JPH08169930A - Polyurethane resin composition, and adhesive, sealant, and binder produced therefrom - Google Patents

Abstract

PURPOSE: To obtain a polyurethane compsn. which is excellent in adhesion to a housing, gives a cured item reduced in exudate content, and has a low viscosity. CONSTITUTION: The compsn. comprises an isocyanate-terminated prepolymer formed from tolylene diisocyanate and a polyol in an equivalent ratio of NCO group to OH group of 1.5-2.5, an isocyanate-terminated prepolymer formed from diphenylmethane diisocyanate and a polyol in an equivalent ratio of NCO group to OH group of 5.0 or higher and/or a uretonimine-modified diphenylmethane diisocyanate and/or a carbodiimide-modified diphenylmethane diisocyanate, an isocyanurate- (and uretedione-) modified hexamethylene diisocyanate, and an amine-based and/or a castor-oil-based polyol as the curative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin composition, and more particularly to an adhesive, a sealant and a binding agent using the resin composition, which comprises a hollow or flat membrane fiber separation membrane. It relates to a fiber binder for medical and industrial fluid separators used, and an adhesive between the fiber binder and a housing, and is particularly suitable for a medical fluid separator using a fiber separation membrane having a high glycerin content. is there. It can also be used as a sealant for electricity.

[0002]

2. Description of the Related Art Conventionally, tolylene diisocyanate (TDI) has been used as a fiber binding agent for medical and industrial fluid separation devices using a hollow or flat membrane fiber separation membrane and an adhesive between the fiber binding portion and a housing. Polyurethanes composed of aromatic isocyanates such as diphenylmethane diisocyanate (MDI) and castor oil-based polyols, amine-based polyols and the like have been used.

Further, in regard to high-performance separation membranes, which have been increasing in recent years, Japanese Patent Application Laid-Open No. 2-127413 discloses TDI.
We have proposed a low-eluate system that can suppress the reaction with glycerin, which is a moisturizing agent contained in the membrane, by combining the isocyanate-based prepolymer and modified MDI.
Similarly, in JP-A-6-136089, there is disclosed a hexamethylene diisocyanate (HDI) modified with an isocyanurate and M in order to realize a low eluent which is less affected by glycerin which is a moisturizing agent and which can also achieve a low viscosity.
Combinations of DI based prepolymers have been proposed.

[0004]

However, although these conventional polyurethanes are suitable for lowering the amount of eluate, they have a mixed viscosity of 4000 cP or less for obtaining good workability and impregnability, and a plastic housing or the like. At least 30 Kg / cm ² with each member was not able to simultaneously achieve the required adhesive strength retention. Especially HDI
Those containing a large amount of a modified product of isoaliphatic isocyanate and / or an isocyanate (NCO) group-terminated prepolymer of an aliphatic isocyanate such as HDI and a polyol have low elution and low viscosity, but have poor adhesiveness, and expansion and contraction, etc. There was a problem in practice due to peeling from the plastic housing due to internal strain or weak external force.

[0005]

[Means for Solving the Problems] As a result of intensive studies and studies, the present inventors have found that polyisocyanate is (1) TD.
NCO-terminated prepolymer of I and polyol, (2)
An NCO group-terminated prepolymer of MDI and polyol and / or MDI uretonimine and / or carbodiimide modified product, (3) HDI isocyanurate modified product or isocyanurate and uretdione modified product. The inventors have found that the use of castor oil-based polyol as a curing agent makes it possible to achieve excellent adhesiveness with a housing, a low eluent, and a low viscosity.

That is, the present invention provides a polyurethane resin composition comprising a polyisocyanate and an amine-based polyol and / or a castor oil-based polyol as a curing agent, wherein (a) TDI and two or more hydroxyl groups per molecule as the polyisocyanate. NCO group / hydroxyl group equivalent ratio of 1.5 to 2.5 with the polyol having
NCO group-terminated prepolymer according to (hereinafter abbreviated as TDI prepolymer). (B) an NCO group-terminated prepolymer (hereinafter abbreviated as MDI prepolymer) having an NCO group / hydroxyl group equivalent ratio of 5.0 or more, and / or MDI of MDI and a polyol having two or more hydroxyl groups in one molecule. Modified uretonimine and / or carbodiimide. (C) A modified HDI isocyanurate or a modified isocyanurate and uretdione. It consists of three components, and the weight ratio of (a) / (b) is 90 /
The polyurethane resin composition is characterized in that the weight ratio of (a) + (b) / (c) is from 10 to 30/70 and from 95/5 to 50/50. Further, it is an adhesive, a sealant and a binding agent using the polyurethane resin composition.

Polyurethane resin composition, adhesive, and sealant that realize a low eluate, an appropriate viscosity, and an improvement in adhesive strength with each member by suppressing the reaction with glycerin adhering to the fiber used as the material to be adhered And a binding agent.

The (a) TDI prepolymer, which is one of the polyisocyanate components of the present invention, is an NCO group / hydroxyl group of TDI and a polyol having 2 or more, preferably 2 to 3 hydroxyl groups in one molecule. It is obtained with an equivalence ratio of 1.5 to 2.5. The TDI used is 2,4-
TDI, 2,6-TDI and the like may be used alone or in a mixture at an arbitrary ratio, and further modified products thereof may be used.
Examples of the polyol used include low molecular weight polyols, polyether polyols, polyester polyols, castor oil-based polyols and the like. The low molecular weight polyol has a molecular weight of 60 to less than 500, preferably a molecular weight of 6
2 to less than 200, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, trimethylolpropane, glycerin, etc. Is mentioned. Particularly preferred low molecular weight polyol is ethylene glycol,
1,3-butanediol, 1,4-butanediol, trimethylolpropane and the like.

The polyether polyol has a molecular weight of 500 to 5000, preferably 700 to 3000.
For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyetherpolyol (liquid polytetramethylene glycol) obtained by copolymerizing tetrahydrofuran and 3-alkyltetrahydrofuran, and two or more polymers of ethylene oxide and propylene oxide. An example is a chipped ether. Particularly preferred are polypropylene glycol, liquid polytetramethylene glycol, and chipped ether.

The polyester polyol has a molecular weight of 500 to 5,000, preferably 900 to 3,000.
Examples thereof include linear or branched polyester-based polyols of carboxylic acids and polyols, polycaprolactone-based polyols produced by ring-opening polymerization of caprolactone, and the like. Castor oil-based polyols include castor oil,
Examples thereof include transesterification of dehydrated castor oil and ricinoleic acid, which is a castor oil fatty acid, and the above-mentioned low molecular weight polyol, polyether polyol, polyester polyol, or esterified polyol. Particularly preferred are castor oil, dehydrated castor oil and the like.

Of these, preferred polyols for obtaining a TDI prepolymer which is liquid at room temperature and has a low viscosity are ethylene glycol, polypropylene glycol, liquid polytetramethylene glycol,
Examples include chipped ether and castor oil-based polyol.

The TDI prepolymer thus obtained contains polyisocyanate and polyol in an amount of 30 to 13
It can be obtained by reacting at 0 ° C, preferably 40 to 90 ° C for 1 to 5 hours. The equivalent ratio of NCO group / active hydrogen group is
It is obtained by carrying out the reaction at 1.5 to 2.5, preferably 1.8 to 2.0.

The (b) MDI prepolymer and / or MDI uretonimine and / or carbodiimide modified product which is one of the polyisocyanate components of the present invention is MD.
In the case of the I prepolymer, it is obtained by an NCO group / hydroxyl group equivalent ratio of 5.0 or more of MDI and a polyol having two or more hydroxyl groups in the molecule. Examples of the polyol used include low molecular weight polyols, polyether polyols, polyester polyols, castor oil-based polyols and the like similar to the above TDI prepolymer.

Of these, preferred polyols are those which are liquid at room temperature and can give low-viscosity polyisocyanates, and are ethylene glycol, polypropylene glycol, liquid polytetramethylene glycol, chipped ether, and castor oil-based polyols. Such a prepolymer has a polyisocyanate and a polyol of 30 to
It can be obtained by reacting at 130 ° C., preferably 40 to 90 ° C. for 1 to 5 hours. The equivalent ratio of NCO group / active hydrogen group is 5.0 or more, preferably 8.0 to 25.0.

Further, modified uretone imine and / or carbodiimide of MDI is prepared by adding MDI to 3-methyl-1-phenyl-3-phospholen-1-oxide and 3-methyl-1-ethyl-3-phospholen-1-oxide. The
A phosphorene-based catalyst such as 3-methyl-1-phenyl-2-phosphoren-1-oxide is used in an amount of 1 to 30 with respect to MDI.
After adding an amount of 0 ppm and heating at a reaction temperature of 50 to 110 ° C., preferably 70 to 90 ° C., and reacting until a target NCO group residual amount is reached, trichlorosilane corresponding to 1 to 10 equivalents of the catalyst is obtained. , Dichlorodiphenylsilane, trichloromonomethylsilane or the like to add an inactivating agent to stop the reaction.

In such a reaction, a carbodiimide group (-N = C = N-) is first formed, but it is converted into uretonimine by leaving it at room temperature for a certain period of time. This reaction is a reversible reaction represented by the following general formula [Formula 1], and it is known that the uretonimine group dissociates into a carbodiimide group and an NCO group at high temperature (usually 80 ° C or higher).

[0017]

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Therefore, the abundance ratios of the carbodiimide group and / or the uretonimine group are different, and almost exist as uretonimine groups when left at room temperature. What can be used in the present invention does not have to be completely converted into uretonimine, and a carbodiimide group may be partially present. On the contrary, it is also possible to use those existing in the form of a carbodiimide group at the time of storage at high temperature, and those containing uretonimine partially. The use of modified uretonimine and / or carbodiimide of MDI is
It is 20 to 60 parts by weight, preferably 30 to 50 parts by weight, relative to 100 parts by weight of DI.

(C) HDI isocyanurate modified product or HDI which is one of the polyisocyanate components of the present invention
Isocyanurate and uretdione modified product of HDI
In the case of the isocyanurate-modified product, the sodium or potassium salt of an aliphatic carboxylic acid such as sodium propionate and potassium caprate is added to HDI as a catalyst, and the reaction is carried out at a reaction temperature of 30 to 110 ° C, preferably 40 to 60 ° C. After carrying out a constant NCO group residual amount, a strong acid such as phosphoric acid is added to 1 to 3 equivalents of the catalyst to stop the reaction, and unreacted HD
It can be obtained by a method of removing the I monomer by thin film distillation. In addition, isocyanurate and uretdione modified products of HDI use HDI with an organic phosphorus compound such as tributylphosphine and triisopropylphosphine as a catalyst, and at a reaction temperature of 30 to 120 ° C., preferably 35 to 70 ° C., a constant NCO. After proceeding to the isocyanurate trimerization and uretdione dimerization reaction until the residual amount of the base is reached and adding 1 to 3 equivalents of a strong acid such as phosphoric acid to the catalyst to stop the reaction, unreacted HDI monomer is formed into a thin film. It can be obtained by a method such as removal by distillation.

Further, these isocyanurate-forming or isocyanurate- and uretdione-forming reactions can be more easily carried out by using a phenolic hydroxy compound or an alcoholic hydroxy compound as a cocatalyst at the same time as the catalyst. Phenolic hydroxy compounds include phenol, cresol, trimethylphenol and the like, and alcoholic hydroxy compounds include ethanol, cyclohexanol, ethylene glycol and the like. The ratio of isocyanurate trimer of HDI and uretdione dimer thus obtained is 10/9.
0-90 / 10% by weight, preferably 25 / 75-75 /
It is 25% by weight, more preferably 40/60 to 60/40% by weight.

Incidentally, a modified HDI isocyanurate,
Alternatively, as a starting material for the isocyanurate and uretdione modified product, HDI alone or a polyol adduct of HDI in which a part of the NCO group of HDI is polyol-added can be used. This polyol has a molecular weight of 50 to 7
000, preferably a divalent one having a molecular weight of 60 to 5,000 is used. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediole. 3-methyl-1,
5-pentanediol, 1,6-hexane glycol,
Neopentyl glycol, 1,8-octane glycol, 1,10-decane glycol, 2,2-diethyl-
1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-
Hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eicosane-1,2-ethylene glycol, 2-n-octacosane-1,2-ethylene glycol, 3-hydroxy-2,2 -Dimethylpropionic acid-3-hydroxy-2,2-dimethylpropyl ester, hydrogenated bisphenol A, polyethylene glycol, polytetramethylene glycol, polypropylene glycol, polybutylene adipate, polyhexamethylene adipate, polycaprolactone and the like. Preferably, 1,3-propanediol, 1,2-
Butanediol, 1,3-butanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-
2-ethyl-1,3-propanediol, 2,2,4-
Trimethyl-1,3-pentanediol, 2-ethyl-
1,3-hexanediol polytetramethylene glycol, polypropylene glycol, and polybutylene adipate. In this case, the polyol addition is 1 of all NCO groups.
It is 0% by weight or less. It is preferably 7% by weight or less.

The polyisocyanate of the present invention is
(A) TDI prepolymer, (b) MDI prepolymer and / or uretoimine of MDI and / or carbodiimide modified product of MDI, (c) HDI modified product, (a) /
(B) = 90/10 to 30/70, preferably 80/2
0-50 / 50, (a) + (b) / (c) = 95/5
The ratio is 50/50, preferably 90/10 to 70/30, and the reaction rate difference of the three polyisocyanate components, the contribution rate to the adhesive strength, and the viscosity are adjusted.

The curing agent of the present invention is an amine-based polyol and / or castor oil-based polyol, and when combined with a polyisocyanate component, it is possible to reduce the amount of eluate by suppressing the reaction with a third component such as glycerin. At the same time, it has achieved high adhesive strength and low viscosity. If the ratio of (a) / (b) to (b) exceeds 70%, the amount of eluate due to the reaction with the third component such as glycerin increases, which is not preferable. When the ratio of (c) in (a) + (b) / (c) is less than 5%, the eluate and viscosity due to the reaction with the third component such as glycerin increase, and when it is more than 50%, the adhesive strength is Drastically reduced.

The amine-based polyol and / or castor oil-based polyol used in the curing agent of the present invention include, for example, amine-based polyols such as mono-, di-, tri-, ethanolamine and N-methyl-N, N '. A low-molecular-weight amine-based polyol such as diethanolamine, or an amine-based polyol obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an amino compound such as ethylenediamine. For example, N,
Examples include N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N', N'-tetrakis [2-hydroxyethyl] ethylenediamine, and the like. Preferred are N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N, N, N, N and N, N because they have good reactivity and physical properties.
N ', N'-tetrakis [2-hydroxyethyl] ethylenediamine.

Examples of the castor oil-based polyol include those similar to those used for the NCO group-terminated prepolymer of the polyisocyanate, and preferred are castor oil, dehydrated castor oil, and castor oil fatty acid ricinoleic acid. It is an esterified polyol of the above and a polyether polyol.

The polyurethane resin composition of the present invention is used as an adhesive, a sealant and a binding agent. When this composition is used for the various purposes, the polyisocyanate and the curing agent have an NCO group / active hydrogen group (equivalent ratio) of 0.8 to 1.3, preferably 0.8 to 1. It is used by blending in the range of 1. The curing conditions in this case are a resin temperature of 15 to 40 ° C. and a curing time of 10 to 90 minutes. If necessary, the temperature of the polyisocyanate and the curing agent should be 30 to 8
The temperature may be 0 ° C. and the curing temperature may be 40 to 120 ° C. Further, by selecting a combination of polyisocyanate and a curing agent composition, it is possible to obtain appropriate workability, curability, and required physical properties. This reaction product (resin) is solid polyurethane and has a hardness of 25.
JIS-A hardness is 60 to 100 at ° C.

In particular, since the polyisocyanate is composed of three characteristic components, the reaction rate, the contribution rate to the adhesive strength, and the viscosity are well balanced, and the curing agent has a low viscosity and good curability. Polyurethane adhesives, sealants, and binders that can be made into a low eluate by suppressing the reaction with a third component such as glycerin because they are / or castor oil-based polyols, and have achieved high adhesive strength and low viscosity. Can be obtained.

The polyurethane resin composition thus obtained and the adhesive, sealant and binding agent using the resin composition are used as fiber separation membranes, particularly fiber end portions of fluid separation devices using hollow fibers. It can be used as a binding agent and a sealing agent. In this case, as a method for binding and sealing the ends of the hollow fibers, for example, the components of the adhesive are weighed and mixed, and then the above-mentioned mixing and kneading is performed on a rotatable radially partitioned distributor. While eccentrically injecting and dispensing the adhesive, the fluid separator is formed by centrifugal molding in which both ends of the fluid separator installed on the rotating rotating plate are uniformly introduced by the centrifugal force and sealed, like the distributor. Can be done in any way. As the hollow fiber, for example, regenerated cellulose,
Examples include those produced from cellulose acetate, cellulose ester, polyethylene, polypropylene, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polymethylmethacrylate, polyurethane, casein, collagen and the like.

As the housing material of the fluid separation device,
Examples of the material include metals such as steel, stainless steel, and aluminum, and plastic materials such as glass, polycarbonate, polystyrene, and polyacrylate. The present invention is particularly suitable for a hemodialysis apparatus using polycarbonate as a housing material.

[0030]

EFFECTS OF THE INVENTION The polyurethane resin composition obtained by the present invention, and the adhesive, sealing agent and binding agent using the composition retain excellent workability, impregnability and adhesiveness, and reduce elution. And a fiber binding material for a medical or industrial fluid separation device using a hollow or flat membrane fiber separation membrane, which is required to have improved sealing / adhesion performance and reduced eluents. It is useful as an adhesive between the binding part and the housing. In particular, since it is possible to significantly reduce the amount of eluate at the fiber-bonded portion, it is extremely useful for a medical fluid separation device that requires direct contact with blood and high safety. Examples of these medical and industrial fluid separation devices include plasma separators, artificial lungs, artificial kidneys, artificial livers, and domestic / industrial water treatment devices. Also,
It can also be effectively used as a sealant and binding agent for electrical and optical fibers.

[0031]

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

TDI prepolymer synthesis (a-1) In a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube, 32 parts of TDI (Nippon Polyurethane Industry Co., Ltd., Coronate T-100, hereinafter the same) was used. Castor oil (number average molecular weight 950, hydroxyl value 160) 68 parts (NCO group / hydroxyl group equivalent ratio 1.9) is reacted for 4 hours at 70 ° C. under nitrogen atmosphere, NCO content 7.3%, viscosity 85000 cP / 25 ° C. TDI prepolymer (a-1) of was obtained.

TDI Prepolymer Synthesis (a-2) In the same reactor as a-1, 26 parts of TDI and liquid polytetramethylene glycol (number average molecular weight 1000, hydroxyl value 112, Hodogaya Chemical Co., Ltd., PTGL- 100
0) 74 parts (NCO group / hydroxyl group equivalent ratio 2.0) were reacted under nitrogen atmosphere at 70 ° C. for 4 hours to give an NCO content of 6.2.
%, Viscosity 22000 cP / 25 ° C TDI prepolymer (a
-2) was obtained.

TDI prepolymer synthesis (a-3) TDI 29 parts, castor oil (number average molecular weight 950, hydroxyl value 160) 34 parts PT in the same reactor as a-1.
37 parts of GL-1000 (equivalent ratio of NCO group / hydroxyl group: 1.95) was reacted at 70 ° C. for 4 hours under a nitrogen atmosphere to obtain N.
A TDI prepolymer (a-3) having a CO content of 6.8% and a viscosity of 51,000 cP / 25 ° C. was obtained.

MDI prepolymer synthesis (b-1) In a reactor equipped with a thermometer, stirrer, nitrogen seal tube and cooling tube, 70 parts of MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) and polypyropyrene glycol / Ricinoleic acid ester (molecular weight 1000, hydroxyl value 112) 30
Part (NCO group / hydroxyl group equivalent ratio 9.3) was reacted at 70 ° C. for 4 hours in a nitrogen atmosphere to obtain an MDI prepolymer (b-1) having an NCO content of 21% and a viscosity of 380 cP / 25 ° C.

Synthesis of MDI prepolymer (b-2) In a reactor similar to that of b-1, 57 parts of MDI and polypropylene glycol (molecular weight 2000, hydroxyl value 56) 4
3 parts (NCO group / hydroxyl group equivalent ratio 10.6) were reacted at 70 ° C. for 4 hours in a nitrogen atmosphere to obtain an MDI prepolymer (b-2) having an NCO content of 17% and a viscosity of 460 cP / 25 ° C.

Synthesis of uretone imine and carbodiimide modified product of MDI (b-3) In a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube and a cooling tube, 100 parts of MDI was added to 0.01 part of catalyst (3-methyl-1). 1-phenyl-3-phosphorene-1-oxide
Equivalent to 10 ppm of MDI as a 0% xylene solution)
Was reacted at 90 ° C for 6 hours in the presence of. The reaction was stopped by adding 0.005 parts of dichlorodiphenylsilane to the reaction solution. The obtained liquid was a pale yellow transparent liquid having an NCO content of 26.2% and a viscosity of 110 cP / 25 ° C., and the uretonimine and carbodiimide modified products were confirmed to be 2% by GPC analysis.
It was confirmed to contain 8.1% and 71.9% MDI. This modified MDI product is designated as (b-3).

Synthesis of uretonimine and carbodiimide modified product of MDI (b-4) In a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube and a cooling tube, 100 parts of MDI was added to 0.01 part of catalyst (3-methyl-1). 1-phenyl-3-phosphorene-1-oxide
Equivalent to 10 ppm of MDI as a 0% xylene solution)
Was reacted at 90 ° C for 5 hours in the presence of. The reaction was stopped by adding 0.005 parts of dichlorodiphenylsilane to the reaction solution. The obtained liquid was a pale yellow transparent liquid, had an NCO content of 27.8% and a viscosity of 60 cP / 25 ° C., and had a uretonimine and carbodiimide modified product in 34.2 by GPC analysis.
%, MDI 65.8% was confirmed. This modified MDI product is designated as (b-4).

MDI prepolymer synthesis (b-5) In a reactor similar to b-1, 63 parts of MDI and polypropylene glycol (molecular weight 2000, hydroxyl value 56) 2
4.6 parts of polypyropyrene glycol / ricinoleic acid ester (molecular weight 1000, hydroxyl value 112) 124 parts (NCO group / hydroxyl group equivalent ratio 10.2) were reacted at 70 ° C. for 4 hours under a nitrogen atmosphere to give an NCO content. An MDI prepolymer (b-5) having a viscosity of 420 cP / 25 ° C. of 19% was obtained.

Synthesis of modified HDI (c-1) 100 parts of HDI and 0.1 part of potassium caprate as a catalyst were added to a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube, and the mixture was heated at 40 ° C. for 6 hours. The reaction was carried out. After stopping the reaction by adding 0.07 part of phosphoric acid to the reaction solution,
The HDI monomer was removed by thin film distillation. The obtained liquid is a pale yellow transparent liquid with an NCO content of 21% and a viscosity of 1800.
The HDI monomer content was 0.7% at cP / 25 ° C., and it was confirmed by infrared absorption spectrum 1680 cm ⁻¹ that it was an isocyanurate trimer. This modified HDI is (c-
1).

Synthesis of modified HDI (c-2) 100 parts of HDI, 0.8 part of 1,3-butanediol, 0.02 part of potassium caprate as a catalyst and phenol as a cocatalyst were placed in a reactor similar to that of c-1. Add 0.1 parts,
The isocyanurate-forming reaction was carried out at 60 ° C. for 5 hours. Phosphoric acid was added to this reaction solution as a terminating agent in an amount of 0.014 part to stop the reaction, and then HDI monomer was removed by thin film distillation. The obtained liquid was a pale yellow transparent liquid and had an NCO content of 21.
The viscosity was 1%, the viscosity was 2200 cP / 25 ° C., the HDI monomer content was 0.4%, and formation of an isocyanurate body was confirmed by infrared absorption spectrum analysis. This modified HDI product is designated as (c-2).

Synthesis of modified HDI (c-3) 100 parts of HDI and 0.2 part of trioctylphosphine as a catalyst were added to a reactor similar to that of c-1, and the mixture was heated at 70 ° C. for 5 hours.
The reaction was carried out over time. After adding 0.06 part of phosphoric acid to the reaction solution to stop the reaction, the HDI monomer was removed by thin film distillation. The obtained liquid is a pale yellow transparent liquid, NCO
The content was 23.2%, the viscosity was 100 cP / 25 ° C., the HDI monomer content was 0.4%, and H determined by GPC analysis.
The uretdione dimer of DI was 32% and the isocyanurate trimer was 44%. This modified HDI is (c-
3).

Synthesis of modified HDI (c-4) 100 parts of HDI and 2-n-butyl-2-ethyl-1,3-propanediol 2.3 in the same reactor as c-1.
Parts and 0.3 parts of tributylphosphine as a catalyst were added, and the reaction was carried out at 70 ° C. for 6 hours. After 0.3 part of methyl paratoluenesulfonate was added to the reaction solution to stop the reaction, the HDI monomer was removed by thin film distillation. The obtained liquid was a pale yellow transparent liquid having an NCO content of 22%, a viscosity of 90 cP / 25 ° C. and an HDI monomer content of 0.4%.
In the infrared absorption spectrum 1680 cm ^-1 in the isocyanurate trimers and 1780 cm ^-1 was confirmed to be the uretdione dimer. HDI obtained by GPC analysis
The uretdione dimer was 48% and the isocyanurate trimer was 32%. This modified HDI product is designated as (c-4).

Production of Polyisocyanate (A-1) The TDI prepolymer (a-1), the MDI prepolymer (b-1) and the HDI modified product (c-1) are used in a weight ratio of (a-1) / ( b-1) = 80/20, (a-1) +
Weigh (b-1) / (c-1) = 90/10, stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
Prepolymer with a content of 11% and a viscosity of 5800 cP / 25 ° C (A
-1) was obtained.

Production of Polyisocyanate (A-2) The TDI prepolymer (a-1), the MDI prepolymer (b-1) and the HDI modified product (c-1) are used in a weight ratio of (a-1) / ( b-1) = 70/30, (a-1) +
Weigh (b-1) / (c-1) = 80/20, stir and mix in a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
Prepolymer with a content of 13.3%, 4500 cP / 25 ° C (A
-2) was obtained.

Production of Polyisocyanate (A-3) The TDI prepolymer (a-1), the MDI prepolymer (b-1) and the HDI modified product (c-1) are used in a weight ratio of (a-1) / ( b-1) = 60/40, (a-1) +
Weigh (b-1) / (c-1) = 70/30, stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
A prepolymer (A-3) having a content of 15.2% and a viscosity of 2800 cP / 25 ° C. was obtained.

Production of Polyisocyanate (A-4) TDI Prepolymer (a-1) and MDI Prepolymer
(B-2) and the HDI modified product (c-1) are (a-1) / (b-2) = 70/30, (a-1) + in weight ratio.
Weigh (b-2) / (c-1) = 80/20, stir and mix in a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
A prepolymer (A-4) having a content of 12.4% and a viscosity of 4700 cP / 25 ° C. was obtained.

Production of polyisocyanate (A-5) TDI prepolymer (a-1) and modified MDI (b-
3) and the modified HDI (c-1) in a weight ratio of (a-
1) / (b-3) = 70/30, (a-1) + (b-
3) / (c-1) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer (A- with 5.2% viscosity of 2500 cP / 25 ° C)
5) was obtained.

Production of polyisocyanate (A-6) TDI prepolymer (a-1) and modified MDI (b-
3) and the modified HDI (c-2) in a weight ratio of (a-
1) / (b-3) = 70/30, (a-1) + (b-
3) / (c-2) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
4.9% prepolymer (A- with a viscosity of 2700 cP / 25 ° C)
6) was obtained.

Production of polyisocyanate (A-7) TDI prepolymer (a-1) and modified MDI (b-
3) and the modified HDI (c-3) in a weight ratio of (a-
1) / (b-3) = 70/30, (a-1) + (b-
3) / (c-3) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer (A- with 5.3% viscosity 1900 cP / 25 ° C)
7) was obtained.

Production of polyisocyanate (A-8) TDI prepolymer (a-1) and modified MDI (b-
3) and the HDI modified product (c-4) in a weight ratio of (a-
1) / (b-3) = 70/30, (a-1) + (b-
3) / (c-4) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
5.4%, viscosity 1800 cP / 25 ℃ prepolymer (A-
8) was obtained.

Production of polyisocyanate (A-9) TDI prepolymer (a-1) and modified MDI (b-
3) and the HDI modified product (c-4) in a weight ratio of (a-
1) / (b-3) = 60/40, (a-1) + (b-
3) / (c-4) = 70/30, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer of 7.4% and viscosity of 1100 cP / 25 ° C (A-
9) was obtained.

Production of polyisocyanate (A-10) TDI prepolymer (a-2) and modified MDI (b-
3) and the modified HDI (c-1) in a weight ratio of (a-
2) / (b-3) = 65/35, (a-2) + (b-
3) / (c-1) = 75/25, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to give an NCO content of 1
Prepolymer (A- with a viscosity of 2.5% and a viscosity of 3100 cP / 25 ° C)
10) was obtained.

Production of Polyisocyanate (A-11) TDI Prepolymer (a-2) and MDI Prepolymer (b-2) / MDI Modified Product (b-3) 50/50 Mixture (b-2 / b-3) ) And the HDI modified product (c-4) in a weight ratio of (a-2) / (b-2 / b-3) = 65/3.
5, a-2) + (b-2 / b-3) / (c-4) = 75
/ 25, and stir-mix for 2 hours at 50 ℃ under nitrogen atmosphere, NCO content 14.4%, viscosity 1400cP
A prepolymer (A-11) at / 25 ° C was obtained.

Production of Polyisocyanate (A-12) The TDI prepolymer (a-1), the MDI prepolymer (b-4) and the HDI modified product (c-4) were used in a weight ratio of (a-1) / ( b-4) 70/30, (a-1) + (b
-4 / (c-4) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer of 4.7% and viscosity of 3100 cP / 25 ° C (A-
12) was obtained.

Polyisocyanate Production (A-13) TDI prepolymer (a-1) and MDI prepolymer (b-1) / MDI modified product (b-4) were used as a mixture of 50/50 and HDI modified product (c). -2), etc., (a-
1) / (b-1 + b-4) = 70/30, (a-1) +
(B-1) + (b-4) / (c-2) = 80/20 were weighed and mixed with stirring under a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 14.1% and a viscosity of 5300 cP / A prepolymer (A-13) at 25 ° C was obtained.

Production of polyisocyanate (A-14) TDI prepolymer (a-3) and modified MDI (b-
4) and the modified HDI (c-1) in a weight ratio of (a-
3) / (b-4) = 70/30, (a-3) + (b-
4) / (c-1) = 80/20, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer of 4.7% and viscosity of 3300 cP / 25 ° C (A-
14) was obtained.

Production of polyisocyanate (A-15) TDI prepolymer (a-3) and modified MDI (b-
5) and the HDI modified product (c-1) in a weight ratio of (a-
3) / (b-4) = 70/30, (a-3) + (b-
5) / (c-1) = 70/30, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours to give an NCO content of 1
Prepolymer of 3.7% and viscosity of 3800 cP / 25 ° C (A-
15) was obtained. Polyisocyanate Production (A-16) MDI 56 parts and polypropylene glycol / ricinoleic acid ester (molecular weight 1000, hydroxyl value 112) 44 parts were reacted at 70 ° C. for 4 hours under nitrogen atmosphere, NCO content 15%, viscosity 1300 cP / 25 ° C. Prepolymer (A-1
6) was obtained.

Production of polyisocyanate (A-17) TDI prepolymer (a-1) and modified MDI (b-
3), the weight ratio is (a-1) / (b-3) = 80/20.
The mixture was stirred and mixed at 50 ° C for 2 hours under a nitrogen atmosphere to give an NCO content of 11.6% and a viscosity of 7500 cP / 25 ° C.
To obtain a prepolymer (A-17).

Polyisocyanate Production (A-18) TDI Prepolymer (a-1) and MDI Prepolymer
The weight ratio of (b-1) and the HDI modified product (c-1) is (a-1) / (b-1) = 20/80, (a-1) +.
Weigh (b-1) / (c-1) = 70/30, stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
Prepolymer with a content of 18% and a viscosity of 1500 cP / 25 ° C (A
-18) was obtained.

Production of Polyisocyanate (A-19) The TDI prepolymer (a-1), the MDI prepolymer (b-1) and the modified HDI (c-1) were used in a weight ratio of (a-1) / ( b-1) = 70/30, (a-1) +
Weigh (b-1) / (c-1) = 40/60, stir and mix in a nitrogen atmosphere at 50 ° C. for 2 hours, and add NCO.
A prepolymer (A-19) having a content of 17.2% and a viscosity of 2100 cP / 25 ° C. was obtained.

Production of polyisocyanate (A-20) MDI prepolymer (b-2) and modified HDI (c-
4) in a weight ratio of (b-1) / (c-4) = 40/60
The resulting mixture was weighed and mixed in a nitrogen atmosphere at 50 ° C. for 2 hours with stirring to obtain a prepolymer (A-20) having an NCO content of 20.0% and a viscosity of 310 cP / 25 ° C.

Production of curing agent (B-1) 70 parts of dehydrated castor oil (molecular weight 950, hydroxyl value 118) and N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine (molecular weight 295, hydroxyl value =
760) 30 parts under nitrogen atmosphere at 50 ° C. for 2 hours with mixing and stirring to obtain active hydrogen content (KOHmg / g) 310, viscosity 1100
A curing agent (B-1) having a cP / 25 ° C was obtained.

Production of curing agent (B-2) 74 parts of castor oil (molecular weight 950, hydroxyl value 160) and N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine (molecular weight 295, hydroxyl value = 7)
60) 26 parts were mixed and stirred under a nitrogen atmosphere at 50 ° C. for 2 hours to obtain an active hydrogen content (KOHmg / g) 316, viscosity, 150
A curing agent (B-2) having a temperature of 0 cP / 25 ° C was obtained.

Production of curing agent (B-3) 80 parts of castor oil (molecular weight 950, hydroxyl value 160) and N, N, N ', N'-tetrakis [2-hydroxypropyl] ethylenediamine (molecular weight 295, hydroxyl value 76)
0) 20 parts of nitrogen was mixed and stirred under a nitrogen atmosphere at 50 ° C. for 2 hours to obtain an active hydrogen content (KOHmg / g) of 280 and a viscosity of 1000 cP.
A curing agent (B-3) at / 25 ° C was obtained.

Examples 1 to 15 Polyisocyanates of Production Examples A-1 to A-15 are shown in Tables 1 and 2. Tables 3 and 4 show combinations of production examples of the polyisocyanate and the curing agent. Various tests were conducted by combining the temperature of the polyisocyanate and the curing agent at 25 ° C. and the NCO / OH equivalent ratio of 1.05. The results are shown in Tables 5 and 6.

Comparative Examples 1 to 5 Table 2 shows the polyisocyanates of Polyisocyanate Production Examples A-16 to A-20. Table 4 shows combinations of Production Examples B-2 to B-3 of the polyisocyanate and the curing agent. The temperature of polyisocyanate and curing agent is 25 ℃, NCO / OH
Various tests were conducted by combining them at an equivalence ratio of 1.05. The results are shown in Table 6.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

[Table 5]

[0073]

[Table 6]

Mixing viscosity: Resin temperature 25 ° C., NCO /
100 g of an OH equivalent ratio of 1.05 was added, and the viscosity immediately after uniform mixing was measured at 25 ° C. Resin filling state: Hollow fiber bonded by centrifugal molding method, 40 ℃
After curing for 1 day, the adhesive part was sliced in a lateral direction of about 2 mm and the presence or absence of an unfilled part in each layer was measured. Eluate test: Measured according to the dialysis-type artificial kidney device approval standard V-4.

[Eluted substance test] Glycerin content: 150
A hollow fiber (weight%) was adhered by a centrifugal molding method, and the resin filling state between the hollow fibers and the eluate of the hollow fiber adhering part in accordance with the dialysis type artificial kidney device approval standard V-4 (Note-1) were measured. . (The eluate is measured after curing at 40 ° C. for 3 days.) (Note-1) Dialysis type artificial kidney device approval standard V-4 In the case of a hollow fiber type dialyzer, a hollow fiber bonded part for one dialyzer Cut out and cut into 1 cm square pieces. 200 ml of water is added to this, and it shakes gently at 40 ° C. for 2 hours. This liquid is used as a test liquid, and water is used as a layer length of 10 mm.
When the absorbance at a wavelength of 280 to 240 nm is measured by the Japanese absorbance measurement method, the absorbance must be 0.05 or less.

[Adhesive Strength Test] Two polycarbonate (thickness 5 mm × width 50 mm × depth 50 mm) plates were used as the adherends for the purpose of knowing the adhesive strength with the housing substrate.
Use a sheet of polyurethane between these two sheets, height 12 mm x
The adhesive strength was measured by injecting and curing so that the width was 10 mm and the depth was 50 mm. Adhesive strength is measured according to JIS A
5755, and the adhesive strength was calculated by the following formula. Adhesive strength (kgf / cm ² ) = Peeling load (kgf) / Adhesive area (cm ² ).

In Examples 1 to 15, the filling condition between the hollow fibers was good, and the amount of eluate was low. Also,
The adhesive strength with polycarbonate, which is a typical housing substrate, was also at a high level. In Comparative Example 1, there was no problem in the filling state between the hollow fibers and the adhesive strength, but the eluate far exceeded the standard value and was not suitable. In Comparative Example 2, there was no problem with the adhesive strength and the eluate, but the resin filling state between the hollow fibers was poor due to the high viscosity and was not suitable. In Comparative Example 3, the filling state between the hollow fibers and the adhesive strength were good, but it failed the elution standard. In Comparative Examples 4 and 5, there was no problem in the filling state between the hollow fibers and the amount of eluate was small and far below the standard, but the adhesive strength was significantly reduced and it was not suitable.

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Claims (4)

[Claims] 1. A polyurethane resin composition comprising a polyisocyanate and an amine-based polyol and / or a castor oil-based polyol as a curing agent, wherein the polyisocyanate has (a) tolylene diisocyanate and two or more hydroxyl groups in one molecule. Isocyanate group / with polyol
An isocyanate group-terminated prepolymer having a hydroxyl group equivalent ratio of 1.5 to 2.5. (B) Isocyanate group-terminated prepolymer of diphenylmethane diisocyanate and a polyol having two or more hydroxyl groups in one molecule at an isocyanate group / hydroxyl group equivalent ratio of 5.0 or more, and / or uretonimine of diphenylmethane diisocyanate and / or Modified carbodiimide. (C) Isocyanurate modified product of hexamethylene diisocyanate or isocyanurate and uretdione modified product. It consists of three components, and the weight ratio of (a) / (b) is 90 /
A polyurethane resin composition, characterized in that the weight ratio of (a) + (b) / (c) is from 10 to 30/70 and is from 95/5 to 50/50. 2. An adhesive comprising the polyurethane resin composition according to claim 1. 3. A sealant comprising the polyurethane resin composition according to claim 1. 4. A binding agent comprising the polyurethane resin composition according to claim 1.