JPH10195159A - Isocyanato-terminated prepolymer, its production and curable polyurethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an isocyanato-terminated prepolymer excellent in storage stability and to provide a curable polyurethane excellent in mechanical properties such as strengths, elongation and hardness. SOLUTION: A polyoxyalkylenepolyol having a hydroxyl value (OHV) and a total degree of unsaturation (C=C) satisfying the following requirements and having CPR which represents the amount of a basic substance in the polyol of 5 or below is reacted with a polyisocyanate compound to produce an isocyanato-terminated prepolymer. A curable polyurethane is obtained by using this compound. The region including an OHV of 10-35mgKOH/g and a C=C of 0.03-0.1meq/g, excluding the ranges defined by formulas a and b: a: C=C >4.59×OHV<-1.34> +0.002 (OHV is 17.6-35.0mgKOH/g), and b: C=C <1.59×OHV<-1.20> (OHV is in the range of 10.0-21.7mgKOH/g).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an isocyanate group-terminated prepolymer, a method for producing the same, and a curable polyurethane composition using the prepolymer. Specifically, the present invention has a hydroxyl value and a total unsaturation satisfy the following formula,
The present invention relates to a curable polyurethane composition using an isocyanate group-terminated prepolymer using a polyoxyalkylene polyol having a CPR of 5 or less. OHV 10-35
mgKOH / g, C = C 0.03-0.1 meq.
A region excluding the range of the following formulas a and b from the range of / g is satisfied. a formula C = C> 4.59 × OHV ^-1.34 +0.002 (however, OHV is in the range of 17.6 to 35.0 mgKOH / g) b formula C = C <1.59 × OHV ^-1.20 (however, OHV Is in the range of 10 to 21.7 mg KOH / g) By using the polyoxyalkylene polyol of the present invention, the storage stability of the isocyanate group-terminated prepolymer is excellent, and the curability is excellent in mechanical properties such as appearance, elongation and hardness. A polyurethane resin is obtained.

[0002]

2. Description of the Related Art An isocyanate group-terminated prepolymer obtained by reacting a polyoxyalkylene polyol having an alkylene oxide as a monomer with a polyisocyanate compound is a one-part composition obtained by using water in the air as a curing agent, Glycols such as 4-butanediol and polypropylene glycol, 3,3'-dichloro-
It is widely used as a two-part composition using a polyamine compound such as 4,4'-diaminodiphenylmethane as a curing agent. Since these one-part and two-part curable polyurethanes are often used for civil engineering and building materials, polymers with propylene oxide as the monomer are mainly used as polyoxyalkylene polyols from the viewpoint of water resistance. . The polyoxyalkylene polyol is generally catalyzed by potassium hydroxide and sodium hydroxide, has a reaction temperature of 105 to 140 ° C., and has a reaction pressure of 5 to 6 kgf / c.
Although it is industrially produced by anionic polymerization of alkylene oxide under the condition of m ² G (591 to 689 kPa), under such reaction conditions, a part of propylene oxide isomerizes to allyl alcohol in the presence of the catalyst. The amount of allyl unsaturated group-containing monol obtained by adding propylene oxide to allyl alcohol increases. The formation of the monol lowers the average number of functional groups of the polyoxyalkylene polyol, inhibits the elongation reaction of the molecular weight during the curable polyurethane reaction, and impairs the mechanical properties of the polyurethane resin.

In order to improve the hardness, elastic modulus, elongation, abrasion resistance and cure of a curable polyurethane produced from an alkylene oxide, particularly a polyoxyalkylene polyol using propylene oxide as a monomer, the content of by-product monols is reduced. Investigations have been made to use reduced polyoxyalkylene polyols. JP-A-2-263
818 and JP-A-2-263819 disclose that propylene oxide and ethylene oxide can be converted to diethylzinc, iron chloride, metal porphyrin, double metal, etc. Low monol polyoxyalkylene polyols have been obtained using cyanide complexes and the like as catalysts. However, as far as the present inventors have examined, the polyoxyalkylene polyol synthesized with such a catalyst has a higher viscosity and it is difficult to remove the catalyst from the polyol, as compared with those using an alkali metal catalyst. Therefore, it was found that the viscosity of the isocyanate group-terminated prepolymer obtained by the reaction with diphenylmethane diisocyanate was high, and the workability was poor.

JP-A-3-72517, JP-A-6-72517
JP 220152 discloses that a polyoxyalkylene polyol having less by-product monol can be obtained by using a double metal cyanide complex as a catalyst, generally using diethyl zinc, iron chloride, a metal porphyrin, a double metal cyanide complex, and the like. It is described that the degree of unsaturation of a normal alkali catalyst such as KOH increases particularly in a high-molecular-weight product, which is inappropriate. If a small amount of catalyst residue remains in the polyoxyalkylene polyol, it induces an undesired side reaction in the reaction with the polyisocyanate, and impairs the mechanical properties of the cured product. The complex is not suitable for the purpose of the present invention.

[0005] In Japanese Patent Publication No. Hei 7-39458, the weight average molecular weight is in the range of 500 to 6,000, and the total unsaturation is U.S. Pat. S. By using a urethane prepolymer composed of an organic polyisocyanate using a polyalkylene oxide whose V (meq./g) satisfies the formula (1), a cured product having less tackiness and having excellent weather resistance and heat resistance can be obtained. Teaching that. (Equation 1) S. V. _{(Meq./g)≦ (M W / f)} × 3.5 × 10 -5 generally diethylzinc, less iron chloride, metal porphyrin, such as double metal cyanide complex as a catalyst of byproduct monool polyoxy It is described that an alkylene polyol can be obtained, and in the case of an ordinary alkali catalyst such as KOH, the degree of unsaturation increases particularly in a high-molecular-weight product, which is not appropriate. It is described in the examples that a special catalyst other than KOH is used.
The polyoxyalkylene polyol satisfying the relationship between the weight average molecular weight and the total degree of unsaturation described in Japanese Patent No. 458 can be produced by a conventional technique using a KOH catalyst. Further, for the above-described reasons, a special catalyst is not suitable for the purpose of the present invention because the viscosity of the polyoxyalkylene polyol increases and it is difficult to remove the catalyst.

In JP-A-7-206965, the number average molecular weight (x) per hydroxyl group is 2,600 or more and the TU value (y, representing total degree of unsaturation, unit meq./g)
It is described that by using a polyether polyol satisfying the following formula (2), a tack that causes surface contamination is small, and a polyurethane-based curable composition having excellent elongation, tensile strength, and the like can be obtained. I have. (Formula 2) y ≦ 2 × 10 ⁻⁵ x−0.015 It is described that a polyether polyol satisfying the above formula can be obtained using cesium hydroxide as a catalyst, and among three polyol production examples, production example 1 Only the relationship of Expression (2) is satisfied, but Production Examples 2 and 3 are out of the range. The hydroxyl value (OHV) and the total degree of unsaturation (C
= C) is out of the range of JP-A-7-206965, and it is also necessary to use cesium hydroxide to synthesize a polyoxyalkylene polyol having a number average molecular weight per hydroxyl group of 2,600 or more, especially 10,000 or more. The reaction time is extremely long, which is not preferable from an industrial point of view such as economy. In the examples, the catalyst was removed by the adsorbent treatment method. However, there is no description of CPR indicating the amount of the basic substance in the polyoxyalkylene polyol specified in the present invention, and the present inventors investigated. Target CP in the range
R polyoxyalkylene polyol was not obtained.

[0007] JP-A-8-198929 discloses a pin cured by an isocyanate group-terminated prepolymer obtained by reacting a polyoxyalkylene polyol-based polyol produced using a cesium-based catalyst with an organic polyisocyanate. It teaches that a sealing material, a waterproofing material, and a flooring material having an appearance with less bubbles such as holes can be obtained. Diethyl zinc, iron chloride, metalloporphyrin,
A low hydroxyl value, low unsaturation polyoxyalkylene polyol obtained by using a double metal cyanide complex as a catalyst does not have much effect of reducing pinholes, and a cesium-based catalyst is used in Comparative Examples. It is shown that pinholes are generated with other alkaline catalysts. The present inventors have examined potassium hydroxide as an alkaline catalyst other than the cesium-based catalyst described for the generation of pinholes, and obtained the same results as those of the polyoxyalkylene polyol using cesium hydroxide as a catalyst. Was done. Further, JP-A-8-198929 does not disclose the production conditions of the polyol and the method of removing the catalyst, and cannot be said to disclose the production conditions of the polyoxyalkylene polyol having a CPR of 5 or less described in the present application.

As described in detail above, since it is difficult to remove the catalyst with a polyoxyalkylene polyol using a catalyst such as diethyl zinc, iron chloride, metal porphyrin, or double metal cyanide complex, the isocyanate reacted with an organic polyisocyanate. The storage stability of the terminal-terminated prepolymer (the viscosity stability of the prepolymer) is poor. Further, since the viscosity of the polyoxyalkylene polyol obtained with a metal catalyst such as diethylzinc or iron chloride increases, the viscosity of the prepolymer reacted with the polyisocyanate compound is high, and the workability is poor. By using cesium hydroxide which is an alkali metal catalyst, the viscosity of the polyoxyalkylene polyol becomes almost the same as that obtained with potassium hydroxide, but when the CPR is more than 5, the isocyanate reacted with the polyisocyanate compound It was found that the viscosity of the base terminal prepolymer increased with time and the appearance became cloudy.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an isocyanate group-terminated prepolymer having good storage stability.
Another object of the present invention is to provide a curable polyurethane composition having excellent mechanical properties such as appearance, elongation, and hardness.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, they have obtained a specific compound synthesized using at least one compound selected from potassium, rubidium and cesium as an alkali metal catalyst. It has been found that an isocyanate group-terminated prepolymer can be obtained by using a polyoxyalkylene polyol having a molecular weight and a total degree of unsaturation of 5 or less and a CPR of 5 or less.

That is, the gist of the present invention is to produce an isocyanate group-terminated prepolymer by reacting a polyisocyanate compound with a polyoxyalkylene polyol.
A polyoxyalkylene polyol obtained by addition-polymerizing an alkylene oxide in the presence of 0.05 to 0.55 mol of an alkali metal catalyst per 1 mol of an active hydrogen compound, wherein the hydroxyl value (hereinafter abbreviated as OHV) after removing the catalyst is obtained. CPR, the unit mgKOH / g) and the total degree of unsaturation (hereinafter abbreviated as C = C, unit meq./g) satisfy the following conditions, and represent the amount of the basic substance in the polyoxyalkylene polyol. The present invention relates to a isocyanate group-terminated prepolymer characterized by using no more than 5, a method for producing the same, and a curable polyurethane composition obtained by a moisture curing reaction or a reaction with a curing agent using the same. OHV 10 to 35 mgKOH / g, C = C
0.03-0.1 meq. A region excluding the range of the following formulas a and b from the range of / g is satisfied. a formula C = C> 4.59 × OHV ^-1.34 +0.002 (however, OHV is in the range of 17.6 to 35.0 mgKOH / g) b formula C = C <1.59 × OHV ^-1.20 (however, OHV Is in the range of 10 to 21.7 mg KOH / g)

BEST MODE FOR CARRYING OUT THE INVENTION

The alkali metal in the present invention is at least one compound selected from potassium, rubidium and cesium. Hydroxides,
Inorganic salts such as carbonates and bicarbonates, and organic salts such as oxalates are preferred. They may be used alone or in combination of two or more. Further, alkali metal alkoxides such as alkali metal methoxide and ethoxide, and simple metals can also be used. Most preferably, the main component is a hydroxide.

The use range of the alkali metal catalyst in the present invention is 0.05 to 0.55 per mol of the active hydrogen compound.
Is a mole. Preferably, 0.10 to 0.50 mol,
More preferably, it is 0.15 to 0.30 mol. 0.0
If the amount is less than 5 mol, the reaction time becomes longer because the consumption rate of the alkylene oxide decreases. If it exceeds 0.55 mol, the isomerization reaction of propylene oxide tends to occur, so that the amount of by-product monool increases.

The active hydrogen compound in the present invention includes alcohols, phenol compounds, polyamines, alkanolamines and the like. For example, water, dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, alkanolamines such as glycerin, monoethanolamine, diethanolamine and triethanolamine, trimethylolpropane, and pentane Polyhydric alcohols such as erythritol, saccharides such as sorbitol, sucrose, methylglucoside, dextrose, fatty acid amines such as ethylenediamine, aromatic amines such as toluylenediamine, diphenylmethanediamine, phenols such as bisphenol A, bisphenol S, and novolak And the like. These active hydrogen compounds can be used in combination of two or more. Further, compounds obtained by addition-polymerizing an alkylene oxide to these active hydrogen compounds by a conventionally known method can also be used. The most preferred of these compounds are dihydric alcohols,
A compound obtained by addition-polymerizing an alkylene oxide to a dihydric alcohol and having a number average molecular weight of up to 2,000, a compound having a number-average molecular weight of not more than 2,000 obtained by addition-polymerizing a trihydric alcohol and a trihydric alcohol to an alkylene oxide. It is. Those having a number average molecular weight of more than 2,000 after addition of alkylene oxide to dihydric alcohols or trihydric alcohols are not preferred because the amount of by-product monool increases.

Examples of the alkylene oxide to be addition-polymerized to the active hydrogen compound include propylene oxide, ethylene oxide, 1,2-butylene oxide, styrene oxide, tetrahydrofuran and the like. Of these, particularly preferred are propylene oxide, 1,2-butylene oxide and ethylene oxide. Most preferred are polyoxyalkylene polyols using propylene oxide as a monomer in an amount of 70 mol% or more.

The polyoxyalkylene polyol produced with the alkali metal catalyst of the present invention has a hydroxyl value (OHV) and a total degree of unsaturation (C = C) after removal of the catalyst satisfying the following conditions, and a polyoxyalkylene polyol. CPR showing the amount of the basic substance in 5 or less is used. OHV
10-35 mgKOH / g, C = C 0.03-
0.1 meq. A region excluding the range of the following formulas a and b from the range of / g is satisfied. a formula C = C> 4.59 × OHV ^-1.34 +0.002 (however, OHV is in the range of 17.6 to 35.0 mgKOH / g) b formula C = C <1.59 × OHV ^-1.20 (however, OHV Is in the range of 10 to 21.7 mg KOH / g.) The hydroxyl value is preferably 10 to 35 mg KOH / g. Particularly preferably, it is 15 to 28 mgKOH / g. The total degree of unsaturation must be within the range specified by the above equation. Total unsaturation of 0.03-0.1 meq. / G is within the range of the formula a, the hydroxyl value, that is, the total unsaturation with respect to the number average molecular weight of the polyoxyalkylene polyol is high, and the resulting curable polyurethane has mechanical properties such as elongation, hardness and elastic modulus. Decrease. Further, in order to synthesize a polyoxyalkylene polyol within the range of the formula b with the alkali metal catalyst described in the present application, it is necessary to considerably lower the reaction temperature of the alkylene oxide. Absent. Although the curability of the obtained curable polyurethane is improved, the curing time is too fast as seen in a one-part cured product such as a sealing material depending on the prescription, so that the curing time needs to be adjusted.

In order to produce a polyoxyalkylene polyol satisfying the above hydroxyl value and total unsaturation, the reaction temperature of propylene oxide in the alkylene oxide is 6
0-98 ° C. When the temperature is lower than 60 ° C., the reaction time of the alkylene oxide becomes longer. If the temperature exceeds 98 ° C., the amount of by-product monool increases, which is not preferable. Preferably it is in the range of 75-96C, most preferably in the range of 80-95C.

The maximum pressure during the reaction of propylene oxide is preferably 4 kgf / cm ² G (493 kPa).
Usually, the reaction of alkylene oxide is carried out by a pressure-resistant reactor. The reaction of propylene oxide may be started from a reduced pressure state or from an atmospheric pressure state. If the maximum pressure exceeds 4 kgf / cm ² G (493 kPa), the amount of by-product monool tends to increase, which is not preferable.

The method for removing the catalyst from the crude polyoxyalkylene polyol after the addition polymerization of the alkylene oxide to the active hydrogen compound is preferably any of the following a to d. a. After adding water in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the crude polyoxyalkylene polyol, the inorganic acid or the organic acid is 0.7 to 1.7 mole times the alkali metal in the crude polyoxyalkylene polyol. Use 50 ~
Neutralize alkali metals at 130 ° C. Thereafter, a reduced pressure treatment is performed using 0.01 to 1.0 part by weight of the adsorbent with respect to 100 parts by weight of the crude polyoxyalkylene polyol, water is distilled off, and the alkali metal salt and the adsorbent are removed by a filtration operation. (Acid neutralization removal method). b. 100 parts by weight of the crude polyoxyalkylene polyol, 5 to 40 parts by weight of an inert organic solvent and water are added to the polyoxyalkylene polyol, and then the inorganic or organic acid is added to the alkali metal in the crude polyoxyalkylene polyol. 0.7 to 1.7 times the molar amount of 5
Neutralize alkali metals at 0-130 ° C. Thereafter, a reduced pressure treatment is performed using 0.01 to 1.0 part by weight of an adsorbent with respect to 100 parts by weight of the crude polyoxyalkylene polyol, water and an organic solvent are distilled off, and an alkali metal salt and an adsorbent are removed by a filtration operation. (Acid neutralization removal method). c. To 100 parts by weight of the crude polyoxyalkylene polyol, 50 to 200 parts by weight of water, and 1 to 200 parts by weight of a hydrocarbon solvent inert to the polyoxyalkylene polyol are added, separated, washed with water, and treated with water and organic by reduced pressure treatment. The solvent is distilled off (water washing method). d. 20 to 200 parts by weight of water is added to 100 parts by weight of the crude polyoxyalkylene polyol, and the mixture is brought into contact with the ion exchange resin at 15 to 100 ° C. or lower. Then, the ion exchange resin is removed by filtration, and dehydration is performed by reduced pressure treatment (ion exchange treatment). Law).

First, the method a and the method b (acid neutralization removal method) will be described. The polyoxyalkylene polyol described in the present application has a high number average molecular weight and a high viscosity, and has a large number of repeating units of a lipophilic oxypropylene group, and the amount of water or an organic solvent used for neutralization reduces CPR. It is an important factor. Since some of the molecular terminals after the polymerization of the polyoxyalkylene polyol are alkali metal alkoxides, the molecular terminals are replaced with hydroxyl groups using water. At that time, the alkali metal hydroxide insoluble in the polyoxyalkylene polyol dissolves in water and is then neutralized by the excess acid used.

Usually, the amount of water used for neutralization of the alkali metal is, as disclosed in JP-B-61-4404, the amount of crude polyoxyalkylene polyol 100
It is 1.8 to 3.5 parts by weight with respect to parts by weight, but it was found that the CPR of the polyoxyalkylene polyol after the neutralization treatment was larger than 5 with such an amount of water. Therefore, upon neutralization, water (method a) or a mixture of water and an organic solvent inert to the polyoxyalkylene polyol (method b) is added to the crude polyoxyalkylene polyol 100.
Use 5 to 40 parts by weight based on parts by weight. Water is an essential component, and when using an organic solvent and water inert to the polyoxyalkylene polyol, the water content in the mixed solvent is preferably at least 20% by weight or more. When the polyoxyalkylene polyol contains 10 mol% or more of oxyethylene groups as hydrophilic groups, the amount of water used may be small. When there is no oxyethylene group, the amount of water used increases. 5
When the amount is less than the weight part, the alkali metal component in the product increases and the CPR becomes larger than 5. When the amount is more than 40 parts by weight, the yield of the polyoxyalkylene polyol decreases, and the energy consumed for dehydration and desolvation increases, which is not preferable from an industrial viewpoint.

Organic solvents inert to polyoxyalkylene polyols include, among hydrocarbon solvents, toluene, hexanes, pentanes, heptane, butanes, lower alcohols, cyclohexane, cyclopentane, xylenes and the like. No. These organic solvents may be partially left in the polyoxyalkylene polyol, but are distilled off by heating and depressurizing. The temperature was 100 to 140 ° C., and the degree of reduced pressure was 10 mmHgabs. The following method is preferable.

As the acid for neutralizing the alkali metal, an inorganic acid or an organic acid is used. Examples of the inorganic acid include phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. Examples of the organic acid include formic acid, oxalic acid, succinic acid, acetic acid, maleic acid, and aqueous solutions thereof. In particular, phosphoric acid and oxalic acid are preferable, and it is good to use in the form of an aqueous solution. These acids are used in an amount of 0.7 to 1.7 times the molar concentration of the alkali metal contained in the crude polyoxyalkylene polyol. The alkali metal is neutralized by using the acid in a slight excess with respect to the alkali metal. Neutralization temperature is 50
Perform in the range of 範 囲 130 ° C. Particularly preferably 70 to 9
5 ° C. The neutralization time depends on the reaction scale.
5 to 3 hours. When the amount of the acid is close to 1.7 mol times, it is preferable to use an acid adsorbent together. The amount of acid is 0.9 ~
1.5 mole times is preferred, and particularly preferred is 1.0 to
It is 1.4 mole times. When it is less than 0.7 mole times, the CPR of the product polyoxyalkylene polyol tends to increase. When the amount is more than 1.7 mole times, the amount of the adsorbent used for removing the acid increases.

After completion of the neutralization reaction, an adsorbent is charged. At that time, it is preferable to add an antioxidant such as t-butylhydroxytoluene (BHT) which is an antioxidant. The antioxidant is used in an amount of 200 to 800 ppm based on the crude polyoxyalkylene polyol. An adsorbent for adsorbing an acid and an alkali component is added to the crude polyoxyalkylene polyol in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight. As the adsorbent, for example, synthetic magnesium silicate, synthetic aluminum silicate, activated clay, and acid clay are used. As the adsorbent, Tomix AD-50
0, Tomix AD-600, Tomix AD-700
(Manufactured by Tomita Pharmaceutical Co., Ltd.), Kyoward 400, Kyoword 500, Kyoword 600, Kyoward 70
0, Kyoward 1000, Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), and the like, which are commercially available under various trade names.

After charging the adsorbent, water and / or organic solvent are distilled off under reduced pressure. Depending on the reaction scale, 1
00 to 140 ° C., 10 mmHgabs. For 3 hours. Thereafter, the polyoxyalkylene polyol is recovered by a filtration operation. At that time, a filter aid such as diatomaceous earth and celite may be used. The acid value in the polyoxyalkylene polyol obtained by such an operation is 0.05 mgKOH / g or less.

Next, the washing process will be described. 50 to 2 parts of water is added to 100 parts by weight of the crude polyoxyalkylene polyol.
1 to 200 parts by weight of an inert hydrocarbon solvent is added to 00 parts by weight and the polyoxyalkylene polyol, and the mixture is stirred and separated. After washing with water, water and the organic solvent are distilled off by reduced pressure treatment. The water used is preferably ion-exchanged water or city water. Water and an organic solvent are added, and the alkali metal in the polyoxyalkylene polyol is extracted into water. Perform stationary liquid separation for 2 to 30 hours, and exchange water. It is preferable to wash with water until the concentration of the alkali metal in the water becomes lower than the detection limit by the ion chromatography method. Wash with water 3 to 5 times, depending on the reaction scale. After washing with water, dehydration by heating and decompression,
The solvent is removed. It is preferable to add the above-mentioned antioxidant before the heat treatment.

The ion exchange treatment will be described. Water is added to 100 parts by weight of crude polyoxyalkylene polyol
After adding 0 to 200 parts by weight and bringing into contact with the ion exchange resin at 15 to 100 ° C. or lower, the ion exchange resin is removed by filtration, and dehydration is performed by reduced pressure treatment. In addition, a method of passing a liquid through an ion exchange tower can also be used. As the ion exchange resin, a cation exchange resin is preferable, and a sulfonated product of a styrene-divinylbenzene copolymer is preferably used. Further, both the gel type and the macroporous type can be used in the present invention. Further, as the properties of the ion exchange resin, both strongly acidic and weakly acidic ones can be used, but strongly acidic ion exchange resins are preferably used. This type of strongly acidic ion exchange resin is Levatit S10
0, S109, SP112, SP120, S1
00LF (manufactured by Bayer AG), Diaion SK1
B, PK208, PK212 (Mitsubishi Chemical), Dowex HCR-S, 50WX1, 50WX2 (Dow Chemical), Amberlite IR120, IR1
22 and 200C (manufactured by Rohm and Haas Co.). It is preferable to use the above-described antioxidant at the time of dehydration.

The CPR after removing the alkali metal from the crude polyoxyalkylene polyol by the method described in detail above is preferably 5 or less. Preferably it is 3 or less, more preferably 1 or less. Most preferably, CPR is zero. CPR is JIS K
It is measured by the method described in 1557. CP
R is a method of indicating the amount of a basic substance present in the polyether, and corresponds to the item of total basicity in ASTM in which the measurement method is the same. If the CPR is more than 5, the concentration of the basic substance in the polyoxyalkylene polyol increases, so that an undesirable side reaction is induced when reacting with the polyisocyanate compound. As far as the present inventors have investigated, when synthesizing a linear prepolymer having a bifunctional polyoxyalkylene polyol and a bifunctional polyisocyanate compound at the isocyanate group end, CPR is 5 or less.
With larger polyoxyalkylene polyols, the amount of free isocyanate groups decreases and the viscosity of the prepolymer increases. That is, since the viscosity of the storage prepolymer gradually increases with time, the CPR of the polyoxyalkylene polyol is preferably 5 or less for the storage stability of the isocyanate group-terminated prepolymer.

The polyisocyanate compound used for producing the isocyanate group-terminated prepolymer is used for producing aromatic, aliphatic, alicyclic and other polyurethanes having two or more isocyanate groups in one molecule. Known ones can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI
-80/20), 65/35 weight ratio (TDI-65 / 3)
5) An isomer mixture, a crude tolylene diisocyanate containing a polyfunctional tar (a polyfunctional tar is a by-product in the production of isocyanate and is a tar-like product containing two or more isocyanate groups in a molecule). The same shall apply hereinafter), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate,
Any mixture of isomers of diphenylmethane diisocyanate, crude diphenylmethane diisocyanate (polymeric MDI) containing tri- or higher polyfunctional tars,
Toluylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, norbornene diisocyanate and carbodiimide modified products of these organic polyisocyanates, buret modified products, or these polyols, monools alone or Prepolymers modified in combination therewith are exemplified. The above polyisocyanate compounds can be used in a mixture at an arbitrary ratio.
Particularly preferably 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 80/20 weight ratio of these organic polyisocyanates (TDI-80 / 2
0), a mixture of isomers in a 65/35 weight ratio (TDI-65 / 35), 4,4'-diphenylmethane diisocyanate and its modified products.

In producing an isocyanate group-terminated prepolymer, an isocyanate index (hereinafter referred to as NCO index), which is a ratio of an equivalent of free isocyanate groups in an organic polyisocyanate compound to an equivalent of active hydrogen groups in a polyoxyalkylene polyol, is used. Abbreviated) is 1.02 to 3.0, preferably 1.08 to 2.0.
5, more preferably 1.1 to 2.0.

Isocyanate group content of the isocyanate group-terminated prepolymer (hereinafter abbreviated as NCO%)
Is 0.2 to 9.0% by weight, preferably 0.3 to 8.0%.
%, More preferably 1.0 to 7.0% by weight. The one-part curable composition is designed to have a low NCO%, and the two-part curable composition is designed to be higher than the one-part curable composition.

The temperature for producing the isocyanate group-terminated prepolymer is preferably from 50 to 120 ° C. Particularly preferably, it is 60 to 105 ° C. At the time of the reaction, it is desirable to carry out the reaction in the presence of an inert gas in order to avoid contact with moisture in the air. Examples of the inert gas include nitrogen, helium, and the like, and nitrogen, which is often used industrially, is preferable. The reaction is carried out while stirring under a nitrogen atmosphere for 2 to 20 hours. A catalyst need not be used, but if used, a catalyst known in the art can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine,
N-ethylmorpholine, dimethylcyclohexylamine, bis [2- (dimethylamino) ethyl] ether,
Triethylenediamine and salts of triethylenediamine, amine salts such as dibutylamine-2-ethylhexoate, and organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, Examples include dibutyltin dilaurate, dibutyltin dichloride, tin 2-ethylhexylate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. These catalysts can be arbitrarily mixed and used. Among these catalysts, organometallic catalysts are particularly preferable, and the amount of the catalyst is 0.0001 to 1.0 part by weight, preferably 0.01 to 0.1 part by weight, per 100 parts by weight of the polyoxyalkylene polyol composition. 8 parts by weight.

Before or after the prepolymer reaction, an organic solvent inert to the polyisocyanate compound or polyoxyalkylene polyol can be used, if necessary. The amount of the organic solvent is at most 40% by weight, preferably at most 20% by weight, based on the total weight of the polyoxyalkylene polyol and the polyisocyanate compound. As such a solvent, aromatic, aliphatic, alicyclic, ketone, ester and ester ether solvents can be used. For example, toluene, xylenes, hexanes, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and the like.

The curable polyurethane composition of the present invention comprises a one-part curable composition which cures by reacting alone with moisture in the air and a two-part curable composition comprising a compound having an active hydrogen group as a curing agent. Can be used for any of the objects.

The one-part curable composition and the two-part curable composition produced by the moisture curing reaction include a curing catalyst,
Fillers, plasticizers, pigments, reinforcing agents, flame retardants, stabilizers and the like are compounded.

The curing catalyst used in the present invention, a filler,
Plasticizers, dyes and pigments, reinforcing agents, flame retardants, stabilizers and the like are listed below. As the curing catalyst, the above-mentioned urethanization catalyst can be used. The amount used is 0.01 to 1. 1 part by weight based on 100 parts by weight of the isocyanate group-terminated prepolymer of the present invention.
0 parts by weight, preferably 0.03 to 0.6 parts by weight.

As the filler, fumed silica, silica, silicic anhydride, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, ferric oxide, hydrogenated castor oil, Zinc stearate and the like can be mentioned, and the addition amount is 10 to 60% by weight, preferably 10 to 50% by weight based on the isocyanate group-terminated prepolymer used in the present invention.

As the plasticizer, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, butyl benzyl phthalate, butyl phthalyl butyl glycolate,
Dioctyl sebacate, tricresyl phosphate, tributyl phosphate, chlorinated paraffin, petroleum ether, and the like can be used in an amount of 5 to 40 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of a curing agent for an isocyanate group-terminated prepolymer. １５15 parts by weight.

Examples of the reinforcing agent include carbon black as a black filler, white carbon and silica as a white filler, kaolin, bentonite, silica silicate, barite, gypsum, bone powder, and dolomite as silicates. It is 1 to 50% by weight, preferably 2 to 30% by weight, based on 100 parts by weight of the curing agent of the isocyanate group-terminated prepolymer.

As the flame retardant, tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (2,2-chloroethyl) phosphate, hexabromocyclododecane, manufactured by Daihachi Chemical Co., Ltd. CR-505 and CR-507, Phosaga manufactured by Monsanto Chemical Co., Ltd.
rd 2XC-20 and C-22-R, Fyrol-16 manufactured by Stoffer Chemical Co., Ltd., and the like, and the amount thereof is 0.1 to 30 parts by weight, preferably 100 parts by weight of the curing agent of the isocyanate group-terminated prepolymer. Is 0.2-20
Parts by weight.

Examples of the stabilizer include an antioxidant, an ultraviolet absorber and a heat stabilizer. The antioxidant is not particularly limited. For example, butylhydroxyanisole, t-
Butylhydroxytoluene, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5,5)
Undecane, distearylthiodipropionate and the like can be mentioned. Examples of the ultraviolet absorber include pt-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like. As a heat stabilizer, Tris (2,
4-di-t-butylphenyl) phosphite, triphenyl phosphite, trilauryl phosphite and the like. The amount of these additives is 200 to 8 parts per 100 parts by weight of the curing agent for the isocyanate group-terminated prepolymer.
00 ppm is preferred. In the present invention, if necessary, a pigment,
The above-mentioned organic solvents, moisture removing agents, and the like can be used.

As a two-part curing type curing agent, at least one of a polyoxyalkylene polyol and a polyamine compound is used. The polyoxyalkylene polyol is preferably a polyoxyalkylene polyol produced by the method described in the present application. But,
The polyoxyalkylene polyol produced by the above-mentioned conventional method can also be used. The average number of functional groups of the polyoxyalkylene polyol used as a curing agent is 2 to 8
It is. Particularly preferred are 2 and 3 polyoxyalkylene polyols. Glycols which do not undergo addition polymerization of alkylene oxide can also be used. For example, it includes linear methylene glycol such as ethylene glycol, 1,4-butanediol and propylene glycol, cyclohexylene such as cyclohexanediol, a spiro ring and a methylene chain. Those containing a bond and derivatives containing various substituents can be used.

As the polyamine compound, diphenylmethanediamine, m-phenylenediamine, 3,3 ′
Aromatic diamines such as -dichloro-4,4'-diaminodiphenylmethane; aliphatic such as isophorone diamine and norbornene diamine; alicyclic diamines; linear aliphatic diamines; alkyl dihydrazides such as carbodihydrazide and adipic dihydrazide; Conventionally known polyamine compounds such as derivatives can be used.

[0044]

EXAMPLES Examples of the present invention will be shown below to clarify aspects of the present invention, but the present invention is not limited to these examples.

A 50% by weight aqueous solution of cesium hydroxide from Kemetal was used as a polymerization catalyst for alkylene oxide. The product has a cesium purity of 99.95% by weight and a rubidium purity of 0.05% by weight. Hereafter, "cesium hydroxide"
Abbreviated. As potassium hydroxide (manufactured by Nippon Soda Co., Ltd.), potassium hydroxide having a purity of 96.0% by weight was used. In use, ion-exchanged water was used as a diluent in the form of a 50% by weight aqueous solution. Hereinafter, it is abbreviated as “potassium hydroxide”.

The hydroxyl value, total unsaturation and CPR of the polyoxyalkylene polyol are in accordance with JIS K 1557.
It was determined by the method described.

Example 1 Polyoxyalkylene polyol A 0.18 mol of “cesium hydroxide” was added to 1 mol of propylene glycol, and the mixture was heated at 85 ° C. and 10 mmHgab.
s. Hereinafter, dehydration under reduced pressure was performed for 3 hours. 10mmHg
abs. At a reaction temperature of 82 to 93 ° C. from a reduced pressure of 3.5 kgf / cm ² G (444 kP
Under the conditions of a), addition polymerization of propylene oxide was performed until the hydroxyl value became 18.5 mgKOH / g. When the internal pressure of the autoclave was no longer changed, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. 35 parts by weight of ion-exchanged water with respect to 100 parts by weight of the crude polyoxyalkylene polyol containing the catalyst and 1 part by weight of the total base component concentration in the crude polyoxyalkylene polyol.
Four mole times phosphoric acid was charged in the form of a 75.1% by weight aqueous solution, and a neutralization reaction was performed at 90 ° C. for 2 hours. After the neutralization reaction, 600 ppm of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the crude polyoxyalkylene polyol. Next, the adsorbent KW-
700 (manufactured by Kyowa Chemical Industry Co., Ltd.) at 5000 ppm, A
3000 ppm of D-600NS (manufactured by Tomita Pharmaceutical Co., Ltd.)
In addition, while dehydrating under reduced pressure, finally 105 ° C., 10m
mHgabs. The following operation was performed for 4 hours. After the pressure was reduced from nitrogen to atmospheric pressure with nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol (acid neutralization removal method). The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 18.6 mgKOH
/ G, the total degree of unsaturation (C = C) is 0.053 meq. /
g and CPR were 0.9.

Example 2 Polyoxyalkylene polyol B 0.22 mol of “cesium hydroxide” was added to 1 mol of glycerin, and the mixture was added at 105 ° C. and 10 mmHgabs. Less than,
Dehydration under reduced pressure was performed for 3 hours. 10 mmHgabs. The addition polymerization of propylene oxide was carried out at a reaction temperature of 81 to 92 ° C. under the conditions of a maximum pressure of 3.8 kgf / cm ² G (473 kPa) from the reduced pressure state until the hydroxyl value became 17.4 mgKOH / g. . When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. Levatit S manufactured by Bayer, which was exchanged with a dilute hydrochloric acid aqueous solution to hydrogen ion type with respect to 100 parts by weight of a crude polyoxyalkylene polyol containing a catalyst
30 parts by weight of -100BG and 80 parts by weight of ion-exchanged water were added, and the mixture was stirred at 60 ° C. for 6 hours under a nitrogen atmosphere. Next, filtration was performed under reduced pressure using 5B filter paper (retained particle size: 3 μm) manufactured by Advantech Toyo Co., Ltd. to remove the ion-exchange resin. 50 parts by weight, hydrogen ion type was replaced by Bayer's Levatit S
20 parts by weight of -100BG were added, and the above-described operation was performed. The ion exchange resin was removed by filtration, and 500 ppm of BHT was added to 100 parts by weight of the polyoxyalkylene polyol containing water. 105 ° C, 10mmH
gabs. Dehydration under reduced pressure was performed for 3 hours under the following conditions to distill off water in the polyoxyalkylene polyol. Further, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. (ion exchange treatment method). The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 17.7 mgKOH / g, and the total degree of unsaturation (C = C) is 0.054 meq. / G, CPR was 1.7.

Example 3 Polyoxyalkylene polyol C 0.36 mol of “potassium hydroxide” was added to 1 mol of propylene glycol, and the mixture was heated at 85 ° C. and 10 mmHgab.
s. Hereinafter, dehydration under reduced pressure was performed for 3 hours. 10mmHg
abs. At a reaction temperature of 78 to 83 ° C. from a reduced pressure of 3.8 kgf / cm ² G (473 kP
Under the conditions of a), addition polymerization of propylene oxide was carried out until the hydroxyl value reached 28.0 mgKOH / g. When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. 100 parts by weight of ion-exchanged water and 50 parts by weight of n-hexane (special grade of reagent, Wako Pure Chemical Industries, Ltd.) are added to 100 parts by weight of the crude polyoxyalkylene polyol containing a catalyst, and the mixture is added at 25 ° C. for 2 hours. The mixture was stirred, allowed to stand for 10 hours, and separated. Thereafter, the aqueous phase was removed, and 10 parts by weight based on 100 parts by weight of the crude polyoxyalkylene polyol further charged.
0 parts by weight of ion-exchanged water was added, and the above operation was repeated twice. After removing the aqueous phase, these extractants were distilled off under reduced pressure from the polyoxyalkylene polyol in which n-hexane and a part of water were dissolved. The condition at this time is 105 ° C.
10 mmHgabs. It was 3 hours below. After the decompression treatment, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. (water washing method). The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 28.3 mgKOH / g, and the total unsaturation (C
= C) is 0.045 meq. / G, CPR was 0.2.

Comparative Example 1 Polyoxyalkylene polyol D 0.22 mol of “cesium hydroxide” was added to 1 mol of glycerin, and the mixture was added at 105 ° C. and 10 mmHgabs. Less than,
Dehydration under reduced pressure was performed for 3 hours. 10 mmHgabs. The addition polymerization of propylene oxide was carried out at a reaction temperature of 81 to 92 ° C. under the conditions of a maximum pressure of 3.8 kgf / cm ² G (473 kPa) from the reduced pressure state until the hydroxyl value became 17.4 mgKOH / g. . When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. KW-700SN as an alkali adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.) based on 100 parts by weight of a crude polyoxyalkylene polyol containing a catalyst
Was added at 5000 ppm, and an adsorption treatment was performed at 80 ° C. for 4 hours. Vacuum filtration was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol. The polyoxyalkylene polyol after purification treatment has a hydroxyl value (OHV) of 17.8.
mgKOH / g, total unsaturation (C = C) 0.054m
eq. / G, CPR was 22.0.

Comparative Example 2 Polyoxyalkylene polyol E 0.36 mol of “potassium hydroxide” was added to 1 mol of propylene glycol, and the mixture was heated at 85 ° C. and 10 mmHgab.
s. Hereinafter, dehydration under reduced pressure was performed for 3 hours. 10mmHg
abs. At a reaction temperature of 77 to 82 ° C. from a reduced pressure of 3.8 kgf / cm ² G (473 kP
Under the conditions of a), addition polymerization of propylene oxide was carried out until the hydroxyl value reached 28.0 mgKOH / g. When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. 6000 ppm of KW-700SN (manufactured by Kyowa Chemical Industry Co., Ltd.) as an alkali adsorbent was added to 100 parts by weight of the crude polyoxyalkylene polyol containing a catalyst, and the mixture was subjected to an adsorption treatment at 80 ° C. for 5 hours. The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 28.2 mgKOH
/ G, the total degree of unsaturation (C = C) is 0.046 meq. /
g and CPR were 12.5.

Comparative Example 3 Polyoxyalkylene polyol F 0.18 mol of “cesium hydroxide” was added to 1 mol of propylene glycol, and the mixture was heated at 85 ° C. and 10 mmHgab.
s. Hereinafter, dehydration under reduced pressure was performed for 3 hours. 10mmHg
abs. At a reaction temperature of 110 to 115 ° C. from the reduced pressure state of
The maximum pressure during the reaction is 5.5 kgf / cm ² G (640 kF
Under the conditions of Pa), addition polymerization of propylene oxide was performed until the hydroxyl value reached 18.0 mgKOH / g. When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. 20 parts by weight of ion-exchanged water based on 100 parts by weight of the crude polyoxyalkylene polyol containing the catalyst, and 1 part by weight of the total base component concentration in the crude polyoxyalkylene polyol.
Oxalic acid (used in the form of a 1/10 normal oxalic acid aqueous solution; manufactured by Wako Pure Chemical Industries, Ltd.) was added at a molar ratio of 00, and 80
A neutralization reaction was performed at 2 ° C. for 2 hours. After completion of the neutralization reaction, t
-Butylhydroxytoluene (BHT) was added to a crude polyoxyalkylene polyol in an amount of 600 p
pm, and 2000 ppm of KW-700 (manufactured by Kyowa Chemical Industry Co., Ltd.) as an adsorbent and KW-500N
S (manufactured by Kyowa Chemical Industry Co., Ltd.) at 1000 ppm and finally 105 ° C., 10 mmHga while dehydrating under reduced pressure.
bs. The following operation was performed for 4 hours. After the pressure was reduced from nitrogen to atmospheric pressure with nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol (acid neutralization removal method). The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 18.2 mgKOH / g, and the total degree of unsaturation (C = C) is 0.110 meq. / G, CPR
Was 2.2.

Comparative Example 4 Polyoxyalkylene polyol G 0.22 mol of "cesium hydroxide" was added to 1 mol of glycerin, and the mixture was added at 105 ° C. and 10 mmHgabs. Less than,
Dehydration under reduced pressure was performed for 3 hours. 10 mmHgabs. The addition polymerization of propylene oxide was carried out at a reaction temperature of 110 to 115 ° C. under a condition of a maximum pressure of 5.4 kgf / cm ² G (630 kPa) from the reduced pressure state until the hydroxyl value became 17.4 mgKOH / g. . When the internal pressure of the autoclave stopped changing, unreacted propylene oxide was recovered under reduced pressure to obtain a crude polyoxyalkylene polyol. 30 parts by weight of ion-exchanged water with respect to 100 parts by weight of the crude polyoxyalkylene polyol containing a catalyst and oxalic acid (1/1) which is 1.02 mole times the concentration of all base components in the crude polyoxyalkylene polyol. It was used in the form of a 10 N aqueous oxalic acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) and neutralized at 90 ° C. for 2 hours. After the neutralization reaction, 600 ppm of t-butylhydroxytoluene (BHT) was added to 100 parts by weight of the crude polyoxyalkylene polyol, and then 5500 ppm of KW-700 (Kyowa Chemical Industry Co., Ltd.) as an adsorbent was added. , KW-500SN (manufactured by Kyowa Chemical Industry Co., Ltd.), and finally 105 ° C., 10 mmHgabs. The operation for 3 hours was performed as follows. After the pressure was reduced from nitrogen to atmospheric pressure with nitrogen, filtration under reduced pressure was performed using 5C filter paper (retained particle size: 1 μm) manufactured by Advantech Toyo Co., Ltd. to purify the polyoxyalkylene polyol (acid neutralization removal method).
The hydroxyl value (OHV) of the polyoxyalkylene polyol after the purification treatment is 17.9 mgKOH / g, and the total degree of unsaturation (C = C) is 0.091 meq. / G, CPR is 1.5
Met.

The hydroxyl value, total unsaturation and CP of the polyoxyalkylene polyols obtained in Examples and Comparative Examples
R is collectively shown in Table 1. As an alkylene oxide polymerization catalyst, CsOH uses “cesium hydroxide” and KOH
Stands for “potassium hydroxide”.

[0055]

[Table 1] Hydroxyl value, total unsaturation and CPR are JIS K1
It was measured according to 557.

Next, isocyanate group-terminated prepolymers were synthesized using the polyoxyalkylene polyols obtained in Examples and Comparative Examples, and then one-part and two-part curable polyurethanes were prepared. The measurement of the isocyanate group content (NCO%) and the viscosity in the isocyanate group-terminated prepolymer was based on JIS K7301. The measurement of physical properties of the curable polyurethane was based on JIS K6301. Unless otherwise specified, the used parts of the raw materials shown in the examples are parts by weight.

Example 4 To polyoxyalkylene polyol A (368.2 parts) and polyoxyalkylene polyol B (561.1 parts), 52.7 parts of TDI-80 / 20 (manufactured by Mitsui Toatsu Chemicals, Inc.) as a polyisocyanate compound was added. The mixture was stirred under a nitrogen atmosphere at 100 ° C. for 6 hours to obtain an isocyanate group-terminated prepolymer. To 100 parts of the obtained isocyanate group-terminated prepolymer, 45 parts of dioctyl phthalate (manufactured by Kyowa Hakko Co., Ltd.), 55 parts of calcium carbonate, and 8 parts of titanium oxide were added, uniformly dispersed by a kneader, and mixed with a one-pack type sealing raw material. did. The obtained one-pack type sealing raw material was evenly spread in a Teflon-coated 2 mm thick mold, and
The composition was cured for 7 days at 55 ° C. and a relative humidity of 55%. Furthermore,
After being placed in an oven heated to 50 ° C. for 7 days to cure, it was used as a sample for measuring physical properties. 50% of the cured product obtained
Tensile stress at elongation 3.5 kg / cm ^2, tensile strength at break 21.4 kg / cm ^2, elongation at break 600%
Met. There was no pinhole in the appearance of the cured product.

Example 5 56.2 parts of TDI-80 / 20 (manufactured by Mitsui Toatsu Chemicals, Inc.) as a polyisocyanate compound was added to 943.8 parts of polyoxyalkylene polyol B at 100 ° C. in a nitrogen atmosphere. After stirring for 6 hours, an isocyanate group-terminated prepolymer was obtained, which was used as a two-component sealing base. N
The CO% is 1.36% by weight and the viscosity is 33,000 cps /
25 ° C. The curing agent was 287.4 parts of polyoxyalkylene polyol B, 120.7 parts of dioctyl phthalate (manufactured by Kyowa Hakko Co., Ltd.), and 554.
6 parts, 31.6 parts of titanium oxide, 5.7 parts of lead octylate (lead content: 25 wt%, manufactured by Active Materials Chemical Co., Ltd.)
What was uniformly dispersed by the kneader was used. The obtained two-pack type sealing raw material was used as a base material: curing agent = 100: 313.
, And uniformly spread in a Teflon-coated 2 mm thick mold and cured for 7 days at 22 ° C. and 55% relative humidity to obtain a sample for measuring physical properties. There was no pinhole in the appearance of the cured product. Tensile stress at 50% elongation of the resulting cured product 3.1 kg / cm ^2, tensile strength at break 21.2 kg / cm ^2, elongation at break 1
100%. Further, in order to examine the storage stability of the main agent, the above isocyanate group-terminated prepolymer was sealed in a metal can under a nitrogen atmosphere, and a heating acceleration test was conducted at 60 ° C. for 14 days. As a result, the NCO% was 1.31% by weight, the viscosity was 35,000 cps / 25 ° C., the tensile stress at 50% elongation of the cured product was 2.9 kg / cm ² , and the tensile strength at break was 2
0.5 kg / cm ² , the elongation at break was 1030%, and no significant change was observed.

Example 6 To 271.5 parts of polyoxyalkylene polyol B and 478.3 parts of polyoxyalkylene polyol C were added 250.2 parts of Cosmonate PH (manufactured by Mitsui Toatsu Chemicals, Inc.) as a polyisocyanate compound. The mixture was stirred at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain an isocyanate group-terminated prepolymer. The NCO% was 7.00% by weight, and the viscosity was 6,000 cps / 25 ° C. To 100 parts of the obtained isocyanate group-terminated prepolymer, 7.1 parts of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) is added, mixed uniformly, and uniformly mixed with a Teflon-coated 2 mm thick mold. After being extended and cured at 100 ° C. for one day, it was used as a sample for measuring physical properties. The hardness of the obtained cured product is 55 for Shore A,
The tensile stress at 100% elongation is 20 kg / cm ² , the tensile strength at break is 160 kg / cm ² , and the elongation at break is 20
0%, and there was no pinhole in the appearance of the cured product.
Further, in order to examine the storage stability of the isocyanate group-terminated prepolymer, the above prepolymer was sealed in a metal can under a nitrogen atmosphere, and a heating acceleration test was conducted at 60 ° C. for 14 days. The result was NCO% 6.95% by weight, viscosity 6,300
cps / 25 ° C., the hardness of the cured product is 55, 1
The tensile stress at 00% elongation is 19 kg / cm ² , the tensile strength at break is 157 kg / cm ² , and the elongation at break is 190
% Did not change significantly.

The following is a comparative example. Comparative Example 5 TDI-80 / 20 (manufactured by Mitsui Toatsu Chemicals, Inc.) (52.7 parts) was added as an isocyanate compound to 368.2 parts of polyoxyalkylene polyol F and 561.1 parts of polyoxyalkylene polyol G, and nitrogen was added. Under the atmosphere,
The mixture was stirred at 100 ° C. for 6 hours to obtain an isocyanate group-terminated prepolymer. Dioctyl phthalate (Kyowa Hakko Co., Ltd.) was added to 100 parts of the obtained isocyanate group-terminated prepolymer.
45 parts), 55 parts of calcium carbonate, and 8 parts of titanium oxide were added and uniformly dispersed by a kneader to obtain a one-pack type sealing raw material. The obtained one-pack type sealing raw material was uniformly spread in a Teflon-coated 2 mm-thick mold and cured at 22 ° C. and a relative humidity of 55% for 7 days. In addition, 50 ° C
The sample was placed in a heated oven for 7 days, cured, and used as a sample for measuring physical properties. The tensile strength at 50% elongation of the obtained cured product was 3.0 kg / cm ² , and the tensile strength at break was 1
3.1 kg / cm ² , elongation at break was 500%. There was no pinhole in the appearance of the cured product.

Comparative Example 6 To 943.8 parts of polyoxyalkylene polyol D was added 56.2 parts of TDI-80 / 20 (manufactured by Mitsui Toatsu Chemicals, Inc.) as a polyisocyanate compound, and the mixture was heated at 100 ° C. under a nitrogen atmosphere. After stirring for 6 hours, an isocyanate group-terminated prepolymer was obtained, which was used as a main component for two-pack sealing. NC
O% is 1.37% by weight, viscosity is 33,500 cps / 2
5 ° C. The curing agent was 287.4 parts of polyoxyalkylene polyol D, 120.7 parts of dioctyl phthalate (manufactured by Kyowa Hakko Co., Ltd.), 554.6 parts of calcium carbonate.
Parts, titanium oxide 31.6 parts, lead octylate (lead content 2
5.7 parts (5 wt%, manufactured by Active Materials Chemical Co., Ltd.) was added, and the mixture was uniformly dispersed by a kneader. The obtained two-pack type sealing raw material was uniformly mixed at a weight ratio of main agent: curing agent = 100: 313, uniformly spread in a Teflon-coated 2 mm thick mold, and dried at 22 ° C. and a relative humidity of 55% under the conditions of 7%. After curing for days, it was used as a sample for measuring physical properties. The tensile stress at 50% elongation of the obtained cured product is 3.1 kg / cm.
^2. The tensile strength at break was 20.9 kg / cm ² , the elongation at break was 1120%, and there was no pinhole in the appearance of the cured product. Also, to investigate the storage stability of the main ingredient,
The prepolymer was sealed in a metal can under a nitrogen atmosphere, and a heating acceleration test was performed at 60 ° C. for 14 days. Result is,
NCO% 1.09% by weight, viscosity 68,000 cps / 2
At 5 ° C., the cured product using the prepolymer had a tensile stress at 50% elongation of 1.5 kg / cm ² , a tensile strength at break of 9.5 kg / cm ² , and an elongation at break of 800%. ,
A decrease in the NCO%, an increase in the viscosity of the prepolymer, and a decrease in the physical properties of the curable polyurethane were observed.

Comparative Example 7 TDI-80 / 20 (manufactured by Mitsui Toatsu Chemicals, Inc.) (56.2 parts) was added as an isocyanate compound to 943.8 parts of polyoxyalkylene polyol G, and the mixture was heated at 100 ° C. under a nitrogen atmosphere. The mixture was stirred for 6 hours to obtain an isocyanate group-terminated prepolymer, which was used as a two-component sealing base. NC
O% is 1.35% by weight, viscosity is 34,000 cps / 2
5 ° C. The curing agent was 287.4 parts of polyoxyalkylene polyol G, 120.7 parts of dioctyl phthalate (manufactured by Kyowa Hakko Co., Ltd.), 554.6 calcium carbonate.
Parts, titanium oxide 31.6 parts, lead octylate (lead content 2
5.7 parts (5 wt%, manufactured by Active Materials Chemical Co., Ltd.) was added, and the mixture was uniformly dispersed by a kneader. The obtained two-pack type sealing raw material was uniformly mixed in a weight ratio of main agent: curing agent = 100: 313, uniformly spread in a Teflon-coated 2 mm-thick die, and dried under a condition of 22 ° C. and a relative humidity of 55%. After curing for days, it was used as a sample for measuring physical properties. There was no pinhole in the appearance of the cured product. 5 of the obtained cured product
0% elongation at a tensile stress 2.5 kg / cm ^2, tensile strength at break 16.1 kg / cm ^2, elongation at break 91
It was 0%. Also, to investigate the storage stability of the main ingredient,
The above isocyanate group-terminated prepolymer was sealed in a metal can under a nitrogen atmosphere, and a heating acceleration test was conducted at 60 ° C. for 14 days. The result was 1.30% by weight of NCO%, viscosity of 3
The tensile stress at 6,000 cps / 25 ° C., 50% elongation of the cured product is 2.3 kg / cm ² , and the tensile strength at break is 1
5.2 kg / cm ² , elongation at break was 880%.

Comparative Example 8 To 271.5 parts of polyoxyalkylene polyol D and 478.3 parts of polyoxyalkylene polyol E, 250.2 parts of Cosmonate PH (manufactured by Mitsui Toatsu Chemicals, Inc.) was added as a polyisocyanate compound. The mixture was stirred at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain an isocyanate group-terminated prepolymer. The NCO% was 6.96% by weight, and the viscosity was 6,100 cps / 25 ° C. To 100 parts of the obtained isocyanate group-terminated prepolymer, 7.1 parts of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) is added, mixed uniformly, and uniformly mixed with a Teflon-coated 2 mm thick mold. After being extended and cured at 100 ° C. for one day, it was used as a sample for measuring physical properties. The hardness of the obtained cured product is 55 for Shore A,
The tensile stress at 100% elongation is 19 kg / cm ² , the tensile strength at break is 163 kg / cm ² , and the elongation at break is 20
0%, and there was no pinhole in the appearance of the cured product.
In order to examine the storage stability of the prepolymer, the prepolymer was sealed in a metal can under a nitrogen atmosphere.
A heating acceleration test was conducted at 14 ° C. for 14 days. The result is NCO%
5.64% by weight, viscosity 11,500 cps / 25 ° C., hardness of the cured product using the prepolymer is 48 at Shore A, and tensile stress at 100% elongation is 12 kg / cm ² ,
The tensile strength at break was 80 kg / cm ² , and the elongation at break was 110%, indicating a decrease in NCO%, an increase in viscosity of the prepolymer, and a decrease in physical properties of the curable polyurethane.

The results of the one-pack type curable polyurethane using the polyoxyalkylene polyol obtained in Examples 1 and 2 are shown in Example 4, and the results of Comparative Examples 3 and 4 are also shown in Comparative Example 5 as in Comparative Examples. . The results are summarized in Table 2.

[0065]

[Table 2]

When the examples and comparative examples are compared, the O
It can be seen that the one-component curable polyurethane using a polyoxyalkylene polyol satisfying the range of HV and C = C is excellent in tensile stress, strength and elongation.

The physical properties of the two-part curable polyurethane were compared using the polyoxyalkylene polyol of the present invention. Those using the polyoxyalkylene polyols of Example 2 are in Example 5, and those using the polyoxyalkylene polyols of Comparative Examples 1 and 4 are Comparative Examples 6 and 7, respectively.
It was shown to.

[0068]

[Table 3]

From the results shown in Table 3, the isocyanate group-terminated prepolymer obtained by using the polyoxyalkylene polyol having a low CPR obtained in the present invention has a high isocyanate group content and viscosity after 14 days at 60 ° C. It can be seen that there was little change in the physical properties of the curable polyurethane (Example 5 and Comparative Example 6). In addition, by comparing Example 5 with Comparative Example 7, it is understood that the curable polyurethane using the polyoxyalkylene polyol obtained in the present invention has excellent mechanical properties.

The properties of the glycol-cured polyurethane obtained using the polyoxyalkylene polyols obtained in Examples 2 and 3 were compared with those in Example 6, and the properties using the polyoxyalkylene polyols obtained in Comparative Examples 1 and 2 were compared. Example 8 is shown.

[0071]

[Table 4]

The isocyanate group-terminated prepolymer using the polyoxyalkylene polyol having a low CPR of the present invention and the curable polyurethane cured with 1,4-butanediol have little change in physical properties after standing at 60 ° C. for 14 days, and have storage stability. It turns out that it is excellent.

[0073]

As described in detail above, it is possible to produce a curable polyurethane having excellent storage stability and mechanical properties by using an isocyanate group-terminated prepolymer with a polyisocyanate compound using the polyoxyalkylene polyol of the present invention. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 65/30 C08G 65/30 (72) Inventor Saku Izukawa 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemicals Inside the corporation

Claims (6)

[Claims] 1. The polyoxyalkylene polyol has a hydroxyl value (hereinafter abbreviated as OHV, unit mgKOH / g) and a total degree of unsaturation (hereinafter abbreviated as C = C, unit meq./g) satisfying the following conditions. An isocyanate group-terminated prepolymer characterized by reacting a polyisocyanate compound with a polyoxyalkylene polyol having a CPR of 5 or less representing the amount of a basic substance in the polyoxyalkylene polyol. OHV 10
３５35 mgKOH / g, C = C 0.03-0.1 m
eq. A region excluding the range of the following formulas a and b from the range of / g is satisfied. a formula C = C> 4.59 × OHV ^-1.34 +0.002 (however, OHV is in the range of 17.6 to 35.0 mgKOH / g) b formula C = C <1.59 × OHV ^-1.20 (however, OHV Is in the range of 10.0 to 21.7 mgKOH / g) 2. 0.05 mole per mole of active hydrogen compound
The reaction temperature is 60 ° C. to 98 ° C., and the maximum pressure during the reaction is 4 kgf / cm.
^{2. The} process for producing an isocyanate group-terminated prepolymer according to claim 1, wherein a polyoxyalkylene polyol obtained by addition polymerization of an alkylene oxide at ² G (493 kPa) or less is used. 3. The polyoxyalkylene polyol produced using at least one compound selected from potassium, rubidium and cesium as an alkali metal catalyst during the alkylene oxide addition polymerization. A method for producing an isocyanate-terminated prepolymer. 4. A polyoxyalkylene polyol having a CPR of 5 or less obtained by performing an operation of removing an alkali metal in a crude polyoxyalkylene polyol after addition polymerization of an alkylene oxide by any one of the methods a to d. The method for producing an isocyanate group-terminated prepolymer according to claim 2, which is used. a. After adding 5 to 40 parts by weight of water with respect to 100 parts by weight of the crude polyoxyalkylene polyol, the inorganic acid or the organic acid is 0.7 to 1.7 mole times the alkali metal in the crude polyoxyalkylene polyol. Use 50 ~
Neutralize alkali metals at 130 ° C. Thereafter, a reduced pressure treatment is performed using 0.01 to 1.0 part by weight of the adsorbent with respect to 100 parts by weight of the crude polyoxyalkylene polyol, water is distilled off, and the alkali metal salt and the adsorbent are removed by a filtration operation. (Acid neutralization removal method). b. 100 parts by weight of the crude polyoxyalkylene polyol, 5 to 40 parts by weight of an inert organic solvent and water are added to the polyoxyalkylene polyol, and then an inorganic acid or an organic acid is added to the alkali metal in the crude polyoxyalkylene polyol. 0.7 to 1.7 times the molar amount of 5
Neutralize alkali metals at 0-130 ° C. Thereafter, a reduced pressure treatment is performed using 0.01 to 1.0 part by weight of an adsorbent with respect to 100 parts by weight of the crude polyoxyalkylene polyol, water and an organic solvent are distilled off, and an alkali metal salt and an adsorbent are removed by a filtration operation. (Acid neutralization removal method). c. To 100 parts by weight of the crude polyoxyalkylene polyol, 50 to 200 parts by weight of water and 1 to 200 parts by weight of a hydrocarbon solvent inert to the polyoxyalkylene polyol are added, and the mixture is separated. Is distilled off (water washing method). d. 20 to 200 parts by weight of water is added to 100 parts by weight of the crude polyoxyalkylene polyol, and the mixture is brought into contact with the ion-exchange resin at 15 to 100 ° C., then the ion-exchange resin is removed by filtration, and dehydration is performed by a reduced pressure treatment (ion exchange treatment method). ). 5. A curable polyurethane composition obtained by a moisture curing reaction of the isocyanate group-terminated prepolymer according to claim 1 or a reaction with a curing agent. 6. The curable polyurethane composition according to claim 5, wherein the curing agent comprises a polyoxyalkylene polyol and / or a polyamine compound.