Shimadzu Corporation), an 18G injection needle (needle part made of SUS304) was immersed in this coating solution, and the injection needle was pulled up at a speed of 1000 mm / min. It was naturally dried at room temperature for 2 hours. Further, the injection needle was irradiated with 20 kGy of γ rays to perform a curing process. The injection needle whose surface is coated with the coating agent 1 is referred to as an injection needle 2, and the injection needle whose surface is coated with the coating agent 2 is referred to as a comparative injection needle 2.

(Measurement of piercing resistance)
The needles 1 and 2 and the comparative needles 1 and 2 were each punctured at a 15 μm angle and a speed of 1000 mm / min on a 50 μm thick polyethylene film using a tensile tester (manufactured by Autograph AG-1kNIS Shimadzu Corporation). The puncture resistance value (kgf) was measured. Specifically, the puncture resistance value with respect to the moving amount of the injection needle was acquired as time series data. Moreover, the maximum resistance value (kgf) and the trunk | drum sliding resistance value (kgf) were computed from the measured value. The above measurement was performed after the needles 1 and 2 and the comparative needles 1 and 2 were punctured 0 times, 5 times, and 10 times into the rubber stopper, respectively, and the graph shows the rubber stopper (for liquid use manufactured by Nidec Rika Glass Co., Ltd.). The measured values were plotted against the number of punctures to a (butyl rubber stopper). In this test, the “maximum resistance value (kgf)” is the maximum piercing resistance value measured near the root of the needle blade surface. Specifically, this is the maximum puncture resistance value in the time series data of the puncture resistance value described above. Further, the “body trunk sliding resistance value (kgf)” is the piercing at the portion where the piercing resistance value becomes constant when passing through the cylindrical portion beyond the blade surface after the maximum resistance value is observed. Resistance value. Specifically, in the time-series data of the puncture resistance value, the average value of the puncture resistance values of the portion where the puncture resistance value becomes substantially constant after the maximum resistance value is observed.

The results are shown in Figs. FIG. 1 shows the measurement results of the piercing resistance (maximum resistance value (kgf)) when coating 1 (heating at 105 ° C. for 24 hours) is applied to the injection needle. FIG. 2 shows the measurement results of the piercing resistance (maximum resistance value (kgf)) when coating 2 (γ-ray irradiation) is applied to the injection needle. FIG. 3 shows the measurement results of the piercing resistance (trunk resistance value (kgf)) when coating 2 (γ-ray irradiation) is applied to the injection needle.

1 and 2, the injection needles 1 and 2 surface-treated with the coating agents 1 and 2 of the present invention are the comparative injection needles 1 and 2 surface-treated with the comparative coating agents 1 and 2 that do not contain the condensate (B1). It can be seen that the piercing resistance is reduced as compared with the above, and the piercing characteristics can be improved. In addition, the increase in puncture resistance after puncturing the rubber stopper is significantly suppressed in the injection needles 1 and 2 according to the present invention as compared with the comparison injection needles 1 and 2, and it is also shown that durability can be improved. . Furthermore, the above effects are judged to be equivalent in both cases where the surface treatment is performed by heating and γ-ray irradiation.

Moreover, from FIG. 3, the injection needle 2 surface-treated by γ-ray irradiation with the coating agent 1 of the present invention is compared with the comparative injection needle 2 surface-treated with the coating agent 2 of Comparative Example 1 that does not contain the condensate (B1). Thus, it can be seen that the piercing resistance of the trunk portion is reduced and the piercing characteristics can be improved.

Furthermore, this application is based on Japanese Patent Application No. 2014-151116 filed on July 24, 2014, the disclosure of which is referenced and incorporated as a whole.

Claims (8)

(1) The following general formula A:

Provided that each R ¹ independently represents a monovalent hydrocarbon group or —OR ⁵ group. In this case, each R ⁵ independently represents a monovalent monovalent hydrocarbon group having 1 to 4 carbon atoms, which is substituted or unsubstituted. Represents a hydrocarbon group of
Each R ² independently represents a monovalent hydrocarbon group;
Each A independently represents an amino group-containing group;
m: n = 1: 5 to 100, and m is an integer from 1 to 100.
An amino group-containing polyorganosiloxane (A) containing at least one amino group in one molecule, represented by the formula:
(2) The following general formula B:

However, R ³ and R ^{3 ′} each independently represents a monovalent hydrocarbon group or a hydroxyl group (—OH), and at least one of R ³ and at least one of R ^{3 ′} are a hydroxyl group (—OH). ) And
Each R ⁴ independently represents a monovalent hydrocarbon group;
p is an integer of 1 to 10,000,
And a compound represented by the following general formula B ′:

Provided that each R ⁷ independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein at least one of R ⁷ is an alkoxy group. ,
r is an integer from 1 to 6;
* Represents a bond position,
A condensate (B) of the compound (B-2) having a group represented by the formula: 0.1 to 30% by mass; and (3) the following general formula C:

However, R ⁹ and R ¹⁰ each independently represent a monovalent hydrocarbon group,
q is an integer of 8 to 1000,
The polydiorganosiloxane (C) is represented by 10 to 89.9% by mass (the total amount of the amino group-containing polyorganosiloxane (A), condensate (B) and polydiorganosiloxane (C) is 100% by mass. is there)
Coating agent containing. The coating agent according to claim 1, wherein the compound (B-2) has at least two groups represented by the general formula B '. The compound (B-2) has the following formula:

Provided that each R ⁷ independently represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein at least one of R ⁷ is an alkoxy group. ,
each r is independently an integer of 1 to 6,
The coating agent of Claim 2 shown by these. The coating agent according to any one of claims 1 to 3, wherein in the general formula B ', all R ⁷ are alkoxy groups. In the general formula A, the amino group-containing group is a γ-aminopropyl group, an N- (β-aminoethyl) aminomethyl group, or a γ- (N- (β-aminoethyl) amino) propyl group. Item 5. The coating agent according to any one of Items 1 to 4. The condensate (B) is contained in a proportion of more than 1 part by weight and 50 parts by weight or less with respect to 100 parts by weight of the amino group-containing polyorganosiloxane (A). The coating agent according to item. A needle obtained by surface-treating a needle by a curing treatment of the coating agent according to any one of claims 1 to 6. The needle according to claim 7, wherein the curing treatment is performed by heating or irradiating a coating film containing the coating agent.

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