JPH06136089A - Composition for polyurethane elastomer - Google Patents

Abstract

PURPOSE:To provide the composition for polyurethane elastomer having excellent physical properties in heat resistance, etc., little in eluted substances and exhibiting excellent performance when used for dialysis type artificial organ devices, and used for polyurethane elastomers. CONSTITUTION:An isocyanate-modified product and an NCO group-terminated prepolymer are used, and an amine polyol and/or a non-amine polyol are used as a curing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to compositions for polyurethane elastomers. More specifically, it relates to a composition for a polyurethane elastomer used as a polyurethane-based sealant, a binding agent and the like.

[0002]

BACKGROUND OF THE INVENTION Polyurethane is a polymer compound having ???-NHCOO ??? in the main chain repeating unit obtained industrially by reacting an organic polyisocyanate with a polyol having a polyester structure or a polyol having a polyether structure. However, depending on the combination of raw materials, it has a wide range of uses such as polyurethane foam, polyurethane rubber, adhesives, fibers and paints.

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

For these sealants and binders, low-viscosity systems that cure quickly at low temperatures have also been studied, and problems with workability and moldability are decreasing. However, in terms of physical properties, the use is limited because of low elasticity, low strength, and poor durability.

On the other hand, in a two-component polyurethane for industrial rolls for paper making, iron making, printing, paper feed rolls, cleaning blades, etc., the above-mentioned aromatic or non-aromatic isocyanate and polyethylene adipate, polybutylene are used. A prepolymer obtained by reacting a polyester polyol such as adipate or a polyether polyol such as polytetramethylene ether glycol or polypropylene glycol is used, and 4,4′-methinebis (2-) is used as a curing agent (active hydrogen-containing compound). High elasticity by reacting with aromatic amines such as chloroaniline) (MOCA) and 4,4′-methylenedianiline (MDA) or aliphatic glycols such as 1,4-butanediol and trimethylolpropane. , Because it is possible to obtain a resin with high physical properties It has been used in the Ku industry.

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

Further, as a means for accelerating the curability at low temperature, a heavy metal catalyst such as Sn, Pb, Zn, Cd or an amine catalyst such as triethylenediamine or triethylamine may be added, but the reactivity may be deteriorated due to deactivation. In addition to the potential for instability, there is a problem in medical applications that it may be dissolved in body fluids and adversely affect the living body. Further, conventional resins have drawbacks such as too high hardness and brittleness, and there is a demand for improvement thereof.

[0008]

SUMMARY OF THE INVENTION The present invention has the disadvantages of the conventional polyurethane-based sealants and binders, namely, high elasticity,
And to obtain good products with high physical properties and fast reactivity,
Higher resin viscosity, heat curing is required, and conversely, those that cure rapidly at low temperature have low physical properties and limited applications, and more eluate increases and they are not biocompatible. It is to improve things.

[0009]

Means for Solving the Problems As a result of intensive studies and studies for improving the conventional drawbacks, the present inventors have found that the improvement can be achieved by using a modified HDI isocyanurate and an MDI-based prepolymer in combination. Heading The present invention has been reached.

That is, the present invention provides a composition for a polyurethane elastomer comprising a polyisocyanate and a curing agent, wherein a modified isocyanate compound (A) and an isocyanate group-terminated prepolymer (B) are used as the polyisocyanate. The present invention relates to a composition for a polyurethane elastomer, which comprises using an amine-based polyol (C) and / or a non-amine-based polyol (D) as a curing agent.

In the present invention, the modified isocyanate compound (A) used as the polyisocyanate is
There are HDI isocyanurate modified products, TDI isocyanurate compounds, and the like, and the most preferred modified products are HDI isocyanurate compounds. The modified product is a polyisocyanate having at least one isocyanurate ring and at least two isocyanate groups in one molecule. This HDI
In the modified isocyanurate of, it is preferable that the content of the HDI monomer is 5% or less. Such isocyanurate conversion of HDI is described in JP-A-57-47319.

The isocyanate group-terminated prepolymer (B) used in the present invention is obtained by reacting an isocyanate group with an active hydrogen group, and is a compound having an isocyanate group for obtaining a prepolymer. ,
Aromatic diisocyanates include, for example, MDI, TDI,
The naphthylene-1,5-diisocyanates, 1,3- and 1,4-phenylene diisocyanates, triphenylmethane-4,4 ', 4 "-triisocyanates, polymethylene polyphenyl polyisocyanates, aliphatic or cycloaliphatic diisocyanates are For example, HDI, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-
Diisocyanate, IPDI, 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- and -1,4-phenyl diisocyanate,
Perhydro-2,4 'and 4,4'-diphenylmethane diisocyanate, polyisocyanate compounds are, for example, 4,4', 4 "-triphenylmethane triisocyanate, diphenyl-4,6,4 ', triisocyanate, 2, 4,4'-diphenyl ether triisocyanate, polymethylene polyphenyl polyisocyanate and the like, or a part of these isocyanates modified to biuret, allophanate, carbodiimide, oxazolidone, amide, imide and the like can be mentioned.

Examples of the compound having an active hydrogen group for obtaining an isocyanate group-terminated prepolymer include low molecular weight polyols, polyether type polyols, polyester type polyols and castor oil type polyols. These can be used alone or as a mixture of two or more kinds. The low molecular weight polyol is divalent, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, hydrogenated bisphenol A, and other trivalent or higher valent (three to eight valent) compounds such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol, and sucrose. The equivalent weight of the low molecular weight polyol is 30 to 200.

As the polyether polyol, alkylene oxide (having 2 to 4 carbon atoms) of the above-mentioned low molecular weight polyol is used.
Alkylene oxides of ethylene oxide, propylene oxide, butylene oxide) and ring-opening polymerization products of alkylene oxides, and specifically include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. The equivalent weight of polyether polyol is 200-1500.

Examples of polyester polyols include polyester polyols, polycaprolactone polyols and polyether ester polyols. Polyester polyols include carboxylic acids (aliphatic saturated or unsaturated carboxylic acids such as adipic acid, azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid,
It is obtained by condensation polymerization of dimerized linoleic acid and / or aromatic carboxylic acid such as phthalic acid and isophthalic acid) with a polyol (the above-mentioned low molecular weight polyol and / or polyether polyol).

Polycaprolactone polyol is a polymerization initiator for glycols and triols, and is used as an initiator for ε-caprolactone, α-methyl-ε-caprolactone and ε-methyl-.
[epsilon] -caprolactone and the like can be obtained by addition polymerization in the presence of a catalyst such as an organometallic compound, a metal chelate compound and a fatty acid metal acylated product. The polyether ester polyol is obtained by subjecting a polyester having a carboxyl group and / or an OH group at the terminal to an addition reaction of an alkylene oxide such as ethylene oxide or propylene oxide. Equivalent weight of polyester polyol is 200-150
It is 0. Examples of castor oil-based polyols include transesterification of castor oil and castor oil or castor oil fatty acid with the aforementioned low molecular weight polyols, polyether polyols and polyester polyols, or esterified polyols. The equivalent weight of castor oil-based polyol is 200 to 15
00.

Among these polyols, preferred are low molecular weight polyols such as 1,4-butanediol and diethylene glycol, polyether polyols such as polyethylene glycol and polypropylene glycol, and amino alcohol polyols such as tetrakishydroxyethyl. Examples of the ethylenediamine, tetrakishydroxypropylethylenediamine and castor oil-based polyol include castor oil and the like.

The isocyanate group / active hydrogen group equivalent ratio for obtaining the isocyanate group-terminated prepolymer of the present invention is 1.2 to 15.0. The reaction can be carried out by a urethanization reaction which is usually performed. The modified isocyanate compound and the isocyanate group-terminated prepolymer in the present invention can be used within the range of 5:95 to 95: 5 (weight ratio).

The amine polyol (C) as a curing agent that can be used in the present invention has a molecular weight of 250.
At -400, oxyalkylated derivatives of amino compounds having two or more active hydrogen atoms can be used. Specific examples include N, N, N ', N'-as amino alcohols.
Propylene oxide (PO) or ethylene oxide adducts with amino compounds such as ethylenediamine such as tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N ′, N′-tetrakis [2-hydroxyethyl] ethylenediamine, or mono. -, Di-, tri-ethanolamine and the like can be mentioned. As the amine-based polyol, those obtained by adding propylene oxide or ethylene oxide to ethylenediamine such as N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine are preferable.

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

As such a curing agent, an amine-based polyol (C) and / or a polyol (D) other than the amine-based (C) can be used. The components (C) and (D) can be used together at any ratio. In this case, when the amount of the amine-based polyol is 10% by weight or less, the curing time becomes long and the workability,
It is not preferable in consideration of productivity. These hardeners include
Depending on the required properties of the binding agent and the sealing agent, it can be used by mixing with an appropriate amount of another polyol.

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

The polyurethane elastomer of the present invention is particularly suitable for polyisocyanates and curing agents (compounds containing active hydrogen).
Is a low-temperature liquid / low viscosity, and shows good curability without using a metal or amine-based catalyst,
Polyurethane with high elasticity and physical properties can be used by operating at room temperature and curing at room temperature without the need for a heating device. Furthermore, the fact that it does not contain an unreacted metal or an amine-based catalyst does not leach into water or body fluid, and it is useful in terms of workability that it is a low temperature liquid and has a low viscosity. Particularly, it shows excellent performances in heat resistance, tensile strength, tear strength, etc. When the eluate is measured with a dialysis type artificial kidney device, the absorbance of the eluate is low and excellent performance is exhibited.

Since the polyurethane elastomer of the present invention is excellent in various physical properties as its attributes, such as hardness, tensile strength, elongation, tear strength, etc., it is possible to utilize these attributes to make various industrial sealing materials such as electric seals. Paper, as a sealing material for automobiles, automobiles, construction, civil engineering, or various cushioning materials.
It can be used for OA equipment parts such as industrial rolls for iron making and printing, paper feed rolls, cleaning blades, etc.

The polyurethane elastomer of the present invention does not contain any unreacted metal or amine catalyst in addition to the above-mentioned excellent physical properties. Therefore, it is advantageous as a hollow fiber binding material for medical and industrial fluid separation devices using the hollow fiber separation membrane. Examples of these medical and industrial fluid separation devices include plasma separators, artificial lungs, artificial kidneys, artificial livers, and domestic / industrial water treatment devices.

[0026]

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

Production of modified isocyanate compound (A) A 500 ml separable flask equipped with a thermometer, a stirrer and a nitrogen seal tube was charged with 300 parts of HDI and 0.3 part of potassium caprate as a catalyst in the flask. The air was replaced with nitrogen and the reaction temperature was raised to 40 ° C. with stirring. It was 42.5% when the NCO content was measured by reacting at the same temperature for 6 hours. The reaction solution was a pale yellow transparent liquid. Phosphoric acid (0.21 part) was added to this reaction solution as a terminating agent, and the mixture was stirred at the reaction temperature for 1 hour, and then free HDI was removed by a molecular distillation apparatus. The obtained liquid is a pale yellow transparent liquid, N
CO content 21.0%, viscosity 2000 mPa · s / 25
C., free HDI content 0.3%. (A)

Production of isocyanate group-terminated prepolymer (B) Production of B-1 Using the same apparatus as in the production of modified product (A), MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Millionate MT) 6
8.1 parts and dehydrated castor oil (made by Ito Oil Co., OH number 120,
Molecular weight 935) 31.9 parts are reacted at 80 ° C. for 4 hours to give an NCO content of 20% and a viscosity of 700 mPa · s / 25 ° C.
Was obtained. This prepolymer is designated as B-1.

Production of B-2 A carbodiimide-modified MD was prepared using the same apparatus as in B-1.
I (Nippon Polyurethane Industry, trade name Millionate MT
L) 676 parts and PPG-2000 (Asahi Denka Kogyo, OH
Valency 56, molecular weight 2000) 324 parts were reacted at 80 ° C. for 4 hours to give an NCO content of 18% and a viscosity of 500 mPa · s.
A prepolymer of / 25 ° C was obtained. This prepolymer is B
-2. Production of B-3 Using the same apparatus as in B-2, 300 parts of HDI and 80 parts of trimethylolpropane were reacted at 80 ° C for 5 hours to give an NCO content of 19.5% and a viscosity of 80000 mPa · s / 2.
A 5 ° C. prepolymer was obtained. This prepolymer is B-3
And

Examples 1 to 8 and Comparative Examples 1 to 4 Polyisocyanates were prepared by mixing in the proportions shown in Table 1. The composition for elastomer is shown in Table 1. The above polyisocyanate and the curing agent were mixed at a resin temperature of 25 ° C. so that the reaction equivalent ratio was 0.95, and cured at 25 ° C. The polyisocyanate curing agent quickly became compatible with each other to form a mixture having an initial viscosity of 1700 mPa · s, a good gelling time, and smooth casting and molding were possible. The hardness, tensile strength, elongation and tear strength of the produced polyurethane are shown in Table 2. Hardness is 25 ℃ and 1 to see heat resistance
It was measured at 20 ° C. At 120 ° C, the rate of decrease in hardness is shown.

The compositions of Examples 1 to 8 and Comparative Examples 1 to 4 are used to pour into a mold set with hollow fibers containing about 70% by weight of glycerin. After the injection, the adhesive molding was completely performed by the centrifugal molding method. The molded hollow bonded portion is left at 25 ° C. for 7 days for complete curing. After that, it is cut into about 1 cm square and 40 g is used as a test piece. The test results are shown in Table 2. Test item and method Dialysis type artificial kidney device standard
No. V-4, the eluate was measured by an absorptiometry according to the elution test (Note-1) of the bonded portion of the hollow fiber. The measurement wavelength was expanded to 300 to 22 nm. Note 1: Content of dialysis-type artificial kidney device V-4 Contents Dissolution test of hollow fiber adhesive part For a hollow fiber type dialyzer, cut out the hollow fiber adhesive part for one dialyzer and measure about 1 cm square. Shred into 200 ml of water is added thereto, and the mixture is gently shaken at 40 ° C. for 2 hours and heated. After cooling, take 1.0 ml of the supernatant and add water to make exactly 50 ml. Using this solution as the test solution and water as the control,
When the absorbance at a wavelength of 280 to 240 nm with a layer length of 10 mm is measured by the Japanese absorbance measurement method, the absorbance must be 0.05 or less.

[0032]

[Table 1]

[0033]

[Table 2]

Claims (2)

[Claims] 1. A polyurethane elastomer composition comprising a polyisocyanate and a curing agent, wherein a modified isocyanate compound (A) and an isocyanate group-terminated prepolymer (B) are used as the polyisocyanate, and the curing agent is A composition for a polyurethane elastomer, which comprises using an amine-based polyol (C) and / or a non-amine-based polyol (D). 2. A modified isocyanate compound (A) and an isocyanate group-terminated prepolymer (B),
(A) is an isocyanurate modified product of hexamethylene diisocyanate and (B) is an isocyanate group-terminated prepolymer obtained by reacting diphenylmethane diisocyanate with a compound having two or more active hydrogen groups in one molecule. The composition for polyurethane elastomers according to claim 1, characterized in that.