JPS6023445A - Room temperature curing composition - Google Patents

Abstract

PURPOSE:To provide a composition curable without causing the undercure at the surface thin layer even in a particular environment having the influences of moisture and light, and giving a cured product having excellent restoration ratio after compression under heating, by compounding specific two kinds of tin compounds to a polyether containing reactive silicone functional group. CONSTITUTION:(A) 100pts.wt. of a polyether containing at least one reactive silicone functional group in the molecule is compounded with (B) 0.01-10pts.wt., preferably 0.1-2pts.wt. of a tin compound of formula (R<1>)3Sn-OOCR<2> (R<1> and R<2> are univalent hydrocarbon group) and (C) 0.01-10pts.wt., preferably 0.5- 5pts.wt. of a bivalent tin compound. The component A is an oxyalkylene polymer having a molecular weight of 500-30,000 and containing the group -R<3>-O- (R<3> is 1-4C bivalent alkylene) as the main chain. The component B is preferably trioctyltin carboxylate, and the component C is preferably tin stearate or tin octylate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to room temperature curable compositions. For more details,
The present invention relates to a room temperature curable composition that is a modified silicone sealant composition with improved thin layer curability.

Room-temperature curable compositions based on polyethers having at least one reactive silicone functional group in the molecule include, for example, two-component architectural sealants consisting of a base agent and a curing agent, and are used as modified silicone sealants. It is commercially available. The curing catalysts used in these two-component building sealants include tin compounds, especially tin compounds.
Although tin compounds of 30% are common, they have the disadvantage of being unstable to moisture, heat, light, and the like. Therefore, the thin layer portion of the tanning base may harden and cause curing failure. On the other hand, tin compounds of 4 (illi), such as diptyltin dilaurate and diptyltin maleate, can also be used as curing catalysts, and they are relatively stable against moisture, heat, light, etc. Although the thin layer portion on the surface of the modified silicone sealant composition used does not cause poor curing, it has the disadvantage that the recovery rate of the cured product after heat compression is reduced.

As a result of extensive research by the present inventors in order to eliminate the above-mentioned drawbacks, (a) 100 parts by weight of a polyether containing at least one reactive silicone functional group in the molecule, (b) General formula: % formula % (wherein R1 and R2 represent the same or different monovalent hydrocarbon groups) (A) 0,01~
10 parts by weight and (c) divalent tin compound (B) 0.01
- By using a room temperature curable composition containing 10 parts by weight, curing failure of the thin layer on the surface when using a modified silicone sealant composition is prevented even under special environmental conditions where moisture, heat, light, etc. are present. The present inventors have discovered that it is possible to achieve the remarkable effect that the cured product has a good recovery rate after heating and compression without causing any problems, and has completed the present invention.

The polyethers having at least one reactive silicone functional group in the molecule used in the present invention are Japanese Patent Publications Nos. 45-66619, 46-12154, 49-
No. 62675, JP-A-50-156599, JP-A No. 51-
No. 75561, No. 54-6096, No. 55-8212
No. 3, No. 55-125620, No. 55-125121
No. 55-131022, No. 55-155155, and No. 55-1!17129. The reactive silicon functional groups referred to here are those that condense or react with moisture or additives, such as hydrolyzable groups or silanol groups bonded to silicon atoms, and are typically Formula (1): () (wherein R4 is a substituted or unsubstituted monovalent group having 1 to 2 carbon atoms (,81i, lhb or triorganosiloxy group, X is a hydroxyl group or a hydrolyzable group of the same or different type) b is an integer of 0.1.2 or 6, C is an integer of 0.1 or 2, m is an integer of D to 18).

Such a polyether having a reactive silicone functional group has, for example, the general formula (2): (wherein R4, X, b,
Q, m are the same as above) and a hydrogenated silicon compound represented by the general formula (8): % formula % (3) (wherein R4 is the same as above, z bar R5-1-R5oR
5-1 (R5 represents a divalent hydrocarbon group having 1 to 2 carbon atoms of the same or different type)) and platinum black, chloroplatinic acid, platinum alcohol compound, platinum olefin. It can be produced by addition reaction using a platinum-based compound such as a platinum complex, a platinum aldehyde complex, or a platinum ketone complex as a catalyst.

In the general formula (2), R4 is a monovalent hydrocarbon group having 1 to 2 carbon atoms, such as an alkyl group such as methyl or ethyl; a cycloalkyl group such as cyclohexyl; an aryl group such as phenyl group; or an aralkyl group such as benzyl group. The group further includes a triorganosiloxy group represented by the general formula: (R6)3SiO- (wherein R represents the same or different monovalent carbon-hydrocarbon group having 1 to 20 carbon atoms) . In general formula (2), or a silanol group or a different or similar hydrolyzable group, a halogen group, a hydride group, an alkoxy group, an anroxy group, a ketoximate group, an amino group, an amide group,
Examples include aminooxy group, mercapto group, and alkenyloxy group. Examples of the hydrogenated silicon compound represented by the general formula (2) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, and methyldimethoxysilane; Silane, phenyldimethoxysilane, 1, 3.3.
5.5.7.Alkoxysilanes such as 7-hebutamethyl-1,1-dimethoxytetrasiloxane; acylonodisilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; bis(dimethylketoximate)methylsilane, Ketoximate silanes such as bis(cyclohexylketoximate)methylsilane and bis(diethylketoximate)trimethylsiloxysilane; hydrosilanes such as dimethylsilane, trimethylsiloxymethylsilane, and 1,1-dimethyl-2,2-dimethyldisiloxane; Silanes: Examples include, but are not limited to, alkenyloxysilanes such as methyltri(isopropenyloxy)silane.

In this method, a hydrogenated silicon compound of general formula (2) is reacted with a polyether having an olefin group of general formula (3), and then some or all of the X groups are further replaced with other hydrolyzable groups. Alternatively, it can be converted to a hydroxyl group. For example, if the X group is a halogen group or a hydride group,
It is preferable to use it after converting it into an oxy group, alkenyloxy group, hydroxyl group, etc. In general formula (8), R is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom. 2 is a divalent organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group or an organic group containing an ether bond, an ester bond, a urethane bond, or a carbonate bond, and a methylene group is particularly preferable.

A specific method for producing polyether having an olefin group represented by general formula (3) is the method disclosed in JP-A-54-6097, or the method in which epoxy compounds such as ethylene oxide and propylene oxide are polymerized. Another example is a method in which an olefin group-containing epoxy compound such as allyl grindyl ether is added and copolymerized to introduce an olefin group into the side chain.

The main chain of the polyether used in the present invention essentially has chemically bonded repeating units of the general formula: % where R7 represents a divalent organic group. Yes It is preferable when most of R7 is a hydrocarbon group having 1 to 4 carbon atoms, and the general formula -R-0- is the general formula: %Formula% (wherein, R3 is a divalent group having 1 to 4 carbon atoms) It is more preferable to have a repeating unit represented by (representing an alkylene group). It may also be a polyether consisting of specific units of R7 or R3.

The molecular weight of the polyether is 500 to 50,000.
can be effectively used, but preferably 6000~
15,000 is good. Such polyethers are disclosed in JP-A-53-129247 and JP-A-54-60.
It can be manufactured by the method disclosed in each publication of No. 97.

General formula used in the present invention: %Formula% (In the formula, R1 and R2 represent the same or different types of monovalent hydrocarbon groups, usually have 1 to 60 carbon atoms, and may have a substituent. ) is, for example, triphenyltin acetate, tripheny/I/tin laurate, triphenyltin maleate, tributyltin acetate, tributyltin laurate, tributyltin naphtate, triphenyltin acetate, trioctyltin laurate. etc. Among the above compounds, trioctyltin carboxylates such as trioctyltin acetate and trioctyltin laurate are particularly preferred.

The amount of the tin compound (A) is 0.01 to 100 parts (parts by weight, hereinafter the same) of the reactive silicone functional group-containing polyether.
It is used in an amount of 10 parts, preferably in a range of 0.1 to 5 parts, more preferably in a range of 0.1 to 2s. If the amount used is less than 0.01 part, the effect of using the tin compound (A), that is, the effect of not causing curing failure even under special environmental conditions such as the presence of moisture, heat, and light, will not be achieved sufficiently. If the amount exceeds 10 parts, other physical properties such as curability and weather resistance may deteriorate.

Examples of the divalent tin compound (B) used in the present invention include silver stearate, tin octylate, and 0.01 to 1
0 parts, preferably 0.1 to 8 parts are used, but 0.5 to 8 parts are used.
More preferably, a range of 5 parts is used.

When the tetravalent tin compound (A)/divalent tin compound (B) (metal component weight ratio) is used in the range of 0.05 to 1.0, the thin layer curability of the composition of the present invention improves. The balance with the recovery rate of the cured product is particularly good.

The composition of the present invention may further contain various fillers, if necessary.
It may contain plasticizers, additives, etc. As the filler, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, kaolin, talc, titanium oxide, zinc oxide, carbon black, etc. are used. As the plasticizer, dioctyl phthalate, butylbenzyl phthalate, chlorinated paraffin, epoxidized soybean oil, etc. are used. The additives used include anti-sagging agents such as hydrogenated castor oil and organic bentonite, colorants, and anti-aging agents. When the composition of the present invention is used, the instability of the curing catalyst against moisture, heat, and light is reduced. This is greatly improved, and curing defects in the thin surface layer portion when using this composition are eliminated. Moreover, the recovery rate of the cured product after heating and compression becomes better.

Hereinafter, the composition of the present invention will be specifically explained with reference to Examples.

Production Example 1 Average molecular weight ff18[10D, terminal group: 100 parts of sulfurized polypropylene oxide, fatty acid-treated calcium carbonate (manufactured by Shiraishi Calciu Co., Ltd., trade name Cl0R) 1
00 parts, 28 parts of rutile-type titanium oxide, 55 parts of dioctyl epoxy hexahydrophthalate, 20 parts of dioctyl phthalate, 6 parts of hydrogenated castor oil, 0.5 parts of carbon black, oligoester acrylate (manufactured by Toagosei Chemical Co., Ltd.) Trade name M-8060) 5 parts, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) 1 part,
Add 1 part of 2-(2'-hydroxy-5', 5'-di-t-butylphenyl)-5-di-tetrapenzotriazole and mix well with a 6-roll paint roll (main ingredient). Created.

Examples 1 to 4 and Comparative Examples The components of the curing agent composition shown in Table 1 were mixed in the amounts shown in Table 1, and the mixture was heated in a homogenizer (Nippon Seiki Seisakusho Co., Ltd.) at 1000
A curing agent composition was prepared by thoroughly mixing and dispersing the mixture by stirring for 15 minutes at 0 times/min.

1 part of the curing agent composition obtained by the above method was mixed with 10 parts of the base material obtained in Production Example 1 to obtain a room temperature curable composition. A sheet with a thickness of 0.075 mm was formed using the obtained composition, and was placed under 35°0180% humidity.
The tack-free time using A5758 was measured for one hour. On the other hand, a sample was prepared according to J.Eng. SA 5758, and the sample was compressed 30% and subjected to conditions of 90'as for 2 weeks, and then allowed to stand at room temperature for 1 day, after which the recovery rate was measured.

The results are shown in Table 1.

Examples 5 to 9 The components of the curing agent composition shown in Table 2 were blended in J11 shown in Table 2, and a curing agent composition was prepared in the same manner as in Example 1.

The obtained curing agent composition and the main ingredient obtained in Production Example 1 were mixed to obtain a room temperature curable composition 81 in the same manner as in Example 1.
The tack-free time and recovery rate were measured. The results are shown in Table 2.

Claims (1)

[Scope of Claims] 1 (a) 100 parts by weight of a polyether containing at least one reactive silicone functional group in the molecule; (b) General formula: % formula % (wherein R1 and R2 are of the same type or Representing different monovalent hydrocarbon groups) tin compound (A) 0.01 to 10
A room temperature curable composition containing 0.01 to 1'0 parts by weight of a divalent tin compound (B) and (C) a divalent tin compound. 2 The main chain of the polyether which is the component (a) is essentially a repeating compound represented by the general formula: % formula % (wherein R represents a divalent alkylene group having 1 to 4 carbon atoms) unit, with a molecular weight of 5
00 to 60,000 oxyalkylene polymer. 6. The composition according to claim 1 or 2, wherein the tin compound (A) as the component (b) is trioctyltin carboxylate.