JP3312393B2 - Polyurethane-based elastomer-forming composition and hollow fiber binder using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane elastomer-forming composition and a hollow fiber binder using the same. More specifically, the present invention relates to a polyurethane-based elastomer-forming composition used as a polyurethane-based sealing agent, a binding agent, and the like, and a hollow fiber binding agent using the same.

[0002]

2. Description of the Related Art Polyurethane is industrially a polymer compound having --NHCOO-- in a main chain repeating unit obtained by reacting an organic polyisocyanate with a polyol having a polyester structure or a polyol having a polyether structure. Depending on the combination of raw materials, there are wide applications such as polyurethane foam, polyurethane rubber, adhesives, fibers, and paints.

[0003] For example, in a hollow fiber binding agent for a medical or industrial fluid separation device using an electrical sealant and a hollow fiber separation membrane, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (TDI) as a main agent (polyisocyanate). Aromatic isocyanates such as MDI) or hexamethylene diisocyanate (H
DI), hydrogenated MDI, isophorone diisocyanate (I
A prepolymer prepared by reacting a non-aromatic isocyanate such as PDI) with a castor oil-based polyol such as castor oil or alcohol-modified castor oil, or a polyether polyol such as polypropylene glycol or polyethylene glycol is used. As the hydrogen-containing compound), castor oil-based polyols such as castor oil and alcohol-modified castor oil, and polypropylene glycol, polyethylene glycol and the like are used.

[0004] In these sealants and binders, low-viscosity systems that cure quickly at low temperatures have been studied, and problems in workability and moldability are decreasing. However, in terms of physical properties, it is low in elasticity, strength and the like, and is inferior in durability.

On the other hand, in the case of two-component polyurethane for OA equipment parts such as industrial rolls for papermaking, ironmaking and printing, paper feed rolls, cleaning blades and the like, the aromatic or non-aromatic isocyanate and polyethylene adipate, polybutylene are used. A prepolymer obtained by reacting a polyester polyol such as adipate or a polyether polyol such as polytetramethylene ether glycol or polypropylene glycol is used. As a curing agent (active hydrogen-containing compound), 4,4′-methinebis (2- Chloroaniline), an aromatic amine such as 4,4'-methylenedianiline, or an aliphatic glycol such as 1,4-butanediol and trimethylolpropane to obtain a resin having high elasticity and high physical properties. Is widely used in industrial fields There.

[0006] However, these systems have low reactivity at low temperatures and require heat curing at 100 ° C or higher to obtain high physical properties. Furthermore, the prepolymer of polyisocyanate and polyol has a high viscosity, and it is difficult to cast into a fine portion.

Further, as a means for accelerating the curability at a low temperature, addition of a heavy metal catalyst such as Sn, Pb, Zn or Cd or an amine catalyst such as triethylenediamine or triethylamine is also performed. In addition to the possibility of instability, there are problems in medical applications, such as elution into body fluids and adverse effects on living organisms. Further, conventional resins have drawbacks such as too high hardness and brittleness, and improvement thereof is demanded.

[0008]

SUMMARY OF THE INVENTION In order to obtain the disadvantages of the conventional polyurethane-based sealants and binders, that is, high elasticity, high physical properties, quick reactivity and good productivity, the present invention requires the use of resin. Higher viscosity, necessity of heat curing, conversely, those that cure quickly at low temperature, have limited physical properties, limited applications, furthermore, there is a large amount of eluted material and there is no biocompatibility, resin It is to improve that the hardness is too high and brittle.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies and studies in order to improve the conventional drawbacks, and as a result, a modified product in which a part of the NCO group of HDI is urethanized and then isocyanurated ( A), and diphenylmethane diisocyanate
Anate (MDI) or N of carbodiimide-modified MDI
The present invention was found to be able to be improved by using a CO group-terminated prepolymer (B) in combination, and reached the present invention.

That is, the present invention relates to a polyurethane-based elastomer-forming composition comprising a polyisocyanate and a curing agent, wherein the polyisocyanate is converted into a part of NCO groups of hexamethylene diisocyanate as a polyol adduct and then isocyanurated. Modified denatured (A), and
Diphenylmethane diisocyanate (MDI) or
A polyurethane elastomer-forming composition comprising an NCO-terminated prepolymer (B) of rubodiimide-modified MDI and an amine-based polyol (C) and / or a non-amine-based polyol (D) as a curing agent. Things.

[0011] The present invention is also a hollow fiber binding agent using the above-mentioned polyurethane elastomer-forming composition.

The polyisocyanate which can be used in the present invention is a modified product (A) in which a part (15% by weight or less) of all NCO groups of HDI is converted into a polyol adduct and then isocyanurated. As a polyol for obtaining a polyol adduct, a polyol having a molecular weight of 3000 or less is used.
Trifunctional polyols are suitable. As the diol, ethylene glycol, diethylene glycol, 1,3-butanediol (1,3BD), 1,4-butanediol, propylene glycol, dipropylene glycol,
Examples include dihydric alcohols such as neopentyl glycol and 1,6-hexane glycol (1,6HD), polyester polyols, and polyether polyols. Examples of the triol include trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane, and polyester polyols and polyether polyols. Polyols can also be used in these blend systems. This urethanization ratio is desirably 15% by weight or less based on all isocyanates. If the content is 15% by weight or more, the characteristics of the isocyanurated bond formed thereafter cannot be sufficiently exhibited. A method in which 15% by weight or less of all NCO groups of HDI is converted into a polyol adduct and then isocyanurated is disclosed in
No. 47321. In the isocyanuration reaction, a metal salt of a carboxylic acid is used as a catalyst, and a phenolic droxy compound,
Secondary amines and the like.

[0013] A jiff that can be used in the present invention.
Phenylmethane diisocyanate (MDI) or carbodi
The NCO-terminated prepolymer of imide-modified MDI is
A compound obtained by reacting a CO group with an active hydrogen group and having an NCO group for obtaining a prepolymer is MDI, or a part of MDI is biuret, allophanate, carbodiimide, oxazolidone, amide,
Some are modified to imides and the like.

Examples of the compound having an active hydrogen group for obtaining a prepolymer include low molecular polyols, polyether polyols, polyester polyols, castor oil polyols and the like. These can be used alone or as a mixture of two or more. As the low molecular polyol, divalent ones, for example, ethylene glycol, diethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
Neopentyl glycol, hydrogenated bisphenol A, etc., 3
Those having a valence of three or more (three to eight valences), such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and souce. The equivalent of the low molecular polyol is 30 to 200.

As the polyether polyol, alkylene oxides of the above-mentioned low molecular weight polyols (C 2-4)
Alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide) and ring-opened polymers of alkylene oxides, and specifically include polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. The polyether polyol having an equivalent weight of 200 to 1500 is used.

As the polyester polyol, there are polyester polyol, polycaprolactone polyol, polyetherester polyol and the like. Polyester polyols include carboxylic acids (aliphatic saturated or unsaturated carboxylic acids such as adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, dimerized linoleic acid and / or aromatic polycarboxylic acids such as phthalic acid , Isophthalic acid) and a polyol (the low-molecular polyol and / or polyether polyol).

Polycaprolactone polyols include ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-
It can be obtained by addition polymerization of ε-caprolactone and the like in the presence of an organic metal compound, a metal chelate compound, a fatty acid metal acylate and the like. The polyetherester polyol is an alkyleneoxy resin such as ethylene oxide, which is a polyester having a terminal carboxyl group and / or an OH group.
It is obtained by the addition reaction of propylene oxide and the like. The equivalent weight of the polyester-based polyol is 200 to 1500.

Examples of castor oil-based polyols include transesterified castor oil and castor oil or castor oil fatty acids with the low-molecular-weight polyols, polyether polyols, and polyester polyols, or esterified polyols. The equivalent of castor oil-based polyol is 200
~ 1500 are used.

Preferred among these polyols are low molecular weight polyols such as 1,4-butanediol, diethylene glycol, polyether polyols such as polyethylene glycol and polypropylene glycol, and amino alcohol polyols such as tetrakishydroxyethyl. Ethylenediamine, tetrakishydroxypropylethylenediamine and castor oil-based polyols.

The NCO group / active hydrogen group equivalent ratio for obtaining the NCO group-terminated prepolymer of the present invention is 7.0-18.
0. The reaction can be carried out by a usual urethanization reaction.

The modified product from HDI in the present invention (A), and diphenylmethane diisocyanate sulfonate (MD
The NCO-terminated prepolymer (B) of I) or the carbodiimide-modified MDI can be used in a range of 5:95 to 95: 5 (weight ratio).

The curing agent that can be used in the present invention is:
An amine-based polyol (C) and / or a non-amine-based polyol (D). As the amine-based polyol (C), an oxyalkylated derivative of an amino compound having two or more active hydrogen atoms can be used. Specific examples include N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine as an amino alcohol,
Propylene oxide (PO) or an ethylene oxide adduct to an amino compound such as ethylenediamine such as N, N, N ', N'-tetrakis [2-hydroxyethyl] ethylenediamine, or mono-, di-, tri-
Ethanolamine and the like can be mentioned. The amine polyol is preferably obtained by adding propylene oxide and ethylene oxide to ethylenediamine such as N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine.

Examples of the polyol (D) other than the amine-based polyol as the curing agent include low-molecular-weight polyols, polyether polyols, castor oil-based polyols, and polyester-based polyols. For these, compounds having an active hydrogen group used for obtaining an isocyanate group-terminated prepolymer can be used.

The amine-based polyol (C) and the non-amine-based polyol (D) as such a curing agent preferably have a weight ratio of 10:90 to 100: 0.
In this case, if the content of the amine-based polyol is 10% by weight or less, the curing time is prolonged, which is not preferable in view of workability and productivity. These curing agents can be used by mixing them with other polyols in appropriate amounts according to the required properties of the binder and the sealant.

The reaction between the polyisocyanate of the present invention and the curing agent is carried out by an isocyanate group / active hydrogen group equivalent ratio of 0.8.
To 1.6, preferably in the range of 0.9 to 1.2. If the ratio is out of the range of 0.8 to 1.6, the resin may not be cured, or the physical properties of the resin may not be exhibited.

The polyurethane-based elastomer-forming composition of the present invention has a low-temperature liquid and low-viscosity polyisocyanate and a curing agent (active hydrogen-containing compound), and can be prepared without using a metal or amine catalyst. Since it shows good curability, it does not require a heating device, can be operated at room temperature,
Polyurethane with high elasticity and high physical properties at room temperature can be used. Further, the absence of unreacted metals or amine catalysts means that there is no elution into water or body fluids, and low-temperature liquidity and low viscosity are useful in terms of workability. In particular, it shows excellent performance in heat resistance, tensile strength, tear strength and the like, and when eluate is measured in a dialysis-type artificial kidney device, the absorbance of the eluate is low and shows excellent performance.

The polyurethane elastomer-forming composition of the present invention has various properties such as hardness,
Because of its excellent tensile strength, elongation, tear strength, etc., it can be used as a sealing material for various industrial applications, such as a sealing material for electric, automobile, construction, civil engineering, or various cushioning materials. Industrial rolls for iron making and printing, paper feed rolls,
It can be used for OA equipment parts such as cleaning blades.

The polyurethane elastomer-forming composition of the present invention, in addition to the above-mentioned excellent physical properties, does not contain a metal or an amine catalyst which is not reacted. Therefore, it is advantageous as a hollow fiber binding agent for medical and industrial fluid separation devices using a hollow fiber separation membrane. Examples of these medical and industrial fluid separators include a plasma separator, an artificial lung, an artificial kidney, an artificial liver, and a domestic / industrial water treatment apparatus.

The binder for hollow fibers of the present invention is characterized by using the above-mentioned polyurethane-based elastomer-forming composition.

[0030]

The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to these. "Part" in Examples and Comparative Examples
And “%” are all “parts by weight” unless otherwise specified,
"% By weight".

Production of Modified Form of HDI (A) Production of A-1 300 parts of HDI was placed in a 500 ml separable flask equipped with a thermometer, a stirrer, and a nitrogen sealed tube, and 1 part of polyol was used.
2.4 parts of 3-BD were charged, the air in the flask was replaced with nitrogen, and the mixture was heated to a reaction temperature of 80 ° C. with stirring, reacted at the same temperature for 2 hours, and the NCO content was measured to be 48.8%. Was. Next, potassium caprate 0.06
And 0.3 part of phenol as a cocatalyst were added, and an isocyanurate-forming reaction was carried out at 60 ° C. for 4.5 hours. 0.042 parts of phosphoric acid was added to this reaction solution as a terminator, and after stirring at the reaction temperature for 1 hour, free HDI was removed by a molecular distillation apparatus. The resulting liquid is a pale yellow transparent liquid with an NCO content of 2
1.0%, viscosity 2200mPa · s / 25 ° C, free HD
The I content was 0.4%. This modified product is designated as A-1.

Production of A-2 300 parts of HDI, 1,3
A reaction was carried out in the same manner as in A-1, using 10.2 parts of BD, 0.06 part of potassium propionate as a catalyst, 0.3 part of phenol, and 0.072 parts of phosphoric acid. After reacting the polyol with HDI, the NCO content was 45.3%. After distillation, the NCO content was 19.2% and the viscosity was 2800 mPa · s /
At 25 ° C., the free HDI content was 0.3%. This modified product is designated as A-2.

Production of A-3 Using the same apparatus as in A-2, 300 parts of HDI, 1,6
3.3 parts HD, 0.03 parts sodium undecylate,
The reaction was carried out in the same manner as in A-1 using 0.198 parts of phosphoric acid. After reacting the polyol with HDI, the NCO content is 48.
6%. After distillation, NCO content 20.5%, viscosity 3000 mPa · s / 25 ° C, free HDI content 0.4%
Met. This modified product is designated as A-3.

HDI 30 using the same device as A-3
0 parts and 80 parts of trimethylolpropane were reacted at 80 ° C. for 5 hours to obtain an NCO content of 19.4% and a viscosity of 80,000.
A prepolymer having mPa · s / 25 ° C. was obtained. This prepolymer is designated as A-4.

Production of isocyanate-terminated prepolymer (B) Production of B-1 MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MT) 318 using the same apparatus as in the production of the modified product (A).
Was reacted at 80 ° C. for 4 hours with an NCO content of 28. %, And a prepolymer having a viscosity of 80 mPa · s was obtained. This prepolymer is designated as B-1.

Preparation of B-2 Carbodiimide-modified MDI using the same apparatus as B-1
(Millionate MT, manufactured by Nippon Polyurethane Industry
L) 233 parts of PPG-2000 (polyether manufactured by Asahi Denka Kogyo) 115 parts were reacted at 80 ° C. for 4 hours to obtain NCO.
A prepolymer having a content of 18.0% and a viscosity of 800 mPa · s / 25 ° C. was obtained. This prepolymer is referred to as B-2.

Examples 1 to 8 and Comparative Examples 1 to 3 Polyisocyanates were prepared by mixing at the ratios shown in Table 1. Table 1 shows the elastomer-forming composition. The polyisocyanate and the curing agent were blended at a resin temperature of 25 ° C. so as to have a reaction equivalent ratio of 0.95, and cured at 25 ° C. The polyisocyanate curing agent was quickly made compatible and uniform, had a good gelation time, and was capable of smooth casting and molding. Table 2 shows the hardness, tensile strength, elongation and tear strength of the produced polyurethane. Hardness was measured at 25 ° C. and 120 ° C. to check heat resistance.

Dissolution Test Using the compositions of Examples 1 to 8 and Comparative Examples 1 to 3, a hollow fiber containing about 70% by weight of glycerin is poured into a set mold. After the injection, the adhesive was completely molded by a centrifugal molding method. The molded hollow adhesive portion is left at 25 ° C. for 7 days to perform complete curing. Then cut into 1cm squares and 40g
Is a test piece. Table 2 shows the test results.

Test Items and Methods Dialysis Type Artificial Kidney Apparatus Standard (Notice 494 by the Director of Pharmaceutical Affairs Bureau, Ministry of Health and Welfare)
No.) The eluate was measured by an absorption measurement method in accordance with the elution test (Note-1) of the V-4 hollow fiber adhesion portion. The measurement wavelength was expanded to 300 to 22 nm. Note-1: Contents of dialysis type artificial kidney device standard V-4

Elution Test of Hollow Fiber Adhesive Portion In the case of a hollow fiber type dialyzer, the hollow fiber adhesive portion of one dialyzer is cut out and cut into a size of about 1 cm square. 200 ml of water is added thereto, and the mixture is gently shaken and heated at 40 ° C. for 2 hours. After cooling, take 1.0 ml of the supernatant and add water to make exactly 5.0 ml. When this solution is used as a test solution, and water is used as a control, the absorbance at a wavelength of 280 to 240 mm with a layer length of 10 mm is measured by the absorbance measurement method of the Japanese Pharmacopoeia. The absorbance must be 0.05 or less.

[0041]

[Table 1]

[0042]

[Table 2]

Examples 9 to 16 and Comparative Examples 4 and 5 The same operation as in Examples 1 to 8 and Comparative Examples 4 and 5 was performed. Details are shown in Tables 3 and 4. The dissolution test was performed similarly. Table 4
Shown in

[0044]

[Table 3]

[0045]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 A61M 1/18 B01D 63/02

Claims (2)

(57) [Claims] A polyurethane elastomer-forming composition comprising a polyisocyanate and a curing agent, wherein the polyisocyanate is a modified product obtained by converting a part of NCO groups of hexamethylene diisocyanate into a polyol adduct and then isocyanurating the polyisocyanate. A) and diphenyl meta
Diisocyanate (MDI) or carbodiimide modification
A polyurethane elastomer-forming composition comprising an NCO group-terminated prepolymer of MDI (B) and an amine-based polyol (C) and / or a non-amine-based polyol (D) as the curing agent. 2. A binder for a hollow fiber, comprising the polyurethane elastomer-forming composition according to claim 1.