JPH0770425A - Room temperature setting composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in tacking properties, deep curability and adhesion by compounding polyoxyalkylene polymer prepared by polymerization using a conjugate metal cyanide complex as a catalyst followed by the introduction of a silicon-containing hydrolyzable group, an air-setting compound and a photo-setting compound. CONSTITUTION:An organic polymer is prepared by polymerizing an alkylene oxide (e.g. propylene oxide) using a conjugate metal cyanide complex (e.g. zinc hexacyanocobaltate) as a catalyst to obtain a polyoxyalkylenediol having a number average molecular weight of >=5000 and introducing a silicon- containing group expressed by the formula [R<1> is 1-20C (substituted) monovalent hydrocarbon; X is hydrolyzable group; (a) is 1, 2 or 3[ at the ratio of >=0.3 per one molecule in terms of the average of the total molecules into the terminal of the obtained polyoxyalkylenediol. 100 pts.wt. of the prepared organic polymer is compounded with 0.01-20 pts.wt. of an air-setting compound (e.g. linseed oil) and/or 0.01-2 pts.wt. of a lightsetting compound (e.g. propyleneglycol dimethacrylate) to obtain the room temperature setting composition having a reduced tackiness on the surface of a cured body and excellent in softness, deep curability and adhesion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a room temperature curable composition which cures in the presence of moisture.

[0002]

2. Description of the Related Art Conventionally, it is used as a sealing material, an adhesive, a coating material, etc. by utilizing the curing reaction of various compounds having a hydrolyzable silicon group at the terminal, which is known as a modified silicone resin. The method is well known and industrially useful.

Forms a siloxane bond by hydrolysis,
Several examples of such compounds having a hydrolyzable silicon group capable of having a high molecular weight or cross-linking are conventionally known (for example, JP-A-3-47820, JP-A-3-72027, and JP-A-3-72027). No. 3-79627,
JP-B-46-30711, JP-B-45-3631
No. 9, JP-B No. 46-17553, etc. ).

[0004]

However, when the modulus of the cured product of the polymer or the cured product of the composition is lowered, these compounds have stickiness on the surface, that is, tackiness, even after the completion of the curing, such as a sealing material. When it is used as a base polymer, it causes joint pollution such as dust adhesion and is a cause of impairing the appearance of buildings.

For the purpose of preventing this tack, for example, JP-A-55-36241 discloses a technique of adding a photocurable compound to a polymer having a hydrolyzable silicon group. However, in these compositions, the photocurable compound does not sufficiently exert its effect until time passes,
For example, tackiness immediately after construction of the sealant cannot be improved, which is a great limitation in use.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained an alkylene oxide obtained by polymerizing alkylene oxide with an initiator using a complex metal cyanide complex (D) as a catalyst. An organic polymer having a polyoxyalkylene polymer (E) having a number average molecular weight of 5,000 or more as a main chain and having a silicon-containing group represented by the following general formula (1) in an average of 0.3 or more per molecule in all molecules ( A) 100 parts by weight and, based on 100 parts by weight, the air-curable compound (B)
A room temperature curable composition containing 0.01 to 20 parts by weight and / or 0.01 to 20 parts by weight of a photocurable compound (C) has a fast curing start-up and maintains a certain pot life. It was found that a room temperature curable composition in which the curability of the surface and the deep part was significantly improved was obtained, and that it was extremely effective in improving the initial tack immediately after application, and reached the present invention. —SiX _a R ¹ _3-a (1) (wherein R ¹ is a substituted or unsubstituted 1 to 20 carbon atom)
Valent hydrocarbon radical. X is a hydrolyzable group. a is 1, 2 or 3. )

The polyoxyalkylene polymer (E) 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 (D). A hydroxyl group-terminated one produced by reacting with alkylene oxide is preferable.

By using the complex metal cyanide complex (D), 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 (E) having a higher molecular weight and a lower viscosity.

The complex metal cyanide complex (D) is preferably a complex containing zinc hexacyanocobaltate as a main component, and its ether and / or alcohol complex is 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 (E) 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 (2). HSiX _a R ¹ _3-a (2) (In the formula, R ¹ , 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 can be used. A method of reacting with a terminal hydroxyl group of an oxyalkylene compound to bond with an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like, or when an alkylene oxide is polymerized, an olefin group-containing epoxy compound such as allyl glycidyl ether is added. And a method of introducing an olefin group into the side chain by copolymerization.

(B) A method of reacting a terminal of a polyoxyalkylene compound having a functional group with a compound represented by the following general formula (3). R ¹ _3-a SiX _a -R ² NCO (3) (wherein R ¹ , X and a are the same as described above, R ² is a carbon number of 1 to 1)
7 divalent hydrocarbon groups)

(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 (4). A method of reacting a W group of a silicon compound. R ¹ _3-a -SiX _a -R ² W (4) (wherein R ¹ , R ² , X and a are the same as above. W is a hydroxyl group,
An active hydrogen-containing group selected from a carboxyl group, a mercapto group and an amino group (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 (4) 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.

In the present invention, the air-curable substance (B) and / or the photo-curable substance (C) are used together with the organic polymer (A). The use of the air-curable substance (B) is effective in improving the initial tack, and the use of the photo-curable substance (C) is effective in improving the stain resistance. Air curable substance (B)
And the photocurable substance (C) are preferably used in combination.

Air-curable substance (B) used in the present invention
As the above, an air-oxidation curable substance having an unsaturated group in the molecule that causes polymerization by oxygen in the air is generally used. Specifically, tung oil, linseed oil, eno oil, soybean oil, sunflower oil, hemp oil, and other drying oils; various alkyd resins, reaction products of drying oil and functional polyoxyalkylenes, reaction products of isocyanate compounds (Urethane oil), acrylic polymer modified with drying oil, epoxy resin,
Silicon resin etc. are mentioned. Further, 1,2-polybutadiene, 1,4-polybutadiene, C _{5 to} C ₈ diene-based polymers and copolymers, and various modified products (maleated modified products, boil oil modified products) of the polymers and copolymers. Etc.) and the like. Among these, a drying oil, a liquid substance (liquid diene polymer) among diene polymers, and modified products thereof are particularly preferable.

Specific examples of the liquid diene polymer include butadiene, chloroprene, isoprene and 1,3-
A liquid polymer obtained by polymerizing or copolymerizing a diene compound such as pentadiene or a monomer such as acrylonitrile or styrene having copolymerizability with these diene compounds is copolymerized so that the diene compound is a main component. Examples thereof include polymers such as NBR and SBR obtained by polymerization, and various modified products thereof (maleated modified product, boil oil modified product, etc.).

The air-curable substance (B) may be used alone or in combination of two or more kinds. Further, the effect may be enhanced by using together with the air-curable substance (B) a catalyst that accelerates the oxidative curing reaction and a metal dryer. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate and zirconium octylate, and amine compounds.

When the air-curable substance (B) is used, the amount used is 0.0 with respect to 100 parts by weight of the organic polymer (A).
It is 1 to 20 parts by weight. If the amount used is less than 0.01 part by weight, the effect of improving the initial tack, which is the purpose of using the air-curable substance (B), is insufficient, and if it exceeds 20 parts by weight, the elongation of the cured product is impaired. The preferred amount used is 1 to 1.
0 parts by weight.

The photocurable substance (C) used in the present invention is a substance which undergoes a chemical change in the molecular structure in a fairly short time by the action of light to cause a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as compounds of this type, and any commercially available compounds can be used. Typical examples are unsaturated acrylic compounds, polyvinyl cinnamates, and azide resins, but unsaturated acrylic compounds are particularly preferable.

The unsaturated acrylic compound is a monomer, an oligomer, or a mixture thereof having one or several acrylic or methacrylic unsaturated groups, and is propylene (or butylene, ethylene) glycol di (meth) acrylate. Or neopentyl glycol di (meth) dimethacrylate monomer or molecular weight 10
000 or less oligoesters are mentioned.

When the photocurable compound (C) is used, the amount used is 0.0 with respect to 100 parts by weight of the organic polymer (A).
It is 1 to 20 parts by weight. When the amount used is less than 0.01 part by weight, the stain resistance, which is the purpose of using the photocurable substance (C), is insufficiently improved, and when it exceeds 20 parts by weight, the elongation of the cured product is impaired. The preferred amount used is 1 to 10 parts by weight.

If desired, the composition of the present invention further comprises
A curing catalyst, a plasticizer, a filler, an adhesiveness-imparting agent, and other additives may be added and used.

As the curing catalyst, compounds known as catalysts for the hydrolysis and condensation reaction 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; dibutylamine-2.
Amine salts such as ethylhexoate; and other acidic and basic catalysts may be used. The curing catalyst is preferably used in an amount of 0.001 to 10 parts by weight, particularly 0.01 to 5 parts by weight, based on 100 parts by weight of the organic polymer (A). preferable.

As the plasticizer, known plasticizers can be used, and specifically, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; dioctyl adipate, isodecyl succinate, dibutyl sebacate, olein. Butyl ester and other aliphatic carboxylic acid esters; pentaerythritol ester and other glycol esters; trioctyl phosphate, tricresyl phosphate and other phosphate esters; epoxidized soybean oil, epoxy benzyl stearate and other epoxy plasticizers; chlorination Paraffin and the like can be used alone or as a mixture of two or more kinds.

As the filler, known fillers can be used, and specifically, fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, Fillers such as diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon, and fibrous fillers such as asbestos, glass fiber and filament. Can be used.

Examples of the adhesiveness-imparting agent include silane coupling agents such as aminosilane and epoxysilane, phenol resin and epoxy resin.

The composition of the present invention may further contain various known additives. As the additive, pigments, various antiaging agents, ultraviolet absorbers and the like can be used.

The room-temperature-curable composition of the present invention cures at room temperature in the presence of moisture and can be used especially for elastic sealants, adhesives, and coating materials.

[0037]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. First, Synthesis Examples 1 to 3 show synthesis examples of the organic polymer (A), and Comparative Synthesis Example 1 shows synthesis examples of polymers used in Comparative Examples.

[Synthesis 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. A polyoxyalkylene diol having an average molecular weight of 17,000 was obtained, the terminal hydroxyl group was converted to an allyl ether group, and methyldimethoxysilane was subjected to an addition reaction using chloroplatinic acid as a catalyst to give an average of 1.6 hydrolyzable silicon groups per molecule. An organic polymer having

[Synthesis 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 JP-A-3-72527. A polyoxyalkylene diol having an average molecular weight of 20,000 was obtained, the terminal hydroxyl group was converted to an allyl ether group, and methyldimethoxysilane was subjected to an addition reaction using chloroplatinic acid as a catalyst to give an average of 1.7 hydrolyzable silicon groups per molecule. An organic polymer having

[Synthesis Example 3] 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. Polyoxyalkylene diol with an average molecular weight of 10,000 was obtained, the terminal hydroxyl groups were converted into allyl ether groups, and methyldimethoxysilane was subjected to an addition reaction using chloroplatinic acid as a catalyst to give an average of 1.2 hydrolyzable silicon groups per molecule. An organic polymer having

[Comparative Synthesis Example 1] Japanese Patent Publication No. 61-49332
Based on the method described in the publication, a polyoxypropylene diol having a number average molecular weight of 3000 was reacted with bromochloromethane and allyl chloride to form a terminal allyl ether group.
The polypropylene glycol-equivalent number molecular weight was 9,700. Methyldimethoxysilane was subjected to an addition reaction with chloroplatinic acid as a catalyst to obtain an organic polymer having an average of 1.2 hydrolyzable silicon groups per molecule.

[Examples 1 to 6] 120 parts by weight of colloidal calcium carbonate (white gloss CCR manufactured by Shiroishi Industry Co., Ltd.) and heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) were added to the polymer compositions shown in Table 1. Whiten SB) 20 parts by weight, DOP
55 parts by weight, hydrogenated castor oil (Disparlon # 305 manufactured by Kusumoto Kasei Co., Ltd.) 3 parts by weight, titanium oxide (Ishihara Sangyo Co., Ltd.)
Taipaque R-820) 5 parts by weight, tin octylate 1 part by weight, laurylamine 0.3 parts by weight, styrenated phenol 0.5 parts by weight, Tinuvin 326 (manufactured by Ciba Geigy Co., Ltd.) 0.5 parts by weight. And the mixture was kneaded with three rolls.
However, in the table, M-8560 and M-400 are polyfunctional acrylates manufactured by Toagosei Kagaku Kogyo.

The pot life of this composition at 20 ° C. and 65% humidity was measured based on the test method of JIS A5758. Moreover, this composition is 5 cm in length, 30 cm in width, and 1 in depth.
The sample was placed in a cm container and exposed outdoors, and the surface tack after 1 hour, 6 hours, 1 day, 3 days, and 28 days was evaluated by touch with a finger. At the same time, in order to evaluate the curability, a sample piece having a length of 5 cm, a width of 3 cm, and a depth of 1 cm was cut out, and the change in hardness with time was measured using a DD2 hardness meter manufactured by Kobunshi Keiki Co., Ltd. After 6 months, the degree of stain on the surface of the test body was observed. The results are shown in Table 1.

The tack was evaluated as follows: ○: almost no tack, Δ: slightly tack, ×: tack. The evaluation of the degree of contamination was A: no contamination, B: slightly contaminated, C: severely contaminated.

[Comparative Examples 1 to 6] Comparative Examples 1 to 3 were the same as Examples 1 to 6 except that the polymer obtained in the synthesis example was used and neither the air-curable composition nor the photo-curable composition was used. The test was conducted. In Comparative Examples 4 to 6, the same test as in Examples 1 to 6 was performed using the hydrolyzable silyl group-containing polyoxypropylene synthesized without using the composite metal cyanide catalyst obtained in the Comparative Synthesis Example. The above results are summarized in Table 2.

Comparative Example 1 compared to the compositions of Examples 1-6
It can be seen that the compositions of Nos. 3 to 3 have a large tack and a large amount of dirt, although they have the same pot life and the same curability.

On the other hand, the compositions of Comparative Examples 4 to 6 are the same as those of Examples 1 to 1.
Despite having a pot life equivalent to the composition of 6,
It takes 3 days or more to reach the final hardness, indicating that the curability is poor. Therefore, the degree of tack is particularly large at the initial stage, and therefore the degree of dirt is also large.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

The organic polymer having a hydrolyzable silicon group produced using the double metal cyanide complex of the present invention,
The combination of the air-curable substance and the photo-curable substance has a low tackiness on the surface of the cured product, as compared with the conventionally known ones.
It has the effects of being excellent in flexibility, deep-part curability, and adhesion to a substrate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08G 65/32 NQH (C08L 71/02 47:00) (C08L 71/02 91:00)

Claims (5)

[Claims] 1. A polyoxyalkylene polymer (E) 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 (D) as a catalyst, and has the following general formula ( 100 parts by weight of an organic polymer (A) having a silicon-containing group represented by 1) with an average of 0.3 or more molecules per molecule, and 0.01 parts by weight of the air-curable compound (B) per 100 parts by weight thereof. Room temperature curable composition containing 20 to 20 parts by weight and / or 0.01 to 20 parts by weight of a photocurable compound (C). —SiX _a R ¹ _3-a (1) (wherein R ¹ is a substituted or unsubstituted 1 to 20 carbon atom)
Valent hydrocarbon radical. X is a hydrolyzable group. a is 1, 2 or 3. ) 2. The room temperature curable composition according to claim 1, wherein the complex metal cyanide complex (D) is a complex containing zinc hexacyanocobaltate as a main component. 3. The alkylene oxide is ethylene oxide,
The room temperature curable composition according to claim 1, which is at least one selected from propylene oxide and butylene oxide. 4. The room temperature curable composition according to claim 1, wherein the air curable compound (B) is at least one selected from the group consisting of a diene polymer, a drying oil, and a modified product thereof. object. 5. The room temperature curable composition according to claim 1, wherein the photocurable compound (C) is at least one selected from unsaturated acrylic compounds.