JP2548032C - - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyurethane elastomer for a sealing material and a binding material. More specifically, the elastomer relates to an electric sealing material and a medical or industrial hollow fiber end binding material. 2. Description of the Related Art Conventionally, in a polyurethane-based binding material used for an electric sealing material and a medical fluid separation device using hollow fibers, as a polyisocyanate component, tolylene diisocyanate (TDI), diphenylmethane diisocyanate ( MDI) and such with an aromatic polyisocyanate is used in, as the polyol component, castor oil polyols, polyether polyols, polyester polyols and a <br/> Mi emissions based polyol is used. However, when an elastomer having such a composition is used as a binding material of a medical fluid separation device using hollow fibers,
Significant reduction of the eluate from the seal is desired. As a means for improving this, Japanese Patent Application Laid-Open No. 60-58156 discloses hexamethylene diisocyanate (HMD).
It has been proposed to use a prepolymer obtained by reacting I) with a polyol as a part of the polyisocyanate component. However, a prepolymer obtained by reacting HMDI with a polyol such as 1,4-butanediol or castor oil generally contains a large amount of unreacted HMDI, and it is difficult to use this as a raw material of a binding material. At the same time, it is not desirable in terms of the safety and health of workers, and at the same time, it is desired that the cured polyurethane has no effect on the reduction of eluted substances and is further reduced. Further, such HMDI has a disadvantage that it has a very low reactivity as compared with aromatic isocyanates such as TDI and MDI, so that the curing speed after casting is low, and thus the productivity is inferior. As a method of accelerating the reaction between such a polyisocyanate and a polyol, Japanese Patent Application Laid-Open No. 58-93716 proposes the use of a metal catalyst or the like.
According to this method, the curing time can be shortened. However, heavy metals such as Sn, Pb, Zn, and Cd are considered to have a bad effect on living organisms and electrical properties when eluted, and are not preferable as medical materials or electrical materials. Furthermore, the raw material of the polyurethane elastomer has a viscosity suitable for the casting operation, and the cured product thereof does not cause deterioration or deterioration in quality in order to develop stable performance even with time. Is required. [0003] [SUMMARY OF THE INVENTION The present inventors have found, after extensive research to improve the conventional drawbacks, as the polyisocyanate component, using certain aliphatic polyisocyanates, certain polyol The present invention has been found to be able to be improved by using a polyurethane elastomer obtained depending on the conditions and conditions, and has led to the present invention. [0004] That is, the present invention provides a method for preparing a polyol adduct of hexamethylene diisocyanate with an isocyanate.
Hexamethylene diisocyanate monomer content of annulated polymerization 5% by weight
The following modified polyisocyanate compound and a mixed polyol are mixed with active hydrogen / NC
Of a polyurethane elastomer for a sealing material reacted at an O equivalent ratio of 0.8 to 1.6
The production method, wherein the mixed polyol comprises 45 to 57% by weight of an amine-based polyol.
%, Polyether polyol partially added with ethylene oxide is 25 to 19 times
Polio oil containing 30% to 24% by weight of castor oil-based polyol
The method described above. The present invention also relates to a polyol adduct of hexamethylene diisocyanate,
Hexamethylene diisocyanate monomer content of annulated polymerization 5% by weight
The following modified polyisocyanate compound and a mixed polyol are mixed with active hydrogen / NC
Manufacture of polyurethane elastomer for binding material which is reacted at O equivalent ratio of 0.8 to 1.6
Wherein the mixed polyol contains 45 to 57% by weight of an amine-based polyol.
, 25 to 19% by weight of a polyether polyol partially added with ethylene oxide
% And a castor oil-based polyol in a proportion of 30 to 24% by weight.
The above method. [0006] modified polyisocyanate compound used in the present invention DETAILED DESCRIPTION OF THE INVENTION are compounds polyol adduct HM DI was isocyanurated polymerization, isocyanurate preparative ring 1 or more in at least one molecule and that Yusuke isocyanate bets based on two or more at the same time. This change
Sex polyisocyanate compound, the content of HMDI (monomer) is 5 wt% or less. Isocyanurate of such HMDI, for example, JP HirakiAkira 57-47
No. 321. [0007] As amine-based polyol of the mixed polyols used in the present invention, oxyalkylated derivative of an amino compound having two or more active hydrogen atoms can be used. Is a specific example N, N, N ', N'- tetrakis [2-hydroxypropyl] ethylene diamine, N, N, N', to N'- tetrakis [2-hydroxyethyl] ethylene diamine such as amino compounds such as ethylenediamine of propylene oxide (PO) or ethylene oxide adduct, or mono -, di -
, Tri-ethanolamine and the like. Amine polyols are N, N, N
Those obtained by adding propylene oxide and ethylene oxide to ethylenediamine such as', N'-tetrakis [2-hydroxypropyl] ethylenediamine are preferable. [0008] Of the mixed polyols used in the present invention, ethylene oxide is partially added.
Polyether polyols are low molecular weight polyols such as alkylene oxide (ethylene
Adduct or ring-opened polymer of this alkylene oxide)
It is preferable to add EO to the terminal of the phenol to make it primary to increase the reactivity.
. It is generally called tipped polyether. Examples of the low-molecular polyol include divalent ones such as ethylene glycol and diglycol.
Ethylene glycol, propylene glycol, 1,4-butanediol, 1,3
-Butanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated
Bisphenol A, trivalent or higher (trivalent to octavalent) such as glycerin
, Trimethylolpropane (TMP), hexanetriol, pentaerythritol
And sorbitol. The castor oil-based polyol among the mixed polyols used in the present invention includes castor oil or polyester polyol of castor oil fatty acid and low molecular weight polyol (
Of castor oil fatty acid diglyceride, monoglyceride, castor oil fatty acid and trimethylol propane and mono-, di- or Trieste Le, castor oil fatty acid and polypropylene glycol, mono- and polyethylene glycol, di-, triesters, etc.). [0010] Each component ratio in the mixed polyol of the present invention, in a mixed polyol, amine polyol Lumpur 45-57 wt% der is, ethylene oxide was added portion Po
25 to 19% by weight of a reether polyol, and 30% of a castor oil-based polyol.
２４24% by weight. If outside this range, workability curing time becomes long, rather a preferable considering productivity, strap, depending on the required characteristics of the seal material, suitable
Used in amount mixed. In the present invention , the reaction ratio between the modified polyisocyanate compound and the mixed polyol is an active hydrogen / NCO equivalent ratio of 0.8 to 1.6, and preferably 0.9 to 1.2. Usually, the active hydrogen / NCO equivalent ratio is set at 1.0, but in order to adjust the setting time and change the physical properties of the resin , the active hydrogen / NCO equivalent ratio is set to 0.8 to 0.8.
It is blended and cured within the range of 1.6. If the value is out of the range of 0.8 to 1.6,
The resin does not cure or does not exhibit physical properties of the resin. The curing temperature is usually at room temperature, and the gel time is usually 5 to 90 minutes.
However, if necessary, by heating to 30 to 80 ° C., the gelation time and the time until complete curing can be reduced, or the required mixed viscosity can be obtained. Resin (base resin and curing agent) for prompt reaction between isocyanate and active hydrogen
Can be heated. However, when the temperature is lower than 30 ° C., the viscosity of the resin increases, which prevents uniform mixing and increases the curing time. On the other hand, when heated to 80 ° C. or higher, the resin itself deteriorates. Further, the curing speed is extremely high, which is not preferable for work. The polyurethane elastomer thus obtained can be used as a fiber end bundling material and a sealing material for a fluid separation device using hollow fibers. On this occasion,
As a method of bundling seal the ends of the hollow fiber, JP Sho 57-58963, to use a centrifugal molding method described in JP 57-58964 Publication it is generally. Examples of hollow fibers include regenerated cellulose, cellulose acetate, cellulose ether, polyethylene, polypropylene, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polyester, polycarbonate, polyvinyl chloride, polyurethane, and casein having properties as a semipermeable membrane. , Collagen and the like. Structures other than the binding material of the medical fluid separation device using the hollow fibers sealed with the binding material of the present invention are described in, for example, JP-A-56-15557 and JP-A-58-75556.
JP-A-58-92423, JP-A-58-206675, JP-A-59-225066, and the like. Examples include plasma separators, artificial lungs, artificial kidneys , or industrial, medical , or general water purifiers and chemical separators. [0012] According to the present invention, a polyurethane elastomer obtained by reacting a modified polyisocyanate compound and mixing polyols, when used as a sealing material and strap, elution amount is rather very small, which is advantageous. In particular, when used as a hollow fiber end bundling material in a medical fluid separation device using a hollow fiber, since harmful metal compounds such as Sn, Zn, Pb, and Cd are not included as a catalyst for curing the polyurethane bundling material, There is no concern that harmful metal compounds enter the living body. Moreover, despite these heavy metal catalysts are not used, has a curing property comparable to the aromatic polyurethane (short especially gel time), further, it maintains a liquid state at room temperature, Since it has a low viscosity suitable for molding work, it is extremely excellent in productivity . Further, since it is substantially free of free HMDI (monomer) which is highly toxic and irritating, it is excellent in safety and health even for workers engaged in molding work. The polyurethane elastomer obtained by the present invention is almost transparent in the thicknesses in these application ranges, has processability suitable for these applications, and is excellent as a binding material for hollow fibers. Medical fluid separation devices using these hollow fibers require high safety and low eluate amount, such as plasma separation devices, artificial lungs, artificial kidneys and other hollow fiber end bundling materials that come into direct contact with blood. It shows particularly excellent characteristics for use in the field where it is used, and is extremely useful industrially. EXAMPLES The present invention will be described in more detail with reference to Examples. "Part" and "
"%" Are "parts by weight" and "% by weight", respectively, unless otherwise specified. Example 1 Isocyanurate of HMDI as a modified polyisocyanate compound (Japan
Made by Polyurethane Industry, trade name Coronate HX: NCO content 21.3%, HMD
I monomer 0.3%. C-HX abbreviated as) 143 parts, mixed polyol Lumpur and to chipped ether (EO addition rate of 20%, molecular weight 2500, hydroxyl value 4 5) 25 parts of castor oil based polyol (hydroxyl value 16 0) 30 parts, and 45 parts of N, N, N ', N'-tetrakis [2-hydroxyethyl] ethylenediamine (THEED ) were blended and cured. The NCO / active hydrogen equivalent ratio is 0.95 . These components were promptly made compatible and homogenous, and there was no odor or irritation to the eyes due to the HMDI monomer during the molding operation. Details are shown in Table 1 . [0014] C-HX180 parts as a second embodiment modified polyisocyanate compound, chipped ether (molecular weight 2500, hydroxyl value 4 5) as a mixed polyol 19 parts, castor oil-based polyol (hydroxyl value 16 0) 24 parts, and THE ED57 Parts , the liquid temperature 50
Cured at ° C. The NCO / active hydrogen equivalent ratio is 1.0 . These components were promptly homogenized to obtain a pale yellow transparent cured product. In addition and odor due to the work in the HMDI monomer stimulus was no. Details are shown in Table 1 . [0015] Comparative Example 1 modified polyisocyanate compound is a C-HX 133 parts of mixed polyol Lumpur in
Castor oil-based polyol (hydroxyl value 120) 60 parts of N, N, N ', the N'- tetrakis [2-hydroxypropyl] ethylenediamine (THPED) 4 0 parts distribution Te
If it was cured. The NCO / active hydrogen equivalent ratio is 1.0 . There was no odor or eye irritation caused by the HMDI monomer in the molding operation. Further, after mixing, the mixture was promptly homogenized to obtain a pale yellow transparent cured product. Details are shown in Table 1 . [0016] TH as Comparative Example 2 modified polyisocyanate compound to C-HX75 parts of polyol
25 parts of EED were blended and cured. Both components having an NCO / active hydrogen equivalent ratio of 1.0 were immediately compatible and uniform after mixing, and there was no odor or irritation to the eyes due to the HMDI monomer in the molding operation. Details are shown in Table 1 . [0017] Comparative Example 3 polyisocyanate chromatography Removing and to HM DI20 4 parts of polypropylene glycol (molecular weight 2000) and 576 parts of reacted for 20 hours at 90 ° C., to obtain a prepolymer terminated NCO. The obtained prepolymer has a viscosity at 25 ° C. of 1200 cP and NCO
The content was 9.8% and the free HMDI was 8.8%. As a polio Lumpur, TH
Using PED, compounding and curing were performed so that the NCO / active hydrogen equivalent ratio was 1.0. Both components were promptly homogenized, but the initial mixing viscosity was high and the gelation time was required for 30 minutes, which was not preferable in terms of work. During the mixing operation, there was a strong odor and eye irritation caused by the HMDI monomer, which was not preferable in terms of work hygiene. See Table 1 for details
To show. [0018] was synthesized Comparative Example 4 MDI315 parts of trifunctional polypropylene polyol (molecular weight 1500) and 275 parts of reacted for 4 hours at 80 ° C. NCO-terminated prepolymer as polyisocyanate. The resulting prepolymer had an NCO content of 14.2% and a viscosity at 25 ° C. of 5200 cP. And polio Lumpur castor oil based polyol (hydroxyl value 160) A mixture of 78 parts of the 332 parts of THPED NC O / active hydrogen equivalent ratio of 1
. 0 and mixed and cured. Details are shown in Table 1 . [ Table 1] The eluting material test method (Junzu dialysis type artificial kidney approval standards V-5) taken by the support and circuit connection pipe used in the dialyzer (each about 200 cm ² or as front and back surface) each about 15 g, about Cut into 2 cm ² (or about 2 cm), put each in a container containing 150 ml of water that has been boiled and cooled beforehand, and placed at 70 ± 5 ° C.
After heating for 1 hour, the content liquid was taken after cooling, and water was added to make 150 ml, which was used as a test liquid. For the blank test solution, use water that has been boiled and cooled in advance. The following test was performed on the test solution and the blank test solution. Ultraviolet absorption spectrum For the test solution, the blank test solution was used as a control, and the layer length was 10 mm and the wavelength was 220 to 350 nm.
When the absorbance at is measured, the absorbance is 0.1 or less. Potassium permanganate reducing substance Take 10.0 ml of test solution in a stoppered Erlenmeyer flask, add 20.0 ml of 0.01 N potassium permanganate solution and 1.0 ml of dilute sulfuric acid, boil for 3 minutes, cool, and add 0.10 g of potassium iodide was added, sealed, shaken and left for 10 minutes.
Titrate with 01N sodium thiosulfate solution (indicator: 5 drops of starch sample). Separately, operate similarly using 10.0 ml of blank test solution. The difference in consumption of the 0.01 N potassium permanganate solution is 1.0 ml or less.

Claims (1)

Claims: 1. A polyol adduct of hexamethylene diisocyanate is converted to an isocyanate.
Hexamethylene diisocyanate monomer content of annulated polymerization 5% by weight
The following modified polyisocyanate compound and a mixed polyol are mixed with active hydrogen / NC
Of a polyurethane elastomer for a sealing material reacted at an O equivalent ratio of 0.8 to 1.6
The production method, wherein the mixed polyol comprises 45 to 57% by weight of an amine-based polyol,
25 to 19% by weight of a polyether polyol partially added with oxide and castor
It is a mixed polyol containing 30 to 24% by weight of an oil-based polyol.
The method as described above. 2. A polyol adduct of hexamethylene diisocyanate is reacted with isocyanate.
Hexamethylene diisocyanate monomer content of annulated polymerization 5% by weight
The following modified polyisocyanate compound and a mixed polyol are mixed with active hydrogen / NC
Manufacture of polyurethane elastomer for binding material which is reacted at O equivalent ratio of 0.8 to 1.6
A manufacturing method, the mixed polyol, 45-57 percent by weight of the amine-based polyol, Echiren'o
25 to 19% by weight of a polyether polyol partially added with oxide and castor
It is a mixed polyol containing 30 to 24% by weight of an oil-based polyol.
The method as described above.