JP3148105B2 - 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]

An organic polymer having a hydrolyzable silicon group at the terminal is disclosed, for example, in Japanese Patent Publication No. Sho.
It is proposed in Japanese Patent Publication No. 5-36319, Japanese Patent Publication No. 46-17553, and Japanese Patent Publication No. 61-18852.

[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.

However, a polyoxyalkylene compound having a relatively short molecular weight proposed in the above-mentioned known example is linked to a high molecular weight by a dihalogen compound, and then a hydrolyzable silicon group is introduced. When a composition comprising an organic polymer having a decomposable silicon group and a filler is cured using a tetravalent organotin compound such as dibutyltin dilaurate or dibutyltin diacetate as a catalyst, the curing rate is sufficiently satisfactory. The curing rate was not sufficient, and the curing speed was particularly insufficient in a portion far from the surface of the cured product, that is, in a deep portion.

As an attempt to solve such disadvantages, Japanese Patent Publication No. 58219/1995 proposes a method using a reaction product of a dialkyltin oxide and an ester compound as a curing catalyst. Was not enough.

Further, a reaction product of a dialkyltin oxide and an ester compound is prepared by using a polyoxyalkylene heavy produced by using a double metal cyanide complex as a catalyst described in JP-A-3-43449 and JP-A-3-79627. When used in combination with hydrolyzable silicon-containing organic polymers produced from coalescence, the curability is significantly improved, while the viscosity of the catalyst-containing formulation increases during storage. In some cases, inconvenience is caused in use.

[0008]

DISCLOSURE OF THE INVENTION The present invention is the following invention which solves such disadvantages and aims at achieving both curability and storage stability.

A hydrolyzable compound represented by the following formula (1) derived from a hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (G) as a catalyst. An organic polymer (A) having a silicon group and having a total amount of ionic impurities of 50 ppm or less, at least one of the following tin compounds (B) to (D) as a curing catalyst, and a filler (E)
A room temperature curable composition comprising, as an essential component.

-R-Six _a R ¹³ _-a (1)

In the formula, R is a divalent organic group, and R ¹ has ¹ 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.

(Tin compound) (B) A tin compound obtained by reacting a dialkyltin oxide and an ester compound. (C) A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound. (D) A tin compound obtained by reacting a tin compound (B) or (C) with a hydrolyzable group-containing silicon compound.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

[Organic polymer] The organic polymer (A) of the present invention has the formula (1)
And a total amount of ionic impurities is 50 ppm or less. The present invention is particularly suitable when the ionic impurity is a ionic impurity containing a metal compound and / or an alkali metal compound resulting from the double metal cyanide complex (G). It is preferable that ionic impurities be 30 ppm or less, and more preferably 20 ppm or less.

Usually, the organic polymer having a hydrolyzable silicon group contains ionic impurities and the like caused by a catalyst used when producing the organic polymer or introducing the hydrolyzable silicon group. It has been found that by reducing the amount of these ionic impurities, the storage stability of the organic polymer (A) and the curable composition of the present invention is improved.

[0015] The reduction method is as follows:
(II) method. Further, there is a method (III) which can be used particularly for removing a metal compound caused by the double metal cyanide complex (G). In particular, the method (I) is 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 (G) 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 (G), and a method of removing a metal compound caused by the double metal cyanide complex (G) after treatment with an oxidizing agent.

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 (G) as a catalyst. The organic polymer (A) is preferably one in which a hydrogen atom in a hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer (F) is substituted by the formula (1).

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

The use of the double metal cyanide complex (G) results in a higher M _w / M _n than using a conventional alkali metal catalyst.
And a hydroxyl group-containing polyoxyalkylene polymer (F) having a lower molecular weight, a higher molecular weight, and a lower viscosity can be obtained.

As the double metal cyanide complex (G), 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, JP-A-4-145
T-Butanol described in No. 123 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.

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 made equal, the higher the number of functional groups, the lower the viscosity. Lower. The physical properties of the cured product of the composition obtained by blending the compounding agent with the organic polymer (A) are determined depending on the number of hydroxyl groups of the polyoxyalkylene polymer (F). It can be freely controlled by its content.

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

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.

Particularly preferred polyoxyalkylene 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 polyoxyalkylene polymer (F) preferably has a molecular weight in terms of hydroxyl value of 5,000 to 30,000, more preferably 8,000 to 30,000.

In the present invention, the hydroxyl value-equivalent molecular weight means the number of functional groups of the initiator used when producing the polyoxyalkylene polymer (F) having a terminal hydroxyl group, and the molecular weight per hydroxyl group of the polyoxyalkylene of the polymer. Means the molecular weight calculated by the product of

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

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

-R-Six _a R ¹³ _-a (1)

In the formula, R is a divalent organic group, and R ¹ is a group having 1 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 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 in the formula (1) is a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amido group, an amino group, an aminooxy group, a ketoximate group, 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 is a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group, a propoxy group and the like. A in the formula (1) is 1, 2 or 3, and 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 (H) of the polymer (F) with a silicon hydride compound represented by the following formula (2).

[0038] ^{_{HSiX a R 1 3-a ···}} (2)

Wherein R ¹ , X and a are the same as described above.

The terminal unsaturated group-introduced product (H) 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 isocyanate group is reacted with a W group of a silicon compound represented by the following formula (3). How to let.

[0043] ^{_{R 1 3-a -SiX a -R}} 2 W ··· (3)

Wherein R ¹ , R ² , X and a are the same as described 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) Formula (3) wherein W is a mercapto group and the unsaturated group of the terminal unsaturated group-introduced product (H) of the polymer (F)
And reacting the mercapto group of the silicon compound.

The removal of the ionic impurities is carried out in the above (a) to (d).
In each method of (d), it is preferable to carry out at an appropriate stage such as before the reaction of each silicon compound, and the total amount is 50 ppm or less. The following method (e) or (f) is preferred.

(E) After the ionic impurities contained in the polymer (F) are converted into a salt essentially insoluble in the polymer (F),
After removing the salt from the polymer (F) to reduce the ionic impurities contained in the polymer (F) to 50 ppm or less, a hydrolyzable silicon group is introduced into the polymer (F),
Organic polymer (A).

(F) The ionic impurities contained in the terminal unsaturated group-introduced product (H) of the polymer (F) are converted into salts essentially insoluble in the terminal unsaturated group-introduced product (H). By removing the salt from the terminal unsaturated group-introduced product (H), ionic impurities contained in the terminal unsaturated group-introduced product (H) are reduced to 50 pp.
m or less, and then the terminal unsaturated group-introduced product (H) and the formula (2)
To produce 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.

[Curing Catalyst] In the present invention, at least one of the following tin compounds (B) to (D) is used as a curing catalyst.

(B) A tin compound obtained by reacting a dialkyltin oxide and an ester compound. (C) A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound. (D) A tin compound obtained by reacting a tin compound (B) or (C) with a hydrolyzable group-containing silicon compound.

As the dialkyltin oxide as a raw material of the tin compounds (B) and (C), those having an alkyl group having 1 to 10 carbon atoms can be used. The two alkyl groups can be the same or different. Preferred are dimethyltin oxide, dibutyltin oxide, dioctyltin oxide and the like.

As the ester compound which is a raw material of the tin compound (B), an alkyl ester of carboxylic acid is preferable.

The carboxylic acids include aromatic carboxylic acids, aliphatic carboxylic acids, and alicyclic carboxylic acids. Monocarboxylic acid or polycarboxylic acid may be used. Further, a carboxylic acid having 1 to 20 carbon atoms is preferable, and a carboxylic acid having 4 to 14 carbon atoms is particularly preferable.

Specifically, aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid and terephthalic acid; aliphatic acids such as lauric acid, 2-ethylhexanoic acid, adipic acid, hexahydrophthalic acid and tetrahydrophthalic acid; There are carboxylic acids and alicyclic carboxylic acids.

The alkyl group in the alkyl ester is preferably a linear or branched alkyl group having 1 to 20 carbon atoms.

The tin compound (B) can be obtained by heating and stirring a dialkyltin oxide and an ester compound. The mixing ratio of the two is not particularly limited, and it is preferable to react 0.25 to 3 mol of the ester compound with respect to 1 mol of the dialkyltin oxide. If the amount is less than 0.25 mol, the reactants are likely to solidify, which is a problem when used as a catalyst.

The reaction can be carried out at any temperature from room temperature to 250 ° C. It is preferably performed at 100 to 180 ° C. Also,
During the reaction, an organic solvent such as toluene may be used.

As the carboxylic acid which is a raw material of the tin compound (C), the compounds mentioned above can be used.

The alcohol compound is preferably an aliphatic alcohol having 1 to 20 carbon atoms, an alicyclic alcohol, or an aromatic alcohol. Monoalcohol or polyalcohol may be used.

Specific examples include methanol, ethanol, propanol, isopropanol, butanol, hexanol, 2-ethylhexanol, lauryl alcohol, cyclohexanol, phenol, nonylphenol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and glycerin. Can be

The tin compound (C) can be obtained by heating and stirring a dialkyltin oxide, a carboxylic acid and an alcohol compound together with an organic solvent such as toluene, and refluxing to remove by-produced water.

The mixing ratio of the dialkyltin oxide, the carboxylic acid and the alcohol compound is not limited as in the case of the tin compound (B), and the carboxylic acid is preferably 0.25 to 3 mol per 1 mol of the dialkyltin oxide. It is preferable that the alcohol compound is equimolar or slightly excess with respect to the carboxylic acid.

As the hydrolyzable group-containing silicon compound which is a raw material of the tin compound (D), alkoxysilanes, partial hydrolysates thereof and condensates thereof can be used.

Examples of the alkoxysilanes include methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and dimethyldiethoxysilane. , Diphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, tetramethoxysilane, tetraethoxysilane and the like.

The tin compound (D) can be obtained by stirring the tin compound (B) or (C) and the hydrolyzable group-containing silicon compound at an arbitrary temperature. The mixing ratio of the tin compound (B) or (C) and the hydrolyzable group-containing silicon compound is not particularly limited, and the hydrolyzable group-containing silicon compound is added to 1 mol of tin atom in the tin compound (B) or (C). The ratio is preferably such that the amount of silicon atoms in the compound is 0.1 to 2 mol.

In the present invention, it is preferable to use a curing catalyst comprising at least one of the tin compounds (B) to (D) in an amount of 0.01 to 10% by weight based on the organic polymer (A). Considering the balance between the curability of the composition and the storage stability, 0.1 to 0.1
It is particularly preferred to use 5 parts by weight.

[Filler] As the filler (E), known fillers can be used. The amount of the filler (E) used is preferably 50 to 800% by weight based on the organic polymer (A). Especially 5
0 to 250% by weight is preferred. The following are specific examples of the filler (E). These may be used alone or in combination of two or more.

Calcium carbonate, fumed silica, precipitated silica, silicic anhydride, hydrated 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 flower, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, fir flour, graphite, aluminum fine powder, flint powder, asbestos, glass fiber, glass filament, Fibrous fillers such as carbon fiber, Kevlar fiber and polyethylene fiber.

[Others] 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 0 to 1 with respect to the organic polymer (A).
00% by weight is preferred. The following are specific examples of the plasticizer.

Dioctyl phthalate, dibutyl phthalate,
Phthalates such as 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; trioctyl phosphate , Phosphidic esters such as tricresyl phosphate; epoxidized soybean oil, epoxy plasticizers such as 4,5-epoxyhexahydrophthalic acid dioctyl, and benzyl epoxystearate; chlorinated paraffins; Polyester-based plasticizers such as polyesters; polyethers such as polyoxypropylene glycol and derivatives thereof; polystyrene oligomers such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile Lil copolymer, polychloroprene,
Polymer plasticizers such as oligomers such as polyisoprene, polybutene, hydrogenated polybutene, and epoxidized polybutadiene.

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

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. Calcium carbonate treated with an organic acid, hydrogenated castor oil, calcium stearate, and stearic acid as thixotropic agents. Zinc, fine powder silica, and the like.

The curable composition of the present invention comprises a sealing material,
It can be used for waterproofing agents, adhesives, coating agents and the like. In particular, it is suitable for applications requiring sufficient strength and high adhesiveness of the cured product itself.

[0075]

The present invention will now be described with reference to Examples (Examples 1 to 6, 15 and 2).
0) and Comparative Examples (Examples 7 to 14, 21 to 33), but the present invention is not limited to only these Examples. First, Production Examples of organic polymers (P1 to P7) as raw materials of the organic polymer (A) are shown in Synthesis Examples 1 to 7 (where P7 is an organic polymer for comparison). In addition, Production Examples of tin compounds (C1 to C5) are shown by Synthesis Examples 8 to 12. 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, and a hydroxyl value of 11.2 mgKOH / g,
Polyoxypropylene triol having a viscosity of 7000 cP at 5 ° C. was obtained. Subsequently, a methanol solution of sodium methoxide 1.1 times equivalent to the hydroxyl group of polyoxypropylene triol was added, and then methanol was distilled off.
Allyl chloride was added to convert the terminal hydroxyl group to an allyloxy group to obtain an organic polymer (P1) having a terminal unsaturated group containing a metal salt as an impurity.

[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.
Polyoxypropylene diol having a KOH / g and a viscosity of 8000 cP at 25 ° C. 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 (P2) containing a metal salt as an impurity. Was.

[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.
An organic polymer (P3) containing KOH / g, a polyoxypropylene diol having a viscosity of 17000 cP at 25 ° C., followed by converting a terminal hydroxyl group to an allyloxy group by the method described in Synthesis Example 1 and containing a metal salt as an impurity. I got

[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 to give a hydroxyl value of 13.2 mg KO.
H / g, a polyoxypropylene tetraol having a viscosity of 6000 cP at 25 ° C. was obtained. Then, a terminal hydroxyl group was converted to an allyloxy group by the method described in Synthesis Example 1, and an organic polymer containing a metal salt as an impurity (P4 ) Got.

[Synthesis Example 5] Polyoxypropylene diol and polyoxypropylene triol obtained in Synthesis Example 3 and 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 and polyoxypropylene tetraol obtained in Synthesis Examples 3 and 4 were mixed at a weight ratio of 4: 1. To base,
An organic polymer (P6) containing a metal salt as an impurity was obtained.

[Synthesis Example 7] According to the method described in JP-B-59-25808, 4 mol of polyoxypropylene diol having a molecular weight of 3,000 in terms of hydroxyl value was reacted with 3 mol of chlorobromomethane in the presence of an alkali, and then allyl chloride was added. Thus, the terminal hydroxyl group was converted to an allyloxy group to obtain an organic polymer (P7) containing a metal salt.

[Synthesis Example 8] Dibutyltin oxide 1 was placed in a glass three-necked flask equipped with a reflux condenser and a stirrer.
Mol and 1 mol of diisononyl phthalate were added, and the mixture was heated at 120 ° C. for 3 hours while stirring under a nitrogen atmosphere to obtain a uniform pale yellow liquid tin compound (C1).

Synthesis Example 9 Dibutyltin oxide 1 was placed in a three-neck glass flask equipped with a reflux condenser and a stirrer.
Mol and 0.6 mol of di-2-ethylhexyl phthalate were added and heated to 120 ° C. for 3 hours while stirring under a nitrogen atmosphere to obtain a uniform pale yellow liquid tin compound (C2).

Synthesis Example 10 1 mol of dibutyltin oxide and 0.5 mol of ethyl octanoate were added to a three-necked glass flask equipped with a reflux condenser and a stirrer, and heated to 120 ° C. for 3 hours while stirring under a nitrogen atmosphere. As a result, a uniform pale yellow liquid tin compound (C3) was obtained.

[Synthesis Example 11] 1 mol of dibutyltin oxide and 300 cm ³ of toluene were placed in a ^three- necked glass flask, stirred and dispersed well, and then 0.5 mol of octanoic acid and 0.5 mol of octyl alcohol were added, followed by heating under reflux. Water produced as a by-product was removed during the heating. When the generation of water stopped, the toluene was distilled off under reduced pressure to obtain a tin compound (C4) as a pale yellow liquid.

Synthesis Example 12 20% by weight of dimethyldimethoxysilane was added to the pale yellow liquid tin compound (C3) obtained in Synthesis Example 10, and the mixture was heated and stirred at 100 ° C. for 2 hours to form a yellow liquid. Of a tin compound (C5) was obtained.

[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 show the viscosities (units: cP) after purification of the 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. Tables 1 and 2 also show the viscosity (unit: cP) of the organic polymers S1 to S14 after production. The content of the methyldimethoxysilylpropyl group as a terminal group was 0.11 mmol / g of the organic polymer.
The range is from 1 to 0.17 mmol. The residual metal ion amounts of the obtained organic polymers S1 to S14 were the same as before the introduction of the methyldimethoxysilylpropyl group.

Examples 15 to 31 Organic Polymers S1 to S14
Of 100 parts by weight, 160 parts of calcium carbonate, 20 parts of titanium oxide, 60 parts of dioctyl phthalate, hydrogenated castor oil 5
And 1 part of a phenolic antioxidant, kneading and heating and dehydrating. 1 part of vinyltrimethoxysilane, 3- (2
-Aminoethyl) aminopropyltrimethoxysilane 1
And kneading under a nitrogen atmosphere, then tin compound (C1
To C6) were further added and kneaded to obtain a curable composition. Here, C6 is dibutyltin dilaurate.

The viscosity immediately after the production of the curable composition (viscosity after production) and the viscosity after storage at 50 ° C. for 14 days (viscosity after storage) were measured. The results are shown in Tables 3 to 5 (however, the unit of viscosity is cP).

Next, 3c was placed in a cylindrical cup having a diameter of 4 cm.
m, and the curable composition is poured at 20 ° C.
For 6 hours in an atmosphere of 65% humidity. Then J
Using a penetrometer conforming to ISK-2530, using a 1.25 g needle for asphalt, the state of curing from the surface to the depth direction was observed. That is, the penetration of the needle from the top to the bottom in the vertical direction for 5 seconds (penetration, unit: cm) was measured. The results are shown in Tables 3 to 5. Higher penetration indicates that hardening from the surface has not progressed.

(Purification method a) 5 g of a 10,000-molecular weight polyoxypropylene polymer obtained by subjecting 10% by weight of ethylene oxide to block polymerization of ethylene oxide to 1 kg of an organic polymer containing metal salts and the like as impurities, 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 magnesia 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 organic polymer.

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

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

According to the present invention, the curable composition has the effects that storage stability is remarkably improved and curability at the deep portion is good.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-62221 (JP, A) JP-A-8-231707 (JP, A) JP-A-6-200013 (JP, A) 502438 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08G 65/00-65/48

Claims (6)

(57) [Claims] 1. A hydroxyl group-containing polyoxyalkylene polymer (F) obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (G) as a catalyst. An organic polymer (A) having a decomposable silicon group and a total amount of ionic impurities of 50 ppm or less, at least one of the following tin compounds (B) to (D) as a curing catalyst, and a filler (E) )
A room temperature curable composition comprising, as an essential component. —R—SiX _a R ¹³ _-a (1) wherein 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 A hydroxyl group or a hydrolyzable group, a is 1, 2 or 3; (Tin compound) (B) A tin compound obtained by reacting a dialkyltin oxide and an ester compound. (C) A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound. (D) A tin compound obtained by reacting a tin compound (B) or (C) with a hydrolyzable group-containing silicon compound. 2. The room-temperature curable composition according to claim 1, wherein the ionic impurity is a ionic impurity containing a metal compound and / or an alkali metal compound derived from the double metal cyanide complex (G). 3. The method according to claim 1, wherein the ionic impurities contained in the organic polymer (A) are converted into a salt essentially insoluble in the organic polymer (A), and the salt is removed from the organic polymer (A). Reduces ionic impurities contained in the organic polymer (A) by 50 pp
m. The room temperature curable composition according to claim 1 or 2, wherein m is not more than m. 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 claim 1 or 2, 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 (H) of the polymer (F),
After forming a salt essentially insoluble in the terminal unsaturated group-introduced product (H), the salt is removed from the terminal unsaturated group-introduced product (H) to be contained in the terminal unsaturated group-introduced product (H). The organic polymer obtained by reducing the ionic impurity to 50 ppm or less and then reacting the terminal unsaturated group-introduced product (H) with a silicon hydride compound represented by the following formula (2). Room temperature curable composition. ^{_{HSiX a R 1 3-a ···}} (2) wherein, 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, 2 or 3. 6. The room temperature 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.