JP3191610B2 - Polyurethane resin composition and adhesive, sealant and binding agent using the composition - 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 resin composition, and more particularly, to an adhesive, a sealant and a binder using the resin composition. The present invention relates to a fiber binding agent for a medical or industrial fluid separation device used, an adhesive between the fiber binding portion and a housing, and is particularly suitable for a medical fluid separation device using a fiber separation membrane having a high glycerin content. is there. Also, it can be used as a sealant for electric use.

[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 and amine-based polyols have been used.

Japanese Patent Application Laid-Open No. 2-127413 discloses a TDI for a high-performance separation membrane which has been increasing in recent years.
We have proposed a low-eluting substance system that can suppress the reaction of the humectant contained in the membrane with glycerin by using a combination of an isocyanate-terminated prepolymer and a modified MDI.
Similarly, Japanese Unexamined Patent Publication (Kokai) No. 6-136089 discloses a low-eluting material with little influence of glycerin as a humectant and a low viscosity.
Combinations of DI prepolymers have been proposed.

[0004]

However, although these conventional polyurethanes are suitable for reducing the amount of eluted substances, they have a mixed viscosity of 4000 cP or less for obtaining good workability and impregnation, and further have a plastic housing and the like. At least 30 kg / cm ² of each member could not attain the required adhesive strength at the same time. In particular, HDI
Modified isoaliphatic isocyanates and / or those containing a large amount of isocyanate (NCO) group-terminated prepolymers of aliphatic isocyanates such as HDI and polyols are poor in adhesiveness but low in effluent and low viscosity, and have swelling and shrinkage. Due to the internal distortion or weak external force, the plastic housing is peeled off, and there is a practical problem.

[0005]

Means for Solving the Problems The present inventors have made intensive studies and studied and 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 uretonimine and / or carbodiimide modified MDI, (3) isocyanurate modified HDI or isocyanurate modified with isocyanurate and uretdione; The inventors have found that by using castor oil-based polyol as a curing agent, the adhesiveness to a housing is excellent, and a low-eluting substance, a low viscosity and the like can be achieved.

That is, the present invention relates to 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 comprises (a) TDI and two or more hydroxyl groups per molecule. NCO group / hydroxyl equivalent ratio of 1.5 to 2.5 with polyol having
(Hereinafter abbreviated as TDI prepolymer). (B) an NCO group-terminated prepolymer (hereinafter abbreviated as MDI prepolymer) of MDI and a polyol having two or more hydroxyl groups in one molecule, having an NCO group / hydroxyl equivalent ratio of 5.0 or more, and / or MDI Modified uretonimine and / or carbodiimide. (C) Modified HDI isocyanurate or modified isocyanurate and uretdione. And the weight ratio of (a) / (b) is 90 /
A polyurethane resin composition characterized by being 10 to 30/70, and the weight ratio of (a) + (b) / (c) being 95/5 to 50/50. Further, it is an adhesive, a sealant and a binding agent using the polyurethane resin composition.

[0007] Polyurethane resin compositions, adhesives and sealants realizing low eluate, suitable viscosity, and improved adhesion to each member by suppressing the reaction with glycerin adhering to the fiber used as the material to be bonded. And binding agents.

[0008] The (a) TDI prepolymer, which is one kind of the polyisocyanate component of the present invention, comprises NDI 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 equivalent ratio of 1.5 to 2.5. The TDI used is 2,4-
TDI, 2,6-TDI and the like can be used alone or in a mixture at an arbitrary ratio, and further, modified products thereof can be used.
Examples of the polyol used include low-molecular-weight polyols, polyether polyols, polyester polyols, castor oil-based polyols, and the like. As the low molecular weight polyol, the molecular weight is 60 to less than 500, preferably 6
Less than 2-200, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, trimethylolpropane, glycerin and the like Is mentioned. Particularly preferred low molecular polyols are ethylene glycol,
1,3-butanediol, 1,4-butanediol, trimethylolpropane and the like.

The polyether polyols have a molecular weight of 500 to 5,000, preferably 700 to 3,000.
For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyether polyol (liquid polytetramethylene glycol) by copolymerization of tetrahydrofuran and 3-alkyltetrahydrofuran, and two or more kinds of polymers of ethylene oxide and propylene oxide Certain tipped ethers and the like are mentioned. Particularly preferred are polypropylene glycol, liquid polytetramethylene glycol, tipped ether and the like.

As the polyester polyol, the molecular weight is from 500 to 5,000, preferably from 900 to 3,000.
Examples thereof include linear or branched polyester-based polyols of a carboxylic acid and a polyol, and polycaprolactone-based polyols formed by ring-opening polymerization of caprolactone. Castor oil-based polyols include castor oil,
Dehydration castor oil, and transesterification or esterification polyol between ricinoleic acid, which is a castor oil fatty acid, and the low-molecular polyol, polyether polyol, polyester polyol, or the like. Particularly preferred are castor oil, dehydrated castor oil and the like.

Among these, preferred polyols for obtaining a TDI prepolymer which is liquid at room temperature and has low viscosity include ethylene glycol, polypropylene glycol, liquid polytetramethylene glycol,
Tipped ether, castor oil-based polyol and the like.

The TDI prepolymer thus obtained comprises a polyisocyanate and a polyol in an amount of 30 to 13
It is obtained by reacting at 0 ° C, preferably 40 to 90 ° C for 1 to 5 hours. The equivalent ratio of NCO groups / active hydrogen groups 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 uretonimine and / or carbodiimide modified MDI, which is one of the polyisocyanate components of the present invention, is an MDI.
In the case of the I prepolymer, it is obtained by an NCO group / hydroxyl equivalent ratio of 5.0 or more between MDI and a polyol having two or more hydroxyl groups in a molecule. Examples of the polyol used include low-molecular polyols, polyether polyols, polyester polyols, and castor oil-based polyols similar to the TDI prepolymer.

Among these, preferred polyols are those which are liquid at room temperature and can produce a low-viscosity polyisocyanate, and include ethylene glycol, polypropylene glycol, liquid polytetramethylene glycol, tipped ether, and castor oil-based polyol. Such a prepolymer comprises a polyisocyanate and a polyol in an amount of 30 to
It is 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, uretonimine and / or carbodiimide modified MDI is obtained by adding 3-methyl-1-phenyl-3-phospholene-1-oxide, 3-methyl-1-ethyl-3-phospholene-1-oxide to MDI. To
A phosphorene-based catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide is used in an amount of 1 to 30 with respect to MDI.
After adding 0 ppm and heating at a reaction temperature of 50 to 110 ° C., preferably 70 to 90 ° C. until the target NCO group remaining amount is reached, trichlorosilane equivalent to 1 to 10 equivalents of the catalyst is added. And a method of adding an inactivating agent such as dichlorodiphenylsilane or trichloromonomethylsilane to stop the reaction.

A carbodiimide group (-N = C = N-) is first formed by such a reaction, but is converted to 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 a high temperature (usually 80 ° C. or higher).

[0017]

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Therefore, the carbodiimide groups and / or uretonimine groups are present in different proportions, and are almost present as uretonimine groups when left at room temperature. Those which can be used in the present invention may not be completely converted to uretonimine, and may partially contain a carbodiimide group. Conversely, those which are present in the form of carbodiimide groups when stored at high temperature, and those in which uretonimine is partially present can also be used. The use of uretonimine and / or carbodiimide modifications of MDI is
It is 20 to 60 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of DI.

(C) HDI isocyanurate-modified or HDI, which is one of the polyisocyanate components of the present invention.
Isocyanurate and uretdione modified products of HDI
In the case of the isocyanurate modified form of above, a sodium or potassium salt of an aliphatic carboxylic acid such as sodium propionate or 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 a certain amount of NCO groups is left, the reaction is stopped by adding 1 to 3 equivalents of a strong acid such as phosphoric acid to the catalyst, and the unreacted HD
It can be obtained by a method of removing the I monomer by thin film distillation or the like. In addition, modified isocyanurate and uretdione of HDI can be obtained by using an organic phosphorus compound such as tributyl phosphine or triisopropyl phosphine as a catalyst in HDI and reacting at a reaction temperature of 30 to 120 ° C., preferably 35 to 70 ° C., and a fixed NCO. The isocyanurate trimerization and uretdione dimerization reactions are advanced until the remaining amount of the group is reached, and the reaction is stopped by adding 1 to 3 equivalents of a strong acid such as phosphoric acid to the catalyst. It can be obtained by a method of removing by distillation or the like.

The isocyanuration or isocyanurate and uretdionation reaction can be carried out more easily by using a phenolic hydroxy compound or an alcoholic hydroxy compound as a co-catalyst at the same time as the catalyst. Examples of the phenolic hydroxy compound include phenol, cresol, and trimethylphenol, and examples of the alcoholic hydroxy compound include ethanol, cyclohexanol, and ethylene glycol. The ratio of the isocyanurate trimer of HDI thus obtained to the uretdione dimer 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.

In addition, an isocyanurate-modified HDI,
Alternatively, as a starting material of the modified isocyanurate and uretdione, in addition to HDI alone, an HDI polyol adduct obtained by partially adding an NCO group of HDI to a polyol can be used. This polyol has a molecular weight of 50 to 7
000, preferably those having a molecular weight of 60 to 5,000 and divalent. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol- 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-pentaneddiol, 2-ethyl-1,3-
Hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eicosan-1,2-ethylene glycol, 2-n-octacosan-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-pentaneddiol, 2-ethyl-
1,3-hexanediol polytetramethylene glycol, polypropylene glycol and polybutylene adipate. In this case, the polyol addition is one of all NCO groups.
0% by weight or less. Preferably, it is at most 7% by weight.

The polyisocyanate of the present invention is as described above,
(A) TDI prepolymer, (b) MDI prepolymer and / or uretimine of MDI and / or carbodiimide modified product of MDI, (c) HDI modified product,
(B) = 90/10 to 30/70, preferably 80/2
0/50/50, (a) + (b) / (c) = 95/5
It is constituted by a limited ratio of 50/50, preferably 90/10 to 70/30, in which the difference in the reaction rate of the three polyisocyanates, the contribution to the adhesive strength, and the viscosity are adjusted.

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

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, N-methyl-N, N '. -A low molecular weight amine polyol such as diethanolamine, or an amine polyol obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to an amino compound such as ethylenediamine. For example, N,
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, and N, N,
N ', N'-tetrakis [2-hydroxyethyl] ethylenediamine.

Examples of the castor oil-based polyol include the same ones as those used for the NCO group-terminated prepolymer of the polyisocyanate. Preferred are castor oil, dehydrated castor oil, and ricinoleic acid, a castor oil fatty acid. And polyether polyols.

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 such various uses, the NCO group / active hydrogen group (equivalent ratio) of the polyisocyanate and the curing agent is 0.8 to 1.3, preferably 0.8 to 1. It is used by being compounded 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, adjust the temperature of the polyisocyanate and the curing agent to 30 to 8
0 ° C and the curing temperature can be in the range of 40-120 ° C. Further, by selecting the combination of the polyisocyanate and the curing agent composition, it is possible to obtain appropriate workability, curability, and required physical properties. The reactant (resin) is a solid polyurethane having a hardness of 25.
It has a JIS-A hardness of 60 to 100 at ° C.

Particularly, the polyisocyanate is composed of three distinctive components, so that the reaction rate, the contribution to the adhesive strength, and the viscosity are well-balanced, and the amine polyol and the curing agent have a low viscosity and a good curability. Polyurethane adhesives, sealants and binders that enable low eluate by suppressing the reaction with tertiary components such as glycerin and / or achieve high adhesion and low viscosity because they are castor oil-based polyols Can be obtained.

The polyurethane resin composition thus obtained and the adhesive, sealant and binding agent using the resin composition are used as a fiber separation membrane, particularly at the fiber end of a fluid separation device using hollow fibers. It can be used as a binding agent and a sealant. In this case, as a method of bundling and sealing the ends of the hollow fibers, for example, the respective components of the adhesive are measured and mixed, and then the above-described mixing and kneading is performed on a rotatable radially-divided distributor. The centrifugal molding of the fluid separator by centrifugal molding in which the adhesive is eccentrically injected and distributed, and equally introduced and sealed by centrifugal force to both ends of the fluid separator installed on the rotating rotating plate in the same way as the distributor. Can be done in a way. As hollow fibers, for example, regenerated cellulose,
Examples include cellulose acetate, cellulose ester, polyethylene, polypropylene, polyamide, polysulfone, polyacrylamide, polyacrylonitrile, polymethyl methacrylate, polyurethane, casein, collagen and the like.

As a 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]

Industrial Applicability The polyurethane resin composition obtained by the present invention, and the adhesive, sealant and binding agent using the composition maintain excellent workability, impregnation property and adhesiveness, and reduce the eluted substances. A fiber binding material for a medical or industrial fluid separation device using a hollow or flat membrane-like fiber separation membrane, which is required to have improved sealing / adhesion performance and reduced eluate, and the fiber It is useful as an adhesive between the binding portion and the housing. In particular, since the eluted material at the fiber bonding portion can be significantly reduced, it is extremely useful for a medical fluid separation device which requires high safety due to direct contact with blood. 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. Also,
It can also be used effectively as a sealant and binding agent for electrical and optical fibers.

[0031]

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these. “Parts” and “%” in Examples and Comparative Examples
All are "parts by weight" and "% by weight" unless otherwise specified.

Synthesis of TDI prepolymer (a-1) In a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube, 32 parts of TDI (manufactured by Nippon Polyurethane Industry, Coronate T-100; the same applies hereinafter) 68 parts of castor oil (number average molecular weight 950, hydroxyl value 160) (equivalent ratio of NCO group / hydroxyl group: 1.9) was reacted at 70 ° C. for 4 hours in a nitrogen atmosphere, NCO content: 7.3%, viscosity: 85,000 cP / 25 ° C. Of TDI prepolymer (a-1) was obtained.

Synthesis of TDI prepolymer (a-2) In the same reactor as in a-1, 26 parts of TDI and liquid polytetramethylene glycol (number average molecular weight 1000, hydroxyl value 112, manufactured by Hodogaya Chemical Co., Ltd., PTGL- 100
0) 74 parts (NCO group / hydroxyl group equivalent ratio: 2.0) were reacted at 70 ° C. for 4 hours in a nitrogen atmosphere to obtain an NCO content of 6.2.
%, A viscosity of 22,000 cP / 25 ° C. and a TDI prepolymer (a
-2) was obtained.

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

Synthesis of MDI prepolymer (b-1) In a reactor equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube, 70 parts of MDI (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and polypropylene pyrene glycol / Ricinoleic acid ester (molecular weight 1000, hydroxyl value 112) 30
Parts (NCO group / hydroxyl group equivalent ratio: 9.3) were reacted under a nitrogen atmosphere at 70 ° C. for 4 hours 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 b-1, 57 parts of MDI and 4 parts of polypropylene glycol (molecular weight: 2,000, hydroxyl value: 56)
Three parts (10.6 equivalent ratio of NCO group / hydroxyl group) 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 modified uretonimine and carbodiimide of MDI (b-3) In a reactor equipped with a thermometer, a stirrer, a nitrogen sealed tube, and a cooling tube, 100 parts of MDI was mixed with 0.01 part of catalyst (3-methyl-1). 1-phenyl-3-phospholene-1-oxide
(As a 0% xylene solution, equivalent to 10 ppm of MDI)
At 90 ° C. for 6 hours. The reaction was stopped by adding 0.005 parts of dichlorodiphenylsilane to the reaction solution. The resulting liquid was a pale yellow transparent liquid having an NCO content of 26.2% and a viscosity of 110 cP / 25 ° C., and GPC analysis showed that uretonimine and carbodiimide-modified product were
It confirmed that it contained 8.1% and 71.9% of MDI. This modified MDI is designated as (b-3).

Synthesis of modified uretonimine and carbodiimide of MDI (b-4) In a reactor equipped with a thermometer, a stirrer, a nitrogen sealed tube, and a cooling tube, 100 parts of MDI was added with 0.01 part of catalyst (3-methyl-1). 1-phenyl-3-phospholene-1-oxide
(As a 0% xylene solution, equivalent to 10 ppm of MDI)
The reaction was carried out 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 resulting liquid was a pale yellow transparent liquid having an NCO content of 27.8% and a viscosity of 60 cP / 25 ° C., and the uretonimine and carbodiimide-modified product were found to be 34.2 by GPC analysis.
%, MDI was confirmed to be 65.8%. This modified MDI is designated as (b-4).

Synthesis of MDI prepolymer (b-5) In a reactor similar to b-1, 63 parts of MDI and 2 parts of polypropylene glycol (molecular weight: 2,000, hydroxyl value: 56) 2
4.6 parts and 124 parts of poly (propylene glycol) / ricinoleate (molecular weight: 1,000, hydroxyl value: 112) (equivalent ratio of NCO group / hydroxyl group: 10.2) were reacted under a nitrogen atmosphere at 70 ° C. for 4 hours to obtain an NCO content. An MDI prepolymer (b-5) having a viscosity of 19% and a viscosity of 420 cP / 25 ° C. 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 sealed tube, and a cooling tube, and the mixture was heated at 40 ° C. for 6 hours. The reaction was performed. After adding 0.07 parts of phosphoric acid to the reaction solution to stop the reaction,
HDI monomer was removed by thin film distillation. The obtained liquid is a pale yellow transparent liquid having an NCO content of 21% and a viscosity of 1800.
cP / 25 ° C., the HDI monomer content was 0.7%, and the infrared absorption spectrum of 1,680 cm ⁻¹ confirmed that it was an isocyanurate trimer. This modified HDI was converted to (c-
1).

Synthesis of modified HDI (c-2) In the same reactor as in c-1, 100 parts of HDI, 0.8 part of 1,3-butanediol, 0.02 part of potassium caprate as a catalyst, and phenol as a co-catalyst 0.1 parts,
The isocyanurate-forming reaction was performed at 60 ° C. for 5 hours. After adding 0.014 parts of phosphoric acid as a terminator to the reaction solution to terminate the reaction, the HDI monomer was removed by thin-film distillation. The resulting liquid is a pale yellow transparent liquid having an NCO content of 21.
The content was 1%, the viscosity was 2200 cP / 25 ° C., the HDI monomer content was 0.4%, and the formation of isocyanurate was confirmed by infrared absorption spectrum analysis. This modified HDI is designated as (c-2).

Synthesis of Modified HDI (c-3) Into the same reactor as in c-1, 100 parts of HDI and 0.2 part of trioctylphosphine as a catalyst were added.
A time reaction was performed. After 0.06 parts of phosphoric acid was added 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 the H content was determined by GPC analysis.
DI uretdione dimer was 32% and isocyanurate trimer was 44%. This modified HDI was converted to (c-
3).

Synthesis of modified HDI (c-4) In a reactor similar to c-1, 100 parts of HDI, 2-n-butyl-2-ethyl-1,3-propanediol 2.3.
And 0.3 parts of tributylphosphine as a catalyst, and reacted at 70 ° C. for 6 hours. After adding 0.3 parts of methyl paratoluenesulfonate to the reaction solution to stop the reaction, the HDI monomer was removed by thin-film distillation. The resulting liquid is a pale yellow transparent liquid having an NCO content of 22%, a viscosity of 90 cP / 25 ° C., 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 determined by GPC analysis
The uretdione dimer was 48% and the isocyanurate trimer was 32%. This modified HDI 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) were prepared by weight ratio of (a-1) / ( b-1) = 80/20, (a-1) +
(B-1) / (c-1) = 90/10, weighed under nitrogen atmosphere at 50 ° C. for 2 hours,
Prepolymer having 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) were mixed at a weight ratio of (a-1) / ( b-1) = 70/30, (a-1) +
(B-1) / (c-1) = 80/20, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO
Prepolymer having a content of 13.3% and 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) were obtained by weight ratio of (a-1) / ( b-1) = 60/40, (a-1) +
(B-1) / (c-1) = 70/30, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere.
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 modified HDI (c-1) were obtained by weight ratio of (a-1) / (b-2) = 70/30, (a-1) +
(B-2) / (c-1) = 80/20, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere.
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 at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 1
Prepolymer (A-5.2%, viscosity 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 at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 1
4.9%, viscosity 2700 cP / 25 ° C prepolymer (A-
6) was obtained.

Production of polyisocyanate (A-7) TDI prepolymer (a-1) and modified MDI (b-
3) and the HDI modified product (c-3) in a weight ratio of (a-
1) / (b-3) = 70/30, (a-1) + (b-
3) Measure so that / (c-3) = 80/20, and stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours to obtain an NCO content of 1
Prepolymer (A-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 modified HDI (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 at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 1
5.4%, viscosity 1800 cP / 25 ° C prepolymer (A-
8) was obtained.

Production of polyisocyanate (A-9) TDI prepolymer (a-1) and modified MDI (b-
3) and the modified HDI (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 at 50 ° C. for 2 hours in a nitrogen atmosphere to obtain an NCO content of 1
Prepolymer of 7.4% viscosity 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) The weight was measured so that / (c-1) = 75/25, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 1
2.5%, viscosity 3100 cP / 25 ° C prepolymer (A-
10) was obtained.

Production of polyisocyanate (A-11) TDI prepolymer (a-2) and MDI prepolymer (b-2) / MDI modified (b-3) 50/50 mixture (b-2 / b-3) ) And the modified HDI (c-4) by weight ratio of (a-2) / (b-2 / b-3) = 65/3
5, a-2) + (b-2 / b-3) / (c-4) = 75
/ 25, and stirred and mixed at 50 ° C for 2 hours under a nitrogen atmosphere to obtain an NCO content of 14.4% and a viscosity of 1400 cP.
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 modified HDI (c-4) were prepared by weight ratio of (a-1) / ( b-4) 70/30, (a-1) + (b
-4 / (c-4) = 80/20, and stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 1
4.7%, viscosity 3100 cP / 25 ° C prepolymer (A-
12) was obtained.

Production of polyisocyanate (A-13) The mixture of TDI prepolymer (a-1) and MDI prepolymer (b-1) / MDI modified (b-4) 50/50 was used to prepare HDI modified (c-13). -2) and (a-
1) / (b-1 + b-4) = 70/30, (a-1) +
(B-1) + (b-4) / (c-2) = 80/20, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 14.1% and a viscosity of 5,300 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) Measure so that / (c-1) = 80/20, and stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours to obtain an NCO content of 1
4.7%, viscosity 3300 cP / 25 ° C prepolymer (A-
14) was obtained.

Production of polyisocyanate (A-15) TDI prepolymer (a-3) and modified MDI (b-
5) and the modified HDI (c-1) in a weight ratio of (a-
3) / (b-4) = 70/30, (a-3) + (b-
5) Measure so that / (c-1) = 70/30, and stir and mix under a nitrogen atmosphere at 50 ° C. for 2 hours to obtain an NCO content of 1
3.7%, viscosity 3800 cP / 25 ° C prepolymer (A-
15) was obtained. Preparation of polyisocyanate (A-16) 56 parts of MDI and 44 parts of polypropylene glycol / ricinoleate (molecular weight: 1,000, hydroxyl value: 112) were reacted at 70 ° C. for 4 hours under a 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), (a-1) / (b-3) = 80/20 in weight ratio
The mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an NCO content of 11.6% and a viscosity of 7,500 cP / 25 ° C.
(A-17) was obtained.

Production of polyisocyanate (A-18) TDI prepolymer (a-1) and MDI prepolymer
(B-1) and the modified HDI (c-1) were obtained by weight ratio of (a-1) / (b-1) = 20/80, (a-1) +
(B-1) / (c-1) = 70/30, and the mixture was stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere.
Prepolymer having a content of 18% and a viscosity of 1500 cP / 25 ° C. (A
-18).

Production of Polyisocyanate (A-19) The TDI prepolymer (a-1), the MDI prepolymer (b-1) and the modified HDI (c-1) were prepared by weight ratio of (a-1) / ( b-1) = 70/30, (a-1) +
(B-1) / (c-1) = 40/60, and the mixture was stirred and mixed at 50 ° C. for 2 hours in a nitrogen atmosphere to obtain an 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) by weight ratio (b-1) / (c-4) = 40/60
The mixture was stirred and mixed at 50 ° C for 2 hours under a nitrogen atmosphere 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 were stirred and mixed at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an active hydrogen content (KOH mg / g) of 310 and a viscosity of 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) In a nitrogen atmosphere, 26 parts were mixed and stirred at 50 ° C. for 2 hours, and the active hydrogen content (KOH mg / g) 316, viscosity, 150
A curing agent (B-2) at 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 were mixed and stirred at 50 ° C. for 2 hours under a nitrogen atmosphere 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 The polyisocyanates of Preparation 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 an 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 Preparation Examples A-16 to A-20. Table 4 shows combinations of the production examples B-2 to B-3 of the polyisocyanate and the curing agent. 25 ℃ of polyisocyanate and curing agent, NCO / OH
Various tests were conducted by combining at an equivalent ratio of 1.05. Table 6 shows the results.

[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 was mixed at an OH equivalent ratio of 1.05, and the viscosity immediately after uniform mixing was measured at 25 ° C. Filled resin: hollow fiber bonded by centrifugal molding, 40 ° C
After curing for 1 day, the bonded portion was sliced to about 2 mm in the horizontal direction, and the presence or absence of an unfilled portion in each layer was measured. Eluate test: Measured according to the dialysis type artificial kidney device approval standard V-4.

[Eluate test] Glycerin content: 150
By weight, hollow fibers were adhered by a centrifugal molding method, and the state of resin filling between the hollow fibers and the eluate of the hollow fiber adhesion portion according to 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, the hollow fiber adhesion part of one dialyzer And cut to a size of about 1 cm square. To this is added 200 ml of water and gently shaken at 40 ° C. for 2 hours. This liquid was used as a test liquid, and the layer length was 10 mm for water.
When the absorbance at a wavelength of 280 to 240 nm is measured by the absorbance measurement method of the Japanese Pharmacopoeia, the absorbance must be 0.05 or less.

[Adhesion Strength Test] For the purpose of knowing the adhesion strength with the housing base material, a polycarbonate (5 mm thick × 50 mm × 50 mm deep) plate was used as an object to be bonded.
12mm high polyurethane between these two
The composition was injected and cured so as to have a width of 10 mm and a depth of 50 mm, and the adhesive strength was measured. JIS A
5755, and the adhesive strength was determined by the following formula. Adhesive strength (kgf / cm ² ) = peeling load (kgf) / adhesive area (cm ² )

In Examples 1 to 15, the filling state between the hollow fibers was good, and the amount of eluted material was low. Also,
The bonding strength with a typical polycarbonate as a housing base material was also at a high level. In Comparative Example 1, there was no problem with the state of filling between the hollow fibers and the adhesive strength, but the eluted material was far beyond the standard value and was unsuitable. Comparative Example 2 had no problem with the adhesive strength and eluted material, but was unsuitable due to high viscosity due to poor resin filling between hollow fibers. In Comparative Example 3, the filling state between the hollow fibers and the adhesive strength were good, but failed the eluate standard. In Comparative Examples 4 and 5, there was no problem in the state of filling between the hollow fibers, and the amount of eluted material was small and much lower than the standard, but the adhesive strength was significantly reduced and was unsuitable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification symbol FI C09J 175/04 C09J 175/04 C09K 3/10 C09K 3/10 D (58) Fields surveyed (Int.Cl. ⁷ , DB name) ) C08G 18/00-18/87 C09J 175/04-175/12 C09K 3/10 B01D 63/00

Claims (4)

(57) [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 comprises (a) tolylene diisocyanate and two or more hydroxyl groups in one molecule. Isocyanate group with polyol /
An isocyanate group-terminated prepolymer having a hydroxyl equivalent ratio of 1.5 to 2.5. (B) an isocyanate group-terminated prepolymer of diphenylmethane diisocyanate and a polyol having two or more hydroxyl groups in one molecule at an isocyanate group / hydroxyl equivalent ratio of 5.0 or more, and / or uretonimine and / or diphenylmethane diisocyanate. Modified carbodiimide. (C) Hexamethylene diisocyanate modified isocyanurate or modified isocyanurate and uretdione. And the weight ratio of (a) / (b) is 90 /
A polyurethane resin composition, wherein the weight ratio of (a) + (b) / (c) 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.