JPH08283389A - Curable composition - Google Patents

Abstract

PURPOSE: To obtain a curable compsn. improved in shelf stability, curability and water-resistant adhesion by using an epoxy resin in combination with a hydrolyzable silicon group-contg. org. polymer derived from an OH-contg. polyoxyalkylene and contg. impurities at most in a specific amt. CONSTITUTION: A hydrolyzable silicon group-contg. org. polymer of the formula (wherein R is an org. group; R<1> is 1-20C hydrocarbon; X is OH or a hydrolyzable group; and a is 1 to 3) is derived from (f) a hydroxyl group-contg. polyoxyalkylene obtd. by polymn. of an alkylene oxide with an initiator in the presence of a double metal cyanide complex as a catalyst. The total amt. of ionic impurities in the component (A) is at most 50ppm, pref. at most 20ppm. A compsn. comprising the component (A) and an epoxy resin is blended with a polyamine or the like as a curing agent to prepare as a coating or sealing material having a rubber elasticity. The impurities in the component (A) are removed from the component (A) after conversion into salts insoluble in the component (A), or removed from the component (f) after conversion into salts insoluble in the component (f). The component (A) is obtd. by a reaction of a modification of the component (f) having terminal unsatd. groups introduced thereinto with a silicon hydride compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which gives a cured product having excellent water-resistant adhesiveness, and particularly has excellent storage stability.

[0002]

2. Description of the Related Art Polyoxyalkylene having a hydrolyzable silicon group at a terminal is used for coating compositions, sealing compositions and the like by taking advantage of the characteristic that a cured product has rubber elasticity.

[0003]

However, it has a drawback that it is generally weak in strength, and it has been difficult to use it alone in applications such as elastic adhesives which require particularly high strength.
In order to improve this strength, a method of using an epoxy resin in combination has been proposed (see Japanese Patent Laid-Open No. 61-268720), but in this case, it has a drawback that the obtained cured product does not have sufficient elongation. ing.

Therefore, the inventors of the present invention disclosed in Japanese Unexamined Patent Publication No. 4-2985 / 1992.
As described in Japanese Patent Publication No. 25, a composition is proposed in which an organic polymer having a high molecular weight and a narrow molecular weight distribution and having a hydrolyzable silicon group is used in combination with an epoxy resin, and a balance between elongation and strength of a cured product is proposed. An excellent and low viscosity composition is obtained. However, depending on the use, there are cases in which the storage stability of the composition and the adhesiveness after curing, especially the water-resistant adhesiveness, are insufficient, and the curability is not preferable.

[0005]

The present invention relates to a curable composition which is improved in storage stability, adhesiveness after curing and curability by using an organic polymer having a low content of impurities.

That is, the present invention is the following inventions. A hydrolyzable silicon group represented by the following formula (1), which is derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing alkylene oxide with an initiator using the complex metal cyanide complex (E) as a catalyst, A curable composition containing, as essential components, an organic polymer (A) having a total amount of ionic impurities of 50 ppm or less, and an epoxy resin (B).

-R-SiX _a R ¹ _3-a (1)

In the formula, R is a divalent organic group, and R ¹ has ¹ carbon atom.
20 substituted or unsubstituted monovalent hydrocarbon groups, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3.

[Organic Polymer] The organic polymer (A) of the present invention
Has a hydrolyzable silicon group represented by the formula (1), and the total amount of ionic impurities is 50 ppm or less. The present invention is particularly suitable when the ionic impurities are ionic impurities containing a metal compound and / or an alkali metal compound derived from the complex metal cyanide complex (E). The ionic impurities are preferably 30 ppm or less, more preferably 20 ppm or less.

Usually, the organic polymer having a hydrolyzable silicon group contains ionic impurities and the like due to the catalyst used in producing the organic polymer and introducing the hydrolyzable silicon group. It was found that the storage stability of the organic polymer (A) and the curable composition of the present invention was improved by reducing the amount of these ionic impurities.

The ionic impurities are also related to the water absorption of the cured product, and the reduction of the water absorption makes it possible to improve the water-resistant adhesiveness and facilitates the reaction during the production of the organic polymer. It had the advantage of improving the curability.

As the reducing method, the following (I) to
Method (II) can be mentioned. In addition, there is (III) as a method which can be used particularly for removing a metal compound derived from the complex metal cyanide complex (E). In particular, the method (I) is preferable because it can reduce ionic impurities effectively and economically.

(I) A method in which an ionic impurity contained in a polymer is converted into a salt which is essentially insoluble in the polymer, and then the salt is removed from the polymer. Specifically, after adding a compound capable of reacting with an ionic impurity to form a salt essentially insoluble in the polymer, water and, if necessary, a nonionic surfactant,
There is a method of precipitating a salt by dehydration and then removing the salt. As the compound capable of forming a salt, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, pyrophosphoric acid, acidic sodium pyrophosphate and the like are preferable. The precipitated salt can be removed by filtration or adsorption.

(II) A method of removing a ionic impurity by adding a solvent to a polymer and then bringing the polymer into contact with an anion exchange resin and / or a cation exchange resin.

(III) A method of removing a metal compound derived from the complex metal cyanide complex (E) after treatment with a pH buffer and optionally ammonia and a chelating agent, after adding an aliphatic alcohol and a chelating agent, A method of removing a metal compound derived from the composite metal cyanide complex (E), a method of removing a metal compound derived from the composite metal cyanide complex (E) after treatment with an oxidizing agent.

The organic polymer (A) is derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing alkylene oxide with an initiator using the double metal cyanide complex (E) as a catalyst. The organic polymer (A) is preferably a hydroxyl group-containing polyoxyalkylene polymer (F) in which the hydrogen atom in the hydroxyl group is replaced by the formula (1).

The hydroxyl group-containing polyoxyalkylene polymer (F) uses the complex metal cyanide complex (E) as a catalyst,
It can be produced by reacting an alkylene oxide with an initiator such as a hydroxy compound.

Due to the use of the complex metal cyanide complex (E), M _w / M _{n is} better than that of the conventional alkali metal catalyst.
It is possible to obtain a hydroxyl group-containing polyoxyalkylene polymer (F) having a low viscosity, a higher molecular weight, and a lower viscosity.

The complex metal cyanide complex (E) is preferably a complex containing zinc hexacyanocobaltate as a main component, and its ether and / or alcohol complex is particularly preferable. Its composition is essentially Japanese Patent Publication No. 46-2725.
Those described in Japanese Patent No. 0 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during the production of the complex. As alcohol, JP-A-4-145
The t-butanol described in JP-A-123 is preferred.

As the initiator, a compound having 2 to 10 active hydrogens is preferable, a polyhydroxy compound is preferable, and a polyhydroxy compound having 2 to 8, especially 2 to 4 hydroxyl groups is preferable. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,
There are 4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sucrose and polyols having a lower molecular weight than the target product obtained by reacting these with alkylene oxide. These may be used alone or in combination of two or more. Further, an unsaturated group-containing monohydroxy compound such as allyl alcohol can also be used.

Preferably, the number of hydroxyl groups of the polyoxyalkylene polymer (F) can be arbitrarily controlled by changing the number of hydroxyl groups of the initiator. When the molecular weights are the same, the higher the number of functional groups, the higher the viscosity. Get lower. Further, the physical properties of the cured product of the composition obtained by blending the organic polymer (A) with the compounding agent are the same as those of the hydrolyzable silicon group of the organic polymer (A) regardless of the number of hydroxyl groups of the polyoxyalkylene polymer (F). It can be freely controlled by the content.

Therefore, the curable composition using the organic polymer (A) of the present invention has excellent physical properties such as strength and elongation and has a low viscosity.

The number of hydroxyl groups per molecule of the polyoxyalkylene polymer (F) used in the present invention is preferably 2-10. From the balance of physical properties such as viscosity, strength and elongation, it is particularly preferable that the number is 2 to 8, especially 2 to 4.

Particularly preferred polyoxyalkylene polymers (F) are polyoxypropylene diols, polyoxypropylene triols and polyoxypropylene tetraols. When used in the following methods (a) and (d), an unsaturated group-terminated polyoxyalkylene monool such as polyoxypropylene glycol monoallyl ether can also be used.

The polyoxyalkylene polymer (F) preferably has a hydroxyl value-converted molecular weight of 5,000 to 30,000, more preferably 8,000 to 30,000.

The hydroxyl value-converted molecular weight of the present invention is the product of the number of functional groups of the initiator used when producing the polyoxyalkylene polymer (F) having a terminal hydroxyl group and the molecular weight of the polymer polyoxyalkylene per hydroxyl group. It refers to the molecular weight calculated in.

The viscosity of the polyoxyalkylene polymer (F) is preferably 50,000 cP or less at room temperature, and preferably 30,000 cP.
The following is particularly preferable.

The organic polymer (A) has a hydrolyzable silicon group represented by the following formula (1).

-R-SiX _a R ¹ _3-a (1)

In the formula, R is a divalent organic group and R ¹ is a carbon atom
To 20 substituted or unsubstituted monovalent hydrocarbon groups, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3.

R in the formula (1) is a divalent organic group. R
¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X in the formula (1) is a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, It is a hydrido group. Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. Preferred X is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group and a propoxy group. A in the formula (1) is 1, 2 or 3, and 2 or 3 is preferable.

Next, the method for producing the organic polymer (A) will be described. In the organic polymer (A) in the present invention, a hydrolyzable silicon group can be introduced into the terminal of the hydroxyl group-containing polyoxyalkylene polymer (F) by the methods described in (a) to (d) below. Such compounds are liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature,
When used as a sealing material or an adhesive, it has desirable characteristics.

(A) A method of reacting the terminal unsaturated group-introduced product (G) of the polymer (F) with a silicon hydride compound represented by the following formula (2).

HSiX _a R ¹ _3-a (2)

However, in the formula, R ¹ , X and a are the same as described above.

Terminal unsaturated group-introduced product (G) of polymer (F)
As a method for obtaining the above, after the terminal hydroxyl group OH of the polymer (F) is OM (M is an alkali metal), it is reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride or with an unsaturated group and a hydroxyl group. There is a method in which a compound having a reactive functional group is reacted with the polymer (F) to bond it with an ester bond, a urethane bond, a carbonate bond or the like. Furthermore, when polymerizing the alkylene oxide in the production of the polymer (F), a method of introducing an unsaturated group into a side chain by copolymerizing an unsaturated group-containing alkylene oxide such as allyl glycidyl ether or a terminal as an initiator It can also be obtained by using an unsaturated group-containing monohydroxy compound.

(B) A compound having an isocyanate group and a hydrolyzable silicon group represented by the formula (1), and a polymer (F)
How to react.

(C) After reacting the polymer (F) with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the isocyanate group is reacted with the W group of the silicon compound represented by the following formula (3). How to make.

R ¹ _3-a -SiX _a -R ² W (3)

In the formula, R ¹ , R ² , X and a are the same as defined above, and W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary). .

(D) A method of reacting the terminal unsaturated group-introduced product (G) of the polymer (F) with a silicon compound represented by the formula (3) in which W is a mercapto group.

The removal of ionic impurities is carried out from the above (a) to.
It is preferable to carry out at an appropriate stage such as before and after reacting each silicon compound in each method (d), and the total amount thereof is set to 50 ppm or less. That is, the following three methods can be exemplified. The third method is particularly preferable.

After introducing a hydrolyzable silicon group into the hydroxyl group-containing polyoxyalkylene polymer (F) to form the organic polymer (A), ionic impurities are removed.

The ionic impurities contained in the polymer (F) are converted into salts essentially insoluble in the polymer (F), and the salts are removed from the polymer (F) to remove the polymer (F). After adjusting the ionic impurities contained in () to 50 ppm or less, a hydrolyzable silicon group is introduced into the polymer (F) to obtain an organic polymer (A).

Terminal unsaturated group-introduced product (G) of polymer (F)
The ionic impurity contained in is converted into a salt essentially insoluble in the terminal unsaturated group-introduced product (G), and the salt is removed from the terminal unsaturated group-introduced product (G) to remove the terminal unsaturated group. After adjusting the ionic impurities contained in the introduction product (G) to 50 ppm or less, the introduction product of the terminal unsaturated group (G) is reacted with the silicon hydride compound represented by the formula (2) to give an organic polymer (A). And

The molecular weight of the organic polymer (A) in the present invention is calculated based on the hydroxyl group-equivalent valence molecular weight of the polymer (F) as a raw material. The molecular weight is 5,000 to 30,000
Is preferred. If it is less than 5,000, the cured product will be hard and the elongation will be low, and if it exceeds 30,000, flexibility and elongation of the cured product will not be a problem, but the viscosity of the polymer itself will be remarkably increased and the practicality will be lowered. Especially 8000-30
000 is preferable.

[Epoxy Resin] The epoxy resin used as the component (B) in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. , Bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, resorcin type epoxy resin, and Examples thereof include, but are not limited to, halides and hydrogenated products thereof, and commonly used epoxy resins can be used.

In the present invention, the components (A) and (B) are used in a weight ratio of (A) component / (B) component of 1/1.
It is preferably from 00 to 100/1. 100 / 1-
100/300 is particularly preferred. If the amount of component (A) is greater than this, the strength of the cured product will be insufficient, and if it is less than this, the elongation will be insufficient.

In the present invention, an epoxy curing agent (C) is used.
It can be used as an ingredient. As the epoxy curing agent (C), aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as metaphenylenediamine, secondary amines, tertiary amines such as tris (dimethylaminomethyl) phenol, And salts thereof, acid anhydrides, polyamide resins,
Examples include polysulfide resins, boron trifluoride complex compounds, imidazoles, dicyandiamides, etc.
It is not limited to these.

The proportion of component (C) used is ((A) by weight).
Component + (B) component)) / (C) component is 100 / 0.1
It is preferably 100/30.

In the present invention, a compound (D) containing an epoxy group or a functional group capable of reacting with an epoxy group and a hydrolyzable silicon group in the same molecule can be used.

Examples of the functional group capable of reacting with the epoxy group in the compound include, but are not limited to, an amino group, a carboxyl group and a mercapto group.
As the hydrolyzable silicon group, the same group as the hydrolyzable silicon group contained in the component (A) is preferable, and the group represented by the formula (1) is preferable.

The compound (D) includes epoxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes.

Specific examples of the epoxy group-containing silanes include 3-glycidoxypropyltrimethoxysilane and 3-
Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- (N, N
-Glycidyl) aminopropyltrimethoxysilane, N
-Glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-
Bis [3- (trimethoxysilyl) propyl] amine,
Etc.

Specific examples of the amino group-containing silanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3.
-Aminopropylmethyldimethoxysilane, N- (2-
Aminoethyl) -3-aminopropyltrimethoxysilane, N, N-bis [(methyldimethoxysilyl) propyl] amine, N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis [ Three
-(Trimethoxysilyl) propyl] ethylenediamine, N-[(3-trimethoxysilyl) propyl] diethylenetriamine, N-[(3-trimethoxysilyl)
Propyl] triethylenetetramine, 3-ureidopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane and the like.

Specific examples of the mercapto group-containing silanes include 3-mercaptopropyltrimethoxysilane and 3
-Mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like.

Specific examples of the carboxyl group-containing silanes include 2-carboxyethyltriethoxysilane and 2-carboxyethyltriethoxysilane.
Examples include carboxyethylphenylbis (2-methoxyethoxy) silane and N- (N-carboxymethyl-2-aminoethyl) -3-aminopropyltrimethoxysilane.

The component (D) is used in a weight ratio of ((A) component + (B) component) / (D) component 100 /
It is preferably 0.1 to 100/30.

Further, in the present invention, a curing accelerating catalyst for accelerating the curing reaction of the hydrolyzable silicon group in the components (A) to (D) in the composition may be used. Examples of curing accelerator catalysts are metal titanates, organosilicon titanates, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate; Other acidic and basic catalysts can be used.

If further necessary for the composition of the present invention,
Fillers, plasticizers, pigments, thixotropic agents, various antiaging agents, ultraviolet absorbers and the like can be used.

As the filler, calcium carbonate, fumed silica, precipitated silica, silicic acid anhydride, silicic acid hydrate and carbon black, magnesium carbonate, diatomaceous earth,
Calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, chaff flour, graphite, aluminum fine Powdery fillers such as powders and flint powders, and fibrous fillers such as asbestos, glass fibers, glass filaments, carbon fibers, Kevlar fibers, and polyethylene fibers can be used. The amount of the filler used is 50 with respect to the organic polymer (A).
~ 800 wt% is preferred. Particularly, 50 to 250% by weight is preferable.

As the plasticizer, phthalates such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate; Alcohol esters such as pentaerythritol ester; phosphoric acid esters such as trioctyl phosphate, tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, benzyl epoxystearate; chlorine Paraffin; polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol, polyethers such as polyoxypropylene glycol and its derivatives, oligomers of polystyrene such as poly-α-methylstyrene and polystyrene S, polybutadiene, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, polymeric plasticizers oligomers such as epoxidized polybutadiene can be used. The amount of the plasticizer used is preferably 0 to 100% by weight based on the organic polymer (A).

Examples of the pigment include inorganic pigments such as iron oxide, chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green, and organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate, stearic acid as a thixotropic agent. Examples thereof include zinc and finely divided silica.

The curable composition of the present invention comprises a sealant,
It can be used as a waterproof material, an adhesive, a coating agent, and the like, and is particularly suitable for applications in which sufficient cohesive force of the cured product itself and dynamic followability to an adherend are required.

[0066]

EXAMPLES Organic polymers produced in Production Examples 1 to 4 (P1 to
Examples and comparative examples in which a cured product is produced by using P4) are shown below. As the compounds S1 and S2 containing an epoxy group or a functional group capable of reacting with the epoxy group and a hydrolyzable silicon group in the same molecule, the compounds shown in Table 1 were used. In addition, a part shows a weight part.

Production Example 1 Propylene oxide was polymerized using dipropylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol. Sodium hydroxide was added to this to deactivate the catalyst and then neutralized with hydrochloric acid, and the precipitated salt was filtered with an adsorbent to obtain a purified product. Isocyanatopropylmethyldimethoxysilane was added to this to undergo a urethanization reaction to convert both terminals into methyldimethoxysilylpropyl groups to obtain an organic polymer P1. The total amount of remaining ionic impurities was 2 ppm. The molecular weight of the organic polymer P1 is 13,500 based on the hydroxyl value converted molecular weight of the raw material polyoxypropylene diol, and the molecular weight distribution (M _w / M _n ).
Was 1.25.

[Production Example 2] Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol. A methanol solution of sodium methoxide was added to this to remove methanol, and then allyl chloride was reacted to convert the terminal hydroxyl group into an allyloxy group. A small amount of water and sodium acid pyrophosphate were added to the reaction product to coagulate the salt, which was then filtered with an adsorbent to obtain a purified product. The molecular weight of the obtained terminal allyl group-containing polyoxyalkylene was 18,200 based on the hydroxyl group-equivalent molecular weight of the raw material polyoxypropylenetriol, and the molecular weight distribution (M
_w / _Mn ) was 1.34.

The obtained terminal allyl group-containing polyoxyalkylene was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the terminals into methyldimethoxysilylpropyl groups to obtain an organic polymer P2. The total amount of remaining ionic impurities was 18 ppm. The molecular weight of the organic polymer P2 was 18,500 based on the hydroxyl value-converted molecular weight of the raw material polyoxypropylene triol, and the molecular weight distribution (M _w / M
_n ) was 1.35.

[Production Example 3] A polyoxypropylene diol having an average molecular weight of 3000 obtained using a KOH catalyst was reacted with dibromomethane in the presence of sodium metal to increase the molecular weight. The terminal hydroxyl groups of the obtained high molecular weight polyoxypropylene diol were terminally allyloxylated in the same manner as in Production Example 2, and the precipitated salt was filtered to obtain a purified product.

The terminal was converted into a methyldimethoxysilylpropyl group in the same manner as in Production Example 2 to obtain an organic polymer P3. The total amount of remaining ionic impurities was 94 ppm. The molecular weight of the organic polymer P3 is 8,50 based on the hydroxyl value-converted molecular weight of the raw material polyoxypropylene diol.
0, the molecular weight distribution (M _w / M _n ) was 2.59.

[Production Example 4] Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol. This terminal hydroxyl group was converted to a terminal allyloxy group in the same manner as in Production Example 2. The emulsified reaction product was filtered through a filter paper to obtain a thin turbid liquid product.

The terminal was converted into a methyldimethoxysilylpropyl group in the same manner as in Production Example 2 to obtain an organic polymer P4. The total amount of remaining ionic impurities was 106 ppm. The molecular weight of the organic polymer P4 is 1 based on the hydroxyl value converted molecular weight of the raw material polyoxypropylene triol.
The molecular weight distribution (M _w / M _n ) was 8,400 and was 1,32.

[Examples 1 and 2 and Comparative Examples 1 and 2] Organic polymers (P1 to P4) 100 obtained in Production Examples 1 to 4
Part, Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) 50 parts, 2, 4, 6
5 parts of tris (dimethylaminomethyl) phenol and 2 parts of dibutyltin dilaurate were added and mixed well to obtain a composition.

A sheet having a thickness of 2 mm was prepared using the composition, and physical properties were measured after curing and curing at 20 ° C. for 7 days and further at 50 ° C. for 7 days. That is, the tensile strength and the elongation at break were measured. Table 2 shows the results.

Also, the adherend surfaces of two aluminum plates having a length of 300 mm, a width of 25 mm, and a thickness of 0.15 mm were wiped with a solvent, and the above composition was applied to both sides of the aluminum plates so that the thickness became 0.5 mm. 5kg of adherend surfaces
The roller was pressed 5 times. Curing was carried out at 20 ° C. for 7 days and at 50 ° C. for 7 days as above.

Immediately after curing the aluminum plate bonding test specimen and after further immersing it in hot water of 50 ° C. for 7 days, the T-type peel strength was measured at a tensile speed of 200 mm / min in accordance with JIS K6854. Table 2 shows the results.

[Examples 3 and 4 and Comparative Examples 3 and 4] 100 parts of organic polymer (P1 to P4), 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), dibutyltin dilaurate 2 parts and 4 parts of compounds S1 to S2 (shown in Table 3) were added and mixed well to obtain a composition.

The same tests as in Example 1 were carried out using these compositions. The results are shown in Table 3.

[Examples 5 and 6 and Comparative Examples 5 and 6] 100 parts of organic polymer (P1 to P4), 50 parts of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), 2, 5 parts of 4,6-tris- (dimethylaminomethyl) phenol, 2 parts of dibutyltin dilaurate, and 2 parts of compounds S1 to S2 were added and mixed well to obtain a composition.

The same tests as in Example 1 were carried out using these compositions. The results are shown in Table 4.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

Industrial Applicability As described above, the curable composition of the present invention has a remarkably excellent mechanical strength and adhesiveness, and the composition has excellent storage stability, water-resistant adhesiveness and curability. Excel.

Claims (8)

[Claims] 1. A hydrolyzate derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing alkylene oxide with an initiator using a complex metal cyanide complex (E) as a catalyst, and represented by the following formula (1): A curable composition comprising a decomposable silicon group and an organic polymer (A) having a total amount of ionic impurities of 50 ppm or less and an epoxy resin (B) as essential components. —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydroxyl group or hydrolyzable group, a is 1, 2 or 3. 2. The curable composition according to claim 1, which contains an epoxy curing agent (C). 3. The curable composition according to claim 1, which contains a compound (D) containing an epoxy group or a functional group capable of reacting with an epoxy group and a hydrolyzable silicon group in the same molecule. 4. The ionic impurities, which are ionic impurities containing a metal compound and / or an alkali metal compound derived from the complex metal cyanide complex (E).
Curable composition in any one of. 5. An ionic impurity contained in the organic polymer (A) is converted to a salt essentially insoluble in the organic polymer (A), and then the salt is removed from the organic polymer (A). The ionic impurities contained in the organic polymer (A) by 50 pp.
m or less, The curable composition in any one of Claims 1-4 characterized by the above-mentioned. 6. An organic polymer (A), wherein an ionic impurity contained in the polymer (F) is converted into a salt essentially insoluble in the polymer (F), and then the salt is added to the polymer (F). ), The ionic impurities contained in the polymer (F) are reduced to 50 p
The curable composition according to any one of claims 1 to 4, which is an organic polymer obtained by introducing a hydrolyzable silicon group into the polymer (F) after adjusting to pm or less. 7. The organic polymer (A) contains an ionic impurity contained in the terminal unsaturated group-introduced product (G) of the polymer (F),
After the salt is essentially insoluble in the terminal unsaturated group-introduced product (G), the salt is removed from the terminal unsaturated group-introduced product (G) to be contained in the terminal unsaturated group-introduced product (G). An organic polymer obtained by reacting the terminal unsaturated group-introduced product (G) with a silicon hydride compound represented by the following formula (2) after adjusting the ionic impurities to 50 ppm or less, 5. Curable composition in any one of. HSiX _a R ¹ _3-a (2) In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3. 8. The curable composition according to claim 1, wherein the hydroxyl group-containing polyoxyalkylene polymer (F) has a hydroxyl value-converted molecular weight of 5,000 to 30,000.