JP3145011B2 - Room temperature curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a method of using as a sealing material, an adhesive or the like by utilizing a curing reaction of various organic polymers having a hydrolyzable silicon group at a terminal such as a modified silicone resin. Is a well-known and industrially useful method.

[0003]

The organic polymer having a hydrolyzable silicon group at the terminal is disclosed, for example, in JP-B-45-36319, JP-B-46-17553, and JP-B-Showa-6.
1-118582 and the like.

[0004] Of the organic polymers having a hydrolyzable silicon group at the terminal, especially those having an alkoxysilyl group as the hydrolyzable silicon group, a so-called curing catalyst is used to impart room-temperature curability. This is usually done. As such a curing catalyst, an organic metal compound such as a metal salt of a carboxylic acid, an acidic or basic compound, and the like are known, and among them, a carboxylate of tin and other organic tin compounds are generally used.

[0005] Room temperature curability obtained by blending an organic polymer having a hydrolyzable silicon group at the end with various fillers, plasticizers, adhesion promoters, thixotropes, curing catalysts, various stabilizers, etc. When the resin composition of (1) is used for a sealing material, an adhesive or the like, the composition is roughly divided into two forms called a one-pack type and a two-pack type.

Of these, those known as two-pack types are divided into a main agent and a curing agent. At the time of use, these two components and, if necessary, a colorant or the like are mixed, applied and cured. is there. The curing agent in the two-pack type generally contains a curing catalyst. As the curing catalyst, a carboxylic acid of lead is used because a cured product exhibits good compression restorability against repeated expansion and contraction. A method using a salt or a divalent tin carboxylate and an organic amine compound, specifically, for example, tin octylate and laurylamine has been proposed (Japanese Patent Publication No. 61-608).
67).

However, in the two-pack type, as an organic polymer having a terminal hydrolyzable silicon group, a polyether compound having a relatively short molecular weight proposed in the above-mentioned known example is linked with a dihalo compound to increase the molecular weight. When the main component is a polymer having a hydrolyzable silicon group and a filler produced by a method of introducing a hydrolyzable silicon group after the use, when tin octylate and laurylamine are used as a curing catalyst, the curing speed, In particular, the curing speed at a portion far from the surface of the cured product, that is, at a deep portion, was insufficient, and was not satisfactory.

Further, as an organic polymer having a hydrolyzable silicon group at a terminal, Japanese Patent Application Laid-Open Nos.
In the case where the main component is an organic polymer containing a hydrolyzable silicon group produced from a polyoxyalkylene polymer produced by using a double metal cyanide complex as a catalyst according to Although the curability is remarkably improved, strict water management (that is, reducing the water content in the base material) is not usually performed when manufacturing the base material, so that the viscosity of the base material increases during long-term storage. In some cases, inconveniences occur during use.

[0009]

DISCLOSURE OF THE INVENTION The present invention is the following invention for solving such a drawback.

The following organic polymer (A), a curing catalyst (B) selected from divalent tin carboxylate, divalent bismuth carboxylate and divalent lead carboxylate, and an organic amine compound ( A room temperature curable composition containing (C) and a filler (D).

(Organic polymer) It is derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (E) as a catalyst. Having a hydrolyzable silicon group, and the total amount of ionic impurities is 50 ppm
The following organic polymer (A).

[0012] ^{_{-R 2 -SiX a R 1 3-}} a ··· (1)

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent organic group, X is a hydroxyl group or a hydrolyzable group, and a is 1 to 3 Is an integer.

[Organic Polymer] The organic polymer (A) is derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (E) as a catalyst. Is done.

By using the double metal cyanide complex (E), M
It is possible to obtain a hydroxyl group-containing polyoxyalkylene polymer (F) having a small _w / _Mn , a higher molecular weight, and a lower viscosity.

As the double metal cyanide complex (E), a complex containing zinc hexacyanocobaltate as a main component is preferable, and an ether and / or alcohol complex thereof is particularly preferable. Its composition is essentially JP-B-46-2725.
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 handling during the production of the complex. As the alcohol, t-butanol is preferable.

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 them with alkylene oxide. These may be used alone or in combination of two or more. Also, unsaturated group-containing monohydroxy compounds such as allyl alcohol can be used.

The organic polymer (A) of the present invention has a total amount of ionic impurities of 50 ppm or less. In particular, the present invention is suitable when the ionic impurity is a ionic impurity containing a metal compound and / or an alkali metal compound derived from the double metal cyanide complex (E). It is preferable that ionic impurities be 30 ppm or less, and more preferably 20 ppm or less.

By reducing the amount of these metallic impurities, the storage stability of the organic polymer (A) and the curable composition of the present invention can be further improved. Property is obtained.

As a method of reducing this, the following (I) to
(III). In particular, there is a method (III) that can be used for removing a metal compound caused by the double metal cyanide complex (E). The method (I) is particularly preferable because ionic impurities can be effectively and economically reduced.

(I) A method in which ionic impurities contained in a polymer are converted into a salt essentially insoluble in the polymer, and the salt is removed from the polymer. Specifically, after adding a compound capable of reacting with ionic impurities 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, sodium acid pyrophosphate and the like are preferable. The precipitated salt can be removed by a filtration operation, an adsorption operation, or the like.

(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 for removing a metal compound caused by a double metal cyanide complex (E) after treating with a pH buffer and optionally ammonia and a chelating agent, adding an aliphatic alcohol and a chelating agent, A method of removing a metal compound caused by the double metal cyanide complex (E), and a method of removing a metal compound caused by the double metal cyanide complex (E) after treatment with an oxidizing agent.

The ionic impurities referred to in the present invention are:
Cations and anions, such as zinc ions, cobalt ions, cyan ions, and chloride ions, caused by the double metal cyanide complex (E); sodium ions and potassium ions mixed as impurities in the step of producing the organic polymer (A) Alkali metal ions, halogen ions, etc .; carboxylate ions generated by oxidation of polyoxyalkylene in the step of producing the organic polymer (A); ester bonds in the step of producing the organic polymer (A),
Includes all anions and cations such as catalytic metal salts added when forming carbonate bonds and the like.

The organic polymer (A) has a hydrogen atom in the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer (F),
Those substituted by the formula (1) are preferred.

The number of hydroxyl groups per molecule of the polyoxyalkylene polymer (F) used in the present invention is preferably 2 to 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.

Preferred polymers (F) are polyoxypropylene diol, polyoxypropylene triol and polyoxypropylene tetraol. Further, when used in the following methods (a) and (d), unsaturated group-terminated polyoxyalkylene monols such as polyoxypropylene glycol monoallyl ether can also be used.

The molecular weight in terms of hydroxyl value of the polyoxyalkylene polymer (F) is preferably 5,000 to 30,000,
000-30000 is more preferable.

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

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

[0031] ^{_{-R 2 -SiX a R 1 3-}} a ··· (1)

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent organic group, X is a hydroxyl group or a hydrolyzable group, and a is 1 to 3 Is an integer.

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 a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a phenyl group and the like.

X is a hydroxyl group or a hydrolyzable group. 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 and a hydride group. Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, particularly preferably 4 or less. Preferred X includes a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group, a propoxy group, and the like. a is an integer of 1 to 3, preferably 2 or 3.

Next, a 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 method described in the following (A) to (D). Such compounds are liquid at room temperature, and the cured product retains flexibility even at relatively low temperatures,
When used as a sealing material, an adhesive or the like, it has preferable characteristics.

(A) A method of reacting the terminal unsaturated group-introduced product (G) of the polymer (F) with the silicon hydride compound represented by the formula (3).

[0037] ^{_{HSiX a R 1 3-a ···}} (3)

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

The terminal unsaturated group-introduced product (G) of the polymer (F)
Can be obtained by converting the terminal hydroxyl group OH of the polymer (F) to OM (M is an alkali metal) and then reacting it with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride. There is a method in which a compound having a reactive functional group is reacted with the polymer (F) and bound by an ester bond, a urethane bond, a carbonate bond, or the like. Further, 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 alkylene oxide having an unsaturated group 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) Compound having isocyanate group and hydrolyzable silicon group represented by formula (1) and polymer (F)
How to react.

(C) After the polymer (F) is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the W group of the silicon compound represented by the formula (4) is reacted with the isocyanate group. How to let.

[0042] ^{_{R 1 3-a -SiX a -R}} 5 W ··· (4)

Wherein R ¹ , X and a are the same as those described above;
R ⁵ is a divalent organic group, 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) Formula (4) wherein W is a mercapto group and the unsaturated group of the terminal unsaturated group-introduced product (G) of the polymer (F)
And reacting the mercapto group of the silicon compound represented by

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

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

The molecular weight of the organic polymer (A) in the present invention is calculated based on the hydroxyl value-converted molecular weight of the polymer (F) as a raw material. The molecular weight is 5,000 to 30,000
Is preferred. If it is lower than 5,000, the cured product is hard and the elongation is low. If it exceeds 30,000, the flexibility and elongation of the cured product are not problematic, but the viscosity of the polymer itself becomes extremely high and the practicality is lowered. Especially 8000-30
000 is preferred.

[Tin Catalyst] In the present invention, a curing catalyst (B) selected from a divalent tin carboxylate, a divalent bismuth carboxylate and a divalent lead carboxylate and an organic amine compound (C) are used. Used. These metal carboxylate salts themselves have an action of accelerating the curing of the organic polymer (A), but are insufficient for the purpose of the present invention, and must be used in combination with the organic amine compound (C).

The curing catalyst (B) is preferably a linear or branched salt of an aliphatic carboxylic acid having 20 or less carbon atoms. Examples of the aliphatic carboxylic acid having 20 or less carbon atoms include heptanoic acid, octylic acid, decanoic acid, lauric acid, and stearic acid. The curing catalyst (B) may be a mixture.

The amount of the metal carboxylate used is preferably 0.01 to 10 parts by weight, particularly preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the organic polymer (A).

The organic amine compound (C) of the present invention is preferably a monoamine having 20 or less carbon atoms or a polyamine having 20 or less carbon atoms. Further, a compound having an amino group and a hydrolyzable silicon group represented by the formula (2) in the molecule is preferable.

[0053] ^{_{-R 3 -SiX 1 b R 4 3}} -b ··· (2)

In the formula, R ³ is a divalent organic group, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X ¹
Is a hydroxyl group or a hydrolyzable group, and b is an integer of 1 to 3.

Examples of the amine having 20 or less carbon atoms include aliphatic mono (or poly) amine having 20 or less carbon atoms, alicyclic mono (or poly) amine having 20 or less carbon atoms, and aromatic mono (or poly) amine having 20 or less carbon atoms. It is preferably selected from mono (or poly) amines. Specifically, the following can be exemplified.

Monoamines: methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine,
Nonylamine, laurylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, cyclopropylamine,
Cyclobutylamine, cyclopentylamine, cyclohexylamine, aniline, N-methylaniline, N, N
-Dimethylaniline, N-ethylaniline, N, N-diethylaniline, toluidine, benzylamine, diphenylamine and the like.

Polyamines: ethylenediamine, diethylenediamine, triethylenediamine, hexamethylenediamine, dodecamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethanolamine, triethanolamine, N,
N, N'N'-tetramethyl-1,3-butanediamine, N, N, N'N'-tetramethylethylenediamine and the like.

Examples of the compound having an amino group and a hydrolyzable silicon group represented by the formula (2) in the molecule include an organic amine compound having a hydrolyzable silicon group in the molecule known as an amino group-containing silane. In particular, a reaction product of a compound having an epoxy group and a hydrolyzable silicon group in a molecule known as an amino group-containing silane and an epoxy group-containing silane is particularly preferable.

As the amino group-containing silane, specifically, γ
-Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane.

Epoxy group-containing silanes reacted with these amino group-containing silanes include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyl. Oxypropylmethyldiethoxysilane and the like.

In the present invention, the organic amine compound (C) is
0.01 to 10 parts by weight based on 100 parts by weight of the organic polymer (A)
It is preferable to use parts by weight. 0.1 to 3 parts by weight is particularly preferred.

In the present invention, a filler (D) is used. The amount of the filler used is 0 to 1 with respect to the organic polymer (A).
000% by weight, especially 50-250% by weight is preferred. The following are specific examples of the filler. These fillers may be used alone or in combination of two or more.

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

In the present invention, a plasticizer can be optionally used. Examples of the plasticizer include phthalic esters such as dioctyl phthalate, dibutyl phthalate, diisononyl phthalate and butylbenzyl phthalate; aliphatic carboxylic esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate Alcohol esters such as pentaerythritol ester; phosphates such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxystearate; Chlorinated paraffins can be used alone or in a mixture of two or more.

The composition of the present invention can further contain various known additives and the like. As the additive, an adhesion imparting agent such as a phenol resin and an epoxy resin, a thixotropic agent such as hydrogenated castor oil, a pigment, various antioxidants, and an ultraviolet absorber can be used.

[0066]

The present invention will now be described with reference to Examples (Examples 1 to 6, 15 and 2).
0, 29 to 34) and Comparative Examples (Examples 7 to 14, 21 to 2)
8, 35 to 45), but the present invention is not limited thereto. First, Synthesis Examples 1 to 7 show production examples of organic polymers P1 to P7 as raw materials of the organic polymer (A) (where P7 is an organic polymer for comparison). Parts indicate parts by weight.

[Synthesis Example 1] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a glycerin-propylene oxide adduct having a molecular weight of 1,000 as an initiator to obtain a hydroxyl value of 11.2 mgKOH / g,
Polyoxypropylene triol having a viscosity of 7000 cP at 5 ° C. was obtained. Subsequently, after adding 1.1 times equivalent of sodium methoxide to the hydroxyl group of polyoxypropylene triol, methanol was distilled off, and allyl chloride was added to convert the terminal hydroxyl group into an allyloxy group, thereby forming a metal salt as an impurity. The resulting organic polymer (P1) was obtained.

[Synthesis Example 2] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using ethylene glycol as an initiator, and the hydroxyl value was 9.3 mg.
A polyoxypropylene diol having KOH / g and a viscosity at 25 ° C. of 8000 cP was obtained. The terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P2) containing a metal salt as an impurity.

[Synthesis Example 3] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using ethylene glycol as an initiator, and the hydroxyl value was 5.6 mg.
Polyoxypropylene diol having a KOH / g and a viscosity at 25 ° C. of 17000 cP was obtained. Subsequently, the terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P3) containing a metal salt as an impurity.

[Synthesis Example 4] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a pentaerythritol-propylene oxide adduct having a molecular weight of 1,000 as an initiator, and the hydroxyl value was 13.2 mg KO.
A polyoxypropylene tetraol having a viscosity of 6000 cP at 25 ° C./H/g was obtained. The terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1 to obtain an organic polymer (P4) containing a metal salt as an impurity.

[Synthesis Example 5] The polyoxypropylene diol obtained in Synthesis Example 3 and the polyoxypropylene triol obtained in Synthesis Example 1 were mixed at a weight ratio of 2: 1.
The terminal hydroxyl group was converted to an allyloxy group by the method described to obtain an organic polymer (P5) containing a metal salt as an impurity.

[Synthesis Example 6] The polyoxypropylene diol obtained in Synthesis Example 3 and the polyoxypropylene tetraol obtained in Synthesis Example 4 were mixed at a weight ratio of 4: 1. Was converted to an allyloxy group to obtain an organic polymer (P6) containing a metal salt as an impurity.

[Synthesis Example 7] According to the method described in JP-B-59-25808, 3 moles of chlorobromomethane were reacted with 4 moles of polyoxypropylene diol having a hydroxyl value-converted molecular weight of 3000 in the presence of an alkali, followed by conversion of allyl chloride. By addition, the terminal hydroxyl group was converted to an allyloxy group to obtain an organic polymer (P7) containing a metal salt.

[Examples 1 to 14] Organic polymers P1 to P7 were purified by purification methods A to A, and the amount of residual metal ions (unit: p
pm). Tables 1 and 2 also show the viscosities (unit: cP) of the purified organic polymers P1 to P7.

Subsequently, a methyldimethoxysilylpropyl group was introduced into the terminal of the organic polymer by a known method using a platinum catalyst to obtain organic polymers S1 to S14. The viscosity of the organic polymers S1 to S14 after production is also shown in the table. The content of the methyldimethoxysilylpropyl group as a terminal group is 0.11 mmol to 0.17 mmol per 1 g of the organic polymer.
Range. The amount of residual metal ions in the obtained organic polymers S1 to S14 was the same as before the introduction of the methyldimethoxysilylpropyl group.

[Examples 15 to 28] Organic polymers (S1 to S1)
4) To 100 parts, 160 parts of calcium carbonate, 60 parts of dioctyl phthalate, 5 parts of hydrogenated castor oil, 1 part of phenolic antioxidant, 0.5 part of ultraviolet absorber and 0.5 part of light stabilizer were added. And kneaded to obtain main ingredients (M1 to M14).

On the other hand, 3 parts of laurylamine, 20 parts of dioctyl phthalate and 60 parts of calcium carbonate were kneaded with 10 parts of the metal carboxylate shown in the right column of Table 8 to obtain a curing agent (K).
1 to K5).

The viscosity immediately after the production of the base material (viscosity after production) (unit: cP) and the viscosity after storage at 50 ° C. for 14 days (viscosity after storage) (unit: cP) were measured. The results are shown in Tables 3 and 4.
Shown in

[Examples 29 to 45] The main ingredients (M
1 to M14) 100 parts and a curing agent (K1 to K5) 8.5 parts were kneaded, and the curable composition was poured into a cylindrical cup having a diameter of 4 cm so as to have a thickness of 3 cm.
It was left for 6 hours in an atmosphere of% humidity. Then JIS
Using a penetrometer compliant with K-2530, the state of curing from the surface to the depth direction was observed. The results are shown in Tables 5 to 7. Higher penetration indicates that hardening from the surface has not progressed.

(Purification Method a) For 1 kg of an organic polymer containing a metal salt or the like as an impurity, 5 g of a polyoxypropylene polymer having a molecular weight of 10,000 obtained by subjecting 10% by weight of ethylene oxide to block polymerization, 50 g of water, and sodium acid pyrophosphate 10 g was added, and the mixture was stirred at 90 ° C. for 1 hour. Subsequently, water was distilled off under reduced pressure at 90 ° C., then 10 g of Kyoward 600 (synthetic magnesium silicate, manufactured by Kyowa Chemical Co., Ltd.) was added. The polymer was dissolved, and insolubles were removed by filtration using filter paper. Thereafter, hexane was distilled off under reduced pressure to obtain a purified product.

(Purification Method A) 1 kg of an organic polymer containing a metal salt or the like as an impurity is dissolved in 3 kg of hexane, and 3 wt%
1 kg of sulfuric acid solution was added, and the mixture was stirred for 1 hour, but the whole became milky. Although left at room temperature for 3 days, a slightly transparent hexane layer was separated into the uppermost layer of about 1/5 of the whole. Therefore, the hexane layer was separated by decantation, and hexane was distilled off under reduced pressure to obtain a purified product.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

[Table 8]

[0090]

As described above, the curable composition of the present invention has remarkably improved storage stability and good curability in deep parts.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-62221 (JP, A) JP-A-7-62218 (JP, A) JP-A 8-231707 (JP, A) JP-A-6-221707 200013 (JP, A) Special Table Hei 6-502438 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (6)

(57) [Claims] An organic amine (A), a curing catalyst (B) selected from a divalent tin carboxylate, a divalent bismuth carboxylate and a divalent lead carboxylate, and an organic amine A room temperature curable composition containing the compound (C) and the filler (D). (Organic polymer) It is derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (E) as a catalyst, and has the formula (1)
An organic polymer (A) having a hydrolyzable silicon group represented by Formula (I) and having a total amount of ionic impurities of 50 ppm or less. ^{_{-R 2 -SiX a R 1 3-}} a ··· (1) wherein, R ¹ is a monovalent hydrocarbon group substituted or unsubstituted 1 to 20 carbon atoms, R ² is a divalent organic radical, X is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3. 2. An organic amine compound (C) having at least 20 carbon atoms.
The room-temperature curable composition according to claim 1 , which is a lower amine or a compound having an amino group and a hydrolyzable silicon group represented by the formula (2) in the molecule. —R ³ —SiX ¹ _b R ⁴ _3-b (2) wherein R ³ is a divalent organic group, and R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. , X ¹ is a hydroxyl group or a hydrolyzable group, and b is an integer of 1 to 3. Wherein the ionic impurities, an ionic impurity comprising the metal compound and / or alkali metal compound due to double metal cyanide complex (E), also claim 1
Is a room temperature curable composition according to 2. 4. The organic polymer (A) converts ionic impurities contained in the polymer (F) into a salt essentially insoluble in the polymer (F), and then converts the salt into the polymer (F). ) To remove ionic impurities contained in the polymer (F) by 50 p.
The room temperature curable composition according to any one of claims 1 to 3 , wherein the composition is an organic polymer obtained by introducing a hydrolyzable silicon group into the polymer (F) after adjusting to pm or less. 5. The organic polymer (A) comprises an ionic impurity contained in the terminal unsaturated group-introduced product (G) of the polymer (F),
After forming a salt 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 reducing the ionic impurity to 50 ppm or less and then reacting the terminal unsaturated group-introduced product (G) with the silicon hydride compound represented by the formula (3).
4. The room temperature curable composition according to any one of items 1 to 3 . ^{_{HSiX a R 1 3-a ···}} (3) formula, R ¹ is a monovalent hydrocarbon group substituted or unsubstituted 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, a is 1
-3. 6. A polymer (F) having a hydroxyl value-converted molecular weight of 50.
Is from 00 to 30,000, serial to claim 1-5
Room temperature-curable composition.