WO2019039611A1 - Curable composition and joint structure obtained by using same - Google Patents

Curable composition and joint structure obtained by using same Download PDF

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Publication number
WO2019039611A1
WO2019039611A1 PCT/JP2018/031460 JP2018031460W WO2019039611A1 WO 2019039611 A1 WO2019039611 A1 WO 2019039611A1 JP 2018031460 W JP2018031460 W JP 2018031460W WO 2019039611 A1 WO2019039611 A1 WO 2019039611A1
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Prior art keywords
curable composition
content
group
calcium carbonate
fire resistance
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PCT/JP2018/031460
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French (fr)
Japanese (ja)
Inventor
池内　拓人
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積水フーラー株式会社
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Priority to JP2019537722A priority Critical patent/JP7175510B2/en
Publication of WO2019039611A1 publication Critical patent/WO2019039611A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • E04B1/94—Protection against other undesired influences or dangers against fire

Definitions

  • the present invention relates to a curable composition and a joint structure using the same.
  • the joint structure of the building structure is configured by filling the joint portion formed between the wall members constituting the wall portion with the cured product of the curable composition as a sealing material.
  • the cured product of the curable composition is an organic substance, it is weak against combustion, and the cured product may fall off from the joint at the time of fire, and a flame may intrude from the joint. There is a problem that the fire resistance performance of the wall becomes insufficient.
  • Patent Document 1 100 parts by mass of a polyalkylene ether having a silicon-containing functional group capable of forming a silanol group by hydrolysis, (B) 20 to 150 parts by mass of (B) microencapsulated ammonium polyphosphate powder And (C) 50 to 150 parts by mass of a calcium carbonate powder and (D) 0.1 to 10 parts by mass of a silanol condensation catalyst.
  • the fireproof sealing material forms a carbonized layer film after foaming due to heat at the time of fire, but since the combustion residue becomes brittle due to the foaming, it is easily broken by the wind pressure of the combustion flame and falls off from the joint And the problem is that the fire resistance of the wall of the building structure is still inadequate.
  • the combustion residue generated by combustion is very strong, and even in the case of a fire, the joint portion is surely kept filled to prevent the flame from flowing from the joint portion, and the wall of the building structure
  • a curable composition capable of imparting excellent fire resistance to a part.
  • the curable composition of the present invention is A polyalkylene oxide having a hydrolyzable silyl group, At least one fire resistance imparting compound selected from the group consisting of antimony compounds and glass frits; And calcium carbonate.
  • the polyalkylene oxide contained in the curable composition has a hydrolyzable silyl group.
  • the hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom.
  • the hydrolyzable group of the hydrolyzable silyl group is not particularly limited.
  • alkoxysilyl group is preferable as the hydrolyzable silyl group because the hydrolysis reaction is mild.
  • alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group And a monoalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group.
  • a dialkoxysilyl group is more preferable, a dimethoxysilyl group is particularly preferable, and a propyldimethoxysilyl group is most preferable.
  • the polyalkylene oxide preferably has 1 to 4 hydrolyzable silyl groups on average in one molecule.
  • the polyalkylene oxide preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.
  • the average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide is the concentration of hydrolyzable silyl groups in the polyalkylene oxide determined by 1 H-NMR, and the polyalkylene determined by the GPC method. It can be calculated based on the number average molecular weight of the oxide.
  • the main chain is a general formula:-(R-O) n- (wherein R represents an alkylene group having 1 to 14 carbon atoms, n is the number of repeating units and is positive)
  • R represents an alkylene group having 1 to 14 carbon atoms
  • n is the number of repeating units and is positive
  • the polymer containing the repeating unit represented by this is an integer of is preferably mentioned.
  • the main chain skeleton of the polyalkylene oxide may be composed of only one kind of repeating unit, or may be composed of two or more kinds of repeating units.
  • Examples of the main chain skeleton of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer.
  • polypropylene oxide is preferable. According to polypropylene oxide, it is possible to provide a curable composition having excellent rubber elasticity and adhesiveness after curing.
  • the number average molecular weight of the polyalkylene oxide is preferably 3,000 to 50,000, and more preferably 10,000 to 30,000.
  • cured material of a curable composition improves that the number average molecular weight of a polyalkylene oxide is 3000 or more. When the number average molecular weight of the polyalkylene oxide is 50000 or less, the coatability of the curable composition is improved.
  • the number average molecular weight of the polyalkylene oxide means a value in terms of polystyrene measured by GPC (gel permeation chromatography) method.
  • GPC gel permeation chromatography
  • Shodex KF800D manufactured by Tosoh Corporation can be used as a GPC column, and chloroform or the like can be used as a solvent.
  • polyalkylene oxide containing a hydrolyzable silyl group those commercially available can be used.
  • Polyalkylene oxides having a main chain of polypropylene oxide and a (methoxymethyl) dimethoxysilyl group at the end of polypropylene oxide are commercially available from Kaneka Corporation under the trade name “HS-2”.
  • Polyalkylene oxides having a main chain of polypropylene oxide and an isopropylmethyldimethoxysilyl group at the end of polypropylene oxide are commercially available from Kaneka Corporation under the trade name "SAX 720".
  • the curable composition contains a fire resistance imparting compound.
  • the fire resistance imparting compound contains at least one compound selected from the group consisting of antimony compounds and glass frits.
  • the fire resistance imparting compound contains either or both of an antimony compound and a glass frit.
  • a glass frit is preferred as the fire resistance imparting compound.
  • the antimony-based compound is not particularly limited, and examples thereof include antimony oxide such as antimony trioxide, antimony pentafluoride, and antimony sulfide. Antimony oxide is preferable, and antimony trioxide is more preferable.
  • the content of the antimony compound in the curable composition is preferably 2 to 120 parts by mass, more preferably 5 to 100 parts by mass, with respect to 100 parts by mass of the polyalkylene oxide having hydrolyzable silyl group properties. 90 parts by weight is particularly preferred.
  • the content of the antimony compound is in the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. it can.
  • Glass frit examples of the glass constituting the glass frit include phosphoric acid based glass, boric acid based glass, bismuth oxide based glass, silica based glass, sodium oxide based glass and the like, and phosphoric acid based glass and boric acid based glass Is preferable, and phosphate glass is more preferable.
  • These glass frits include B 2 O 3 , P 2 O 5 , ZnO, SiO 2 , Bi 2 O 3 , Al 2 O 3 , BaO, CaO, MgO, MnO 2 , ZrO 2 , TiO 2 , CeO 2 , SrO , V 2 O 5 , SnO 2 , Li 2 O, Na 2 O, K 2 O, CuO, Fe 2 O 3 or the like at a predetermined component ratio.
  • the softening point of the glass constituting the glass frit is preferably 350 to 650 ° C., more preferably 360 to 560 ° C., particularly preferably 370 to 540 ° C., and most preferably 380 to 520 ° C.
  • the content of the glass frit in the curable composition is preferably 1 to 80 parts by mass, more preferably 3 to 70 parts by mass, with respect to 100 parts by mass of the hydrolyzable silyl group-containing polyalkylene oxide. Parts by weight are particularly preferred, and 5 to 50 parts by weight are most preferred.
  • the content of the glass frit is in the above range, the combustion residue of the cured product of the curable composition can be stably held in the joint portion, and the wall portion of the building structure can be provided with excellent fire resistance performance. .
  • the fire resistance imparting compound contains an antimony compound and a glass frit
  • the ratio of the content of the antimony compound to the content of the glass frit is 0. 1 to 9 is preferable, 0.5 to 8 is more preferable, 0.8 to 7 is particularly preferable, and 1.6 to 6 is most preferable.
  • the curable composition contains calcium carbonate.
  • the calcium carbonate is not particularly limited, and examples thereof include colloidal calcium carbonate, ground calcium carbonate, light calcium carbonate and the like, colloidal calcium carbonate and ground calcium carbonate are preferable, and both colloidal calcium carbonate and ground calcium carbonate are preferable. It is more preferable to contain.
  • the average particle size of calcium carbonate is preferably 0.01 to 5 ⁇ m, and more preferably 0.05 to 2.5 ⁇ m. According to calcium carbonate having such an average particle diameter, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. can do.
  • the average particle diameter of calcium carbonate is a magnified image of 20000 ⁇ magnification using SEM, and the diameter of 10 arbitrary calcium carbonates shown in the photograph is measured, and the arithmetic mean of the diameter of each calcium carbonate It says the value.
  • the diameter of calcium carbonate means the diameter of the perfect circle of the minimum diameter which can surround calcium carbonate.
  • calcium carbonate is preferably surface-treated with a fatty acid or fatty acid ester. According to calcium carbonate surface-treated with a fatty acid or fatty acid ester, etc., it is possible to impart thixotropy to the curable composition and to suppress aggregation of calcium carbonate.
  • the content of calcium carbonate in the curable composition is preferably 1 to 700 parts by mass, more preferably 5 to 300 parts by mass, with respect to 100 parts by mass of the hydrolyzable silyl group-containing polyalkylene oxide. Parts by weight are particularly preferred.
  • the content of calcium carbonate in the curable composition is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the fire resistance performance excellent in the wall portion of the building structure Can be granted.
  • the ratio of the content of calcium carbonate to the content of the fire resistance imparting compound is preferably 2 to 20, more preferably 2 to 10 Preferably, 2 to 5 are particularly preferred.
  • the ratio of the content of calcium carbonate to the content of the fire resistance imparting compound is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure Excellent fire resistance performance.
  • the ratio of the content of calcium carbonate to the content of the antimony compound is preferably 2 to 20. And 2 to 10 are more preferable, and 2 to 5 are particularly preferable.
  • the ratio of the content of calcium carbonate to the content of the antimony compound is within the above range, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is Excellent fire resistance can be imparted.
  • the ratio of the content of calcium carbonate to the content of glass frit is preferably 3 to 10, and 4 to 10 8 is more preferable, and 4 to 6 is particularly preferable.
  • the ratio of the content of calcium carbonate to the content of glass frit is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure is excellent. Fire resistance performance can be imparted.
  • the curable composition may contain an acrylic polymer.
  • the acrylic polymer may have a hydrolyzable silyl group.
  • the hydrolyzable group of the hydrolyzable silyl group is not particularly limited.
  • alkoxysilyl group is preferable as the hydrolyzable silyl group because the hydrolysis reaction is mild.
  • alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group And a monoalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group.
  • a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.
  • the acrylic polymer preferably has 0.3 or more hydrolyzable silyl groups on average in one molecule, and 0.5 or more hydrolyzable silyl groups. Is preferred.
  • the acrylic polymer preferably has, on average, 2.0 or less hydrolyzable silyl groups in one molecule, and has 1.8 or less hydrolyzable silyl groups. Is preferred.
  • the number of hydrolyzable silyl groups in the acrylic polymer is 0.3 or more, the curability of the curable composition is improved.
  • the number of hydrolyzable silyl groups in the acrylic polymer is 2.0 or less, the mechanical strength or extensibility of the cured product of the curable composition is improved.
  • the acrylic polymer preferably has a hydrolyzable silyl group at the side chain or end of the main chain, and has a hydrolyzable silyl group at at least one of both ends of the main chain. It is more preferable to have hydrolyzable silyl groups at both ends of the main chain.
  • having a hydrolyzable silyl group in the side chain of the main chain skeleton means that a hydrolyzable silyl group is contained as a side chain in the main chain skeleton, and It includes both cases where hydrolyzable silyl group is contained in part of the side chain.
  • the flexibility of the cured product of the curable composition is improved, and the maximum load of the cured product of the curable composition is obtained.
  • the elongation at the time is high, and the cured product can reliably keep the joint portion filled.
  • the method for introducing a hydrolyzable silyl group into an acrylic polymer is not particularly limited. For example, after introducing an unsaturated group into a copolymer of monomers constituting the main chain skeleton, a hydrolyzable silyl is introduced. The method of making it act on the hydrosilane which has group, and hydrosilylating etc. are mentioned.
  • the average number of hydrolyzable silyl groups per molecule in the acrylic polymer can be determined by the concentration of hydrolyzable silyl groups in the acrylic polymer determined by 1 H-NMR, and the GPC method. It can be calculated based on the number average molecular weight of the acrylic polymer.
  • the main chain skeleton of the acrylic polymer is a copolymer of a monomer containing methyl (meth) acrylate and butyl (meth) acrylate, a single amount containing n-butyl (meth) acrylate and n-octadecyl (meth) acrylate Copolymers are preferred, copolymers of monomers containing methyl methacrylate and butyl acrylate, copolymers of monomers containing n-butyl acrylate and n-octadecyl acrylate are more preferable, and n-butyl acrylate is preferable Particularly preferred is a copolymer of monomers containing n-octadecyl acrylate.
  • (meth) acrylate means methacrylate and / or acrylate.
  • the content of the methyl (meth) acrylate component is preferably 3 to 70% by mass, and more preferably 5 to 50% by mass.
  • the content of the methyl (meth) acrylate component being 3% by mass or more, the adhesiveness of the cured product of the curable composition is improved.
  • the content of the methyl (meth) acrylate component is 70% by mass or less, the flexibility of the cured product of the curable composition is improved, and the elongation at the maximum load of the cured product of the curable composition is increased, and curing is achieved. It is possible to reliably hold the state in which the object has filled the joint.
  • the content of the butyl (meth) acrylate component is preferably 30 to 97% by mass, and more preferably 50 to 95% by mass.
  • the content of the butyl (meth) acrylate component is 30% by mass or more, the flexibility of the cured product of the curable composition is improved, and the elongation at the maximum load of the cured product of the curable composition is increased, and curing is achieved. It is possible to reliably hold the state in which the object has filled the joint.
  • the monomer used for the polymer constituting the main chain skeleton may further contain other monomers in addition to methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate .
  • Other monomers include, for example, styrene, styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene and the like
  • Derivatives compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate, etc., maleic anhydride, N-vinyl pyrrolidone, N-vinyl morpholine, methacrylo Nitrile, acrylonitrile
  • a well-known method can be used, For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method, living Various polymerization methods such as a cationic polymerization method and a living radical polymerization method can be mentioned.
  • the weight average molecular weight of the acrylic polymer is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and particularly preferably 3,000 to 15,000. According to the acrylic polymer having a weight average molecular weight in the above range, the flexibility of the cured product of the curable composition is improved, the elongation at maximum load of the cured product of the curable composition is increased, and the cured product is The state in which the joint portion is filled can be reliably maintained.
  • the content of the acrylic polymer in the curable composition is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. 100 parts by weight is particularly preferred.
  • the adhesiveness of a curable composition improves that content of the acrylic polymer in a curable composition is 5 mass parts or more.
  • the content of the acrylic polymer in the curable composition is 300 parts by mass or less, the flexibility of the cured product of the curable composition is improved, and the elongation at maximum load of the cured product of the curable composition is high. As a result, the cured product can reliably hold the joint portion filled.
  • plasticizer for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, phthalic acid Phthalates such as dinonyl, diisodecyl phthalate, diisoundecyl phthalate, and bisbutyl benzyl phthalate; Polyalkylenes such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, etc. Glycol is mentioned. Among them, polyalkylene glycol is preferable, and polypropylene glycol is more preferable.
  • the number average molecular weight of the polyalkylene glycol is preferably 1000 to 10000, and more preferably 2000 to 5000. When the number average molecular weight of the polyalkylene glycol is within the above range, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. Can.
  • the number average molecular weight of the polyalkylene glycol is a value measured by converting the number average molecular weight of the polyalkylene oxide into polystyrene by GPC (gel permeation chromatography) method.
  • GPC gel permeation chromatography
  • the content of the plasticizer in the curable composition is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.
  • the curable composition preferably further contains a dehydrating agent. According to the dehydrating agent, when the curable composition is stored, it is possible to suppress that the curable composition is cured by water contained in the air or the like.
  • silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthoformate And ester compounds such as ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate.
  • dehydrating agents may be used alone or in combination of two or more. Among them, vinyltrimethoxysilane is preferable.
  • the content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.
  • the content of the dehydrating agent in the curable composition is 0.5 parts by mass or more, the effects obtained by the dehydrating agent are sufficiently obtained.
  • the curable composition has excellent curability when the content of the dehydrating agent in the curable composition is 20 parts by mass or less.
  • the curable composition preferably contains a silanol condensation catalyst.
  • the silanol condensation catalyst is a catalyst for promoting the dehydration condensation reaction of silanol groups formed by hydrolysis of a hydrolyzable silyl group or the like contained in a polyalkylene oxide having a hydrolyzable silyl group.
  • silanol condensation catalyst 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin lauric acid) ) Oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (monoester malate), tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis (triethoxy silicate), bis (dibutyltin bis triethoxy silicate) And organic tin compounds such as dibutyltin oxybisethoxy silicate; and organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate.
  • silanol condensation catalyst 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane is preferred. According to such a silanol condensation catalyst, the curing rate of the curable composition can be easily adjusted.
  • the content of the silanol condensation catalyst in the curable composition is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.
  • the curing rate of the curable composition can be increased, and the time required for curing of the curable composition can be shortened.
  • the curable composition has an appropriate curing rate to improve the storage stability and the handleability of the curable composition. be able to.
  • the curable composition may contain other additives such as a thixotropic agent, an antioxidant, a UV absorber, a pigment, a dye, an antisettling agent, and a solvent.
  • a thixotropic agent, a UV absorber, and an antioxidant are preferably mentioned.
  • the thixotropic agent may be any agent capable of exhibiting thixotropic properties in the curable composition.
  • a thixotropic agent hydrogenated castor oil, fatty acid bisamide, fumed silica and the like are preferably mentioned.
  • the content of the thixotropic agent in the curable composition is preferably 0.1 to 200 parts by mass, and more preferably 1 to 150 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.
  • the content of the thixotropic agent in the curable composition is 0.1 parts by mass or more, thixotropic properties can be effectively imparted to the curable composition.
  • the content of the thixotropic agent in the curable composition is 200 parts by mass or less, the curable composition has an appropriate viscosity, and the handleability of the curable composition is improved.
  • the content of the ultraviolet light absorber in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. .
  • antioxidants examples include hindered phenol-based antioxidants, monophenol-based antioxidants, bisphenol-based antioxidants, polyphenol-based antioxidants and the like, and hindered phenol-based antioxidants are preferably mentioned.
  • the content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. .
  • the curable composition preferably contains a hindered amine light stabilizer. According to the hindered amine light stabilizer, a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing can be provided.
  • hindered amine light stabilizer for example, a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine ⁇ 1,3,5-triazine ⁇ N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, polycondensate, poly [ ⁇ 6- (1,1,3,3- Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6) -Tetramethyl 4-piperidyl) imin
  • NOR type hindered amine light stabilizer is mentioned preferably. According to the NOR type hindered amine light stabilizer, it is possible to provide a curable composition in which a decrease in rubber elasticity with time after curing is suppressed.
  • the NOR type hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in a piperidine ring skeleton via an oxygen atom (O).
  • the carbon number of the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18.
  • Examples of the alkyl group include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups (saturated alicyclic hydrocarbon groups).
  • linear alkyl group for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group Groups and the like.
  • branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl and the like.
  • a cyclic alkyl group saturated alicyclic hydrocarbon group
  • a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example.
  • a hydrogen atom constituting an alkyl group may be substituted by a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a hydroxyl group.
  • Examples of the NOR type hindered amine light stabilizer include hindered amine light stabilizers represented by the following formula (I).
  • NOR type hindered amine light stabilizer When a NOR type hindered amine light stabilizer is used, it is preferable to use a combination of a NOR type hindered amine light stabilizer and a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber. This makes it possible to provide a curable composition in which the decrease in rubber elasticity with time after curing is suppressed to a higher level.
  • the content of the hindered amine light stabilizer in the curable composition is preferably 0.01 to 20 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. More preferable.
  • the curable composition can be produced by adding the above-described compound to the polyalkylene oxide, the fire resistance imparting compound and calcium carbonate as required, and mixing them.
  • the maximum load elongation of the cured product of the curable composition is preferably 300 to 800%, more preferably 400 to 700%, and particularly preferably 570 to 650%.
  • the maximum load elongation of the cured product of the curable composition is measured in the following manner. First, an H-type test body is produced using a curable composition according to JIS A1439 4.21. Specifically, using two aluminum plates (50 mm long ⁇ 50 mm wide ⁇ 3 mm thick) alumite-treated, a rectangular parallelepiped space (long 12 mm ⁇ horizontal 50 mm ⁇ height 12 mm). The curable composition is filled into this space so that air does not enter.
  • the curable composition After loading the curable composition, the curable composition is left to stand for 14 days under an atmosphere of temperature 23 ° C. and relative humidity 50%. Thereafter, the curable composition is further left to stand for 14 days in an atmosphere at a temperature of 30 ° C.
  • an H-type test body in which two aluminum plates are bonded and integrated by the cured product of the curable composition is produced. Then, with respect to the H-shaped test body immediately after preparation, a tensile test at a tensile speed of 50 mm / min is performed in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% according to JIS A1439, and elongation at maximum load [%] taking measurement.
  • Burn residual ⁇ of the cured product of the curable composition is preferably 0.2 ⁇ 3.5N / mm 2, more preferably 0.5 ⁇ 3N / mm 2, 0.65 ⁇ 2.5N / mm 2 Gayori
  • 1.0 to 2.0 N / mm 2 is particularly preferred.
  • the combustion residue strength of the cured product of the curable composition is measured in the following manner. First, the curable composition is applied on a zinc sheet so as to have a thickness of 10 mm, a width of 10 mm and a length of 50 mm, and the curable composition is cured for 1 month in an environment of 23 ° C. and 50% relative humidity. And the curable composition is cured to obtain a cured product.
  • the cured product of the curable composition is left to burn in a thermostat at 600 ° C. for 30 minutes, taken out of the thermostat, and left in an atmosphere at 23 ° C. for 3 hours to obtain a combustion residue.
  • the film strength of the combustion residue is measured by compressing the combustion residue with a 1.5 mm diameter needle at a compression speed of 50 mm / min using a universal testing machine, and the film strength is the combustion residue strength of the cured product of the curable composition. I assume.
  • the joint structure obtained includes the wall member constituting the wall portion of the building structure, and the cured product of the curable composition filled in the joint portion formed between the adjacent wall members.
  • a wall part of a building structure an outer wall, an inner wall, a ceiling part etc. are mentioned, for example.
  • a wall member, an outer wall member, an inner wall member, a ceiling member etc. are mentioned, for example.
  • the joint portion is not particularly limited, and examples include joint portions in the outer wall, the inner wall, and the ceiling of the building structure. Since the curable composition can maintain excellent rubber elasticity for a long time after curing, it causes joints due to expansion or contraction of members due to temperature change such as air temperature or sunshine, or by action such as vibration or wind pressure. It can keep up with the change of the width of the frame and prevent the damage of the member and the water leakage into the building structure. Therefore, it is suitably used to seal a joint having a large change in width, also called a "working joint", such as a joint in an outer wall of a building structure.
  • the joints in the outer wall of the building structure include, for example, joints made of joints between outer wall members such as mortar boards, concrete boards, ceramic siding boards, metal siding boards, ALC boards, and metal sheets. .
  • cured material of a curable composition produces a strong combustion residue by combustion, and this combustion residue certainly hold
  • the combustion residue generated by combustion is very strong, and the combustion residue fills the joint and reliably maintains the closed state even in the case of a fire, thereby ensuring that the joint remains closed. It is possible to prevent the spread of the flame and to provide the wall part of the building structure with excellent fire resistance.
  • Polyalkylene oxide having hydrolyzable silyl group (polyalkylene oxide having a main chain skeleton of polypropylene oxide and having a propyldimethoxysilyl group at the end of the main chain, average number of propyldimethoxysilyl groups per molecule: 1. Four, number average molecular weight: 20000, manufactured by Kaneka Corp.
  • VY0053 main component: P 2 O 5 , AI 2 O 3 and R 2 O, R is an alkali metal atom, softening temperature: 550 ° C.
  • Glass frit C boric acid glass, manufactured by Nippon Frit Co., "CY0086”, main component: B 2 O 3 , ZnO and RO, R is an alkaline earth metal atom, softening temperature: 569 ° C.
  • Acrylic polymers (acrylic polymers containing methyldimethoxysilyl groups at both ends of the main chain, average number of methyldimethoxysilyl groups per molecule: 1.7, number average molecular weight: 28,000, manufactured by Kaneka Corporation Product name "SA310S”) ⁇
  • Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, manufactured by Nitto Kasei Co., Ltd., trade name "NEOSTAN U-130"
  • Dehydrating agent (viny
  • Examples 1 to 13 and Comparative Examples 1 and 2 Polyalkylene oxide having hydrolyzable silyl group, antimony trioxide, colloidal calcium carbonate, calcium carbonate calcium, glass frits AC, acrylic polymer, silanol condensation catalyst, dehydrating agent, aminosilane coupling agent, benzotriazole type UV absorber, hindered phenolic antioxidant, NH type hindered amine light stabilizer, thixotropic agent and aliphatic amine in the amounts shown in Table 1, using a planetary mixer under a vacuum atmosphere The curable composition was obtained by mixing until uniform over 60 minutes.
  • the present invention produces a very strong combustion residue upon combustion.
  • a joint structure can be obtained by applying the curable composition to the joint.
  • the cured product of the present invention forms a combustion residue in the event of a fire, and the combustion residue securely fills the joint and keeps the blockage even in the case of a fire, thereby preventing the flame from flowing from the joint.
  • Excellent fire resistance can be imparted to the wall portion of the building structure.

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Abstract

The present invention provides a curable composition that has an extremely solid combustion residue generated from combustion, reliably holds a state in which joints are filled even during fires so as to prevent flames from flaring from joints, and is capable of imparting excellent fire resistance to walls in a building structure. This curable composition has an extremely solid combustion residue generated from combustion since said composition contains: a polyalkylene oxide having a hydrolyzable silyl group; at least one fire-resistance-imparting compound selected from the group consisting of antimony compounds and glass frits; and calcium carbonate. The combustion residue fills joints so as to reliably hold the blocked state even during fires and prevent flames from flaring from joints, and is capable of imparting excellent fire resistance to walls in a building structure.

Description

硬化性組成物及びこれを用いてなる目地構造Curable composition and joint structure using the same
　本発明は、硬化性組成物及びこれを用いてなる目地構造に関する。 The present invention relates to a curable composition and a joint structure using the same.
　建築構造物の目地構造は、壁部を構成している壁部材間に形成された目地部に、硬化性組成物の硬化物をシーリング材として充填することによって構成されている。 The joint structure of the building structure is configured by filling the joint portion formed between the wall members constituting the wall portion with the cured product of the curable composition as a sealing material.
　上記目地構造において、硬化性組成物の硬化物は有機物であるため、燃焼に対して弱く、火災時に硬化物が目地部から脱落し、目地部から炎が廻り込むことがあり、建築構造物の壁部の耐火性能が不十分となるという問題点を有している。 In the joint structure described above, since the cured product of the curable composition is an organic substance, it is weak against combustion, and the cured product may fall off from the joint at the time of fire, and a flame may intrude from the joint. There is a problem that the fire resistance performance of the wall becomes insufficient.
　そこで、特許文献１には、（Ａ）末端に加水分解によってシラノール基を形成しうるケイ素含有官能基をもつポリアルキレンエーテル１００質量部、（Ｂ）マイクロカプセル化ポリリン酸アンモニウム粉末２０～１５０質量部、（Ｃ）炭酸カルシウム粉末５０～１５０質量部及び（Ｄ）シラノール縮合触媒０．１～１０質量部からなることを特徴とする耐久性を有する防火性シーリング材が開示されている。 Therefore, in Patent Document 1, (A) 100 parts by mass of a polyalkylene ether having a silicon-containing functional group capable of forming a silanol group by hydrolysis, (B) 20 to 150 parts by mass of (B) microencapsulated ammonium polyphosphate powder And (C) 50 to 150 parts by mass of a calcium carbonate powder and (D) 0.1 to 10 parts by mass of a silanol condensation catalyst.
特許第３８４８３７９号公報Patent No. 3848 379
　しかしながら、防火性シーリング材は、火災時の熱によって発泡した後、炭化層膜を形成するが、発泡により燃焼残渣が脆くなるため、燃焼炎の風圧によって容易に破壊し、目地部からの脱落を生じ、建築構造物の壁部の耐火性能が依然として不十分であるという問題点を有する。 However, the fireproof sealing material forms a carbonized layer film after foaming due to heat at the time of fire, but since the combustion residue becomes brittle due to the foaming, it is easily broken by the wind pressure of the combustion flame and falls off from the joint And the problem is that the fire resistance of the wall of the building structure is still inadequate.
　本発明は、燃焼により生成された燃焼残渣が非常に強固であり、火災時においても目地部を充填した状態を確実に保持して目地部からの炎の回り込みを阻止し、建築構造物の壁部に優れた耐火性能を付与することができる硬化性組成物を提供する。 According to the present invention, the combustion residue generated by combustion is very strong, and even in the case of a fire, the joint portion is surely kept filled to prevent the flame from flowing from the joint portion, and the wall of the building structure Provided is a curable composition capable of imparting excellent fire resistance to a part.
　本発明の硬化性組成物は、
　加水分解性シリル基を有するポリアルキレンオキサイドと、
　アンチモン系化合物及びガラスフリットからなる群から選ばれた少なくとも一種の耐火性付与化合物と、
　炭酸カルシウムとを含有する。 The curable composition of the present invention is
A polyalkylene oxide having a hydrolyzable silyl group,
At least one fire resistance imparting compound selected from the group consisting of antimony compounds and glass frits;
And calcium carbonate.
［ポリアルキレンオキサイド］
　硬化性組成物に含まれているポリアルキレンオキサイドは、加水分解性シリル基を有している。加水分解性シリル基とは、珪素原子に１～３個の加水分解性基が結合してなる基である。 [Polyalkylene oxide]
The polyalkylene oxide contained in the curable composition has a hydrolyzable silyl group. The hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom.
　加水分解性シリル基の加水分解性基としては、特に限定されず、例えば、水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などが挙げられる。 The hydrolyzable group of the hydrolyzable silyl group is not particularly limited. For example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, an acid amide group, an aminooxy group, mercapto And alkenyloxy groups.
　なかでも、加水分解性シリル基としては、加水分解反応が穏やかであることから、アルコキシシリル基が好ましい。アルコキシシリル基としては、トリメトキシシリル基、トリエトキシシリル基、トリイソプロポキシシリル基、及びトリフェノキシシリル基などのトリアルコキシシリル基；プロピルジメトキシシリル基、メチルジメトキシシリル基、及びメチルジエトキシシリル基などのジアルコキシシリル基；並びに、ジメチルメトキシシリル基、及びジメチルエトキシシリル基などのモノアルコキシシリル基が挙げられる。なかでも、ジアルコキシシリル基がより好ましく、ジメトキシシリル基が特に好ましく、プロピルジメトキシシリル基が最も好ましい。 Among them, an alkoxysilyl group is preferable as the hydrolyzable silyl group because the hydrolysis reaction is mild. Examples of alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group And a monoalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group. Among them, a dialkoxysilyl group is more preferable, a dimethoxysilyl group is particularly preferable, and a propyldimethoxysilyl group is most preferable.
　ポリアルキレンオキサイドは、１分子中に平均して、１～４個の加水分解性シリル基を有していることが好ましい。ポリアルキレンオキサイドにおける加水分解性シリル基の数が上記範囲内にあると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。また、ポリアルキレンオキサイドは、その主鎖の両末端のうち少なくとも一方に加水分解性シリル基を有していることが好ましい。 The polyalkylene oxide preferably has 1 to 4 hydrolyzable silyl groups on average in one molecule. When the number of hydrolyzable silyl groups in the polyalkylene oxide is in the above range, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the fire resistance performance excellent in the wall portion of the building structure Can be granted. The polyalkylene oxide preferably has a hydrolyzable silyl group at at least one of both ends of its main chain.
　なお、ポリアルキレンオキサイド中における、１分子当たりの加水分解性シリル基の平均個数は、1Ｈ－ＮＭＲにより求められるポリアルキレンオキサイド中の加水分解性シリル基の濃度、及びＧＰＣ法により求められるポリアルキレンオキサイドの数平均分子量に基づいて算出することができる。 The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide is the concentration of hydrolyzable silyl groups in the polyalkylene oxide determined by 1 H-NMR, and the polyalkylene determined by the GPC method. It can be calculated based on the number average molecular weight of the oxide.
　ポリアルキレンオキサイドとしては、主鎖が、一般式：－（Ｒ－Ｏ）n－（式中、Ｒは炭素数が１～１４のアルキレン基を表し、ｎは、繰り返し単位の数であって正の整数である。）で表される繰り返し単位を含有する重合体が好ましく挙げられる。ポリアルキレンオキサイドの主鎖骨格は一種のみの繰り返し単位からなっていてもよいし、二種以上の繰り返し単位からなっていてもよい。 As the polyalkylene oxide, the main chain is a general formula:-(R-O) n- (wherein R represents an alkylene group having 1 to 14 carbon atoms, n is the number of repeating units and is positive) The polymer containing the repeating unit represented by this is an integer of is preferably mentioned. The main chain skeleton of the polyalkylene oxide may be composed of only one kind of repeating unit, or may be composed of two or more kinds of repeating units.
　ポリアルキレンオキサイドの主鎖骨格としては、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリブチレンオキサイド、ポリテトラメチレンオキサイド、ポリエチレンオキサイド－ポリプロピレンオキサイド共重合体、及びポリプロピレンオキサイド－ポリブチレンオキサイド共重合体などが挙げられる。なかでも、ポリプロピレンオキサイドが好ましい。ポリプロピレンオキサイドによれば、硬化後に優れたゴム弾性及び接着性に優れる硬化性組成物を提供することができる。 Examples of the main chain skeleton of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. Among them, polypropylene oxide is preferable. According to polypropylene oxide, it is possible to provide a curable composition having excellent rubber elasticity and adhesiveness after curing.
　ポリアルキレンオキサイドの数平均分子量は、３０００～５００００が好ましく、１００００～３００００がより好ましい。ポリアルキレンオキサイドの数平均分子量が３０００以上であると、硬化性組成物の硬化物の機械的強度又は伸び性が向上する。ポリアルキレンオキサイドの数平均分子量が５００００以下であると、硬化性組成物の塗工性が向上する。 The number average molecular weight of the polyalkylene oxide is preferably 3,000 to 50,000, and more preferably 10,000 to 30,000. The mechanical strength or extensibility of the hardened | cured material of a curable composition improves that the number average molecular weight of a polyalkylene oxide is 3000 or more. When the number average molecular weight of the polyalkylene oxide is 50000 or less, the coatability of the curable composition is improved.
　なお、本発明において、ポリアルキレンオキサイドの数平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法によって測定されたポリスチレン換算した値を意味する。ＧＰＣ法による測定においては、例えば、ＧＰＣカラムとして東ソー製Ｓｈｏｄｅｘ　ＫＦ８００Ｄを用い、溶媒としてクロロホルムなどを用いることができる。 In the present invention, the number average molecular weight of the polyalkylene oxide means a value in terms of polystyrene measured by GPC (gel permeation chromatography) method. In the measurement by the GPC method, for example, Shodex KF800D manufactured by Tosoh Corporation can be used as a GPC column, and chloroform or the like can be used as a solvent.
　加水分解性シリル基を含有しているポリアルキレンオキサイドは、市販されているものを用いることができる。例えば、カネカ社製　商品名「ＭＳポリマー　Ｓ－２０３」、「ＭＳポリマー　Ｓ－３０３」、「サイリルポリマー　ＳＡＴ－２００」、「サイリルポリマー　ＳＡＴ－３５０」及び「サイリルポリマー　ＳＡＴ－４００」、旭硝子社製　商品名「エクセスター　ＥＳＳ－３６２０」、「エクセスター　ＥＳＳ－２４２０」、「エクセスター　ＥＳＳ２４１０」及び「エクセスター　ＥＳＳ３４３０」などが挙げられる。 As the polyalkylene oxide containing a hydrolyzable silyl group, those commercially available can be used. For example, trade name "MS Polymer S-203", "MS Polymer S-303", "Syryl Polymer SAT-200" manufactured by Kaneka Corporation, "Syryl Polymer SAT-350" and "Syryl Polymer SAT-400", Asahi Glass Co., Ltd. trade name "Exester ESS-3620", "Exester ESS-2420", "Exester ESS 2410", "Exester ESS 3430" and the like.
　主鎖がポリプロピレンオキサイドで且つポリプロピレンオキサイドの末端に（メトキシメチル）ジメトキシシリル基を有しているポリアルキレンオキサイドは、カネカ社から商品名「ＨＳ－２」にて市販されている。 Polyalkylene oxides having a main chain of polypropylene oxide and a (methoxymethyl) dimethoxysilyl group at the end of polypropylene oxide are commercially available from Kaneka Corporation under the trade name “HS-2”.
　主鎖がポリプロピレンオキサイドで且つポリプロピレンオキサイドの末端にイソプロピルメチルジメトキシシリル基を有しているポリアルキレンオキサイドは、カネカ社から商品名「ＳＡＸ７２０」にて市販されている。 Polyalkylene oxides having a main chain of polypropylene oxide and an isopropylmethyldimethoxysilyl group at the end of polypropylene oxide are commercially available from Kaneka Corporation under the trade name "SAX 720".
［耐火性付与化合物］
　硬化性組成物は、耐火性付与化合物を含有している。耐火性付与化合物は、アンチモン系化合物及びガラスフリットからなる群から選ばれた少なくとも一種の化合物を含有している。 [Fireproofing compound]
The curable composition contains a fire resistance imparting compound. The fire resistance imparting compound contains at least one compound selected from the group consisting of antimony compounds and glass frits.
　即ち、耐火性付与化合物は、アンチモン系化合物及びガラスフリットの何れか一方又は双方を含有している。耐火性付与化合物としてはガラスフリットが好ましい。 That is, the fire resistance imparting compound contains either or both of an antimony compound and a glass frit. A glass frit is preferred as the fire resistance imparting compound.
［アンチモン系化合物］
　アンチモン系化合物としては、特に限定されず、例えば、三酸化アンチモンなどの酸化アンチモン、五フッ化アンチモン、硫化アンチモンなどが挙げられ、酸化アンチモンが好ましく、三酸化アンチモンがより好ましい。 [Antimony compounds]
The antimony-based compound is not particularly limited, and examples thereof include antimony oxide such as antimony trioxide, antimony pentafluoride, and antimony sulfide. Antimony oxide is preferable, and antimony trioxide is more preferable.
　硬化性組成物中におけるアンチモン系化合物の含有量は、加水分解性シリル基性を有するポリアルキレンオキサイド１００質量部に対して２～１２０質量部が好ましく、５～１００質量部がより好ましく、８～９０質量部が特に好ましい。アンチモン系化合物の含有量が上記範囲内にあると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 The content of the antimony compound in the curable composition is preferably 2 to 120 parts by mass, more preferably 5 to 100 parts by mass, with respect to 100 parts by mass of the polyalkylene oxide having hydrolyzable silyl group properties. 90 parts by weight is particularly preferred. When the content of the antimony compound is in the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. it can.
［ガラスフリット］
　ガラスフリットを構成しているガラスとしては、たとえば、リン酸系ガラス、ホウ酸系ガラス、酸化ビスマス系ガラス、珪酸系ガラス、酸化ナトリウム系ガラスなどが挙げられ、リン酸系ガラス、ホウ酸系ガラスが好ましく、リン酸系ガラスがより好ましい。これらのガラスフリットは、Ｂ2Ｏ3、Ｐ2Ｏ5、ＺｎＯ、ＳｉＯ2、Ｂｉ2Ｏ3、Ａｌ2Ｏ3、ＢａＯ、ＣａＯ、ＭｇＯ、ＭｎＯ2、ＺｒＯ2、ＴｉＯ2、ＣｅＯ2、ＳｒＯ、Ｖ2Ｏ5、ＳｎＯ2、Ｌｉ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ、ＣｕＯ、Ｆｅ2Ｏ3などを所定の成分割合で調整して得ることができる。 [Glass frit]
Examples of the glass constituting the glass frit include phosphoric acid based glass, boric acid based glass, bismuth oxide based glass, silica based glass, sodium oxide based glass and the like, and phosphoric acid based glass and boric acid based glass Is preferable, and phosphate glass is more preferable. These glass frits include B 2 O 3 , P 2 O 5 , ZnO, SiO 2 , Bi 2 O 3 , Al 2 O 3 , BaO, CaO, MgO, MnO 2 , ZrO 2 , TiO 2 , CeO 2 , SrO , V 2 O 5 , SnO 2 , Li 2 O, Na 2 O, K 2 O, CuO, Fe 2 O 3 or the like at a predetermined component ratio.
　ガラスフリットを構成しているガラスの軟化点は３５０～６５０℃が好ましく、３６０～５６０℃がより好ましく、３７０～５４０℃が特に好ましく、３８０～５２０℃が最も好ましい。ガラスフリットを構成しているガラスの軟化点が上記範囲内にあると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。なお、ガラスフリットを構成しているガラスの軟化点は、ガラスの粘度が１０７．６ｄＰａ・ｓ（ｌｏｇη＝７．６）となる温度である。 The softening point of the glass constituting the glass frit is preferably 350 to 650 ° C., more preferably 360 to 560 ° C., particularly preferably 370 to 540 ° C., and most preferably 380 to 520 ° C. When the softening point of the glass constituting the glass frit is in the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the fire resistance performance excellent in the wall portion of the building structure Can be granted. The softening point of the glass constituting the glass frit is a temperature at which the viscosity of the glass is 107.6 dPa · s (log == 7.6).
　硬化性組成物中におけるガラスフリットの含有量は、加水分解性シリル基性を有するポリアルキレンオキサイド１００質量部に対して１～８０質量部が好ましく、３～７０質量部がより好ましく、４～６０質量部が特に好ましく、５～５０質量部が最も好ましい。ガラスフリットの含有量が上記範囲内にあると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 The content of the glass frit in the curable composition is preferably 1 to 80 parts by mass, more preferably 3 to 70 parts by mass, with respect to 100 parts by mass of the hydrolyzable silyl group-containing polyalkylene oxide. Parts by weight are particularly preferred, and 5 to 50 parts by weight are most preferred. When the content of the glass frit is in the above range, the combustion residue of the cured product of the curable composition can be stably held in the joint portion, and the wall portion of the building structure can be provided with excellent fire resistance performance. .
　耐火性付与化合物がアンチモン系化合物及びガラスフリットを含有している場合、アンチモン系化合物の含有量とガラスフリットの含有量との比率（アンチモン系化合物の含有量／ガラスフリットの含有量）は０．１～９が好ましく、０．５～８がより好ましく、０．８～７が特に好ましく、１．６～６が最も好ましい。 When the fire resistance imparting compound contains an antimony compound and a glass frit, the ratio of the content of the antimony compound to the content of the glass frit (the content of the antimony compound / the content of the glass frit) is 0. 1 to 9 is preferable, 0.5 to 8 is more preferable, 0.8 to 7 is particularly preferable, and 1.6 to 6 is most preferable.
［炭酸カルシウム］
　硬化性組成物は、炭酸カルシウムを含有している。 [Calcium carbonate]
The curable composition contains calcium carbonate.
　炭酸カルシウムとしては、特に限定されず、例えば、コロイダル炭酸カルシウム、重質炭酸カルシウム、軽質炭酸カルシウムなどが挙げられ、コロイダル炭酸カルシウム及び重質炭酸カルシウムが好ましく、コロイダル炭酸カルシウム及び重質炭酸カルシウムを双方含有していることがより好ましい。 The calcium carbonate is not particularly limited, and examples thereof include colloidal calcium carbonate, ground calcium carbonate, light calcium carbonate and the like, colloidal calcium carbonate and ground calcium carbonate are preferable, and both colloidal calcium carbonate and ground calcium carbonate are preferable. It is more preferable to contain.
　炭酸カルシウムの平均粒子径は、０．０１～５μｍが好ましく、０．０５～２．５μｍがより好ましい。このような平均粒子径を有している炭酸カルシウムによれば、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。なお、炭酸カルシウムの平均粒子径は、ＳＥＭを用いて倍率２００００倍の拡大写真を撮影し、写真にあらわれた任意の１０個の炭酸カルシウムの直径を測定し、各炭酸カルシウムの直径の相加平均値をいう。なお、炭酸カルシウムの直径とは、炭酸カルシウムを包囲し得る最小径の真円の直径をいう。 The average particle size of calcium carbonate is preferably 0.01 to 5 μm, and more preferably 0.05 to 2.5 μm. According to calcium carbonate having such an average particle diameter, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. can do. In addition, the average particle diameter of calcium carbonate is a magnified image of 20000 × magnification using SEM, and the diameter of 10 arbitrary calcium carbonates shown in the photograph is measured, and the arithmetic mean of the diameter of each calcium carbonate It says the value. In addition, the diameter of calcium carbonate means the diameter of the perfect circle of the minimum diameter which can surround calcium carbonate.
　また、炭酸カルシウムは、脂肪酸や脂肪酸エステルなどにより表面処理されているのが好ましい。脂肪酸や脂肪酸エステルなどにより表面処理されている炭酸カルシウムによれば、硬化性組成物にチキソトロピー性を付与できると共に炭酸カルシウムが凝集することを抑制することができる。 Further, calcium carbonate is preferably surface-treated with a fatty acid or fatty acid ester. According to calcium carbonate surface-treated with a fatty acid or fatty acid ester, etc., it is possible to impart thixotropy to the curable composition and to suppress aggregation of calcium carbonate.
　硬化性組成物中における炭酸カルシウムの含有量は、加水分解性シリル基性を有するポリアルキレンオキサイド１００質量部に対して１～７００質量部が好ましく、５～３００質量部がより好ましく、１０～２３０質量部が特に好ましい。硬化性組成物中における炭酸カルシウムの含有量が上記範囲内であると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 The content of calcium carbonate in the curable composition is preferably 1 to 700 parts by mass, more preferably 5 to 300 parts by mass, with respect to 100 parts by mass of the hydrolyzable silyl group-containing polyalkylene oxide. Parts by weight are particularly preferred. When the content of calcium carbonate in the curable composition is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the fire resistance performance excellent in the wall portion of the building structure Can be granted.
　硬化性組成物中において、炭酸カルシウムの含有量と耐火性付与化合物の含有量との比（炭酸カルシウムの含有量／耐火性付与化合物の含有量）は２～２０が好ましく、２～１０がより好ましく、２～５が特に好ましい。炭酸カルシウムの含有量と耐火性付与化合物の含有量との比が上記範囲内であると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 In the curable composition, the ratio of the content of calcium carbonate to the content of the fire resistance imparting compound (content of calcium carbonate / content of fire resistance imparting compound) is preferably 2 to 20, more preferably 2 to 10 Preferably, 2 to 5 are particularly preferred. When the ratio of the content of calcium carbonate to the content of the fire resistance imparting compound is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure Excellent fire resistance performance.
　耐火性付与化合物がアンチモン系化合物を含有している場合、炭酸カルシウムの含有量とアンチモン系化合物の含有量との比（炭酸カルシウムの含有量／アンチモン系化合物の含有量）は２～２０が好ましく、２～１０がより好ましく、２～５が特に好ましい。炭酸カルシウムの含有量とアンチモン系化合物の含有量との比が上記範囲内であると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 When the fire resistance imparting compound contains an antimony compound, the ratio of the content of calcium carbonate to the content of the antimony compound (content of calcium carbonate / content of antimony compound) is preferably 2 to 20. And 2 to 10 are more preferable, and 2 to 5 are particularly preferable. When the ratio of the content of calcium carbonate to the content of the antimony compound is within the above range, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is Excellent fire resistance can be imparted.
　耐火性付与化合物がガスフリットを含有している場合、炭酸カルシウムの含有量とガラスフリットの含有量との比（炭酸カルシウムの含有量／ガラスフリットの含有量）は３～１０が好ましく、４～８がより好ましく、４～６が特に好ましい。炭酸カルシウムの含有量とガラスフリットの含有量との比が上記範囲内であると、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 When the fire resistance imparting compound contains a gas frit, the ratio of the content of calcium carbonate to the content of glass frit (content of calcium carbonate / content of glass frit) is preferably 3 to 10, and 4 to 10 8 is more preferable, and 4 to 6 is particularly preferable. When the ratio of the content of calcium carbonate to the content of glass frit is within the above range, the combustion residue of the cured product of the curable composition is stably held in the joint portion, and the wall portion of the building structure is excellent. Fire resistance performance can be imparted.
［アクリル系重合体］
　硬化性組成物は、アクリル系重合体を含有していてもよい。アクリル系重合体は、加水分解性シリル基を有していてもよい。 [Acrylic polymer]
The curable composition may contain an acrylic polymer. The acrylic polymer may have a hydrolyzable silyl group.
　加水分解性シリル基の加水分解性基としては、特に限定されず、例えば、水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などが挙げられる。 The hydrolyzable group of the hydrolyzable silyl group is not particularly limited. For example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoxime group, an amino group, an amide group, an acid amide group, an aminooxy group, mercapto And alkenyloxy groups.
　なかでも、加水分解性シリル基としては、加水分解反応が穏やかであることから、アルコキシシリル基が好ましい。アルコキシシリル基としては、トリメトキシシリル基、トリエトキシシリル基、トリイソプロポキシシリル基、及びトリフェノキシシリル基などのトリアルコキシシリル基；プロピルジメトキシシリル基、メチルジメトキシシリル基、及びメチルジエトキシシリル基などのジアルコキシシリル基；並びに、ジメチルメトキシシリル基、及びジメチルエトキシシリル基などのモノアルコキシシリル基が挙げられる。なかでも、トリアルコキシシリル基がより好ましく、トリメトキシシリル基が特に好ましい。 Among them, an alkoxysilyl group is preferable as the hydrolyzable silyl group because the hydrolysis reaction is mild. Examples of alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group And a monoalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group. Among them, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.
　アクリル系重合体は、１分子中に平均して、０．３個以上の加水分解性シリル基を有しているのが好ましく、０．５個以上の加水分解性シリル基を有しているのが好ましい。アクリル系重合体は、１分子中に平均して、２．０個以下の加水分解性シリル基を有しているのが好ましく、１．８個以下の加水分解性シリル基を有しているのが好ましい。アクリル系重合体における加水分解性シリル基の数が０．３個以上であると、硬化性組成物の硬化性が向上する。アクリル系重合体における加水分解性シリル基の数が２．０個以下であると、硬化性組成物の硬化物の機械的強度又は伸び性が向上する。また、アクリル系重合体は、主鎖の側鎖又は末端に加水分解性シリル基を有していることが好ましく、主鎖の両末端のうち少なくとも一方に加水分解性シリル基を有していることがより好ましく、主鎖の両末端に加水分解性シリル基を有していることが特に好ましい。 The acrylic polymer preferably has 0.3 or more hydrolyzable silyl groups on average in one molecule, and 0.5 or more hydrolyzable silyl groups. Is preferred. The acrylic polymer preferably has, on average, 2.0 or less hydrolyzable silyl groups in one molecule, and has 1.8 or less hydrolyzable silyl groups. Is preferred. When the number of hydrolyzable silyl groups in the acrylic polymer is 0.3 or more, the curability of the curable composition is improved. When the number of hydrolyzable silyl groups in the acrylic polymer is 2.0 or less, the mechanical strength or extensibility of the cured product of the curable composition is improved. The acrylic polymer preferably has a hydrolyzable silyl group at the side chain or end of the main chain, and has a hydrolyzable silyl group at at least one of both ends of the main chain. It is more preferable to have hydrolyzable silyl groups at both ends of the main chain.
　アクリル系重合体において、主鎖骨格の側鎖に加水分解性シリル基を有しているとは、主鎖骨格に側鎖として加水分解性シリル基を有している場合と、主鎖骨格の側鎖の一部に加水分解性シリル基を有している場合の双方を含む。 In the acrylic polymer, having a hydrolyzable silyl group in the side chain of the main chain skeleton means that a hydrolyzable silyl group is contained as a side chain in the main chain skeleton, and It includes both cases where hydrolyzable silyl group is contained in part of the side chain.
　アクリル系重合体を、上述した、加水分解性シリル基を有するポリアルキレンオキサイドと組み合わせて用いることにより、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。 By using the acrylic polymer in combination with the above-described polyalkylene oxide having a hydrolyzable silyl group, the flexibility of the cured product of the curable composition is improved, and the maximum load of the cured product of the curable composition is obtained. The elongation at the time is high, and the cured product can reliably keep the joint portion filled.
　アクリル系重合体への加水分解性シリル基の導入方法としては、特に限定されず、例えば、主鎖骨格を構成する単量体の共重合体に不飽和基を導入した後、加水分解性シリル基を有するヒドロシランを作用させてヒドロシリル化する方法などが挙げられる。 The method for introducing a hydrolyzable silyl group into an acrylic polymer is not particularly limited. For example, after introducing an unsaturated group into a copolymer of monomers constituting the main chain skeleton, a hydrolyzable silyl is introduced. The method of making it act on the hydrosilane which has group, and hydrosilylating etc. are mentioned.
　なお、アクリル系重合体中における、１分子当たりの加水分解性シリル基の平均個数は、1Ｈ－ＮＭＲにより求められるアクリル系重合体中の加水分解性シリル基の濃度、及びＧＰＣ法により求められるアクリル系重合体の数平均分子量に基づいて算出することができる。 The average number of hydrolyzable silyl groups per molecule in the acrylic polymer can be determined by the concentration of hydrolyzable silyl groups in the acrylic polymer determined by 1 H-NMR, and the GPC method. It can be calculated based on the number average molecular weight of the acrylic polymer.
　アクリル系重合体の主鎖骨格は、メチル（メタ）アクリレート及びブチル（メタ）アクリレートを含む単量体の共重合体、ｎ－ブチル（メタ）アクリレート及びｎ－オクタデシル（メタ）アクリレートを含む単量体の共重合体が好ましく、メチルメタクリレート及びブチルアクリレートを含む単量体の共重合体、ｎ－ブチルアクリレート及びｎ－オクタデシルアクリレートを含む単量体の共重合体、がより好ましく、ｎ－ブチルアクリレート及びｎ－オクタデシルアクリレートを含む単量体の共重合体が特に好ましい。主鎖骨格が上記共重合体であるアクリル系重合体によれば、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。なお、（メタ）アクリレートは、メタクリレート及び／又はアクリレートを意味する。 The main chain skeleton of the acrylic polymer is a copolymer of a monomer containing methyl (meth) acrylate and butyl (meth) acrylate, a single amount containing n-butyl (meth) acrylate and n-octadecyl (meth) acrylate Copolymers are preferred, copolymers of monomers containing methyl methacrylate and butyl acrylate, copolymers of monomers containing n-butyl acrylate and n-octadecyl acrylate are more preferable, and n-butyl acrylate is preferable Particularly preferred is a copolymer of monomers containing n-octadecyl acrylate. According to the acrylic polymer whose main chain skeleton is the above copolymer, the flexibility of the cured product of the curable composition is improved, and the elongation at maximum load of the cured product of the curable composition is increased, and the cured product Can securely hold the state in which the joint portion is filled. In addition, (meth) acrylate means methacrylate and / or acrylate.
　アクリル系重合体において、メチル（メタ）アクリレート成分の含有量は、３～７０質量％が好ましく、５～５０質量％がより好ましい。メチル（メタ）アクリレート成分の含有量が３質量％以上であることによって、硬化性組成物の硬化物の接着性が向上する。メチル（メタ）アクリレート成分の含有量が７０質量％以下であることによって、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。 In the acrylic polymer, the content of the methyl (meth) acrylate component is preferably 3 to 70% by mass, and more preferably 5 to 50% by mass. By the content of the methyl (meth) acrylate component being 3% by mass or more, the adhesiveness of the cured product of the curable composition is improved. When the content of the methyl (meth) acrylate component is 70% by mass or less, the flexibility of the cured product of the curable composition is improved, and the elongation at the maximum load of the cured product of the curable composition is increased, and curing is achieved. It is possible to reliably hold the state in which the object has filled the joint.
　アクリル系重合体において、ブチル（メタ）アクリレート成分の含有量は、３０～９７質量％が好ましく、５０～９５質量％がより好ましい。ブチル（メタ）アクリレート成分の含有量が３０質量％以上であることによって、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。 In the acrylic polymer, the content of the butyl (meth) acrylate component is preferably 30 to 97% by mass, and more preferably 50 to 95% by mass. When the content of the butyl (meth) acrylate component is 30% by mass or more, the flexibility of the cured product of the curable composition is improved, and the elongation at the maximum load of the cured product of the curable composition is increased, and curing is achieved. It is possible to reliably hold the state in which the object has filled the joint.
　アクリル系重合体において、主鎖骨格を構成している重合体に用いられる単量体は、メチルアクリレート、メチルメタクリレート、ブチルアクリレート、及びブチルメタクリレートの他に、さらに他のモノマーを含んでいてもよい。他のモノマーとしては、例えば、スチレン、インデン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－クロロスチレン、ｐ－クロロメチルスチレン、ｐ－メトキシスチレン、ｐ－ｔｅｒｔ－ブトキシスチレン、ジビニルベンゼンなどのスチレン誘導体、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、安息香酸ビニル、珪皮酸ビニルなどのビニルエステル基を持つ化合物、無水マレイン酸、Ｎ－ビニルピロリドン、Ｎ－ビニルモルフォリン、メタクリロニトリル、アクリロニトリル、アクリルアミド、メタクリルアミド、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－ベンジルマレイミド、ｎ－プロピルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、ｔｅｒｔ－アミルビニルエーテル、シクロヘキシルビニルエーテル、２－エチルヘキシルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、２－クロロエチルビニルエーテル、エチレングリコールブチルビニルエーテル、トリエチレングリコールメチルビニルエーテル、安息香酸（４－ビニロキシ）ブチル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、テトラエチレングリコールジビニルエーテル、ブタン－１，４－ジオール－ジビニルエーテル、ヘキサン－１，６－ジオール－ジビニルエーテル、シクロヘキサン－１，４－ジメタノール－ジビニルエーテル、イソフタル酸ジ（４－ビニロキシ）ブチル、グルタル酸ジ（４－ビニロキシ）ブチル、コハク酸ジ（４－ビニロキシ）ブチルトリメチロールプロパントリビニルエーテル、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、シクロヘキサン－１，４－ジメタノールモノビニルエーテル、ジエチレングリコールモノビニルエーテル、３－アミノプロピルビニルエーテル、２－（Ｎ，Ｎ－ジエチルアミノ）エチルビニルエーテル、ウレタンビニルエーテル、ポリエステルビニルエーテルなどのビニロキシ基を持つ化合物などを挙げることができる。これらのモノマーは、単独で用いられても二種以上が併用されてもよい。 In the acrylic polymer, the monomer used for the polymer constituting the main chain skeleton may further contain other monomers in addition to methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate . Other monomers include, for example, styrene, styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene and the like Derivatives, compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate, etc., maleic anhydride, N-vinyl pyrrolidone, N-vinyl morpholine, methacrylo Nitrile, acrylonitrile, acrylamide, methacrylamide, N-cyclohexyl maleimide, N-phenyl maleimide, N-lauryl maleimide, N-benzyl maleimide, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether Tert-Butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl Ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4- Dimethanol-divinyl ether, isophthalic acid di (4-vinyloxy) Butyl, di (4-vinyloxy) butyl glutarate, di (4-vinyloxy) butyl trimethylolpropane trivinylether succinate, 2-hydroxyethylvinylether, 4-hydroxybutylvinylether, 6-hydroxyhexylvinylether, cyclohexane-1,4 -Compounds having a vinyloxy group such as dimethanol monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and the like can be mentioned. These monomers may be used alone or in combination of two or more.
　アクリル系重合体の重合方法としては、特に限定されず、公知の方法を用いることができ、例えば、フリーラジカル重合法、アニオン重合法、カチオン重合法、ＵＶラジカル重合法、リビングアニオン重合法、リビングカチオン重合法、リビングラジカル重合法などの各種重合法などが挙げられる。 It does not specifically limit as a polymerization method of an acryl-type polymer, A well-known method can be used, For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method, living Various polymerization methods such as a cationic polymerization method and a living radical polymerization method can be mentioned.
　アクリル系重合体の重量平均分子量は、１０００～５００００が好ましく、２０００～３００００がより好ましく、３０００～１５０００が特に好ましい。重量平均分子量が上記範囲内であるアクリル系重合体によれば、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。 The weight average molecular weight of the acrylic polymer is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and particularly preferably 3,000 to 15,000. According to the acrylic polymer having a weight average molecular weight in the above range, the flexibility of the cured product of the curable composition is improved, the elongation at maximum load of the cured product of the curable composition is increased, and the cured product is The state in which the joint portion is filled can be reliably maintained.
　硬化性組成物中におけるアクリル系重合体の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して５～３００質量部が好ましく、１０～２００質量部がより好ましく、３０～１００質量部が特に好ましい。硬化性組成物中におけるアクリル系重合体の含有量が５質量部以上であると、硬化性組成物の接着性が向上する。硬化性組成物中におけるアクリル系重合体の含有量が３００質量部以下であると、硬化性組成物の硬化物の柔軟性が向上し、硬化性組成物の硬化物の最大荷重時伸びが高くなり、硬化物が目地部を充填した状態を確実に保持することができる。 The content of the acrylic polymer in the curable composition is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. 100 parts by weight is particularly preferred. The adhesiveness of a curable composition improves that content of the acrylic polymer in a curable composition is 5 mass parts or more. When the content of the acrylic polymer in the curable composition is 300 parts by mass or less, the flexibility of the cured product of the curable composition is improved, and the elongation at maximum load of the cured product of the curable composition is high. As a result, the cured product can reliably hold the joint portion filled.
［可塑剤］
　可塑剤としては、例えば、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジイソブチル、フタル酸ジノルマルヘキシル、フタル酸ビス（２－エチルヘキシル）、フタル酸ジノルマルオクチル、フタル酸ジイソノニル、フタル酸ジノニル、フタル酸ジイソデシル、フタル酸ジイソウンデシル、及びフタル酸ビスブチルベンジルなどのフタル酸エステル；ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール、ポリプロピレングリコールなどのポリアルキレングリコールが挙げられる。なかでも、ポリアルキレングリコールが好ましく、ポリプロピレングリコールがより好ましい。 [Plasticizer]
As the plasticizer, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, phthalic acid Phthalates such as dinonyl, diisodecyl phthalate, diisoundecyl phthalate, and bisbutyl benzyl phthalate; Polyalkylenes such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, etc. Glycol is mentioned. Among them, polyalkylene glycol is preferable, and polypropylene glycol is more preferable.
　ポリアルキレングリコールの数平均分子量は、１０００～１００００が好ましく、２０００～５０００がより好ましい。ポリアルキレングリコールの数平均分子量が上記範囲内である場合、硬化性組成物の硬化物の燃焼残渣が目地部に安定的に保持され、建築構造物の壁部に優れた耐火性能を付与することができる。 The number average molecular weight of the polyalkylene glycol is preferably 1000 to 10000, and more preferably 2000 to 5000. When the number average molecular weight of the polyalkylene glycol is within the above range, the combustion residue of the cured product of the curable composition is stably held at the joint portion, and the wall portion of the building structure is provided with excellent fire resistance performance. Can.
　なお、本発明において、ポリアルキレングリコールの数平均分子量は、ポリアルキレンオキサイドの数平均分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）法によって、ポリスチレン換算されて測定された値である。具体的な測定方法や測定条件は、上述したポリアルキレンオキサイドと同様である。 In the present invention, the number average molecular weight of the polyalkylene glycol is a value measured by converting the number average molecular weight of the polyalkylene oxide into polystyrene by GPC (gel permeation chromatography) method. The specific measuring method and measuring conditions are the same as the polyalkylene oxide mentioned above.
　硬化性組成物中における可塑剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して１～５０質量部が好ましく、１０～４０質量部がより好ましい。 The content of the plasticizer in the curable composition is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.
　［脱水剤］
　硬化性組成物は、脱水剤をさらに含んでいるのが好ましい。脱水剤によれば、硬化性組成物を保存している際に、空気中などに含まれている水分によって硬化性組成物が硬化することを抑制することができる。 [Dehydrating agent]
The curable composition preferably further contains a dehydrating agent. According to the dehydrating agent, when the curable composition is stored, it is possible to suppress that the curable composition is cured by water contained in the air or the like.
　脱水剤としては、ビニルトリメトキシシラン、ジメチルジメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、フェニルトリメトキシシラン、及びジフェニルジメトキシシランなどのシラン化合物；並びにオルトギ酸メチル、オルトギ酸エチル、オルト酢酸メチル、及びオルト酢酸エチル等のエステル化合物などを挙げることができる。これらの脱水剤は、単独で用いられても二種以上が併用されてもよい。なかでも、ビニルトリメトキシシランが好ましい。 As a dehydrating agent, silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthoformate And ester compounds such as ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among them, vinyltrimethoxysilane is preferable.
　硬化性組成物中における脱水剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して０．５～２０質量部が好ましく、１～１５質量部がより好ましい。硬化性組成物中における脱水剤の含有量が０．５質量部以上であると、脱水剤により得られる効果が十分に得られる。また、硬化性組成物中における脱水剤の含有量が２０質量部以下であると、硬化性組成物が優れた硬化性を有する。 The content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the dehydrating agent in the curable composition is 0.5 parts by mass or more, the effects obtained by the dehydrating agent are sufficiently obtained. In addition, the curable composition has excellent curability when the content of the dehydrating agent in the curable composition is 20 parts by mass or less.
［シラノール縮合触媒］
　硬化性組成物は、シラノール縮合触媒を含有していることが好ましい。シラノール縮合触媒とは、加水分解性シリル基を有するポリアルキレンオキサイドが含有する加水分解性シリル基などが加水分解することにより形成されたシラノール基同士の脱水縮合反応を促進させるための触媒である。 [Silanol condensation catalyst]
The curable composition preferably contains a silanol condensation catalyst. The silanol condensation catalyst is a catalyst for promoting the dehydration condensation reaction of silanol groups formed by hydrolysis of a hydrolyzable silyl group or the like contained in a polyalkylene oxide having a hydrolyzable silyl group.
　シラノール縮合触媒としては、１，１，３，３－テトラブチル－１，３－ジラウリルオキシカルボニル－ジスタノキサン、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫フタレート、ビス（ジブチル錫ラウリン酸）オキサイド、ジブチル錫ビス（アセチルアセトナート）、ジブチル錫ビス（モノエステルマレート）、オクチル酸錫、ジブチル錫オクトエート、ジオクチル錫オキサイド、ジブチル錫ビス（トリエトキシシリケート）、ビス（ジブチル錫ビストリエトキシシリケート）オキサイド、及びジブチル錫オキシビスエトキシシリケートなどの有機錫系化合物；テトラ－ｎ－ブトキシチタネート、及びテトライソプロポキシチタネートなどの有機チタン系化合物などが挙げられる。これらのシラノール縮合触媒は、単独で用いられても二種以上が併用されてもよい。 As a silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin lauric acid) ) Oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (monoester malate), tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis (triethoxy silicate), bis (dibutyltin bis triethoxy silicate) And organic tin compounds such as dibutyltin oxybisethoxy silicate; and organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more.
　シラノール縮合触媒としては、１，１，３，３－テトラブチル－１，３－ジラウリルオキシカルボニル－ジスタノキサンが好ましい。このようなシラノール縮合触媒によれば、硬化性組成物の硬化速度を容易に調整することができる。 As a silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane is preferred. According to such a silanol condensation catalyst, the curing rate of the curable composition can be easily adjusted.
　硬化性組成物中におけるシラノール縮合触媒の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して１～１０質量部が好ましく、１～５質量部がより好ましい。硬化性組成物中におけるシラノール縮合触媒の含有量が１質量部以上であると、硬化性組成物の硬化速度を速くして、硬化性組成物の硬化に要する時間の短縮化を図ることができる。また、硬化性組成物中におけるシラノール縮合触媒の含有量が１０質量部以下であると、硬化性組成物が適度な硬化速度を有し、硬化性組成物の貯蔵安定性及び取扱性を向上させることができる。 The content of the silanol condensation catalyst in the curable composition is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the silanol condensation catalyst in the curable composition is 1 part by mass or more, the curing rate of the curable composition can be increased, and the time required for curing of the curable composition can be shortened. . In addition, when the content of the silanol condensation catalyst in the curable composition is 10 parts by mass or less, the curable composition has an appropriate curing rate to improve the storage stability and the handleability of the curable composition. be able to.
［他の添加剤］
　硬化性組成物は、チキソ性付与剤、酸化防止剤、紫外線吸収剤、顔料、染料、沈降防止剤、及び溶剤など他の添加剤を含んでいてもよい。なかでも、チキソ性付与剤、紫外線吸収剤、及び酸化防止剤が好ましく挙げられる。 [Other additives]
The curable composition may contain other additives such as a thixotropic agent, an antioxidant, a UV absorber, a pigment, a dye, an antisettling agent, and a solvent. Among them, a thixotropic agent, a UV absorber, and an antioxidant are preferably mentioned.
　チキソ性付与剤は、硬化性組成物にチキソトロピー性を発現せることができるものであればよい。チキソ性付与剤としては、水添ひまし油、脂肪酸ビスアマイド、ヒュームドシリカなどが好ましく挙げられる。 The thixotropic agent may be any agent capable of exhibiting thixotropic properties in the curable composition. As a thixotropic agent, hydrogenated castor oil, fatty acid bisamide, fumed silica and the like are preferably mentioned.
　硬化性組成物中におけるチキソ性付与剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して０．１～２００質量部が好ましく、１～１５０質量部がより好ましい。硬化性組成物中におけるチキソ性付与剤の含有量が０．１質量部以上であると、硬化性組成物にチキソトロピー性を効果的に付与することができる。また、硬化性組成物中におけるチキソ性付与剤の含有量が２００質量部以下であると、硬化性組成物が適度な粘度を有し、硬化性組成物の取扱性が向上する。 The content of the thixotropic agent in the curable composition is preferably 0.1 to 200 parts by mass, and more preferably 1 to 150 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the thixotropic agent in the curable composition is 0.1 parts by mass or more, thixotropic properties can be effectively imparted to the curable composition. In addition, when the content of the thixotropic agent in the curable composition is 200 parts by mass or less, the curable composition has an appropriate viscosity, and the handleability of the curable composition is improved.
　紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤などが挙げられ、ベンゾトリアゾール系紫外線吸収剤が好ましい。硬化性組成物中における紫外線吸収剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して０．１～２０質量部が好ましく、０．１～１０質量部がより好ましい。 As a ultraviolet absorber, a benzotriazole type ultraviolet absorber, a benzophenone series ultraviolet absorber, etc. are mentioned, A benzotriazole type ultraviolet absorber is preferable. The content of the ultraviolet light absorber in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. .
　酸化防止剤としては、例えば、ヒンダードフェノール系酸化防止剤、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、及びポリフェノール系酸化防止剤などが挙げられ、ヒンダードフェノール系酸化防止剤が好ましく挙げられる。硬化性組成物中における酸化防止剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して０．１～２０質量部が好ましく、０．３～１０質量部がより好ましい。 Examples of the antioxidant include hindered phenol-based antioxidants, monophenol-based antioxidants, bisphenol-based antioxidants, polyphenol-based antioxidants and the like, and hindered phenol-based antioxidants are preferably mentioned. Be The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. .
［光安定剤］
　硬化性組成物は、ヒンダードアミン系光安定剤を含んでいることが好ましい。ヒンダードアミン系光安定剤によれば、硬化後に優れたゴム弾性をより長期間に亘って維持することができる硬化性組成物を提供することができる。 [Light stabilizer]
The curable composition preferably contains a hindered amine light stabilizer. According to the hindered amine light stabilizer, a curable composition capable of maintaining excellent rubber elasticity for a longer period of time after curing can be provided.
　ヒンダードアミン系光安定剤としては、例えば、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート及びメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートの混合物、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ジブチルアミン・１，３，５－トリアジン・Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル－１，６－ヘキサメチレンジアミンとＮ－（２，２，６，６－テトラメチル－４－ピペリジル）ブチルアミンとの重縮合物、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールとの重縮合物などが挙げられる。 As a hindered amine light stabilizer, for example, a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dibutylamine · 1,3,5-triazine · N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, polycondensate, poly [{6- (1,1,3,3- Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6) -Tetramethyl 4-piperidyl) imino}], etc. polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol.
　ヒンダードアミン系光安定剤としては、ＮＯＲ型ヒンダードアミン系光安定剤が好ましく挙げられる。ＮＯＲ型ヒンダードアミン系光安定剤によれば、硬化後に経時的なゴム弾性の低下が抑制されている硬化性組成物を提供することができる。 As a hindered amine light stabilizer, NOR type hindered amine light stabilizer is mentioned preferably. According to the NOR type hindered amine light stabilizer, it is possible to provide a curable composition in which a decrease in rubber elasticity with time after curing is suppressed.
　ＮＯＲ型ヒンダードアミン系光安定剤は、ピペリジン環骨格に含まれている窒素原子（Ｎ）に酸素原子（Ｏ）を介してアルキル基（Ｒ）が結合しているＮＯＲ構造を有している。ＮＯＲ構造におけるアルキル基の炭素数は、１～２０が好ましく、１～１８がより好ましく、１８が特に好ましい。アルキル基としては、直鎖状のアルキル基、分岐鎖状のアルキル基、及び、環状のアルキル基（飽和脂環式炭化水素基）が挙げられる。 The NOR type hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) contained in a piperidine ring skeleton via an oxygen atom (O). The carbon number of the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18. Examples of the alkyl group include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups (saturated alicyclic hydrocarbon groups).
　直鎖状のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基などが挙げられる。分岐鎖状のアルキル基としては、例えば、イソプロピル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチルなどが挙げられる。環状のアルキル基（飽和脂環式炭化水素基）としては、例えば、シクロペンチル基、シクロヘキシル基、シクロオクチル基などが挙げられる。また、アルキル基を構成している水素原子が、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）又はヒドロキシル基などで置換されていてもよい。 As a linear alkyl group, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group Groups and the like. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl and the like. As a cyclic alkyl group (saturated alicyclic hydrocarbon group), a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. In addition, a hydrogen atom constituting an alkyl group may be substituted by a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or a hydroxyl group.
　ＮＯＲ型ヒンダードアミン系光安定剤としては、下記式（Ｉ）で示されるヒンダードアミン系光安定剤が挙げられる。 Examples of the NOR type hindered amine light stabilizer include hindered amine light stabilizers represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　ＮＯＲ型ヒンダードアミン系光安定剤を用いる場合、ＮＯＲ型ヒンダードアミン系光安定剤と、ベンゾトリアゾール系紫外線吸収剤又はトリアジン系紫外線吸収剤とを組み合わせて用いることが好ましい。これにより、硬化後に経時的なゴム弾性の低下がより高く抑制されている硬化性組成物を提供することができる。 When a NOR type hindered amine light stabilizer is used, it is preferable to use a combination of a NOR type hindered amine light stabilizer and a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber. This makes it possible to provide a curable composition in which the decrease in rubber elasticity with time after curing is suppressed to a higher level.
　硬化性組成物中におけるヒンダードアミン系光安定剤の含有量は、加水分解性シリル基を有するポリアルキレンオキサイド１００質量部に対して０．０１～２０質量部が好ましく、０．１～１０質量部がより好ましい。 The content of the hindered amine light stabilizer in the curable composition is preferably 0.01 to 20 parts by mass, and preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. More preferable.
　硬化性組成物は、ポリアルキレンオキサイド、耐火性付与化合物及び炭酸カルシウムに、必要に応じて上記化合物を加えた上で混合することによって製造することができる。 The curable composition can be produced by adding the above-described compound to the polyalkylene oxide, the fire resistance imparting compound and calcium carbonate as required, and mixing them.
　硬化性組成物の硬化物の最大荷重時伸びは、３００～８００％が好ましく、４００～７００％がより好ましく、５７０～６５０％が特に好ましい。なお、硬化性組成物の硬化物の最大荷重時伸びは、下記の要領で測定される。先ず、硬化性組成物を用いて、ＪＩＳ　Ａ１４３９　４．２１に準拠してＨ型試験体を作製する。具体的には、アルマイト処理を施したアルミニウム板（縦５０ｍｍ×横５０ｍｍ×厚み３ｍｍ）２枚を用い、これらのアルミニウム板の間にスペーサーを挟むことによってアルミニウム板間の中央部に直方体状の空間（縦１２ｍｍ×横５０ｍｍ×高さ１２ｍｍ）を形成する。この空間に硬化性組成物を空気が入らないように充填する。硬化性組成物の充填後、温度２３℃、相対湿度５０％の雰囲気下で硬化性組成物を１４日間放置する。しかる後、硬化性組成物をさらに温度３０℃の雰囲気下で１４日間放置する。硬化性組成物を養生させて硬化させることにより、２枚のアルミニウム板が硬化性組成物の硬化物によって接着一体化されてなるＨ型試験体を作製する。そして、作製直後のＨ型試験体について、温度２３℃、相対湿度５０％の雰囲気下で、引張速度５０ｍｍ／分での引張試験をＪＩＳ　Ａ１４３９に準拠して行い、最大荷重時伸び［％］を測定する。 The maximum load elongation of the cured product of the curable composition is preferably 300 to 800%, more preferably 400 to 700%, and particularly preferably 570 to 650%. The maximum load elongation of the cured product of the curable composition is measured in the following manner. First, an H-type test body is produced using a curable composition according to JIS A1439 4.21. Specifically, using two aluminum plates (50 mm long × 50 mm wide × 3 mm thick) alumite-treated, a rectangular parallelepiped space (long 12 mm × horizontal 50 mm × height 12 mm). The curable composition is filled into this space so that air does not enter. After loading the curable composition, the curable composition is left to stand for 14 days under an atmosphere of temperature 23 ° C. and relative humidity 50%. Thereafter, the curable composition is further left to stand for 14 days in an atmosphere at a temperature of 30 ° C. By curing and curing the curable composition, an H-type test body in which two aluminum plates are bonded and integrated by the cured product of the curable composition is produced. Then, with respect to the H-shaped test body immediately after preparation, a tensile test at a tensile speed of 50 mm / min is performed in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% according to JIS A1439, and elongation at maximum load [%] taking measurement.
　硬化性組成物の硬化物の燃焼残渣強度は、０．２～３．５Ｎ／ｍｍ2が好ましく、０．５～３Ｎ／ｍｍ2がより好ましく、０．６５～２．５Ｎ／ｍｍ2がより好ましく、１．０～２．０Ｎ／ｍｍ2が特に好ましい。硬化性組成物の硬化物の燃焼残渣強度は、下記の要領で測定される。先ず、硬化性組成物を亜鉛鉱板上に厚さ１０ｍｍ、幅１０ｍｍ、長さ５０ｍｍとなるように塗布し、硬化性組成物を２３℃及び相対湿度５０％の環境下にて１ヶ月間養生し、硬化性組成物を硬化させて硬化物を得る。 Burn residual渣強of the cured product of the curable composition is preferably 0.2 ~ 3.5N / mm 2, more preferably 0.5 ~ 3N / mm 2, 0.65 ~ 2.5N / mm 2 Gayori Preferably, 1.0 to 2.0 N / mm 2 is particularly preferred. The combustion residue strength of the cured product of the curable composition is measured in the following manner. First, the curable composition is applied on a zinc sheet so as to have a thickness of 10 mm, a width of 10 mm and a length of 50 mm, and the curable composition is cured for 1 month in an environment of 23 ° C. and 50% relative humidity. And the curable composition is cured to obtain a cured product.
　硬化性組成物の硬化物を６００℃の恒温槽に３０分間放置して燃焼させた後に恒温槽から取り出し、２３℃の雰囲気下にて３時間放置して燃焼残渣を得る。 The cured product of the curable composition is left to burn in a thermostat at 600 ° C. for 30 minutes, taken out of the thermostat, and left in an atmosphere at 23 ° C. for 3 hours to obtain a combustion residue.
　万能試験機を用いて１．５ｍｍ径のニードルによって燃焼残渣を５０ｍｍ／分の圧縮スピードで圧縮することによって燃焼残渣の皮膜強度を測定し、皮膜強度を硬化性組成物の硬化物の燃焼残渣強度とする。 The film strength of the combustion residue is measured by compressing the combustion residue with a 1.5 mm diameter needle at a compression speed of 50 mm / min using a universal testing machine, and the film strength is the combustion residue strength of the cured product of the curable composition. I assume.
　硬化性組成物を目地部に施工して目地構造を得る方法としては、硬化性組成物を目地部に充填した後に養生させて硬化させる方法が用いられる。得られる目地構造は、建築構造物の壁部を構成している壁部材と、互いに隣接する壁部材間に形成された目地部に充填された、硬化性組成物の硬化物とを含む。建築構造物の壁部としては、例えば、外壁、内壁、天井部などが挙げられる。壁部材としては、例えば、外壁部材、内壁部材、天井部材などが挙げられる。 As a method of applying the curable composition to the joint portion to obtain a joint structure, a method of filling the joint portion with the curable composition and then curing and curing it is used. The joint structure obtained includes the wall member constituting the wall portion of the building structure, and the cured product of the curable composition filled in the joint portion formed between the adjacent wall members. As a wall part of a building structure, an outer wall, an inner wall, a ceiling part etc. are mentioned, for example. As a wall member, an outer wall member, an inner wall member, a ceiling member etc. are mentioned, for example.
　目地部は、特に制限されないが、建築構造物の外壁、内壁、及び天井における目地部などが挙げられる。硬化性組成物は、硬化後に優れたゴム弾性を長期間に亘って維持することができることから、気温や日照等の温度変化による部材の膨張や収縮による、或いは振動や風圧などの作用による目地部の幅の変化に対して優れた追随性を呈し、部材の損傷や建築構造物内への漏水を防止することができる。したがって、建築構造物の外壁における目地部など、所謂、「ワーキングジョイント」とも呼ばれる幅の変化が大きい目地部をシーリングするために好適に用いられる。 The joint portion is not particularly limited, and examples include joint portions in the outer wall, the inner wall, and the ceiling of the building structure. Since the curable composition can maintain excellent rubber elasticity for a long time after curing, it causes joints due to expansion or contraction of members due to temperature change such as air temperature or sunshine, or by action such as vibration or wind pressure. It can keep up with the change of the width of the frame and prevent the damage of the member and the water leakage into the building structure. Therefore, it is suitably used to seal a joint having a large change in width, also called a "working joint", such as a joint in an outer wall of a building structure.
　建築構造物の外壁における目地部としては、例えば、モルタル板、コンクリート板、窯業系サイディングボード、金属系サイディングボード、ＡＬＣ板、及び金属板などの外壁部材同士の接合部にできる目地部が挙げられる。 The joints in the outer wall of the building structure include, for example, joints made of joints between outer wall members such as mortar boards, concrete boards, ceramic siding boards, metal siding boards, ALC boards, and metal sheets. .
　そして、硬化性組成物の硬化物は、燃焼によって強固な燃焼残渣を生成し、この燃焼残渣は、火災時においても建築構造物の目地部を充填し閉塞した状態を確実に保持して目地部を通じた炎の回り込みを阻止し、建築構造物の壁部に優れた耐火性能を付与することができる。 And the hardened | cured material of a curable composition produces a strong combustion residue by combustion, and this combustion residue certainly hold | maintains the state which filled and obstruct | occluded the joint part of a building structure also in the time of a fire, and a joint part Can prevent the spread of flames and can impart excellent fire resistance to the wall of a building structure.
　本発明の硬化性組成物は、燃焼により生成された燃焼残渣が非常に強固であり、この燃焼残渣は、火災時においても目地部を充填し閉塞した状態を確実に保持して目地部からの炎の回り込みを阻止し、建築構造物の壁部に優れた耐火性能を付与することができる。 In the curable composition of the present invention, the combustion residue generated by combustion is very strong, and the combustion residue fills the joint and reliably maintains the closed state even in the case of a fire, thereby ensuring that the joint remains closed. It is possible to prevent the spread of the flame and to provide the wall part of the building structure with excellent fire resistance.
　以下に、本発明を実施例を用いてより具体的に説明するが、本発明はこれに限定されない。 Hereinafter, the present invention will be more specifically described using examples, but the present invention is not limited thereto.
　実施例及び比較例の硬化性組成物の製造において下記の原料を使用した。 The following raw materials were used in manufacture of the curable composition of an Example and a comparative example.
・加水分解性シリル基を有するポリアルキレンオキサイド（主鎖骨格がポリプロピレンオキサイドからなり且つ主鎖の末端にプロピルジメトキシシリル基を有するポリアルキレンオキサイド、１分子あたりのプロピルジメトキシシリル基の平均個数：１．４個、数平均分子量：２００００、カネカ社製　商品名「ＭＳポリマー　Ｓ－３０３」）
・三酸化アンチモン（日本精鉱社製　「ｐａｔｏｘ－Ｃ」、Ｓｂ2Ｏ3）
・コロイダル炭酸カルシウム（白石工業社製　商品名「ＣＣＲ」、平均粒子径：８０ｎｍ）
・重質炭酸カルシウム（日東粉化社製　商品名「ＮＣＣ２３１０」、平均粒子径：１μｍ）
・ガラスフリットＡ（リン酸系ガラス、日本フリット社製　「ＶＹ０１４４」、主成分：Ｐ2Ｏ5、ＡＩ2Ｏ3及びＲ2Ｏ、Ｒはアルカリ金属原子、軟化温度：４０４℃）
・ガラスフリットＢ（リン酸系ガラス、日本フリット社製　「ＶＹ００５３」、主成分：Ｐ2Ｏ5、ＡＩ2Ｏ3及びＲ2Ｏ、Ｒはアルカリ金属原子、軟化温度：５５０℃）
・ガラスフリットＣ（ホウ酸系ガラス、日本フリット社製　「ＣＹ００８６」、主成分：Ｂ2Ｏ3、ＺｎＯ及びＲＯ、Ｒはアルカリ土類金属原子、軟化温度：５６９℃）
・アクリル系重合体（メチルジメトキシシリル基を主鎖の両末端に含有するアクリル系重合体、１分子当たりのメチルジメトキシシリル基の平均個数：１．７個、数平均分子量：２８０００、カネカ社製　商品名「ＳＡ３１０Ｓ」）
・シラノール縮合触媒（１，１，３，３－テトラブチル－１，３－ジラウリルオキシカルボニル－ジスタノキサン、日東化成社製　商品名「ネオスタンＵ－１３０」）
・脱水剤（ビニルトリメトキシシラン、日本ユニカ社製　商品名「ＮＵＣシリコーンＡ１７１」）
・アミノシランカップリング剤（Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、信越化学社製　商品名　ＫＢＭ－６０３」）
・ベンゾトリアゾール系紫外線吸収剤（ＢＡＳＦジャパン社製　製品名「チヌビン３２６」
・ヒンダードフェノール系酸化防止剤（ＢＡＳＦジャパン社製　製品名「イルガノックス１０１０」）
・ＮＨ型ヒンダードアミン系光安定剤（ＢＡＳＦジャパン社製　製品名「チヌビン７７０」
・揺変剤（脂肪酸アマイドワックス、楠本化成社製　製品名「ディスパロン＃６５００」）
・脂肪族アミン（ステアリルアミン） · Polyalkylene oxide having hydrolyzable silyl group (polyalkylene oxide having a main chain skeleton of polypropylene oxide and having a propyldimethoxysilyl group at the end of the main chain, average number of propyldimethoxysilyl groups per molecule: 1. Four, number average molecular weight: 20000, manufactured by Kaneka Corp. Brand name "MS polymer S-303")
・ Antimony trioxide (Nippon Gas concentrate "patox-C", Sb 2 O 3 )
-Colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name "CCR", average particle size: 80 nm)
・ Heavy calcium carbonate (manufactured by Nitto Powder Co., Ltd., trade name “NCC 2310”, average particle diameter: 1 μm)
Glass frit A (phosphate glass, manufactured by Nippon Frit Co., "VY0144", main component: P 2 O 5 , AI 2 O 3 and R 2 O, R is an alkali metal atom, softening temperature: 404 ° C.)
Glass frit B (phosphate glass, manufactured by Nippon Frit Co., Ltd. "VY0053", main component: P 2 O 5 , AI 2 O 3 and R 2 O, R is an alkali metal atom, softening temperature: 550 ° C.)
Glass frit C (boric acid glass, manufactured by Nippon Frit Co., "CY0086", main component: B 2 O 3 , ZnO and RO, R is an alkaline earth metal atom, softening temperature: 569 ° C.)
Acrylic polymers (acrylic polymers containing methyldimethoxysilyl groups at both ends of the main chain, average number of methyldimethoxysilyl groups per molecule: 1.7, number average molecular weight: 28,000, manufactured by Kaneka Corporation Product name "SA310S")
· Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, manufactured by Nitto Kasei Co., Ltd., trade name "NEOSTAN U-130")
Dehydrating agent (vinyltrimethoxysilane, manufactured by Nippon Unica, trade name "NUC silicone A 171")
· Aminosilane coupling agent (N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603 ")
・ Benzotriazole-based UV absorber (manufactured by BASF Japan Ltd., product name "Tinuvin 326"
・ Hindered phenolic antioxidant (manufactured by BASF Japan, product name “Irganox 1010”)
・ NH type hindered amine light stabilizer (manufactured by BASF Japan, product name “Tinuvin 770”
・ Thickling agent (fatty acid amide wax, manufactured by Kushimoto Chemical Co., Ltd., product name "Disperon # 6500")
・ Aliphatic amine (stearylamine)
（実施例１～１３及び比較例１、２）
　加水分解性シリル基を有するポリアルキレンオキサイド、三酸化アンチモン、コロイダル炭酸カルシウム、重質炭酸カルシウム、ガラスフリットＡ～Ｃ、アクリル系重合体、シラノール縮合触媒、脱水剤、アミノシランカップリング剤、ベンゾトリアゾール系紫外線吸収剤、ヒンダードフェノール系酸化防止剤、ＮＨ型ヒンダードアミン系光安定剤、揺変剤及び脂肪族アミンを表１に示した配合量となるようにして、プラネタリーミキサーを用いて真空雰囲気下にて６０分間に亘って均一になるまで混合することによって硬化性組成物を得た。 (Examples 1 to 13 and Comparative Examples 1 and 2)
Polyalkylene oxide having hydrolyzable silyl group, antimony trioxide, colloidal calcium carbonate, calcium carbonate calcium, glass frits AC, acrylic polymer, silanol condensation catalyst, dehydrating agent, aminosilane coupling agent, benzotriazole type UV absorber, hindered phenolic antioxidant, NH type hindered amine light stabilizer, thixotropic agent and aliphatic amine in the amounts shown in Table 1, using a planetary mixer under a vacuum atmosphere The curable composition was obtained by mixing until uniform over 60 minutes.
　硬化性組成物の硬化物について、燃焼残渣強度及び最大荷重時伸びを上記の要領で測定し、その結果を表１に示した。 With respect to the cured product of the curable composition, the combustion residue strength and the elongation at maximum load were measured as described above, and the results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（関連出願の相互参照）
　本出願は、２０１７年８月２４日に出願された日本国特許出願第２０１７－１６１６５５号に基づく優先権を主張し、この出願の開示はこれらの全体を参照することにより本明細書に組み込まれる。 (Cross-reference to related applications)
This application claims priority based on Japanese Patent Application No. 2017-161655 filed on Aug. 24, 2017, the disclosure of which is incorporated herein by reference in its entirety. .
　本発明は、燃焼により非常に強固な燃焼残渣を生成する。硬化性組成物を目地部に施工することによって目地構造を得ることができる。本発明の硬化物は、火災時において燃焼残渣を生成し、この燃焼残渣は、火災時においても目地部を充填し閉塞した状態を確実に保持して目地部からの炎の回り込みを阻止し、建築構造物の壁部に優れた耐火性能を付与することができる。 The present invention produces a very strong combustion residue upon combustion. A joint structure can be obtained by applying the curable composition to the joint. The cured product of the present invention forms a combustion residue in the event of a fire, and the combustion residue securely fills the joint and keeps the blockage even in the case of a fire, thereby preventing the flame from flowing from the joint. Excellent fire resistance can be imparted to the wall portion of the building structure.

Claims (8)

  1. 　加水分解性シリル基を有するポリアルキレンオキサイドと、
    　アンチモン系化合物及びガラスフリットからなる群から選ばれた少なくとも一種の耐火性付与化合物と、
    　炭酸カルシウムとを含有することを特徴とする硬化性組成物。     A polyalkylene oxide having a hydrolyzable silyl group,
    At least one fire resistance imparting compound selected from the group consisting of antimony compounds and glass frits;
    A curable composition comprising calcium carbonate.
  2. 　耐火性付与化合物がガラスフリットを含有していることを特徴とする請求項１に記載の硬化性組成物。 The curable composition according to claim 1, wherein the fire resistance imparting compound comprises a glass frit.
  3. 　アクリル系重合体を更に含有することを特徴とする請求項１又は請求項２に記載の硬化性組成物。 The curable composition according to claim 1, further comprising an acrylic polymer.
  4. 　炭酸カルシウムの含有量と耐火性付与化合物の含有量との比率（炭酸カルシウムの含有量／耐火性付与化合物の含有量）が２～２０であることを特徴とする請求項１～３の何れか１項に記載の硬化性組成物。 The ratio of the content of calcium carbonate to the content of the fire resistance imparting compound (content of calcium carbonate / content of fire resistance imparting compound) is 2 to 20. The curable composition according to item 1.
  5. 　炭酸カルシウムの含有量とガラスフリットの含有量との比率（炭酸カルシウムの含有量／ガラスフリットの含有量）が３～１０であることを特徴とする請求項２に記載の硬化性組成物。 The curable composition according to claim 2, wherein the ratio of the content of calcium carbonate to the content of glass frit (content of calcium carbonate / content of glass frit) is 3 to 10.
  6. 　耐火性付与化合物がアンチモン系化合物及びガラスフリットを含有しており、上記アンチモン系化合物の含有量と上記ガラスフリットの含有量との比率（アンチモン系化合物の含有量／ガラスフリットの含有量）が０．１～９であることを特徴とする請求項１～５の何れか１項に記載の硬化性組成物。 The fire resistance imparting compound contains an antimony-based compound and a glass frit, and the ratio of the content of the antimony-based compound to the content of the glass frit (content of the antimony-based compound / content of the glass frit) is 0. The curable composition according to any one of claims 1 to 5, which is 1 to 9.
  7. 　ガラスフリットがリン酸系ガラスフリットであることを特徴とする請求項２に記載の硬化性組成物。 The curable composition according to claim 2, wherein the glass frit is a phosphate glass frit.
  8. 　建築構造物の壁部を構成している壁部材と、
    　上記壁部材間に形成された目地部に充填された請求項１～７の何れか１項に記載の硬化性組成物の硬化物と
    を含むことを特徴とする目地構造。     A wall member constituting a wall portion of a building structure;
    A joint structure comprising: a cured product of the curable composition according to any one of claims 1 to 7 filled in the joint portion formed between the wall members.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019216358A1 (en) * 2018-05-08 2019-11-14 積水フーラー株式会社 Synthetic resin composition, fire-proof material, sealing material, adhesive, and joint structure

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0881674A (en) * 1994-09-13 1996-03-26 Mitsui Kinzoku Toryo Kagaku Kk Fireproof sealing material
JPH0892490A (en) * 1994-09-26 1996-04-09 Asahi Glass Co Ltd Curable composition
JPH08134344A (en) * 1994-11-15 1996-05-28 Konishi Kk Refractory sealing material composition
JP2002256127A (en) * 2001-03-05 2002-09-11 Three Bond Co Ltd Sealing material composition for lithium ion cell
JP2004137316A (en) * 2002-10-16 2004-05-13 Asahi Denka Kogyo Kk Fireproof sealing material
JP2010168588A (en) * 2010-03-09 2010-08-05 Asahi Glass Co Ltd Methods for producing hydrolyzable silyl group-containing oxyalkylene polymer and curable composition
JP2018039997A (en) * 2016-08-31 2018-03-15 積水フーラー株式会社 Curable composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0881674A (en) * 1994-09-13 1996-03-26 Mitsui Kinzoku Toryo Kagaku Kk Fireproof sealing material
JPH0892490A (en) * 1994-09-26 1996-04-09 Asahi Glass Co Ltd Curable composition
JPH08134344A (en) * 1994-11-15 1996-05-28 Konishi Kk Refractory sealing material composition
JP2002256127A (en) * 2001-03-05 2002-09-11 Three Bond Co Ltd Sealing material composition for lithium ion cell
JP2004137316A (en) * 2002-10-16 2004-05-13 Asahi Denka Kogyo Kk Fireproof sealing material
JP2010168588A (en) * 2010-03-09 2010-08-05 Asahi Glass Co Ltd Methods for producing hydrolyzable silyl group-containing oxyalkylene polymer and curable composition
JP2018039997A (en) * 2016-08-31 2018-03-15 積水フーラー株式会社 Curable composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019216358A1 (en) * 2018-05-08 2019-11-14 積水フーラー株式会社 Synthetic resin composition, fire-proof material, sealing material, adhesive, and joint structure

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