JPH02142850A - Room temperature-curing composition - Google Patents

Abstract

PURPOSE:To obtain a room temperature-curing composition useful as a sealing material which can give a cured product without leaving surface stickiness by mixing a hydrolyzable silicon group-terminated polyalkylene ether with a polyoxyalkylene monoether, a filler and a curing catalyst. CONSTITUTION:A room temperature-curing composition is obtained by mixing 100 pts.wt. polyalkylene ether (desirably polypropylene ether) of an MW of about 1000-30000, desirably 5000-15000, terminated with a hydrolyzable silicon functional group with 10-100 pts.wt., desirably 30-70 pts.wt. polyoxyalkylene monoether (desirably polyoxypropylene mono-(1-7C)-alkyl ether or polyoxypropylene monophenyl ether) 5-300 pts.wt., desirably 50-200 pts.wt. filler and 0.1-10 pts.wt., desirably 0.5-5 pts.wt. silanol condensation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to room temperature curable compositions, and more particularly to room temperature curable compositions useful as sealants that cure at room temperature into a rubber-like substance upon contact with moisture in the air. Regarding.

BACKGROUND ART AND PROBLEMS It has long been known that polyethers having hydrolyzable silicone functional groups are useful as sealants, and demand has particularly increased rapidly in recent years as sealants for joints in buildings. This type of sealant generally contains phthalate esters such as dioctyl phthalate, fatty acid esters such as dioctyl adipate, or chlorine in order to improve the workability of the sealant and adjust the rubber properties of the resulting cured product. Contains chemically paraffin etc. as a plasticizer,
It is used. However, sealing materials containing the above-mentioned plasticizers have the drawback that adhesiveness occurs on the surface of the cured product, and dust adheres to the surface, causing contamination. In addition, there are many cases where the surface of the sealant is overcoated with paint, and in such cases, if a plasticizer is used, the plasticizer will inevitably migrate to the paint, softening the paint and causing stickiness, which will cause the surface to become sticky. Problems such as dust adhesion and contamination have arisen.

An object of the present invention is to provide a room-temperature curable composition that is extremely useful as a sealant and does not cause adhesion on the surface of the cured product and does not cause contamination of the top coated paint.

Means for Solving the Problems The present inventors have conducted extensive research in order to achieve the above object. As a result, by using polyoxyalkylene monoether without using conventionally commonly used plasticizers, it is possible to have excellent workability and to impart excellent rubber properties to the resulting cured product. At the same time, it has been found that a room temperature curable composition can be obtained which is extremely useful as a sealing material and does not cause adhesion on the surface of the cured product and does not cause contamination of the top coated paint.

The present invention was completed based on this knowledge.

That is, the present invention comprises: (A) 100 parts by weight of a polyalkylene ether with a molecular weight of about 1,000 to about 30,000 and having a hydrolyzable silicone functional group at the end of the molecular chain; (B) polyoxyalkylene with a molecular weight of about 500 to about 5,000. The present invention relates to a room temperature curable composition comprising 10 to 100 parts by weight of monoether, (C) 5 to 300 parts by weight of filler, and (D) 0.1 to 10 parts by weight of curing catalyst.

As the component (A) used in the present invention, a wide variety of conventionally known components can be used. Preferred specific examples include, for example, the following formula [wherein R1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms selected from an alkyl group and a phenyl group, and X is a hydride group, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group] group, a group selected from alkenyloxy group, amide group, acid amide group, isopropenoxy group, oxime group, aminoxy group and mercapto group, a is 0.1 or 2,
R2 represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, R3 represents a divalent organic group having 1 to 20 carbon atoms, and b represents 0 or 1.

] Examples include polyalkylene ethers having a hydrolyzable silicone functional group shown at the molecular chain end. The hydrolyzable group bonded to the silicon atom is preferably an alkoxy group, and more preferably a methoxy group from the viewpoint of curability. (A
) The main chain of the polyalkylene ether component is essentially -R
It consists of chemically bonded repeating units represented by -C1 (R is a divalent alkyl group). These repeating units may be bonded not only in one type but also in a mixture of two or more types.

In the present invention, polyalkylene ethers having a main chain of polyether produced from propylene oxide as a raw material (ie, polypropylene ethyl) are preferred because they are liquid at room temperature even if they have a high molecular weight.

In the present invention, the molecular weight of the polyalkylene ether used as component (A) is about 1oo.

to about 30,000, preferably about 5
000 to about 15,000. Molecular weight is about 100
If it is less than 0, the resulting cured product will have poor flexibility, while if it exceeds about 30,000, the viscosity of the composition will become high and workability will decrease, resulting in inconvenience. In the present invention, such polyalkylene ethers may be used alone or in combination of two or more.

The polyalkylene ether which is the component (A) can be produced by various methods, but a preferred method is, for example, by the following formula [wherein R1, X and a are the same as above]. ] and the silicon hydride compound represented by the following formula % formula % (3) [wherein R2, R3 and b are the same as above. ] In the presence of a platinum catalyst, an addition reaction may be carried out with a polyether having a terminal olefin.

Component (B) used in the present invention is used as a sealing material, which is a feature of the present invention, to maintain the surface of a non-tacky cured product without reducing the required workability or the physical properties of the rubber of the obtained cured product. It is an essential component in order to obtain a composition that does not cause staining of the formed and top coated paint.

Component (B) is represented by the following formula % formula % (4) [wherein R4 is an alkyl group having 1 to 8 carbon atoms, 2 to 8 carbon atoms]
8 represents an alkenyl group, a phenyl group, a phenyl group or a benzyl group having an alkyl group having 1 to 9 carbon atoms as a substituent on the phenyl ring, R5 is an alkylene group having 2 to 4 carbon atoms, and n is the general formula (4 ) has a molecular weight of 500 to 50
Indicates an integer in the range of 00. ] It is a compound shown by. Not only one type of alkylene group but also two or more types of alkylene groups may be bonded. When two or more types of alkylene groups are bonded,
The state of the connection may be block-like or random.

In the present invention, the alkylene group is preferably a propylene group because it is liquid at room temperature even if it has a high molecular weight.

Specific examples of the compound of general formula (4) include polyoxypropylene monomethyl ether, polyoxypropylene monoethyl ether, polyoxypropylene mono-n-propyl ether, polyoxypropylene monoisopropyl ether, polyoxypropylene mono n-butyl ether, polyoxypropylene monoisobutyl ether, polyoxypropylene mono t-butyl ether, polyoxypropylene mono n-amyl ether, polyoxypropylene monoisoamyl ether, polyoxypropylene mono n-hexyl ether, polyoxypropylene mono 2- Examples include ethylhexyl ether, polyoxypropylene monoallyl ether, polyoxypropylene monophenyl ether, polyoxypropylene monocresyl ether, polyoxypropylene monooctylphenyl ether, polyoxypropylene monononylphenyl ether, polyoxypropylene monobenzyl ether, etc. . Among these, polyoxypropylene mono C1-7 alkyl ether, polyoxypropylene monophenyl ether and polyoxypropylene monocresyl ether are particularly preferred.

In the present invention, the molecular weight of the polyoxyalkylene monoether used as component (B) is about 500 to about 5000.
preferably from about 1000 to about 30
A range of 00 is preferable. If the molecular weight is less than about 500, adhesion tends to occur on the surface of the cured product, while if it exceeds about 5,000, the viscosity of the composition increases and workability is reduced. In the present invention, such polyoxyalkylene monoethers may be used alone or in combination of two or more.

The polyoxyalkylene monoethyl component (B) can be produced by various methods, but a common method is to carry out an addition reaction between a monohydric alcohol and an alkylene oxide using an alkali or an acid as a catalyst.

Examples of the monohydric alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, Examples include aliphatic alcohols such as 2-ethylhexyl alcohol and allyl alcohol, and aromatic alcohols such as phenol, cresol, octylphenol, nonylphenol, and benzyl alcohol.

Furthermore, examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.

In the present invention, 100 parts by weight of component (A) (hereinafter simply "parts")
Component (B) is usually blended in an amount of 10 to 100 parts, preferably 30 to 70 parts, per portion (denoted as ). If the amount of component (B) is too small, the resulting cured product will become too hard, impairing the flexibility required for a sealant, and will increase the viscosity of the composition, reducing workability, which is not preferred. On the other hand, if the amount of component (B) is too large, the resulting cured product will become too soft, which is not preferable.

Component (C) used in the present invention is used for purposes such as adjusting the flow characteristics of the composition of the present invention, reinforcing the cured product, and improving economic efficiency.

As component (C), a wide variety of conventionally known components can be used,
For example, reinforcing fillers such as silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined silica, clay, talc, titanium oxide, bentonite, organic bentonite. , ferric oxide, zinc oxide, activated zinc white, shirasu balloon, etc., asbestos, glass fiber, filament, etc. fibrous fillers, and these can be used singly or in combination of two or more. used.

The blending amount of component (C) is usually 5 to 300 parts, preferably 50 to 200 parts, per 100 parts of component (A). If the blending amount of component (C) is too small, it becomes difficult to obtain a non-flowable composition and the reinforcing effect becomes insufficient, which is not preferable. Furthermore, if the amount of component (C) is too large, the viscosity of the composition increases and workability decreases, which is not preferable.

As the component (D) used in the present invention, a known silanol condensation catalyst can be used. For example, metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, tin octylate, dibutyltin laurate, dibutyltin maleate, dibutyltin phthalate, amine salts such as dibutylamine-2-ethylhexoate, etc. Other known silanol condensation catalysts such as acidic catalysts and basic catalysts can be effectively used, and these catalysts may be used alone or in a mixture of two or more.

The blending amount of component (D) is usually 0.1 to 10 parts, preferably 0.5 to 5 parts, per 100 parts of component (A). If the amount of component (D) blended is too small, it will be difficult to obtain an appropriate curing speed, and conversely, if the amount of component (D) blended is too large, the curing will be too fast or the rubber of the cured product obtained. Both are unfavorable because the strength decreases.

In addition to the above-mentioned components, the composition of the present invention includes thixotropes such as hydrogenated castor oil, light stabilizers such as hindered amines and hindered phenols, antioxidants, ultraviolet absorbers, phenolic resins, and silane coupling agents. An adhesion imparting agent, an organic pigment such as phthalocyanine blue, etc. can be appropriately blended.

Effects of the Invention According to the present invention, there is provided a room temperature curable composition that does not cause adhesion on the surface of the cured product and is extremely useful as a sealing material that does not cause contamination of the top coated paint.

EXAMPLES Examples and comparative examples are given below to further clarify the present invention.

Examples 1 to 4 To 100 parts of polypropylene ether having a methoxysilyl group and a group H3(CHaO)2Si÷CH2+2 at the end of the molecular chain and having an average molecular distance of about 8000, propylene and butanol in the number of parts shown in Table 1 below were added. Add polyoxypropylene mono-n-butyl ether obtained by adding oxide, calcium carbonate filler, titanium oxide pigment, hydrogenated castor oil thixotropic agent, and hindered amine light stabilizer, and knead uniformly with three rolls. After mixing,
Tin octylate and laurylamine were added and mixed uniformly to prepare compositions (cured products) of Examples 1 to 4.

The fillers, thixotropic agents, and stabilizers in Table 1 are specifically as follows.

Hakuenka CC-R: Fatty acid-treated colloidal calcium carbonate, NS#1000 manufactured by Shiraishi Kogyo Co., Ltd.: Heavy calcium carbonate, JR600A Niltyl titanium oxide manufactured by Nitto Funka Kogyo Co., Ltd., Disparon #305 manufactured by Teikoku Kako Co., Ltd.: Hydrogenated castor Oil-based thixotropic agent, Sanol LS-770 manufactured by Kusumoto Kasei Co., Ltd.: hindered amine-based light stabilizer,
The following tests were conducted using the compositions of Examples 1 to 4 manufactured by Sankyo Co., Ltd., and the results are also shown in Table 1.

(1) Measurement of viscosity at 20°C immediately after preparation using a Nibruckfield rotational viscometer.

(2) Extrudability test immediately after preparation: JIS A 57
According to 58.

(3) Tensile adhesion test: Based on JIS A 5758.

(4) Measurement of adhesive strength on the surface of cured product using a tack tester:
The sample was cured at 20°C for 7 days, and the thickness was 10n+rA, 5
After creating a 0mm square test piece, PICMA-TACK・
It is attached to TESTER (manufactured by Toyo Seiki ■), and the adhesion force on the surface of the test piece is measured at a subminiature time of 5 seconds and an up speed of 50 n+m/min.

(5) Paint contamination test: Place the sample on a slate board for about 5 FBI
After curing and curing at 20° C. for 3 days, the coating shown in Table 1 was applied to a thickness of about 0.5 mm (wet) and exposed on an outdoor exposure table with an inclination angle of 45°. Exposure for 3 months and observe the status of contamination.

Comparative Examples 1-2 Phthalic acid plasticizer in the parts shown in Table 1 for 100 parts of polypropylene ether having a hydrolyzable silicone functional group, the same as that used in Examples 1-4 (Comparative Example 1 only) , a calcium carbonate filler, a titanium oxide pigment, a hydrogenated castor oil thixotropic agent, and a hindered amine light stabilizer were added and mixed uniformly with a triple roll, then tin octylate and laurylamine were added and mixed uniformly. Comparative Example 1
Compositions (cured products) of Examples 1 to 2 were prepared and tested in the same manner as for the compositions of Examples 1 to 4. The results are also shown in Table 1.

Examples 5 to 8 Polypropylene ether 1 with an average molecular weight of 10.
00 parts, polyoxypropylene monophenyl ether obtained by adding propylene oxide to phenol, a calcium carbonate filler, a titanium oxide pigment, an amide wax thixotropic agent, and a hindered amine type in the parts shown in Table 2. A light stabilizer is added and the mixture is uniformly kneaded with a triple roll, followed by dehydration at 120'C and 5 torr under reduced pressure for 2 hours. After dehydration, the mixture was cooled to 60°C, dibutyltin laurate (Stan BL) and laurylamine in the numbers shown in Table 2 were added as curing catalysts, and filled into a polyethylene cartridge with good airtightness. -8 compositions (cured products) were prepared.

The compositions of Examples 5 to 8 were tested in the same manner as the compositions of Examples 1 to 4, and the results are shown in Table 2.

The fillers, thixotropic agents, and stabilizers in Table 2 are specifically as follows.

NS#2300: Heavy calcium carbonate, Nitto Funka Kogyo Co., Ltd. Disparon #6500 Niamite wax-based thixotropic agent, Kusumoto Kasei Co., Ltd. Tinuvin 327: Hindered phenol-based ultraviolet absorber, Nippon Ciba Geigy Co., Ltd. Comparative example 3-4 For 100 parts of polypropylene ether having a hydrolyzable silicone functional group, which is the same as that used in Examples 5-8, add the adipate ester plasticizer (
Comparative Example 3 only), calcium carbonate filler, titanium oxide pigment, amide wax thixotropic agent, hindered amine light stabilizer, and hindered phenol ultraviolet absorber were added and mixed uniformly with three rolls. , 120℃, 5
Dehydrate for 2 hours under heat and reduced pressure of Tor. After dehydration, the formulation was cooled to 60°C, dibutyltin dilaurate and laurylamine in the numbers shown in Table 2 were added as curing catalysts, and the compositions of Comparative Examples 3 and 4 were filled into a polyethylene cartridge with good airtightness. A cured product) was prepared.

The same tests as those for the compositions of Examples 1 to 4 were conducted using the compositions of Comparative Examples 3 and 4, and the results are also shown in Table 2.

Claims (1)

[Scope of Claims] [1] (A) 100 parts by weight of a polyalkylene ether with a molecular weight of about 1,000 to about 30,000 and having a hydrolyzable silicone functional group at the end of the molecular chain; (B) a polyalkylene ether with a molecular weight of about 500 to about 5,000; A room temperature curable composition comprising 10 to 100 parts by weight of a polyoxyalkylene monoether, (C) 5 to 300 parts by weight of a filler, and (D) 0.1 to 10 parts by weight of a curing catalyst. [2] The composition according to claim [1], wherein the main chain of component (A) is polypropylene ether. [3] Component (B) is polyoxypropylene mono C_1_
-_7 The composition according to claim 1, which is at least one selected from the group consisting of alkyl ether, polyoxypropylene monophenyl ether, and polyoxypropylene monocresyl ether.