JPS63319007A - Hollow yarn binding material - Google Patents

Abstract

PURPOSE:To obtain a polyurethane binding material having superior adhesive property even after sterilization in an autoclave, producing no cancer and causing no yellowing by sterilization with gamma-rays, by using an aliphatic or alicyclic polyisocyanate and an oxycarboxylic acid. CONSTITUTION:A polyisocyanate obtd. by dissolving hexamethylene diisocyanate or the like in a solvent and bringing it into a reaction is used as a polyisocyanate component. An oxycarboxylic acid represented by a general formula (HO)n-R-(COOH)m (where R is a bi-, ter- or quatervalent org. group and each of n and m is 1, 2 or 3), e.g., ricinolic acid is used as at least a part of a polyol component. Both the components are blended, cured and used as a binding material in a fluid separating device for medical treatment using hollow yarns or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a urethane-based binding material used in medical fluid separation devices, for example, artificial dialysis devices such as dialyzers.

[Conventional technology]

Conventionally, as the polyisocyanate component of polyurethane-based binding materials, JP-A-33-4/49J, JP-A-5-102λq3, JP-A-Sho, tll-/3269g',
JP-A-37-/! ;! No. 226, JP-A-11-937/
As seen in the publication No. 2, tolylene diisocyaner)
Aromatic polyisocyanates such as (Tl)I), 4(,≠!-diisocyanatodiphenylmethane (MDI)) have been used.
In Publication No. 0 and Japanese Patent Application No. 60-27439, aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI) and hydrogenated u,+'-diphenylmethane diisocyanate (water gMDI) are used. A method using an alicyclic polyisocyanate has also been proposed.

On the other hand, as the y +)ol component, as described in the above-mentioned publication, castor oil-based giriol, polyether-based giriol, polyester-based coryol, polyamino-based polyol, etc. are used.

[Problem that the invention seeks to solve]

Among conventional techniques, binding materials using aromatic polyisocyanates may produce aromatic amines such as tolylene diamine from TDI and g, II'-diaminodiphenylmethane from MDI by hydrolysis. These aromatic amines are strongly suspected to be carcinogenic, and the use of materials using aromatic polyisocyanates in medical fluid separation devices that come into direct contact with biological components such as blood is not recommended for the health and safety of test subjects. This is extremely problematic, and there are currently increasing efforts to regulate it.

On the other hand, materials using aliphatic or alicyclic 11J isocyanates are free from such concerns and can be said to be more preferable. However, when aliphatic or alicyclic polyisocyanates are combined with conventional Giriol components, the adhesion to the container of the fluid separation device is poor, and the adhesive surface between the container and the binding material peels off, especially after autoclave sterilization. (container peeling) occurs.

For this reason, sterilization methods such as ethylene oxide gas sterilization and gamma ray sterilization must be used, but these methods use highly toxic gases and require special equipment to emit radiation, which is not desirable in terms of production. I can't say it's a thing. Further, in the case of a binding material using aromatic geryisocyanate, there is an additional drawback that it yellows severely upon sterilization with gamma rays.

Therefore, it has been desired to develop a binding material that has better adhesion than conventional binding materials even after autoclave sterilization even when aliphatic or alicyclic polyisocyanates are used.

In other words, the development of a constituent component having the following properties has been awaited for a urethane-based binding material.

(1) Excellent adhesion and no peeling of the container even after autoclave sterilization. (2) No aromatic polyisocyanate is used, so there is no possibility of carcinogenic aromatic amines being generated. (3) Gamma ray sterilization No yellowing.

[Means for solving problems]

In view of the above points, the present inventors have conducted intensive research and found that an aliphatic or alicyclic polyisocyanate is used as the polyisocyanate component, and an oxycarboxylic acid is used as at least a part of the polyol component. The inventors have found a solution to this problem and have completed the present invention.

That is, the present invention uses an aliphatic or alicyclic golyisocyanate as a polyisocyanate component in a polyurethane-based binding material used in a medical fluid separation device, and has the general formula % (%) (formula %) as a polyol component. The present invention relates to a binding material characterized by using an oxycarboxylic acid in which R is a divalent to divalent organic group, and n and m are integers from 1 to 3.

As the aliphatic or alicyclic g+) isocyanate used in the present invention, hexamethylene diisocyanate C
HDI),) Limethylhexamethylene diisocyanate, ethylene diisocyanate, tetramethylene diisocyanate, dodecane diisocyanate, terincyanatomethyl-to! -Octamethylene diisocyanate, cyclobutane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate (IPDI),
Isocyanates such as water g+, u'-diphenylmethane diisocyanate (hydrogenated MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate, and their biuret, incyanurate, as well as various y IJols. or a mixture thereof. Among these, diisocyanate itself is highly volatile, has mucosal irritation and lung damage-inducing properties, and is highly irritating to the skin, making it unfavorable from the safety and health standpoint of workers. It is recommended to keep it as low as possible, preferably 0.7% or less. Furthermore, the gellisocyanate component must be solvent-free and have a viscosity so low that it does not interfere with the operations of mixing with the polyol component and casting. Its viscosity is 100 at 25°C.
0 cps or less is preferable.

Such polyisocyanate components are disclosed in, for example, Japanese Patent Application No. 6
0-27 As stated in Otsu No. 594' specification, H
After reacting DI and water at a HD I/water molar ratio t~30, unreacted T (HDI biuret incyanate obtained by removing DI, or
As shown in the specification of No. 20/672, the general formula % formula % (wherein R1 to R4 represent an alkyl group or a benzyl group having carbon number/-1, each may be the same or different, and R1 The total number of carbon atoms in ~R4 is da~/λ, and R
8 represents an alkyl group, a 7-enyl group, or a benzyl group having a carbon number of / to /r. ) is a tetraalkylammonium carboxylate with the structure:
After using 400p and stopping the reaction when the conversion rate to HDI (7) polyisocyanurate was lo Nto%, surplus T (HDI polyisocyanurate obtained by removing DI or JP-A-Sho t/ -21!;/lr publication, from T(DI and molecule fik zoo/!;00 polycaprolactone polyol) to N
NCO-terminated prepolymer obtained by reacting with Colo H equivalent ratio jNI10 and then removing unreacted MDI,
Alternatively, in a similar method, it can be easily synthesized as an NCO-terminated prepolymer obtained by using other polyols instead of polycaprolactone pyriol, such as castor oil or an ester polyol of castor oil fat and a low molecular weight polyol, In addition, mixtures thereof are also preferably used.

In the present invention, the polyol component used in combination with the polyisocyanate component has the general formula % (% formula %) (wherein R is an organic group having a co-value to a da-value, and n and m represent integers from / to 3.) of oxycarboxylic acids are essential. Such oxycarboxylic acids include milk syrup, apple syrup, citric acid, tartaric acid, methylolpropionic acid, dimethylolpropionic acid, monoisopropyl citrate, citric acid/ethyl, malic acid monoglyceride, glycolic acid,
Hydroacrylic acid, oxybutyric acid, glyceric acid, tartronic acid, oxyvaleric acid, oxycaproic acid, oxyalanic acid, oxycaprylic acid, oxypelargonic acid, oxycapric acid, oxyundecanoic acid, oxylauric acid,
Oxytridecanoic acid, oxymyristic acid, oxypentadecanoic acid, oxypalmitic acid, ox7carboxylic acid,
Oxysaturated acids such as oxystearic acid, oxynonadecanoic acid, oxyarachidic acid, oxyheneicosanoic acid, oxybehenic acid, oxytridecanoic acid, oxyarachidic acid, oxytridecanoic acid, oxytriacontanoic acid, oxytetratriafuntanoic acid, Propenylglycolic acid, j, oxy-2,17-hentadienoic acid, halasorbic acid, β-oxyhydrosorbic acid, ≠-oxy73
-Tetradecane alcohol, ampuletolic acid, isoampretolic acid, 9-oxy/2-octadecenoic acid, ricinoleic acid, ricinoelaidic acid, oxyheneicosenoic acid, oxynavonic acid, camolenic acid, deside -Dioxy-1
0. /oxyalkenoic acids such as 2-octadecadienoic acid, dioxymyristic acid, λ,5-dioxypentadecane acid, dioxypalmitic acid, dioquinstearic acid,
Examples include polyoxy acids such as dioxyarachic acid, dioxytriacontane, trioxyhexadecanoic acid, and tetraoxyhexadecanoic acid. Among these, ox-7 carboxylic acids which are liquid at room temperature, such as linoleic acid, are preferred, and mixtures thereof can also be used.

The above-mentioned oxycarboxylic acid is usually used as one of the polyol components in a state where it is mixed with other polyol components, and the amount used is O0/ to 50% by weight, preferably 1 to 20% by weight in terms of the binding material. used to include.

As the polyol component other than the above-mentioned oxycarbonate, various conventionally known polyol components and polyamines can be used.

Examples of such giriol components include castor oil, a portion of castor oil fatty acid and low molecular weight polyol, or all polyester polyols (7) castor oil-based polyols, ethylene glycol, pyripropylene glycol, polytetramethylene glycol, etc. Polyester polyols (f!!
) Polycaprolactone polyols produced by ring-opening polymerization of caprolactone, aromatic polyhydric alcohols such as bisphenol A, aliphatics such as he-6-hexanediol,
Polycarbonate polyols made from ring group polyhydric alfurs, polyolefin triols such as terminal hydroxyl-terminated H+)butadiene and its hydrogenated products, N, N, 1
'F,N'-tetrakis(cohydroxypropyl)ethylenediami/,NININ'IN'-tetrakis(2
- Adducts of propylene oxide or ethylene oxide to amino/compounds such as ethylenediamine, - amine polyols such as triethanolamine, and also ethylene glycol, /, 3-propanediol, /, 2-propanediol , hegubutanediol, /, 3-butanediol, neopentyl glycol, coethyl-/, 3-hexanediol, trimethylolpropane, glycerin, and other low molecular weight polyols. Furthermore, for example, the above-mentioned polyols and the above-mentioned aliphatic or alicyclic diincyanates such as MDI, IPDI, and hydrogenated MDI can be combined with NG.
Pyriurethane-based diols obtained by reacting at an O10H equivalent ratio of 1 or less can also be suitably used.

Examples of the pyriamines include -ethylenediamine-diethylenetriamine, monoethanolamine, jetanolamine, inphorondiamine, xylylenediamine, and the like.

These other polyol components are generally mixed with a hot solvent as appropriate depending on the required performance of the binding material, and
It is necessary to have a viscosity so low that it does not interfere with mixing with the polyisocyanate component or casting pears. The viscosity is preferably r 000 cps or less at .j, lt'C.

The polyisocyanate component and the triol component are N C
010H equivalent ratio OJ~/, 4. Preferably 0.9~/,
It is used as a binding material for medical fluid separation devices made of hollow fibers, etc.

The hardness of the binding material after curing is suitably about 30 to 70 Shore D in view of the requirements of the cutting process after binding.

Curing is usually carried out at room temperature or under heating at ao-to°C,
At this time, the method of binding and sealing the ends of hollow fibers, etc. is as follows:
For example, Special Publication No. 17-31943, Special Publication No. 57-Jr.
? Generally, a centrifugal molding method such as that described in Publication No. 41I is used. In order for this casting and molding operation to be carried out smoothly, the initial viscosity of the mixture of the polyisocyanate component and the polyol component must be approximately 10,005 pH or less, preferably J
OOOcps or less, and 11000 as a guideline for the time until the resin loses fluidity due to the curing reaction after mixing.
Time to reach 0 cp is 30 to 3 minutes, more preferably 75 to 3 minutes
Preferably it is 6 minutes.

If this 10000cpt* arrival time is too long,
This not only has a negative effect on the productivity of medical fluid separation devices, but also causes the binding resin to penetrate into the hollow interior through the holes in the outer wall of the hollow fibers, resulting in the fatal drawback of finally clogging the hollow fibers. .

Examples of p-materials such as hollow fibers to be sealed with the binding material of the present invention include regenerated cellulose, cellulose acetate, cellulose ether, polyethylene, polypropylene, doryamide, polysulfone, polyacrylamide, which has properties as a semipermeable membrane, Examples include those manufactured from pyriacrylonitrile, polyester, polycarbonate, polyvinyl chloride, pyriurethane, casein, collagen, and the like.

The structure of the medical fluid separation device other than the binding material is, for example, disclosed in Japanese Patent Application Laid-Open No. 2003-120001. ;7! ; No. 7, JP-A-Sho r, r-73! i
jt issue, JP-A Sho Jr-92 goo 3, JP-A Sho r, r-,
206737, JP-A No. 3 DE-122JO6T, etc. can be mentioned, and examples of specific uses include, for example, artificial kidneys, artificial lungs, plasma separation, etc. Examples include devices.

〔Effect of the invention〕

The thus obtained aliphatic or alicyclic polyurethane binding material used in the medical fluid separation device does not contain aromatic polyisocyanate in the polyisocyanate component.
The characteristic of aliphatic or alicyclic polyisocyanate is that there is no concern about carcinogenicity caused by aromatic amines due to hydrolysis, and the adhesive strength after autoclave sterilization is dramatically improved, preventing container peeling. This is a very rare event that does not occur.

Furthermore, by taking advantage of this feature, it is also possible to apply it to adhesives for laminating films for retorts.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The present invention should not be limited to this.

In the examples, "parts" indicate parts by weight, and "%" indicates weight i1%.

Production example 1 HDI l&rO part and water/! 300 parts of methyl cellulsolve acetate as solvent, / 7 at 40'C
After reacting for an hour, a thin film evaporator was used (approximately /lO℃,
Approximately 0.2 TmHg (Hereinafter, this condition was used when using a thin film evaporator), unreacted I (DI and solvent etc. were removed and collected. Viscosity change 000 cpt*/2!; "C, NCO
Content 23.3%, free HDI□,! % of HDI biuret was obtained.

Production Example: After reacting 1000 parts of HDI, 330 parts of xylene, and 20 parts of he-3-butanediol at 10°C for one hour, 0.2 parts of tetramethylammonium coethylhexanoate was added.
9% phosphoric acid was added as a stopper to stop the reaction, and heating was continued for 7 hours at 60"C.
Cooled to room temperature. The precipitated tetramethylammonium
The phosphorous salt is removed by filtration, and unreacted H is removed using a thin film evaporator.
DI was collected. Viscosity, 2JOOcps/2j”C1N
C0 content @2/, 2%, free IHDI O,x% HDI
An incyanurate polyisocyanate was obtained.

Production Example 3 HD I rlr 9.11 parts Caprolactone Giriall "Plak7il 301r" (manufactured by Daicel Chemical Industries, Ltd.)
Product name, number average molecular weight rro, hydroxyl value/9j')20
After reacting with 0 parts at 10''C for 1 hour, unreacted HDI was removed using a thin film evaporator. Viscosity: rao.

cps/2 jo(:, NCO content 94%, free HD IO, 2% NCO-terminated preglymer was obtained.

Production example French HDI 10/1 part and castor oil polyol "H73XJ"
(manufactured by Ito Oil Co., Ltd., trade name, hydroxyl value core 0) was reacted with 210 parts at 100° C. for 4 hours, and unreacted MDI was removed using a thin film evaporator. Viscosity AOOOcpJ, 2j” (
, NCO-terminated prethalimer with NCO content/0.1% was obtained.

Manufacturing example! 1 part MDIj Togiri propylene glycol (molecular weight 1
000. The hydroxyl value //λ)≠io part was reacted at 100° C. for 1 hour. Viscosity 2 de00 eps /2 j ”C
An aromatic polyisocyanate containing 1NC0 ffi/lJ% was obtained.

Examples and Comparative Examples gI The polyisocyanates of Preparation Examples 1 to j were used as NCO components, and N,N,N,N'-tetrakis(hydroxypropyl)ethylenediamine (THPD), N,N,biv-
Tetrakis(hydroxyethyl)ethylenediamine (T
HEI)), polyether polyol rBMJ! IJ(
Manufactured by Jiryuka, product name, hydroxyl value r3/'), castor oil type,
l+J All "H7JXJ (manufactured by Ito Oil Co., Ltd., trade name, hydroxyl value -70), [(j4!J (manufactured by Ito Oil Co., Ltd., trade name, swimsuit base value /10), etc. were evaluated using as OH components.

The results are shown in Section 1II.

(Margin below)

Claims (3)

[Claims] (1) In the polyurethane-based binding material used in medical fluid separation devices, an aliphatic or alicyclic polyisocyanate is used as the polyisocyanate component, and the polyol component has the general formula (HO)_n-R-(COOH). A binding material characterized in that an oxycarboxylic acid of _m (in the formula, R is a divalent to tetravalent organic group, and n and m are integers of 1 to 3) is used as at least a part thereof. (2) The binding material according to claim 1, wherein the aliphatic polyisocyanate is a polyisocyanate synthesized using hexamethylene diisocyanate (HDI). (3) The binding material according to claim 1, wherein the oxycarboxylic acid is ricinoleic acid.