JPH0790171A - Curing composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a cured product excellent in adhesiveness, weather resistance, mechanical properites, etc., by mixing an organic polymer of a specified composition with a polymer made from a polymerizable-unsaturation-containing monomer and having at least one silicon- containing group in a specified ratio. CONSTITUTION:An alkylene oxide is polymerized in the presence of a composite metal cyanide complex (e.g. zinc hexacyanocobaltate) as a catalyst and an initiator (e.g. hydroxy compound) to produce a polyoxyalkylene polymer of a number-average molecular weight of 5000 or above. At least 0.3, on the average per molecule, silicon-containing group of the formula (wherein R is a 1-20C monovalent hydrocarbon group; X is a hydrolyzable group; and a is 1, 2 or 3) is introduced into the terminal of the polymer. 100 pts.wt. obtained organic polymer is,mixed with 0.1-1000 pts.wt. polymer made from a polymerizable- unsaturation-containing monomer and having at least one silicons-containing group of the formula in the polymer (e.g. acrylic acid/ vinylmethyldimethylsiloxane copolymer).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified curable composition, and more particularly to a curable composition having remarkably excellent adhesion, weather resistance and mechanical properties.

[0002]

2. Description of the Related Art Various polymers having a hydrolyzable silicon group at a terminal thereof, which are conventionally known as modified silicone resins, take advantage of the fact that the cured product has rubber elasticity, so that coating compositions and sealing compositions can be obtained. It is used for such purposes.

Known polymers having such a terminal hydrolyzable silicon group are, for example, Japanese Patent Publication Nos. 45-36319, 46-12154, and 49-32.
673, JP-A-50-156599, JP-A-51-73561, JP-A-54-6096, JP-A-55-82123, and JP-A-55-12.
3620, JP-A-55-125121, JP-A-55-131022, JP-A-55-1351.
35, JP-A-55-137129, and the like.

[0004]

All of these organic polymers have weaknesses in performance due to the structure of the main chain and the like. For example, the polymer described in JP-A-51-73561 has a urethane bond in the main chain and at the terminal, and therefore the weather resistance is deteriorated. Also, Japanese Patent Laid-Open No. 50-
The polymer described in Japanese Patent No. 156599 has insufficient adhesion to various adherends, and has a problem in weather resistance due to hydrogen atoms bonded to tertiary carbon because the main chain is polyether. is there.

In order to solve these drawbacks, JP-A-59-122541 proposes a composition comprising a polyether containing a reactive silicon group and a vinyl polymer having a reactive silicon group. Has been done. According to this method, the adhesiveness and the weather resistance are improved to some extent, but the physical properties such as elongation and strength of the cured product are insufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to solve such drawbacks, and by using a polyoxyalkylene polymer polymerized with a specific catalyst as a main chain, weather resistance is improved. It is intended to provide a curable composition which is excellent and has excellent physical properties such as elongation. That is, a polyoxyalkylene polymer (D) having a number average molecular weight of 5000 or more, which is obtained by polymerizing alkylene oxide with an initiator using a complex metal cyanide complex (C) as a catalyst, has a main chain represented by the following general formula (1). Organic polymer (A) having a total of 0.3 or more silicon-containing groups per molecule on average per molecule, and 100 parts by weight of the organic polymer (A) has a silicon-containing group represented by the following general formula (1) as polymer 1 1 per molecule
It is a curable composition containing 0.1 to 1000 parts by weight of a polymer (B) of a polymerizable unsaturated group-containing monomer having one or more. —SiX _a R ¹ _3-a (1) where R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydrolyzable group, and a is 1, Two
Or 3.

The polyoxyalkylene polymer (D) used as the main chain of the organic polymer (A) in the present invention is an initiator such as a hydroxy compound having at least one hydroxyl group in the presence of the complex metal cyanide complex (C). A hydroxyl group-terminated one produced by reacting with alkylene oxide is preferable.

By using the complex metal cyanide complex (C), the M _w / M _n is narrower than that of the polyoxyalkylene polymer produced by using the conventional alkali metal catalyst,
It is possible to obtain a polyoxyalkylene polymer (D) having a higher molecular weight and a lower viscosity.

The complex metal cyanide complex (C) is preferably a complex containing zinc hexacyanocobaltate as a main component, and its ether and / or alcohol complex is preferable. As the composition, those essentially described in JP-B-46-27250 can be used. As the ether, glymes such as glyme and diglyme are preferable, and glyme is particularly preferable from the viewpoint of handling during production of the complex. As the alcohol, t-butanol described in JP-A-4-145123 is preferable.

The number of functional groups of the polyoxyalkylene polymer (D) is preferably 2 or more, and particularly preferably 2 to 4. Specific examples include a polyoxyethylene compound, a polyoxypropylene compound, a polyoxybutylene compound, a polyoxyhexylene compound, a polyoxytetramethylene compound and a copolymer thereof.

Particularly preferred polyoxyalkylene polymers are polyoxypropylene diols, polyoxypropylene triols and polyoxypropylene tetraols. When used in the following methods (a) and (d), an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monool can also be used.

R ¹ in the general formula (1) is a substituted or unsubstituted monovalent organic 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 methyl group, ethyl group, propyl group, propenyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X in the general formula (1) 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, an acid amide 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 hydrolyzable groups include lower alkoxy groups having 4 or less carbon atoms, particularly methoxy group, ethoxy group, propoxy group, propenyloxy group and the like.

In the general formula (1), a is 1, 2 or 3, and particularly preferably 2 or 3.

Next, the method for producing the organic polymer (A) will be described. The organic polymer (A) in the present invention is preferably one produced by introducing a silicon-containing group at the terminal of a polyoxyalkylene polymer having a functional group as described below. Such compounds are liquid at room temperature, and
The cured product retains flexibility even at a relatively low temperature and has favorable properties when used as a sealing material, an adhesive or the like.

(A) A method of reacting a polyoxyalkylene compound having a functional group with an olefin group introduced at the terminal and a hydrosilyl compound represented by the following general formula (4). HSiX _a R ¹ _3-a (4) However, in the formula, R ¹ , X, and a are the same as described above. Here, as a method of 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 an ether bond, an ester bond, a urethane bond, a method of bonding by a carbonate bond, or the like, Alternatively, a method of introducing an olefin group into a side chain by adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing the alkylene oxide when polymerizing the alkylene oxide may be used.

(B) A method of reacting a terminal of a polyoxyalkylene compound having a functional group with a compound represented by the following general formula (5). ^{_{R 1 3-a SiX a -R}} 5 NCO ··· (5) provided that wherein R ^1, X, a are as defined above, R ⁵ is a divalent hydrocarbon group having 1 to 17 carbon atoms.

(C) After the end of the polyoxyalkylene compound having a functional group is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the isocyanate group is represented by the following general formula (6). A method of reacting a W group of a silicon compound. R ¹ _3-a -SiX _a -R ⁵ W (6) where R ¹ , R ⁵ , X and a are the same as defined above, W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group (1 It is an active hydrogen-containing group selected from primary or secondary).

(D) An olefin group is introduced at the terminal of a polyoxyalkylene compound having a functional group, and the olefin group is reacted with the mercapto group of the silicon compound represented by the general formula (6) in which W is a mercapto group. How to make.

The number of silicon-containing groups is 0.3 or more per molecule on the average of all molecules.

As the organic polymer (A) in the present invention, an organic polymer having a number average molecular weight of 5,000 to 30,000 can be used. The number average molecular weight of the organic polymer (A) is 500.
When it is lower than 0, the cured product is hard and has low elongation. When the number average molecular weight exceeds 30,000, flexibility and elongation of the cured product are not problematic, but the viscosity of the polymer itself is remarkably increased. It becomes less practical. The number average molecular weight is particularly preferably 8,000 to 30,000.

The component (B) used in the present invention is represented by the polymerizable unsaturated group-containing monomer (F) represented by the following general formula (2), a carbon-carbon double bond and the above general formula (1). Compound containing a silicon-containing group (G)
A polymer that can be produced by copolymerization with CH ₂ ═C (R ² ) (R ³ ) ... (2) where R ² is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R ³ is 1 to 1 carbon atoms. Twenty monovalent organic groups. Is.

Specific examples of the polymerizable unsaturated group-containing monomer (F) include styrene-based monomers such as styrene and α-methylstyrene; acrylic acid, methacrylic acid or their esters, acrylics such as acrylamide and methacrylamide, and methacryl. -Based monomers; cyano group-containing monomers such as acrylonitrile and 2,4-dicyanobutene-1; vinyl ester-based monomers such as vinyl acetate; isoprene, butadiene and other diene-based monomers; glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; And olefins other than these, unsaturated esters, halogenated olefins, vinyl ethers and the like.

The silicon compound (G) containing a carbon-carbon double bond and a silicon-containing group is represented by the following general formula (3). R ⁴ SiX _a R ¹ _3-a (3) However, in the formula, R ¹ , X and a are the same as described above, and R ⁴ is an organic residue having a polymerizable unsaturated group.

Specific examples of the silicon compound (G) represented by the general formula (3) include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyl. Vinylsilane such as trichlorosilane; acryloxysilane such as 3-acryloxypropylmethyldimethoxysilane and 3-acryloxypropyltrimethoxysilane; methacryloxy such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane Examples thereof include silane, and 3-methacryloxypropyltrimethoxysilane is particularly preferable. In addition to these, for example, polysiloxane compounds having 2 to 30 silicon atoms and the like can be used as long as they have a silicon atom bonded to a C—C double bond and a hydrolyzable group.

The polymerizable unsaturated group-containing monomer (F) and the silicon compound (G) can be appropriately selected according to the purpose. However, a cyano group-containing monomer such as acrylonitrile and an epoxy group-containing monomer such as glycidyl acrylate and glycidyl methacrylate. It is preferable to use a styrene-based monomer such as styrene, or 3-methacryloxypropyltrimethoxysilane because it can exhibit particularly excellent adhesiveness and mechanical properties. Further, especially when rubber elasticity is required after curing, it is preferable to use an acrylate ester.

In the present invention, these polymerizable unsaturated group-containing monomers (F) may be used alone or in combination of two or more. Further, the polymerizable unsaturated group-containing monomer (F) may be polymerized in advance so that the olefin group may remain on the side chain or terminal, and then reacted with the silicon compound (G).

The silicon compound (G) represented by the general formula (3) is based on the polymerizable unsaturated group-containing monomer (F).
It is preferable to use in the range of 0.001 to 50% by weight,
When rubber elasticity is required after curing, it is preferably used in the range of 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight.

The polymerizable unsaturated group-containing monomer can be polymerized by a usual method. As the polymerization initiator, various compounds capable of polymerizing a polymerizable unsaturated group-containing monomer such as a radical generator can be used, and in some cases, polymerization can be performed by radiation or heat without using a polymerization initiator.
Examples of the polymerization initiator include peroxide type, azo type,
Alternatively, there are redox type polymerization initiators and metal compound catalysts. Specific examples of the polymerization initiator often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide and diisopropyl peroxy carbonate. Moreover, it is also possible to use a solvent as needed.

In the present invention, a curing catalyst may be used if necessary. As the curing catalyst, compounds known as catalysts for hydrolysis and condensation reactions of hydrolyzable silicon groups can be used. That is, metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, tin octylate and dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate; and other acidic catalysts and Basic catalysts can be used. The amount of the curing catalyst used is preferably in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the component (A) and the component (B) in total, and particularly 0.01 to 5 parts by weight.
It is preferred to use parts by weight.

The composition of the present invention may contain a filler, a reinforcing agent, an anti-sagging agent, an adhesive agent and the like. As a filler,
Talc, clay, silica, etc., as a reinforcing agent, carbon black, fine powder silica, etc .; as pigments, inorganic pigments such as iron oxide, chromium oxide, titanium oxide, and organic pigments such as phthalocyanine blue, phthalocyanine green; Are organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate, zinc stearate, fine powder silica and the like; examples of the adhesive agent include aminosilane and epoxysilane.

A plasticizer may be optionally used in the present invention. As the plasticizer, known plasticizers can be used, and specifically, dioctyl phthalate, dibutyl phthalate,
Phthalates such as butylbenzyl phthalate; Aliphatic carboxylic esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, butyl oleate; Glycol esters such as pentaerythritol ester; Trioctyl phosphate, tricresyl phosphate, etc. Phosphoric acid esters of; epoxy resin such as epoxidized soybean oil and benzyl epoxy stearate; chlorinated paraffins;

The composition of the present invention may further contain various known additives. As the additives, adhesion promoters such as phenol resin and epoxy resin, various antiaging agents, ultraviolet absorbers and the like can be used.

The curable composition of the present invention comprises a sealing agent,
It can be used as waterproofing agent, adhesive, coating agent, etc.,
In particular, it is suitable for applications in which the cured product itself requires sufficient strength and high adhesiveness.

[0035]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Reference Examples 1 and 2 show production examples of the organic polymer (A), and Reference Example 3 shows production examples of the organic polymer used in Comparative Examples. Next, Reference Examples 4 to 5 show production examples of the polymer (B) of the polymerizable unsaturated group-containing monomer.

[Reference Example 1] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a diethylene glycol-propylene oxide adduct having a molecular weight of 1000 as an initiator according to the method described in Japanese Patent Application Laid-Open No. 3-72527. Polyoxypropylene diol having an average molecular weight of 19000 was obtained, the terminal hydroxyl group was converted to an allyl ether group, and methyldimethoxysilane was subjected to an addition reaction with chloroplatinic acid as a catalyst to give an average of 1.
An organic polymer (P1) having 6 silicon-containing groups was obtained.

[Reference Example 2] Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a glycerin-propylene oxide adduct having a molecular weight of 1000 as an initiator according to the method described in Japanese Patent Application Laid-Open No. 3-72527. Polyoxypropylene triol having an average molecular weight of 15,000 is obtained, the terminal hydroxyl group is converted to an allyl ether group, and methyldimethoxysilane is subjected to an addition reaction using chloroplatinic acid as a catalyst to give an average of 1.4 silicon-containing groups per molecule. A polymer (P2) was obtained.

[Reference Example 3] Polyoxypropylene diol having a number average molecular weight of 4000 was reacted with bromochloromethane based on the method described in JP-B-61-49332, and the terminal hydroxyl group was further reacted with allyl chloride.
After forming the terminal allyl ether group, methyldimethoxysilane was subjected to an addition reaction using chloroplatinic acid as a catalyst to obtain an organic polymer (P3). The number average molecular weight of this organic polymer in terms of polyoxypropylene diol was 11,000.

Reference Example 4 Glycidyl Methacrylate 6
0 g, acrylonitrile 30 g, 3-methacryloxypropyltrimethoxysilane 10 g, toluene 100 g as a solvent, azobisisobutyronitrile 1 as an initiator
Polymerization was carried out for 4 hours at 90 ° C. under N ₂ atmosphere to obtain a 50% solution of the polymer (P4).

[Reference Example 5] n-butyl acrylate 95
g, 3-methacryloxypropyltrimethoxysilane 5
g, and 1 g of azobisisobutyronitrile as an initiator were polymerized for 5 hours at 90 ° C. in an N ₂ atmosphere to give a polymer (P
5) was obtained.

[Examples 1 to 3 and Comparative Examples 1 and 2] In Reference Example 4, 100 parts by weight of the organic polymers shown in Table 1 among the organic polymers P1 to P3 produced in Reference Examples 1 to 3 were used. After mixing the produced polymer (P4) of the unsaturated group-containing monomer in parts by weight shown in Table 1, toluene was distilled off. 150 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 50 parts by weight of dioctyl phthalate, 5 parts of hydrogenated castor oil
By weight, 1 part by weight of a phenolic antioxidant, 1 part by weight of aminosilane, and 1 part by weight of dibutyltin dilaurate were kneaded under a condition that moisture was not contained to obtain a curable composition.

A sheet having a thickness of 2 mm was prepared from these and cured at 20 ° C. for 7 days, and further at 50 ° C. for 7 days, and then JIS.
Punching properties were measured with a No. 3 dumbbell [50% modulus (M ₅₀ ), strength at break (T _s ) and elongation at break (E
_l )]. Further, the tensile shear strength for aluminum was measured according to JIS H4000 A1050P. The results are shown in Table 1.

[Example 4 and Comparative Examples 3 to 4] Instead of P4, the polymer of the polymerizable unsaturated group-containing monomer produced in Reference Example 5 was added to 100 parts by weight of the organic polymer shown in Table 1. A curable composition was obtained in the same manner as in Examples 1 to 3 except for mixing. The dumbbell physical properties were measured in the same manner as in Examples 1 to 3, and the sunshine weatherometer 200 was used.
The surface after 0 hours was observed. The results are shown in Table 2.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

The combination of the organic polymer having a silicon-containing group produced using the double metal cyanide complex and the polymer of the polymerizable unsaturated group-containing monomer of the present invention containing a silicon-containing group is Further, it has an effect of exhibiting excellent adhesiveness and weather resistance and exhibiting excellent mechanical properties as compared with those conventionally known.

Claims (5)

[Claims] 1. A polyoxyalkylene polymer (D) having a number average molecular weight of 5000 or more, which is obtained by polymerizing alkylene oxide with an initiator using the complex metal cyanide complex (C) as a catalyst, and has the following general formula ( 1) The organic polymer (A) having a total of 0.3 or more silicon-containing groups per molecule on average, and 100 parts by weight of the organic polymer (A), a silicon-containing group represented by the following general formula (1) A curable composition containing 0.1 to 1000 parts by weight of a polymer (B) of a polymerizable unsaturated group-containing monomer having one or more per polymer molecule. —SiX _a R ¹ _3-a (1) where R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydrolyzable group, and a is 1, Two
Or 3. 2. The curable composition according to claim 1, wherein the complex metal cyanide complex (C) is a complex containing zinc hexacyanocobaltate as a main component. 3. The alkylene oxide is ethylene oxide,
The curable composition according to claim 1, which is at least one selected from propylene oxide and butylene oxide. 4. A polymer (B) of a polymerizable unsaturated group-containing monomer, a polymerizable unsaturated group-containing monomer (F) represented by the following general formula (2), a carbon-carbon double bond and hydrolysis. The curable composition according to claim 1, which is a polymer that can be produced by copolymerization with a silicon compound (G) containing a functional group. CH ₂ ═C (R ² ) (R ³ ) ... (2) where R ² is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R ³ is 1 to 1 carbon atoms. Twenty monovalent organic groups. 5. The silicon compound (G) is one type or two or more types represented by the following general formula (3).
Curable composition. R ⁴ SiX _a R ¹ _3-a (3) However, in the formula, R ¹ , X and a are the same as described above, and R ⁴ is an organic residue having a polymerizable unsaturated group.