JP2000264947A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition which gives cured products having low moisture permeability, has a good inner curing property, even when a hydrophobic polymer having excellent moisture resistance, weather resistance and heat resistance is used, and may be a one pack type curable composition, by mixing a polyurethane prepolymer with an alkali(ne earth) metal hydroxide. SOLUTION: This curable composition comprises (A) a polyurethane prepolymer which has a number-average mol.wt. of 1,000-10,000, preferably 2,000-50,000, and gives cured products having a moisture permeability of 1-100 g/m2/24 hr, preferably 1-50 g/m2/24 hr, (preferably a polyurethane prepolymer consisting mainly of isobutylene units or hydrogenated conjugated diene units and having 1.3-9 NCO groups per molecule on the average), (B) one or more alkali(ne earth) metal hydroxides (for example, calcium hydroxide) preferably in an amount of 10-300 pts.wt. per 100 pts.wt. of the component A, and if necessary, furthermore (C) a curable catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable composition which can be used for a sealing material or an adhesive.
The present invention relates to a curable composition having excellent internal curability, moisture resistance, weather resistance, and heat resistance.

[0002]

2. Description of the Related Art A polymer having an isocyanate group at a terminal of a polyether polymer is easily moisture-cured by atmospheric moisture. Further, it is known that the polymer itself has excellent internal curability due to its high moisture permeability, and is used as a sealing agent and the like. However, this polymer has problems in terms of storage stability and in that cracks are easily generated in the cured product. In order to solve this problem, JP-A-5-295064 discloses that a prepolymer having at least two terminal isocyanate groups, a monoisocyanate compound as an essential component, and a mixture of calcium hydroxide, which has storage stability. It has been proposed for the purpose of being good and capable of suppressing the occurrence of cracks in the cured product. In this composition, since a monoisocyanate compound having a relatively low boiling point is used, it is not preferable in terms of safety and health of an operator who handles the curable composition.

Further, a sealing material using this polyether polymer has good moisture permeability, however, it is insufficient in moisture resistance, and insufficient in weather resistance and heat resistance. JP-A-1-163255 and JP-A-1-170 describe curable compositions having excellent heat resistance, weather resistance and water resistance.
JP-A-604 and JP-A-1-170658 describe a curable composition comprising a saturated hydrocarbon-based polymer having a hydrolyzable silyl group and a hydrogenated polydiene-based polymer. These polymers and curable compositions have low moisture permeability of the polymer and are excellent in moisture resistance and water resistance, and therefore have low permeability to atmospheric moisture. Therefore, the surface is easily cured by the permeation of atmospheric moisture, but the interior is insufficiently cured. Therefore, in order to sufficiently perform internal curing, water is added to the curable composition at the time of use, or a curing catalyst is separated from the cross-linkable curable polymer and water at the time of use, and a method of adding the curing catalyst at the time of use is employed. Conventionally, it has been difficult to prepare a one-pack type curable composition with a hydrophobic polymer having low moisture permeability.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a cured product which has a low moisture permeability and uses a hydrophobic polymer which is excellent in moisture resistance, weather resistance and heat resistance. It is an object of the present invention to provide a curable composition which has a good composition and can be formed into a one-pack type.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, when a hydroxide such as an alkali metal is mixed with a specific polyurethane prepolymer having low moisture permeability, the prepolymer It has been found that the internal curability of the cured product is improved despite the fact that the material itself is hydrophobic, and the present invention has been completed.

That is, a first aspect of the present invention is a curable composition containing the following components (A) and (B). (A) a number average molecular weight of 1,000 to 100,000;
Polyurethane prepolymer moisture permeability of the cured product is 1~100g / m ² / 24h. (B) One or more hydroxides of alkali metals or alkaline earth metals.

A second aspect of the present invention is that the component (A) is a prepolymer mainly composed of an isobutylene unit or a hydrogenated conjugated diene unit, and has an average of 1.3 to 3 NCO groups per molecule.
The curable composition according to the first aspect of the present invention, which is a prepolymer having 9 pieces. A third aspect of the invention is the curable composition according to the first or second aspect of the invention, wherein the component (A) is mainly composed of a hydrogenated conjugated diene unit, and the hydrogenated conjugated diene unit contains a hydrogenated cyclohexadiene unit. It is.

A fourth aspect of the present invention is the curable composition according to any one of the first to third aspects of the present invention, wherein the component (B) is calcium hydroxide. A fifth aspect of the invention is the first aspect of the invention, wherein the component (B) is 10 to 300 parts by weight with respect to 100 parts by weight of the component (A).
5. The curable composition according to any one of items 1 to 4. The sixth aspect of the invention is as follows.
(C) The curable composition according to any one of the first to fifth aspects of the invention, further comprising a curing catalyst as a component.

Hereinafter, the present invention will be described in detail. The curable composition of the present invention, as the component (A), the number-average molecular weight of 1,000 to 100,000, requires that moisture permeability of the cured product contains a polyurethane prepolymer is 1~100g / m ² / 24h . The component (A) has a number average molecular weight of 1,000 to 100,000. When the number average molecular weight is 1,000 or less, it is difficult to obtain a good cured product, and when the number average molecular weight is 100,000 or more, the viscosity is high and it is difficult to handle. Preferably it is 2000-50000. More preferably, it is 3000 to 30,000.

Further, (A) component, the moisture permeability when the formation of the cured product is of 1~100g / m ² / 24h,
It is significantly lower than prepolymers conventionally used for sealing agents. The moisture permeability of the cured product is 100g
/ Moisture resistance of the m ² / 24h or less value, if the cured product obtained from the composition is sufficient. In addition, moisture permeability of 1g / m ^2/2
If it is 4 hours or more, the internal curing of the cured product proceeds promptly, and a satisfactory cured product with sufficient curing can be obtained. Preferably the moisture permeability is 1~50g / m ² / 24h, more preferably 2~30g / m ² / 24h.

The moisture permeability of the cured product is defined as the moisture permeability of the cured film after adding 0.01 part by weight of dibutyltin dilaurate (hereinafter sometimes abbreviated as BTL) to 100 parts by weight of the prepolymer. Cast to a Teflon board so that the thickness is about 100 microns. After curing for 14 days at 20 ° C. and 60% humidity, a crosslinked cured film was prepared. Based on the moisture permeability test method of a moisture-proof packaging material (the cup method) (JIS z0208), which is a Japanese Industrial Standard, 40 ° C. and a relative humidity of 90 were used. %, A value measured on a film having a thickness of 100 microns.

The component (A) may be any polyurethane prepolymer satisfying the above conditions, that is, any component having an average of more than 1 NCO group per molecule. Further, it is preferable to have an average of 1.3 to 9 NCO groups per molecule. -NCO in one molecule of prepolymer
If the number of groups exceeds one on average per molecule, the curing performance can be exhibited. Further, when the number is more than 1.3, the curing is likely to be sufficient, and when the number is less than 9, the flexibility of the cured product is easily maintained, and good physical properties are easily obtained. More preferably, the number is 1.5 to 8. The amount of -NCO groups in the prepolymer is determined based on, for example, the Siggia-Hanna method described in the Analytical Chemistry Handbook (edited by the Analytical Chemistry Society of Japan, published by Maruzen Co., Ltd.) The groups can be reacted and the excess amine can then be quantified by titration with an acid.

The component (A) is preferably a prepolymer mainly composed of isobutylene units or hydrogenated conjugated diene units (hereinafter sometimes abbreviated as hydrogenated diene units). Here, the term "mainly composed of an isobutylene unit or a hydrogenated diene unit" means that 50% by weight or more, preferably 75% by weight or more of the prepolymer is an isobutylene unit or a unit derived from a conjugated diene compound (hereinafter, conjugated diene compound). Diene units.) Is hydrogenated.

The conjugated diene compound includes, for example, butadiene, isoprene, chloroprene, cyclohexadiene and the like, and preferably butadiene and 1,3-cyclohexadiene. As units other than the isobutylene unit or the hydrogenated diene unit among the units constituting the prepolymer, a unit having copolymerizability with the isobutylene unit or the conjugated diene unit can be used.

Specific examples of units copolymerizable with an isobutylene unit or a conjugated diene unit include propylene, 1-butene, pentene, 2-methyl-1-butene, 3-methyl-1-butene, vinylcyclohexane, and cyclopentadiene. , Methyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, β-pinene, vinyltrichlorosilane, vinyldimethylmethoxysilane, allyltrichlorosilane, allyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxy Silane, 3-
Methacryloxytrimethoxysilane, 3-methacryloxymethyldimethoxysilane, and the like.

The prepolymer mainly composed of isobutylene unit, which is one type of the component (A), is obtained, for example, from a polymer having chlorine atoms at both terminals obtained by the inifer method (US Pat. No. 4,276,394). After the preparation, it can be hydrolyzed using potassium hydroxide or the like to synthesize a terminal polyol, and then can be obtained by leading to a polyurethane prepolymer. Or, for example, in Japanese Patent Laid-Open Publication No.
No. 904, etc., after preparing a polymer having a terminal halogen and an acetate group, a terminal polyol is synthesized using a method known in the art such as hydrolysis to a hydroxyl group using sodium alkoxide. And then to a polyurethane prepolymer.

The prepolymer mainly composed of hydrogenated conjugated diene units is obtained by subjecting a conjugated diene to living anion polymerization using a dilithium polymerization catalyst synthesized from sec-butyllithium / triethylamine / m-diisopropenylbenzene, for example. A prepolymer having a hydroxyl group by reacting a compound capable of forming a hydroxyl group by reacting with a polymerization terminal such as propylene oxide as a reaction terminator, and then deactivating the polymerization terminal with a compound having active hydrogen such as alcohol and water. Are synthesized. By hydrogenating this prepolymer using a hydrogenation catalyst such as palladium, a terminal polyol can be synthesized and led to a polyurethane prepolymer. Alternatively, commercially available polybutadiene glycol can be hydrogenated to lead to a polyurethane prepolymer. Of course, a commercially available hydrogenated polybutadiene polyol (such as Polytail of Mitsubishi Chemical Corporation) can be used to lead to a polyurethane prepolymer.

The method for deriving a polyol from a polyol into a polyurethane prepolymer is as follows. A polymer mainly composed of an isobutylene unit having an OH group or a hydrogenated conjugated diene unit is provided with two or more isocyanate (-NCO) groups in one molecule. It can be obtained by reacting a polyisocyanate compound having the same. Examples of the polyisocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPD).
I), polyisocyanates such as diisocyanates such as hydrogenated MDI, polyfunctional isocyanates such as polymeric diphenylmethane diisocyanate, or diisocyanates such as TDI and HDI are modified by reaction with isocyanurate, urethane, biuret, etc. And the like.
Further, a modified polyfunctionalized isocyanate group obtained by partially modifying an isocyanate group with an alcohol compound or the like can also be used.

From the viewpoint of the weather resistance of the cured product obtained from the prepolymer of the present invention, HDI, IPDI, hydrogenated MDI,
And these diisocyanates are isocyanurate,
It is preferable to use those modified and polyfunctionalized by a reaction such as urethane or biuret. In order to obtain a polyurethane prepolymer by reacting a polymer mainly composed of an isobutylene unit having an OH group or a hydrogenated conjugated diene unit with a polyisocyanate compound, the molar ratio of NCO / OH is preferably 2 or more. When the NCO / OH ratio is 2 or more, the resulting polyurethane prepolymer is less likely to have an excessively high molecular weight, and the molecular weight distribution is small, which is favorable. More preferably, it is 2.2 to 15.

When a relatively low boiling point compound such as hexamethylene diisocyanate is used as the polyisocyanate compound, the excess unreacted polyisocyanate compound is removed from the polyurethane prepolymer using a thin film distillation apparatus or the like. can do. However, in the present invention, the unreacted polyisocyanate compound partially used in the prepolymerization reaction may be used as it is, as long as the physical properties of the curable composition are acceptable. The allowable amount is preferably not more than 20 parts by weight of the polyisocyanate compound per 100 parts by weight of the polyurethane prepolymer. If the amount exceeds 20 parts by weight, the internal curability of the cured product may be reduced, and the physical properties of the cured product may be deteriorated. It is more preferably at most 10 parts by weight.

When a conjugated diene unit is used as the component (A), it is preferable to partially include a cyclohexadiene unit. When a cyclohexadiene unit is included, the mechanical properties such as the tensile strength of the cured product and the physical properties of the cured product such as weather resistance are further superior to those obtained from the butadiene unit. This is presumed to be due to the introduction of a cyclohexyl group as a hard segment of the prepolymer by hydrogenation. When used as a sealing material, an adhesive or the like, the cyclohexadiene unit in the prepolymer is preferably 1 to 50% by weight based on all units of the prepolymer. When the content is 1% by weight or more, mechanical properties such as tensile strength and physical properties such as weather resistance tend to be easily exhibited, and when the content is 50% by weight or less, the modulus of the cured product tends to remain within a range suitable for use. Preferably it is 5 to 40% by weight.

In the curable composition of the present invention, one or more alkali metal or alkaline earth metal hydroxides are used as the component (B). From the safety in handling,
Alkaline earth metal hydroxides are preferred. When the curable composition of the present invention is used as a sealing material, it is desirable to use calcium hydroxide. Conventionally, calcium carbonate has been used as a filler for sealing materials,
This is because when calcium hydroxide is used as the component (B), it is considered that the calcium hydroxide becomes calcium carbonate when it is hardened, and after all, the amount of calcium carbonate to be added as a sealing material can be reduced.

The hydroxides of alkali metals or alkaline earth metals may contain oxides, carbonates and the like.
Although the principle of good internal curability of the curable composition of the present invention is not clear, it is speculated that the following reaction occurs and internal curing proceeds. First, a hydroxide of an alkali metal and / or an alkaline earth metal, which is a component (B) (hereinafter, calcium hydroxide is described as an example of a component (B)) absorbs carbon dioxide gas in the atmosphere and forms a carbonate. Water is generated (formula (1)). Next, the water generated by this reaction reacts with the NCO group of the urethane prepolymer to generate a urea bond (curing reaction), and at the same time, generates carbon dioxide gas (formula (2)). Further, the reaction between the generated carbon dioxide gas and calcium hydroxide causes generation of calcium carbonate and generation of water (formula (3)). The reaction cycle of (Equation (2)) and (Equation (3)) proceeds and cures.

[0024]

Embedded image

In the curable composition of the present invention, it is desirable to reduce the water content as much as possible from the viewpoint of storage stability. Specifically, it is preferable to use a water content of less than 0.6% with respect to the composition. When the water content is 0.6% or more, the storage stability of the curable composition is poor. The content is more preferably 0.5% or less, and further preferably 0.3% or less. In particular, attention must be paid to the component (B) because it easily contains water.

When the hydroxide of the component (B) is used in the form of a powder, it is preferable that the hydroxide has a small particle size.
There is no particular limitation as long as it can be easily mixed with the components.
The mixing ratio of the component (A) and the component (B) is 100% for the component (A).
It is desirable that the component (B) be 10 to 300 parts by weight with respect to parts by weight. When the amount of the component (B) is more than 10 parts by weight based on 100 parts by weight of the component (A), the internal curing of the curable composition due to the curing of the component (B) becomes sufficient. When the amount of the component (B) is 300 parts by weight or less, the physical properties of the cured product are good, and a good cured product is easily obtained. More preferably, component (A) 10
Component (B) is 20 to 200 parts by weight with respect to 0 parts by weight. More preferably, the component (B) is 20 to 100 parts by weight based on 100 parts by weight of the component (A).

It is preferable that the curable composition of the present invention further contains a curing catalyst as the component (C). Examples of curing catalysts include tin dicarboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, dibutyltin oxide, dibutyltin diacetylacetate, zirconium tetraacetylacetonate, and titanium tetraacetylacetate. Chelate compounds such as nato, lead octylate, lead naphthenate, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7-ene (DBU) N-ethylmorpholine,
Triethylamine, N, N, N ', N'-tetramethyl 1,3-butanediamine, 1,4-diazabicyclo (2,2,2) octane, 1,5-diazabicyclo (4,3,0) non-5 -Ene (DBN) and the like.

When using the curable composition of the present invention, various additives may be added as necessary. Examples of such additives include physical property modifiers such as silane coupling agents and other silane compounds, heavy calcium carbonate, various calcium carbonates such as precipitated calcium carbonate, calcium oxide, clay, talc, carbon black, Silica powders such as fumed silica and precipitated silica, various fillers such as silicic acid and glass fiber, process oils, polybutenes, hydrogenated polybutenes, plasticizers such as chlorinated paraffins, ultraviolet absorbers, for example, Ciba Specialty Chemicals Co., Ltd. TINUVIN320, TIN
Antioxidants such as UVIN326 and TINUVIN327, for example, Ciba Specialty Chemicals Co., Ltd.
IRGANOX1076, IRGANOX1010,
IRGANOX1425WL, IRGANOX3314
And hindered amine light stabilizers (HALS), for example, TIN of Ciba Specialty Chemicals Co., Ltd.
UVIN622LD, CHIMASSORB944L
D, TINUVIN 765 and the like, and blend light stabilizers, for example, TI of Ciba Specialty Chemicals Co., Ltd.
NUVIN B75, etc., lubricants, pigments such as titanium oxide, adhesion-imparting agents, UV-curable resins, for example, Alonix M-309, -305, -305, trade names of Toagosei Chemical Industry Co., Ltd.
310, -315, -350, -400, -408,-
450 and the like.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the embodiments. In addition, various physical properties were measured as follows. (1) Molecular weight and molecular weight distribution The resin was dissolved in tetrahydrofuran and measured by GPC (gel permeation chromatography). The molecular weight was expressed in terms of standard polystyrene.

The GPC conditions were as follows: the column was Shodex KF-801 + KF-802 + KF80 manufactured by Showa Denko KK
4 in total, and the carrier flow rate is 1 ml / m
in. Shodex Standard of Showa Denko KK was used as the standard polystyrene. (2) Moisture permeability of cured product 0.01 parts by weight of dibutyltin dilaurate (hereinafter sometimes abbreviated as BTL) is added to 100 parts by weight of the prepolymer, and a Teflon plate is added so that the cured film thickness becomes 100 microns. Cast to Then 20 ℃, humidity 6
Cured at 0% for 14 days to make a crosslinked cured film. Using this film, the moisture permeability was measured at 40 ° C. and 90% RH according to the Japanese Industrial Standard JIS z0208 moisture permeability test method (cup method) for a moisture-proof packaging material. (3) Amount of unreacted polyisocyanate compound The amount of unreacted polyisocyanate compound after the polyurethane prepolymerization reaction was determined by dissolving the reactant in tetrahydrofuran and performing liquid chromatography.

In the liquid chromatography method, the column is Shodex KF-801 + KF-8 manufactured by Showa Denko KK
02 + KF804 were measured in series at a carrier flow rate of 1 ml / min. (4) Internal curability The curable composition is placed in a polypropylene container having a depth of 20 mm or more so that the thickness of the curable composition becomes 20 mm or more. The container containing the kneaded material was placed in a thermo-hygrostat at 20 ° C. and 60% humidity, and after 3 days and 7 days, the cured product was cut out and the thickness of the cured portion from the surface of the cured product was measured.

[0032]

[Production Example 1] <Production of hydroxyl group-containing resin (a-1)> 1 L
Attach a vane-type stirrer, a three-way cock, and a vacuum line to the pressure-resistant glass autoclave, and heat and dry the polymerization vessel at 100 ° C. for 1 hour while evacuating the vacuum line. The pressure was restored. Thereafter, 290 ml of methylene chloride dried by calcium hydride treatment was introduced into the autoclave from one of the three-way cocks using a syringe. Further, 10 ml of a methylene chloride solution in which 10 mmol of 2,4,4,6-tetramethylpentane-2,6-diacetate as an initiator was dissolved was added. Next, isobutylene 40 dehydrated by passing through a column filled with barium oxide is used.
After connecting a liquefied gas sampling tube made of pressure-resistant glass with a needle valve and containing a g thereof to a three-way cock, the container body was immersed in a dry ice-acetone bath at -70 ° C to stir and cool the inside of the polymerization container. After cooling, the internal pressure was reduced by a vacuum line, and then the needle valve was opened. Isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, nitrogen was flowed from one of the three-way cocks to return to normal pressure, and the inside of the polymerization vessel was kept at -20 ° C with stirring. Next, a boron trichloride solution (containing 20 mmol of boron trichloride) was added from a three-way cock using a syringe to initiate polymerization. After 30 minutes, the polymerization was terminated by adding pyridine. After termination of polymerization,
Unreacted isobutylene, methylene chloride, and pyridine were distilled off while the temperature was kept low, and the remaining polymer was dissolved in 400 ml of n-hexane and washed with water until neutral. Thereafter, the n-hexane solution was heated to a bath temperature of 60 to
The solution was concentrated to about 80 ml at 70 ° C. under a reduced pressure of 20 to 30 mmHg, and this solution was added to 1 L of acetone to precipitate and separate the polymer. The polymer thus obtained was dissolved again in 400 ml of n-hexane, dried over anhydrous magnesium sulfate and filtered, and the n-hexane was distilled off under reduced pressure to obtain an isobutylene polymer.

The obtained polymer had a polystyrene-equivalent number average molecular weight (Mn) of 4,500 by GPC and a ratio of number average molecular weight / weight average molecular weight (Mn / Mw) of 1.8. In addition, as measured by NMR, it had 1.9 —C (CH ₃ ) ₂ —OC (O) CH ₃ groups per molecule. 1 g of sodium methoxide was added to 10 g of this polymer, and the mixture was heated and stirred under reduced pressure at 80 ° C. for 9 hours. Thereafter, 1 g of water was added, and the mixture was further heated and stirred at 80 ° C. for 9 hours. After cooling to room temperature, the reaction solution was dissolved in n-hexane. This solution was added to 300 ml of acetone to precipitate and separate the polymer. 30 ml of the polymer thus obtained was again used.
Was dissolved in cyclohexane, dried over anhydrous magnesium sulfate, and filtered. The cyclohexane was distilled off under reduced pressure to obtain an isobutylene polymer. The obtained polymer had a polystyrene-equivalent number average molecular weight (Mn) of 4,400 as measured by GPC and a ratio of number average molecular weight / weight average molecular weight (Mn / Mw) of 1.
Nine. The hydroxyl value measured by a method using acetic anhydride and pyridine was 23 mgKOH / g, and had 1.8 OH groups per molecule. <Preparation of polyisocyanate prepolymer (P-1)>
In a 200 ml three-necked flask equipped with a cooling tube, thermometer and stirrer sufficiently dried with nitrogen, a hydroxyl group-containing resin (a-
1) 30 g, toluene 70 g, and 11.8 g of duranate TSS-100 (containing 17.5 wt% of -NCO group) of Asahi Kasei Corporation were charged and heated and stirred at 90 ° C. Then, a 1% solution of dibutyltin dilaurate in toluene 0.1
g was further added and heated and stirred at 90 ° C. for 1 hour. Thereafter, the mixture was concentrated under reduced pressure to remove the solvent. GP of the collected material obtained
The number average molecular weight (Mn) in terms of polystyrene by C is 6
500, the ratio of number average molecular weight / weight average molecular weight (Mn / M
w) was 2.4. As a result of liquid chromatography analysis, 3.0 g of unreacted duranate TSS-100 was obtained.
Met. 0.0369 mol of -NCO groups in the recovered material
The resulting polyurethane prepolymer had an average of 6.2 -NCO groups per molecule.

Table 1 shows the measurement results of the moisture permeability of the prepolymer (P-1).

[0035]

[Production Example 2] <Preparation of polymerization catalyst> 1M sec-butyllithium (hereinafter s-BuL) in a dry argon atmosphere
Triethylamine (hereinafter referred to as T)
EA) is calculated as s-BuLi / TEA = 1/1 (mol / mo)
l). Further, m-diisopropenylbenzene (hereinafter, m-DIPB) was added to this solution with s-BuL.
i / TEA / m-DIPB = 2/2/1 (mol / mo
1 / mol). After completion of the dropwise addition, the mixture was stirred at 25 ° C. for 24 hours to obtain a polymerization catalyst liquid. <Production of OH group-containing resin (a-2)> The inside of a 5 L autoclave dried according to a conventional method was replaced with dry argon.
1200 g of cyclohexane, 116 g (125 mmol in terms of Li atom) of the polymerization catalyst solution prepared by the above method, and 19 g of tetramethylethylenediamine were injected into the autoclave. After maintaining the liquid temperature in the autoclave at 40 ° C., adding 61 g of styrene, and stirring for 30 minutes,
1640 g of a 33 wt% butadiene cyclohexane solution
Was added and stirred for another 30 minutes. Thereafter, 17 ml of propylene oxide was added and stirred for 90 minutes.

Thereafter, the polymer was separated with a large amount of methanol, washed with methanol, and dried at 50 ° C. under vacuum. This polymer was dissolved again in cyclohexane to form a 10 wt% solution. 2.5 kg of this polymer solution was put into a 5 L autoclave, and 5% Pd-supported carbon black was added to the autoclave at the same time.
50 g were dispersed. After replacing the gas phase in the autoclave with hydrogen, a hydrogen pressure of 45 kg / cm ² -G, 160 ° C.
For 2 hours. Thereafter, the temperature was lowered, and the Pd-supporting carbon black was separated by filtration. The obtained polymer solution was separated with a large amount of methanol, further washed with methanol, and dried under vacuum. The obtained polymer had a polystyrene-equivalent number average molecular weight (Mn) of 11,000 by GPC and a ratio of number average molecular weight / weight average molecular weight (Mn / Mw) of 1.27. As measured by NMR, 100% of the unsaturated hydrocarbon bonds and 93% of the styrene benzene ring contained in the polymer before hydrogenation were hydrogenated. When the hydroxyl value was measured by a method using acetic anhydride and pyridine, it was 9.7 mgKOH / g.
It contained 9 OH groups. <Preparation of polyisocyanate prepolymer (P-2)>
In a 200 ml three-necked flask equipped with a cooling tube, thermometer and stirrer sufficiently dried with nitrogen, a hydroxyl group-containing resin (a-
2) 30 g, toluene 70 g, polyisocyanate compound (Duranate 24A, manufactured by Asahi Kasei Kogyo Co., Ltd.)
3.8 g was charged and heated and stirred at 90 ° C. Thereafter, 0.1 g of a toluene solution of 1% dibutyltin dilaurate was added, and the mixture was heated with stirring at 90 ° C. for 1 hour. Thereafter, the mixture was concentrated under reduced pressure to remove the solvent. The obtained recovered product had a polystyrene-equivalent number average molecular weight (Mn) of 21,000 by GPC and a ratio of number average molecular weight / weight average molecular weight (Mn / Mw) of 1.7.
Met. As a result of liquid chromatography analysis, the amount of unreacted duranate 24A was 0.95 g. -NCO groups in the recovered product were 0.0160 mol, and the obtained polyurethane prepolymer had an average of 6.9 -NCO groups per molecule. Table 1 shows the measurement results of the moisture permeability of the prepolymer (P-2).

[0037]

[Production Example 3] <Production of hydroxyl group-containing resin (a-3)> The inside of a 5-L autoclave dried according to a conventional method was replaced with dry argon. 1200 g of cyclohexane, 116 g (125 mmol in terms of Li atom) of a polymerization catalyst solution prepared by the method described in Production Example 2, and 19 g of tetramethylethylenediamine were injected into the autoclave. The liquid temperature in the autoclave was maintained at 40 ° C., 1455 g of a 33 wt% cyclohexane solution of butadiene was added, and the mixture was stirred for 30 minutes. Then, 120 g of 1,3-cyclohexadiene was added, and the mixture was further stirred for 30 minutes. Thereafter, 17 ml of propylene oxide was added and stirred for 90 minutes.

Thereafter, 8 g of methanol was added to stop the reaction. Thereafter, the polymer was separated with a large amount of methanol, washed with methanol, and dried at 50 ° C. in vacuo. This polymer was dissolved again in cyclohexane to obtain a 20 wt% solution. 2.5 kg of this polymer solution was put into a 5 L autoclave, and 5% Pd-supported carbon black was added to the autoclave at the same time.
20 g were dispersed. After replacing the gas phase in the autoclave with hydrogen, a hydrogen pressure of 45 kg / cm ² -G, 100 ° C.
For 2 hours. Thereafter, the temperature was lowered, and the Pd-supporting carbon black was separated by filtration. The obtained polymer solution was separated with a large amount of methanol, further washed with methanol, and dried under vacuum. When the obtained polymer A was measured by NMR, 99% of the unsaturated hydrocarbon bonds contained in the polymer before hydrogenation were hydrogenated. The number average molecular weight (Mn) in terms of polystyrene by GPC is 14,000,
The ratio of the number average molecular weight / the weight average molecular weight (Mn / Mw) was 1.17. The hydroxyl value measured by the method using acetic anhydride and pyridine was 8.6 mgKOH / g. <Preparation of polyisocyanate prepolymer (P-3)>
In a 200 ml three-necked flask equipped with a cooling tube, thermometer and stirrer sufficiently dried with nitrogen, a hydroxyl group-containing resin (a-
3) 30 g, toluene 70 g, and 3.8 g of Duranate 24A of Asahi Kasei Corporation were charged and heated and stirred at 90 ° C. Thereafter, 0.1 g of a toluene solution of 1% dibutyltin dilaurate was added, and the mixture was heated with stirring at 90 ° C. for 1 hour. Thereafter, the mixture was concentrated under reduced pressure to remove the solvent. G of the collected material obtained
The number average molecular weight (Mn) in terms of polystyrene by PC was 19000, and the ratio of number average molecular weight / weight average molecular weight (Mn)
/ Mw) was 2.0. As a result of liquid chromatography analysis, the amount of unreacted duranate 24A was 0.83 g. The recovered product had 0.0167 mol of -NCO groups, and the obtained polyurethane prepolymer had an average of 6.9 -NCO groups per molecule. Table 1 shows the measurement results of the moisture permeability of the prepolymer (P-3).

[0039]

[Production Example 4] <Polyisocyanate prepolymer (P-
Preparation of 4)> 300 g of the hydroxyl group-containing resin (a-3) and 38.7 g of hexamethylene diisocyanate were placed in a 200 ml three-necked flask equipped with a cooling tube, a thermometer, and a stirrer sufficiently dried with nitrogen, and heated and stirred at 90 ° C. Then, the reaction was carried out for 1 hour. Thereafter, the temperature was raised to 160 ° C., and a reaction was performed at 160 ° C. for 1 hour. Thereafter, unreacted hexamethylene diisocyanate was removed using a thin film distillation apparatus. GP of the collected material obtained
The number average molecular weight (Mn) in terms of polystyrene by C is 1
5000, a ratio of number average molecular weight / weight average molecular weight (Mn /
Mw) was 1.5. As a result of gas chromatography analysis, the remaining amount of hexamethylene diisocyanate in the recovered product was 0.5% or less. The -NCO groups in the recovered product were 0.069 mol, and had an average of about 3 -NCO groups per molecule of the obtained polyurethane prepolymer. Table 1 shows the measurement results of the moisture permeability of the prepolymer (P-4).
Shown in

[0040]

Example 1 The prepolymer (P-
1) 100 parts by weight, 100 parts by weight of process oil (Diana Process Oil PW-32 manufactured by Idemitsu Kosan Co., Ltd.)
50 parts by weight of calcium hydroxide (Activated calcium hydroxide CLS-B manufactured by Shiroishi Kogyo Co., Ltd., 90 ° C. using a vacuum dryer)
And dried under vacuum for 4 hours) and 0.05 parts by weight of dibutyltin dilaurate (BTL), and kneaded under a nitrogen atmosphere to obtain a curable composition. The internal curability was evaluated using this curable composition. Table 2 shows the composition and evaluation results.
Shown in

[0041]

Examples 2 to 4 Curable compositions having the composition shown in Table 2 were obtained using the prepolymers obtained in Production Examples 2 to 4, respectively. This internal curability was evaluated. Table 2 shows the evaluation results.

[0042]

Comparative Example 1 The prepolymer, process oil and dibutyltin dilaurate obtained in Production Example 1 were prepared in the same manner as in Example 1 except that calcium hydroxide was not added.
And kneaded with the following composition. Using this kneaded material, the internal curability was evaluated. Table 2 shows the evaluation results.

[0043]

Comparative Examples 2 to 4 Production Examples 2 to 4 were carried out in the same manner as in Examples 2 to 4 except that calcium hydroxide was not added.
The prepolymer, process oil, and dibutyltin dilaurate obtained in 4 were blended and kneaded according to the blending composition shown in Table 2.
Using this kneaded material, the internal curability was evaluated. Table 2 shows the evaluation results.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

According to the present invention, the cured product has good internal curability while using a hydrophobic polymer having excellent moisture resistance, weather resistance and heat resistance.
A liquid-formable curable composition is obtained.

Continued on front page F-term (reference) 4H017 AA04 AA24 AB03 AB07 AC04 AC16 AC17 AC19 4J002 CK051 DE086 EE047 EG047 EG067 EN027 EU107 EU117 EU137 EU237 EZ037 EZ047 FD010 FD157 GJ01 GJ02 4J034 BA03 DA02 GA03 DP07 GA07 HB08 HC03 HC12 HC17 HC22 HC35 HC46 HC52 HC61 HC63 HC64 HC67 HC71 HC73 JA42 KA01 KB04 KC16 KC17 KC18 KD01 KD02 KD05 KD12 KE02 LA33 MA03 QA05 QB04 QB17 RA08 4J040 EF181 EF251 EF321 HA146 HA04 HB24 HC01 HC08

Claims (6)

[Claims] 1. A curable composition containing the following components (A) and (B). (A) a number average molecular weight of 1,000 to 100,000;
Polyurethane prepolymer moisture permeability of the cured product is 1~100g / m ² / 24h. (B) One or more hydroxides of alkali metals or alkaline earth metals. (2) The component (A) is a prepolymer mainly composed of an isobutylene unit or a hydrogenated conjugated diene unit,
The curable composition according to claim 1, which is a prepolymer having an average of 1.3 to 9 NCO groups per molecule. 3. The curable composition according to claim 1, wherein the component (A) is mainly composed of a hydrogenated conjugated diene unit, and the hydrogenated conjugated diene unit contains a hydrogenated cyclohexadiene unit. 4. The curable composition according to claim 1, wherein the component (B) is calcium hydroxide. 5. The method according to claim 5, wherein 100 parts by weight of the component (A) is
The curable composition according to claim 1, wherein the component (B) is 10 to 300 parts by weight. 6. The curable composition according to claim 1, further comprising a curing catalyst as the component (C).