JPS6159739B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to medical needle protectors made from specially crosslinked block copolyester. More specifically, the present invention relates to a medical needle protector made of an elastic polymer that is particularly excellent in hygiene and heat resistance, can be injection molded, and is then crosslinked. Conventionally, caps made of rubber or other thermoplastic resins have been used as protectors for medical needles such as injection needles and intravenous drip needles. This protactor is roughly divided into hard and soft products depending on the hardness of the material. Hard protactors are made of materials such as polypropylene or polyethylene, but when these hard protactors are attached to a needle, if they come in contact with the teeth of the needle, the teeth become sharp, causing pain to the person receiving the injection. When it is applied or penetrated into other rubber or plastic membranes or walls, it creates debris from the rubber or plastic, which is undesirable. Furthermore, when used in a needle attached to an infusion container, the sealing performance is poor and the liquid content tends to leak out during steam sterilization, which is undesirable. These drawbacks can be improved by using a protactor made of soft materials, but soft materials such as rubber require the addition of large amounts of additives and vulcanization accelerators. There are many additives whose use in medical devices is questionable from a sanitary standpoint. Other soft materials such as soft synthetic resin include soft polyvinyl chloride, but the hygiene of the plasticizers contained therein is also considered problematic when used for medical purposes. Other soft resins, such as transparent silicone rubber, have molding difficulties in that they cannot be injection molded or are expensive, and vinyl acetate resin, polyptadiene resin, etc. cannot be sterilized by steam sterilization (121℃, 60 minutes). It has no thermal properties and is difficult to mold. Among these conditions particularly required for medical needle protectors, the airtightness of the needle tip is extremely important. When using conventional medical instruments for treatment,
Even if a secondary infection occurs, the path of inflow of pathogenic bacteria is not clear, leading to various problems. If the needles used in the above medical instruments are completely sealed and then steam sterilized, there is no risk of secondary infection. That is,
If a material made of a soft resin that does not contain substances undesirable from a sanitary standpoint and can withstand steam sterilization is used as a material for medical needle protectors, an extremely useful protector will emerge. Thermoplastic polyester elastomer has been proposed as a material that satisfies these requirements. Although this polyester elastomer is certainly suitable and compensates for the drawbacks of conventional materials, it is still desired to have excellent heat resistance, chemical resistance, and fitting properties (no falling out when attached to a needle). ing. The present inventors have studied improvements in this respect and have arrived at the present invention. That is, the present invention provides a medical needle protector made of resin, in which the material has an average molecular weight of about 300 to 300.
5,000 and a polyoxyalkylene glycol and/or aliphatic polyester having a carbon number to oxygen number ratio of 2.0 to 4.5 as a soft segment and an aromatic polyester as a hard segment, the proportion of the soft segment is It accounts for 20-80% by weight of the block copolyester, and the portion insoluble in orthochlorophenol is 20% by weight.
As described above, the present invention relates to a medical needle protector characterized by being made of a crosslinked elastic polymer.
Here, the method for measuring the insoluble portion is a cross-linked elastic polymer.
Add 1.2g to 100ml of orthochlorophenol and add 100g to 100ml of orthochlorophenol
Stir and dissolve at ℃ for 1 hour. After cooling, quickly filter with a 3G glass filter, thoroughly wash the insoluble residue on the filter with acetone, dry, leave to cool in a desiccator, measure the weight, and divide by the weight before immersion heating. Find the weight percent. The elastomeric polymer used in the present invention mainly consists of block copolyester. Examples of the polyoxyalkylene glycol as a soft segment constituting the block copolyester include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and poly(oxyethylene-oxypropylene) block (or random) copolyether glycol. , poly(oxyethylene-oxypropylene) block (or random) copolyether glycol, and the like. The ratio of carbon number to oxygen number is between 2.0 and 4.5. Moreover, these average molecular weights are about 300-5000. Furthermore, these may be used alone or in combination of two or more. In addition, the aliphatic polyester used as a soft segment together with or in place of the polyoxyalkylene glycol is mainly composed of a polyester in which both the acid component and the glycol component are selected from aliphatic or alicyclic compounds. or those whose main constituent is an aliphatic or alicyclic oxyacid,
Particularly preferred are polymers having a glass transition temperature below room temperature. Suitable examples of such aliphatic polyesters include adivic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, ε-hydroquinecabronic acid, 4-β-
Hydroquine ethoxycyclohexanecarboxylic acid,
Ethylene glycol, trimethylene glycol,
By combining an acid component selected from propylene glycol, tetramethylene glycol, 1,6-hexanediol, diethylene glycol, 1,1-cyclohexanedimethylol, functional derivatives thereof, etc. with a glycol component or an oxyacid component. Mention may be made of the polyesters produced which have the above-mentioned properties. Although a small proportion of an aromatic compound component can be copolymerized with such aliphatic polyester, since the aromatic compound component has the effect of increasing the glass transition temperature, it is natural that the copolymerization proportion is limited by itself. It is. Further, polyoxyalkylene glycol may be copolymerized into the aliphatic polyester described above. The aromatic polyester constituting the hard segment of the block copolyester is a polyester whose main acid component is essentially terephthalic acid and/or 2,6-naphthalene dicarboxylic acid and whose main glycol component is a glycol having 2 to 10 carbon atoms. Although the main target is other third components such as isophthalic acid, diphenyl dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-
Even if hydroxyethoxybenzoic acid, diethylene glycol, bisβ-hydroxyethoxyphenyl sulfone, 2,2-bisβ-hydroxyethoxyphenylpropane, the components used in the aliphatic polyesters mentioned above, and their functional derivatives are copolymerized, good. In that case, the third component may be one or more types, but it is preferably about 30 mol% or less of the total components. Also, polyfunctional compounds such as trimesic acid, trimethylolpropane, bentaerythritol and functional derivatives thereof, and/or monofunctional compounds such as methoxypolyoxyethylene glycol, o-benzoylbenzoic acid and functional derivatives thereof. The above may be copolymerized to the extent that the polymer is substantially linear. The block copolyester in the present invention is a block copolyester which is substantially composed of the above-mentioned aromatic polyester, aliphatic polyester and/or polyoxyalkylene glycol,
The soft segment of the aliphatic polyester and/or polyoxyalkylene glycol accounts for 20-80% by weight. As mentioned above, various dicarboxylic acids and diols can be used for the block copolyester used in the present invention, but a particularly preferable composition for producing a proctor by injection molding etc. is a hard segment aromatic polyester. Polytetramethylene phthalate, polytrimethylene terephthalate, polyhexamethylene terephthalate, etc. Polyoxyalkylene glycol of soft segment is polytetramethylene glycol, and aliphatic polyester is polyethylene adipate, polytetramethylene adipate, These include polyhexamethylene adipate and polyethylene sebacate. It is difficult to limit the particularly preferable range of the soft segment because it varies depending on the application, but it is
70% by weight is preferred, particularly 30-65% by weight. Those within this range have good physical properties and good molding cycleability. For example, in the case of a polyester ether block copolymer, the method for producing the block copolyester used in the present invention involves appropriate transesterification of dimethyl ester of terephthalic acid and a low molecular weight diol, particularly tetramethylene glycol and polytetramethylene glycol. It can be prepared by reacting in the presence of a small proportion of a catalyst, such as an organic titanate, and then distilling off the excess low molecular weight diol from the resulting prepolymer under reduced pressure. In the case of a polyester block copolymer, the above-mentioned aromatic polyester and aliphatic polyester are melt-mixed and a blocking reaction is carried out. The blocking reaction is preferably carried out in the presence of a titanium catalyst. This blocking reaction varies depending on various conditions such as the type of two or more polyesters to be reacted, their terminal group concentration, reaction temperature, and moisture content in the reaction system, but generally it is carried out for 5 to 120 minutes, at 150°C or higher, and in particular to 200℃
It is further carried out at a temperature of 230° C. or higher, which is higher than the melting point of the polyester. For the above-mentioned most preferred combination of two or more polyesters, a temperature of 230°C or higher and lower than 260°C is optimal. The atmosphere during melt-mixing for carrying out the blocking reaction may be under increased pressure, reduced pressure, or normal pressure, and in any case, an inert atmosphere is preferable. Generally, the blocking reaction is substantially completed after being carried out for 3 to 120 minutes, but to confirm this more specifically, the polymer is sampled from within the system as the reaction progresses, and its softening point and elastic recovery rate are measured. This can be done appropriately by researching the method in advance. It has also been revealed that the point at which the softening point reaches its maximum value generally coincides with the point at which the reaction system becomes transparent; therefore, usefully, the point at which the reaction system becomes transparent can also be used for judgment. It is valid.
These points coincide with the point at which the blocking reaction is substantially complete. In the above blocking reaction, it is preferable to add a phosphorus compound to the reaction system when the reaction is completed. The phosphorus compound has the effect of substantially deactivating or suppressing the catalytic activity of the titanium-based catalyst present in the reaction system, and at the stage where the blocking reaction has progressed appropriately, it prevents the subsequent randomization reaction from proceeding. Stop and suppress to the maximum extent possible. Block copolyesters are thus obtained, and these reactions can be carried out either continuously or batchwise. For example, polyester-ester block copolyester is prepared by melt-mixing the copolyester and passing it through an extruder together with a phosphorus compound.
There are methods such as deactivating the titanium-based catalyst, or directly feeding the phosphorus compound into a reaction tank in which the blocking reaction is carried out in a batch manner, deactivating or suppressing it, and then taking it out. If it is desired to impart transparency to the medical needle protector of the present invention, this can be achieved by making the polyester polymer portion a copolymer. As will be described in more detail later, when trying to impart transparency to the intended protactor, for example, tetramethylene glycol can be used as the main diol component and ethylene glycol, cyclohexanedimethanol, etc. in an amount of 10 to 40 mol%. Favorable effects can be obtained when mixed with glycol. These are ester-forming derivatives, such as bis-
Adding it in the form of β-hydroxyethyl terephthalate is useful for controlling the copolymerization ratio of the product at a constant level. Any method may be used to mold the block polyester obtained as described above into a protector for a medical needle, such as an injection needle, but melt injection molding is advantageous. The medical needle protector referred to in the present invention corresponds to a device or a cap for a metal needle that is attached to a medical device such as a syringe, an infusion, a blood transfusion set, a plastic container for drip, etc. . This needle can be used, for example, to insert directly into the human body or to connect other parts or instruments through a plastic or rubber membrane wall.
Gaseous chemicals pass through it. A medical needle protector is used not only to prevent dust from adhering to the needle and from coming in contact with or adhering to bacteria, but also to protect the needle from deteriorating its sharpness due to contact with other objects. Although there is no practical problem if the medical needle protector is opaque, it is preferable if it is transparent as described above because the condition of the needle tip can be observed with the protector attached. In the present invention, the protactor material must be crosslinked so that the insoluble portion of orthochlorophenol is 20% by weight or more. Crosslinking of the block copolyester must be carried out while maintaining the shape of the protactor. This includes, for example, radiation such as neutron beams, electron beams, gamma rays, etc., light energy in a broad sense such as ultraviolet rays, X-rays, etc.
This can be achieved by irradiating with microwaves or the like. In particular, in order to increase the speed and density of crosslinking, it is recommended that the block copolyester contain a group that is sensitive to the above-mentioned crosslinking process and promotes crosslinking of the block copolyester. This is preferable because it increases and effectively achieves this. In order to make the block copolyester contain a group that is sensitive to such crosslinking treatment and promotes the crosslinking of the block copolyester, a compound having the group is blended, or copolymerized, or a combination of both methods is used. is used. The aforementioned groups are preferably aliphatic unsaturated groups which are substantially stable under the melting conditions of the block copolyester. Here, "substantially stable under the melting conditions of the block copolyester" means that when the block copolyester is held at the melting temperature of the block copolyester, for example (melting point + 20°C) for 15 minutes in an inert gas atmosphere, the This means that the aliphatic unsaturated group exists stably without any reaction between the group-based unsaturated groups or between the unsaturated group and the copolyester. As such an unsaturated group, a non-conjugated aliphatic unsaturated group is more preferable, and in particular, the following formula (i) A non-conjugated group having at least one hydrogen atom at the α-position carbon with respect to the polymerization represented by, for example, an allyl group, a substituted allyl group, etc. is preferable. In the group represented by the above general formula (i), the bond
(a), (b), (c) and (d) are bonded to a hydrogen atom or an organic group, and bond (e) is bonded to an organic group. (a),
The organic groups bonded to the bonds in (b), (c), (d) and (e) may be independent, or may be bonded to each other to form a ring structure. When forming a ring structure, the double bond in formula (i) can also constitute a part of the ring structure. In this case, this ring structure may be an alicyclic ring structure, a heterocyclic ring structure, etc., but it does not form an aromatic nucleus. A more preferable structure of the group represented by the above general formula (i) is represented by the following general formula (ii). [However, in the formula, R ₁ , R ₂ and R ₃ are the same or different and each represents a member selected from the group consisting of a hydrogen atom and an organic group. ] In the general formula (ii), preferred examples of organic groups for R ₁ , R ₂ and R ₃ include C ₁ to C ₆ alkyl, more preferably C ₁ to C ₃ alkyl. can. Among the groups represented by formula (ii), ie, allyl and substituted allyl, preferred are allyl, metaallyl and crotyl, with allyl being particularly preferred. Such an aliphatic unsaturated group can be incorporated into the block copolyester by copolymerizing and/or mixing the compound (A) having the aliphatic unsaturated group with the block copolyester. When copolymerizing the compound (A) with a block copolyester, the compound (A) must be stable without decomposing under the copolymerization conditions.
In addition to aliphatic unsaturated groups that are stable under the copolymerization conditions, ester-forming functional groups (such as carboxyl groups, hydroxyl groups, etc.) or ester-forming functional groups that form under the polymerization conditions of block copolyesters. It is necessary to have at least one functional group, preferably two functional groups. An example of the latter functional group is an epoxy group. Also compound (A)
When blending into block copolyester,
Not only is the aliphatic unsaturated group in the compound (A) stable under melt-kneading with the block copolyester, but it is also preferable that the compound (A) itself is stable. If A) is also melt blended, the resulting composition will be orthochlorophenol.
It is necessary that there is substantially no insoluble matter that does not dissolve at 35°C, and that the [η] of the copolyester does not decrease significantly. Therefore, compounds that contain highly reactive ester-forming functional groups (for example, highly reactive esters, highly reactive hydroxyl groups, highly reactive carboxyl groups, etc.), and furthermore, decompose at the melting temperature of the copolyester. Compounds that are oxidized or gasified are not preferred as blending compounds. Compound (A) containing a group represented by the above general formula (i)
A specific example is given below. First, regarding the case of copolymerization with a block copolyester, preferred examples of such compounds include the general formula (iii). Examples include compounds represented by and ester-forming derivatives of the compounds. In the general formula (iii), R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms or organic groups, and examples of the organic group include aliphatic groups, preferably C ₁ to C ₆ alkyl groups, More preferably C ₁ ~
_C3 alkyl group: alicyclic group, preferably _C5 - _C12
Examples include cycloalkyl groups. Also R ₄ ,
R ₅ , R ₆ and R ₇ are

[Formula] and may be combined with each other or with Q or T'. The above Q and Q' are a direct bond or a divalent or higher organic group, preferably a divalent or higher C _1
-C20 aliphatic group, divalent or more _C6 - _C12 aromatic group, or divalent or more heterocyclic group.
Further, R ₈ and R ₉ are the same groups as R ₄ to R ₇ . _R4 ～ _R7
is preferably a hydrogen atom or methyl or

[Formula] (where R ₈ and R ₉ are each a hydrogen atom or methyl), particularly preferably a hydrogen atom or

[Formula] is mentioned. In addition, in the above general formula (iii), n, m, n' and
m' is 0 or a number greater than or equal to 1, and l is a number greater than or equal to 1. Furthermore, n+m≧1, preferably n+m+l
(n′+m′)=2. As is clear from the above, the compound represented by the general formula (iii) has at least one --OH and/or --COOH, preferably two. Such compounds include, for example, 3-(or 4-
--) Iclohexene 1,2-dicarboxylic acid, 2-
(or 3-)cyclohexene 1,1-dicarboxylic acid, 4-diclohexene 3,6-dimethyl 1,2
-dicarboxylic acid, 2-cyclohexene 1,4-dicarboxylic acid, 3-(or 2-)hexene 1,6-
dicarboxylic acid, 2-butene 1,4-(or 1,1
-) dicarboxylic acid, 3-butene 1,2-dicarboxylic acid, 2-cyclohexenylethane 1,2-dicarboxylic acid, bicyclo[2,2,1]-5-pentene-2,3-dicarboxylic acid, allyloxy (or Carboxylic acids and oxycarboxylic acids such as methalyloxy or crotyloxy)benzoic acid, 4-allyl-3-oxybenzoic acid, 2-(or 3-)cyclohexenecarboxylic acid, N-allyl (or methalyl or crotyl) trimellitic acid imide, etc. Acids and ester-forming derivatives thereof (for example, lower alkyl esters such as methyl, ethyl, and propyl; aryl esters such as phenylester; acid anhydrides, etc.); 3-(or 4-)cyclohexene 1,2- Dimethanol, 2-(or 3- or 1-)cyclohexene 1,1-dimethanol, 1-(or 2-)cyclohexene 1,4-
dimethanol, 2-cyclohexene 1,4-diol, 2-butene 1,4-diol, 2-(1-
butenyl)propane 1,3-diol, 3-bentene 1,2-diol, 3-hexene-3-methyl 1,6-diol, 2-butene-2,3-dimethyl 1,4-diol, 4-allyloxy Phenol 2,5-diallyl (or dimethallyl or dicrotyl)-1,4-dioxybezene, 2,2-
Bis[3-allyl (or metaallyl or crotyl)-4-hydroxyphenyl]propane, bis(3-allyl-4hydroxyphenyl) sulfone, 2,2-bis[3-allyl (or metaallyl or crotyl)-4 -Hydroxyethoxyphenyl]propane, bis(3-allyl-4-hydroxyethoxyphenyl)sulfone, allylbis(β
Hydroxyethyl) isocyanurate, N,N-
Examples include hydroxy compounds such as diallyl-4-oxybenzamide, and ester-forming derivatives thereof (eg, lower fatty acid esters). Furthermore, as a preferable example of a compound that changes into a compound represented by the general formula (iii) above under the polymerization conditions of the block copolyester and becomes a copolymerizable compound, bisallyloxy (or metaallyloxy or crotyloxy)benzene, 2, 2-bis[4-allyloxy or crotyloxy)phenyl]propane, 1,1-bis(4-allyloxyphenyl)
Examples include cyclohexane, bis(4-allyloxyphenyl)sulfone, and the like. Next, as compounds having an aliphatic unsaturated group that can be blended with the block copolyester, those having two or more groups represented by the general formula (i) are more strongly resistant to the actinic radiation treatment described below. This is preferable because a catenary structure can be obtained in the molded body. Examples of such compounds include the following compounds. () A compound having an amide bond and/or an imide bond; (1) A compound represented by the following formula (iv), Q ₁ {X(Q′ ₁ A) _n ″} _o ″ ...(iv) Provided that formula (iv) ), A is: a monovalent group having the structure represented by the above formula (i); preferably an allyl group or a substituted allyl group represented by the above formula (ii); X is: -CONR ₁₁ - (wherein R ₁₁ is a hydrogen atom or a C ₁ to C ₆ alkyl group),

【formula】

[Formula] (Here, R ₁₁ is as described above, and two R _11s may be the same or different) and a member selected from the group consisting of -O-. Q ₁ is: C ₂ - C ₂₀ mono- to tetravalent aliphatic group, C ₄ -
C ₁₂ mono- to tetravalent alicyclic group,

[Formula] (where R ₁₂ is a hydrogen atom, a C ₆ to C ₁₂ aryl group,
1 consisting of a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkyloxy group, a nitro group or a halogen atom)
~tetravalent group,

A mono- to tetravalent group consisting of [Formula] (where R ₁₂ is as above) and

[Formula] [Here, Y is -O-, -CO-, -SO ₂ -, -NR ₁₁ - (However, R ₁₁ is the same as above), -O (CH ₂ CH ₂ ) _l ′O- (However, l ' is an integer of 1 to 3), a member selected from the group consisting of C ₂ to C ₁₂ alkylene], a group selected from the group consisting of monovalent to tetravalent groups, where X is -O- In this case, Q ₁ is preferably the above-mentioned aliphatic group or alicyclic group; the above-mentioned aliphatic group is a C ₂ -C ₂₀ alkylene group, 2 -
Tetravalent olefin residue

[Formula] etc. are preferable, and As a ring group

1 to 4 consisting of [formula] The basis of valence,

Mono- to tetravalent group consisting of [Formula]

Preferred examples include divalent to tetravalent groups consisting of the formula: _Q'1 is: a direct bond or a divalent or higher valent group in _Q1 , preferably a direct bond or a _C1-5 alkylene group. m″ and n″ are each an integer from 1 to 4, m″×
It is preferable that n″≧2. Examples of such compounds of formula (iv) include the following compounds: N,N′-diallyl (or dimethallyl or dicrotyl)aziboamide, N, N'-diallyl (or dimethallyl or dicrotyl) sebecamide, N,N'-diallyl (or dimethallyl or dicrotyl) decanedicarboxyamide, N,
N'-diallyl (or dimethallyl or dicrotyl) terephthalamide, N,N'-diallyl (or dimethallyl or dicrotyl) isophthalamide,
N, N′diallyl (or dimethallyl or dicrotyl) naphthalene dicarboxamide, N,
N'-diallyl (or dimethallyl or dicrotyl) hexahydroterephthalamide, N,N'-diallyl (or dimethallyl or dicrotyl) diphenoxyethanedicarboxamide, N,N',
N″-triallyl (or trimetaallyl or tricrotyl) trimesic acid amide, N, N,
N'N'-tetraallyl (or tetramethallyl or tetracrotyl) adipamide, N, N,
N',N'-tetraallyl (or tetramethallyl or tetracrotyl) sebacaramide, N,N,
N',N'-tetraallyl (or tetramethallyl or tetracrotyl)decanedicarboxamide, N,N,N',N'-tetraallyl (or tetramethallyl or tetracrotyl)terephthalamide, N,N,N',N '-tetraallyl (or tetramethallyl or tetractyl) isophthalamide, N,N,N',N'-tetraallyl (or tetramethallyl or tetracrotyl) naphthalene dicarboxamide, N,N-diallyl (or dimethallyl or dicrotyl) benzamide, N,
N,N',N'-tetraallyl (or tetramethallyl or tetrachlor)hexahydroterephthalamide, N,N,N',N'-tetraallyl (or tetramethallyl or tetracrotyl)diphenoxyethanedicarboxamide, N ,N,N′,
N', N'', N''-hexaaryl (or hexametaallyl or hexacrotyl) trimesic acid amide, N, N, N'N', N'', N''-hexaallyl (or hexametaallyl or hexacrotyl) trimellitic acid amide, N, N, N', N', N'', N'', N
, N-octaallyl (or octamethallyl or octacrotyl) pyromellitic acid amide,
N,N'-diallyl (or dimethallyl or dicrotyl)pyromellitimide, N,N'-diallyl (or dimethallyl or dicrotyl)benzophenone-3,4,3',4'-tetracarboxylic acid bisimide, N,N'- Diallyl (or dimethallyl or dicrotyl) butane-1,2,3,4-tetocarboxylic acid bisimide, N,N'-diallyl (or dimethallyl or dicrotyl) diclopentane-1,2,3,4-tetracarboxylic acid bisimide, ethylene Bis[N-allyl (or N-methallyl or N-crotyl) trimellitimide]
Amide, Tetramethylenebis[N-allyl (or N-methallyl or N-crotyl) trimellitic acid imide]amide, Hexamethylenebis[N-allyl (or N-methallyl or N-crotyl) trimellitic acid imide]amide, Decamethylene Bis[N-allyl (or N-methallyl or N-cucrotyl) trimethimide] amide, dodecamethylene bis[N-allyl (or N-methallyl or N-crotyl) trimellitimide] amide,

[Formula] (A: allyl or metaallyl or crotyl), N,N'-diallyl (or dimethallyl or dicrotyl) trimellitic acid amide imide, N,
N,N'-triallyl (or trimetaallyl or tricrotyl) trimellitic acid amide imide, ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis(2-
propylenecarboxamide), ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis[2-(or 3-)
butenecarpoxyamide], ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis[2-(or 3- or 4-
-) pentenecarboxamide], ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis[2- (or 3-
or 4- or 5-) hexenecarboxamide], N-allyl (or crotyl or meta-allyl) 2-propylenecarboxamide, N-allyl (or crotyl or meta-allyl) 2-(or 3)
-) Butenecarboxamide, N-allyl (or crotyl or metaallyl) 2-(or 3- or 4)
--) Propenecarboxamide, N-allyl (or crotyl or metaallyl) 2-(or 3- or 4- or 5-)hexenecarboxamide, N,
N-diallyl (or dicrotyl or dimethallyl) 2-propylenecarboxamide, N,N-
Diallyl (or dicrotyl or dimethallyl) 2
-(or 3-)butenecarboxamide, N,N
- Diallyl (or dicrotyl or dimethallyl)
2-(or 3-or 4-) propenecarboxamide, N,N-diallyl (or dicrotyl or dimethallyl) 2-(or 3- or 4- or 5-)
hexenecarboxamide, N,N'-diallyl (or dicrotyl or dimethallyl) 3-(or 2)hexene 1,6-dicarboxamide, N,
N'-diallyl (or dicrotyl or dimethallyl) 2-butene 1,4-dicarboxamide,
N,N,N',N'-tetraallyl (or tetracrotyl or tetramethallyl) 3-(or 2)hexene 1,6-dicarboxamide, N,N,
N',N'-tetraallyl (or tetracrotyl or tetramethallyl) 2-butene 1,4-dicarboxamide, ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis2-(or 3-)cyclohexenecarboxamide, ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis3-(or 4-)cyclohexene 1,2
-Dicarboximide, ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis2-(or 3-)cyclohexene 1,1-dicarboximide, ethylene (or trimethylene or tetramethylene or hexamethylene or decamethylene) bis2 -Cyclohexene 1,4-dicarboximide, N-allyl (or crotyl or metaallyl) 2-(or 3-)cyclohexenecarboxamide, N-allyl (or crotyl or metaallyl) 3-(or 4-)cyclohexene 1,2 -Dicarboximide, N-
Allyl (or crotyl or metaallyl) 2-(or 3-)cyclohexene 1,1-dicarboximide, N-allyl (or crotyl or metaallyl) 2-cyclohexene 1,4-dicarboximide, N-allyl (or crotyl or (methallyl) picyclo[2,2,1]-5-hebutene 2,
3-dicarboximide, N,N-diallyl (or dicrotyl or dimethallyl) 2-(or 3
--) Cyclohexenecarboxamide, N, N,
N',N'-tetraallyl (or tetracrotyl or tetramethallyl) 3-(or 4-)cyclohexene 1,2-dicarboxamide, N,N,
N',N'-tetraallyl (or tetracrotyl or tetramethallyl) 2-(or 3-)cyclohexene 1,1-dicarboxamide, N,N,
N',N'-tetraallyl (or tetracrotyl or tetramethallyl) 2-cyclohexene 1,4
-dicarboxamide, N,N,N',N'-tetraallyl (or tetracrotyl or tetramethallyl)bicyclo[2,2,1]-5-heptene 2,3-dicarboximide, N,N'-diallyl (or dicrotyl or dimethallyl) 2-cyclohexene 1,4-dicarboxamide. () Derivatives of cyanuric acid or isocyanuric acid; Compounds represented by the following formula (v) or (iv) However, in formulas (v) and (vi), a plurality of A's may be the same or different, and at least two of them are the above group A, and the rest are the group A or one of the above _Q1. It is the basis of valence. Q ₂ is a divalent to tetravalent group in Q ₁ above. Q′ ₂ is a divalent group in Q ₁ above. and r is 0 or 1, preferably 1, p is an integer of 0 to 10, and q is an integer of 1 to 3. Examples of such compounds represented by formulas (v) and (vi) include the following compounds. triallyl (or tricrotyl or trimetaallyl) isocyanurate, diallyl (or dicrotyl or dimethallyl) methyl isocyanurate, diallyl (or dicrotyl or dimethallyl) ethyl isocyanurate, diallyl (or dicrotyl or dimethallyl) decyl isocyanurate, diallyl (or dichlor or methalyl) ) dodecyl isocyanurate, diallyl (or dicrotyl or dimethallyl) myristyl isocyanurate, diallyl (or dicrotyl or dimethallyl) cetyl isocyanurate, diallyl (or dicrotyl or dimethallyl) stearyl isocyanurate, ethylene bis[diallyl (or dicrotyl or dimethallyl) isocyanurate] ], tetramethylenebis[diallyl (or dicrotyl or dimethallyl) isocyanurate],
Hexamethylenebis[diallyl (or dicrotyl or dimethallyl) isocyanurate], decamethylenebis[diallyl (or dictyl or dimethallyl) isocyanurate], oxydiethylenebis[diallyl (or dicrotyl or dimethallyl)isocyanurate], dioxytriethylenebis[ Diallyl (or dicrotyl is dimethallyl) isocyanurate], polyethylene allyl (or metaallyl or crotyl) isocyanurate whose terminal end is a diallyl isocyanurate residue, polytetramethylene allyl (or metaallyl or crotyl) whose terminal end is a diallyl isocyanurate residue Isocyanurate, polyhexamethylene allyl (or metaallyl or crotyl) isocyanurate whose terminal end is a diallyl isocyanurate residue, polydecamethylene allyl (or metaallyl or crotyl) isocyanurate whose terminal end is a diallyl isocyanurate residue, triallyl (or trimetaallyl or triclotyl) cyanurate,
Diallyl (or dimethallyl or dicrotyl) methyl cyanurate, diallyl (or dimethallyl or dicrotyl) ethyl cyanurate, diallyl (or dimethallyl or dicrotyl) decyl cyanurate, diallyl (or dimethallyl or dicrotyl) dodecyl cyanurate, diallyl (or dimethallyl or dicrotyl) ) myristyl cyanurate, diallyl (or dimethallyl or dicrotyl) cetyl cyanurate, diallyl (or dimethallyl or dicrotyl) stearyl cyanurate, tetramethylenebis[diallyl (or dimethallyl or dicrotyl) cyanurate], hexamethylenebis[diallyl (or dimethallyl or dicrotyl)], dicrotyl) cyanurate], decamethylenebis[diallyl (or dimethallyl or dicrotyl)
cyanurate], oxydiethylenebis[diallyl (or dicrotyl or dimethallyl) cyanurate], dioxytriethylenebis[diallyl (or dicrotyl or dimethallyl) cyanurate], polytetramethylene allyl (or metaallyl or crotyl) cyanurate, polyhexamethylene allyl (or metaallyl or crotyl) cyanurate, which terminates in a diallyl cyanurate residue, polydecamethylene allyl (or metaallyl or crotyl) cyanurate, which terminates in a diallyl cyanurate residue. Examples of these compounds include Zb, Organ.Khim,
2 (10), p1742-34 (1965) (Russ), or J.
It can be easily synthesized by the method shown in Am.Chem.soc, 73p3003 (1951). () A compound having a reactive functional group (for example, a polymer obtained from a compound represented by the general formula (iii) above); (1) A polyester represented by the following formula (vii) or (viii) [However, in the formula, A and Q ₂ have the same definition as above, and Q ₃ is

A 3- to (k+2)-valent group consisting of [Formula] (where R ₁₂ is the same as defined above)

[Formula] (where R ₁₂ is the same as the above definition) with a valence of 3 to (k+2)

A 3-(k+2)-valent group consisting of [Formula], where k is an integer of 1-4, s is 0 or 1,
t is an integer greater than 2 and K×t≧2. ] It is a polymer having the repeating unit. In such a polymer, the polymer (vii) has s=1
In the case of Q ₂ ′(COOH) ₂ or its ester-forming derivatives (e.g. C ₁ -C ₃ alkyl esters, C ₆ -
C ₁₂ aryl ester, acid halide),
When S=0, a compound such as COCl ₂ , COBr ₂ , diaryl carbonate, etc. is reacted with 〓〓(OH) ₂ or its ester-forming derivative (e.g., lower fatty acid ester, alkali metal salt, etc.) by a conventionally known method. When s=1, the compound (viii) is obtained by

[Formula] or its ester formation sexual derivatives, and when s=0

[Formula] can be obtained by reacting its ester-forming derivatives by a conventionally known method. In the present invention, the terminals of these polymers become the terminals of the components forming the compound represented by the above formula, but, for example, alkyl- or aryl-
Preferably, the terminal is converted into an ester. Examples of such polymers of formulas (vii) and (viii) are:
Examples include polymers having the following repeating units. (However, A in the following compounds is allyl, metaallyl, or crotyl.) These are relatively unreactive compounds. (2) Polyamide Poly(ethylene-2-butene 1,4-dicarboxamide), poly(tetramethylene-2-butene 1,4-dicarboxamide), poly(hexethylene-2-butene 1,4-dicarboxyamide) amide), poly(decamethylene-2-butene 1,4-
dicarboxamide), poly(ethylene 3-(or 2-)hexene 1,6-dicarboxamide), poly(tetramethylene 3-(or 2-)hexene 1,6-dicarboxamide), poly(hexamethylene -3- (or 2-) hexene 1,6
-dicarboxamide), poly(decamethylene 3)
-(or 2-)hexene 1,6-dicarboxamide), Next, as a compound having intermediate performance between the copolymer type and the mixed type, polyesters that are relatively easy to transesterify, such as polyethylene-
2-butene 1,4-dicarboxylate, polytetramethylene-2-butene 1,4-dicarboxylate, polyethylene-3-(or 2-)hexene 1,6-dicarboxylate, polytetramethylene-3- (or 2-) hexene 1,6-dicarboxylate, poly-2-butene adipate, poly 2-butene sebacate, poly 2-(or 3-)
or 1-) Linear polyesters such as cyclohexene 1,1-dimethylene terephthalate, poly 2-(or 3- or 1-)cyclohexene 1,1-dimethylene terephthalate, or other acid components and/or glycol components. A copolymer with a high degree of polymerization (for example, one with an intrinsic viscosity of 0.4 or more is exemplified). Even if this copolymer partially reacts with the copolyester elastomer during melt blending and/or molding, the entire polymerization It can be used without causing a decrease in the degree of oxidation.As the compound having an aliphatic unsaturated group, a copolymer compound is preferable.In addition, as a mixed type compound, the above-mentioned compound () or () is preferable. In the present invention, the usage ratio of the compound having an aliphatic unsaturated group is 0.0001 to 0.0001 as an aliphatic unsaturated group per 100 g of polymer, whether copolymerized or mixed. 0.5 equivalent, preferably
It is 0.005 to 0.3 equivalent, more preferably 0.01 to 0.1 equivalent. The crosslinked protector of the present invention is obtained by, for example, copolymerizing and/or mixing a compound having an aliphatic unsaturated group in a block copolyester, and molding the polymer into a desired form by, for example, injection molding. It can be obtained by crosslinking treatment. The copolymer type is particularly preferred in order to reduce the amount of steam residue KMnO ₄ consumed in the elution test.
A polymer copolymerized with a compound having an aliphatic unsaturated group can be obtained by, for example, reacting the above-mentioned acid component, glycol component, and the compound having an aliphatic unsaturated group using a conventionally known linear polyester manufacturing method. You can get it by twisting it. In this case, a polyester in which a compound having an aliphatic unsaturated group is copolymerized in excess of the desired amount is prepared in advance, and this is melt-blended with a copolyester having no aliphatic unsaturated groups or copolymerized in a small proportion. urge,
A so-called master batch method is also preferably used. In particular, as described in JP-A No. 51-38390, a method for producing a block copolymer by melt-mixing an aromatic linear polyester and an aliphatic linear polyester to cause a block reaction. In this case, a method is preferably employed in which an aliphatic unsaturated group-containing compound is copolymerized only on one side. Further, a block copolyester obtained by blending a compound having an aliphatic unsaturated group can be obtained by mixing the blocked copolyester and the compound having an aliphatic unsaturated group using a mechanical mixing means such as an S-type blender or a V-type blender. Then, using a kneading machine such as an extruder, the copolyester is heated to a temperature at or above the melting point of the copolyester, preferably at or above the melting point of the copolyester, or 60°C below the melting point.
It is preferably obtained by a method of uniformly mixing in a high temperature range. In the present invention, next, a crosslinked structure is introduced into the protector obtained by melt molding. The following method is exemplified as a method for crosslinking the protector. (A) Temperature from room temperature to melting point (Tm), preferably above the glass transition point (Tg) of the copolyester (Tm
-10), more preferably (Tg+10)
Means of irradiating with ultraviolet light, preferably in the presence of a photoinitiator, at a temperature of ~(Tm-20)°C; (B) electron beam irradiation at a dose of, for example, 0.01 Mrad to 100 Mrad at a temperature of room temperature to Tm, preferably Tg ~ ( Means for irradiating under temperature conditions such as Tm-10)°C, preferably (Tg+10) to (Tm-20)°C; (C) Means for irradiating radiation; (D) Means for (A) to (C) above. Any combination of the following. Among these, method (A) is particularly preferred. The crosslinking treatment method (A) above is preferably carried out in the presence of a photoreaction initiator. In this case, the photoreaction initiator is also incorporated into the copolyester by copolymerizing or blending it with the copolyester, similarly to the compound having an aliphatic unsaturated group. Therefore, the copolyester does not decompose during melting,
Also, it is preferable to use one that does not cause a reaction that would cause the photoreaction initiation effect to be lost. Such photoinitiators include (1)
Preferred examples include aromatic ketones, (2) benzyl and its derivatives, (3) benzoin and its derivatives, and (4) polynuclear quinones. Examples of such compounds that can be blended include benzophenone, 4-methylbenzophenone, 4-nitrobenzophenone, 3-methylbenzophenone,
4,4-dimethylbenzophenone, 3,3-dimethylbenzophenone, 3,4-dimethylbenzophenone, 4-phenylbenzophenone, 3-phenylbenzophenone, 3,3-dinitrobenzophenone Non,4,4-dinitrobenzophenone,3-
Nitrobenzophenone, 3-methoxybenzophenone, 4,4-dimethoxybenzophenone, 3,
3-dimethoxybenphenone, bis(4-diphenyl)ketone, bis(3-diphenyl)ketone,
3,4-dimethylbenzophenone, 3,4,
3′,4′-tetramethylbenzophenone, Michler's ketone, anthraquinone, nitroanthraquinone, phenanthraquinone, acetophenone, propiophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoinpropyl ether, benzoin butyl ether, benzoin phenyl ether, α-methylbenzoin methyl ether, α-phenylbenzoin ethyl ether, α-benzylbenzoin ethyl ether, benzyl dimethyl ketal,
Benzyl diethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl ethylene ketal, benzyl trimethylene ketal, benzyl neobenzene ketal, benzyl bis(2-methoxyethyl) ketal naphthyl phenyl ketone, bisnaphthyl ketone, ethylene bis(benzoylbenzamide) ), tetramethylenebis(benzoylbenzamide), hexamethylenebis(benzoylbenzamide), decamethylenebis(benzoylbenzamide), dodecamethylenebis(benzoylbenzamide), hexamethylenebis(4-acetylbenzamide), hexamethylenebis[(4 -methylbenzoyl)benzamide], ethylenebis[(4-nitrobenzoyl)benzamide], dodecamethylenebis[(4-
methoxybenzoyl)benzamide], dibenzoylbenzene, bis(4-methylbenzoyl)benzene, ethylene bis(benzoyl phenyl ether), bis(benzoylmethyl) ether, tris(benzoylphenoxy)benzene, bis(4-methoxybenzoyl) methyl ether), etc. Also German published patent specification 1769168
No., No. 1769853, No. 1807297, No. 1807301,
Photoreaction initiators listed in No. 1919678 and No. 1949010 that are substantially stable during melting of the polymer can be used as appropriate. Examples of copolymerizable compounds include benzophenone 4,4-dicarboxylic acid. The above-mentioned photoreaction initiation inhibitor can be incorporated into the block copolyester by blending or copolymerization, or by immersion in a bath containing an appropriate combination of carriers, dispersants, etc. known for dyeing polyester fibers. It can also be blended by spraying such a liquid. The preferred proportion of the photoinitiator used is 0.01 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, even more preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the block copolyester.
It is 5 parts by weight. In addition, compounds in which the aliphatic unsaturated group-containing compound itself is a photoreaction initiator, such as N-allyl (or crotyl or metaallyl) benzoylbenzamide, N-allyl (or crotyl or metaallyl) anthraquinone carboxide amide , N-allyl (or crotyl or metaallyl) benzoyl phthalimide, N,N-
Compounds such as sialyl (or dicrotyl or dimethallyl) benzoylbenzamide, N,N'-sialyl (or dicrotyl or dimethallyl) benzophenone tetracarboxamide, etc.
It is a preferred compound for the embodiment of crosslinking treatment (A). In the present invention, the most preferred method for manufacturing the protector is as follows. A linear block copolyester containing allyl and/or substituted allyl groups and a photoreaction initiator is melted and molded into the shape of a protector, and then crosslinked by irradiation with ultraviolet rays. Alternatively, a copolyester containing allyl and/or substituted allyl groups and a reaction initiator is melted and molded into the shape of a protector, and then crosslinked by irradiation with an electron beam. The protector can be molded by a conventionally known method for molding thermoplastic resin, and high-speed production is possible. The protector of the present invention may be dissolved by heating and soaking in orthochlorophenol, which is a good solvent for non-crosslinked block copolyester. The degree of crosslinking is 20% by weight or more, expressed as an undissolved residual amount,
It is preferably 30% by weight or more, particularly preferably 50% by weight or more. The conditions for heating and dipping in orthochlorophenol may be any conditions as long as they dissolve the non-crosslinked block copolyester, and preferably conditions are used to measure the reduced specific viscosity. That is, 1.2 g of the crosslinked elastic polymer was placed in 100 ml of orthochlorophenol, and the mixture was stirred and dissolved at 100° C. for 1 hour. After cooling, it was quickly passed through a 3G glass filter, thoroughly washed with acetone to remove insoluble residue on the filter, dried, left to cool in a desiccator, then weighed, and divided by the weight before immersion heating. Find the weight percent. Non-crosslinked block copolyester has no undissolved residue, and the dissolved solution can be directly transferred to a viscosity tube to measure the reduced specific viscosity. Although the block copolyester constituting the protector of the present invention is highly crosslinked, it has elastic properties similar to those of thermoplastic elastic polymers, and has elongation at break of, for example, 50% or more at room temperature. . Preferably 70% or more, more preferably 100%
It has a breaking elongation of the above. Furthermore, this crosslinked block copolyester has chemical resistance, dimensional stability,
Excellent mechanical properties and heat resistance. For example, the protector of the present invention has a high degree of heat resistance that does not melt even at 300° C. depending on the conditions. When the soft segment of the block copolyester constituting the protector of the present invention is polyoxyalkylene glycol, it tends to cause problems in the "foaming" item in the "pharmacopeia test", which is an important required property. In such a case, the aluminum compound and/or zirconium compound is used in such a manner that the amount of aluminum and/or zirconium ions is 10 to 10%.
An effective method is to contain the amount of about 1000 ppm. Specific examples include aluminum acetate, aluminum oxalate, aluminum benzoate,
Examples include aluminum phosphate and zirconium acetate. Another effective method for making block copolyester transparent is to use polymer-soluble sodium carboxylates, such as sodium aliphatic, alicyclic, and aromatic carboxylates, especially when polyoxyalkylene glycol is used as the soft segment. This is a method of adding a proportion, particularly about 0.01 to 5% by weight. Specific examples of these include sodium stearate, sodium oleate, sodium laurate, and sodium montanate. In particular, a block copolymer using a polyester mainly composed of terephthalic acid and tetramethylene glycol or trimethylene glycol as an aromatic polyester component is also characterized by a fast crystallization rate and easy molding. The block copolyester thus obtained preferably has a softening point of 130°C or higher. If the difficulty point is lower than this, steam sterilization required for medical equipment tends to be difficult. Although it is not necessarily necessary to add stabilizers to the material constituting the protector of the present invention, stabilizers such as heat stabilizers and light stabilizers can be included as necessary. However, since it is used for medical purposes, sufficient attention should be paid to the toxicity of the additive. Further, other additives such as pigments, dyes, crystal nucleating agents, reinforcing agents, etc. may be added. Hereinafter, aspects of the present invention will be illustrated by way of Examples. In addition, all "parts" in the examples represent "parts by weight." In addition, each test item in the example was measured according to the following method. (1) Softening point: Measured using a Picatuto softening point measuring device. (2) Specific viscosity: Determined from the solution viscosity measured at 35°C by dissolving 1.2 g of the polymer in 100 ml of orthochlorophenol. (3) D hardness: Measured by Shore D hardness measuring device. It is a measure of elasticity; the lower the value, the softer and more elastic the material is. (4) Total light transmittance: Measured using a Poitzk integrating sphere microturbidity meter (manufactured by Nippon Seimitsu Kogaku Co., Ltd., SEP-TU type). This is a measure of transparency; the higher the value, the more transparent the material is. The sample used was a sheet-like molded product with a thickness of 2 mm. Examples 1 to 7

[Table] Transesterification of the above preparation composition (160-220℃)
The reaction was stopped when 85% of the theoretical amount of methanol was distilled out, and then polycondensation reaction (240°C, 3.5 hours)
was carried out under high vacuum to obtain an aromatic polyester with a reduced viscosity of 1.08.

[Table] The above charging composition was treated in the same manner as the above aromatic polyester reaction (however, the polycondensation time was 5 hours).
An aliphatic polyester with a reduced viscosity of 1.07 was obtained. <Production of block copolyester> 25 parts of the above aromatic polyester and 50 parts of aliphatic polyester were mixed and stirred at 250° C. under high vacuum for 40 minutes, and the dissolved polymer became transparent. At this stage, 0.12 parts of phosphorous acid was added, and further 30 parts of phosphorous acid was added under normal pressure.
Stir for 1 minute. The obtained polymer (A) has a diameter of 3 to 4 mm and a length of 3 to 4 mm.
It was made into a mm chip. The properties of this product were as shown in Table 1.

[Table] <Production of polyether polyester block copolymer> The raw materials shown in Table 2 were charged into a polymerization apparatus and reacted to obtain polymers (indicated by symbols B to G).
The reaction was carried out at 180 ml after adding the raw materials shown in the table.
The methanol produced by heating to ~220°C was distilled to over 80% of the theoretical amount, then the temperature was raised to 240°C, and a weak vacuum of approximately 30 mmHg (absolute pressure) was applied for 30 minutes.
The reaction was carried out for 30 minutes, followed by further polymerization for 200 minutes under high vacuum of 0.1 to 0.3 mmHg (absolute pressure). <Production of polyester containing a reaction initiator as a constituent component> 298 parts of 4,4-benzophenonedicarboxylic acid dimethyl ester, 236 parts of hexamethylene glycol, and 0.2 parts of tetrabutyl titanate were charged according to the method for producing polyester as described above. , conduct transesterification polymerization reaction and reduce viscosity (η・sp/c) 0.62
Polyester (H) was obtained. Polyesters A to G were dried at 100°C for 2 hours, and then 2% by weight of polyester H and 4% by weight of diallyl monoglycidyl isocyanurate were mixed uniformly, and a needle protector attached to a plastic container for infusion was melted. Injection molded. The protector has a length of 47 mm, an outer diameter of 8 mm at the part that touches the base of the needle, and an inner diameter of 4 mm, tapering toward the needle tip, so that the inner wall of the protector wraps around the needle tip. . The dimensions of the needle to which this protector is attached are 1.7 mm in outer diameter, 37 mm in length, 6 mm in the teeth at the tip of the needle, and 4.5 mm in diameter and 5 mm in length at the base of the needle.
It is supported by resin. 120℃ so that the molded product is evenly exposed to light.
The sample was irradiated with a 2KW high-pressure mercury lamp (30W/cm) for 2 minutes. In this molded article, the insoluble portion now occupies most of the ηsp/c measurement conditions. Table 3 shows the insolubility rate. Furthermore, a migration test was conducted on this molded product. When using polymers for medical purposes, migration of impurities from the material becomes an important issue. Therefore the transferability was tested and its hygiene is shown in the example below. The test method is as per the Ministry of Health and Welfare Notification No. 301 dated August 10, 1972.
I did it based on the number. The results are shown in Table 3.

【table】

【table】

[Table] Comparative Examples 1 and 2 Protectors were manufactured using commercially available medical silicone rubber and vinyl chloride resin for intravenous drip, and the same migration test as in Examples 1 to 7 was conducted. The results are also listed in Table 3. Example 8 In Examples 1 to 7, the protector made of polymers A to G was treated with a disposable anticoagulant.
The needle at the tip of a frozen tirobe was placed in a blood collection bag containing ACD solution, and left for 10 days after sterilization. A portion of the ACD fluid was then cultured, but no bacterial growth was observed. This indicates that no bacteria entered through the gaps in the protector. Example 9 Polymer A obtained in Examples 1 to 5,
Protectors were molded using B, C, D, and E in the same manner as in Examples 1 to 7. Using this molded article and the molded articles obtained in Examples 1 to 7, the device properties of the protector were tested. That is, these protectors were attached to the needles, the taper was directed downward, micro vibrations were applied at 300 cycles/minute, and the time until they fell off was measured. The results are shown in Table 4.

[Table] From the above table, it can be seen that the fit of the protector of the present invention is improved.

Claims (1)

[Scope of Claims] 1. A medical needle protector made of resin, which is made of soft polyoxyalkylene glycol and/or aliphatic polyester having an average molecular weight of about 300 to 5000 and a ratio of carbon number to oxygen number of 2.0 to 4.5. A block copolyester having a segment and an aromatic polyester as a hard segment,
The elastic polymer is crosslinked so that the proportion of the soft segment is 20 to 80% by weight of the block copolyester, and the insoluble portion in orthochlorophenol is 20% by weight or more as measured under the following conditions. Characteristic medical needle protector. Add 1.2 g of the crosslinked elastic polymer to 100 ml of orthochlorophenol and stir and dissolve at 100°C for 1 hour.
After cooling, quickly filter it with a 3G glass filter.
The undissolved residue on the filter is thoroughly washed with acetone, dried, allowed to cool in a desiccator, then weighed, and divided by the weight before immersion heating to determine weight %.