JP3341272B2 - Two-component polyurethane binding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane adhesive,
The present invention relates to a two-component polyurethane binding material that can be suitably used as a sealing material or a binding material. The two-component polyurethane tying material of the present invention is, in particular, a medical material using a hollow fiber separation membrane, a tying material for a hollow fiber constituting an industrial fluid separation device, an adhesive between the hollow fiber tying part and a housing, Also, it can be suitably used for applications such as electric sealing materials.

[0002]

2. Description of the Related Art In applications such as adhesives, sealing materials and binding materials, polyurethane compositions (compositions that give polyurethane by a chemical reaction) are generally made of plastics,
It shows excellent adhesion to a wide range of materials including polar materials such as metals, woods and inorganic materials. The excellent adhesiveness of such a composition for polyurethane is based on the high reactivity and polarity of the NCO (isocyanate) group, which is one of the reactive groups providing the polyurethane structure, and is also the other reactive raw material. By selecting an active hydrogen compound, it is possible to design a wide range of adhesive properties, and it is easy to control reactivity, and the resulting polyurethane is generally rich in flexibility, excellent in impact resistance, low temperature resistance, etc. It is believed to be based on

[0003] Polyurethane compositions used for applications such as adhesives, sealants or binding materials include a "one-pack" (one-pack type) in which adhesive strength is developed based on the reaction between terminal NCO groups and moisture.
component type) and a "two-component type" (two-comp
onent type). In view of versatility and easy availability of stable performance, "two-pack" polyurethane compositions are overwhelmingly used.

[0004] In recent years, attention has been paid to the antithrombotic properties of polyurethane in addition to its mechanical properties, dynamic durability and flexibility, and the application of polyurethane to medical applications has been promoted. For example, as a polyurethane bonding / binding agent for a medical fluid separation device using hollow fibers (for example, an artificial organ such as an artificial kidney or an artificial liver), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MD)
Polyurethanes composed of aromatic isocyanates such as I) and castor oil-based polyols, polyether-based polyols, polyester-based polyols and amine-based polyols are frequently used. In polyurethane used for medical applications, it is particularly important to suppress as much as possible eluting substances which may elute into the body fluid upon contact with the body fluid and adversely affect the living body.

Recently, hollow fibers having a high glycerin content as a humectant have been developed in order to increase the porosity of the above-mentioned hollow fibers for a fluid separation device for the purpose of enhancing the functions. As a polyurethane bonding / binding agent applied to these glycerin-containing hollow fibers, JP-A-2-12413 discloses T
There has been proposed a low-eluate system using a combination of a DI-based NCO-terminated prepolymer and a modified MDI, and capable of suppressing the reaction with humectant glycerin.

In addition, Japanese Unexamined Patent Publication (Kokai) No. 215822/1990 proposes to use a modified isocyanurate of hexamethylene diisocyanate (HDI) to reduce the dissolution of the seal portion of an artificial organ. .

Furthermore, Japanese Patent Application Laid-Open No. 58-75556 proposes a non-foamed urethane composed of a cycloaliphatic (alicyclic) diisocyanate and an aromatic (aromatic) polyamine or alkyl polyol.

[0008]

However, in these conventional compositions for polyurethane, low viscosity and rapid curing properties for obtaining good workability and moldability, and adhesion (including hollow fiber membranes). However, it was still insufficient to simultaneously satisfy low elution and low foaming while suppressing the reaction with glycerin or moisture adhering to the (applied) portion.

[0009] Therefore, when the conventional composition for polyurethane is used, it is difficult to cope with highly functional (high glycerin-containing) hollow fiber fibers which have been progressing in recent years, and good workability and moldability or low elution are required. There has been a strong demand for realization of physical properties and low foaming properties that substantially eliminate the influence of moisture and the like attached to the bonded portion.

[0010] An object of the present invention is to provide a polyurethane binding material having excellent defoaming properties and low viscosity.

Another object of the present invention is to provide a polyurethane binding material having good curability.

Another object of the present invention is to provide a polyurethane binding material which can reduce the amount of eluted substances based on the suppression of the reaction with tertiary components such as glycerin and water.

Still another object of the present invention is to provide a polyurethane binding material which has low viscosity and good curability, and at the same time, enables low elution and low foaming.

[0014]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in combination of an isocyanate compound and an isocyanate group-terminated prepolymer (polyisocyanate) formed by the reaction of a castor oil-based polyol,
It has been found that the use of a curing agent composed of aminobenzoic acid ester / polyol at a specific ratio is extremely effective in achieving the above object.

The two-component polyurethane composition of the present invention
The two-pack polyurethane tying material is based on the above findings, and more specifically, a polyisocyanate comprising an isocyanate group-terminated prepolymer formed by a reaction between an isocyanate compound and a castor oil-based polyol; )

[0016]

Embedded image

(Wherein, R represents a divalent to trivalent polyol reactive residue, and n represents a number of 2 to 3).
A curing agent contained in the range of 0:90 to 90:10. The present invention also provides
The isocyanate compound is an aromatic isocyanate,
Or aromatic isocyanate / aliphatic isocyanate
The above two-component polyurethane binding material comprising a mixed system;
Is a divalent to trivalent polyether polyol reactive residue.
The two-component polyurethane tying material, characterized in that:
The above polyol in the curing agent is a castor oil-based polio
, N, N, N ', N'-tetrakis (2-hydroxy
(Cypropyl) ethylenediamine and N, N, N ', N'
-Tetrakis (2-hydroxyethyl) ethylene diamine
The two-pack type, characterized in that it is at least one of
Polyurethane binding material; and the above two-component polyurethane binding
Provide a binding method characterized by binding hollow fibers with materials
I do.

Hereinafter, the present invention will be described in detail.

(Polyisocyanate) The polyisocyanate which is one of the components constituting the two-pack type polyurethane binding material of the present invention comprises an isocyanate group-terminated prepolymer formed by a reaction between an isocyanate compound and a castor oil-based polyol.

(Isocyanate Compound) In the present invention, as the isocyanate compound, an isocyanate compound selected from an aromatic isocyanate group, an aliphatic isocyanate group, and an alicyclic isocyanate group is used alone or in combination of two or more as required. (Combinations within each group described above and / or combinations between different groups) can be used.

More specifically, such isocyanate compounds include, for example, 2,4-tolylene diisocyanate (also referred to as 2,4-toluene diisocyanate), 2,6-tolylene diisocyanate, and 2,4-tolylene diisocyanate. Isocyanate / 2,6-tolylene diisocyanate mixture, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate /
4,4′-diphenylmethane diisocyanate mixture,
aromatic isocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, naphthalene-1,5-diisocyanate and xylylene diisocyanate; hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, lysine diisocyanate, dodecamethylene diisocyanate, 1,6,11 −
Aliphatic isocyanates such as undecane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexylene diisocyanate. If necessary, one or more of these isocyanate compounds may be used as a carbodiimide, uretdione, uretimine, buret, or isocyanurate modified product.

Among the above, it is preferable to use an aromatic isocyanate or a combination of an aromatic isocyanate and an aliphatic isocyanate from the viewpoint of easily realizing high reactivity. Tolylene diisocyanate (TD
I) polyisocyanate, diphenylmethane diisocyanate (MDI) polyisocyanate, or T
A combination of a DI-based polyisocyanate / MDI-based polyisocyanate, or a combination thereof (TDI-based polyisocyanate and / or MDI-based polyisocyanate) with H
It is particularly preferable to use in combination with a DI polyisocyanate.

(Castor oil-based polyol) The "castor oil-based polyol" which gives an isocyanate group-terminated prepolymer by reacting with the isocyanate compound includes castor oil, dehydrated castor oil, or a modified product thereof; or ricinoleic acid, a castor oil fatty acid; Polyols produced by transesterification or esterification with low molecular weight polyols, polyether polyols and polyester polyols can be used.

The "low molecular polyol" used for the transesterification or esterification includes a molecular weight of 60 to 5
It is preferred to use a polyol of 00. Specific examples of such a low molecular polyol include, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. And trimethylolpropane.

The “polyether polyol” used in the above-mentioned transesterification or esterification includes a molecular weight of 5
00-5,000 polyether polyols can be preferably used. Specific examples of such polyether polyols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, copolyether polyol in which tetrahydrofuran (THF) and 3-alkyltetrahydrofuran are copolymerized (hereinafter referred to as “liquid polytetramethylene glycol”). And ethylene oxide (EO) and tipped ether which is a polymer of two or more kinds of propylene oxide (PO).

The “polyester polyol” used in the above-mentioned transesterification or esterification includes a molecular weight of 5
00 to 5,000 polyester polyols are preferably used. Specific examples of such a polyester polyol include, for example, a linear or branched polyester-based polyol produced from a carboxylic acid and a polyol, and a polycaprolactone-based polyol produced by ring-opening polymerization of caprolactone.

Among the above-mentioned polyols for transesterification or esterification, the above-mentioned polyols at room temperature (25
C), it is preferable to use ethylene glycol, polypropylene glycol, liquid polytetramethylene glycol, and / or tipped ether from the viewpoint of easily obtaining a low-viscosity polyisocyanate which is liquid at C.

The "isocyanate group-terminated prepolymer" as the polyisocyanate constituting the two-pack type polyurethane binding material of the present invention comprises an isocyanate group-terminated prepolymer formed by the reaction of the above polyisocyanate with a castor oil-based polyol. The reaction conditions for forming the prepolymer are not particularly limited as long as an isocyanate group-terminated prepolymer having reactivity with a curing agent (active hydrogen-containing compound) described later is provided. For example, the above isocyanate compound and castor oil-based polyol may be used. From 40 to 9
It is preferably obtained by reacting at 0 ° C. for 1 to 5 hours. In this case, the reaction is preferably performed at an equivalent ratio of isocyanate group / active hydrogen group of 1.5 to 40.0 (further, 1.8 to 30).

The isocyanate (NCO) group-terminated prepolymer thus obtained usually has low viscosity and good fluidity. The viscosity at 25 ° C. of this isocyanate group-terminated prepolymer (in a state immediately before reacting with a curing agent described later) is 300 to 9,000 c.
It is preferably about ps (preferably about 400 to 7,000 cps). Such a viscosity can be measured, for example, using a B-type viscometer under the following measurement conditions.

<Viscosity Measurement Conditions> Viscometer Model name: DVL-B, manufactured by Tokimec Co., Ltd.
II Rotor No: 3 Rotor rotation speed: 60, 30, 12 rpm The isocyanate (NCO) content (isocyanate content) of the above isocyanate group-terminated prepolymer is as follows:
10-2 (in the state immediately before reacting with a curing agent described later)
It is preferably about 3% (more preferably about 14 to 18%). Such an isocyanate content can be measured according to, for example, JIS K1603-1985 as follows.

<Measurement Method of Isocyanate Content> After excess dibutylamine is added to a sample and allowed to react sufficiently, unreacted dibutylamine is back-titrated with a hydrochloric acid standard solution to obtain an isocyanate group content.

(Curing Agent) The curing agent constituting the two-pack type polyurethane binding material of the present invention together with the above-mentioned polyisocyanate is represented by the following general formula (Formula 3)

[0033]

Embedded image

(In the above formula, R represents a divalent to trivalent polyol reactive residue, and n represents a number of 2 to 3.) and a polyol.

(Aminobenzoic acid ester) The method for obtaining the above-mentioned aminobenzoic acid ester is not particularly limited. For example, it can be obtained by reacting a divalent or trivalent polyol with p-nitrobenzoyl chloride in the presence of a dehydrochlorinating agent. The method of reducing the obtained nitro compound by an ordinary method is preferably used.

As the polyol used for the purpose of obtaining the above-mentioned aminobenzoic acid ester, dihydric to trihydric polyols can be used without any particular limitation, but the ester exchange with the ricinoleic acid, a castor oil fatty acid, or the esterification can be used. Low-molecular polyols, polyether polyols, and / or polyester polyols similar to the polyols to be used for the polymerization are preferably used. Among these, it is preferable to use a polyether polyol from the viewpoint of high reactivity and easy viscosity reduction,
It is particularly preferable to use divalent polytetramethylene glycol and / or liquid polytetramethylene glycol.

(Other Polyols) The "other polyols" constituting the curing agent together with the aminobenzoic acid ester include the above-mentioned "castor oil-based polyol"; or the above-mentioned transesterification or esterification with ricinoleic acid, a castor oil fatty acid. Low-molecular-weight polyols, polyether polyols, polyester polyols similar to the polyols to be used; amine-based polyols in which an alkylene oxide (eg, propylene oxide, ethylene oxide, etc.) is added to an amino compound (eg, ethylene diamine, etc.) Can be used. Specific examples of such an “amine-based polyol” include, for example,
N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine and the like can be mentioned.

Among the above polyols, it is particularly preferable to use a castor oil-based polyol, an amine-based polyol, or a mixed polyol thereof.

GPC of the aminobenzoic acid ester (ge
The number average molecular weight by l permeation chromatography is preferably about 600 to 4000 (more preferably about 900 to 3000). The amine value of the aminobenzoic acid ester is preferably about 185 to 25 KOH mg / g (more preferably about 125 to 35 KOH mg / g).

In the measurement of the number average molecular weight, for example, the following measurement conditions are suitably used.

<GPC Measurement Conditions> • Apparatus: Tosoh HLC-8020 • COLUMN: Tosoh TSKgel G2000H (exclusion limit molecular weight 1 × 10 ⁴ ) TSKgel G3000H (exclusion limit molecular weight 6 × 10 ⁴ ) TSKgel G4000H (exclusion limit molecular weight 4 × 10 ⁵ ) TSKgel G5000H (exclusion limit molecular weight 4 × 10 ⁶ ) Guardcolumn TSKguardcolumn H _XL -H ・ MOBILE PHASE: THF ・ FLOW RATE: 1.0 ml / min ・ OVEN TEMP: 40 ° C. ・ Sample concentration: 0.5 wt / vol% The amine value can be measured, for example, by the method described in the literature (JIS K7237).

(Weight Ratio of Aminobenzoate / Polyol) The "curing agent" constituting the two-pack type polyurethane binding material of the present invention is a 10:90 weight ratio of the aminobenzoate to the other polyol. Included at ~ 90: 10. When the amount of the aminobenzoate is less than this range, it is difficult to simultaneously achieve low eluate and low foaming as a two-pack polyurethane tying material . On the other hand, when the amount of the aminobenzoic acid ester is larger than this range, the viscosity of the two-pack type polyurethane binding material increases, and the workability and moldability deteriorate. The weight ratio between the aminobenzoic acid ester and the “other polyol” is preferably in the range of 20:80 to 80:20.

The viscosity of the above curing agent at 25 ° C. is 4,
000 cps or less, preferably 500 to 3,
More preferably, it is about 000 cps. The viscosity of this curing agent can be measured under the same conditions as the viscosity of the “isocyanate group-terminated prepolymer” described above.

The active hydrogen content (KOH mg
/ G) is preferably about 50 to 700 (more preferably about 80 to 300). The active hydrogen content is J
It can be measured by the method described in ISK1557-1970.

(Usage of Isocyanate Group-Ended Prepolymer / Curing Agent) When used as a polyurethane adhesive, a sealing material or a tying material, the two-pack type polyurethane tying material of the present invention is cured with the above isocyanate group-terminated prepolymer. Agent (active hydrogen-containing compound) and isocyanate group / active hydrogen group (equivalent ratio) = about 0.8 to 1.3 (furthermore, 0.8 to 1.3).
It is preferable to mix and cure in the range of about 1.1). The curing conditions at this time are usually resin (prepolymer)
Both the temperature and the curing temperature are preferably room temperature to 40 ° C. The curing time is preferably from 10 to 90 minutes.

The curing properties of the two-pack type polyurethane tying material of the present invention are as follows: at a resin temperature of 25 ° C., the isocyanate group-terminated prepolymer and the curing agent are converted into NCO groups / OH groups (equivalent ratio) =
It is preferable that the gel time when mixed at 1.05 is about 5 to 20 minutes (further about 7 to 15 minutes). This gelation time can be measured by the following method.

<Measurement Method for Gelation Time> The isocyanate-terminated prepolymer and the curing agent are adjusted to 25 ° C.

In a 150 ml polystyrene cup, an isocyanate-terminated prepolymer and a curing agent were mixed with NCO / OH
100 g is blended at a group (equivalent ratio) of 1.05.

Mix and stir for 1 minute with a glass rod and let stand at 25 ° C.

The tip of the microspatula is brought into contact with the surface of the mixture at regular intervals, and the time during which the mixture has no fluidity and there is no stringing from the surface of the mixture is defined as the gelation time.

The two-pack type polyurethane tying material of the present invention is prepared by mixing the isocyanate group-terminated prepolymer and the curing agent uniformly at a resin temperature of 25 ° C. with an NCO group / OH group (equivalent ratio) = 1.05. Has a viscosity (25 ° C.) of 3,000 c
ps or less (and about 1,000 to 2,200 cps)
It is preferable that This viscosity can be measured under the same conditions as the viscosity of the “isocyanate-terminated prepolymer” described above.

When using the two-component polyurethane binding material of the present invention, the resin temperature can be set to about 30 to 80 ° C. and the curing temperature can be set to about 40 to 120 ° C., if necessary.

(Use) In the present invention, by selecting the above-mentioned isocyanate group-terminated prepolymer and a curing agent (active hydrogen-containing compound), the use (adhesive, sealing material, binding material, etc.) and / or adherend ), Appropriate workability, curability, and physical properties can be obtained.

In the present invention, the "isocyanate group-terminated prepolymer" produced from the above-mentioned castor oil-based polyol has good defoaming properties, low viscosity and good reactivity; The aminobenzoic acid ester used as an agent has significantly faster reactivity (reactiveity over the third component) than the third component such as glycerin, water and the like, and has an appropriate pot life. Based on the possibility, a low-eluting, low-foaming composition for a two-pack polyurethane having low viscosity and good curability can be obtained. Two-component type polyurethane composition that have a such properties, polyurethane adhesives, in particular suitably used as a sealing material or bundling material.

[0055] The two-component type polyurethane composition polyurethane adhesive using a sealing material or strapping material, the fiber ends unity fluid separation apparatus using hollow fibers, and can be suitably used as a sealing material. In such an embodiment, as a method of binding and sealing the ends of the hollow fibers described above, for example, JP-A-57-58963 and JP-A-57-58963.
It is possible to use a centrifugal molding method as described in, for example, -58964.

The material and the outer diameter of the hollow fiber to which the polyurethane adhesive, the sealing material or the binding material is to be applied are not particularly limited. For example, regenerated cellulose, cellulose acetate, cellulose ester, polyethylene, polypropylene, polyamide, polysulfone, Those made of materials such as polyacrylamide, polyacrylonitrile, polymethyl methacrylate, polyurethane, casein, collagen and the like can be used. The outer diameter of the hollow fiber is about 100 to 500 μm (further, 200 to 400 μm).
m).

When a two- pack type polyurethane composition (polyurethane adhesive, sealant or binding agent, etc.) is used as an electrical or optical fiber sealant, a filler, a plasticizer, It is possible to add known additives such as anti-sagging agents.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, all “parts” and “%” in the following Examples and Comparative Examples are based on weight (that is,
Parts by weight, weight%).

[0059]

EXAMPLES Production Example 1 (Isocyanate group-terminated prepolymer (A-1) Production Example) MDI (diphenylmethane diisocyanate) 56
And is reacted with 44 parts of polypropylene glycol / ricinoleate (molecular weight = 1,000, hydroxyl value = 112) at 70 ° C. for 4 hours under a nitrogen atmosphere to obtain an isocyanate having an NCO content of 15% and a viscosity of 1300 cps (25 ° C.). A group-terminated prepolymer (A-1) was obtained.

Production Example 2 (Isocyanate group-terminated prepolymer (A-2) Production Example) Carbodiimide-modified MDI (isocyanate content 2
9%) and 76 parts of polypropylene glycol / ricinoleate (molecular weight = 2,000, hydroxyl value = 56)
And 24 parts under a nitrogen atmosphere at 70 ° C. for 4 hours.
A prepolymer (A-2) having a CO content of 21% and a viscosity of 450 cps (25 ° C.) was obtained.

Production Example 3 ( Preparation example of isocyanate group-terminated prepolymer (A-3)) 20 parts of tolylene diisocyanate (TDI) and 41 parts of castor oil (molecular weight = 950, hydroxyl value = 160) were mixed in a nitrogen atmosphere at 70%. The mixture was reacted at 4 ° C. for 4 hours to obtain a prepolymer having an NCO content of 7.9% and a viscosity of 70,000 cps (25 ° C.).

Subsequently, carbodiimide-modified MDI (isocyanate content 29%) was added to the prepolymer obtained above.
39 parts were added and mixed and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to obtain an NCO content of 16% and a viscosity of 1,800 cps (25
° C) of the prepolymer (A-3).

Production Example 4 ( Production example of isocyanate group-terminated prepolymer (A-4)) 50 parts of MDI and trimethylolpropane / ricinoleate (molecular weight = 630, hydroxyl value = 270) 2
5 parts under a nitrogen atmosphere at 70 ° C. for 4 hours.
A prepolymer having an O content of 16% and a viscosity of 1800 cps (25 ° C.) was obtained.

Subsequently, to the prepolymer obtained above, 25 parts of isocyanurate-modified hexamethylene diisocyanate (isocyanurate-modified HDI) (isocyanate content: 23%) was added, and mixed and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere. Content 17%, viscosity 2,000 cps
(25 ° C.) of the prepolymer (A-4) was obtained.

Production Example 5 (Isocyanate group-terminated prepolymer (A-5) Production Example) 23 parts of TDI and 50 parts of castor oil (molecular weight = 950, hydroxyl value = 160) were reacted at 70 ° C. for 4 hours in a nitrogen atmosphere. , NCO content 7%, viscosity 95,000 cps
(25 ° C.) was obtained.

Subsequently, carbodiimide-modified MDI (isocyanate content 29%) was added to the prepolymer obtained above.
27 parts were added and mixed and stirred at 50 ° C. for 4 hours under a nitrogen atmosphere to obtain an NCO content of 13% and a viscosity of 6,500 cps (25
C) prepolymer (A-5).

Production Example 6 ( Preparation Example of Isocyanate-terminated Prepolymer (A-6)) 56 parts of MDI and 44 parts of polypropylene glycol (molecular weight = 1,000, hydroxyl value = 112) were mixed at 70 ° C. in a nitrogen atmosphere at 4 ° C. Reaction time, NCO content 15%,
Prepolymer (A-6) having a viscosity of 950 cps (25 ° C.)
I got

Production Example 7 (Synthesis example of aminobenzoic acid ester) In a 1-liter four-necked flask, 200 g of polytetramethylene glycol having a number average molecular weight of 1,000 and 48 g of triethylamine were placed.
And 200 ml of benzene were added to prepare a polytetramethylene glycol solution. Separately, 74.2 g of p-nitrobenzoyl chloride was dissolved in 200 ml of benzene and prepared for a dropping reaction.

The polytetramethylene glycol solution obtained above was heated to 40 to 50 ° C. with stirring, and the p-nitrobenzoyl chloride solution was added dropwise to the polytetramethylene glycol solution over 2 hours. After the completion of the dropwise addition, the temperature was raised and the reaction was carried out under reflux for 1.5 hours. After allowing to cool, the reaction mixture was filtered to remove the precipitated triethylamine hydrochloride, and the obtained filtrate was concentrated under reduced pressure to obtain a dinitro intermediate.

Next, 122.8 g of iron powder, 6 g of acetic acid (catalyst), 500 ml of toluene as a solvent, and 200 ml of water were placed in a two-liter four-necked flask. Separately, the dinitro intermediate obtained in the above reaction was dissolved in 200 ml of toluene and prepared for a dropping reaction.

The solution containing the iron powder and the catalyst obtained above was heated with stirring, and the dinitro intermediate solution was added dropwise to the solution under reflux over 1.5 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature under reflux for 5 hours.

After acetic acid was neutralized by adding sodium hydrogen carbonate to the obtained reaction mixture, the mixture was filtered while hot to remove iron sludge, and water was removed by liquid separation. Then, toluene was distilled off to obtain polytetramethylene glycol bis (p-aminobenzoate) as an aminobenzoic acid ester. The number average molecular weight of this aminobenzoic acid ester is 1,
240 (measured by GPC), amine value 91 KOHm
g / g.

Production Example 8 ( Production Example of Curing Agent B-1) Castor oil (molecular weight = 950, hydroxyl value = 160): 22 parts and N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine ( (Molecular weight = 295, hydroxyl value = 760) 8 parts and the polytetramethylene glycol bis (p) obtained in Production Example 7
-Aminobenzoate) (molecular weight 1240, amine value =
91) and 70 parts thereof were mixed and stirred at 50 ° C for 2 hours under a nitrogen atmosphere to obtain a curing agent (B-1) having an active hydrogen content (KOHmg / g) of 160 and a viscosity of 2,500 cps (25 ° C). .

Production Example 9 ( Production Example of Curing Agent B-2) Dehydrated castor oil (molecular weight = 95)
0, hydroxyl value = 118) and 50 parts of polytetramethylene glycol bis (2-aminobenzoate) (molecular weight: 1240, amine value = 91) obtained in Production Example 7 at 50 ° C. under a nitrogen atmosphere. Mixing and stirring for 2 hours, active hydrogen content (KOHmg / g) 104, viscosity 1,900
A curing agent (B-2) having cps (25 ° C.) was obtained.

Production Example 10 ( Production Example of Curing Agent B-3) 53 parts of castor oil (molecular weight = 950, hydroxyl value = 160) and N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine (molecular weight) = 295, hydroxyl value = 760) 17 parts and 30 parts of polytetramethylene glycol bis (p-aminobenzoate) obtained in Production Example 7 (molecular weight 1,240, amine value = 91) were mixed under a nitrogen atmosphere. The mixture was stirred at 50 ° C. for 2 hours, and the active hydrogen content (KOH mg / g) was 24.
0, a curing agent having a viscosity of 2,200 cps (25 ° C.) (B-
3) was obtained.

Production Example 11 ( Production Example of Curing Agent B-4) 64 parts of polypropylene glycol (molecular weight = 1,000, hydroxyl value = 112), N,
N, N ', N'-tetrakis (2-hydroxyethyl)
Ethylenediamine (molecular weight = 270, hydroxyl value = 82
0) 16 parts and the polytetramethylene glycol / aminobenzoic acid ester obtained in Production Example 7 (molecular weight: 1,24
0, amine value = 91) 20 parts with 50 parts under a nitrogen atmosphere.
C. for 2 hours with stirring, and the active hydrogen content (KOHmg /
g) A curing agent (B-4) having a viscosity of 240 and a viscosity of 2,200 cps (25 ° C) was obtained.

Production Example 12 (Curing Agent B-5 Production Example) 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 = 760) and 20 parts under a nitrogen atmosphere at 50 ° C. for 2 hours with stirring to obtain an active hydrogen content (KOH mg / g) of 280 and a viscosity of 1,000 cps.
(25 ° C.) curing agent (B-5) was obtained.

Production Example 13 ( Production Example of Curing Agent B-6) Dehydrated castor oil (molecular weight = 95)
0, hydroxyl value = 118) 75 parts, N, N, N ', N'
And 25 parts of tetrakis (2-hydroxypropyl) ethylenediamine (molecular weight = 295, hydroxyl value = 760) are mixed and stirred at 50 ° C. for 2 hours under a nitrogen atmosphere to obtain an active hydrogen content (KOH mg / g) of 280 and a viscosity of 950 cps.
(25 ° C.) curing agent (B-6) was obtained.

Examples 1 to 4 and Comparative Examples 1 to 4 Prepolymers of isocyanate group-terminated prepolymers (A-1) to (A-4) produced in Production Examples 1 to 4 described above and Production Examples 8 to 11 described above. (B-1) to (B-)
The curing agent of 4) was combined at a resin temperature of 25 ° C. and an NCO / OH equivalent ratio of 1.05 as shown in Table 1 below, and the following evaluation was performed.

Further, the isocyanate group-terminated prepolymers (A-1) and (A-3), and the prepolymers (A-5) and (A-6) produced in Production Examples 5 to 6 and The agent (B-1) and the curing agents (B-5) and (B-6) produced in Production Examples 12 and 13 were used in combination as shown in Table 1 below in the same manner as in the above Examples. The same evaluation was performed.

[0081]

[Table 1]

<Evaluation Method> 100% at a mixed viscosity resin temperature of 25 ° C. and an NCO / OH equivalent ratio of 1.05.
g (total weight) and the viscosity was measured immediately after uniform mixing.

Viscometer Model name: manufactured by Tokimec Co., Ltd., trade name: DVL-BII Rotor No .: 3 Rotor rotation speed: 30 rpm Measurement atmosphere: 25 ° C. Gelation time Resin temperature was 25 in accordance with the “gelation time measurement method” described above.
100 g (total weight) were blended at a temperature of 1.05 and an NCO / OH equivalent ratio of 1.05, and the gelling time of the above composition which was uniformly mixed was measured.

[0084] The resin-filled state, the bubble residual state, eluting material test Glycerin content: 150 wt%, water content: 5% by weight of the hollow fiber (outer diameter: 260 .mu.m, inner diameter: 200 [mu] m, length:
40 g of the sealing and bundling composition (Table 1) obtained above was poured into a mold in which 10,000 pieces (20 cm) were arranged. After the injection, the hollow fibers were bonded by a centrifugal molding method, and the hollow fibers were bound and bonded together, and the hollow fibers were sealed and bonded to a housing (material: polycarbonate). After the sealing adhesion, the composition was cured by being left at 40 ° C. for 1 day (24 hours).

After the above curing, the state of filling the resin between the hollow fibers,
The state of remaining air bubbles and the eluted material from the bonded portion of the hollow fiber were evaluated.

Resin-filled state After curing at 40 ° C. for one day as described above, the bonded portion between the hollow fibers is sliced in a transverse direction (a direction perpendicular to the longitudinal direction of the hollow fibers) to a thickness of about 2 mm, and the hollow portion of polyurethane is formed. The presence or absence of a resin-unfilled portion between the hollow fibers in the yarn bonding portion was evaluated by microscope observation at a magnification of 50 times.

[0087] bubbles remaining state 40 ° C. as described above, after curing of the day, the adhered portion of the hollow fiber together, then sliced into approximately 2mm thick laterally in the same manner as described above, hollow fiber periphery of the hollow fiber bonding portion by polyurethane Was evaluated using a microscope with a magnification of 50 times.

Eluate of hollow fiber adhesion portion According to the following “dialysis type artificial kidney device approval standard V-4”,
The amount of the eluate of the hollow fiber adhesion portion was measured using "absorbance" (the eluate was measured after curing at 40 ° C for 3 days (72 hours)).

<Dialysis type artificial kidney device approval standard V-4> In the case of a hollow fiber type dialyzer, a 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 50 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 nm with a layer length of 10 mm is measured by the absorbance measurement method of the Japanese Pharmacopoeia (Japanese Pharmacopoeia). .

Table 2 below shows the results of the performance tests as the above-mentioned sealing and binding agents.

[0091]

[Table 2]

As shown in Table 2 above, when the sealant / binder compositions of Examples 1 to 5 were used, there were no residual air bubbles due to foaming and the mixing viscosity was low. The filling state between the hollow fibers was good, and complete adhesion between the hollow fibers and between the hollow fibers and the housing was achieved.
Furthermore, the eluate was at a low level, and there was no problem.

On the other hand, when the compositions for the sealing and binding agents of Comparative Examples 1 and 2 were used, there was no problem in the workability and the filling state between the hollow fibers based on the low mixing viscosity. However, since many bubbles remained due to foaming, and the eluted material far exceeded the reference value, it was not suitable for the eluate standard.

On the other hand, when the composition for a sealing / bundling agent of Comparative Example 3 was used, it passed in terms of the eluted matter, but the resin filling state between the hollow fibers was poor due to the high viscosity. , Foaming was observed.

When the composition for a sealant / bundling agent of Comparative Example 4 was used, the state of filling between the hollow fibers was good and the eluate was acceptable, but bubbles remained due to foaming. Many were unsuitable in this regard.

[0096]

As described above, according to the present invention, a polyisocyanate comprising an isocyanate group-terminated prepolymer formed by reacting an isocyanate compound with a castor oil-based polyol;

[0097]

Embedded image

(In the above formula, R represents a divalent to trivalent polyol reactive residue, and n represents a number of 2 to 3.) An aminobenzoic acid ester represented by the formula:
0: 90 to 90: curing agent comprising in the range of 10 and; two-component type polyurethane strapping material composed is provided.

When the two-pack polyurethane tying material of the present invention is used, not only the amount of eluted material but also the amount of foam can be reduced based on its excellent impregnation and adhesiveness.
The binding material can be suitably used, for example, as a polyurethane adhesive, a sealing material or a binding material.

Therefore, the two-component polyurethane of the present invention
Bundling material is a field in which the improvement of adhesive sealing performance and reduction of eluted matter are required, for example, as a medical device using a hollow fiber separation membrane, a hollow fiber sealing material or a binding material of an industrial fluid separation device. It can be suitably used. Among them,
When using the two-pack polyurethane binding material of the present invention,
Since it is possible to significantly reduce the eluate at the hollow fiber bonding portion, it can be used very suitably in medical fluid separation devices that require particularly high safety based on direct contact with body fluids such as blood. is there.

Examples of the medical or industrial fluid separation device in which the two-pack type polyurethane binding material of the present invention can be suitably used include a plasma separator, an artificial organ (artificial lung, artificial kidney, artificial liver, etc.), household And industrial water treatment equipment.

Further, the two-component polyurethane binding of the present invention
The material can be preferably used as a sealing material and / or a bundling material for electrical use, optical fiber, etc. by utilizing its impregnation and adhesiveness.

[0103]

────────────────────────────────────────────────── (5) References JP-A-59-51943 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/10 C08G 18/32 C08G 18 / 65-18/66

Claims (5)

(57) [Claims] 1. A polyisocyanate comprising an isocyanate group-terminated prepolymer formed by reacting an isocyanate compound with a castor oil-based polyol; and a polyisocyanate represented by the following general formula: (In the above formula, R represents a divalent to trivalent polyol reactive residue, and n represents a number of 2 to 3.) The aminobenzoic acid ester represented by the formula: 9
Two-component type polyurethane strap, characterized in that they are composed of: a curing agent comprising in the range of 0:10. 2. The two-component polyurethane tying material according to claim 1, wherein the isocyanate compound comprises aromatic isocyanate or a mixed system of aromatic isocyanate and aliphatic isocyanate. 3. The method according to claim 1, wherein R is a divalent to trivalent polyether polyether.
2. A thiol-reactive residue.
2. The two-component polyurethane binding material according to 2. 4. The method according to claim 1, wherein the polyol in the curing agent is
Castor oil-based polyol, N, N, N ', N'-tetraki
(2-hydroxypropyl) ethylenediamine and
N, N, N ', N'-tetrakis (2-hydroxyethyl
G) at least one of ethylenediamine
The two-part posiy according to any one of claims 1 to 3, wherein
Urethane binding material. 5. The method according to claim 1, wherein
Characterized by binding hollow fibers with liquid polyurethane binding material
And unity method.