JP5719495B2 - Two-component urethane-based curable composition, flooring adhesive and repair agent using the same, and flooring construction method and repairing method - Google Patents

Description

  The present invention relates to a two-component urethane-based curable composition that can be cured at room temperature, a flooring adhesive and a repair agent using the same, a flooring construction method and a repairing method, and the two-component urethane of the present invention. The system curable composition is useful as an adhesive, an injection agent, a coating agent, a waterproofing agent, a paint, and a sealing material.

  Polyurethane resin makes use of its excellent rubber elasticity, weather resistance, friction resistance, and chemical resistance, and various types of elastomers, coating agents, sealing materials, paints, waterproof coating materials, flooring materials, wall materials, adhesives, etc. Widely used in the field. In the field of architecture, polyurethane resin is used in many exterior materials and interior materials.

  The flooring material is made of natural, synthetic resin, or other various flooring materials that are placed on the concrete, ALC, wood, etc., which are the base materials, without any gaps, or pasted with an adhesive. Furthermore, it is constructed by putting a heat insulating material between the flooring and the base. In recent years, as a measure against living noise, a cushioning material, which is a foam made of synthetic resin, is inserted between the base and flooring so that the sound does not resonate downstairs, etc., or a wooden system with a cushioning material on the lining Flooring materials are often used. However, when a person repeatedly passes through the flooring portion such as when the ground is uneven, the cushioning material, the adhesive, etc. are broken, and the flooring sinks or produces a creaking sound. As countermeasures against these problems, elastic adhesives and the like have been devised, but it is still difficult to say that the flooring, which is repeatedly loaded by walking, has sufficient durability. In addition, there is a repair method in which all the flooring material is removed and the flooring material is reconstructed in order to repair the defect that has occurred, but it is often costly and partially repaired. However, many of the materials used for partial repair have hard physical properties after curing, and even if repairs are performed, the problem further expands around the repaired part, or a problem occurs again at the same part, and a repeated load is applied. As a repair material for flooring, it is not a material having sufficient performance for durability (for example, Patent Document 1).

  In addition, as a countermeasure against sick house syndrome and reduction of the burden on the global environment, a TVOC countermeasure product has been demanded particularly for interior materials. As for adhesives, measures such as reducing the amount of organic solvents used, changing to less harmful and harmless ones, and not using organic solvents are being studied and commercialized. There is a need for solvent-free environmentally friendly adhesives and repair agents for flooring.

Japanese Patent Application No. 2003-53715

  The object of the present invention is a completely solvent-free, organic solvent-free, odorless, low viscosity, good workability, excellent filling into gaps, good curability, good adhesion, and a cured product to be obtained. Provides urethane-based curable compositions that have excellent water resistance, chemical resistance, and cyclic load resistance, and can be cured at room temperature, flooring adhesives and repair agents, and flooring construction and repair methods using the same. It is to be.

  The two-component urethane-based curable composition of the present invention includes a component (A) containing a polyol having an ethylenically unsaturated bond and a catalyst, a component containing an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer ( A two-component urethane-based curable composition comprising B), which does not contain an organic solvent, and the equivalent ratio of the hydroxyl group of component (A) to the isocyanate group of component (B) is OH / NCO = 0.8 to 1.1 It is. Such a two-component urethane-based curable composition does not contain an organic solvent, has a low odor, has a low viscosity, good workability, and is excellent in repeated load resistance.

Each component used in the two-component urethane-based curable composition of the present invention will be described below.

(A) Polyol having an ethylenically unsaturated bond A polyol having an ethylenically unsaturated bond has at least two hydroxyl groups having a carbon-carbon double bond and an active hydrogen group in the molecule. The number average molecular weight of the polyol having an ethylenically unsaturated bond is preferably 300 to 20,000, particularly preferably 500 to 10,000. Examples thereof include a polyol having a photocurable unsaturated bond, a polyol having an oxygen curable unsaturated bond, and the like.

  As a polyol having a photocurable unsaturated bond, radical polymerization of (meth) acrylate monomers containing a hydroxyl group such as hydroxyethyl (meth) acrylate and other (meth) acrylic acid alkyl ester monomers is started. Examples thereof include a copolymer having a (meth) acryloyl group and a polyester polyol having a (meth) acryloyl group or a cinnamoyl group, which are copolymerized in the presence or absence of an agent.

  Examples of the polyol having an oxygen curable unsaturated bond include hydrocarbon polyols and polyester polyols having an oxygen curable unsaturated bond. Specifically, polybutadiene polyols, polyisoprene polyols, diene-based liquid (co) polymer modified products (maleinized modified products, boiled oil modified products, etc.), maleic acid, fumaric acid and other unsaturated polymers. Examples include dehydration condensation products of carboxylic acids and polyhydric alcohols, drying oils, various modified products of drying oils, and mixtures thereof. Among these, drying oil and various modified products of drying oil are preferable, and castor oil-based polyol is most preferable in the present invention.

  The castor oil-based polyol in the present invention is a polymer derived from castor oil. For example, an alkylene oxide adduct of castor oil, an epoxidized product of castor oil, a halide of castor oil, a transesterified product of castor oil and polyhydric alcohol, and the like can be used. Among these, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6- Hexanediol, Neopentyl glycol, Trimethylolpropane, Ditrimethylolpropane, Trimethylolethane, Glycerin, Diglycerin, Pentaerythritol, Dipentaerythritol, Polyester polyol, Polycaprolactone polyol, Polytetramethylene glycol polyol, Polybutadiene polyol, Polycarbonate polyol, An acrylic polyol etc. are mentioned.

  For modification of the urethane-based curable composition, cyclic ether compounds such as propylene oxide are subjected to ring-opening addition polymerization using low-molecular monoalcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol that are optionally used as initiators. Also, polyoxyalkylene monools such as polyoxypropylene monools can be used. The “system” such as polyoxyalkylene monool is 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding the hydroxyl group in 1 mol of the molecule. If it is constituted, it means that the remaining part may be modified with ester, urethane, polycarbonate, polyimide, poly (meth) acrylate, polyolefin, etc., but 95% by mass or more of the part excluding the hydroxyl group Most preferred are those composed of polyoxyalkylene.

  As the castor oil-based polyol, those having a hydroxyl value of 200 mgKOH / g or less and secondary hydroxyl groups in the total hydroxyl groups of 80% by mass or more, preferably 90% by mass or more are used. By using such a castor oil-based polyol, a urethane-based curable composition having both excellent curability and elongation can be obtained. If the hydroxyl value is greater than 200 mg KOH / g, the extensibility and pot life will be insufficient.

  The acid value of the castor oil-based polyol is desirably 10 mgKOH / g or less, and more desirably 5 mgKOH / g or less. When the acid value is within such a range, the film forming property is enhanced.

(B) Organic isocyanate compound, isocyanate group-containing urethane prepolymer Examples of the organic isocyanate compound include organic polyisocyanate and organic monoisocyanate that is optionally used for modification of the isocyanate group-containing urethane prepolymer. , Aromatic organic polyisocyanates in which isocyanate groups are bonded to aromatic hydrocarbons, or broadly defined aliphatic organic polyisocyanates in which isocyanate groups are bonded to aliphatic hydrocarbons (this includes aromatic aliphatic organic Polyisocyanate and narrowly defined aliphatic organic polyisocyanate are included).

  Examples of the aromatic organic polyisocyanate include diphenylmethane diisocyanates (MDIs) such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, or a mixture thereof. Examples include toluene diisocyanates (TDIs) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate or mixtures thereof, and diphenyl ether diisocyanate.

  Examples of the araliphatic organic polyisocyanate include xylylene diisocyanate, and the narrowly defined aliphatic organic polyisocyanate includes aliphatic polyisocyanate and alicyclic polyisocyanate. Examples include methylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate, and butylene diisocyanate. Examples of the alicyclic polyisocyanate include cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), and isophorone diisocyanate.

  In addition, carbodiimide-modified products, biuret-modified products, allophanate-modified products, dimers, trimers, or polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI) and the like of these diisocyanates may be mentioned. A combination of more than one species can be used. Among these, aromatic polyisocyanate is preferable in terms of excellent curability and elasticity of the cured product, and 4,4′-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) are preferred. Further preferred.

  Moreover, as modification | denaturation of the said urethane type curable composition, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-octadecyl monoisocyanate etc. are mentioned as organic monoisocyanate used by the case.

  The isocyanate group-containing urethane prepolymer is obtained by reacting an organic polyisocyanate compound and an active hydrogen-containing compound with an excess of isocyanate groups with respect to active hydrogen (group). As the organic polyisocyanate compound, the same organic polyisocyanate compound can be used.

  The isocyanate group-containing urethane prepolymer in the present invention can be synthesized by either a batch charge reaction method or a multistage charge reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. The isocyanate group / active hydrogen (group) equivalent ratio of the isocyanate group of the organic polyisocyanate to the high-molecular polyol and / or low-molecular polyol, and optionally the active hydrogen (group) of the chain extender is 1.1 to 5. 0 / 1.0 is preferable, and 1.3 to 2.0 / 1.0 is more preferable. The isocyanate group-containing urethane prepolymer thus obtained preferably has an isocyanate group content of 0.1 to 15.0% by mass, particularly preferably 0.3 to 10.0% by mass, most preferably 0.4. It is -5.0 mass%. When the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since there are few crosslinking points in a prepolymer, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, it is difficult to prevent foaming due to carbon dioxide gas, which is not preferable.

  Examples of the active hydrogen-containing compound include a high molecular polyol, a high molecular polyamine, a low molecular polyol, a low molecular amino alcohol and a low molecular polyamine, and the low molecular polyol and low molecular amino alcohol as a chain extender used in some cases. , Low molecular polyamines, polymers used for modifying isocyanate group-containing urethane prepolymers, low molecular monools, and the like.

  Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene polyol, hydrocarbon polyol, poly (meth) acrylate polyol, animal and plant polyol, these copolyols, or a mixture of two or more of these. Etc.

  The number average molecular weight of the polymer polyol is 500 or more, preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 20,000. If the number average molecular weight is less than 500, rubber elastic properties such as elongation after curing of the resulting curable composition deteriorate, and if it exceeds 100,000, the viscosity of the resulting isocyanate group-containing urethane prepolymer becomes too high, Since workability deteriorates, it is not preferable.

  Examples of the polyester polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, acid esters, or acid anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9- Nonanediol, diethylene glycol, dipropylene glycol, , 4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular polyols such as trimethylolpropane, glycerin, pentaerythritol, butylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, etc. Examples thereof include polyester polyols or polyester amide polyols obtained by a dehydration condensation reaction with one or more low molecular amino alcohols such as low molecular polyamines, monoethanolamine, and diethanolamine.

  Also, for example, lactone polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular polyols, low molecular polyamines, and low molecular amino alcohols as initiators. A polyol is mentioned.

  Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular polyols and phosgene used for the synthesis of the above-described polyester polyol, or esters of the low molecular polyols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by an exchange reaction is mentioned.

  Examples of the polyoxyalkylene polyol include low molecular polyols, low molecular polyamines, low molecular amino alcohols, polycarboxylic acids, sorbitol, mannitol, sucrose used for the synthesis of the above-described polyester polyols. 1 or more of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using one or more of low molecular weight polyhydric alcohols such as saccharides such as glucose and low molecular weight polyphenols such as bisphenol A and bisphenol F as initiators A polyoxyethylene-based polyol, a polyoxypropylene-based polyol, a polyoxybutylene-based polyol, a polyoxyethylene, which is obtained by ring-opening addition polymerization or copolymerization (hereinafter, “polymerization or copolymerization” is referred to as (co) polymerization). Ramechiren polyols, poly - (oxyethylene) - (oxypropylene) - random or block copolymer polyols, further polyester polyether polyol initiator polyester polyols and polycarbonate polyols described above, such as polycarbonate polyether polyols. Moreover, the polyol which made these various polyols and organic isocyanate react by hydroxyl group excess with respect to an isocyanate group, and made the molecular terminal a hydroxyl group is also mentioned.

  The number of average alcoholic hydroxyl groups per molecule of the polyoxyalkylene polyol is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3.

  Furthermore, the polyoxyalkylene-based polyol is produced at the time of production thereof by cesium hydride, cesium methoxide, cesium alkoxide such as cesium ethoxide, cesium-based compounds such as cesium hydroxide, diethyl zinc, iron chloride, metalloporphyrin, phosphazenium compound, The total unsaturation obtained by using a double metal cyanide complex such as a double metal cyanide complex such as a zinc hexacyanocobaltate glyme complex or diglyme complex as a catalyst is 0.1 meq / g or less. 07 meq / g or less, particularly 0.04 meq / g or less is preferable, and molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC) = Mw / Mn] is 1.6 or less, especially 1.0 Having a narrow 1.3, viscosity of the resulting diisocyanate sulfonate group-containing urethane prepolymer can reduce, and rubber elasticity properties after curing of the resulting cured composition is preferable in that is good.

  Examples of the hydrocarbon-based polyol include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol, and halogenated poly such as chlorinated polypropylene polyol and chlorinated polyethylene polyol. Examples include alkylene polyols.

  As a poly (meth) acrylate-based polyol, a (meth) acrylate monomer containing a hydroxyl group such as hydroxyethyl (meth) acrylate and another (meth) acrylic acid alkyl ester monomer are used as radical polymerization initiators. And those copolymerized in the presence or absence of.

  Low molecular polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol. 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol , Trimetrole propane, glycerin, pentaerythritol and the like. Examples of the low molecular amino alcohol include monoethanolamine and diethanolamine. Examples of the low molecular weight polyamine include butylene diamine, hexamethylene diamine, xylylene diamine, and isophorone diamine.

(C) Catalyst The catalyst includes metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron, such as stannous octylate and tin octenoate, and organic such as octyl acid, octenoic acid and naphthenic acid. Salts with acids, metal chelate compounds such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), salts of organic metals and organic acids such as dibutyltin dilaurate, dioctyltin dilaurate, triethylenediamine, triethylamine, Known urethanization catalysts such as organic amines such as tri-n-butylamine and salts thereof can be used. Of these, dibutyltin dilaurate, which has a large effect of promoting the urethanization reaction and has no irritating odor and low odor, is preferred.

  The compounding amount of the catalyst is 0.01 with respect to a total of 100 parts by mass of the active hydrogen group-containing compound contained in component (A) and the organic isocyanate compound and / or isocyanate group-containing urethane prepolymer contained in component (B). It is preferable to mix -1.0 mass part.

(D) Additive An additive can be further blended in the two-component urethane-based curable composition of the present invention. Examples of the additive include a plasticizer, a weather resistance stabilizer, a filler, a thixotropic agent, an adhesion improver, a storage stability improver (dehydrating agent), and a colorant. These additives can be arbitrarily added in an appropriate combination depending on the purpose and use of the composition.

  The plasticizer is used for the purpose of adjusting the rubber elastic properties of the curable composition or improving the workability by reducing the viscosity. For example, dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, butyl phthalate Phthalates such as benzyl, dioctyl adipate, diisodecyl succinate, dibutyl sebacate, butyl oleate, etc., alcohol esters such as pentaerythritol ester, trioctyl phosphate, tricresyl phosphate, etc. Phosphoric esters, chlorinated paraffins, polyoxyalkylenes not containing hydroxyl groups obtained by etherification or esterification of polyether polyols used for the synthesis of the above isocyanate group-containing urethane prepolymers, especially sugars such as sucrose Polysaccharide polyols containing no hydroxyl groups, such as etherified or esterified polyether polyols obtained by addition polymerization of ethylene oxide or propylene oxide to polyhydric alcohols, polystyrene oligomers such as poly-α-methylstyrene, polystyrene, Examples thereof include oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and hydrogenated polybutene, and plasticizers that do not react with isocyanate groups such as (meth) acrylate copolymer. These can be used alone or in combination of two or more.

  The plasticizer is 0 to 200 parts by mass with respect to a total of 100 parts by mass of the active hydrogen group-containing compound contained in component (A) and the organic isocyanate compound and / or isocyanate group-containing urethane prepolymer contained in component (B). In particular, it is preferable to blend 10 to 70 parts by mass.

  Specific examples of the weathering stabilizer include hindered phenolic antioxidants, hindered amine antioxidants, ultraviolet absorbers, and photocurable compounds.

  Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzenepropane Examples include acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-1 (octyloxy) -decanoate. 4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like having a low molecular weight of less than 1,000, dimethyl succinate 1- (2 -Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine 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}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro- 1,3,5-triazi Condensates, manufactured by Asahi Denka Kogyo Co., Ltd., trade names Adeka tabs LA-63P, LA-68LD and the like having a molecular weight of 1,000 or more. These can be used alone or in combination. Moreover, a low molecular weight thing and a high molecular weight thing can also be used in combination.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine-based UV absorbers, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butyl Examples thereof include benzoate ultraviolet absorbers such as phenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. Specifically, for example, an isocyanate group-containing urethane resin is added to a hydroxyl group-containing acrylate. Urethane acrylates and urethane methacrylates reacted with compounds and hydroxyl group-containing methacrylate compounds, ester acrylates such as trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, ester methacrylates, ester acrylates such as ethylene oxide or propylene oxide adducts of bisphenol A, Polyester acrylate and polyester methacrylate such as ester methacrylate and polyethylene adipate polyol acrylate and methacrylate Examples thereof include polyether acrylates such as acrylates and methacrylates of polyether polyols and polyether methacrylates, or polyvinyl cinnamates, azide resins, and the like, and have a molecular weight of 10,000 or less and a molecular weight of 5,000 or less. Preferred are monomers and oligomers, particularly those containing two or more acryloyl groups and / or methacryloyl groups on average per molecule.
These can be used alone or in admixture of two or more.

  A weathering stabilizer is 0-30 mass with respect to a total of 100 mass parts of the active hydrogen group containing compound contained in a component (A) and the organic isocyanate compound and / or isocyanate group containing urethane prepolymer contained in a component (B). Parts, particularly 0.1 to 20 parts by mass is preferred.

  Fillers, thixotropic agents, adhesion improvers, storage stability improvers (dehydrating agents), and colorants are used to reinforce and increase physical properties, improve adhesion, improve storage stability, and color, respectively. It can be used by blending with the curable composition of the present invention.

  Fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, precipitated silica, synthetic silica, calcium carbonate, carbonic acid Inorganic powder fillers such as magnesium, alumina, calcium oxide, magnesium oxide, fibrous fillers such as glass fibers and carbon fibers, inorganic balloon fillers such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, etc. Inorganic fillers, or fillers whose surfaces are treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp flour, cotton chips, rubber powder, thermoplastic or thermosetting resin fine powder, Powders such as polyethylene, hollow bodies, organic balloons such as Saran microballoons Other organic fillers such as Jo fillers, also listed and flame retardant fillers such as magnesium hydroxide and aluminum hydroxide, the particle diameter 0.01~1,000μm is preferred.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite and fatty acid amide. can do.

  The adhesion improver is used for blending in the curable composition of the present invention to improve the adhesion after curing, and examples thereof include a coupling agent, an epoxy resin, and an organic polyisocyanate.

  Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based compounds, or partial hydrolysis condensates thereof. Among these, silane-based coupling agents or partial hydrolysis-condensation products thereof. Is preferable because of its excellent adhesiveness.

  Specific examples of the silane coupling agent include methyl silicate, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxy. Silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dibutyldimethoxysilane, diphenyldimethoxy Silane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, tri Phenylmethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Low molecular weight compounds containing alkoxysilyl groups such as propylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc., having a molecular weight of 500 or less, preferably 400 or less, or these silane-based cups A compound having a molecular weight of 200 to 3,000 may be mentioned as one or two or more partially hydrolyzed condensates of the ring agent. These can be used alone or in combination of two or more.

  Examples of the storage stability improver include vinyltrimethoxysilane, calcium oxide, p-toluenesulfonyl isocyanate and the like which react with moisture present in the composition.

Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
These can be used alone or in admixture of two or more.

  The total amount of the filler, thixotropic agent, adhesion improver, storage stability improver (dehydrating agent) and colorant is the same as the active hydrogen group-containing compound and component (B) contained in component (A). It is preferable that it is 0-200 mass parts with respect to a total of 100 mass parts of the organic isocyanate compound and / or isocyanate group containing urethane prepolymer contained.

(E) Mixing ratio of component (A) and component (B) The mixing ratio of component (A) and component (B) is such that the equivalent ratio of the hydroxyl group of component (A) to the isocyanate group of component (B) is OH / NCO. = 0.8 to 1.1. Thereby, the repeated load resistance of the obtained cured product is remarkably excellent.

  Although it does not specifically limit as a manufacturing method of the curable composition of this invention, For example, the polyol and catalyst which have an ethylenically unsaturated bond are used as an essential component using a stainless steel or iron reactor, stirring, and a mixing apparatus. The component (B) which contains the component (A) to contain and an organic isocyanate compound and / or an isocyanate group containing urethane prepolymer as an essential component is manufactured. These productions may be carried out in the presence or absence of additive components. The production of component (A) includes a method in which a polyol having an ethylenically unsaturated bond and a catalyst are added, and if necessary, an additive component is added and kneaded, followed by degassing under reduced pressure. You may manufacture under a heating as needed. When blending a filler as an additive component, it is preferable to add a storage stability improver (dehydrating agent) in order to prevent the generation of carbon dioxide gas due to the reaction between contained moisture and isocyanate groups (anti-foaming). . The component (B) can be produced by a method of preparing an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer, adding an additive component as necessary, kneading, and degassing under reduced pressure. You may manufacture under a heating as needed. When blending a filler as an additive component, it is preferable to add a storage stability improving agent (dehydrating agent) as in the case of the component (A). The isocyanate group-containing urethane prepolymer of component (B) is separately reacted and synthesized. For example, the reaction synthesis may be carried out at room temperature to 120 ° C. for 1 to 10 hours by using an organic isocyanate compound and an active hydrogen group-containing compound using, for example, a stainless steel or iron reaction device, agitation, and a mixing device. . In the case of the component (A) containing an adhesion improver as an additive or the component (B) reacts with moisture to cause hydrolysis or thickening, so that the stirring / mixing of the reaction synthesis does not touch moisture. It is preferable to carry out in a sealed state and in a state where moisture is shut off such as in a nitrogen gas atmosphere. Examples of the stirring / mixing device include a planetary mixer made of stainless steel or iron, a kneader, an agitator, a nauter mixer, a line mixer, and the like. Moreover, it is preferable to store the container in a container that can block moisture during sealing. The container is not particularly limited. For example, a metal drum can made of stainless steel or iron, a pail can or bag container made of metal or synthetic resin, a laminated paper or synthetic resin cartridge container, etc. There are various types.

  The thus-prepared two-component urethane-based curable composition of the present invention has a viscosity ([viscosity] in a test method described later) measured immediately after mixing the two components of 200 to 700 (mPa · s / 25 ° C. In addition, in the flowability test ([flowability] in the test method described later), the diameter of the two-component urethane-based curable composition spreading in a circle after 15 minutes is 5 cm to 19 cm. . When the viscosity is less than 200 (mPa · s / 25 ° C.) or the flowability exceeds 15 cm after 10 seconds, it is difficult to obtain a coating thickness and sufficient adhesion between the two-component urethane-based curable composition and the flooring material is obtained. When the two-component urethane-based curable composition of the present invention is injected through the injection needle by drilling a hole of about 1 mmφ on the flooring or waterproof material, it flows out from the gap or space where the injection is attempted. As a result, it becomes difficult to prevent the floor material from sinking and flooring (squeaking noise). Further, when the viscosity exceeds 700 (mPa · s / 25 ° C.) or the flowability is less than 5 cm after 10 seconds, it is difficult to inject the two-component urethane-based curable composition of the present invention through the injection needle. Become. Furthermore, it becomes difficult to fill gaps and spaces, and it becomes difficult to fill and penetrate into spaces such as peeling points, backing materials (backing materials), or heat insulating materials. As a result, floor material sinks and squeals (squeak noise) ) Is difficult to prevent.

  The curability of the two-component urethane-based curable composition of the present invention is such that gel time ([gel time] of the test method described later) is 15 minutes to 20 minutes, and curability ([curability] of the test method described later) is. It becomes 7 cm to 18 cm after 1 minute and 5 cm to 15 cm after 3 minutes. If the gel time is less than 15 minutes or the curability is less than 7 cm after 1 minute, the thickening after mixing the two components becomes too early, making it difficult to apply and inject, and fill gaps and spaces. It becomes difficult, and it becomes difficult to fill and penetrate into a space such as a peeling site, a backing material (backing material), or a heat insulating material, and as a result, it is difficult to prevent the floor material from sinking and floor noise (squeak noise). If the gel time exceeds 20 minutes, or if the curability exceeds 15 cm after 3 minutes, the thickening after mixing the two components is too slow and it will flow out from the gaps or spaces where it is going to be injected, resulting in a decrease in filling properties. In other words, time is required for curing curing after the application of the two-component urethane-based curable composition, resulting in increased costs.

  The cured product after the reaction-curing of the two-component urethane-based curable composition of the present invention has a JIS A hardness of 30 to 70, preferably 40 to 60. The cured product has a storage elastic modulus (E ′) at 5 ° C. of 2.5 to 50.0 MPa, a storage elastic modulus (E ′) at 23 ° C. of 2.5 to 50.0 MPa, and a storage elastic modulus of 35 ° C. ( E ′) is 2.5 to 50.0 MPa. By doing this, the flooring and repaired parts will have excellent walking feeling with no sense of incongruity, such as a soft sunk feeling or a hard feeling when walking, and after maintaining and maintaining durability to withstand repeated loads In this case, the repaired portion is the starting point and does not peel or break (crush) again, and the above-mentioned defect does not spread around the repaired portion. When the storage elastic modulus (E ′) at 5 ° C. is less than 2.5 MPa, the storage elastic modulus (E ′) at 23 ° C. is less than 2.5 MPa, and the storage elastic modulus (E ′) at 35 ° C. is less than 2.5 MPa, There is a feeling of soft sinking of the material and the repaired part, the storage elastic modulus (E ′) at 5 ° C. exceeds 50 MPa, the storage elastic modulus (E ′) at 23 ° C. exceeds 50 MPa, and the storage elastic modulus at 35 ° C. (E When ') exceeds 50 MPa, it is difficult to have a sense of incongruity such as a hard feel and an excellent walking feeling.

  Further, the two-component urethane-based curable composition of the present invention has excellent adhesiveness to a backing material (backing material) or a heat insulating material, and is used for a portion (floor material or the like) where a repeated load is applied. However, the two-component urethane-based curable composition does not peel from the backing material (backing material) or the heat insulating material, or does not repeatedly cause the same problem at the repaired site, and the floor material sinks or floors. It can prevent squealing (squeaking noise).

Next, the flooring construction method of the present invention will be described. The foundation to which the construction method of the present invention is applied is a foundation of a building formed of various materials. Specifically, the two-component urethane-based curable composition of the present invention includes mortar, concrete, fiber reinforced cement board. It can be suitably applied to a building foundation formed of plywood or various resin foam moldings. Floor materials and waterproofing materials suitable for the construction method of the present invention are made of resin or wood, and for example, there are various shapes such as large and small tile shapes, sheet shapes, long sheet shapes, etc. Is made of polyvinyl chloride, soft polyvinyl chloride, polyolefin such as polypropylene and polystyrene, polyurethane, synthetic rubber such as styrene-butadiene rubber, polycarbonate, polyphenylene oxide, polyester such as polybutylene terephthalate, melamine resin Made of various resins (including foams) such as ABS, natural rubber, and ABS resin, and the surface layer is made of the above-mentioned various resins. Polyurethane, polyolefin, synthetic rubber as a backing material (backing material) Examples include those in which various types of resins (including foams) are laminated in one or more layers. That. Examples include so-called flooring materials. The two-component urethane-based curable composition of the present invention may be quantitatively mixed and applied to the base, and then the flooring may be laid on top and bonded by pressing, or applied to the flooring, It may be laid on the base from the adhesive application side and pressed to adhere, and further applied to both the base and the flooring, and then the adhesive applied surfaces are joined and pressed to adhere However, from the viewpoint of ease of work, a method of applying an adhesive only to the base surface in advance and bonding is preferable. Further, when the flooring material has a backing material (backing material), the amount applied to the flooring material side can be increased, or the backing material (backing material) can be impregnated for use. Specifically, it is preferable that the two-component urethane-based curable composition of the present invention is applied to a base and then subjected to pressure bonding. As a coating method, a method using a trowel such as a comb iron, a spatula, a brush, a roll coater or the like, or a bead or spot using a gun equipped with a dedicated static mixer type nozzle. The method of apply | coating to a shape, the method of spray coating, etc. can be used. The coating amount of two-component urethane curable composition of the present invention, 100 to 1000 g / ^{m 2,} it is preferred even at 150~500g / ^{m 2.}

  Next, the repair method will be described. In the repair method using the two-component urethane-based curable composition of the present invention, the repair location is a small area, and the floor material or waterproof material is removed and the floor material or waterproof material is newly applied. This is useful when a large amount of money is required or when it is necessary to complete the work in a short time. This is effective when, for example, the floor material is bent or a squeak noise is caused by walking due to partial peeling (collapse) of the floor material or waterproof material. Specifically, about 1 mmφ reaching the adhesive, backing material (backing material) or heat insulating material on the flooring or waterproofing material at equal intervals or irregularly at the repair site or at several locations around the repair site The two-component urethane-based curable composition of the present invention is injected through an injection needle. The injection of the two-component urethane-based curable composition of the present invention can be performed using a two-liquid gun and a static mixer type nozzle.

  By the above construction method or repair method, the two-component urethane curable composition of the present invention can be constructed with the same feeling as a one-pack type. In addition, because of its low viscosity, it has excellent workability and good filling into gaps, so that it penetrates and penetrates into spaces such as peeling points and the destruction (collapse) of backing materials (backing materials) or insulation materials for a short time. It hardens and adheres firmly. Walking is possible in about 1 hour after the construction, and the repaired portion is excellent in walking feeling with no sense of incongruity during walking. Furthermore, the cured product of the two-component urethane-based curable composition of the present invention retains durability capable of withstanding repeated loads, and the repaired portion does not peel or break (crush) after repair. In addition, the defect does not spread around the repaired area.

  Furthermore, since the two-component urethane-based curable composition of the present invention is solventless and odorless or has a low odor, it is a material that is friendly to the living environment and is friendly to the global environment.

  Although the Example of this invention is shown below, it cannot be overemphasized that it is not limited to this.

[Synthesis of Isocyanate Group-Containing Urethane Prepolymer PU-1]
Synthesis example 1
To a reaction vessel equipped with a stirrer, a thermometer, a nitrogen seal tube and a heating / cooling device, 100.0 g of polyoxypropylenediol (Asahi Glass Co., Ltd., trade name Exenol 3021, number average molecular weight 3300) was charged while stirring the nitrogen gas However, 63.0 g of MR200 (Nippon Polyurethane Industry Co., Ltd. Crude MDI, NCO%: 31.5) was charged. The mixture was stirred at a reaction temperature of 70 ° C. to 80 ° C. for 4 hours, and when the isocyanate group content by titration was 10.6% by mass or less, the reaction was terminated (actually measured value 10.3% by mass) and cooled. Isocyanate group-containing urethane prepolymer PU-1 was synthesized.

Example 1
732 g of castor oil-modified polyol (URIC H-30, hydroxyl value 160.9, average functional group number 2.7 manufactured by Ito Oil Co., Ltd.) while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and heating / cooling device And 1.30 g of dibutyltin dilaurate were charged. After stirring and mixing at room temperature, the mixture was further degassed under reduced pressure at room temperature for 15 minutes to prepare component (A). Next, 650.0 g of DINP (diisononyl phthalate) and 350.0 g of MR200 (Nippon Polyurethane Industry Crude MDI, NCO%: 31.5) were charged into the same apparatus as described above. After stirring and mixing at room temperature, the mixture was further degassed under reduced pressure for 15 minutes at room temperature to prepare component (B). Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 0.8, the It used for the test.

Example 2
Component (A) was prepared in the same manner as in Example 1 except that the castor oil-modified polyol was changed to 870 g. Next, component (B) was prepared in the same manner as in Example 1. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 0.95, the It used for the test.

Example 3
Component (A) was prepared in the same manner as in Example 1 except that 1007 g of castor oil-modified polyol was used. Next, component (B) was prepared in the same manner as in Example 1. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 1.1, the It used for the test.

Example 4
Component (A) was prepared in the same manner as in Example 1 except that 289 g of castor oil-modified polyol was used. Next, component (B) was prepared in the same manner as in Example 1 except that 350 g of an isocyanate group-containing urethane prepolymer PU-1 synthesized instead of 350 g of MR200 was used. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 0.95, the It used for the test.

Example 5
Component (A) was prepared in the same manner as in Example 1 except that 870 g of castor oil-modified polyol and 6.50 g of dibutyltin dilaurate were used. Next, 560 g of DINP (diisononyl phthalate), 90.0 g of colloidal silica (manufactured by Tokuyama, Leoseal) and 350 g of MR200 were charged in the same apparatus as in Example 1 and stirred at room temperature, followed by degassing under reduced pressure at room temperature for 15 minutes. Component (B) was prepared. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 0.95, the It used for the test.

Comparative Example 1
Component (A) was prepared in the same manner as in Example 1 except that 641 g of castor oil-modified polyol was used. Next, component (B) was prepared in the same manner as in Example 1. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 0.7, the It used for the test.

Comparative Example 2
Component (A) was prepared in the same manner as in Example 1 except that the castor oil-modified polyol was changed to 1098 g. Next, component (B) was prepared in the same manner as in Example 1. Subsequently, the component (B) The component (A), the equivalent ratio of the isocyanate groups of the hydroxyl groups and of component (A) (B) is formulated such that the OH / NCO = 1.2, the It used for the test.

Comparative Example 3
A two-component epoxy adhesive (Bond Quick Mender manufactured by Konishi Co., Ltd.) was used.

Test method [viscosity]
Each of a component (A) and a component (B) was left still in a 25 degreeC thermostat for 1 hour. Next, the component (A) and the component (B) were mixed, and immediately using a B8M type rotational viscometer at 25 ° C., No. The value was read after 2 rotors, 60 rotations and 1 minute after starting.
[Flowability]
Two lines intersecting at right angles are drawn at the center of a smooth base (such as a slate plate), and further, a line that equally divides the angle is drawn between the two lines. Next, the component (A) and the component (B) are mixed, and 25 g of the mixture is poured from the height of 15 cm onto the intersection of the two lines after 1 minute of mixing. After a certain period of time has elapsed after the mixture has dropped , the tip of the mixture that has flowed and spread in a substantially circular shape on the base surface is marked at three points (points) that pass on any three different straight lines of the four straight lines. Etc.). After the mixture is cured, the diameters (cm) of the three cured products are measured, and the average value is defined as the flowability value.

[Odor]
Immediately after mixing the component (A) and the component (B), they were evaluated by a sensory test. Evaluation is ○ when there is almost no solvent odor and / or chemical-like odor, △ when the solvent odor and / or chemical-like odor is still felt or slightly felt, and when the solvent odor and / or chemical-like odor is strong Or it was set as x when it felt clearly.

[Geltime]
After mixing each component of the example and the comparative example in a cup at a predetermined ratio in an atmosphere of 23 ° C. and 50% RH, the sample was quickly lifted to a height of 15 cm from the cup with a stirrer. The time from the start of mixing until the sample snaps back by this operation was measured.
[Curing property]
In the flow test, the mixture is held for a certain time after mixing the components (A) and (B). Next, a fluidity test is performed. The diameter (cm) of 3 places after the fall of 15 minutes after mixing is measured, and 3 average value is made into the value of sclerosis | hardenability.

[Foaming]
Ingredient (A) and ingredient (B) were mixed and degassed and immediately filled into a container of 70 mm square and about 25 mm thickness. After standing for 7 days in a JIS standard at 23 ° C. and 50% relative humidity to cure and cure, the cured product was visually observed to evaluate the presence or absence of foaming. Alternatively, the component (A) and the component (B) are mixed and degassed, and immediately applied to the surface of the lauan plywood having a thickness of 3 mm in a bead shape having a width of 20 mm × vertical height of 10 mm × length of 100 mm, and 23 ° C. Cured for 7 days at 50% relative humidity. Next, the vicinity of the center of the width of the cured product was cut longitudinally using a cutter, and the presence or absence of foaming inside the cured product was observed visually. The case where foaming was not recognized or very little was evaluated as ◯, and the case where many foams were observed was evaluated as × .

[hardness]
After mixing component (A) and component (B), they were allowed to stand for 7 days in a JIS standard at 23 ° C. and 50% relative humidity and cured by curing to produce a cured product having a size of about 70 mm square and a thickness of about 25 mm. Using a spring type hardness tester, the Shore A hardness of the cured product was measured.
[Elastic modulus]
After mixing component (A) and component (B), they were cured and cured in a standard state (23 ° C., 50% RH) for 2 days to produce a sheet having a thickness of 2 mm. Dynamic viscoelasticity spectrum (sample shape: length (L) width (W) thickness (t) below, measurement temperature using dynamic viscoelasticity measuring device (Orientec Co., Ltd., RHEOVIBRON DDV-01 / 25FP) -100 ° C to + 100 ° C, measurement frequency: 11 Hz, rate of temperature increase: 2 ° C / min), and storage elastic modulus (E ') (MPa) at 5 ° C, 23 ° C, and 35 ° C was determined.

[Repetitive load resistance]
A groove having a width of 40 mm, a length of 150 mm, and a depth of 3 mm was formed on the surface of an ALC plate having a length of 150 mm, a width of 150 mm, and a thickness of 60 mm so as to form a cross at the center. On this ALC plate, a 150 mm long x 150 mm wide x 20 mm thick heat insulating material (foamed phenol foam) is layered, and a flooring material (with a surface wood-based backing material, 13.5 mm thick including the backing material) is stacked, A frame was provided on the peripheral side surface so that the ALC plate, the heat insulating material, and the flooring material did not shift, and a double-sided tape was used around the heat insulating material between the heat insulating material and the flooring material. From the top of the flooring material to the central part of the cross-shaped groove, a 100 mm load was repeatedly pushed 60,000 times at a rate of 10 times / minute with a 40 mmφ cylinder, and a gap (due to the collapse of the foam) Formed). Using this material as a test specimen, a hole of 1 mmφ × about 23 mm was made in the center of the cross groove from above the flooring material, and a dedicated gun (with a static mixer nozzle) was injected until the mixture emerged from the inlet. After curing at 23 ° C and 50% RH for 1 hour, 100kg load is repeated 60,000 times at a rate of 10 times / min with a 40mmφ cylinder from the top of the flooring material to the center of the cross groove in the standard state. Pressed. Subsequently, the heat insulating material was taken out from the test body and equally divided along a line connecting two of the corners passing through the central portion. The central void portion (due to the collapse of the foam) was visually observed, and the case where the void portion was not expanded and grown was evaluated as ◯, and the case where the void portion was expanded around was evaluated as x.

Claims (6)

A component (A) containing a castor oil-based polyol having an oxygen-curable ethylenically unsaturated bond and a urethanization catalyst, and a component (B) containing an organic isocyanate compound and / or an isocyanate group-containing urethane prepolymer, For flooring, which does not contain an organic solvent, and is composed of a two-component urethane-based curable composition in which the equivalent ratio of the hydroxyl group of component (A) to the isocyanate group of component (B) is OH / NCO = 0.8 to 1.1 Repair agent.   The flooring repair agent according to claim 1, wherein the organic isocyanate compound is an aromatic polyisocyanate compound.   The flooring repair agent according to claim 2, wherein the aromatic polyisocyanate compound is polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). The flooring repair agent according to any one of claims 1 to 3 , wherein the urethanization catalyst is dibutyltin dilaurate. The repair method of the flooring using the repair agent for flooring of any one of Claims 1-4 . A two-component urethane-based curable composition is poured into a hole made in a flooring material, and the two-component urethane-based curable composition is infiltrated into a space between a flooring material and a base or a backing material or a heat insulating material and cured. The floor material repairing method according to claim 5 , wherein the floor material sinks and / or the occurrence of a creaking sound is prevented.