Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups

Definitions

• 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.
• the present invention relates to a polysulfide curable composition useful as a sealing material.
• 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.
• 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.
• 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
• 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.
• the present invention has been completed based on the above findings, and includes the following preferred embodiments: [1] (A) a polysulfide ether polymer;
• 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.
• the curable composition according to the above [3] which is 20 to 450 parts by weight,
• a two-component curable composition comprising:
• 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.
• 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.
• 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:
• R is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 6 to 200]
• m is an integer from ! to 2
• m refers to those having a thiol-containing group, and usually have a number average molecular weight of 600 to 200,000, preferably ⁇ .
• 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
• H OC H Sx) part is 3 to 70%, and structural unit (b): — (CH CH ( ⁇ H) CH m 2m 2 4 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.
• a polyol (D) in addition to the polysulfide polymer as a substrate.
• polystyrene resin examples 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).
• polyols for example, ethylene glycol, propylene glycolol, glycerin, trimethylololepropane, pentaerythritolol, sonolebitol, sucrose, and the like, as well as propylene oxide or propylene oxide).
• 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.
• the power produced by S is mentioned.
• 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.
• tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 3,3,1 dimethyl-1,4,4'-biphenyl diisocyanate, 1,4 phenolic diene Isocyanate, xylylene diisocyanate, tetramethyl
• 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.
• 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.
• organic tin compound examples include tin octylate, tin naphthenate, tin stearate, dibutyltin ditatoate, dibutyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmalate, dibutyltin diester.
• 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.
• 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.
• 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.
• 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!
• 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.
• 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.
• plasticizer examples include phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, and alkylbenzenes. These may be used alone or in combination. it can.
• 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.
• 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).
• 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.
• the curable composition according to the present invention comprises:
• a base comprising, and
• the base (1) further comprises (D) a polyol.
• the base (1) can contain additives such as the above fillers in addition to the above components.
• 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.
• 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.
• the viscosity was 16000 mPa's.
• the obtained polysulfide composition was subjected to a performance test, and the results are shown in Table 1.
• 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.
• 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.
• 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.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)

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Citations (5)

• 2006
  • 2006-10-16 JP JP2006281233A patent/JP5101076B2/ja active Active
• 2007
  • 2007-10-15 WO PCT/JP2007/070053 patent/WO2008047746A1/ja not_active Ceased
  • 2007-10-15 CN CN2007800386838A patent/CN101528801B/zh not_active Expired - Fee Related

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