JPH0129821B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable composition with good restorability that includes an oxyalkylene polymer containing a crosslinkable silicone functional group. Blends of organic polymers containing crosslinkable silicone functionality that can cure into rubber-like materials on exposure to atmospheric moisture can be used, for example, in architectural sealants. In this case, from the viewpoint of physical properties and cost, the polymer is not used alone but in the form of a composition containing a plasticizer, filler, etc. In order to keep up with fluctuations due to humidity differences in the joints of buildings, the resilience of the sealant that fills the joints is important. The present inventors have already applied for a patent for a curable composition that has excellent strength, elongation, storage stability, adhesion, weather resistance, and restorability (Japanese Patent Application Laid-Open No. 55-9669), but this time Furthermore, a curable composition with improved restorability was invented. That is, the present invention uses a plasticizer containing a specific epoxy group as a plasticizer in a formulation of an oxyalkylene polymer containing crosslinkable silicone functional groups. The epoxy group-containing plasticizer used in the present invention can generally be commercially available, such as epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. can be mentioned. It can be used in an amount of 1 to 150 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the oxyalkylene polymer.
Such plasticizers include di-(2-ethylhexyl)-4,5-epoxycyclohexane-
Examples include 1,2-dicarboxylate, epoxyoctyl stearate, and epoxybutyl stearate. Among these plasticizers, G-
It is said that alicyclic epoxy compounds such as (2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate do not increase the viscosity of the composition even at low temperatures and do not reduce workability as a sealant. This is preferable in this respect. Further, even when mixed with other general-purpose plasticizers that do not contain epoxy groups, the good restorability can be maintained. Although it is unclear how the epoxy group acts in the composition of the present invention, when using an epoxy compound that can be crosslinked and hardened, such as an epoxy resin, substantial crosslinking and hardening is possible. It is necessary to use it in a state where it does not occur and acts as a plasticizer. In the present invention, tin salts of organic carboxylic acids such as tin octylate, tin laurate, and tin ferzatic acid and/or iron naphthenate are used as curing catalysts. When using these curing catalysts,
A cured product with better restorability than when using other catalysts can be obtained. The amount of curing catalyst used is 100% of the polymer
It is preferably 0.001 to 10 parts by weight. In the polyoxyalkylene polymer of the present invention, the main chain is essentially an -R'-O- group (R' is a divalent alkylene group having 1 to 4 carbon atoms), and at least one terminal is cross-linked. Possesses silicon functionality. Those having a molecular weight of 300 to 15,000 are preferred. The terminal crosslinkable silicon functionality may be, for example, of the formula (Here, a is an integer of 0 to 2, R〓 is a monovalent hydrocarbon group, and X is a hydroxyl group or a hydrolyzable group.) Examples of the hydrolyzable group include a halogen group, a hydride 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. A method for producing such a polyoxyalkylene polymer is disclosed in Japanese Patent Application Laid-open No. 50-156599.
It is shown in the publication No. In addition, as a crosslinkable silicone functional group, the formula [In the formula, R〓 is the same or different hydrocarbon group having 1 to 20 carbon atoms or triorganosiloxy group, R〓 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is -R-, -R-O-R
-, -R-OC(O)-, -R-C(O)-, -R
-NHC(O)-, -C(O)- (wherein R is the same or different divalent hydrocarbon group having 1 to 20 carbon atoms), Y is a hydroxyl group or different or the same type of hydrolyzable group, b is an integer of 0 to 3,
c is an integer from 0 to 2, provided that 1≦b+c≦4, l is 0
or 1, m is an integer selected from 0 to 18, and n is 0 or 1]. Methods for producing polyoxyalkylene polymers having such terminal groups are disclosed, for example, in JP-A-55-123620 and JP-A-55-131021. The compositions of the present invention may further contain various fillers, additives, and the like. Common fillers such as calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate, and carbon black can be used in an amount of 0 to 300 parts by weight based on 100 parts by weight of the polyoxyalkylene polymer. .
Suitable anti-sagging agents include hydrogenated castor oil, silicic anhydride, and organic bentonite. As the anti-aging agent, various types classified as ultraviolet absorbers, radical chain inhibitors, peroxide decomposers, etc. can be used alone or in combination. In order to adjust the physical properties of the composition of the present invention,
Reactive silicone compounds as shown in JP-A-53-129247, polysiloxanes as shown in JP-A-55-21453, JP-A-55-36241
It may contain an ultraviolet curable resin as shown in the above publication. When the group bonded to the terminal silicon group of the polyoxyalkylene polymer is a hydroxyl group, it is preferable to use a reactive silicone compound in combination. Specific examples are given below. Example 1 Oxypropylene polymer 100 with an average molecular weight of 9000 and having (CH ₃ O) ₂ Si(CH ₃ ) groups at 80% of all terminals
Based on parts by weight, di(2-ethylhexyl)
50 parts by weight of 4,5-epoxycyclohexane-1,2-dicarboxylate (EPS), 6 parts by weight of hydrogenated castor oil as an anti-sag agent, as an antioxidant
Add 1 part of NS-6,2,2'-methylenebis-(4-methyl-6-tert-butylphenol),
After stirring thoroughly with a spatula, pass through three paint rolls three times. Take 30 parts by weight of the blend and add tin octylate to it.
Add 0.3 parts by weight and mix thoroughly with a subachuura, then add 23 parts by weight.
It is cured for 7 days in an atmosphere of 60% humidity at 50°C, and further cured for 7 days in an atmosphere of 50°C and 55% humidity.
The thus obtained cured product was immersed in hot water at 50°C for one day, left at 23°C and 60% humidity for one day, compressed by 30% at 90°C, and left for 7 days. After this, uncompress it and use it for 1 day.
The recovery rate after being left at 23°C and 60% humidity was 62%. As a comparative example, di-(2-ethylhexyl)-
A similar test with a composition using DOP in place of 4,5-epoxycyclohexane-1,2-dicarboxylate yielded 30%. As another comparative example, a similar test was conducted on a composition using 1 part by weight of dibutyltin dilaurate instead of 0.3 parts by weight of tin octylate, and the result was 8%. Furthermore, di-(2-ethylhexyl)-4,5-
A similar test using a composition using DOP in place of epoxycyclohexane-1,2-dicarboxylate and 1 part by weight of dibutyltin dilaurate in place of 0.3 parts by weight of tin octylate yielded 0%. Example 2 Oxypropylene polymer 100 with an average molecular weight of 8000 and having (CH ₃ O) ₂ Si(CH ₃ ) groups at 80% of all terminals
To the parts by weight, add 55 parts by weight of a mixture of plasticizers as shown in Table 1, 6 parts by weight of hydrogenated castor oil as an anti-sagging agent, and 1 part of NS-6 as an antioxidant, and mix thoroughly with a spatula. After stirring, pass through three paint rolls three times. Take 30 parts by weight of the blend and add tin octylate to it.
After adding 0.2 parts by weight and 0.1 parts by weight of laurylamine, and thoroughly mixing with a sorrel, the recovery rate was measured after curing in the same manner as in Example 1, and the results were as shown in Table 1.

【table】

【table】 Example 3 80% of all ends

[Formula] Oxypropylene polymer 100 with an average molecular weight of 8000 and having groups
Based on parts by weight, di(2-ethylhexyl)
50 parts by weight of 4,5-epoxycyclohexane-1,2-dicarboxylate (EPS), 6 parts by weight of hydrogenated castor oil as an anti-sag agent, as an antioxidant
Add 1 part of NS-6, stir thoroughly with a spatula, and pass through 3 paint rolls. 30 parts by weight of the mixture was added, 0.3 parts by weight of tin 2-ethylhexanoate was added thereto, and the mixture was thoroughly mixed with a sorrel, and after curing in the same manner as in Example 1, the recovery rate was measured and found to be 65%. . As a comparative example, di-(2-ethylhexyl)-
When a similar test was conducted using DOP instead of 4,5-epoxycyclohexane-1,2-dicarboxylate, it was 30%. Reference example 1 Oxypropylene polymer 100 with an average molecular weight of 8000 and having (CH ₃ O) ₂ Si(CH ₃ ) groups at 80% of all terminals.
To the weight part, add 50 parts by weight of epoxidized soybean oil, 110 parts by weight of calcium carbonate, 30 parts by weight of titanium oxide, 6 parts by weight of hydrogenated castor oil as an anti-sagging agent, and 1 part of NS-6 as an antioxidant. After stirring thoroughly, pass through three paint rolls three times. Take 30 parts by weight of the blend and add tin octylate to it.
Add 0.3 parts by weight and mix thoroughly with a subachuura, then add 23 parts by weight.
It is cured for 7 days in an atmosphere of 60% humidity at 50°C, and further cured for 7 days in an atmosphere of 50°C and 55% humidity.
The thus obtained cured product was immersed in hot water at 50°C for one day, left at 23°C and 60% humidity for one day, compressed by 30% at 90°C, and left for 7 days. After this, uncompress it and use it for 1 day.
The recovery rate after being left at 23°C and 60% humidity was 60%. As a comparative example, instead of epoxidized soybean oil
A similar test using DOP showed a rate of 30%. Reference example 2 80% of all ends of the molecular chain 50 parts by weight of epoxidized soybean oil, 110 parts by weight of calcium carbonate, and 30 parts by weight of titanium oxide for 100 parts by weight of an oxypropylene polymer having an average molecular weight of 7500.
Parts by weight, Hydrogenated castor oil 6 parts by weight, Antioxidant NS
-6 Add 1 part, stir thoroughly with a spatula, and pass through 3 paint rolls 3 times. Take 30 parts by weight of the blend and add tin octylate to it.
After adding 0.3 parts by weight and thoroughly mixing with a spatula, the recovery rate was measured after curing in the same manner as in Example 1 and found to be 60%. As a comparative example, DOP instead of epoxy soybean oil
When a similar test was conducted on a device using
It was %. Reference example 3 At 80% of all ends of the molecular chain

[Formula] Oxypropylene polymer 100 with an average molecular weight of 8000 and having groups
Based on parts by weight, di(2-ethylhexyl)
50 parts by weight of 4,5-epoxycyclohexane-1,2-dicarboxylate (EPS), 6 parts by weight of hydrogenated castor oil as an anti-sag agent, as an antioxidant
Add 1 part of NS-6, stir thoroughly with a spatula, and pass through 3 paint rolls. 30 parts by weight of the mixture was added, 0.6 parts by weight of methyltri(cyclohexylamino)silane was added, and the mixture was sufficiently mixed with a soaker. After curing in the same manner as in Example 1, the recovery rate was measured and found to be 60%. As a comparative example, di-(2-ethylhexyl)-
When a similar test was conducted using DOP instead of 4,5-epoxycyclohexane-1,2-dicarboxylate, it was 30%.

Claims (1)

[Claims] 1 (A) The main chain essentially consists of an -R'-O- group (R' is a divalent alkylene group having 1 to 4 carbon atoms), and at least one terminal is cross-linked. 100 parts by weight of an oxyalkylene polymer having a molecular weight of 300 to 15,000 and having a possible silicone functional group; (B) a group consisting of epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives and mixtures thereof; A curable composition containing 1 to 150 parts by weight of a plasticizer containing an epoxy group in the molecule selected from (C) 0.001 to 10 parts by weight of a tin() salt of an organic carboxylic acid and/or iron naphthenate. . 2 The silicon functional group has the formula (Here, a is an integer of 0 to 2, R〓 is a monovalent hydrocarbon group, and X is a hydroxyl group or a hydrolyzable group.) . 3 The silicon functional group has the formula [In the formula, R〓 is the same or different type of hydrocarbon group or organosiloxy group having 1 to 20 carbon atoms, and R〓 is a hydrogen atom or a substituted or unsubstituted group having 1 to 20 carbon atoms.
valence hydrocarbon group, Z is -R-, -R-O-R-,
-R-OC(O)-, -R-C(O)-, -R-
NHC(O)-, -C(O)- (wherein R is the same or different divalent hydrocarbon group having 1 to 20 carbon atoms), Y
is a hydroxyl group or a different or similar hydrolyzable group, b is an integer of 0 to 3, c is an integer of 0 to 2,
However, 1≦b+c≦4, l is 0 or 1, m is 0 to 18
an integer selected from n is 0 or 1] The curable composition according to claim 1. 4. The curable composition according to claim 3, wherein Z is _-CH2- . 5. The curable composition according to claim 1, wherein the -R'-O- group is -CH( _CH3 ) _-CH2O- . 6 The molecular weight of the oxyalkylene polymer is 3000~
12,000.