JPS6235421B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to room temperature curable compositions, and particularly to one-component modified silicone rubber compositions that are stable for long periods of time under sealed conditions and rapidly cure and convert into rubber-like materials when exposed to moisture. Above all,
The present invention provides a one-component room temperature curable modified silicone rubber composition that has excellent adhesion to various adherends. Conventionally, room-temperature curable compositions include two-component type and one-component type.
The liquid type is known, but the two-component type requires mixing the base agent and curing agent in a predetermined ratio before use, and does not require such complicated mixing operations1.
The liquid type has a great advantage in terms of workability. Conventionally, silicone-based, urethane-based, polysulfide-based, and modified silicone-based rubbers are known as this type of one-component room-temperature curable rubber. One-part silicone generally cures quickly and has excellent weather resistance, but it contaminates stone, has poor surface coating properties, attracts dust due to static electricity, easily grows mold, and is expensive. It has the disadvantage of being Furthermore, although one-part urethane is inexpensive, it generally cures slowly, leaves a sludge on the surface for a long period of time, has poor storage stability, and has problems with weather resistance, heat resistance, and adhesion. It has the disadvantages of yellowing and foaming. Moreover, polysulfide 1 solution requires the addition of peroxides such as lead peroxide, calcium peroxide, barium peroxide, etc., and has problems in toxicity, storage stability, heat resistance, and dynamic weather resistance. Furthermore, if used after long-term storage, curing failure may occur. On the other hand, one-part modified silicone has excellent storage stability and anti-mold properties, does not stain stones like one-part silicone, and does not leave surface tack like one-part urethane. However, especially in the case of one-part modified silicone with an alkoxysilane type terminal,
Adhesion to adherends was not sufficient, and in many cases it was necessary to perform primer treatment. As is well known, applying primer treatment is often omitted as it is a cumbersome task, except in cases where the work is carried out under strict construction control, such as in the case of mid-to-high-rise or super-high-rise buildings. When used in general household applications, it is required to firmly adhere to various adherends without primer treatment. The present invention solves the drawbacks of the conventional one-part modified silicone and provides a one-part room-temperature curable modified silicone composition that has strong adhesive strength on various adherends even without a primer. That is, the present invention provides: (a) 100 parts by weight of a body having a hydrolyzable silicone functional group capable of crosslinking at the terminal and whose main chain is essentially a polyether; (b) H ₂ NCH ₂ CH ₂ CH ₂ Si _{( OCH3 ) 3 , H2NCH2CH2NHCH2CH2CH2Si _ _}
(OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH _{2
CH2CH2Si ( OC2H5 ) 3} , a reaction product of an amino group-substituted alkoxysilane and an epoxysilane compound. Under sealed conditions, 0.01 to 20 parts by weight of an amino group-substituted alkoxysilane selected from the reaction product of an amino group-substituted alkoxysilane and a methacryloxysilane compound or a derivative compound thereof (c) and 0.01 to 10 parts by weight of a curing catalyst are mixed. The present invention relates to room temperature curable compositions that are stable and cure upon exposure to moisture. The polymers used in the present invention having terminally crosslinkable hydrolyzable silicone functional groups and whose main chain is essentially a polyether are defined as polymers whose main chain essentially has the formula -R ¹ -O- ( 1) Contains a chemically bonded repeating unit represented by (wherein R ¹ is a divalent alkylene group having 1 to 4 carbon atoms) and whose terminal functional group is represented by the formula [In the formula, Z is -R-, -ROR-,

【formula】 【formula】

[Formula] and

[Formula] (wherein R is the same or different divalent hydrocarbon group having 1 to 20 carbon atoms), R ² is hydrogen or a carbon number 1
~20 substituted or unsubstituted monovalent organic groups, R ³
is a substituted or unsubstituted monovalent organic group or triorganosiloxy group having 1 to 20 carbon atoms, R ⁴ is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, a
is an integer of 0 or 1, b is an integer of 0, 1 or 2, c
is an integer of 0, 1 or 2, m is an integer of 0 to 18, x is a halogen, an alkoxy group, an alkenyloxy group,
Refers to a polymer represented by a group or atom selected from an acyloxy group, an amino group, an aminooxy group, an oxime group, and an amide group. These polymers have, for example, the formula (In the formula, Z, R ² and a are the same as above) to a polyether having the formula A compound represented by the formula (in which R ³ , R ⁴ , b, c, m, and x are the same as above) is reacted at a temperature range from room temperature to 200°C using a known hydrosilylation catalyst such as chloroplatinic acid. It can be easily obtained by The chemically bonded repeating unit represented by the formula -R ₁ -O-(1) includes, for example, -CH ₂ O-, -
CH ₂ CH ₂ O―,

【formula】

Specific examples include [Formula]--CH ₂ CH ₂ CH ₂ CH ₂ O-. These may be used alone or in a mixed form, but polyoxypropylene is particularly preferred. Specific examples of the terminal hydrolyzable silicone functional group include:

[Formula] - halogenated silyl group such as SiCl ₃ ,

[Formula] ―Si(OCH ₃ ) ₃ , ―Si(OCH ₃ ) ₂ OSi(CH ₃ ) ₃ ,

[Formula] - Alkoxysilyl group such as Si(OC ₂ H ₅ ) ₃ ,

【formula】

【formula】

Alkenyloxysilyl such as [Formula] group,

【formula】

[Formula] acyloxysilyl group,

【formula】

An aminosilyl group such as [Formula],

【formula】

Like [expression] aminooxysilyl group,

【formula】

Oxime siri such as [formula] group,

【formula】

An example is an amidosilyl group as shown in the following formula. An alkoxysilyl group is particularly preferred because it is easy to handle. Specific examples of the amino group-substituted alkoxysilane or amino group-substituted alkoxysilane derivative compound used in the present invention include H ₂ NCH ₂ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ , (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CHCH ₂ CH ₂ C
Amino group-substituted alkoxysilanes such as H ₂ Si (OC ₂ H ₅ ) ₃ and the above amino group-substituted alkoxysilanes

【formula】

A reaction product with an epoxysilane compound such as [Formula] or Examples include reactants with methacryloxysilane compounds such as. The reaction between an amino group-substituted alkoxysilane and an epoxysilane compound or an acryloylsilane compound is carried out by mixing 0.2 to 5 moles of the silane compound per 1 mole of the amino group-substituted alkoxysilane, and reacting at a temperature of 1 to 8 degrees Celsius at room temperature to 180°C. It can be easily obtained by stirring for hours.
In the reaction between an amino group-substituted alkoxysilane and an epoxysilane compound, the following reaction products are obtained, for example. Further, in the reaction of an amino group-substituted alkoxysilane and a methacryloxysilane compound, the following reaction products are obtained, for example. The above amino group-substituted alkoxysilane or amino group-substituted alkoxysilane derivative compound is used in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the polyether polymer having a hydrolyzable silicone functional group capable of crosslinking at the terminal.
Preferably, parts by weight are used. This is because at the end of 0.01 parts by weight, it is difficult to develop the expected adhesive properties, and when it exceeds 20 parts by weight, it has a negative effect on the physical properties of the rubber after curing. In the present invention, the curing catalyst is used in an amount of 0.01 to 10 parts by weight based on the polyether polymer. Specific examples of curing catalysts used include tin octylate, dibutyltin dilaurate, dioctyltin maleate, and dibutyltin dilaurate. Known silanol condensation catalysts such as tin compounds such as octoate, dibutyltin oxide, and dioctyltin oxide, titanate ester compounds such as tetrabutoxytitanium and tetraisopropyloxytitanium, and amines are used. According to the present invention, the adhesiveness of a modified silicone-based one-component composition is significantly improved, and a room-temperature curable composition having strong adhesive strength not only to glass, stone, and metal but also to plastic and wood can be obtained. The compositions of the present invention may further contain various fillers, plasticizers,
It may contain additives and the like. As a filler,
For example, calcium carbonate, kaolin, talc, titanium oxide, silica, aluminum silicate, zinc oxide, magnesium oxide, carbon black, etc. are used.
Examples of plasticizers include dioctyl phthalate,
Butylbenzyl phthalate, chlorinated paraffin,
Epoxidized soybean oil and other common oils can be used. As additives, anti-sagging agents such as hydrogenated castor oil and organic bentonite, colorants, and anti-aging agents are used. The composition thus obtained is prepared in a substantially moisture-free state and then stored under seal. Hardening does not progress during the storage period, but when taken out of the container and exposed to the atmosphere, hardening immediately progresses from the surface, making it ideal for buildings, automobiles, etc.
It is useful as an elastic sealant for ships, civil engineering, etc., and can also be used as casting rubber, molding material, paint, and adhesive. The present invention will be specifically described below with reference to Examples. Comparative example 1 80% of all ends

[Formula] 100 parts by weight of an oxypropylene polymer having an average molecular weight of 8200, 140 parts by weight of calcium carbonate, 30 parts by weight of DOP,
A room temperature curable composition was obtained by kneading 20 parts by weight of titanium oxide, 6 parts by weight of hydrogenated castor oil, 1 part by weight of styrenated phenol as an antioxidant, and 1 part by weight of dibutyltin dilaurate in a substantially water-free state. Comparative Examples 2 to 4 In addition to the composition of Comparative Example 1,

[Formula] (A1120, Nippon Unicar) 1 part by weight, or

[Formula] (A174, Nippon Unicar) 1 part by weight, or HSCH ₂ CH ₂ CH ₂ Si
1 part by weight of (OCH ₃ ) ₃ was added and kneaded in a substantially moisture-free state to obtain a room temperature curable composition. Reference example 1 In a 200ml eggplant flask with _N2 substitution
_{NH2CH2NH2NHCH2CH2CH2Si ( OCH3 ) 3 _ _ _}
(A1120, Nippon Unicar) 22.2g and

[Formula] (A187 Nippon Unicar) 23.6g was added and _N2 was heated at 130℃ for 3 hours.
The reaction was carried out by stirring under a stream of air. The reaction product was a pale red liquid, and it was confirmed from the infrared spectrum that the characteristic absorption derived from epoxy groups and amino groups had decreased. Reference example 2 In a 200ml eggplant flask with _N2 substitution
_{NH2CH2CH2NHCH2CH2CH2Si ( OCH3 ) 3 _ _ _}
(A1120, Nippon Unicar) 22.2g and

[Formula] Add 24.8g of (A174, Nippon Unicar) and heat to 120℃.
The mixture was stirred for 3.5 hours under a N ₂ stream to obtain a reaction product. The reaction product was a pale red liquid, and it was confirmed from the infrared spectrum that the characteristic absorption derived from acryloyl groups and amino groups had decreased. Examples 1 to 4 In addition to the composition of Comparative Example 1
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃
(A1120, Nippon Unicar) 0.5 parts by weight or
0.5 parts by weight of H ₂ NCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ (A1100, Nippon Unicar) or 1 part by weight of the product obtained in Reference Example 1 or 1 part by weight of the product obtained in Reference Example 2. In addition, the mixture was kneaded in a substantially moisture-free state to obtain a room temperature curable composition. These compositions were stable for long periods of time under sealed conditions, and upon exposure to moisture, they immediately began to cure and turned into good rubber elastic bodies. Table 1 shows the characteristic values of each room temperature curable composition obtained in Examples 1 to 4 and Comparative Examples 1 to 4.

【table】

Claims (1)

[Scope of Claims] 1 (a) A polymer having a crosslinkable hydrolyzable silicone functional group and whose main chain is essentially a polyether.
100 parts by weight (b) H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂
An amino-substituted alkoxysilane selected from CH ₂ CH ₂ Si(OC ₂ H ₅ ) ₃ , a reaction product of an amino-substituted alkoxysilane and an epoxysilane compound, and a reaction product of an amino-substituted alkoxysilane and a methacryloxysilane compound. or a derivative compound thereof (c) 0.01 to 20 parts by weight (c) A curing catalyst 0.01 to 10 parts by weight. A room temperature curable composition which is stable under sealed conditions and hardens when exposed to moisture. 2. The composition according to claim 1, wherein the crosslinkable hydrolyzable silicone functional group is an alkoxysilyl group. 3. The composition of claim 1, wherein the polyether is essentially polyoxypropylene. 4. Claim 1, wherein the amino group-substituted alkoxysilane or its derivative compound is a reaction product of an amino group-substituted alkoxysilane and an epoxysilane or a reaction product of an amino group-substituted alkoxysilane and a methacryloxysilane compound. Composition of.