JP3083596B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a hydrolyzable silicon-containing polymer useful as a moisture-curable sealant.

[0002]

2. Description of the Related Art Polyoxyalkylene compounds having at least one hydrolyzable silicon group in a molecule are compounded with various compounding agents, and are used for applications such as sealing agents. Had a tackiness (stickiness) left on the surface, and dust and the like adhered to the surface, causing a deterioration in appearance.

[0003]

Problems to be Solved by the Invention
In No. 1, the diene polymer is used in an amount of 0.1 to 100 parts by weight of the oxyalkylene polymer containing a hydrolyzable silicon group.
It is disclosed that a curable composition contained in a range of 10 parts by weight is effective in reducing tack.

However, a diene polymer is essentially incompatible with a polymer whose main chain is substantially composed of polyoxyalkylene, and the mere passage of the diene polymer into the polyoxyalkylene polymer results in a lapse of time. At the same time, phase separation occurs and the composition of the composition becomes non-uniform, which is problematic in practice.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, and comprises at least one hydrolyzable silicon group per polymer molecule and a main chain skeleton comprising a polyoxyalkylene. The present invention has been found that a curable composition containing a polymer and a polydiene-polyoxyalkylene copolymer and / or a hydrogenated polydiene-polyoxyalkylene copolymer has low residual tack on the surface of a cured product. It is a thing.

As the polymer containing a hydrolyzable silicon group in the present invention, various polymers having at least one hydrolyzable silicon group in one molecule and having a main chain substantially composed of polyoxyalkylene are used. it can.

[0007] For example, Japanese Patent Application Laid-Open Nos.
72527, JP-A-3-79627, JP-B-46-30
711, JP-B-45-36319, JP-B-46-175
53 and the like, and a polymer having a main chain skeleton consisting essentially of polyoxyalkylene is preferred. The preparation of such polymers is exemplified in the above-mentioned literature.

The main chain of the polymer containing a hydrolyzable silicon group essentially consists of a polyoxyalkylene chain. The hydrolyzable silicon group-containing polymer is produced by introducing a hydrolyzable silicon group into a polyoxyalkylene compound having a functional group as described below.

The polyoxyalkylene compound is prepared by reacting an initiator such as a polyhydroxy compound having at least one hydroxyl group with a monoepoxide such as an alkylene oxide in the presence of a catalyst such as an alkali metal catalyst, a double metal cyanide complex catalyst, and a metal porphyrin. Hydroxyl-terminated ones produced by the above method are preferred. The number of functional groups of the polyoxyalkylene compound is preferably 2 or more, and particularly preferably 2 or 3.

Particularly preferred polyoxyalkylene compounds are polyoxypropylene diol and polyoxypropylene triol. When used in the following method (1), an olefin-terminated polyoxyalkylene compound such as an allyl-terminated polyoxypropylene monol can also be used.

The hydrolyzable silicon group is represented by the general formula (a)
And a silyl group represented by -SiX _a R _3-a ... (a)

[0012] wherein R is or a monovalent 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, eg if a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an amino group, and the like ketoximate group. 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 lower alkoxy groups having 4 or less carbon atoms, particularly methoxy and ethoxy groups. a is 1, 2 or 3, and particularly preferably 2 or 3.

[0013] formula (a) silyl groups table with more than 50% on average in the entire terminal groups, it preferably contains 70% or more.

The method of the introduction of the general formula (a) to the polyoxyalkylene compound silyl groups table particularly without limitation, may be introduced, for example, by the following method.

(1) A method of reacting a polyoxyalkylene compound having an olefin group introduced into a terminal with a hydrosilyl compound represented by the general formula (b).

HSiX _a R _3-a (b) (where R, X and a are the same as above)

Here, as a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene compound, and the compound is bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like. method of, or during the polymerization of alkylene oxides, such as a method of introducing an olefin group in the side chain are exemplified by copolymerization by adding an olefin group-containing epoxy compound such as allyl glycidyl ether.

(2) A method of reacting a compound represented by the general formula (c) with a terminal of a polyoxyalkylene compound.

R _3-a -SiX _a -R ¹ NCO (c) (wherein R, X and a are the same as above; R ¹ has 1 to 17 carbon atoms)
Divalent hydrocarbon group. )

(3) The terminal of the polyoxyalkylene compound is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, and the isocyanate group is treated with a W group of a silicon compound represented by the general formula (d). How to react.

R _3-a -SiX _a -R ¹ W (where R, R ¹ , X and a are the same as above. W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group (1 Active hydrogen-containing group selected from primary or secondary).)

(4) A method of introducing an olefin group into the terminal of the polyoxyalkylene compound and reacting the olefin group with a mercapto group of a silicon compound represented by the general formula (d) wherein W is a mercapto group.

The hydrolyzable silicon group-containing polymer of the present invention is three-dimensionally cured by a crosslinking reaction when it comes into contact with moisture.

The molecular weight of the polymer containing a hydrolyzable silicon group in the present invention is preferably from 2,000 to 50,000.
15,000 to 30,000 are preferred.

Polydiene-polyoxyalkylene copolymer
Body or the hydrogenated polydiene - polyoxyalkylene copolymers can be obtained by adding an alkylene oxide in the presence of a catalyst in polydiene or hydrogenated poly <br/> diene emissions having an active hydrogen-containing group.

[0026]

[0027]

The polydiene usually has a terminal functional group. Examples of the functional group include a hydroxyl group, a carboxyl group, a mercapto group, a halogen atom and the like, and particularly those having a hydroxyl group or a carboxyl group are generally used. The hydrogenated polydiene is a hydride of this polydiene, and is one in which the unsaturated groups in the polydiene are reduced or eliminated.

The oxyalkylene chain is formed by ring-opening polymerization of an alkylene oxide. That is, it is obtained by sequentially performing ring-opening polymerization of an alkylene oxide on a functional group having a reactive hydrogen atom (active hydrogen) such as a hydroxyl group, a carboxyl group, or a mercapto group among the above functional groups. The polydiene - polyoxyalkylene copolymer or the hydrogenated polydiene - end groups of the polyoxyalkylene copolymer is a hydroxyl group.

The above polydiene-polyoxyalkylene
Polymer and / or hydrogenated polydiene-polyoxyal
The initiator for producing the kylene copolymer is a hydroxyl group or
Carboxy group-containing polydiene and / or hydrogenated polydiene
Preferably it is a ligene. Polydienes or hydrogenated polydienes have high hydrophobicity, and therefore, alkali catalysts (KOH) widely used as alkylene oxide polymerization catalysts are known.
Is difficult to use. Therefore, it is preferable to use a double metal cyanide complex as the catalyst. Double metal cyanide complex catalysts are known as catalysts for alkylene oxide polymerization. Preferred catalysts are those containing zinc, such as cobalt zinc cyanide glyme complex.

The polymerization reaction, a hydroxyl group or a carboxyl group-containing Porijie comma other as the initiator can be carried out by adding the alkylene oxide at any temperature conditions in the mixture of the composite metal cyanide complex as hydrogenated polydiene But,
If necessary, the reaction can be carried out in the presence of a solvent.

Examples of usable solvents include hydrocarbon solvents,
Examples thereof include halogenated hydrocarbon solvents and ether solvents. As the hydrocarbon solvent, specifically, hexane,
Examples of halogenated hydrocarbon solvents such as cyclohexane, methylcyclohexane, benzene, toluene and xylene include methylene chloride, chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, chlorobenzene,
And dichlorobenzene.

Examples of the ether solvent include diethyl ether, tetrahydrofuran, dioxane, glyme, diglyme and the like. These may be used alone or arbitrarily mixed as needed.

Hydroxy or carboxyl group-containing polydiene
Ethene or hydrogenated polydiene is
, Chloroprene, 1,3-pentadiene, cyclopen
Homopolymer or copolymer of diene such as tadiene,
Or one or more of them and another copolymerizable monomer (eg,
For example, styrene, acrylonitrile, (meth) acrylic acid
And liquid at low temperature to solid with a low melting point.
It is a polymer that is a body. Especially liquid at room temperature is preferred
No. Specifically as hydroxyl or polydiene carboxyl group-containing, hydroxyl or carboxyl group-containing, liquid 1,2-polybutadiene, liquid 1,4-polybutadiene, liquid polychloroprene, liquid polyisoprene, 1,
3- polypentadiene , styrene-butadiene copolymer, acrylonitrile-butadiene copolymer , butadiene
-Isoprene copolymer; butadiene-pentadiene copolymer
Examples thereof include polymers, but are not particularly limited thereto.

Examples of the hydrogenated polydiene containing a hydroxyl group or a carboxyl group include a hydroxyl group or a carboxyl group.
Of liquid hydrogenated polybutadiene, liquid hydrogenated 1,4
-Polybutadiene, liquid hydrogenated polychloroprene, liquid hydrogenated polyisoprene, hydrogenated styrene-butadiene copolymer, hydrogenated acrylonitrile-butadiene copolymer, and the like, but are not particularly limited thereto.

As the alkylene oxide used for the polymerization of the above copolymer, ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and alkyl or allyl or aryl glycidyl ethers, specifically, methyl Examples include glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether. In particular, propylene oxide or butylene oxide are preferred.

Further, the polydiene - polyoxyalkylene copolymer or the hydrogenated polydiene - polyoxyalkylene copolymers Porijie comma others 5-90% by weight of residues of hydrogenated polydiene in the molecule, in particular Is 25-85% by weight ,
It is preferred to contain. If it exceeds 90% by weight, the effect of improving compatibility becomes insufficient, and if it is less than 5% by weight, the effect of reducing tack becomes insufficient.

The amount of the polydiene-polyoxyalkylene copolymer and / or the hydrogenated polydiene-polyoxyalkylene copolymer used is determined by the amount of the hydrolyzable silicon group-containing polymer 10
5 to 70 parts by weight , preferably 5 to 70 parts by weight, particularly 5 to 5 parts by weight
50 parts by weight are preferred. If the amount is less than 5 parts by weight, the effect of reducing the residual tack is insufficient, and if it exceeds 70 parts by weight, the curability decreases.

Preparation of the composition of the present invention prepared using the hydrolyzable silicon group-containing polymer of the present invention and a polydiene-polyoxyalkylene copolymer and / or a hydrogenated polydiene-polyoxyalkylene copolymer There is no particular limitation on the method.

When used as a two-component type sealing agent, a hydrolyzable silicon-containing polymer and a polydiene-polyoxyalkylene copolymer and / or a hydrogenated polydiene-polyoxyalkylene copolymer or the like can be used . Yo
If necessary, a method of mixing and using a curing catalyst to be used may be used.

Specific examples of the catalyst include, for example, titanium such as tetrabutyl titanate and tetrapropyl titanate.
Acid esters, dibutyltin dilaurate, dibutyltin maleate, organic tin compounds such as dibutyltin diacetate, tin octylate, tin naphthenate, lead octylate, butylamine, octylamine, cybutylamine, monoethanolamine, diethanolamine, triethanol Amines, diethylenetriamine, triethylenetetramine,
Oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,
Xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo [5,4,0]
Amine compounds such as undecene-7 (DBU) or salts thereof such as carboxylic acids, low molecular weight polyamide resins obtained from excess polyamine and polybasic acid, reaction of excess polyamine with epoxy compound Examples of the product include known silanol condensation catalysts such as a silane coupling agent having an amino group , for example, γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. These may be used alone or in combination of two or more.

The composition of the present invention may further contain various fillers, additives and the like, if necessary. Examples of fillers include those commonly used such as heavy and light calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate and carbon black. Examples of plasticizers are dioctyl phthalate, butylbenzyl phthalate,
Chlorinated paraffin, epoxidized soybean oil and the like which are usually used can be mentioned.

As the anti-sagging agent, hydrogenated castor oil, silicic anhydride or organic bentonite is suitable. UV absorbers as antioxidant, or in itself from among various classified as radical chain prohibition or peroxide decomposing agents and the like may be used in combination.

[0044]

The polydiene-polyoxyalkylene copolymer and / or hydrogenated polydiene-polyoxyalkylene copolymer of the present invention has good compatibility with the hydrolyzable silicon group-containing polymer and good dispersibility. Moreover, the physical properties are not significantly reduced by the addition of the copolymer, and the weather resistance is good.

The effect of improving the adhesion of dust and the residual tack is that polydiene is copolymerized with an alkylene oxide and is used in a liquid state without phase separation. It can be estimated that tack is reduced.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, comparative examples and application examples, but the present invention is not limited to these examples.

(Production Examples) Production Examples of Polydiene-Polyoxyalkylene Copolymers A to D

A: 100 parts by weight of R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd., liquid terminal hydroxyl group 1,4-polybutadiene) was added to zinc hexacyanocobaltate / diglyme complex 0.06
The mixture was stirred at 120 ° C. under nitrogen, 50 parts by weight of propylene oxide was added over 1 hour, and the mixture was reacted at that temperature for 1 hour.

B: 100 parts by weight of propylene oxide is 2
It was obtained by performing the same operation as in A except that it was added over time.

C: 233 parts by weight of propylene oxide
It was obtained by performing the same operation as in A except that it was added over time.

D: PBG-200 instead of R-45HT
0 (manufactured by Nippon Soda, liquid 1,2-polybutadiene glycol) was obtained by performing the same operation as in B except that 100 parts by weight was used.

Example 1 30 parts by weight of copolymer A may be added to 100 parts by weight of a linear propylene oxide polymer having an average molecular weight of 17000 and containing a methyldimethoxysilyl group at 95% of all terminals. After stirring, composition E was obtained.

[0053] (Example 2) may be added to the copolymer B of 40 parts by weight with respect to the linear propylene oxide polymer 100 parts by weight of average molecular weight 22000 containing methyl dimethoxy silyl group to 88% of the total end After stirring, composition F was obtained.

[0054] (Example 3) may be added to the copolymer C of 10 parts by weight of linear propylene oxide polymer 100 parts by weight of the average molecular weight of 30,000 containing methyl dimethoxy silyl group to 99% of the total end After stirring, composition G was obtained.

[0055] (Example 4) may be added to the copolymer D of 45 parts by weight of linear propylene oxide polymer 100 parts by weight of the average molecular weight of 20,000 containing methyl dimethoxy silyl group to 92% of total end After stirring, composition H was obtained.

Comparative Example 1 A composition I was obtained in the same manner as in Example 1 except that R-45HT was used instead of the copolymer A.

Table 1 shows the storage stability of the compositions E to I obtained in Examples 1 to 4 and Comparative Example 1 after a lapse of 7 days at 50 ° C.

[0058]

[Table 1]

The system containing the polydiene-polyoxyalkylene copolymer had better compatibility than the system containing the liquid polybutadiene, and no change was observed even after 7 days or more at 50 ° C. after production.

(Application Examples 1 to 4) Compositions E to H obtained in Examples 1 to 4, calcium carbonate, dioctyl phthalate, an antioxidant, dibutyltin dilaurate (DBTDL) and titanium oxide were mixed as shown in Table 2. The mixture was thoroughly mixed with three paint rolls at a ratio (parts by weight), and a sheet having a thickness of about 3 mm was produced. A cured product sheet was obtained at 23 ° C., 55% humidity, and sheet production conditions for 7 days. Table 2 shows the physical properties of the obtained sheet.

(Comparative Example 2) Instead of the compositions E to H, a propylene oxide polymer having an average molecular weight of 17000 containing a methyldimethoxysilyl group at 95% of all terminals (hereinafter referred to as polymer J) was used. Except for the above, a cured product sheet was obtained according to the application examples. Table 2 shows the physical properties of the obtained sheet.

In Table 2, the evaluation of dust adhesion is as follows. ：: Good, with no dust. Δ: Slightly dusty and slightly defective. X: Dust easily adheres and is defective. The residual tack was a Pikmac tester manufactured by Toyo Seiki Seisaku-sho, load 5
The measurement was performed at 00 g.

[0063]

[Table 2]

[0064]

As compared with liquid polybutadiene, the polydiene-polyoxyalkylene copolymer has good compatibility and is stable, and the cured product obtained from this composition has flexibility, elongation,
It has excellent strength and has improved dust adhesion and residual tack.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-149851 (JP, A) JP-A-4-8728 (JP, A) JP-A-2-142850 (JP, A) JP-A-59-1984 25828 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 71/00-71/14 C08G 65/00-65/48

Claims (5)

(57) [Claims] 1. A polymer containing a hydrolyzable silicon group having at least one hydrolyzable silicon group per molecule of a polymer and having a main chain skeleton of polyoxyalkylene, and a polydiene-polyoxyalkylene copolymer and / or Or a curable composition containing a hydrogenated polydiene-polyoxyalkylene copolymer. 2. A polydiene-polyoxyalkylene copolymer and / or a hydrogenated polydiene-polyoxyalkylene copolymer in an amount of 5 to 70 parts by weight based on 100 parts by weight of the polymer containing a hydrolyzable silicon group. the curable composition according to 1. 3. The hydrolyzable silicon-containing polymer having a molecular weight of 2
The curable composition according to claim 1, which has a molecular weight of 000 to 50,000. 4. A polydiene-polyoxyalkylene copolymer
Body or the hydrogenated polydiene - polyoxyalkylene copolymers, hydroxyl or a initiator Porijie comma <br/> other hydrogenated polydienes containing carboxyl groups, obtained by ring-opening polymerization of an alkylene oxide Claims 1 and 2
Or the curable composition according to 3 . 5. A polydiene-polyoxyalkylene copolymer.
Body or the hydrogenated polydiene - polyoxyalkylene copolymer, Porijie comma others are those 5 containing 90% by weight in the molecule the residue of hydrogenated polydiene, according to claim 1,
5. The curable composition according to 3 or 4.