JPH08231854A - Room-temperature-curing composition - Google Patents

Abstract

PURPOSE: To obtain a curing composition excellent in storage stability by mixing a specified organic polymer having hydrolyzable silicon groups in the molecule with a curing catalyst and a filler. CONSTITUTION: This composition comprises an organic polymer having hydrolyzable silicon groups each having a Si-bonded hydrolyzable group in the molecule and a total content of ionic impurities of 50ppm or below, a curing catalyst, and a filler. It is desirable that the hydrolyzable silicon group of the organic polymer is -R-SiXa R3-a (wherein R is a bivalent organic group; R<1> is a 1-20C monovalent hydrocarbon group; X is a hydrolyzable group; and a is 1, 2 or 3).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable composition which cures in the presence of moisture.

[0002]

2. Description of the Related Art Polyethers having a hydrolyzable silicon group (which represents a silicon group having a hydrolyzable group directly bonded to a silicon atom) capable of forming a siloxane bond by hydrolysis and having a high molecular weight or crosslinking are known. (For example, JP-A-3-47825, JP-A-3-72527,
JP-A-3-79627, JP-B-46-30711, JP-B-45-36319, and JP-B-46-17553).

[0003]

Since these polyethers having a hydrolyzable silicon group have a step of reacting with an organic halogen compound or the like under alkaline conditions as a production condition, salts are by-produced and their removal is eliminated. Will be needed. It is known that the residual salt increases the water absorption of a cured product obtained by curing a polyether having a hydrolyzable silicon group and deteriorates the water resistance.

When an alkali metal or an alkali metal compound such as an alkali metal, an alkali metal hydroxide or an alkali metal hydride is used as an alkali in the above reaction, it may have a hydrolyzable silicon group produced in some cases. The storage stability of a curable composition produced by adding a filler, a catalyst and the like to polyether may be significantly deteriorated.

The raw material of the polyether having a hydrolyzable silicon group is generally produced by ring-opening polymerization reaction of a cyclic ether with an initiator. As a polymerization catalyst used at the time of production, other than the alkali metal compound is used. With respect to the hydrolyzable silicon group-containing polyether produced using a metal compound, the storage stability of a curable composition produced by adding a filler, a catalyst and the like may be significantly deteriorated.

A composition obtained by adding a filler, a catalyst and the like to a polyether having a hydrolyzable silicon group is used as a sealing agent, an adhesive and the like. Poor storage stability causes an increase in viscosity with time and extrusion. Workability is deteriorated, which is extremely unfavorable.

[0007]

DISCLOSURE OF THE INVENTION The present invention is the following invention which is intended to improve such problems, particularly the storage stability of the curable composition. An organic polymer (A), a curing catalyst (B), which has a hydrolyzable silicon group having a hydrolyzable group directly bonded to a silicon atom in the molecule, and contains a total amount of ionic impurities of 50 ppm or less, And a curable composition containing a filler (C).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[Organic Polymer] The organic polymer (A) of the present invention is preferably derived from a hydroxyl group-containing polyether (D). The hydroxyl group-containing polyether (D) is preferably produced by subjecting a cyclic ether to ring-opening polymerization reaction in the presence of an initiator such as a hydroxy compound and a catalyst.

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, particularly 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, sorbitol, sucrose, and polyols having a lower molecular weight than the target product obtained by reacting these with a cyclic ether. These may be used alone or in combination of two or more. Unsaturated group-containing monohydroxy compounds such as allyl alcohol and its cyclic ether adducts can also be used.

Examples of cyclic ethers include alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and hexylene oxide, and tetrahydrofuran.

As the catalyst, generally used alkali metals such as sodium, potassium and cesium, complex metal cyanide complexes and metal porphyrin complexes can be used.

The organic polymer (A) in the present invention is particularly derived from a hydroxyl group-containing polyether (D) obtained by polymerizing a cyclic ether with an initiator using the complex metal cyanide complex (E) as a catalyst. preferable.

By using the complex metal cyanide complex (E) in the preparation of the hydroxyl group-containing polyether (D), M _w / M _n can be improved over the conventional alkali metal catalyst.
And a hydroxyl group-containing polyether (D) having a high molecular weight and a low viscosity is obtained.

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 preferable. As the composition, those essentially described in JP-B-46-27250 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 the alcohol, t-butanol described in JP-A-4-145123 is preferable.

In the present invention, preferably, the number of hydroxyl groups in the hydroxyl group-containing polyether (D) can be arbitrarily controlled by changing the number of hydroxyl groups in the initiator. When the molecular weights are the same, the higher the number of functional groups is, the higher the number of functional groups becomes. The viscosity becomes low.

The physical properties of the cured product of the composition obtained by blending the organic polymer (A) with the compounding agent are such that the hydrolysis of the organic polymer (A) does not depend on the number of hydroxyl groups of the hydroxyl group-containing polyether (D). It can be freely controlled by the content of the functional silicon group. Therefore, it has the same physical properties as conventional products such as strength and elongation,
A composition using the low-viscosity organic polymer (A) is obtained.

The number of hydroxyl groups per molecule of the hydroxyl group-containing polyether (D) 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 hydroxyl group-containing polyethers (D) are polyoxypropylene diol, polyoxypropylene triol and polyoxypropylene tetraol. 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 hydroxyl group-containing polyether (D) preferably has a hydroxyl value-converted molecular weight of 5,000 to 30,000,
It is more preferably 8,000 to 30,000. The hydroxyl group-equivalent molecular weight of the hydroxyl group-containing polyether may be arbitrary depending on the purpose. If a low hydroxyl value-converted molecular weight is used, the curable composition generally produced from it has a low viscosity, and the cured product has a small elongation but is hard and has high strength. For example, the curable composition produced therefrom has a high viscosity, and the cured product can be soft and have a large elongation.

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

The viscosity of the hydroxyl group-containing polyether (D) is preferably 50,000 cP or less at room temperature, and particularly preferably 30,000 cP or less.

The hydrolyzable silicon group having a hydrolyzable group directly bonded to a silicon atom in the organic polymer (A) is preferably a group represented by the following formula (1).

-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, X is a hydroxyl group or a hydrolyzable group, 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, There 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, especially a methoxy group,
Examples thereof include ethoxy group and propoxy group. Equation (1)
In the formula, a is 1, 2 or 3, and 2 or 3 is preferable.

The organic polymer (A) is preferably the one having a hydrogen atom in the hydroxyl group of the hydroxyl group-containing polyether (D) substituted by the formula (1).

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 at the terminal of the hydroxyl group-containing polyether (D) by the methods described in (a) to (d) below. Such a compound is a liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and a sealing material,
When used as an adhesive or the like, it has desirable characteristics.

(A) A method of reacting the terminal unsaturated group-introduced product (F) of the hydroxyl group-containing polyether (D) 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.

As a method for obtaining the terminal unsaturated group-introduced product (F) of the hydroxyl group-containing polyether (D), the terminal hydroxyl group OH of the hydroxyl group-containing polyether (D) is changed to OM (M is an alkali metal), and then chlorinated. Method of reacting with unsaturated group-containing halogenated hydrocarbon such as allyl or a compound having an unsaturated group and a functional group capable of reacting with a hydroxyl group is reacted with a hydroxyl group-containing polyether (D) to form an ester bond, a urethane bond or a carbonate. There is a method of combining by combining. Furthermore, when polymerizing an alkylene oxide in the production of the hydroxyl group-containing polyether (D), a method or an initiator for introducing an unsaturated group into a side chain by copolymerizing an unsaturated group-containing alkylene oxide such as allyl glycidyl ether It can also be obtained by using a monohydroxy compound having a terminal unsaturated group as.

(B) A method of reacting a compound having a hydrolyzable silicon group represented by the formula (1) with an isocyanate group and a hydroxyl group-containing polyether (D).

(C) After the hydroxyl group-containing polyether (D) is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the isocyanate group has a W of a silicon compound represented by the following formula (3). Method of reacting groups.

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). Is.

(D) Reaction of the unsaturated group of the terminal unsaturated group-introduced product (F) of the hydroxyl group-containing polyether (D) with the mercapto group of the silicon compound represented by the formula (3) in which W is a mercapto group. How to make.

The organic polymer (A) of the present invention has a total amount of ionic impurities of 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 when the organic polymer is produced or when the hydrolyzable silicon group is introduced. 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.

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 the 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 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 methods (e) and (f) can be exemplified.

Ionic impurities and the like are removed, the increase in viscosity of the product when each silicon compound is reacted is suppressed, and the curing catalyst (B) and the filler (C) are added to produce a cured product. Since the storage stability of the composition is improved (f)
Is particularly preferable.

(E) After making the ionic impurities contained in the hydroxyl group-containing polyether (D) essentially insoluble in the hydroxyl group-containing polyether (D), the salt is removed from the polymer (B). By setting the ionic impurities contained in the hydroxyl group-containing polyether (D) to 50 ppm or less, a hydrolyzable silicon group is introduced into the hydroxyl group-containing polyether (D) to obtain an organic polymer (A).

(F) The ionic impurities contained in the terminal unsaturated group-introduced product (F) of the hydroxyl group-containing polyether (D) are essentially salts insoluble in the terminal unsaturated group-introduced product (F). After that, the salt is removed from the terminal unsaturated group-introduced product (F) to reduce the ionic impurities contained in the terminal unsaturated group-introduced product (F) to 50 ppm or less, and then the terminal unsaturated group-introduced product (F). ) With a silicon hydride compound represented by the formula (2) to give an organic polymer (A).

The molecular weight of the organic polymer (A) in the present invention is calculated based on the hydroxyl group-equivalent molecular weight of the hydroxyl group-containing polyether (D) as the raw material. The molecular weight is 50
00-30000 is preferable. When it is lower than 5,000, the cured product becomes hard and has low elongation. When it exceeds 30,000, the flexibility and elongation of the cured product are not problematic, but the viscosity of the polymer itself is remarkably increased and the practicality is lowered. Particularly, 8000 to 30,000 is preferable.

[Curing catalyst] In the present invention, the curing catalyst (B) is essential for curing the organic polymer. When the curing catalyst (B) is not used, it is difficult to obtain a significant reaction rate in the crosslinking reaction of the hydrolyzable silicon group. The amount of the curing catalyst used is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight, based on the organic polymer (A). Examples of the curing catalyst (B) include the following compounds.

Alkyl titanates, organosilicon titanates, salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, amine salts such as dibutylamine-2-ethylhexoate, and other acids. Catalysts and basic catalysts.

[Filler] As the filler (C), known fillers can be used. The amount of the filler used is the organic polymer (A)
50 to 800% by weight is preferable. 50-250
Weight percent is particularly preferred. Specific examples of the filler include the following. These fillers may be used alone or in combination of two or more.

Calcium carbonate, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, Powdered fillers such as zinc oxide, activated zinc oxide, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, asbestos, glass fiber, glass filament, Fibrous fillers such as carbon fiber, Kevlar fiber and polyethylene fiber.

[Other Additives] In the present invention, a plasticizer can be optionally used. Known plasticizers can be used as the plasticizer. The amount of the plasticizer used is preferably 0 to 100% by weight based on the organic polymer (A). The following may be mentioned as specific examples of the plasticizer.

Dioctyl phthalate, dibutyl phthalate,
Phthalates such as butylbenzyl phthalate; aliphatic carboxylic esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate; alcohol esters such as pentaerythritol ester; trioctyl phosphate, tricresyl phosphate Epoxidized soybean oil, epoxy plasticizer such as 4,5-epoxy hexahydrophthalate dioctyl, benzyl epoxy stearate, etc .; chlorinated paraffins; polyesters of dibasic acid and dihydric alcohol, etc. Polyester plasticizers, polyethers such as polyoxypropylene glycol and its derivatives, poly-α-methylstyrene, polystyrene oligomers such as polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, poly Ropuren, polyisoprene, polybutene, hydrogenated polybutene, polymeric plasticizers oligomers such epoxidized polybutadiene.

The composition of the present invention may further contain various known additives. As the additive, an adhesiveness-imparting agent such as phenol resin or epoxy resin, a thixotropic agent such as hydrogenated castor oil, a pigment, various antiaging agents, an ultraviolet absorber or the like can be used.

Inorganic pigments such as iron oxide, chromium oxide and titanium oxide and organic pigments such as phthalocyanine blue and phthalocyanine green are used as the pigments. Organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate and zinc stearate are used as anti-sagging agents. Examples of the adhesive include aminosilane and epoxysilane.

The curable composition of the present invention comprises a sealant,
It can be used as a waterproofing agent, an adhesive, a coating agent and the like. In particular, it is suitable for applications in which the cured product itself requires sufficient strength and high adhesiveness.

The curable composition of the present invention itself has very good storage stability, but further, by reducing the coexisting inorganic acid and / or organic acid, the storage stability becomes better.

[0059]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Parts indicate parts by weight. First, Synthesis Examples 1 to 14 show production examples of organic polymers (P1 to P14) which are raw materials of the organic polymer (A).

(Synthesis Example 1) Propylene oxide was polymerized using glycerin as an initiator and cesium hydroxide as a catalyst to obtain polyoxypropylenetriol having a hydroxyl value of 13.5 mgKOH / g. Terminal hydroxyl group-OH
Was changed to -ONa and then the terminal hydroxyl group was converted to an allyloxy group by reaction with allyl chloride to obtain an organic polymer (P1) containing impurities such as metal salts.

(Synthesis Example 2) Propylene oxide was polymerized using diethylene glycol as an initiator and zinc hexacyanocobaltate as a catalyst to give a hydroxyl value of 28.0 mgK.
OH / g of polyoxypropylene diol was obtained. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyloxy group, to obtain an organic polymer (P2) containing impurities such as metal salts.

(Synthesis Example 3) In accordance with the method described in JP-A-61-215623, propylene oxide was polymerized with an allyl alcohol as an initiator using an aluminum-porphyrin complex as a catalyst, and subsequently reacted with allyl bromide. ,
An organic polymer (P3) having an allyloxy group at the terminal and containing impurities such as a metal salt was obtained. When the amount of double bonds in this product was analyzed, it contained 0.125 mmol / g of double bonds.

(Synthesis Example 4) Propylene oxide was polymerized using pentaerythritol as an initiator and cesium hydroxide as a catalyst to obtain polyoxypropylene tetraol having a hydroxyl value of 13.1 mgKOH / g. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyloxy group, to obtain an organic polymer (P4) containing impurities such as metal salts.

(Synthesis Example 5) Hydroxyl group value obtained by polymerizing propylene oxide using diethylene glycol as an initiator and zinc hexacyanocobaltate as a catalyst.
A 1: 1 weight ratio of 2 mg KOH / g polypropylene diol and polypropylene triol having a hydroxyl value of 33.4 mg KOH / g obtained by polymerizing propylene oxide using glycerin as an initiator and zinc hexacyanocobaltate as a catalyst. The resulting polymer is reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyloxy group, and an organic polymer containing impurities such as metal salts (P5)
I got

(Synthesis Example 6) Hydroxyl value obtained by polymerizing propylene oxide using diethylene glycol as an initiator and zinc hexacyanocobaltate as a catalyst.
2 mg KOH / g of polypropylene diol and polyoxypropylene tetraol having a hydroxyl value of 44.1 mg KOH / g, obtained by polymerizing propylene oxide with pentaerythritol as an initiator and zinc hexacyanocobaltate as a catalyst, in a weight ratio of 5 The mixture of 1 to 1 was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyloxy group to obtain an organic polymer (P6) containing impurities such as metal salts.

(Synthesis Example 7) Polyoxypropylene diol having a hydroxyl value of 37.4 was reacted with potassium hydroxide, chlorobromomethane and allyl chloride according to the method described in Japanese Examined Patent Publication No. 56-5249 to extend the chain and gel permeation chromatography. Organic polymer containing impurities such as metal salt having a number average molecular weight of 13,000 (in terms of polystyrene) by graph analysis (P7)
I got

(Synthesis Example 8) Propylene oxide was polymerized using a glycerin-propylene oxide adduct having a molecular weight of 1000 as an initiator and zinc hexacyanocobaltate as a catalyst to give a hydroxyl value of 11.2 mgKOH / g and a viscosity at 25 ° C of 7,000 cP. Polyoxypropylene triol was obtained. Subsequently, 1.1 times equivalent of sodium methoxide to the hydroxyl group of polyoxypropylene triol was added, then methanol was distilled off, and allyl chloride was added to convert the terminal hydroxyl group to an allyloxy group to convert metal salt as an impurity. An organic polymer (P8) having a terminal unsaturated group containing was obtained.

(Synthesis Example 9) Propylene oxide was polymerized using ethylene glycol as an initiator and zinc hexacyanocobaltate as a catalyst to give a hydroxyl value of 9.3 mgKOH.
/ G, a viscosity at 25 ° C. of 8000 cP was obtained, and the terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P9) containing a metal salt as an impurity.

(Synthesis Example 10) Propylene oxide was polymerized using ethylene glycol as an initiator and zinc hexacyanocobaltate as a catalyst to give a hydroxyl value of 5.6 mg KO.
H / g, a polyoxypropylene diol having a viscosity at 25 ° C. of 17,000 cP was obtained, and subsequently, the terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P10) containing a metal salt as an impurity. It was

(Synthesis Example 11) Propylene oxide was polymerized using a pentaerythritol-propylene oxide adduct having a molecular weight of 1000 as an initiator and zinc hexacyanocobaltate as a catalyst to obtain a hydroxyl value of 13.2 mgKOH /
g, polyoxypropylene tetraol having a viscosity at 25 ° C. of 6000 cP was obtained, and then the terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P11) containing a metal salt as an impurity. .

(Synthesis Example 12) Propylene oxide was polymerized using a sorbitol-propylene oxide adduct as an initiator and zinc hexacyanocobaltate as a catalyst to give a hydroxyl value of 16.8 mgKOH / g and a viscosity at 25 ° C of 80.
An organic polymer containing a metal salt as an impurity (P1) was obtained by converting the terminal hydroxyl group into an allyloxy group by the method described in Synthesis Example 1 and obtaining polyoxypropylene hexaol of 00 cP.
2) was obtained.

Synthesis Example 13 Synthesis Example 10 and Synthesis Example 8
After mixing the polyoxypropylene diol and the polyoxypropylene triol used in step 2 in a weight ratio of 2: 1,
The terminal hydroxyl group was converted into an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P13) containing a metal salt as an impurity.

(Synthesis Example 14) Synthesis Example 10 and Synthesis Example 1
The polyoxypropylene diol used in 1 and polyoxypropylene tetraol were mixed at a weight ratio of 4: 1, and then the terminal hydroxyl group was converted into an allyloxy group by the method described in Synthesis Example 1 to contain an organic polymer containing a metal salt as an impurity ( P1
4) was obtained.

(Examples 1 to 7) The organic polymers P1 to P7 were purified by the purification method A or the purification method B, and the amount of the residual metal salt was measured. Table 1 shows the results. Then, a methyldimethoxysilylpropyl group was introduced at the terminal of the organic polymer by a known method using a platinum catalyst.

(Examples 8 to 14) Organic polymers P1 to P7 were used for purification by the method of (purification method a) as a purification method, and the purification was insufficient, or the method of (purification method c) However, the amount of residual metal salt of the organic polymer which was not sufficiently purified was measured. The results are shown in Table 2. Then, a methyldimethoxysilylpropyl group was introduced at the terminal of the organic polymer by a known method using a platinum catalyst.

(Examples 15 to 24) Organic polymers P8 to P14
Was purified by the following purification method A or purification method A, and the amount of residual metal salt was measured. It is shown in Tables 3 to 4 together with the viscosity of the organic polymer after purification. Then, a methyldimethoxysilylpropyl group was introduced at the terminal of the organic polymer by a known method using a platinum catalyst. The viscosities after introduction of the methyldimethoxysilylpropyl group are also shown in Tables 3-4.

(Examples 25 to 31) Organic polymers P8 to P14
An organic polymer which was purified by the method of (Purification method A) and was insufficiently purified or an attempt was made by the method of (Purification method C) but the purification was insufficient. The amount of residual metal salt and the viscosity after purification were measured. The results are shown in Table 4. Then, a methyldimethoxysilylpropyl group was introduced at the terminal of the organic polymer by a known method using a platinum catalyst. Table 4 also shows the viscosity after introduction of the methyldimethoxysilylpropyl group.

In the above Examples 1 to 31, the content of the methyldimethoxysilylpropyl group was in the range of 0.11 mmol to 0.17 mmol per 1 g of the organic polymer. In any of the examples, the amount of residual metal salt of the organic polymer after introducing the methyldimethoxysilylpropyl group was the same as that before introducing the methyldimethoxysilylpropyl group.

(Curable Composition) In the above Examples 1 to 31, 160 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, and 60 parts of dioctyl phthalate were used with respect to 100 parts by weight of the organic polymer having a methyldimethoxysilylpropyl group introduced therein. Parts by weight, hydrogenated castor oil 5 parts by weight, phenolic antioxidant 1 part by weight, and kneading to heat and dehydrate, vinyltrimethoxysilane 1 part by weight, 3- (2-aminoethyl) aminopropyltrimethoxysilane [H ₂ N (CH ₂ ) ₂
1 part by weight of NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ] was added and the mixture was kneaded in a nitrogen atmosphere.

Further, 1 part by weight of dibutyltin dilaurate was added and kneaded again to obtain a curable composition. Tables 1 to 4 show the results of measuring the viscosity of this composition at 25 ° C. after production and the viscosity at 25 ° C. after storage at 50 ° C. for 14 days.

However, in Examples 15 to 19 and Examples 23 to 29, a curable composition was obtained without adding dibutyltin dilaurate, and the composition had a viscosity at 25 ° C. after its preparation and after storage at 50 ° C. for 14 days. Tables 1 to 4 show the results of measuring the viscosities of the above.

(Purification method a) 5 g of a polyoxypropylene polymer having a molecular weight of 10,000 and having a molecular weight of 10,000 and having 50 g of water and 50 g of an acid pyrophosphoric acid per 1 kg of an organic polymer containing an ionic impurity such as a metal salt. Sodium (10 g) was added, and the mixture was stirred at 90 ° C for 1 hr.
Then, after distilling off water at 90 ° C. under reduced pressure, Kyoward 600 (synthetic magnesia silicate, manufactured by Kyowa Chemical Co., Ltd.) was added to 1
0 g was added, and the mixture was dehydrated under reduced pressure at 90 ° C. for 1 hour, then 2 liters of hexane was added to dissolve the organic polymer, and the insoluble matter was removed by filtration using a filter paper. Then, hexane was distilled off under reduced pressure to obtain a purified organic polymer.

(Purification method a) 1 kg of an organic polymer containing an ionic impurity such as a metal salt is dissolved in 2 liters of methanol containing 0.1 liter of water, and a cation exchange resin (Diaion SK-1B, Mitsubishi) is used. Glass column filled with chemicals and anion exchange resin (Diaion SA-10A,
Liquid was sequentially passed through a glass column filled with Mitsubishi Chemical).
The solution obtained was distilled off under reduced pressure to obtain a purified organic polymer.

(Purification method c) According to the method described in JP-B-61-25739, 1 kg of an organic polymer containing an ionic impurity such as a metal salt is dissolved in 3 kg of hexane to obtain 3% by weight.
1 kg of sulfuric acid water was added and stirred for 1 hour, but the whole became cloudy. Although it was left at room temperature for 3 days, a slightly transparent hexane layer separated into the uppermost layer about 1/5 of the whole, so the hexane layer was separated by decantation, and hexane was distilled off under reduced pressure to obtain a purified organic polymer. It was

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

[0089]

The curable composition of the present invention has remarkably excellent storage stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Higuchi 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory

Claims (8)

[Claims] 1. An organic polymer (A), which has a hydrolyzable silicon group having a hydrolyzable group directly bonded to a silicon atom in the molecule, and has a total amount of ionic impurities of 50 ppm or less, and cured. A curable composition containing a catalyst (B) and a filler (C). 2. The curable composition according to claim 1, wherein the hydrolyzable silicon group of the organic polymer (A) is 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 has 1 to 20 carbon atoms.
Is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, and a is 1, 2 or 3. 3. The curable composition according to claim 1, wherein the organic polymer (A) is derived from a hydroxyl group-containing polyether (D). 4. An organic polymer (A) is derived from a hydroxyl group-containing polyether (D) obtained by polymerizing a cyclic ether in the presence of a double metal cyanide complex (E) as a catalyst and an initiator. The curable composition according to any one of claims 1 to 3. 5. The curable composition according to claim 4, wherein the ionic impurities are ionic impurities containing a metal compound and / or an alkali metal compound derived from the complex metal cyanide complex (E). 6. An organic polymer (A), wherein an ionic impurity contained in a hydroxyl group-containing polyether (D) is converted into a salt essentially insoluble in the hydroxyl group-containing polyether (D), and then the salt is added. After removing the ionic impurities contained in the hydroxyl group-containing polyether (D) from the hydroxyl group-containing polyether (D) to 50 ppm or less, a hydrolyzable silicon group is introduced into the hydroxyl group-containing polyether (D). The curable composition according to any one of claims 1 to 5, which is the obtained organic polymer. 7. The organic polymer (A) essentially comprises the ionic impurities contained in the terminal unsaturated group-introduced product (F) of the hydroxyl group-containing polyether (D) in the terminal unsaturated group-introduced product (F). A salt that is insoluble in water, and then the salt is removed from the terminal unsaturated group-introduced product (F) to reduce the ionic impurities contained in the terminal unsaturated group-introduced product (F) to 50 ppm or less. The curable composition according to any one of claims 1 to 5, which is an organic polymer obtained by reacting an unsaturated group-introduced product (F) with a silicon hydride compound represented by the following formula (2). 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, a is 1, 2 or 3. 8. The hydroxyl group-containing polyether (D) has a hydroxyl value-converted molecular weight of 5,000 to 30,000.
Curable composition in any one of -7.