JPH0426357B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a moisture-curable sealant composition, and more particularly to a sealant composition having particularly bottom modulus and excellent adhesion. Conventional technology and problems to be solved Conventionally, moisture-curing sealants, so-called modified sealants, have been used to make architectural joints watertight and airtight, and are made of polyoxyalkylene ether main chain polymers with hydrolyzable silicon groups at the molecular ends. Known from silicone sealants. However, sealants for architectural joints are functionally required to have high elongation, low modulus, and excellent durability in order to follow changes in expansion and contraction. There is a need for a material with excellent adhesive properties that can be effectively bonded. Therefore, the inventors of the present invention conducted extensive studies in view of such requests, and found that if a reaction product of a specific amino compound and a carbonyl compound is blended into the above-mentioned modified silicone sealant, it can be used as a desired sealing material for architectural joints. The inventors have discovered that a useful composition can be obtained, and have completed the present invention. Structure and Effects of the Invention That is, the present invention has a polyoxyalkylene ether main chain polymer having a hydrolyzable silicon group at the end of the molecule as a main component, and a polyoxyalkylene ether main chain polymer having primary and/or secondary amino groups therein. A composition comprising a reaction product of an amino compound and a carbonyl compound, wherein the amino compound is 1,8-p-
Menthanediamine; aminoalkyltrialkoxysilane; reaction product of an excess of aminoalkyltrialkoxysilane with glycidoxyalkyltrialkoxysilane; and a group of reaction products of aminoalkyltrialkoxysilane and bisphenol type epoxy resin. and the carbonyl compound is isobutyraldehyde; and the formula: R ¹ -CO-CH ₂ -CO-R ² [wherein R ¹ and R ² are the same or different and each represent a lower alkyl group or a lower alkoxy group]. is selected from the group of β-dicarbonyl compounds represented by The present invention provides a moisture-curable sealant composition. The polyoxyalkylene ether main chain polymer (hereinafter abbreviated as silicon-containing polyether polymer) having a hydrolyzable silicon group at the molecular end in the present invention is disclosed in JP-A-50-156599 and JP-A-52-73998. In detail in the official bulletin, "disclosed," is replaced with "disclosed,"
Its chemical structure has polyoxyalkylene in the main chain and reactive alkoxysilyl groups at both ends.For example, a commercially available product named ``MS Polymer'' is available from Kanekabuchi Chemical Co., Ltd. I can do it. The amino compound having a primary and/or secondary amino group used in the present invention includes 1,8-
p-menthanediamine; N-(β-aminoethyl)
Aminomethyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,
Aminoalkyltrialkoxysilane such as N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; silane, etc.] and a reaction product between the aminoalkyltrialkoxysilane and a bisphenol type epoxy resin. Particularly desirable are the reaction products of aminoalkyltrialkoxysilanes and glycidoxyalkyltrialkoxysilanes, or the reaction products of aminoalkyltrialkoxysilanes and bisphenol-type epoxy resins. The carbonyl compound used in the present invention includes isobutyraldehyde; and the formula: R ¹ -CO-CH ₂ -CO-R ² [wherein R ¹ and R ² are the same or different and each represent a lower alkyl group or a lower alkoxy group] β-dicarbonyl compounds represented by (for example, acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate,
methylethyl malonate, etc.). The reaction between the amino compound and the carbonyl compound is carried out under the same conditions as the usual dehydration condensation reaction between an amine and an aldehyde or ketone, for example, in the presence of a water-absorbing agent or while distilling water off under heating under reflux. More specifically, a carbonyl compound (in the case of a β-dicarbonyl compound, one of the two keto groups is reacted) in a stoichiometrically equivalent or excess amount of the amino compound is added to toluene,
A water absorbing agent such as a molecular sieve or anhydrous magnesium sulfate is added to a suitable organic solvent such as xylene or benzene, and the mixture is reacted at room temperature or under heating with stirring. The reaction product of the amino compound and carbonyl compound obtained as described above (hereinafter referred to as amino group-blocked amine compound) or the mixture is usually 0.05 to 5% in the composition containing the above polymer as a component.
(% by weight, the same applies hereinafter), preferably 0.1 to 3.0%. The reaction product is hydrolyzed by moisture and water vapor in the air and returns to the original amino compound and carbonyl compound, so it is possible to accelerate the silanol condensation reaction by hydrolysis of the polymer and to reduce the It becomes modulus and leads to improved durability. Also,
The above-mentioned aminoalkyltrialkoxysilane, an amino compound which is a reaction product of aminoalkyltrialkoxysilane and a bisphenol type epoxy resin or glycidoxyalkyltrialkoxysilane, or a special carbonyl compound such as a β-dicarbonyl compound. By using it, the adhesion to glass, plastic plates, metals, painted steel plates, etc. can be improved. If the amount of the amino group blocked amine compound is less than 0.05%, the desired physical adhesiveness cannot be obtained, and if it is more than 5%, the desired effect cannot be obtained and the physical properties tend to deteriorate. Further, in curing the composition of the present invention, a silanol condensation catalyst may or may not be used. If condensation catalysts are used, alkyl titanates; organosilicon titanates; metal salts of carboxylic acids such as tin octylate, dibutyltin laurate and dibutyltin maleate, dibutyltin phthalate; dibutylamine-2-ethyl Known silanol condensation catalysts such as amino acids such as xoates; and other acidic and basic catalysts are usefully used. The amount of these condensation catalysts is preferably 0 to 10% based on the silicon-containing polyether polymer. When an alkoxy group is used as the hydrolyzable group, it is preferable to use a condensation catalyst since the curing rate is slow if this polymer alone is used. In this case, a tin carboxylate is particularly preferred as the condensation catalyst. The silicon-containing polyether polymer in the present invention can be modified by incorporating various fillers. Fillers include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay,
Fillers such as talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used. . If you want to obtain a hardened composition with high strength using these fillers, mainly use fume silica, precipitated silica, anhydrous silicic acid, hydrated silicic acid,
Fillers selected from carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and activated zinc white are added to silicon-containing polyether polymers.
Favorable results can be obtained if the amount is used in the range of 1 to 100 parts per 100 parts (by weight, hereinafter the same). In addition, when it is desired to obtain a cured composition with low strength and high elongation, fillers mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon are used. Favorable results can be obtained if the amount is used in the range of 5 to 200 parts per 100 parts of the silicon-containing polyether polymer. Of course, these fillers may be used alone, or
Two or more types may be mixed. In the present invention, it is more effective to use a plasticizer in combination with a filler because the elongation of the cured product can be increased and a large amount of filler can be mixed.
As the plasticizer, commonly used
For example, phthalate esters such as dioctyl phthalate, dibutyl phthalate, butylbenzyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate; diethylene glycol dibenzoate, pentaerythritol ester, etc. Glycol esters such as butyl oleate, methyl acetyl ricinoleate, etc.; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc.; Epoxidized soybean oil, epoxy stearic acid Epoxy plasticizers such as benzyl; plasticizers such as chlorinated paraffin alone or in combination
It can optionally be used in the form of a mixture of more than one species. Preferable results can be obtained when the amount of plasticizer is used in the range of 0 to 100 parts per 100 parts of the silicon-containing polyether polymer. In the blended composition of the present invention, fillers,
It is mainly used as a plasticizer and a condensation catalyst, but it also includes the optional use of additives such as adhesion promoters such as phenolic resins and epoxy resins, pigments, anti-aging agents, and ultraviolet absorbers. . The composition of the present invention includes a one-part composition and a two-part composition.
Any liquid composition is possible. When used as a two-component composition, for example, it is divided into components consisting of a silicon-containing polyether polymer, an amino-blocked amine compound, a filler consisting of a filler and a plasticizer, a plasticizer, and a condensation catalyst, and the composition is prepared immediately before use. Good results can be obtained by using a mixture of both components. When used as a one-component composition, a silicon-containing polyether polymer, an amino group blocked amine compound,
The filler, plasticizer, and condensation catalyst are thoroughly dehydrated and dried and then mixed in the absence of moisture, and can be used as a one-component composition with good storage stability in cartridges and the like. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 Production of amino group blocked amine compound In a reaction tank purged with dry nitrogen gas, 150 parts of dehydrated toluene, 22.2 parts of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and Molecular as an absorbent were added. Add 15 parts of sieves and gradually add 20 parts of acetylacetone while stirring at room temperature.
After the addition is complete, the reaction is allowed to continue for an additional 4 hours at room temperature with stirring. After the reaction is completed, the water-absorbing agent is removed by suction to obtain a toluene solution of the amino-blocked amine compound. This solution has an active ingredient content of 22% and is stored dry. Next, the following ingredients are mixed and stirred to prepare a moisture-curable sealant composition. Components Silicon-containing polyether polymer (MSP-20A, manufactured by Kanekabuchi Chemical Co., Ltd., containing polyoxypropylene in the main chain,
Specific gravity 1.01, viscosity (23℃) 130±50 poise, average molecular weight approximately 8000...45 parts Dioctyl phthalate...10 parts Above amino group blocked amine compound solution
...3.0 parts calcium carbonate ...45 parts titanium oxide ...3.5 parts dibutyltin dilaurate ...0.5 anhydrous silica powder ...1.0 part Example 2 Production of amino group blocked amine compound 22.1 parts of γ-aminopropyltriethoxysilane and γ -Glycidopropyltrimethoxysilane 7.03
(molar ratio, 1:0.3) was added to 150 parts of dehydrated toluene, and heated and reacted at 50° C. for several hours with stirring to obtain a mixed solution containing aminoalkoxysilane having unreacted amino groups and imino groups. Add 15 parts of molecular sieves to a toluene solution of 179.13 parts of the above mixture, dropwise add 26 parts of ethyl acetoacetate to this at room temperature while stirring, and stir this mixture at room temperature for 6 hours to react to form an amino-blocked amine compound. Obtain a solution. Next, a moisture-curable sealant composition is prepared in the same manner as in Example 1 except for using the amino-blocked amine compound solution. Example 3 Production of amino group blocked amine compound 170 g of 1,8-p-menthadiamine and 260 g of isobutyraldehyde were subjected to a dehydration condensation reaction and removal of the shaking medium in the same manner as in Example 1 to obtain an amino group blocked amine compound solution. . Next, a moisture-curable sealant composition is prepared in the same manner as in Example 1 except for using the amino-blocked amine compound solution. Example 4 Production of amino group blocked amine compound 17.0 parts of 1,8-p-menthadiamine and 26.4 parts of dimethyl malonate were subjected to dehydration condensation reaction and solvent removal in the same manner as in Example 1 to prepare an amino group blocked amine compound solution. get. Next, a moisture-curable sealing material composition is prepared in the same manner as in Example 1 except for using the amino-blocked amine compound solution. Example 5 Bisphenol type liquid epoxy resin (Epicote 828, manufactured by Yuka Ciel Epoxy Co., Ltd., viscosity (25°C)
120-150 poise, epoxy equivalent 184-194, specific gravity
1.17, molecular weight approximately 380) and 22.2 parts of γ-(2-aminoethyl)aminopropyltrimethoxysilane at 50°C for 24 hours, and 45.0 parts of a reaction product.
20.0 parts of acetylacetone is subjected to the reaction in the same manner as in the production of the amino-blocked amino compound in Example 1. Next, a moisture-curable sealant composition is prepared in the same manner as in Example 1 using the obtained reaction product. Comparative Example In formulating the moisture-curable sealant composition of Example 1, a sealant composition is prepared using an epoxy resin (Epicote 828) instead of the amino group blocked amine compound solution. Test Example The moisture-curing sealants prepared in Examples 1 to 5 and Comparative Examples were formed into a sheet with a thickness of approximately 2.0 mm on a peeling paper, cured at 20°C for 2 weeks, and then molded into dumbbells according to JIS K6301. Subjected to physical property tests, initial physical properties, water resistance (immersed in water for 14 days), heat resistance (80
Physical properties after heat aging (℃/14 days) [tensile strength (TS),
100% modulus (100% M), 300% modulus,
Measure modulus (300%M) and elongation (Elong). In addition, an H-shaped test piece was prepared using an aluminum plate and a glass plate according to JISA5758, and
After curing and curing for a week, a tensile adhesion test was conducted. The results are shown in Table-1. 【table】

Claims (1)

[Scope of Claims] 1. An amino compound and a carbonyl compound having a main component of a polyoxyalkylene ether main chain polymer having a hydrolyzable silicon group at the end of the molecule, and having a primary and/or secondary amino group therein. 1,8-p-menthanediamine;
selected from the group of aminoalkyltrialkoxysilanes; reaction products of an excess of aminoalkyltrialkoxysilanes and glycidoxyalkyltrialkoxysilanes; and reaction products of aminoalkyltrialkoxysilanes and bisphenol-type epoxy resins. and the carbonyl compound is isobutyraldehyde; and the formula: R ¹ -CO-CH ₂ -CO-R ² [wherein R ¹ and R ² are the same or different and each represent a lower alkyl group or a lower alkoxy group] A moisture component selected from the group of β-dicarbonyl compounds shown in Curable sealant composition.