JP3090970B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which gives a cured product having high strength and high elongation.

[0002]

2. Description of the Related Art As a one-component room temperature curable composition , a terminal
A polyoxyalkylene compound having a hydrolyzable silyl group is known.

[0003]

Polyoxyalkylene compound having a hydrolyzable silyl group at the terminal [0005] The cured product is a coating composition utilizing the characteristics of having a rubber elasticity, it is used for applications such as sealing composition However, it generally has a drawback that the strength is weak, and it has been difficult to use it alone for an elastic adhesive particularly requiring strength. In order to improve the strength, a method using an epoxy resin in combination has been proposed (Japanese Patent Application Laid-Open No. 61-268720). In this case, the elongation is significantly reduced. It has had cormorant drawbacks.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a composition obtained by adding an epoxy group-containing compound to a polyoxyalkylene compound having at least one hydrolyzable silyl group in the molecule. This is based on the finding that a cured product having high elongation and high strength can be obtained by using a compound having a high molecular weight and a narrow molecular weight distribution as a compound.

That is, the present invention provides a composite metal cyanide
A ring-opening addition polymerization of a monoepoxide having 3 or more carbon atoms was carried out in the presence of a complex catalyst and an initiator .
And a molecular weight distribution (weight average molecular weight M _w / number average molecular weight M) obtained by introducing a hydrolyzable silyl group into at least a part of the molecular terminal of the compound.
_n ) having a polyoxyalkylene compound (A ) of 1.35 or less , and an epoxy group-containing compound (B) .
Curable composition, and the polyoxyalkylene compound
A curable composition comprising a compound (A), an epoxy group-containing compound (B), and a compound (C) containing a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the same molecule. .

In the present invention, it is essential to use, as the polyoxyalkylene compound (A), a compound having a high molecular weight and a narrow molecular weight distribution, whereby the desired cured product having high strength and high elongation can be obtained for the first time. Can be

[0007] High molecular weight and molecular weight narrow polyoxyalkylene compound of distribution (A) is a double coupling metal cyanide complex body <br/> monoepoxides opening addition as a catalyst for polymerization initiators presence of 3 or more carbon atoms of using with opening of the monoepoxide
Performs addition polymerization obtained by introducing a hydrolyzable silyl group and then at least a portion of the molecular end of the compound obtained.

[0008] double if metal cyanide complexes are excellent as a catalyst for production of unsaturated monool to manufacture very small, in particular high molecular weight polyoxyalkylene compound. This catalyst is known and described, for example, in the following U.S. Pat. USP. 3278457,3278458,327845
9,3427256,3427334,3427335,3829505,3941849.

This catalyst is considered to have, for example, the structure of the following general formula (1). ^{_{M 1 a [M 2 x (}} CN) y] b (H 2 O) c L d (M 1 Y a) e (1) provided that, M ¹ is Zn (II), Fe (II ), Fe (III) , Co
(II), Co (III), Ni (II), Al (III), Sr (II),
Mn (II), Cr (II), Cr (III), Cu (II), Sn (I
I), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), etc., wherein M ² is Fe (II), Fe (III), Zn (II), C
o (II), Co (III), Cr (II), Cr (III), Mn (I
I), Mn (III), Ni (II), Mo (VI), V (IV), V (V)
L is an organic ligand, Y is an anion which forms a salt with M ¹ such as halogen, and a, b, c, d,
e, x and y are positive integers depending on the valence and coordination number of the metal.

In the general formula (1), M ¹ is preferably Zn (II), and M ² is Fe (II), Fe (III), Co (II), Co (II).
I) is preferred. Examples of the organic ligand L include ketone, ether, aldehyde, ester, alcohol,
Amides and the like. Composite metal cyanide complex represented by the general formula (1), a metal salt _{^{M 1 Y a (M 1,}} a, Y is the same manner as described above.) And poly cyanometalate _{^{(salt) Z e [M 2 x (}} C
Similarly ^{_{N) y] f (M 2}} , e, x, y are as described above, Z is hydrogen, alkali metal, alkaline earth metal, f is a positive integer that varies by coordination number Z, the valence of M ² ) Are mixed with each other or a mixed solvent solution of water and an organic solvent, and the resulting complex metal cyanide is brought into contact with the organic ligand L, and then the excess solvent and the organic ligand L are removed. It is manufactured by

Polycyanometallate (salt) _Ze [M ² _x (C
N) _{y] f} is Lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts. Particularly preferred are ordinary alkali metal salts, ie, sodium and potassium salts.

[0012] As the number 3 or more monoepoxide carbon used in the present invention, propylene oxide, 1,2-butylene oxide, include aliphatic alkylene oxide, such as epichlorohydrin, and aromatic alkylene oxides such as styrene oxide and the like However, aliphatic alkylene oxides are particularly preferred, and propylene oxide is particularly preferred. Also, a small amount of ethylene oxide can be used together with this.

The initiator used in the present invention may be a compound containing a polyhydric active hydrogen such as a polyhydric alcohol, a polyphenol or a polycarboxylic acid, or an active hydrogen containing an unsaturated group such as an unsaturated alcohol, a phenol or an unsaturated carboxylic acid. Compounds and the like can be used.

In the present invention, it performs a ring-opening addition polymerization of the composite metal cyanide complex catalyst and initiator monoepoxide presence having 3 or more carbon atoms, and then the resulting compound
A polyoxyalkylene compound containing a hydroxyl group and / or an unsaturated group at the molecular terminal of the product is produced. Then, also a terminal hydroxyl group to at least one introducing a hydrolyzable silyl group to convert the terminal unsaturated groups to hydrolyzable silyl group or a hydrolyzable silyl group-containing organic group in the molecule. Lupo polyoxyalkylene compound put to the present invention (A) is at least one on average in one molecule a hydrolyzable silyl group-containing terminal residues, preferably at least about 1.3 or Yes.

As a method for introducing a hydrolyzable silyl group or a hydrolyzable silyl group-containing organic group, for example, the following methods can be specifically exemplified, but are not limited to only those methods.

[0016] (i) at least one in partial child preferably only one isocyanate - having bets group and at least one hydrolyzable silyl group, for example, represented by the following formula (2)
Such a specific organosilicon compound (a) is reacted with a terminal hydroxyl group of a polyoxyalkylene compound. X _3-a -Si (R _a ) -R'-NCO (2)

[0017] R is or a hydrocarbon group a halogenated hydrocarbon group, 8 or less carbon atoms, preferably of 6 or less alkyl group or fluoroalkyl group. 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,
Examples include an acyloxy group, an amide group, an amino group, an aminooxy group, and a ketoxime group. Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less,
Particularly, 4 or less is preferable. Preferred hydrolyzable groups are alkoxy groups having 4 or less carbon atoms, particularly methoxy and ethoxy groups.

[0018] pressurized hydrolyzable silyl group, specifically,
For example trimethoxysilyl groups, methyl dimethoxy silyl group, triethoxy silyl group, methyldiethoxysilyl group, ethyl diethoxy silyl group, Toributo alkoxysilyl group, methyl dibutoxy silyl group, tris (2-methoxyethoxy) silyl group, tri Examples include an acetoxysilyl group and a methyldiacetoxysilyl group.

R ′ represents a divalent organic group. Preferably a divalent organic group or a bond of 1 to 17 carbon atoms as R ', in particular a divalent hydrocarbon group. The hydrocarbon group may contain an aromatic nucleus. Preferred hydrocarbon groups are alkylene group, an alkylene group having 1 to 8 carbon atoms, particularly preferably an alkylene group having 2 to 6 carbon atoms, eg <br/> if dimethylene group, trimethylene group, a tetramethylene group Polymethylene groups are preferred. Further, R ′ 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.

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

[0021] Although illustrated compounds wherein R 'or a hydrocarbon group which is a bond Specific examples of the (a) below, the organic silicon 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) -Si (CH ₃ ) _2- (CH ₂ ) ₃ -NCO (CH ₃ O) ₃ -Si-NCO (CH ₃ O) ₂ -Si- (NCO) ₂

(B) After reacting a compound (b) having an unsaturated group and an isocyanate group represented by the following formula (3) with a polyoxyalkylene polyol, a hydrolyzable group represented by the following formula (4) is added. Having a silicon hydride compound (c)
It is reacted in the presence of Zoku遷transfer metal.

[0023] R ² is a divalent organic group, preferably a lower A Le Killen group. R ^3, R ^4, R ⁵ or each hydrogen atom is a lower alkyl group. R ² is a divalent organic group R ¹ and the same carbon number 1 to 17 are preferred, especially 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, especially 2 to 2 carbon atoms.
Preferred is an alkylene group of 6, for example, a polymethylene group such as a dimethylene group, a trimethylene group, and a tetramethylene group. Further, R ² 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.

[0024] As the compound (b), for example allyl isocyanate, 2-isocyanate an ethyl methacrylate,
Examples include isopropenyl- α, α- dimethylbenzyl isocyanate, with allyl isocyanate being most preferred.

As the silicon hydride compound (c), a silicon hydride compound having a hydrolyzable silyl group described above is preferable. Further, after reacting with a halohydrosilane in which X is a halogen such as a chlorine atom as the silicon hydride compound (c), the halogen is hydrolyzed other than a halogen such as an alkoxy group.
Can be converted to a functional group . Silicon hydride compound (c)
Reaction of an unsaturated group can be carried out using a known catalyst such as platinum.

(C) reacting a terminal unsaturated group-containing halogen compound with a terminal hydroxyl group of a polyoxyalkylene compound;
Or terminal unsaturated group is obtained by the reacting a polyoxyalkylene compound of terminal unsaturated groups with the above-mentioned silicon hydride compound due to the initiator and (c) in the presence of a VIII Zoku遷transfer metal. Specifically, allyl chloride can be exemplified as the terminal unsaturated group-containing halogen compound.

The polyoxyalkylene compound (A) obtained by the above method has a molecular weight of 3500 to 50,000.
, And particularly from 6,000 to 3,000 0 is preferable. Molecular weight distribution, Sunawa Chi weight average molecular weight M _w of the number-average molecular weight M _n
The ratio M _w / M _n of is 1.35 or less, particularly 1.25 or more
Below is preferred.

The epoxy group-containing compound (B) used in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A Novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, resorcinol type epoxy resin, and the like Examples thereof include a logenide and a hydrogenated product, but the present invention is not limited to these, and a commonly used epoxy resin compound may be used.

In the present invention, a compound (C) containing a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the same molecule can be used. Examples of the functional group capable of reacting with the epoxy group in the compound (C) include an amino group, a carboxyl group, a mercapto group, and an epoxy group, but are not particularly limited thereto. Examples of the hydrolyzable silyl group in the compound (C) include the same functional groups as the hydrolyzable silyl group contained in the polyoxyalkylene compound (A).

Examples of the compound containing a functional group capable of reacting with an epoxy group and a hydrolyzable silyl group in the same molecule such as the compound (C) include, for example, N- (2-
Aminoethyl) -3-aminopropyl methyl dimethoxysilane, N- (2- aminoethyl) -3-aminopropyltrimethoxysilane, bi scan [3- (methyldimethoxysilyl) propyl] amine, N, N '- bis [ 3- (methyldimethoxysilyl) propyl] ethylenediamine,
N, N '- bi scan [3- (trimethoxysilyl) propyl] ethylenediamine, N - [(3-trimethoxysilyl) propyl] diethylenetriamine, N - [(3-trimethoxysilyl) propyl] triethylenetetramine, N, N- di-glycidyl-3-aminopropyltrimethoxysilane, N- glycidyl -N, N- bis [3-
(Methyldimethoxysilyl) propyl] amine, N-glycidyl-N, N-bis [3- (trimethoxysilyl)
Propyl] amine, 3 - glycidoxypropyl methyldimethoxysilane, 3 - glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane can be mentioned up. Even if these compounds are used alone,
Also, two or more kinds may be used in combination.

In the present invention, the amount of the epoxy group-containing compound (B) used per 100 parts by weight of the polyoxyalkylene compound (A) is from 1 to 200 parts by weight, especially from 30 to 200 parts by weight.
80 parts by weight are preferred. When the amount of the polyoxyalkylene compound (A) is more than this, the strength of the cured product becomes insufficient, and when it is less than this, the elongation becomes insufficient.

In the present invention, the compound (C) is used in an amount of 0 to 30 parts by weight, preferably 0.5 to 4 parts by weight, per 100 parts by weight of the mixture of the polyoxyalkylene compound (A) and the epoxy group-containing compound (B). Parts by weight are preferred.

In the present invention, a curing agent for curing the epoxy group-containing compound can be used in combination. Epoxy resin curing agents that can be used include diethylene triamine,
Aliphatic polyamines such as triethylenetetraamine, aromatic polyamines such as metaphenylenediamine, secondary amines, tertiary amines such as tris (dimethylaminomethyl) phenol, tertiary amine salts, acid anhydrides, polyamide resins, polysulfide resins, boron trifluoride complex compounds, imidazoles, and the like dicyandiamide can be exemplified, but not limited thereto.

Further, in the composition, a curing accelerating catalyst for accelerating the curing reaction of the hydrolyzable silyl group of the polyoxyalkylene compound (A) to the compound (C) may be used. The curing accelerating catalyst, alkyl titanates, organosilicon titanates, tin 2-ethylhexanoate and dibutyltin metal salts of such carboxylic acids dilaurate: dibutylamine-2-ethylhexyl Sano benzoate, etc., such amine salts of: and It may use other acidic catalysts and basic catalysts.

The composition of the present invention may further include
Reinforcing agents, fillers, plasticizers, anti-sagging agents and the like may be included. Carbon black as a reinforcing agent, such as finely divided silica, calcium carbonate as a filler, talc, clay, silica, etc., as the plasticizer dioctyl phthalate, dibutyl phthalate, dioctyl adipate, chlorinated paraffins and petroleum plasticizers is, iron oxide pigments, chromium oxide, inorganic pigments and phthalocyanine blue and titanium oxide, and organic pigments such as phthalocyanine green, organic acid-treated calcium carbonate as anti-sagging agents such as agents,
Hydrogenated castor oil, calcium stearate, zinc stearate, finely divided silica can be mentioned up.

The curable composition of the present invention comprises a sealing agent,
Can be used for waterproofing agents, adhesives, coatings, etc.,
Particularly, it is suitable for applications requiring sufficient cohesive force of the cured product itself and dynamic followability to the adherend, particularly for an elastic adhesive.

[0037]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

[Production Example 1] Propylene oxide was polymerized using zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. To this was added isocyanatepropylmethyldimethoxysilane, and a urethanation reaction was performed to convert hydroxyl groups at both ends into methyldimethoxysilyl groups. The number average molecular weight and the molecular weight distribution of the obtained terminally hydrolyzable silyl group-containing polyoxyalkylene compound were measured by gel permeation chromatography.
As a result of analysis using a gel (hereinafter, GPC) , the number average molecular weight was 10,000 and the molecular weight distribution ( _Mw / _Mn ) was 1.15.

[0039] [Production Example 2] Polymerization was conducted in the propylene oxide in the zinc hexacyanocobaltate catalyst and diethylene glycol as an initiator, to obtain a polyoxypropylene di-ol. Allyl chloride was added thereto to convert the hydroxyl groups at both ends into allyl groups. Then, methyl dimethoxysilane was reacted with the obtained polyoxyalkylene compound containing an allyl group at the terminal in the presence of a platinum catalyst to convert the allyl group to a methyldimethoxysilyl group. As a result of analyzing the number average molecular weight and the molecular weight distribution of the obtained terminal hydrolyzable silyl group-containing polyoxyalkylene compound by GPC, the number average molecular weight was 10%.
000, and the molecular weight distribution ( _Mw / _Mn ) was 1.20.

[0040] After the polyoxypropylene triol [Production Example 3] The average molecular weight of 3000 was terminated Sodium reduction of metal sodium were high molecular weight is reacted with dibromomethane. The resulting high molecular weight polyoxypropylene triol similar manner the terminal hydroxyl group as in Production Example 2 of were converted to methyldimethoxysilyl group. The number average molecular weight and molecular weight distribution of the obtained terminally hydrolyzable silyl group-containing polyoxyalkylene compound are represented by G
As a result of analysis by PC, the number average molecular weight was 10,000, and the molecular weight distribution ( _Mw / _Mn ) was 1.68.

[0041] [Example 1] 100 parts by weight of the polymer obtained in Preparation Example 1, Epikote 828 (Yuka Shell Epoxy Co., Ltd. of bisphenol A type epoxy resin) 50 parts by weight, 2,4,6-scan
After 5 parts by weight of ( dimethylaminomethyl) phenol and 2 parts by weight of dibutyltin dilaurate were mixed well, a sheet having a thickness of 2 mm was prepared, and physical properties were measured after curing at 20 ° C. for 7 days and further at 50 ° C. for 7 days. , Breaking strength (hereinafter, T
b ) = 98 kg / cm ² , elongation at break (hereinafter, Eb ) = 1
A cured product having a high strength of 200% and a high elongation was obtained.

[0042] [Example 2] 100 parts by weight of the polymer obtained in Production Example 2, 50 parts by weight of Epikote 828, 2,4,6-scan (dimethylaminomethyl) phenol 5 parts by weight, dibutyltin dilaurate 2wt After 2 parts by weight of 3 -aminopropylmethyldimethoxysilane were mixed well, a sheet having a thickness of 2 mm was prepared and cured at 20 ° C. for 7 days and further cured at 50 ° C. for 7 days. 78 kg / cm ² , Eb
= 900% and a cured product with high strength and high elongation was obtained.

[0043] [Comparative Example 1] 100 parts by weight of the polymer obtained in Production Example 3, 50 parts by weight of Epikote 828, 2,4,6-tris (di-methylaminomethyl) phenol 5 parts by weight, dibutyltin dilaurate 2wt After 2 parts by weight of 3 -aminopropylmethyldimethoxysilane were mixed well, a sheet having a thickness of 2 mm was prepared and cured at 20 ° C. for 7 days and further cured at 50 ° C. for 7 days. 72 kg / cm ² , Eb
= Only a cured product with a low elongation of 300% was obtained.

[0044]

As described above, a hydrolyzable silyl group-containing polyoxyalkylene having a high molecular weight and a narrow molecular weight distribution is used.
By using a ren compound as a component in the curable composition, a cured product having high strength and high elongation can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 59/40 C08L 63/00-63/10 C08L 71/02

Claims (4)

(57) [Claims] 1. A double metal cyanide complex catalyst and an initiator
Ring opening of monoepoxide having 3 or more carbon atoms in the presence of eta
It is obtained by performing polymerization and then introducing a hydrolyzable silyl group into at least a part of the molecular terminal of the obtained compound .
It contains a polyoxyalkylene compound (A) having a molecular weight of 3,500 to 50,000 and a molecular weight distribution (weight average molecular weight M _w / number average molecular weight M _n ) of 1.35 or less , and an epoxy group-containing compound (B). Curable composition. 2. A polyoxyalkylene compound (A) 100
1 to 200 parts by weight of the epoxy group-containing compound (B)
The curable composition according to claim 1, which contains parts by weight. 3. A catalyst for a double metal cyanide complex and an initiator.
Ring opening of monoepoxide having 3 or more carbon atoms in the presence of eta
Polymerization is carried out, and the resulting compound has a small number of molecular terminals.
At least partially obtained by introducing a hydrolyzable silyl group,
Molecular weight 3500 to 50,000 and molecular weight distribution (weight
(Average molecular weight M _w / number average molecular weight M _n ) of 1.35 or less
Certain polyoxyalkylene compounds (A) containing epoxy groups
Organic compound (B) and functional group capable of reacting with epoxy group
Group containing a hydrolyzable silyl group in the same molecule
A curable composition containing the compound (C). 4. A polyoxyalkylene compound (A) 100
1 to 200 parts by weight of the epoxy group-containing compound (B)
The curable composition according to claim 3, wherein the curable composition contains more than 0 to 30 parts by weight of the compound (C) based on 100 parts by weight of the mixture of (A) and (B).