JP3477120B2 - Two-component curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a two-component curable composition, and more specifically, by using a specific curing catalyst in combination with a basic compound, the composition has excellent surface and internal curability, low modulus and high elongation. The present invention relates to a two-component curable composition having a curable physical property, which is particularly useful as a sealing material for construction.

[0002]

2. Description of the Related Art Sealing materials for construction of this type include, for example, alkoxysilyl group-containing isobutylene polymers, fillers , plasticizers and
A two-component type curable composition is used which comprises a main agent containing water and a curing agent containing a curing catalyst. Then, tin compounds such as tin octylate are widely used as a curing catalyst, but the surface and internal curability is poor,
It was the current situation that the thin layer curability was poor, and the cured physical properties were not particularly satisfactory with respect to modulus and elongation.

[0003]

Therefore, the present inventors have
Upon proceeding with earnest studies to solve the problems of the curing catalyst, it was found that the above problems can be solved completely by using a bismuth system instead of the tin system and using a basic compound in combination, The present invention has been completed.

That is, the present invention is a two-component type curable composition comprising a main agent containing an alkoxysilyl group-containing isobutylene polymer, a filler, a plasticizer and water , and a curing agent containing a curing catalyst. The present invention provides a two-component curable composition characterized by using the following amount of an organic carboxylic acid bismuth salt as the curing catalyst, and using the following amount of a basic compound in combination therewith.

The above-mentioned alkoxybutyl group-containing isobutylene-based polymer (hereinafter simply referred to as isobutylene-based polymer) in the present invention means that the main chain skeleton is composed of at least isobutylene units. A monomer (for example, an olefin having 4 to 12 carbon atoms, vinyl ether, aromatic vinyl compound, vinylsilanes, allylsilanes, etc.) may be contained], and the both ends of the molecule have, for example, the formula:

[Chemical 1] [In the formula, R and R'are the same or different and each has 1 to 1 carbon atoms.
Lower alkyl of 5; and c is an integer of 1 to 3], preferably having a molecular weight of 100.
The term 0 to 40000 refers to a room temperature waxy or highly viscous liquid, and it can be generally produced by using an all-terminal functional isobutylene-based polymer obtained by a cationic polymerization method called an inifer method (JP-A-8-
231758). As a typical commercial product,
formula

[Chemical 2] [In the formula, n is 5 to 400 and m is 5 to 400]
An example is the "Epion" series manufactured by Kanegafuchi Chemical Industry Co., Ltd., which has a chemical structure of

As the filler in the present invention, heavy calcium carbonate, fatty acid-treated calcium carbonate, porous calcium carbonate, calcium silicate, fume silica, precipitated silica, carbon black, talc, titanium oxide, asbestos, glass fiber, mica , Graphite, diatomaceous earth, clay, silicic acid anhydride, clay, magnesium carbonate, quartz, fine aluminum powder, flint powder, zinc dust and the like.

As the plasticizer in the present invention, hydrocarbon type oil, paraffin type process oil, dialkyl phthalate (dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate etc.), α-olefin oxide, C ₆ -C ₁₂ alkyl of trimellitic acid are used. Esters, dibasic acid esters (dioctyl adipate, dioctyl sebacate, etc.), fatty acid esters, polyalkylene glycol esters (diethylene glycol dibenzoate, triethylene glycol dibenzoate, etc.), phosphoric acid esters (tricresyl phosphate, Tributyl phosphate, etc.) and the like.

Specific examples of the organic carboxylic acid bismuth salt used as the curing catalyst in the present invention include bismuth octylate, bismuth neodecanoate, bismuth naphthenate and the like, and one or a mixture of two or more thereof is used. . The amount used is selected in the range of 0.001 to 10 % ( % by weight, the same applies hereinafter) in the total amount of the composition. If it is less than 0.001%, not cured, also it exceeds 10%, the curing rate becomes faster, a negative impact on the coating workability.

As the basic compound used in combination with this curing catalyst, for example, butylamine, octylamine,
Laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminoisopropylamine, xylylenediamine,
Amine compounds such as triethylenediamine; guanidine compounds such as guanidine and diphenylguanidine; other, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1, 8-diazabicyclo (5.4.0) undecene-7 and the like can be mentioned, and one kind or a mixture of two or more kinds thereof is used. The usage is
It is selected in the range of 1 to 100 parts with respect to 100 parts of the organic carboxylic acid bismuth salt (parts by weight, the same applies hereinafter). If the amount is less than 1 part, the summing effect cannot be obtained, and if the amount exceeds 100 parts,
Name desirable cure properties of the sealant.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The two-component curable composition according to the present invention comprises the above-mentioned isobutylene polymer, filler, and plasticizer.
In a system in which a main component containing water and water and a curing agent containing a curing catalyst, or a toner containing a mixture of a pigment / plasticizer, etc., if necessary, is added and mixed immediately before use. Composed. Further, if necessary, a usual adhesive agent (epoxy compound, silane coupling agent, etc.), an antioxidant (hindered phenols, mercaptans, sulfides, dithiocarboxylic acid salts, thioureas, thiophosphates) on the main agent side. , Thioaldehydes, etc.), dripping inhibitor (hydrogenated castor oil derivative; metal soap such as calcium stearate, aluminum stearate, barium stearate), photocurable resin, physical property adjusting agent (various silane coupling agents) ), moisture retention sheet material (such as a hydrate-free machine salts), thixotropic agent, UV absorber (hindered amines, benzotriazoles, etc.), antiozonants, light stabilizers, etc., Likewise curing agent On the side, the above-mentioned filler, plasticizer, thixotropic agent, co-catalyst (tertiary amine compound) and the like may be added in appropriate amounts.

[0011]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Example 1 and Comparative Example 1 (1) Main agent The following parts of the respective components were blended to obtain a main agent. Component portion isobutylene-based polymer (1) 150 fatty treated calcium 80 Heavy calcium carbonate 60 hydrocarbon-based oil 60 epoxy adhesion agent 5 photocurable resin 3 hindered phenolic antioxidant 1 benzotriazole ultraviolet absorber 1 Hindered amine UV absorber 1 Water 5 Total 366 Note 1: "Epion EP505S" manufactured by Kaneka Kagaku Kogyo Co., Ltd. (molecular weight about 20000, polymer content / hydrocarbon oil = 100/50)

(2) Hardener A hardener is prepared by mixing the following parts in the respective components. Ingredients Example 1 Comparative Example 1 Bismuth octylate 13.5-tin octylate-13.5 Laurylamine 1.95 1.95 Paraffinic process oil 28.4 28.4 Heavy calcium carbonate 106 106 106 Thickener 0. 75 0.75 Total 150.6 Total 150.6

(3) Two-component type curable composition and performance test To 100 parts of the above-mentioned base material, 10 parts of a curing agent and 4 parts of a toner (a mixture of pigment / plasticizer etc.) were added, mixed by stirring, and then vacuum degassing. A two-component curable composition was prepared and subjected to the following performance test, and the results are shown in Table 1 below. Curability (i) Pot life Under the conditions of 10 ° C, 23 ° C or 30 ° C, the spatula finishing time (h) is measured. (Ii) Internal curing Under the conditions of 5 ° C, 10 ° C or 20 ° C, the consistency after 24 hours is measured using the consistency tester described in JIS K2220, and at the same time, the internal cured state is visually judged. ◯: Cured up to the inside, good ×: Uncured inside (iii) Uncured thin layer Applied with a thickness of 0.1 mm, 0.2 mm or 0.4 mm,
After 60 hours at 60 ° C., it is touched with a finger and examined for uncured state. Cured physical properties JIS A1439 H-type test bodies (type 2) described in the tensile adhesion test items for architectural sealing materials were produced using an aluminum plate, and after curing and curing, 50% at a tensile speed of 50 mm / min, 150% tensile stress (M ₅₀ , M ₁₅₀ ), maximum tensile stress (Tmax) and elongation at maximum load (Emax) are determined.

[0014]

[Table 1]

[0015]

From the results shown in Table 1, the bismuth-based catalyst of the present invention (Example 1) is excellent in surface and internal curability as compared with the tin-based catalyst (Comparative Example 1). It is recognized that the curing phenomenon can be improved. On the other hand, regarding the cured physical properties, it is recognized that the bismuth catalyst tends to have lower modulus and higher elongation than the tin catalyst. The composition of the present invention is mainly used as a sealing material for construction, but in addition to this, it is also used as a sealing material for automobiles, electric appliances, civil engineering, and other adhesives, paints, coating materials, potting materials, molded products, etc. Can be applied.

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-11-246762 (JP, A) JP-A-11-29713 (JP, A) JP-A-8-127724 (JP, A) JP-A-8- 325466 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 23 / 00-23 / 22 C08K 5 / 00-5 / 59

Claims (4)

(57) [Claims] 1. A two-component curable composition comprising a main agent containing an alkoxysilyl group-containing isobutylene polymer, a filler, a plasticizer and water , and a curing agent containing a curing catalyst. an organic carboxylic bismuth salt, and this was combined with a basic compound, an organic mosquito
The amount of bismuth rubonate is 0.001 to the total amount of the composition.
10% by weight of the organic carboxylic acid bismuth salt 10
1 to 100 parts by weight of the basic compound is used with respect to 0 parts by weight
2-component curable composition characterized by that. 2. The two-component curable composition according to claim 1, wherein the organic carboxylic acid bismuth salt is bismuth octylate, bismuth neodecanoate and / or bismuth naphthenate. 3. The two-component curable composition according to claim 1, wherein the basic compound is laurylamine. 4. The organic carboxylic bismuth salt is a bismuth octylate, a basic compound is 2-component curable composition according to any one of claims 1 to 3 is laurylamine.