JP2906497B2 - Moisture curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hydrolyzable silyl group-containing polyether compound containing a urethane bond and capable of curing into a rubber-like substance when exposed to atmospheric moisture, as a curing component. To a moisture-curable resin composition.

[Prior art] As a two-component type room temperature-curable resin, thiochol-based resins and urethane-based resins are known, but in any case, pot life after two-component mixing, work simplicity and the like are still satisfactory. In order to solve these drawbacks, a one-component type is being actively developed. As the one-component type, thiochol type, urethane type, silicone type and the like are generally used, but each has its merits and demerits in terms of curing properties, adhesiveness, price, and the like, and none have yet been found to satisfy all. We focus on silicone-based one-component moisture-curable compounds that can be cured at room temperature.
Various studies have been made on a method for obtaining this at low cost.

Conventionally, as a method for obtaining a silicone-based one-component type at low cost,
A method of reacting a compound having a hydrolyzable silyl group and an active hydrogen-containing group with an isocyanate group-containing prepolymer obtained by reacting an excess equivalent amount of a polyisocyanate compound with a polyoxyalkylene polyol. A method is known in which a compound having an unsaturated group and an active hydrogen-containing group is reacted and then reacted with a hydrosilane having a hydrolyzable group (USP3408321, US Pat.
P3448072, USP3592795, USP3632557).

[Problem to be Solved by the Invention] When a moisture-curable resin is used as a sealing agent or the like, it is necessary that the cured product has a large elongation. This elongation depends on the properties and molecular weight of the polymer chains in the moisture-curable compound. For example, the polyester chain contains many cohesive ester bonds and the cured product has a small elongation. The ether bond of the polyoxyalkylene chain has a small cohesiveness, and thus provides a large elongation. On the other hand, the larger the molecular weight of the polymer chain, the greater the elongation.

However, polyoxyalkylene polyols are difficult to produce high molecular weight polyoxyalkylene polyols due to a side reaction of a ring-opening addition polymerization reaction forming an oxyalkylene group having 3 or more carbon atoms, which is the main oxyalkylene group. . For example, the molecular weight of polyoxypropylene diol is usually 3000 or less. In order to increase the molecular weight of the polyoxyalkylene polyol, polyoxyalkylene polyol is used in an increased amount. The polyoxyalkylene polyol used for this multiplication is a diol, and the multiplication of a polyol having three or more hydroxyl groups is not used because the number of branches increases.

A typical example of multimerization is multimerization with a polyisocyanate compound. That is, when a polyoxyalkylene diol is reacted with a polyisocyanate compound, a method of producing a high-molecular-weight prepolymer by reducing the excess equivalent amount of the polyisocyanate compound is used.
However, this method results in a large number of urethane bonds between the polyoxyalkylene chains, and the cured product has a small elongation due to the cohesiveness of the urethane bonds.

A method in which polyoxyalkylene diol is multiplied by only an ether bond (for example, a method in which a hydroxyl group is converted to sodium alkoxide and reacted with dichloromethane:
240320) is known, but this method is a complicated method and is expensive. Further, it is difficult to control the molecular weight of the product in the multimerization, and the molecular weight distribution of the formed multimer is wide.

[Means for Solving the Problems] The present invention provides a moisture-curable resin composition containing, as a curing component, a hydrolyzable silyl group-containing polyether compound that gives a cured product with large elongation. This polyether compound in the present invention is obtained by converting a terminal hydroxyl group into a hydrolyzable silyl group-containing terminal residue using a polyoxyalkylene polyol having an extremely high molecular weight as a raw material, and the terminal residue is a polyether alkylene polyol. It has a urethane bond linked to an oxyalkylene chain. This urethane bond is formed by a reaction between a hydroxyl group and an isocyanate group of the polyoxyalkylene polyol. That is, the present invention is the following invention.

A polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide in the presence of a double metal cyanide complex catalyst, wherein the hydroxyl value x (unit: mgKOH / g) is 5
~ 35, total unsaturation y (unit: meq / g) is 0.07 or less and x
When> 10, y ≦ 0.9 / (x−10), the number of hydroxyl groups is 2 to 8, and the content of oxyalkylene groups having 3 or more carbon atoms is 60% by weight or more and the content of oxyethylene groups is less than 2% by weight. A polyoxyalkylene chain derived from a polyoxyalkylene polyol, and at least 1.3 hydrolyzable silyl group-containing terminal residues at the terminal of the polyoxyalkylene chain on average, the terminal residue being a polyoxyalkylene A moisture-curable resin composition having a hydrolyzable silyl group-containing polyether compound having a urethane bond linked to a chain as a curing component.

Polyoxyalkylene polyol in the present invention,
It is obtained by subjecting an initiator having two or more functional groups capable of reacting with an alkylene oxide to ring-opening addition polymerization of the alkylene oxide. Usually, in this case, it is produced using an alkali catalyst such as an alkali metal hydroxide.
However, when produced using this catalyst, a polyoxyalkylene polyol having a high degree of unsaturation is produced as described below, and the production ratio is high, so that it is difficult to produce an extremely high molecular weight polyoxyalkylene polyol. It is. The polyoxyalkylene polyol in the present invention needs to be a polyoxyalkylene polyol having a low degree of unsaturation obtained using a catalyst as described below.

Further, the polyoxyalkylene polyol in the present invention has a residue of an initiator, a polyoxyalkylene chain composed of a large number of oxyalkylene groups derived from an alkylene oxide, and a hydroxyl group present at the end of the polyoxyalkylene chain. It is preferable that the polyoxyalkylene chain does not substantially contain a bond generated by multiplying the polyoxyalkylene polyol, in addition to the urethane bond described above.

In the present invention, the polyoxyalkylene polyol used as a raw material has a hydroxyl value x (unit: mgKOH / g) in the range of 5 to 35, and a total degree of unsaturation y (unit: meq / g).
It is important to use one that satisfies y ≦ 0.9 / (x−10) when it is 0.07 or less and x> 10. Only by using such a high molecular weight polyoxyalkylene polyol, it becomes possible to obtain a high molecular weight hydrolyzable silyl group-containing polyether compound. When this is used as a sealing agent, the properties of the cured product can be made extremely large in elongation, and it can be applied to a wide range of applications.

When the total degree of unsaturation is 0.07 or less and x> 10, y ≦
By using a polyoxyalkylene polyol having a ratio of 0.9 / (x−10), it is possible to avoid a decrease in physical properties based on an unsaturated monol as a by-product.

In the above equation, x is about 22.9 and y is 0.07. Therefore, in the present invention, when x is in the range of about 22.9 to 35, y
Is according to the above formula, and when x is about 22.9 or less, y is 0.07 or less.

More preferred hydroxyl value x of the polyoxyalkylene polyol in the present invention is from 5 to 28, particularly from 5 to 24. Further, a more preferable upper limit of the total degree of unsaturation y is 0.04. In addition, the number of hydroxyl groups of the polyoxyalkylene polyol (hereinafter, sometimes referred to as N), that is, the average number of hydroxyl groups per molecule is 2 to 8, and more preferably 2 to 4.

As described below, in the present invention, the oxyalkylene group in the polyoxyalkylene polyol has 60% by weight or more, preferably 70% by weight or more, of an oxyalkylene group having 3 or more carbon atoms. Other oxyalkylene groups,
That is, since the oxyalkylene group is hydrophilic, a large amount thereof has an unfavorable effect on the physical properties of the final curable resin.

Examples of the oxyalkylene group having 3 or more carbon atoms include 1,2-
Propylene oxide, 1,2-butylene oxide or 2,3
An oxyalkylene group having 3 to 4 carbon atoms derived from -butylene oxide is preferred. Particularly preferably, 1,2-propylene oxide (hereinafter, simply referred to as propylene oxide)
Is an oxypropylene group derived from 1,2-butylene oxide or 2,3-butylene oxide (hereinafter, both are simply referred to as butylene oxide) can be substituted for part or all of propylene oxide. Ethylene oxide can be used in combination with other alkylene oxides. The amount of oxyethylene groups in the polyoxyalkylene polyol is less than 2% by weight. When two or more oxyalkylene groups are present in the polyoxyalkylene polyol, they may be present in random or block form.

The polyoxyalkylene polyol usually has an unsaturated monool due to a side reaction during its production. Generally speaking, the lower the hydroxyl value of a polyoxyalkylene polyol, the higher the degree of unsaturation. This is because the lower the hydroxyl value, the larger the amount of the oxyalkylene group having 3 or more carbon atoms, particularly the oxypropylene group, which is the main oxyalkylene group of the polyoxyalkylene polyol. This is because the reaction amount of the alkylene oxide increases, and accordingly, the side reaction of the alkylene oxide (a side reaction that generates an unsaturated group) increases to increase the degree of unsaturation.

The side reaction of the alkylene oxide having 3 or more carbon atoms is as follows:
This is likely to occur when the reaction catalyst is an alkali catalyst such as an alkali metal compound (alkali hydroxide). In particular, it is almost impossible to produce a polyoxyalkylene polyol having a low degree of unsaturation and a low hydroxyl value using an alkali catalyst. In the present invention, a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate complex is used. The catalyst and a method for producing a polyoxyalkylene polyol using the catalyst are described, for example, in the following patents.

USP3278457, USP3278458, USP3278459, USP3427334,
USP3427335, USP3829505, USP3941849, USP4355188, US
P4472560, USP4721818.

The above polyoxyalkylene polyol is produced by a method of subjecting an alkylene oxide to ring-opening addition polymerization of an alkylene oxide alone or a method of subjecting a polyvalent initiator to ring-opening addition polymerization of an alkylene oxide. And at least one of butylene oxide or ethylene oxide. Particularly preferably, only propylene oxide,
Alternatively, it and ethylene oxide are used.

Polyhydric initiators used for producing the polyoxyalkylene polyol include polyhydric alcohols, polyhydric phenols, polyamines, alkanolamines and the like.

For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Neopentyl glycol, 1,4-butanediol, 1,6-
Hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, dextrose, sucrose, bisphenol A, ethylenediamine, and a lower molecular weight (ie, higher hydroxyl group) than the target product obtained by reacting at least one of them with an alkylene oxide (Valent) polyoxyalkylene polyol.

These initiators may use only one kind,
Two or more kinds may be used in combination. Particularly preferred polyhydric initiators are polyhydric alcohols, polyhydric phenols, and low molecular weight polyoxyalkylene polyols obtained by adding an alkylene oxide to any of them.

Hereinafter, the polyoxyalkylene polyol in the present invention is represented by A (OH) _n . A is an n-valent residue obtained by removing hydroxyl groups from a polyoxyalkylene polyol, and n is equal to the number N of hydroxyl groups. The hydrolyzable silyl group-containing polyether compound having a hydrolyzable silyl group-containing terminal residue represented by the following formula (1) is preferably a compound represented by the following formula. p is 1.3 to n, more preferably p is 1.5 to n.

The hydrolyzable silyl group-containing polyether compound according to the present invention has a hydrolyzable silyl group-containing terminal residue represented by the following formula (1) in an average of at least 1.3 per molecule.
, Preferably at least about 1.5.

This residue is linked to the polyoxyalkylene chain except for the hydroxyl group at the end of the polyoxyalkylene chain. Preferably, this residue is present at that position in place of two or more, preferably all, hydroxyl groups of the polyoxyalkylene polyol.

m is preferably 0, 1 or 2. More preferably, m is 0 or 1. B is a divalent organic group or a bond (that is, Si and NH are directly bonded), and B may be a divalent organic group having a urethane bond, a urea bond, or another bond. In the formula, R is a monovalent hydrocarbon group or a halogenated hydrocarbon group, and has 8 or less carbon atoms, preferably 6 carbon atoms.
The following are alkyl groups and fluoroalkyl groups. Particularly preferred are lower alkyl groups such as a methyl group and an ethyl group.

X is a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group and the like. Among these, the carbon number of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred hydrolyzable groups are alkoxy groups having 4 or less carbon atoms, particularly methoxy and ethoxy groups. Specific examples of the hydrolyzable silyl group include the following.

Trimethoxysilyl group, methyldimethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, ethyldiethoxysilyl group, tributoxysilyl group, methyldibutoxysilyl group, tris (2-methoxyethoxy) silyl group, triacetoxy silyl group, methyl diacetoxy silyl _{group, [(CH 3) 2 C} = N-O] 3 Si -, [(CH 3) 2 N] 3 Si-, [CH 3 CON (CH 3)] 3 Si-, _{[(C 2 H 5) 2} N] 3 Si-.

The polyether compound having the residue represented by the formula (1) is formed, for example, by the following method.

(I) A compound (a) having a hydrolyzable silyl group and an isocyanate group is reacted with a polyoxyalkylene polyol. This compound (a) is, for example, a compound represented by the following formula (2).

In this case, R ¹ matches B in the above formula (1).
X, R and m are the same as those in the formula (1), and R ¹ is a divalent organic group. R ¹ is preferably a divalent organic group having 1 to 17 carbon atoms or a bond, and particularly preferably a divalent hydrocarbon group. The hydrocarbon group may contain an aromatic nucleus. A preferred hydrocarbon group is an alkylene group, and is an alkylene group having 1 to 8 carbon atoms, particularly an alkylene group having 2 to 6 carbon atoms. For example, a polymethylene group such as a dimethylene group, a trimethylene group, and a tetramethylene group is preferable. Further, R ¹ may be an organic group containing a urethane bond, a urea bond, or another bond generated by a reaction between an isocyanate group and an active hydrogen-containing group. This case will be described later in (iii).

Further, the compound (a) applicable to this method is not limited to the compound represented by the formula (2), a compound having two or more hydrolyzable silyl groups and an isocyanate group,
A compound having two or more isocyanate groups and a hydrolyzable silyl group may be used.

Specific examples of the compound (a) in which R ¹ is a hydrocarbon group or a bond are shown below, but the compound (a) is not limited to these compounds.

_{(C 2 H 5 O) 3} Si- (CH 2) 3 NCO, (CH 3 O) 3 Si- (CH 2) 3 NCO, (CH 3 O) 2 (CH 3) Si- (CH 2) 3 NCO _{, (CH 3 O) 3 Si} -NCO, (CH 3 O) 2 Si (NCO) 2.

(Ii) After reacting the compound (b) having an α, β-unsaturated group and an isocyanate group with a polyoxyalkylene polyol, the compound is reacted with a hydrosilane (c) having a hydrolyzable group. This compound (b) and hydrosilane (c)
Are represented, for example, by the following formulas (3) and (4), respectively, and the resulting residue is represented by the following formula (5).

R ² is a divalent organic group, preferably a lower alkylene group. R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a lower alkyl group. R ² is preferably a divalent organic group having 1 to 17 carbon atoms, similar to R ^1, and particularly preferably a divalent hydrocarbon group.
The hydrocarbon group may contain an aromatic nucleus. Preferred hydrocarbon groups are alkylene groups, alkylene groups having 1 to 8 carbon atoms, particularly alkylene groups having 2 to 6 carbon atoms,
For example, polymethylene groups such as dimethylene group, trimethylene group, and tetramethylene group are preferable. As a further R ^2,
It may be an organic group containing a urethane bond, a urea bond, or a bond generated by a reaction with another active hydrogen-containing group, and this case will be described later (iv).

Examples of the compound (b) include allyl isocyanate, 2-isocyanateethyl methacrylate, and isopropenyldimethylbenzyl isocyanate.
Allyl isocyanate is most preferred.

As the hydrosilane (c), the hydrosilane having a hydrolyzable silyl group described above is preferable. Further, using a halohydrosilane where X is a halogen such as a chlorine atom as the hydrosilane (c), the halogen is converted into a hydrolyzable silyl group other than a halogen such as an alkoxy group after forming the residue of the formula (5). can do. The reaction between the hydrosilane (c) and the α, β-unsaturated group can be carried out using a known catalyst such as platinum.

(Iii) A compound (d) having a hydrolyzable silyl group and an active hydrogen-containing group capable of reacting with an isocyanate group, a polyisocyanate compound (e), and a polyoxyalkylene polyol are simultaneously or sequentially reacted. Examples of the active hydrogen-containing group include a hydroxyl group, a primary amino group,
There are secondary amino group, carboxyl group, mercapto group, etc.
Particularly, a hydroxyl group, a primary amino group, and a secondary amino group are preferable.
The compound (d) and the polyisocyanate compound (e) are, for example, those represented by the following formulas (6) and (7), respectively.

X, R and m are the same as those in the above formula (1), and R ⁶ is 2
A valence organic group, Z is an active hydrogen-containing group, D is a residue of the polyisocyanate compound excluding the isocyanate group, and k is an integer of 2 or more. R ⁶ is preferably a divalent hydrocarbon group like R ¹ and R ^2, and particularly preferably has 1 to 8 carbon atoms, more preferably 2 carbon atoms.
~ 6 alkylene groups are preferred. Most preferably, it is a polymethylene group having 2 to 6 carbon atoms. D is a residue of an aromatic, aliphatic, alicyclic or other polyisocyanate compound, and k is preferably an integer of 2 to 4, particularly preferably 2.

The above three reactions can be carried out simultaneously, but are preferably carried out sequentially. As a first method, an isocyanate group-containing prepolymer is produced by reacting a polyoxyalkylene polyol with an excess equivalent of a polyisocyanate compound (e), and the compound (d) is reacted therewith to obtain a target compound. The polyoxyalkylene polyol reacts with the polyisocyanate compound (e) and may be multiplied, but the multimerization causes two or more urethane bonds between the polyoxyalkylene chains. Since this multiplication is not so preferable, it is preferable that the multiplication is small even if it occurs.

Therefore, it is preferable that one hydroxyl group of the polyoxyalkylene polyol be reacted at a rate at which one molecule of the polyisocyanate compound (e) reacts. Preferably, N moles or more of the polyisocyanate compound (e) is reacted with 1 mole of the polyoxyalkylene polyol, and the unreacted polyisocyanate compound (e) is removed as necessary. As a result, a prepolymer represented by the following formula (8) is obtained, and the desired product is obtained by reacting the prepolymer with the compound (d).

A [OCONH-D (NCO) _k-1 ] _n (8) A second method of sequentially reacting the compound (d) and the polyisocyanate compound (e) in such a ratio that at least one isocyanate group remains. And reacting this product with a polyoxyalkylene polyol. The reaction of the compound (d) with the polyisocyanate compound (e) produces a product represented by the following formula (9).

Here, j is an integer of 1 or more smaller than k, and Z 'is a value obtained by removing a hydrogen atom from Z.

In the formula (9), when kj is 1, similarly to the compound of the formula (2) in the above (i), the compound represented by the formula (9) is reacted with a polyoxyalkylene polyol to obtain the desired product. Obtainable.

 Examples of the compound (d) include the following compounds.

γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-
Aminopropyltrimethylsilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane,
γ-hydroxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane.

Examples of the polyisocyanate compound (e) include the following compounds.

Tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate,
Methylene bis (cyclohexyl isocyanate), bis (isocyanatomethyl) cyclohexane, 1,6,11-undecane triisocyanate.

Modified prepolymers, nullates, carbodiimides, and other modified polyisocyanates.

(Iv) A compound (f) having an α, β-unsaturated group and an active hydrogen-containing group is used in place of the compound (d) in the method (iii), and the compound (e) is used in combination with the polyisocyanate compound (e). (Iii) from alkylene polyol
, A polyether compound having an α, β-unsaturated group is produced, and then the hydrosilane (c) in the above (ii) is reacted with the α, β-unsaturated group to form a hydrolyzable silyl group. Let it form. This compound (f) is, for example, a compound represented by the following formula (10).

R ³ , R ⁴ , R ⁵ , R ⁶ and Z have the same meaning as described above.
Examples of the compound (f) include allyl alcohol and allylamine.

The hydrolyzable silyl polyether compound of the present invention is three-dimensionally cured by a crosslinking reaction when it comes into contact with moisture. The curing mechanism is as follows. First, the hydrolyzable group X is substituted with a hydroxyl group, and then the SiOH groups are condensed to form a cross-link, and a siloxane bond (Si-O-Si) is formed or the SiOH group and the Si
Either siloxane bonds and HX are formed and cured by reaction with the X group.

The hydrolysis rate varies depending on the atmospheric temperature, relative humidity, and the type of the hydrolyzable group. Therefore, an appropriate hydrolyzable group must be selected according to the conditions of use.

During storage, the curable polyether compound must be kept from contact with moisture as much as possible, such as by placing it in dry N ₂ .

In the curing reaction, a curing acceleration catalyst may or may not be used. Examples of the curing accelerator include metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, tin octylate and dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate; Other acidic and basic catalysts can be used. More preferably, this catalyst is blended in an amount of 0.01 to 5% by weight based on the polyether compound.

If necessary, the polyether compound of the present invention may further contain a reinforcing agent, a filler, a plasticizer, a sagging agent, a crosslinking agent, and the like.

Reinforcing agents include carbon black, finely divided silica, etc., fillers include calcium carbonate, talc, clay, silica, etc., and plasticizing agents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffin, and petroleum plasticizers. As pigments, iron oxide, iron chromium, inorganic pigments such as titanium oxide and organic pigments such as phthalocyanine blue and phthalocyanine green, as an anti-sagging agent, organic acid-treated calcium carbonate,
Examples include hydrogenated castor oil, aluminum stearate, calcium stearate, zinc stearate, and finely divided silica. Examples of the cross-linking agent include compounds in which a hydrogen atom of the hydrosilane is converted to a hydrolyzable group or an alkyl group, such as methyltrimethoxysilane and tetraethoxysilane.

Moisture-curable resin composition of the present invention, buildings, aircraft,
It can be suitably used as a coating composition for automobiles and the like and a sealing composition or an analogue thereof.

[Examples] Polyoxyalkylene polyols used in Examples and Comparative Examples described later were synthesized by the following methods. That is, the molecular weight
A polyoxyalkylene polyol of 400 to 600 is used as an initiator, and a double metal cyanide complex catalyst composed of a zinc hexacyanocobaltate complex is added. The reaction was performed to obtain a crude polyoxyalkylene polyol. Further deactivate the catalyst by adding an aqueous solution of sodium hydroxide, dehydrated under reduced pressure after adding synthetic magnesium silicate, and then filtered to remove inorganic compounds such as catalyst residues, the following polyol A, B and C were obtained.

The following polyol D is a polyoxyalkylene polyol synthesized by ring-opening addition polymerization of propylene oxide at about 120 ° C. using potassium hydroxide as a catalyst.

Polyol A: hydroxyl value 12.5 (mgKOH / g), total unsaturation 0.0
20 (meq / g) polyoxypropylene diol.

Polyol B: hydroxyl value 6.3 (mgKOH / g), total unsaturation 0.02
5 (meq / g) polyoxypropylene diol.

Polyol C: hydroxyl value 5.6 (mgKOH / g), total unsaturation 0.02
7 (meq / g) polyoxypropylene triol.

Polyol D: hydroxyl value 65.0 (mgKOH / g), total unsaturation 0.0
38 (meq / g) polyoxypropylene diol.

Example 1 9.2 parts of allyl isocyanate was added to 500 parts of polyol A (parts by weight, the same applies hereinafter), and this was subjected to NCO by IR under a nitrogen stream.
The reaction was continued at 50 ° C. until no groups were detected, to obtain a polyol containing a terminal unsaturated group.

Then the resulting product methyldimethoxysilane 13.0
And 0.003 part of a platinum / ethylene complex, and the mixture is reacted at 100 ° C. for 1 hour with stirring. After the reaction was completed, unreacted methyldimethoxysilane was distilled off under reduced pressure to obtain a polyether compound having an average of 1.70 methyldimethoxysilyl groups at terminals. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room temperature curable synthetic resin.

Example 2 21.0 parts of isocyanatopropylmethyldimethoxysilane OCNCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OC
H ₃ ) ₂ was added, and the reaction was continued at 50 ° C. under a nitrogen stream until no NCO group was detected by IR. After the completion of the reaction, a polyether compound having 1.83 methyldimethoxysilyl groups at the terminal on average was obtained. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Example 3 10.5 parts of isocyanatopropylmethyldimethoxysilane was added to 500 parts of polyol B, and NCO was measured by IR under a nitrogen stream.
The reaction was continued at 50 ° C until no groups were detected. After completion of the reaction, a methyldimethoxysilyl group was added to the terminal at an average of 1.
A polyether compound having 62 was obtained. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Example 4 To 500 parts of polyol B was added 8.4 parts of isocyanatopropylmethyldimethoxysilane, and the reaction was continued at 50 ° C. under a nitrogen stream until no NCO group was detected by IR. After the completion of the reaction, the average methyl dimethoxysilyl group was 1.30.
To obtain a polyether compound. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Example 5 To 9.5 parts of isocyanatopropylmethyldimethoxysilane was added to 500 parts of polyol C, and the reaction was continued at 50 ° C. under a nitrogen stream until no NCO group was detected by IR. After completion of the reaction, a methyldimethoxysilyl group was averaged 1.53
To obtain a polyether compound. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Comparative Example 1 113 parts of isocyanatopropylmethyldimethoxysilane was added to 500 parts of polyol D, and the reaction was continued at 50 ° C. under a nitrogen stream until no NCO group was detected by IR. After the completion of the reaction, a methyldimethoxysilyl group was averaged at an end of 1.93.
To obtain a polyether compound. 5 parts of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Example 6 100 parts of polyol A was placed in a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 3.9 parts of 2,4-tolylene diisocyanate was added thereto.
The reaction was carried out at 8 ° C. for 8 hours to obtain a prepolymer having NCO% = 0.8%. Subsequently, 100 parts of this prepolymer was reacted with 3.4 parts of γ-aminopropyltrimethoxysilane at 80 ° C. for 5 hours,
A polyether compound having an average of 1.56 trimethoxysilyl groups at the terminals was obtained. Thereafter, 1.0 part of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room-temperature-curable synthetic resin.

Example 7 100 parts of polyol B was placed in a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 1.9 parts of 2,4-tolylene diisocyanate was added thereto.
The reaction was carried out at 8 ° C. for 8 hours to obtain a prepolymer having an NCO% of 0.5%. Subsequently, 2.1 parts of γ-aminopropyltrimethoxysilane were reacted with 100 parts of this prepolymer at 80 ° C. for 5 hours,
A polyether compound having an average of 1.60 trimethoxysilyl groups at the terminals was obtained. Thereafter, 1 part of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room temperature-curable synthetic resin.

Example 8 100 parts of polyol C was placed in a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 1.7 parts of 2,4-tolylene diisocyanate was added thereto.
The reaction was carried out at 8 ° C. for 8 hours to obtain a prepolymer having an NCO% of 0.4%. Subsequently, 1.7 parts of γ-aminopropyltrimethoxysilane was reacted with 100 parts of this prepolymer at 80 ° C. for 5 hours,
A polyether compound having an average of 1.46 trimethoxysilyl groups at the terminals was obtained. Thereafter, 1 part of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room temperature-curable synthetic resin.

Comparative Example 2 100 parts of polyol D was placed in a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 20.5 parts of 2,4-tolylene diisocyanate was added thereto.
The reaction was carried out at 8 ° C. for 8 hours to obtain a prepolymer having NCO% = 4.1%. Subsequently, 100 parts of this prepolymer was reacted with 17.0 parts of γ-aminopropyltrimethoxysilane at 80 ° C. for 5 hours,
A polyether compound having an average of 1.58 trimethoxysilyl groups at the terminals was obtained. Thereafter, 1 part of dibutyltin dilaurate was added as a curing catalyst to obtain a one-component room temperature-curable synthetic resin.

The synthetic resins of the above Examples and Comparative Examples were cured at 50 ° C. and 60% humidity. Table 1 shows the physical properties of the cured product.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-157424 (JP, A) JP-A-62-1430 (JP, A) JP-A-61-57616 (JP, A) JP-A 54-1979 60399 (JP, A) JP-A-54-6097 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18/48-18/50 C08G 18/83 C08L 71/02- 71/03

Claims (5)

(57) [Claims] 1. A polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide in the presence of a double metal cyanide complex catalyst, having a hydroxyl value x (unit: m
gKOH / g) is 5 to 35, and the total degree of unsaturation y (meq / g) is 0.07.
Y ≦ 0.9 / (x−10), when x> 10, the number of hydroxyl groups is 2 to 8, and the content of oxyalkylene groups having 3 or more carbon atoms is 60% by weight or more and the content of oxyethylene groups is A polyoxyalkylene chain derived from less than 2% by weight of a polyoxyalkylene polyol, and at least 1.3 on average a hydrolyzable silyl group-containing terminal residue at the end of the polyoxyalkylene chain; Has a urethane bond linked to a polyoxyalkylene chain,
A moisture-curable resin composition comprising a hydrolyzable silyl group-containing polyether compound as a curing component. 2. The moisture-curable resin composition according to claim 1, wherein the polyoxyalkylene polyol is not a polyoxyalkylene polyol obtained by multiplying two or more molecules of a polyoxyalkylene polyol having a higher hydroxyl value. 3. A polyether compound containing a hydrolyzable silyl group and a compound having a hydrolyzable silyl group and an isocyanate group is reacted with a polyoxyalkylene polyol and a compound having a hydrolyzable silyl group and an isocyanate group in an average of 1.3 or more per equivalent of the latter. The moisture-curable resin composition according to claim 1, which is obtained by the above method. 4. An isocyanate group-containing prepolymer obtained by reacting a polyoxyalkylene polyol with an excess equivalent of a polyisocyanate compound, and an active hydrogen-containing group capable of reacting with an isocyanate group. The moisture-curable resin composition according to claim 1, which is obtained by reacting a compound having a hydrolyzable silyl group with a compound having an average of 1.3 or more to an equivalent amount per molecule of the former. 5. The hydrolyzable silyl group-containing polyether compound is obtained by combining a polyoxyalkylene polyol and a compound having an isocyanate group and an α, β-unsaturated group with an average of at least 1.3 molecules per molecule of the former. Equivalent reaction,
The moisture-curable resin composition according to claim 1, which is obtained by reacting a hydrosilane having a hydrolyzable group.