WO2008047746A1

WO2008047746A1 - Polysulfide curable composition

Info

Publication number: WO2008047746A1
Application number: PCT/JP2007/070053
Authority: WO
Inventors: Tomoyuki Torii; Yoshiyuki Tobita; Masahito Mori
Original assignee: Sunstar Giken Kabushiki Kaisha
Priority date: 2006-10-16
Filing date: 2007-10-15
Publication date: 2008-04-24
Also published as: JP2008095038A; CN101528801A; JP5101076B2; CN101528801B

Abstract

Disclosed is a curable composition containing (A) a polysulfide ether polymer, (B) a terminal isocyanate group-containing urethane prepolymer and/or a polyisocyanate compound and (C) a curing catalyst containing an organic tin compound and an organic carboxylic acid metal salt (particularly, an organic carboxylic acid alkaline earth metal salt). The curable composition enables to secure a sufficient working life even under high temperature high humidity conditions, while being greatly improved in foaming during curing and having an excellently balanced workability.

Description

Specification

Polysulfide curable composition

Technical field

[0001] This patent application claims priority with respect to Japanese Patent Application No. 2006-281233, which is hereby incorporated by reference in its entirety.

The present invention provides a polysulfide-based curable composition, and more specifically, the pot life required for work can be secured even in a high temperature and high humidity environment, and foaming during curing is remarkably suppressed. In particular, the present invention relates to a polysulfide curable composition useful as a sealing material.

Background art

[0002] Conventionally, polysulfide-based curable compositions! /, Particularly in a high-temperature and high-humidity environment, carbon dioxide gas is generated due to the reaction between the isocyanate group of the curing agent component and the moisture in the work environment or in the member, The foaming phenomenon that excessively swells has become a problem in terms of design, waterproofing, and adhesive strength. Polysulfide-based sealing materials are often used for stones and tile joints with relatively small capacities and joints, and the amount of sealing material that can be applied per unit time is small! /. A pot life of at least 2 hours is required after mixing with the curing agent.

[0003] However, if the reaction rate is adjusted by increasing the amount of catalyst in order to suppress the foaming phenomenon in a high-temperature and high-humidity environment, the rate of thickening after mixing the base / curing agent increases, and the required usable Time cannot be secured and workability is significantly reduced. In addition, if the catalyst is reduced to slow the reaction rate in order to ensure the pot life, the reaction between isocyanate and moisture will be relatively increased, which will adversely affect foamability.

[0004] Under such circumstances, as a means for suppressing foaming and ensuring the pot life, Japanese Patent Laid-Open No. 10-121031 (Patent Document 1) uses a curing catalyst comprising a tertiary amine and / or an organometallic compound. It has been proposed to contain acidic phosphate ester as a curing retarder. The effect is reduced after storage, and a sufficient effect can be obtained in high-temperature and high-humidity environments in midsummer. There was no problem. Japanese Patent Laid-Open No. 2000-273438 (Patent Document 2) proposes to limit the ratio between a specific isocyanate compound and an isocyanate group / thiol group and to contain a reaction retarder! / In the midst of summer! / It was difficult to adjust the balance between pot life and foaming in the environment.

Patent Document 1: Japanese Patent Laid-Open No. 10-121031

Patent Document 2: Japanese Patent Laid-Open No. 2000-273438

Disclosure of the invention

Problems to be solved by the invention

[0005] The object of the present invention is to ensure a working life necessary for work in a high-temperature and high-humidity environment! The object is to provide a polysulfide-based curable composition.

Means for solving the problem

[0006] As a result of diligent studies to solve the above problems, the present inventors have used a polysulfide-based curable composition in combination with an organotin compound and an organic carboxylic acid metal salt as a curing catalyst. As a result, it was found that the necessary pot life could be secured even under adverse conditions such as high temperature and high humidity, and that the reaction between isocyanate and moisture could be suppressed, and foaming could be significantly suppressed.

[0007] The present invention has been completed based on the above findings, and includes the following preferred embodiments: [1] (A) a polysulfide ether polymer;

(B) a terminal isocyanate group-containing urethane prepolymer and / or a polyisocyanate compound,

(C) a curable composition comprising an organotin compound and a curing catalyst comprising an organic carboxylic acid alkaline earth metal salt,

[2] The curable composition according to the above [1], which is an alkaline earth metal salt of an organic carboxylate, barium organic carboxylate and / or calcium organic carboxylate,

[3] The curable composition according to the above [1] or [2], further comprising (D) a polyol, and [4] (D) the blending amount of the polyol is 100 parts by weight of the (A) polysulfide ether polymer. On the other hand, the curable composition according to the above [3], which is 20 to 450 parts by weight,

[5] (D) Polyol power The curable composition according to the above [3] or [4], which is a polyoxyalkylene polyol,

(6) (1) (A) a polysulfide ether polymer,

(C) a base comprising an organic tin compound and a curing catalyst comprising an organic carboxylic acid alkaline earth metal salt, and

(2) (B) Curing agent comprising terminal isocyanate group-containing urethane prepolymer and / or polyisocyanate compound

A two-component curable composition comprising:

[7] The curable composition according to the above [6], wherein the base (1) further comprises (D) a polyol, [8] (1) the base and (2) the curing agent, Weigh and mix in at least one weight ratio selected from the range of 35, and (i> 45mm x hl8mm after filling into a cylindrical container, the cured product swelled from the container after standing for 24 hours in a 50 ° C atmosphere The curable composition as described in [6] or [7] above, wherein the foaming height is 1.5 mm or less.

The invention's effect

[0008] The curable composition according to the present invention has sufficient curability by using an organic tin compound and an organic carboxylic acid metal salt (particularly, an organic carboxylic acid alkaline earth metal salt) as a curing catalyst. At the same time, it can exhibit a sufficient pot life even in a high-temperature and high-humidity environment, and can exhibit a foaming property that is remarkably suppressed during curing. Therefore, the curable composition according to the present invention can be suitably used particularly as a two-component polysulfide sealing material.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] The curable composition according to the present invention comprises (A) a polysulfide ether polymer, (B) a terminal isocyanate group-containing urethane prepolymer and / or a polyisocyanate compound, (C) an organic tin compound and an organic carboxyl. A curing catalyst comprising an acid metal salt (especially an alkaline earth metal salt of an organic carboxylic acid). The curable composition preferably further comprises (D) a polyol.

[0010] Polysulfide polyether polymer (A) used as a base in the present invention (hereinafter simply referred to as " "Polysulfide polymer") is a compound with the formula:

One (R 0) n-

[Wherein R is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 6 to 200], and a formula:

-(C H OC H OC H-Sx) (a)

2 4 m 2m 2 4

(CH CH (OH) CH Sx) (b)

twenty two

[Wherein m is an integer from !! to 2 and X is an integer from 1 to 5], and the terminal is represented by the formula:

-C H OC H OC H SH and / or

2 4 m 2m 2 4

-CH CH (OH) CH-SH

twenty four

(Where m is an integer from !! to 2), and refers to those having a thiol-containing group, and usually have a number average molecular weight of 600 to 200,000, preferably ί. Examples of commercial products include “LP-282” (number average molecular weight 3500) manufactured by Toray Fine Chemical Co., Ltd. The ether part and the structural units (a) and (b) can have an arbitrary arrangement, and the proportion occupied by the polyether part is 2 to 95% (% by weight, the same applies hereinafter), and the structural unit (a ) ： — (CH OC

twenty four

H OC H Sx) —part is 3 to 70%, and structural unit (b): — (CH CH (〇H) CH m 2m 2 4 2

-Sx) preferably partly;!-50%. Polysulfide bond Sx included

2

The amount is preferably 1-60%.

The curable composition according to the present invention can preferably contain a polyol (D) in addition to the polysulfide polymer as a substrate. In this case, it is possible to obtain a particularly good balance of workability such as foamability (non-foamability) and pot life in a high temperature and high humidity environment.

Examples of the polyol include various conventionally known polyols (for example, ethylene glycol, propylene glycolol, glycerin, trimethylololepropane, pentaerythritolol, sonolebitol, sucrose, and the like, as well as propylene oxide or propylene oxide). Polyethers obtained by addition polymerization of ethylene oxide and alkylene oxides such as ethylene oxide; ethylene glycol, propylene glycol and oligoglycols thereof Butylene glycol, hexylene glycol, polytetramethylene ether glycols; Poly-force prolatatone polyols; Polycarbonate polyols; Polyester polyols such as polyethylene adipate; Polybutadiene polyols; Has a hydroxyl group such as castor oil Higher fatty acid esters; polyether polyols or polymer polyols obtained by grafting a bull monomer to polyester polyols) and the like. Examples of commercially available products include “Sanyux PP3000” (diol having a molecular weight of 3000) manufactured by Sanyo Chemical Industries, Ltd. These may be used alone or in a mixture of two or more.

The blending amount of the polyol can be usually selected in the range of 20 to 450 parts (preferably 25 to 300 parts) with respect to 100 parts (parts by weight, the same applies hereinafter) of the polysulfide polymer (A). If it is less than 20 parts, it may be difficult to adjust the pot life, and if it exceeds 450 parts, the durable adhesiveness tends to decrease.

The curable composition according to the present invention uses a terminal isocyanate group-containing urethane prepolymer and / or polyisocyanate compound (B) as a curing agent.

Examples of the urethane isocyanate containing the terminal isocyanate group include reacting an excessive amount of polyisocyanate with respect to various polyols (usually OH / NCO = 1 / l.3 to 1 / 3.0). The power produced by S is mentioned. Preferably, for example, addition polymerization of propylene oxide or propylene oxide and alkylene oxide such as ethylene oxide to polyhydric alcohols such as ethylen glycol, propylene glycol, glycerin, trimethylol propane, pentaerythritol, sonorebitol, sucrose, etc. Polyether polyols; ethylene glycol, propylene glycol and their oligoglycols; butylene glycol, hexylene glycol, polytetramethylene ether glycols; poly force prolataton polyols; polycarbonate polyols; Polyester polyols; polybutadiene polyols; higher fatty acid esters having a hydroxyl group such as castor oil; Ether polyols or polymeric polyol one Honoré acids grafted to Bulle monomer to the polyester polyols and the like. These may be used alone or in a mixture of two or more. Examples of the polyisocyanate compound include aromatic, aliphatic or alicyclic. Anything that will be used. Suitably, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3,1 dimethyl-1,4,4'-biphenyl diisocyanate, 1,4 phenolic diene Isocyanate, xylylene diisocyanate, tetramethyl

--4, 4, monodiisocyanate, crude TDI, crude MDI, polymethylene'polyphenylisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, their isocyanurates, carposimidides And beuret compounds. These may be used alone or in a mixture of two or more. The amount of the above curing agent is such that the equivalent ratio (NCO) / (SH + OH) of isocyanate group (NCO) in the curing agent to thiol group (SH) and hydroxyl group (OH) in the base is 0.8 ! · 7 (preferably 1. 0 to; 1.3). If it is less than 0.8, the physical properties of the cured product are deteriorated and the surface tack becomes strong. On the other hand, if it exceeds 1.7, it is difficult to suppress foaming.

[0013] The curing catalyst (C) in the curable composition according to the present invention comprises an organic tin compound and an organic carboxylic acid metal salt. That is, in the present invention, an organic tin compound and an organic power rubonic acid metal salt are used in combination as a curing catalyst.

Examples of the organic tin compound include tin octylate, tin naphthenate, tin stearate, dibutyltin ditatoate, dibutyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmalate, dibutyltin diester. Acetate, 1,1,3,3-Tetrabutyl-1,3-dilauryloxycarbonyl rosystanxane, dibutinole tin-dioxy bisbisethoxysilicate, dibutinoletin oxide, dibutinoletin oxide and phthalate reactant, dibutyltin A reaction product of an oxide and a maleate ester, dibutyltin diacetylacetonate, and the like are preferable. Examples of commercially available products include “Neostan U-360” manufactured by Nitto Kasei Corporation. These may be used alone or in a mixture of two or more.

[0014] Examples of the organic carboxylic acid metal salt used in combination with the above organic tin compound include, for example, organic barium carbonate, organic calcium carbonate, organic magnesium magnesium, strontium organic carbonate, titanium organic carboxylate, organic carboxylic acid Zirconium, organic power Examples thereof include zinc rubonate and iron organic carboxylate. Here, examples of the organic carboxylic acid include octylic acid, neodecanoic acid, naphthenic acid and the like. These may be used alone or in a mixture of two or more. Of these, organic alkaline earth metal salts of organic carboxylates are preferred, and barium organic carboxylates and / or calcium organic carboxylates are particularly desirable. As the organic barium carboxylate and the organic calcium carboxylate, barium salts such as octyl acid, neodecanoic acid, naphthenic acid, and the like, calcium salts, particularly, barium octylate and calcium octylate are preferable. Further, an amine catalyst may be used in combination.

[0015] The amount of the organotin compound used is usually 0.0 in the total amount of the base component (including polysulfide polyether polymer (A) and polyol (D) if present); %, Preferably 0.02 to 2.0% by weight. If the amount used is less than 0.01% by weight, defects such as deterioration of physical properties, foaming, delay of the next process, etc. may occur due to insufficient curing speed, and if the amount used exceeds 3.0% by weight. The curing rate is too high, and there is a tendency that sufficient pot life cannot be secured.

The amount of the organic carboxylic acid metal salt used is usually in the range of 0.0;! To 3.0% by weight, preferably 0.02-2% by weight, based on the total amount of the base component (same as above). Can be selected as follows. If the amount used is less than 0.01% by weight, the combined effect may not be sufficient, foaming properties and pot life will not be improved, and even if the amount used exceeds 3.0% by weight There is no significant difference in the improvement effect!

[0016] The curable composition according to the present invention contains additives known in the art such as a plasticizer, a filler, an anti-aging agent, and an adhesion-imparting agent, if necessary, in addition to the above-described components. You can leave. The amount used is not particularly limited, and can be used within an appropriate amount range known in the art.

[0017] Examples of the plasticizer include phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, and alkylbenzenes. These may be used alone or in combination. it can.

[0018] Examples of the filler include heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, my strength, clay, glass beads, shirasu balloon, glass balloon, and silica balloon. , Plastic balloon, powder co Balloons such as plastic balloons, inorganic particles such as plastic particles, glass fibers and metal fibers, organic fibers such as polyethylene fibers and polypropylene fibers, aluminum borate, carbide, nitride nitride, potassium titanate, graph Examples include needles, needle-like crystalline fillers such as calcium carbonate, magnesium borate, titanium diboride, chrysotile, wollastonite, aluminum flakes, aluminum powder, iron powder, etc. Can be used as a mixture.

[0019] Other additives include, for example, a coloring agent (Bengara, titanium oxide, carbon black, other coloring pigments, dyes, etc.), an organic solvent (acetone, methyl ethyl ketone, rig in, ethyl acetate, tetrahydrofuran). , N-hexane, heptane, isoparaffinic high-boiling solvents, etc.), adhesives (silane coupling agents such as aminosilane, mercaptosilane, epoxysilane, epoxy compounds, etc.), UV absorbers, light stabilizers (benzotriazoles) , Hindered amines, etc.), antioxidants (hindered phenols, etc.), thixotropic agents (colloidal silica, organic bentonite, fatty acid amide, hydrogenated castor oil, etc.), solvents (aliphatic hydrocarbons, aromatic hydrocarbons, etc.) ) And the like.

[0020] The curable composition according to the present invention comprises:

(1) (A) a polysulfide ether polymer,

(C) a curing catalyst comprising an organic tin compound and an organic carboxylic acid metal salt (particularly an organic carboxylic acid alkaline earth metal salt);

A base comprising, and

It can also be used in the embodiment of a two-component curable composition comprising the above. Suitably, the base (1) further comprises (D) a polyol. Furthermore, the base (1) can contain additives such as the above fillers in addition to the above components.

[0021] The two-component curable composition preferably comprises a base (1) and a curing agent (2) in a ratio of 100 to 10 to 35 (preferably 100 to 15 to 25, in particular Weigh and mix in at least one weight ratio selected from the range of 100 to 23), fill (i> 45mmX hl8mm cylindrical container (preferably made of polypropylene), and leave in 50 ° C atmosphere for 24 hours. Curing bulging from later container The foaming height of the product is preferably 1.5 mm or less, more preferably 1. Omm or less.

This is useful when the curable composition of the present invention is used as a combination force S of the base and the curing agent, particularly as a sealing material.

Example

[0022] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto by any means!

[Examples;! To 4 and comparative examples;! To 3]

Using each component in parts by weight shown in Table 1 below, a base and a curing agent were uniformly mixed to produce a polysulfide composition. The urethane prepolymers in Table 1 are prepared by blending polypropylene glycol and xylylene diisocyanate so that (NCO) / (OH) is 1 · 85.

It was obtained by reacting at ° C for 14 hours, and the NCO content was 3.0%

The viscosity was 16000 mPa's.

The obtained polysulfide composition was subjected to a performance test, and the results are shown in Table 1.

[0023] [Evaluation method]

1.Foaming

The base and curing agent are weighed and mixed at a weight ratio of 100 to 23, filled into a (i> 45mm x hl8mm cylindrical container (material: polypropylene), and then swelled from the container after being left for 24 hours in a 50 ° C atmosphere. The foam height of the cured sealant was measured.

2.pot life

The base and curing agent were mixed and placed on a polysheet to a thickness of about 3 mm. This was left in an atmosphere of 50 ° C, touched with a finger at regular intervals, and the time until it did not adhere to the finger was measured as the pot life. As long as the pot life is 2.0 hours or more, work on site will not be hindered.

3. Curability

The base and curing agent were mixed and left in an atmosphere of 20 ° C. After 24 hours, the consistency was measured. When the measured consistency is 80 or less, the sealing material is cured, rubber elasticity with almost no flow, adhesion, and adhesion is exhibited, and it is cured until the next process is possible, so the curability is good. It can be judged.

[table 1]

(Note 1) Toyo Fine Chemical Co., Ltd.

(Note 2) “SANNICS PP3000” manufactured by Sanyo Chemical Industries, Ltd .: Diol with a molecular weight of 3000

(Note 3) “Neostan U-360” manufactured by Nitto Kasei Co., Ltd.

(Note 4) “Neolite SPTJ” manufactured by Takehara Chemical Industry Co., Ltd. From the results in Table 1, the compositions of the present invention (Examples;! To 4) differ from the comparative examples not according to the present invention, and have excellent foaming properties. (Non-foaming), pot life, curability, etc. were found to have a balance of workability, and the compositions of the present invention (Examples;! To 4) were 40 ° C '90 No foaming was observed even in construction in the atmosphere, and workability such as pot life was good.

Claims

The scope of the claims

[1] (A) a polysulfide ether polymer;

(C) A curable composition comprising an organic tin compound and a curing catalyst comprising an organic carboxylic acid alkaline earth metal salt.

[2] The curable composition according to claim 1, which is an alkaline earth metal salt of an organic carboxylate and is an organic barium carboxylate and / or an organic calcium carboxylate.

[3] The curable composition according to claim 1 or 2, further comprising (D) a polyol.

[4] The curable composition according to claim 3, wherein the blending amount of (D) polyol is 20 to 450 parts by weight with respect to 100 parts by weight of (A) polysulfide ether polymer.

[5] The curable composition according to claim 3 or 4, wherein the curable composition is a polyoxyalkylene polyol.

[6] (1) (A) a polysulfide ether polymer,

A two-component curable composition comprising:

7. The curable composition according to claim 6, wherein the base (1) further comprises (D) a polyol.

[8] (1) Base and (2) curing agent are weighed and mixed in at least one weight ratio selected from the range of 100 to 10 to 35, and after filling (i> 45mm x hl8mm cylindrical container) The curable composition according to claim 6 or 7, wherein the foamed height of the cured product swelled from the container after being left for 24 hours in a 50 ° C atmosphere is 1.5 mm or less.