JPS5817154A - Room temperature curing composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which is stable in a sealed state and cures upon exposure to moisture, prepared by adding a hydrolyzable organotitanium compd. or a particle hydrolyzate thereof to a polyoxyalkylene polymer with a hydrolyzable functional silicon group. CONSTITUTION:The compsn. is prepared by blending 100pts.wt. polyoxyalkylene polymer (pref. having a molecular weight of 300-15,000 and used in such an amount that the total mol of hydrolyzable functional groups may be 2-8, pref. 2.5-5 times as much as that of water contained in the system), 0-300pts.wt filler, 0-200pts.wt. plastisizer and 0.1-10pts.wt. silanol condensation catalyst. The compsn. is of one-pack type, has a good storage stability, cures at room temperature and is useful as sealant for building.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to curable compositions comprising polyoxyalkylene-based polymers containing hydrolyzable silicone functional groups that cure by absorbing atmospheric moisture. In particular, it relates to moisture-curable compositions that can be of one-component type.

It can harden to a rubbery substance on exposure to air or moisture.

Compounds of polyoxyalkylene polymers containing hydrolyzable silicone functional groups are available in two types: one is a two-component type that can be applied to architectural sealants, and the other is anhydrous. Under the conditions, the main agent,
There is a one-component type in which a curing agent is mixed in advance and is stable in a sealed state, and hardens by absorbing moisture when exposed to the atmosphere. 2
Liquid type requires time and effort to mix the base agent and hardening agent.

Mixed products also have some drawbacks in usage, such as having to be used up within a certain amount of time, but with the one-component type, there is no need for mixing, and once the container is sealed, it can be used after a certain amount of time. It is much more convenient, as it can also be used as a liquid, but its storage stability is an issue.

Up until now, methods for improving storage stability have included adding methanol to the formulation and removing water by azeotropic dehydration (Japanese Unexamined Patent Publication No. 73729/1983). A method of adding the compound (Japanese Patent Laid-open No. 55-127460) is known, but the former has the disadvantage that the operation is complicated, and the latter has the disadvantage of deteriorating the cured physical properties. The present inventors have discovered that the above-mentioned deficiencies can be overcome by adding a hydrolyzable silicone functional group or a partial hydrolyzate thereof, and obtain a one-component curable composition containing a hydrolyzable silicone functional group with good storage stability. According to the present invention, which makes it possible to
There is no need for complicated processes related to azeotropic dehydration, equipment for recovering azeotropic solvents, etc., and there is no need for expensive hydrolyzable silicon compounds, as well as good hardness and chemical properties. , the advantages are obvious.

The hydrolyzable organic titanium compound or its partially hydrolyzable compound used in the present invention is a general term for organic titanium compounds that react in the presence of water alone or in the presence of a catalyst, and the molecular weight is not particularly limited. Although it is not Q, 1 is usually used from 200 to 2,500. Specific examples of such compounds include Ti(0-icaHg)4.
Ti(0-nc4Hs)4゜Ti(OCHjICH(
C2Hs)CaHs)4. Ti(0-CtyHas)
**Ti (0-icaHy)2(QC(CHs)C
HCOCH8:12°Ti (0-nc4Hs)2(
OC2H4N(CzH40H)2:12°Ti(OH)
2(OCH(CH8)COOH)2-Ti(OCH2C
H(C2H5)CH(OH)C8H7)4°Ti(0-
n04Hs)+(OCOCttHas)*0-n-C4
H9 0-n-C4H9 ■-Propoxytitanium tri-i-stearate.

Examples include i-propoxytitanium dimethacrylate-1-stearate, i-propoxytitanium tris(4-aminobenzoate), i-propoxytitanium tris(dioctyl phosphate), etc. These compounds can be used as fillers, plasticizers, etc. It causes a condensation reaction with the water originally present in the compounding agent alone or in the presence of a silanol condensation catalyst, reducing the water content in the system in a short time.

That is, the compound generally has a higher hydrolyzability than the terminal silicon functional group of the polyoxyalkylene polymer, and therefore acts as a dehydrating agent by first reacting with moisture in the system. The remaining small amount of the compound and its partial hydrolyzate serve to ensure the long-term storage stability of the composition. The amount of the compound to be used is such that the total number of moles of the hydrolyzable functional groups of the compound is at least twice the number of moles of water in the system for the above reasons. O tends to reduce the physical properties after curing and slow down the curing speed, so the upper limit is naturally determined based on the desired curing speed.
To obtain normal characteristics, the number of moles of water in the system must be multiplied by ~8
It is preferable to use twice the amount, and more preferably 2.5 times to 5 times the amount, since it is possible to obtain a composition with good storage stability and properties during curing. It is also applicable to the present invention to partially replace a titanium compound or its partial hydrolyzate with a hydrolyzable silicone compound such as Si(OC2H5)4* As the polyoxyalkylene polymer of the present invention The main chain is essentially an -R1-0- group (R1 is represented by an alkylene group having 1 to 4 carbon atoms) and contains a hydrolyzable silicone functional group at at least one end. Those having a molecular weight of 300 to 15,000 are preferred. Here, "essentially" indicates that the main chain may contain a bonding unit other than an alkylene group having 1 to 4 carbon atoms or a polymerized unit,
Usually, it is preferably 500 parts by weight or more, and 80% by weight or more in the main chain of -R1-○-year units. The terminal hydrolyzable silicone functional group has 1, for example, [wherein Z is -R-,
-R-0-R-, -R-QC-.

-RNH8- and -g- (R is the same or different carbon number 1
~20 divalent hydrocarbon group) %R is hydrogen, the same or different substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, or a triorganosiloxy group.

t is a substituted or unsubstituted monovalent organic group or organosiloxy group having 1 to 20 carbon atoms, % R' is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, and a is 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]. A method for producing a polyoxyalkylene polymer having such a terminal group is described, for example, in JP-A-50-15659.
9. The silanol condensation catalyst used in the composition of the present invention is as shown in JP-A-55-12.3620.
Metal-organic carboxylates such as tin octylate, tin stearate, iron naphthenate, and lead octylate; Organic tin, amines such as laurylamine, ethanolamine, alkyl titanates, etc. can be used alone or in combination. Fillers that can be used in the present invention include calcium carbonate, kaolin, talc, titanium oxide, aluminum silicate, and carbon. Common plasticizers such as black are usually in the range of 0.1 to 300 parts by weight per 100 parts by weight of the polyoxyalkylene polymer.Plasticizers include DOP (dioctyl phthalate), B B, P (butylbenzyl phthalate). , chlorinated paraffin.

The amount of epoxidized soybean oil and other conventional substances ranges from 0 to 200 parts by weight per 100 parts by weight of the polyoxyalkylene polymer. There is no problem in using the amount as is.a If the moisture content can be reduced with simple pretreatment, it is of course possible to use a product that has had some moisture removed by heat drying, pretreatment, etc. In that case, the amount of the hydrolyzable organic titanium compound or its partial hydrolyzate added can be reduced.

In addition, the composition of the present invention may contain various additives. For example, suitable anti-sag agents include hydrogenated castor oil, silicic anhydride, or 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, it is possible to
129247, polysiloxane shown in JP-A-55-21453, JP-A-55-21453.
It can also contain an ultraviolet curable resin shown in No. 5-36241.

The present invention will be explained below with reference to examples. Example I CH8 Oxypropylene polymer '10 with an average molecular weight of 8000 and having 80% of all terminals Ic (CHaO)2si4
0 parts by weight, 34 parts by weight of %DOP, 140 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 0.5 parts by weight of carbon black, 4 parts by weight of hydrogenated castor oil as an anti-sagging agent, and 4 parts by weight of hydrogenated castor oil as an anti-aging agent. 6(2,2-
Methylene-bis(4-methyl-6-t-butyl-phenol)],]Sanol L8-770C Bis2.2.6.
6-titramethyl-4-piperidine) sebacate 964
1 part was added and uniformly kneaded using a sealed mixer.

Among the raw materials used here, calcium carbonate and titanium oxide were dried in advance (180°C9 vacuum drying).
was used. When I measured the moisture content after kneading, it was 600.
It was ppm. Here, 6.5 parts by weight of tree n-
Butoxytitanium monostearate (4 mols of water)
．． Then, 1 part by weight of di-n-butyltin-dilaurate was added and stirred, taking care not to expose the mixture to the outside air. It was taken out and stored at 50°C in a sealed container, and was stable for more than 1 month. Further, when this material was exposed to the outside air, it was cured in 6 hours.

In addition, H-shaped test pieces were prepared according to JIS5758 and heated at 28°C.
After curing for 14 days at , 60°C humidity and 14 days at 30°C, a tensile test was conducted at a rate of 50+n@/min. The results were a 50 timidulus of 8.0 kg/Crrl, a strength at break of 6.2 kq/ctrl, and an elongation of 550 inches.

Example 2 80. of all ends of CH8'.
Average molecular weight 56o with a wide range of (CHaO)2si- groups
o to 100 parts by weight of oxypropylene polymer, DO
34 parts by weight of P, 140 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, parts by weight of O, S, 4 parts by weight of monohydrogenated castor oil as an anti-sagging agent, Tsukrak NS-θ, Sanol LS- as an anti-aging agent. Add 1 part of each of 770.

Knead in a sealed mixer until homogeneous. All of these raw materials were commercially available products and were used as they were. After kneading, the moisture content was measured and found to be 2500 ppm. This was heated to 90°C and evacuated under reduced pressure (10'nmHg) for 3
It took 0 minutes. When the water volume was measured, it was 700 ppm. To this, 5.6 parts by weight of tetrakis(2-ethylhexoxy)titanium (the number of hydrolyzable functional groups is 4.0 times as much as the number of moles of water) was added, and after uniformly mixing and stirring, di-n-butyltin oxide was added. 2 parts by weight of an equimolar solution of DOP was added and stirred for 1 hour.

When Tonomo d was stored at 50°C under moisture exclusion, it was stable for more than 1 month. Also, when this was exposed to the outside air, 1
0 Also cured in time. As a result of conducting the test on the H-type test piece in the same manner as in Example 1, it was found that 50 thymodules 8.3 k
Q/Cd, strength at break 6.5kg/ctrl, elongation 47
It was 0chi.

34 parts by weight of DOP, 140 parts by weight of calcium carbonate, 20 parts by weight of titanium oxide, 0.5 parts by weight of carbon black, and 4 parts by weight of hydrogenated castor oil as an anti-sagging agent for 100 parts by weight of an oxypropylene polymer having an average molecular weight of 8,000.
Parts by weight, Tsukrak MS-6 as anti-aging agent. Add 1 part of each of Sanol LS-776 and knead with a sealed mixer until uniform. These raw materials were commercially available products and were used as they were. After kneading, I measured the water content and it was 200 (l).
It was ppm. After evacuation in the same manner as in Example 2, the moisture content was 510 pPm. After adding 4 parts by weight of tetra-n-butoxytitanium (the number of hydrolyzable functional groups is 4.7 times the number of moles of water) and uniformly dispersing it, di-
1 part of n-butyltin-dilaurate was added and stirred for 1 hour.

When this material was taken out so as not to be exposed to the outside air and stored in a sealed container at 50''C, it was stable for over 3 weeks.Also, when this material was exposed to the outside air, it became tack-free within 3 hours. Furthermore, as a result of testing on the H-type test piece in the same manner as in Example 1, the 50 timidulus was 8.5 k.
v", strength at break 7.8'kg/ctrl, elongation 45 (
It was l.

Reference Example 1' A composition obtained by performing all the same operations as in Example 1 except that tri-n-butoxytitanium monostearate was not added was stored at 50°C in a closed container, but after one week, It had thickened and was unbearable to use.

Reference Example 2 A product obtained by performing all the same operations as in Example 2 except that the amount of tetrakis(2-ethylhexoxy)titanium used was 1.4 parts by weight (the number of hydrolyzable functional groups was 1.0 times the amount of water). The resulting composition was stored at 50°C in a sealed container, but after one week it thickened and became unusable.

Patent applicant□ Kanebuchi Chemical Industry Co., Ltd. Agent: Patent attorney, Makoto Asano -

Claims (6)

[Claims] (1) A curable composition containing a polyoxyalkylene polymer having a hydrolyzable silicone functional group, characterized in that a hydrolyzable organic titanium compound or a partially hydrolyzed product thereof is added. A room temperature curable composition that is stable under normal conditions and can be cured by exposure to moisture. (2) (5) The room temperature according to claim 1, which contains 0 to 300 parts by weight of filler and 200 parts by weight of plasticizer θ to 100 parts by weight of the polyoxyalkylene polymer. Curable composition. (3) The total number of moles of the hydrolyzable functional groups of the hydrolyzable organic titanium compound or its partial hydrolyzate is ■, (B)
The room temperature curable composition according to claim 1 or 2, wherein the amount is about twice or more of the total number of moles of water introduced into the system. (4) A hydrolyzable organic titanium compound or a partial hydrolyzate thereof is added to a mixture of (A), 03) and (O) Claims 1, 2 or 3 The room temperature curable composition described. (5) Claims 1 and 2 contain 0.1 to 10 parts by weight of a silanol condensation catalyst per 100 parts by weight of the polyoxyalkylene polymer. Room temperature curable composition according to item 3 or 4. (6) A claim in which a sila-1-nol condensation catalyst is added to a mixture of the components (A), Q3), and Ω and a hydrolyzable organic titanium compound or a partial hydrolyzate thereof, which have been blended in advance. 6. Room temperature curable composition according to item 5.