JPS6411071B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition containing as active ingredients a hydrolyzable silicon- and/or silanol-containing polyether that can cure at room temperature into a rubber-like substance on contact with moisture, and a sulfur-containing compound. The present inventors have already discovered that moisture-curable polyethers having silicon groups are useful as sealants, and have previously proposed methods and compositions for their production. Room-temperature-curing sealants whose main component is moisture-curable polyether with silicon groups are inexpensive and have excellent performance, but depending on the composition, their adhesion to metals is insufficient. . As a result of intensive studies to improve this point, the present inventors found that by adding a sulfur-containing compound, the objective could be achieved without impairing the excellent properties of moisture-curable polyether having silicon groups. They have discovered that it can be achieved, and have arrived at the present invention. That is, the present invention provides A containing at least one hydrolyzable silicon group and/or silanol group, and the main chain is essentially -R-O- (R is a divalent alkylene group).
100 parts by weight of a polyether having chemically bonded repeating units represented by the formula and having a molecular weight of 500 to 15,000, and B: inorganic sulfur or containing at least two or more sulfur atoms in the molecule. The present invention relates to a room temperature curable composition containing 0.01 to 20 parts by weight of an organic compound. In the present invention, a room-temperature-curable polyether having a silicon group is one whose main chain essentially has chemically bonded repeating units represented by -R-O- (R is a divalent alkylene group). and is made of polyether with a molecular weight of 500 to 15,000, and 1
It is a polymer having in its molecule at least one hydrolyzable group bonded to a silicon atom. Here, what is meant by essentially having -R-O- units means that the polyether may contain a small amount of other bonding units depending on the method for producing the polyether, as described below. Hydrolyzable groups bonded to silicon atoms typically include hydride groups, halogen groups, alkoxy groups, acyloxy groups, ketoximate groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. It will be done. Room-temperature-curable polyethers having silicon groups can be produced by various known methods, but are preferably produced by the formula (Here, a is an integer of 0 to 2, ^R1 is a monovalent hydrocarbon group, and X is a hydrolyzable group); and a silicon hydride compound of the formula ( ^R2 is hydrogen or a monovalent organic group having 1 to 20 carbon atoms,
R ³ is a divalent organic group having 1 to 20 carbon atoms, and b is an integer of 0 or 1.

Examples include polyethers having a silyl group represented by the formula: Specifically, this type of polyether is disclosed in Japanese Patent Application Laid-open No. 50-156599,
Unexamined Japanese Patent Publications 1986-6096, 13768-1980, 1982-13768
82123, by the method disclosed in JP-A-55-131022. In addition to this, Tokukai Sho
55-13767, JP-A-55-123620, JP-A-55-
125121, JP 55-131021, JP 55-137129,
It is also possible to use polyethers containing room temperature curable silicon groups obtained by the method disclosed in JP-A-55-135135. These polyethers may be used alone or in combination of two or more. The sulfur-containing compounds that can be used in the present invention include inorganic sulfur (monoclinic, orthorhombic, amorphous) and organic sulfur compounds containing at least 2 or more, preferably 4 or more, sulfur atoms in the molecule. , Specific examples of the latter include dibenzothiazyl disulfide, 2-(N,N-diethylthiocarbamoylthio)benzothiazole, 2-(4'-morpholinodithio)benzothiazole, tetramethylthiuram disulfide, and tetraethylthiuram. Examples include disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, zinc butylxanthate, and polysulfide. Compositions containing these sulfur-containing compounds, such as ebonite, can also be added. These sulfur-containing compounds may be used alone or in combination of two or more. The sulfur-containing compound is effective if added in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the silyl group-containing polyether, and preferably in an amount of 0.1 to 5 parts by weight. If the amount is less than 0.01 part by weight, the effect will be small, and if it exceeds 20 parts by weight, the physical properties may be adversely affected. Metals whose adhesion is improved by the present invention include aluminum, nickel, iron, zinc, bronze,
Examples include brass and stainless steel, but the effect on aluminum is particularly remarkable. 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 lausite and dibutyltin manate, 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% by weight based on the silicon-containing polyether. When an alkoxy group is used as the hydrolyzable group X, 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 of the present invention can be modified by incorporating various fillers. Fillers include fume silica, precipitated silica, silicic anhydride,
Reinforcing fillers such as hydrated silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated Fillers such as castor oil and whitebait 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, you can use mainly fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black,
Favorable results can be obtained if a filler selected from surface-treated finely divided calcium carbonate, calcined clay, clay and activated zinc white is used in an amount of 1 to 100 parts by weight per 100 parts by weight of silicon-terminated polyether.
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 it is used in an amount of 5 to 200 parts by weight per 100 parts by weight of the silicon-containing polyether. Of course, these fillers may be used alone or in a mixture of two or more. 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; and diethylene glycol dibenzoate, pentaerythritol ester, etc. Glycol esters; Aliphatic esters such as butyl oleate, methyl acetyl ricinoleate, etc.; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, etc.; Epoxidized soybean oil, benzyl epoxy stearate Epoxy plasticizers such as; plasticizers such as chlorinated paraffin alone or in combination
It can be used arbitrarily in the form of a mixture of more than one type. Preferable results are obtained when the amount of plasticizer is used in the range of 0 to 100 parts by weight per 100 parts by weight of the silicon-containing polyether. Fillers, plasticizers, condensation catalysts are mainly used in the compounded composition of the present invention, but additives such as adhesion promoters such as phenolic resins and epoxy resins, pigments, anti-aging agents, ultraviolet absorbers, etc. are also used. It also includes being used arbitrarily. 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, a component consisting of a silicon-containing polyether, an organic silane polymer, a filler, and a plasticizer and a component consisting of a filler, plasticizer, and condensation catalyst are separated, and both components are mixed immediately before use. Good results can be obtained by using a mixture of the ingredients. When used as a one-component composition, the silicon-containing polyether, organic silane polymer, filler, plasticizer, and condensation catalyst are sufficiently dehydrated and dried, then mixed in the absence of moisture, and stored in a cartridge or the like. It can also be used as a one-component composition with good storage stability. The compositions of the present invention are particularly useful as one-part and two-part elastic sealants and can be used as sealants for buildings, ships, automobiles, roads, etc. Furthermore,
It can be used alone or with the aid of a primer to adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., and therefore can be used in various types of sealing compositions and adhesive compositions. Furthermore, it is useful as a food packaging material, a casting rubber material, a molding material, and a paint. Examples will be specifically described below. Example 1 Average molecular weight 8000, as a terminal group

[Formula] Polypropylene oxide 100 with 80% of all end groups
20 parts by weight of epoxyhexahydrophthalate dioctyl, 20 parts by weight of dioctyl phthalate, 120 parts by weight of fatty acid-treated calcium carbonate, 6 parts by weight of hydrogenated castor oil, 8 parts by weight of titanium oxide, 0.5 parts by weight of carbon black, 2, 2'-methylene-bis-(4-methyl-6-tert-butylphenol)
1 part by weight, 2(2'-hydroxy-3',5'-di-tert
-butylphenyl)-5-chlorobenzotriazole (1 part by weight), 5 parts by weight of a photocurable oligomer (trade name: Aronix M8060, manufactured by Toagosei Chemical Industry Co., Ltd.) and 0.3 parts by weight of inorganic sulfur were added and mixed with three paint rolls. The main ingredient was prepared. Separately, 3 parts by weight of tin octylate, 0.75 parts by weight of laurylamine, 6.25 parts by weight of dioctyl phthalate, and 20 parts by weight of titanium oxide were added and mixed and dispersed using a homogenizer to prepare a curing agent. The base resin and curing agent obtained in this way were mixed in a ratio of 10:1.
An H-type test piece of an anodized aluminum plate was prepared according to JIS-A-5758, and the physical properties were measured after curing under the curing conditions shown in Table 1. The results are shown in Table 1 together with a comparative example conducted under the same conditions as Example 1 except that 0.3 parts by weight of sulfur was not added. In the table, interfacial failure indicates separation at the interface between the aluminum plate and the cured product at the time of breakage, and cohesive failure indicates breakage of the cured product itself. Also, RT refers to room temperature, and STD refers to the standard curing conditions specified by JIS (7 days at room temperature + 50℃).
day).

[Table] Example 2 The same conditions as in Example 1 were carried out except that 1 part by weight of dipentaethylenethiuram tetrasulfide was used instead of 0.3 part by weight of sulfur. The results are shown in Table-2.

【table】

Claims (1)

[Claims] 1. A at least one hydrolyzable silicon group and/or
or contains a silanol group, and the main chain is essentially -R
100 parts by weight of polyether having chemically bonded repeating units represented by -O- (R is a divalent alkylene group) and having a molecular weight of 500 to 15,000 and B inorganic sulfur or molecule 1. A room-temperature curable composition comprising 0.01 to 20 parts by weight of an organic compound containing at least two or more sulfur atoms. 2 A group consisting of a hydride group in which a hydrolyzable silicon group is bonded to a silicon atom, a halogen group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminoxy group, a mercapto group, and an alkenyloxy group. Tomo1
The room temperature curable composition according to claim 1, which is a seed. 3 The hydrolyzable silicon group has the formula [Formula] (where a is an integer of 0 to 2, R ¹ is a monovalent hydrocarbon group,
The room-temperature curable composition according to claim 1, wherein X represents a hydrolyzable group. 4. The room temperature curable composition according to claim 3, wherein X is a _CH3O- group.