JPS6228177B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a room temperature curable composition, and in particular provides a room temperature curable rubber composition with improved adhesion to mortars. Room-temperature curable compositions Especially in the sealant field, it is difficult to firmly adhere sealants when the adherend is mortar, ALC, or PC. Because the body itself is porous, the primer penetrates into the adherend and makes it difficult to form a paint film.Increasing the viscosity of the primer solution to improve film properties will actually worsen workability and storage stability. ,
Furthermore, since water easily penetrates into the adherend itself, the primer itself is likely to be soaked in water. This method is not always sufficient because of the problem that the primer is immersed in a strong alkaline substance contained in the adherend. On the other hand, methods have been considered to impart adhesive properties to the sealant itself and allow it to adhere without a primer, but this is still insufficient and often causes the sealant to easily peel off from the adhesive surface, especially in a tensile test immediately after a water resistance test. The present inventors have developed a silicone-modified epoxy resin as an active ingredient in a room-temperature curable composition whose base polymer is a polymer having a hydrolyzable silicon group at the end and whose main chain is essentially a polyether. It was discovered that by adding , self-adhesiveness to not only glass, metal, and stone, but especially mortars, can be strengthened, and the material can sufficiently withstand a tensile test after a mortar water resistance test, leading to the present invention. That is, the present invention comprises (a) 100 parts by weight of a polymer having a crosslinkable hydrolyzable silicon group at the terminal and whose main chain is essentially polyether; (b) 0.01 to 20 parts by weight of a silicone-modified epoxy resin. , (c) a room temperature curable composition containing 10 parts by weight or less of a curing catalyst. The polyether used in the present invention includes Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 46-12154, and Japanese Patent Publication No. 1973-12154.
156599, JP-A-53-136583, JP-A-54-6096, etc. are used, and those with a molecular weight of 300 to 20,000 are particularly preferred. As a repeating unit of polyether, for example, -CH ₂ O
−, −CH ₂ CH ₂ O−,

【formula】

[Formula] -CH ₂ CH ₂ CH ₂ CH ₂ O-, etc. are exemplified. These may be used alone or in a mixed form, but polyoxypropylene is particularly preferred. Terminal hydrolyzable groups include alkoxy groups, alkenyloxy groups, acyloxy groups, ketoximate groups,
A silyl group having two or more silicon atoms such as a silyl group or a silyloxysilyl group to which a group selected from an amide group, an acid amide group, an aminooxy group, an amino group, and a mercapto group is bonded can be included. In particular, alkoxysilyl groups are preferred because they are easy to handle. The silicone-modified epoxy resin used in the present invention is defined as a reaction product of a compound having two or more epoxy functional groups in one molecule on average and a silicone compound having a functional group that can react with the epoxy group. can. Compounds having two or more epoxy functional groups in one molecule on average include so-called epoxy resins, such as bisphenol A-
There are many types such as epichlorohydrin type, isobrominated product, epoxy novolac type, alicyclic epoxy type, aliphatic epoxy type, etc. Specifically, Epicote 828, 834, 1001, 1004, 1007, 1050, 152
(manufactured by Yuka Ciel Epoxy Co., Ltd.), DER−
732, 736 (all manufactured by Dow Chemical Company), Araldite-6005, 6010, 6020, 6030, 6040, 6050 (all manufactured by Ciba Geigy), etc. Basically, any type of epoxy resin can be used, but those having a relatively small epoxy equivalent are preferred. As the silicone compound having a functional group capable of reacting with an epoxy functional group, a silicone compound having an amino group, a mercapto group, a carboxylic acid group, etc. is used. In particular, silanes containing mercapto groups are effective. It is desirable that the silicone compound has a hydrolyzable functional group on the silicon atom. Specifically, _{NH2 - CH2CH2CH2Si} ( _{OCH3 ) 3} ,
_{NH2CH2CH2NHCH2CH2CH2Si ( OCH3 ) 3 , _ _
HSCH2CH2CH2Si ( OCH3 ) 3} ,
Examples include silicone compounds such as (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CO ₂ H and partially hydrolyzed condensates of silicone functional groups of the compounds. In addition, other silicone compounds having functional groups that can react with amino groups, mercapto groups, and carboxylic acid groups, such as On the other hand, a reaction product obtained by reacting an excess amount of a silicone compound containing an amino group, a mercapto group, or a carboxyl group, and a partially hydrolyzed condensate of a silicone functional group can also be used. In short, a silicone compound that has been modified with the necessary amount of functional group capable of reacting with the epoxy functional group of the epoxy resin remaining can be used for the purpose of the present invention. Modification with a silicone compound having a functional group capable of reacting with the epoxy functional group of the epoxy resin can be carried out at any equivalent ratio of the functional group capable of reacting with the epoxy functional group to the epoxy functional group from 0.1 to 3.0. However, a range of 0.1 to 1.0 is preferable from the viewpoint of performance and economy. The reaction may be carried out without a solvent or, if necessary, in an inert organic solvent. There are no particular restrictions on the reaction conditions, but it is preferably carried out at 50 to 150°C for 30 minutes to 3 hours. On this occasion,
A catalyst such as 2,4,6-tris(diaminomethyl)phenol or the like may be used if necessary. Furthermore, due to the nature of the compound being handled, it is preferable to carry out the reaction under anhydrous conditions. The curing catalysts used in the present invention include metal organic carboxylates of tin octylate, tin stearate, iron naphthenate, and lead octylate; di-n-butyltin dilaurate, di-n-butyltin diphthalate, and Organic tin compounds such as a reaction product of -n-butyltin oxide and dioctyl phthalate; known silanol condensation catalysts such as alkyl titanate compounds and amines may be used alone or in mixtures. The composition of the present invention may further contain various fillers, plasticizers, additives, etc., if necessary.
Fillers include calcium carbonate, silica powder,
Kaolin, talc, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, carbon black, etc. are used. As the plasticizer, dioctyl phthalate, butylbenzyl phthalate, epoxidized soybean oil, chlorinated paraffin, and others are used.
As additives, hydrogenated castor oil, anti-sagging agents such as organic bentonite, coloring agents, anti-aging agents, etc. are used. The composition of the present invention can be applied not only to a two-pack type but also to a one-pack type room temperature curable composition. In the latter case,
It is obtained by preparing the composition of the present invention in a substantially water-free state, can withstand long-term storage if stored in a sealed state, and immediately begins to harden from the surface if exposed to the atmosphere. The present invention provides a room-temperature curable composition that has excellent adhesion not only to glass, metal, and stone, but also to mortars in particular. Of course,
It is very useful in the case of mortar, concrete, ALC, and PC, and in areas where these are interlocked. The composition of the present invention is useful as an elastic sealant in fields such as buildings and civil engineering, and can also be used as a paint and adhesive. The present invention will be described in more detail with reference to Examples below. Reference example 1 Epicoat 828 (manufactured by Yuka Ciel Epoxy Co., Ltd.)
and 0.4, 0.7, and 1.0 equivalents of each epoxy group.
Add HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 2・4・6
-Tris(dimethylaminomethyl)phenol was added in a catalytic amount and stirred at 110°C for 1 hour under a _N2 seal to obtain silicone-modified epoxy resins with different modification rates. Reference example 2 Epicote 834 (manufactured by Yuka Ciel Epoxy Co., Ltd.)
and 0.8 equivalent of the epoxy group.
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was reacted in a 50% solution of toluene at 110°C for 1 hour in the presence of a 2,4,6-tris(dimethylaminomethyl)phenol catalyst to form a silicone-modified epoxy resin toluene 50%. % solution was obtained. Reference example 3 Epicote 1001 (manufactured by Yuka Ciel Epoxy Co., Ltd.)
and 0.5 equivalent to the epoxy group.
HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was reacted in a toluene 50% solution state at 90°C for 1 hour in the presence of a 2,4,6-tris(dimethylaminomethyl)phenol catalyst to form a silicone-modified epoxy resin toluene 50%. % solution was obtained. Examples 1 to 5 80% of the terminal

[Formula] 100 parts by weight of polypropylene oxide polymer with an average molecular weight of 8200 as a base, calcium carbonate white gloss
CCR140 parts by weight, dioctyl phthalate 30 parts by weight, titanium oxide 20 parts by weight, Disparon 4 parts by weight, Tinuvin 327 1 part by weight, Nokrac NS-6
1 part by weight of dibutyltin dilaurate and 1 part by weight of dibutyltin dilaurate were kneaded in a substantially water-free state, and the silicone-modified epoxy resins obtained in Reference Examples 1 to 3 were added in the proportions shown in Table 1. and mixed to obtain a composition. This was prepared according to JIS 5758 using mortar as an H-type test piece without a primer, and after curing at room temperature for 14 days, then at 30℃ for another 14 days, and immediately after immersing it in water at 20℃ for 7 days. Tensile tests were conducted at a speed of 1/min. The results are shown in Table-2.
Additionally, as comparative examples, results are also shown when the epoxy resin itself was added and when it was not added at all.

【table】

【table】

Table 3 also shows the results of the H-type test conducted on the composition of Example 2 using various adherends in the same manner.

[Table] In Tables 2 and 3, CF and AF represent cohesive failure and interfacial failure, respectively.
failure). Cohesive failure occurs when a test piece breaks in a tensile test, but the breakage point is not on the adhesive surface with the adherend but on the cured rubber portion. Moreover, interfacial failure refers to a case where the above-mentioned fracture location is the adhesive surface with the adherend. Therefore, in the case of cohesive failure, it indicates that the adhesiveness to the adherend is high. Table-2, Table-3
It is clear from the results that the cured product using the composition of the present invention has excellent adhesion to adherends. In addition, this room temperature curable composition has a temperature of 50% in a closed container.
℃ for more than one month, and when exposed to the atmosphere, hardening started immediately from the surface.

Claims (1)

[Claims] 1 (a) A polymer having a crosslinkable hydrolyzable silicon group and whose main chain is essentially a polyether
100 parts by weight, (b) silicone-modified epoxy resin
(c) 10 parts by weight or less of a curing catalyst. 2. The composition according to claim 1, wherein the hydrolyzable silicon group in (a) is an alkoxysilyl group. 3. A composition according to claim 1, wherein the main chain of (a) is essentially polyoxypropylene. 4. The composition according to claim 1, wherein (b) is a reaction product of an epoxy resin and a silicone compound having a hydrolyzable functional group on a silicon atom. 5. The composition according to claim 1, wherein (b) is a partially silicone-modified epoxy resin with a modification rate of 0.1 to 1.0.