JPH0912861A - Curable composition - Google Patents

Abstract

PURPOSE: To obtain a room-temp.-curable compsn. which has satisfactory adhesive properties, depth curability, and storage stability by compounding a polymer produced by a specific process and having hydrolyzable silicon groups with a specific compd. CONSTITUTION: This compsn. contains an org. polymer which is derived from a hydroxylated polyoxyalkylene polymer obtd. by polymerizing an alkylene oxide using an initiator in the presence of a composite metal cyanide complex as the catalyst and has hydrolyzable silicon groups represented the formula: -R-SiXa R<1> 3-a (R is an org. group; R<1> is an optionally substd. 1-20C hydrocarbon group; X is a hydroxyl or hydrolyzable group; and a is 1-3) and a total content of ionic impurities of 50ppm or lower, a reaction product obtd. by reacting a hydrolyzable silicon group represented by the formula: -R<2> -SiX<1> b R<3> 3-b (R<2> is an org. group; R<3> is an optionally substd. 1-20C hydrocarbon group; X<1> is a hydroxyl or hydrolyzable group; and b is 1-3) with at least one low-molecular functional compd., and a filler.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a room temperature curable composition which is cured in the presence of moisture and has excellent adhesiveness, curability and storage stability.

[0002]

2. Description of the Related Art Conventionally, it is well known to use various polymers having a hydrolyzable silicon group in the molecule, such as known as modified silicone resins, for sealing materials, adhesives and the like. , Industrially useful.

[0003]

Organic polymers having such hydrolyzable silicon groups are disclosed, for example, in Japanese Examined Patent Publication No.
36319, JP-B-46-17553, JP-B-61-1
8582 and the like. The composition produced using such an organic polymer is used for various purposes mainly for construction. However, since the organic polymer itself is essentially a polyether in these compositions, the adhesive strength of the composition itself to the adherend is not sufficient, and in many cases, the adhesiveness to the substrate is improved. It was necessary to add an adhesiveness-imparting agent for the purpose of adding a primer and to impart adhesiveness to the substrate to be adhered.

Among such compositions, an adhesiveness-imparting agent is generally added to the curable composition known as a one-component type in order to improve the adhesiveness to a substrate. As such an adhesiveness-imparting agent, a silicon compound containing various hydrolyzable silicon groups known as a silane coupling agent is generally used.

An organic compound having a hydrolyzable silicon group described in the above-mentioned known examples, which is produced by a method of introducing a hydrolyzable silicon group after a polyether compound having a relatively short molecular weight is connected with a dihalo compound so as to have a high molecular weight. A polymer,
A mixture of a silane coupling agent for improving the adhesiveness, a filler, and the like, when cured using a tin compound that is usually used as a curing catalyst, the curing rate is not sufficient, especially with the air of the cured body. Part far from the contact surface of
The curing rate at the so-called deep part was insufficient.

In an attempt to solve these drawbacks, a hydrolyzable silicon group produced from a polyoxyalkylene polymer produced by using the complex metal cyanide complex described in JP-A-3-43449 and JP-A-3-79627 as a catalyst has been proposed. When the organic polymer and the silane coupling agent are used in combination, the curability is improved, but on the other hand, the viscosity of the mixture containing these raw materials increases during storage, which causes inconvenience in use. There were cases.

[0007]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks and to provide a room temperature curable composition satisfying all of adhesiveness, deep-part curability and storage stability of a compound. The present invention is the following invention.

A room temperature curable composition containing the following organic polymer (A), the following silicon compound (B) and filler (C).

(Organic polymer (A)) Derived from a hydroxyl group-containing polyoxyalkylene polymer (E) obtained by polymerizing alkylene oxide with an initiator using the complex metal cyanide complex (D) as a catalyst, and the formula (1) ) Has a hydrolyzable silicon group and the total amount of ionic impurities is 50 p.
An organic polymer (A) having a pm or less.

-R-SiX _a R ¹ _3-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.

(Silicon compound (B)) At least 2 of the low molecular weight compound (B-1) having a hydrolyzable silicon group represented by the formula (2) and a functional group, or a low molecular weight compound (B-1). Reaction product (B-2) obtained by reacting seeds.

-R ² -SiX ¹ _b R ³ _3-b (2)

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

"Organic Polymer" The organic polymer (A) is derived from a hydroxyl group-containing polyoxyalkylene polymer (E) obtained by polymerizing an alkylene oxide with an initiator using a complex metal cyanide complex (D) as a catalyst. To be done.

By using the complex metal cyanide complex (D), M can be obtained rather than using a conventional alkali metal catalyst.
A hydroxyl group-containing polyoxyalkylene polymer (E) having a smaller _w / _Mn , a higher molecular weight and a lower viscosity can be obtained.

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

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

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 (D). The ionic impurities are preferably 30 ppm or less, more preferably 20 ppm or less.

By reducing the amount of these metal impurities, the storage stability of the organic polymer (A) and the curable composition of the present invention is further improved, and the action of the curing catalyst is not hindered, resulting in excellent curing. Sex is obtained.

As the reducing method, the following (I) to
The method (III) can be mentioned. In particular, there is (III) as a method that can be used for removing the metal compound caused by the complex metal cyanide complex (D). The method (I) is particularly preferable because it can reduce ionic impurities effectively and economically.

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

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

(III) A method of removing a metal compound derived from the complex metal cyanide complex (D) 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 (D), a method of removing a metal compound derived from the composite metal cyanide complex (D) after treatment with an oxidizing agent.

The ionic impurities referred to in the present invention are
Cations and anions such as zinc ion, cobalt ion, cyan ion, and chlorine ion resulting from the complex metal cyanide complex (D); sodium ion and potassium ion mixed as impurities in the step of producing the organic polymer (A). Such as an alkali metal ion, a halogen ion; a carboxylate ion produced by polyoxyalkylene being oxidized in the step of producing the organic polymer (A); an ester bond 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 (E),
Those substituted with formula (1) are preferred.

The number of hydroxyl groups per molecule of the polyoxyalkylene polymer (E) 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.

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

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

The term "hydroxyl number-converted molecular weight" as used in the present invention means a polyoxyalkylene polymer (E) containing a terminal hydroxyl group.
The molecular weight calculated by the product of the number of functional groups of the initiator used for the production of and the molecular weight per hydroxyl group of the polyoxyalkylene of the polymer.

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

-R-SiX _a R ¹ _3-a (1)

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

R in the formula (1) is a divalent organic group. R
¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are 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, and the hydrolyzable group is, for example, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group or a hydride 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. Examples of preferable X include a lower alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group and a propoxy group. a is 1, 2 or 3, and preferably 2 or 3.

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

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

HSiX _a R ¹ _3-a (3)

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

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

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

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

R ¹ _3-a -SiX _a -R ⁴ W (4)

However, in the formula, R ¹ , X and a are the same as described above,
R ⁴ is a divalent organic group, 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) in which the unsaturated group of the terminal unsaturated group-introduced product (F) of the polymer (E) and W is a mercapto group.
The method of reacting the mercapto group of the silicon compound represented by.

The removal of ionic impurities is carried out from the above (a) to.
In each step (d), it is preferably carried out at an appropriate stage such as before reacting each silicon compound, and the total amount thereof is set to 50 ppm or less. That is, the following method can be exemplified.

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

Terminal unsaturated group-introduced product (F) of polymer (E)
The ionic impurities contained in the salt are essentially insoluble in the terminal unsaturated group-introduced product (F), and the salt is removed from the terminal unsaturated group-introduced product (F) to remove the terminal unsaturated group. After adjusting the ionic impurities contained in the introduction product (F) to 50 ppm or less, the reaction product with the terminal unsaturated group introduction product (F) is reacted with the 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 value-converted valence molecular weight of the polymer (E) as a raw material. The molecular weight is 5,000 to 30,000
Is preferred. 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. Especially 8000-30
000 is preferred.

[Silicon Compound] In the present invention, the silicon compound (B) is essential for obtaining a composition which enhances the adhesive force to an adherend and exhibits a strong adhesive force without the treatment with a primer. The silicon compound (B) is a low molecular compound (B-1) having a hydrolyzable silicon group and a functional group represented by the formula (2), or two kinds of the low molecular compound (B-1). The reaction product (B
-2).

-R ² -SiX ¹ _b R ³ _3-b (2)

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

"Low molecular weight compound (B-1)" R ² is preferably the same group as R, R ³ is preferably the same group as R ¹ above, and X ¹ is the same as X. It is preferably a group. b is the same as the above a. The low molecular weight compound (B-1) has one or more, preferably one or two hydrolyzable silicon groups represented by the formula (2).

The low molecular weight compound (B-1) has a molecular weight of 30.
00 or less, particularly 1000 or less, further 500 or less,
Is preferred.

The functional group contained in the low molecular weight compound (B-1) is a hydroxyl group, a mercapto group, an amino group, an epoxy group,
Examples include an acryloyloxy group, a methacryloyloxy group, and a urethane group. The low molecular weight compound (B-1) has one or more functional groups and may have two or more functional groups. The functional group is preferably an amino group.

The low molecular weight compound (B-1) is particularly preferably a silicon compound having an amino group-containing group. The amino group-containing group means a group obtained by removing a hydrogen atom from the amino group of the amino group-containing compound. This amino group-containing compound may have two or more amino groups. Specific amino group-containing compounds include, for example, monoamines such as alkylamines and arylamines, and polyamines such as alkylenediamines and polyalkylenepolyamines. As the amino group-containing compound, polyethylene polyamines such as ethylene diamine and diethylene triamine are preferable.

The low molecular weight compound (B-1) is preferably a compound in which the above-mentioned amino group-containing group is bonded to at least one hydrolyzable group represented by the formula (2). The following compounds are mentioned as such a silicon compound.

N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-
(Β-Aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane Silane, N, N'-bis (γ-triethoxysilylpropyl) ethylenediamine, N-γ-trimethoxysilylpropyl-N'-β-
Aminoethyl - ethylenediamine H ₂ NCH ₂ CH ₂ N
HCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH
₃ ) ₃ , N-γ-methyldimethoxysilylpropyl-
N'-beta-aminoethyl - ethylenediamine H ₂ NCH
₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
(OCH ₃ ) ₂ (CH ₃ ).

Other low molecular weight compounds (B-1) include the following compounds.

The following compounds may be mentioned as the silicon compound containing an epoxy group. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane.

Examples of the silicon compound containing a methacryloyloxy group include the following compounds. γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-
Methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltriethoxysilane.

Examples of the silicon compound having a mercapto group include the following compounds. γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane.

Examples of the silicon compound containing a urethane group include isocyanate group-modified products of a silicon compound containing an isocyanate group. That is, a reaction between a silicon compound containing an isocyanate group such as γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropylmethyldimethoxysilane and an active hydrogen compound such as ammonia, monoamine, polyamine, monool, polyol, or thioalcohol. It is a thing. It may be an allophanate modified product or a biuret modified product.

"Reactant (B-2)" Low molecular weight compound (B-
Reaction product (B-2) obtained by reacting two or more of 1)
Is particularly preferably a reaction product of a silicon compound containing an amino group-containing group and a silicon compound containing an epoxy group or a methacryloyloxy group.

In this reaction, a silicon compound containing an epoxy group or a methacryloyloxy group is mixed at a ratio of 0.2 to 5 mol with respect to 1 mol of a silicon compound containing an amino group-containing group, and the temperature is from room temperature to 180 ° C. It is easily obtained by stirring in a range of nitrogen atmosphere.

The silicon compound (B) is used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the organic polymer (A). If the amount is less than 0.01 parts by weight, the expected adhesiveness is unlikely to be exhibited, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected.

"Filler (C)" A filler (C) is used in the present invention. The amount of the filler (C) used is 0 to 1000% by weight, especially 50 to 250, relative to the organic polymer (A).
% By weight is preferred. The following may be mentioned as specific examples of the filler (C). These may be used alone,
More than one species may be used in combination.

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 white, 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.

In the present invention, a plasticizer can be optionally used. The following can be illustrated as a plasticizer. These may be used alone or in a mixture of two or more.

Dioctyl phthalate, dibutyl phthalate,
Phthalates such as diisononyl phthalate and butylbenzyl phthalate. Aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate. Alcohol esters such as pentaerythritol ester. Phosphate esters such as trioctyl phosphate and tricresyl phosphate. Epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxystearate. Chlorinated paraffin.

In the present invention, a curing catalyst can be used to cure the organic polymer (A). As the curing catalyst, compounds known as catalysts for hydrolysis and condensation reactions of hydrolyzable silicon groups can be used. That is, metal titanates, organosilicon titanates, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate, amine salts such as dibutylamine-2-ethylhexoate, and other acidic salts. Catalysts and basic catalysts can be used. The amount of the curing catalyst used is 0.001 to 10 parts by weight, and particularly 0.01 to 100 parts by weight of the organic polymer (A).
The range of 5 to 5 parts by weight is preferable.

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.

[0073]

EXAMPLES The present invention will be described below with reference to Examples (Examples 1 to 6, 15 to 2).
0) and comparative examples (Examples 7 to 14, 21 to 31), but the present invention is not limited thereto. In addition, a part shows a weight part.

Synthesis Examples 1 to 7 are production examples of the organic polymers P1 to P7 which are raw materials of the organic polymer (A) (however, P7).
Is an organic polymer for comparison). Synthesis examples 8 to 12 are production examples of silicon compounds K1 to K5.

The silicon compound K6 is N- (β-aminoethyl) -γ-propyltrimethoxysilane. The tin compound Q1 is dibutyltin bisacetylacetonate (Narsem tin manufactured by Nippon Kagaku Sangyo Co., Ltd.), Q2 is a heated mixture of dialkyltin oxide and dioctyl phthalate (No. 918, manufactured by Sansha Machine Synthesis), and Q3 is dibutyltin dilaurate.

[Synthesis Example 1] Polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate glyme complex with a glycerin-propylene oxide adduct having a molecular weight of 1000 as an initiator, and a hydroxyl value of 11.2 mgKOH /
A polyoxypropylene triol having a viscosity of 7,000 cP at 25 ° C. 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. The contained organic polymer (P1) was obtained.

[Synthesis Example 2] Propylene oxide was polymerized using a zinc hexacyanocobaltate glyme complex with ethylene glycol as an initiator to give a hydroxyl value of 9.3.
A polyoxypropylene diol having mgKOH / 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 using a zinc hexacyanocobaltate glyme complex with ethylene glycol as an initiator to give a hydroxyl value of 5.6.
A polyoxypropylene diol having mgKOH / g and a viscosity at 25 ° C. of 17,000 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 using a zinc hexacyanocobaltate glyme complex with a pentaerythritol-propylene oxide adduct having a molecular weight of 1000 as an initiator to give a hydroxyl value of 13.2 mg.
Polyoxypropylene tetraol having a KOH / g and a viscosity at 25 ° C. of 6000 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 (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 in a weight ratio of 2: 1, and then Synthesis Example 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, and then the terminal hydroxyl group was prepared by the method described in Synthesis Example 1. Was converted to an allyloxy group to obtain an organic polymer (P6) containing a metal salt as an impurity.

[Synthesis Example 7] Polyoxypropylene diol having a hydroxyl value-converted molecular weight of 3000 and chlorobromomethane were reacted at a molar ratio of 4: 3 in the presence of an alkali according to the method described in JP-B-59-25808, and then allyl chloride was added. When added, the terminal hydroxyl group was converted to an allyloxy group to obtain an organic polymer (P7) containing a metal salt.

[Synthesis Example 8] γ-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane were mixed at a molar ratio of 1: 1 under a nitrogen atmosphere to prepare 1
The reaction was carried out by heating at 00 ° C. for 3 hours to obtain a silicon compound K1.

[Synthesis Example 9] N- (β-aminoethyl)-
γ-Propyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane were mixed in a nitrogen atmosphere at a molar ratio of 2: 3 and heated at 100 ° C. for 3 hours to cause a reaction to obtain a silicon compound K2.

[Synthesis Example 10] N- (β-aminoethyl)
-Γ-Propylmethyldimethoxysilane and γ-glycidyloxypropylmethyldimethoxysilane were mixed at a molar ratio of 1: 1 under a nitrogen atmosphere and heated at 100 ° C. for 3 hours to cause a reaction to obtain a silicon compound K3.

[Synthesis Example 11] N- (β-aminoethyl)
-Γ-Propyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane were mixed in a nitrogen atmosphere at a molar ratio of 1: 1 and heated at 100 ° C. for 3 hours to cause a reaction to obtain a silicon compound K4.

[Synthesis Example 12] γ-mercaptopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane were mixed in a nitrogen atmosphere at a molar ratio of 1: 1 and heated at 100 ° C. for 4 hours to react. A silicon compound K5 was obtained.

[Examples 1 to 14] Organic polymers P1 to P7 were purified by the purification method A or the purification method B, and the residual metal ion amount (unit: ppm) was measured. Purified organic polymer P1
Tables 1 and 2 also show the viscosities (unit: cP) of to P7.

Then, a methyldimethoxysilylpropyl group was introduced at the end of the organic polymer by a known method using a platinum catalyst to obtain organic polymers S1 to S14. The viscosity (unit: cP) after production of the organic polymers S1 to S14 is also shown in the table.
The content of the methyldimethoxysilylpropyl group as an end group is 0.11 mmol / g per 1 g of the organic polymer.
It is in the range of 0.17 mmol. Obtained organic polymer S
The amount of residual metal ions of 1 to S14 was the same as before the introduction of the methyldimethoxysilylpropyl group.

[Examples 15 to 31] Organic polymers (S1 to S1)
4) To 100 parts, add 160 parts of calcium carbonate, 20 parts of titanium oxide, 60 parts of dioctyl phthalate, 5 parts of hydrogenated castor oil, 1 part of phenolic antioxidant, heat dehydration while kneading, and vinyltrimethoxy After 1 part of silane and 2 parts of the silicon compound shown in the table were added and kneaded in a nitrogen atmosphere, 1.5 parts of the tin compound shown in the table as a curing catalyst were added and further kneaded to obtain a curable composition. .

The viscosity of the curable composition immediately after production (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 to 5.

Next, this curable composition was kneaded to give a diameter of 4c.
The curable composition was poured into a m-shaped cylindrical cup so as to have a thickness of 3 cm, and left in an atmosphere of 20 ° C. and 65% humidity for 6 hours. After that, a state of curing from the surface to the depth direction was observed by using a penetration meter according to JIS-K2530. The results are shown in Tables 3 to 5. The higher the penetration, the less the hardening from the surface.

Further, this curable composition was prepared according to JIS-A57.
Based on No. 58, a test body was prepared by using an aluminum plate as an adherend, and the adhesive strength and the broken state between the adherend and the cured curable composition were observed. The results are shown in Tables 3 to 5. The fracture state is represented by CF for cohesive fracture and AF for interfacial peeling.

(Purification Method a) 5 g of a polyoxypropylene polymer having a molecular weight of 10,000, which was obtained by block-polymerizing ethylene oxide at the terminal 10% by weight, with respect to 1 kg of an organic polymer containing impurities such as metal salts, 50 g of water, and sodium acid pyrophosphate. 10 g was added, and the mixture was stirred at 90 ° C. for 1 hour. Then, after distilling off the water under reduced pressure at 90 ° C., 10 g of Kyoward 600 (synthetic magnesim silicate, manufactured by Kyowa Chemical Co., Ltd.) was added, dehydrated under reduced pressure at 90 ° C. for 1 hour, and then 2 liters of hexane was added to the organic solution. The polymer was dissolved, and insoluble materials were removed by filtration using a filter paper. Then, 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 was 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 the mixture was left standing at room temperature for 3 days, a slightly transparent hexane layer was separated in the uppermost layer by 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 product.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

EFFECTS OF THE INVENTION The curable composition of the present invention has remarkably improved storage stability and good curability in deep areas.

Claims (7)

[Claims] 1. A room temperature curable composition comprising the following organic polymer (A), the following silicon compound (B) and filler (C). (Organic polymer (A)) Derived from a hydroxyl group-containing polyoxyalkylene polymer (E) obtained by polymerizing alkylene oxide with an initiator using the complex metal cyanide complex (D) as a catalyst, and represented by the formula (1). An organic polymer (A) having a hydrolyzable silicon group and having a total amount of ionic impurities of 50 ppm or less. —R—SiX _a R ¹ _3-a (1) In the formula, R is a divalent organic group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is Hydroxyl group or hydrolyzable group, a is 1, 2 or 3. (Silicon compound (B)) A low molecular compound (B-1) having a hydrolyzable silicon group represented by the formula (2) and a functional group is reacted alone or with at least two kinds of the low molecular compound (B-1). The reaction product (B-2) thus obtained. —R ² —SiX ¹ _b R ³ _3-b (2) In the formula, R ² is a divalent organic group, R ³ 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 1, 2 or 3. 2. The low molecular compound (B-1) is γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ
Glycidyloxypropyltrimethoxysilane, γ-
Glycidyloxypropylmethyldimethoxysilane, γ
-Methacryloyloxypropyltrimethoxysilane,
The room temperature curable composition according to claim 1, which is a silicon compound selected from γ-methacryloyloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane. 3. The room temperature curable composition according to claim 1, wherein the reaction product (B-2) is a reaction product of a silicon compound containing an amino group-containing group and a silicon compound containing an epoxy group or a methacryloyloxy group. . 4. The ionic impurities are ionic impurities containing a metal compound and / or an alkali metal compound derived from the double metal cyanide complex (D).
A room temperature curable composition according to any one of 1. 5. The organic polymer (A), wherein the ionic impurities contained in the polymer (E) are converted into salts essentially insoluble in the polymer (E), and then the salt is added to the polymer (E). ), The ionic impurities contained in the polymer (E) are reduced to 50 p
The room temperature curable composition according to any one of claims 1 to 4, which is an organic polymer obtained by introducing a hydrolyzable silicon group into the polymer (E) after adjusting it to pm or less. 6. The organic polymer (A) contains an ionic impurity contained in the terminal unsaturated group-introduced product (F) of the polymer (E),
After the salt is essentially insoluble in the terminal unsaturated group-introduced product (F), the salt is removed from the terminal unsaturated group-introduced product (F) to be contained in the terminal unsaturated group-introduced product (F). An organic polymer obtained by reacting the terminal unsaturated group-introduced product (F) with the silicon hydride compound represented by the formula (3) after adjusting the ionic impurities to 50 ppm or less.
Room temperature curable composition according to any one of 4 to 4. HSiX _a R ¹ _3-a (3) In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is 1, 2 or 3. 7. The polymer (E) has a hydroxyl value-converted molecular weight of 50.
The room temperature curable composition according to any one of claims 1 to 6, which is 00 to 30000.