WO2017077722A1 - 微紛体コーティングアミンおよびそれを含有する組成物 - Google Patents
微紛体コーティングアミンおよびそれを含有する組成物 Download PDFInfo
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- WO2017077722A1 WO2017077722A1 PCT/JP2016/060104 JP2016060104W WO2017077722A1 WO 2017077722 A1 WO2017077722 A1 WO 2017077722A1 JP 2016060104 W JP2016060104 W JP 2016060104W WO 2017077722 A1 WO2017077722 A1 WO 2017077722A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Definitions
- the present invention relates to a fine powder coating amine and a one-component heat curable composition containing the fine powder coating amine as a curing agent component.
- the one-component heat-curable composition using the fine powder coating amine and the surface-treated solid amine compound described in Patent Documents 1 to 3 can be sufficiently cured when cured at a relatively low temperature. Therefore, it has been found that the desired breaking strength may not be obtained.
- the present invention can provide excellent curability and physical properties, particularly good breaking strength, even when a one-component thermosetting composition containing a fine particle coating amine as a curing agent component is cured at a relatively low temperature.
- a one-component heat curable composition containing a fine powder coating amine is provided.
- the present invention includes the following.
- the fine powder coating amine according to any one of [1] to [3], wherein the weight ratio of the fine powder to the solid amine is 1 / 0.001 to 1 / 0.5.
- the fine powder is at least one selected from the group consisting of polyvinyl chloride, titanium oxide, calcium carbonate, clay, carbon, alumina, talc, zinc oxide and silica, according to [1] to [4] The fine powder coating amine according to any one of the above.
- a one-component heat-curable composition comprising the fine-particle coating amine according to any one of [1] to [5].
- the one-component thermosetting composition according to [6] comprising an isocyanate component.
- the one-component heat-curable composition containing the fine-particle coating amine of the present invention as a curing agent component has excellent curability and physical properties, particularly good breakage, even when cured at a relatively low curing temperature, for example, 100 ° C. The strength can be obtained stably.
- the fine powder coating amine of this invention has sufficient activity as a hardening
- the fine powder-coated amine of the present invention is obtained by coating the surface of a solid amine having a melting point of 50 ° C. or more and a center particle size of 20 ⁇ m or less with a fine powder having a center particle size of 2 ⁇ m or less, and measuring with a differential scanning calorimeter.
- the amount of heat at the second absorption peak (hereinafter also referred to as second absorption peak heat amount) is 220 J / g or less.
- the second absorption peak calorie is obtained by measuring the endothermic amount at the heat absorption peak measured after the first heat absorption peak (melting point) measured by the differential scanning calorimeter when the fine powder coated amine is heated. That is.
- the second absorption peak heat quantity is expressed by the following formula: RNH 2 + CO 2 + H 2 O ⁇ RNH 3 + CO 3 H ⁇ It is surmised that it is caused by the amino group carbonated by the reaction shown in FIG. 1, and the fine particle coating amine contains more active amino groups (NH 2 ) that are not carbonated as the second absorption peak calorific value is lower. It will have high activity as a curing agent.
- the fine powder coating amine of the present invention has a second absorption peak calorie of 220 J / g or less, preferably 200 J / g or less, and more preferably 150 J / g or less.
- the lower limit value of the second absorption peak heat amount is not particularly limited, but is, for example, 0 J / g or more.
- the second absorption peak calorific value exceeds 220 J / g, it is not sufficiently activated at a relatively low curing temperature, such as 100 ° C., and high activity is obtained as a curing agent in a one-component thermosetting composition. Absent.
- the second absorption peak calorific value is a value measured according to the second absorption peak measurement method described in the examples of the present specification, unless otherwise specified.
- any aromatic or aliphatic amine can be used as long as the melting point is 50 ° C. or higher.
- Examples thereof include 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminobiphenyl, 2,4′- Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine Aromatic amines such as 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, 1,12-dodecanediamine, 1,10-decanediamine,
- the solid amine has a center particle size of 20 ⁇ m or less.
- the lower limit value of the center particle size is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, further preferably 2 ⁇ m or more, and particularly preferably 3 ⁇ m or more.
- the upper limit value of the central particle size is preferably 15 ⁇ m or less, more preferably 12 ⁇ m or less, further preferably 10 ⁇ m or less, particularly preferably 8 ⁇ m or less, especially 6 ⁇ m or less.
- the range of the center particle diameter may be any combination of these upper limit value and lower limit value, for example, 1 ⁇ m to 15 ⁇ m, preferably 1 ⁇ m to 12 ⁇ m, more preferably 1.5 ⁇ m to 10 ⁇ m, still more preferably It is 2 ⁇ m to 8 ⁇ m, particularly preferably 3 ⁇ m to 6 ⁇ m.
- 1 ⁇ m to 15 ⁇ m preferably 1 ⁇ m to 12 ⁇ m, more preferably 1.5 ⁇ m to 10 ⁇ m, still more preferably It is 2 ⁇ m to 8 ⁇ m, particularly preferably 3 ⁇ m to 6 ⁇ m.
- the center particle size is a particle size obtained by using a dry unit of a laser diffraction / scattering particle size distribution measuring apparatus and having a passing portion integrated distribution of 50%.
- the center particle diameter of the solid amine is a value measured according to the measurement method of the center particle diameter described in the examples of the present specification unless otherwise specified.
- inorganic fine powder and organic fine powder can be used.
- the inorganic fine powder include titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina, talc and the like.
- the organic fine powder include polyvinyl chloride, polyacrylic resin, polystyrene, polyethylene, urea resin and the like. These can be used alone or as a mixture of two or more.
- the fine powder has a center particle size of 2 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less, especially 0.05 ⁇ m or less.
- the lower limit value of the center particle diameter of the fine powder is not particularly limited, but is, for example, 0.001 ⁇ m or more.
- the center particle size of the fine powder is a value measured according to the method for measuring the center particle size described in the examples of the present specification, unless otherwise specified.
- the weight ratio of solid amine to fine powder is preferably 1 / 0.001 to 1 / 0.5, more preferably 1 / 0.01 to 1 / 0.5.
- the weight ratio of the fine powder to the solid amine is within the above range, storage stability can be obtained efficiently.
- Fine powder coating amine of the present invention 1) a step of pulverizing a solid amine having a melting point of 50 ° C. or higher into a solid amine having a center particle size of 20 ⁇ m or less by using a pulverizer; and 2) a solid amine obtained in step 1) and 2 ⁇ m or less.
- the steps 1) and 2) are carried out at a temperature of 30 ° C. or lower, preferably 25 ° C. or lower, more preferably 20 ° C. or lower, and / or a relative humidity of 70% or lower, preferably 65% or lower. Preferably, it is performed in an atmosphere of 55% or less.
- a temperature of 30 ° C. or lower preferably 25 ° C. or lower, more preferably 20 ° C. or lower, and / or a relative humidity of 70% or lower, preferably 65% or lower.
- it is performed in an atmosphere of 55% or less.
- a high-speed impact mixing pulverizer such as a jet mill or a hammer mill can be used.
- a jet mill is preferable because particle size adjustment is easy and a sharp particle size distribution can be obtained, and contamination such as metal powder is suppressed, and in particular, raw materials collide with each other by using opposed compressed gas flows.
- a counter-type jet mill that pulverizes in this manner is preferable.
- the air pressure (0.4 to 0.8 MPa), the classification rotational speed (3000 to 12000 rpm), and the pulverization time can be appropriately adjusted according to the processing amount, the desired particle size, and the like. it can.
- inert gas such as nitrogen gas, as compressed gas instead of compressed air.
- the pulverized solid amine is mixed with fine powder using a mixing stirrer.
- a mixing stirrer As a result, static electricity is generated and fine powder adheres to the surface of the solid amine, or the solid amine is locally melted and fixed due to heat generated by friction, impact, compression shear, etc. generated by the mechanical force of the mixing stirrer.
- the fine powder may be fixed, physically anchored or embedded on the surface of the solid amine, or chemically activated and fixed. In this way, the active amino group (NH 2 ) on the surface of the solid amine is covered with the fine powder.
- the mixing stirrer for example, a Henschel mixer, a hybridizer, a jet mill or the like can be used.
- the Henschel mixer is preferable because it can embed fine powder strongly on the surface of the solid amine and make it difficult to peel off.
- mixing time (1-30 minutes)
- blade type for example, upper blade: Y special 4, lower blade: combination of S0, etc.
- rotational speed (10 to 100 m / sec) can be adjusted.
- the Henschel mixer can be mixed with a solid amine that has been filled with an inert gas such as nitrogen gas and pulverized, and a fine powder.
- the fine powder can be charged into the pulverizer simultaneously with the solid amine and / or into the mixing stirrer after step 1). Therefore, a fine powder coating amine can be produced by adding fine powder after pulverization of solid amine and / or simultaneously with solid amine, and pulverizing and mixing, using a jet mill instead of a mixing stirrer.
- the second absorption measured by a differential scanning calorimeter in which the surface of a solid amine having a melting point of 50 ° C. or higher and a center particle size of 20 ⁇ m or less is coated with a fine powder having a center particle size of 2 ⁇ m or less.
- a fine powder coating amine having a heat quantity at the peak of 220 J / g or less is obtained.
- the fine powder coated amine of the present invention can be activated at a temperature of 50 ° C. to 150 ° C., preferably 60 ° C. to 120 ° C.
- the one-component thermosetting composition of the present invention contains the fine powder coating amine.
- the one-component heat-curable composition of the present invention is at least one selected from the group consisting of an isocyanate component, a hydrolyzable silyl group-containing component, an epoxy resin component, and a mixture thereof in addition to the fine powder coating amine. Comprising.
- isocyanate component examples include polyisocyanate compounds, terminal active isocyanate group-containing urethane prepolymers, and mixtures thereof.
- polyisocyanate compound examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
- examples thereof include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), crude MDI, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,4-phenylene diisocyanate, p-toluenesulfonyl isocyanate, n-octadecyl isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, crude TDI, polymethylene polyphenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate ,
- a terminally active isocyanate group (NCO) -containing urethane prepolymer (hereinafter also referred to as a terminal NCO prepolymer) has an excess amount of a polyisocyanate compound in an ordinary polyol component, for example, an equivalent ratio of OH / NCO is 1 / 1.2- It can manufacture by making it react so that it may become 3.5.
- the polyisocyanate compound the aforementioned polyisocyanate compounds can be used.
- the reaction may be carried out by using an appropriate reaction solvent (for example, ethyl acetate, toluene, xylene, etc.) and a reaction catalyst (for example, an organic tin catalyst such as dibutyltin dilaurate, a bismuth catalyst such as bismuth octylate, 1,4-diaza [ 2.2.2] in the presence of a tertiary amine catalyst such as bicyclooctane, etc., usually at room temperature to 60 to 90 ° C. for 1 to 7 hours.
- the obtained terminal NCO-containing prepolymer usually has a terminal NCO content of 0.5 to 5% (% by weight, the same applies hereinafter) and a viscosity of 5000 to 500,000 Pa ⁇ s at 20 ° C.
- polyol component examples include addition polymerization of propylene oxide or an alkylene oxide such as propylene oxide and ethylene oxide to a polyhydric alcohol such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose.
- a polyhydric alcohol such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose.
- Polyether polyols ethylene glycol, propylene glycol and their oligoglycols; butylene glycol, hexylene glycol, polytetramethylene ether glycols; polycaprolactone polyols; polycarbonate polyols; polyester polyols such as polyethylene adipate; Polyols; higher fatty acid groups having hydroxyl groups such as castor oil Ethers; polyether polyols or polymeric polyols grafted vinyl monomer to the polyester polyols and the like. If it is an expert, the said polyol component can be suitably selected and used according to the intended purpose and use conditions of a one-pack type thermosetting composition.
- the one-component heat-curable composition of the present invention is composed of a system in which the above-mentioned isocyanate component and fine powder coating amine are blended, if necessary, it is tough against the physical properties of the cured product, particularly compression set, etc.
- an appropriate amount of a bifunctional or higher functional epoxy resin can be added as an additional component.
- Examples of the epoxy resin include bisphenol A type, F type, AD type, phenol type, cresol type, cycloaliphatic type, glycidyl ester type, glycidylamine type, and the like is particularly preferable.
- the epoxy resin can be used in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the isocyanate component. If it is in the said range, the physical property of an epoxy resin can be exhibited, without impairing the rubber
- the mixing ratio of the isocyanate component and the fine powder coating amine is preferably 0.9 to 1.3, more preferably 0.95 to 1.2, and still more preferably 1. equivalent ratio of NCO to NH 2 after heating activity. It can be set to be 0 to 1.1.
- hydrolyzable silyl group-containing component examples include a modified silicone polymer, an acrylic polymer having an alkoxysilyl group, a polyisobutylene polymer having an alkoxysilyl group, and a mixture thereof.
- the modified silicone polymer has a polyoxyalkylene ether as a main chain skeleton and a hydrolyzable group (for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid) at the terminal or side chain.
- a hydrolyzable group for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid
- a liquid polymer having a silyl group having an amide group, an aminooxy group, a mercapto group, an alkenyloxy group, etc. is designated.
- those having polyoxypropylene ether as the main chain skeleton and a number average molecular weight of 9000 to 25000 are preferable.
- modified silicone polymer examples include, for example, MS polymer series (“MS polymer S-203”, etc.) manufactured by Kaneka Corporation and “Exester” (registered trademark) series, manufactured by Asahi Glass Co., Ltd.
- Acrylic polymer having an alkoxysilyl group means that the main chain skeleton is composed of at least a (meth) acrylate unit [a single monomer that can be copolymerized with a (meth) acrylate ester in addition to a (meth) acrylate unit] (May contain units of olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, etc.)], polymers containing alkoxysilyl groups in the molecule .
- a (meth) acrylate unit a single monomer that can be copolymerized with a (meth) acrylate ester in addition to a (meth) acrylate unit
- alkyl acrylate preferably having 2 to 4 alkyl carbon atoms
- alkyl acrylate preferably having 2 to 4 alkyl carbon atoms
- alkyl acrylate preferably having 2 to 4 alkyl carbon atoms
- alkyl acrylate preferably having 2 to 4 alkyl carbon atoms
- Hexyl acrylate 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, etc.
- vinylalkoxysilanes eg vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyldimethylmethoxysilane
- One or two selected from the group of (meth) acryloxyalkoxysilane for example, ⁇ -methacryl
- Monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, propyl acrylate, pentyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, cyclohexyl Methacrylate such as methacrylate; Styrene or its derivatives ( ⁇ -methyl styrene, chloromethyl styrene, etc.); Fumaric acid diester such as diethyl fumarate, dibutyl fumarate, dipropyl fumarate; Vinyl chloride, vinylidene chloride, ethylene fluoride, fluorine Vinyl halides such as vinylidene fluoride and vinylene fluoride]] 100 parts (parts by weight, the same applies hereinafter) And alk
- the alkoxysilyl group-containing polyisobutylene-based polymer has a main chain skeleton composed of at least isobutylene units [in addition to isobutylene units, monomers that can be copolymerized with isobutylene (for example, olefins having 4 to 12 carbon atoms, vinyl ethers, aromatics).
- isobutylene for example, olefins having 4 to 12 carbon atoms, vinyl ethers, aromatics.
- a unit of an aromatic vinyl compound, vinyl silanes, allyl silanes, etc.)] containing alkoxysilyl groups at both ends of the molecule, and preferably having a number average molecular weight of 1000 to 40,000 and a room temperature waxy or highly viscous liquid.
- the weather resistance is excellent, and the physical properties after curing can be adjusted to low modulus and high elongation.
- an acrylic-modified modified silicone polymer commercially available as an acrylic polymer containing an alkoxysilyl group obtained by polymerization in a modified silicone polymer (for example, “MS polymer S-943” manufactured by Kaneka Corporation). Etc.)
- the compatibility of the components in the one-component thermosetting composition is good, and the weather resistance can be improved by the interaction with the modified silicone polymer or the crosslinking reaction by hydrolysis of the alkoxysilyl group.
- the physical properties after curing can be adjusted to low modulus and high elongation.
- a solventless acrylic polymer having no functional group that is liquid at normal temperature and obtained by continuous bulk polymerization under high temperature and high pressure can be blended.
- the solvent-free acrylic polymer having no functional group that is liquid at room temperature is an acrylic monomer having no functional group [for example, an acrylate or methacrylate used in the polymerization method (ii) of the alkoxysilyl group-containing acrylic polymer.
- the acrylic polymer includes an alkoxysilyl group-containing acrylic polymer polymerized in a modified silicone polymer, and a solvent-free acrylic polymer that does not have a normal temperature liquid functional group obtained by continuous bulk polymerization at high temperature and high pressure. It may be a mixture with a polymer. Solventless acrylic polymers that do not have liquid functional groups at room temperature have a plasticizer replacement effect, and cured one-part thermosetting compositions have low modulus and high elongation after curing, and workability is improved. And can contribute to improvement of weather resistance.
- the blending amount may be selected within the range of 0.1 to 20 parts by weight of the fine powder coating amine with respect to 100 parts by weight of the hydrolyzable silyl group-containing polymer, preferably 1 to 15 parts by weight. More preferably, it is 2 to 12 parts by weight. If the fine powder coating amine is less than 0.1 part by weight, it may not be able to be cured in a short time by heating. On the other hand, if the fine powder coating amine exceeds 20 parts by weight, the economic effect may not be obtained.
- epoxy resin component those which are known per se in the one-component thermosetting composition can be used.
- examples thereof include bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, pyrocatechol, resorcinol, cresol novolac, tetrabromobisphenol A, trihydroxybiphenyl, bisresorcinol, bisphenol hexafluoroacetone, Glycidyl ether type obtained by reaction of polychlorophenol such as tetramethylbisphenol F and bixylenol with epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc.
- Glycidyl ether type obtained by reaction of hydroxycarboxylic acid such as p-oxybenzoic acid and ⁇ -oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Polyglycidyl ester type derived from polycarboxylic acid such as hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid; glycidyl derived from aminophenol, aminoalkylphenol, etc.
- Aminoglycidyl ether type glycidylaminoglycidyl ester type derived from aminobenzoic acid; aniline, toluidine, tribromoaniline, xylylenediamine, diaminocyclohexane, Glycidylamine type derived from bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone; epoxidized polyolefin, glycidylhydantoin, glycidylalkylhydantoin, triglycidylcyanurate, etc .; Examples thereof include monoepoxy compounds such as ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, glycidyl benzoate, and styrene oxide, and these can be used alone or as a mixture of two
- thermosetting composition of the present invention can be blended with appropriate amounts of usual additives such as a curing catalyst, a filler, a solvent, and a plasticizer, as necessary.
- the curing catalyst examples include DBU [1,8-diazabicyclo (5.4.0) undecene-7], DBU phenol salts, DBU octylates, DBU formates, and the like; monoamines (such as triethylamine), diamines (N , N, N ′, N′-tetramethylethylenediamine etc.), triamine (tetramethylguanidine etc.), cyclic amine (triethylenediamine etc.), alcohol amine (dimethylaminomethanol etc.), ether amine [bis (2-dimethylaminoethyl etc.) ) Ethers and the like; Sn-based (dibutyltin dilaurate, tin octylate, etc.), Pb-based (lead octylate, etc.), Zn-based (zinc octylate, etc.) organic carboxylic acid metal salts; 2-methyl And imidazoles such as imidazole and 1,
- the filler examples include heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, mica, clay, glass beads, shirasu balloon, glass balloon, silica balloon, balloon such as plastic balloon, Glass fiber, inorganic fiber such as metal fiber, organic fiber such as polyethylene fiber and polypropylene fiber, aluminum borate, silicon carbide, silicon nitride, potassium titanate, graphite, acicular crystalline calcium carbonate, magnesium borate, diboride Needle-like crystalline fillers such as titanium, chrysotile, and wollastonite can be used.
- the solvent examples include solvents having a small polarity, such as aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, ethers, esters, and ketones.
- solvents having a small polarity such as aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, ethers, esters, and ketones.
- an aliphatic hydrocarbon solvent is desirable.
- plasticizer examples include dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trioctyl phosphate, epoxy plasticizer, toluene-sulfonamide, chloroparaffin, adipic acid Esters, polypropylene glycol esters, paraffinic hydrocarbons, naphthenic hydrocarbons, castor oil, and the like can be used.
- thixotropic agents As further additives, thixotropic agents, ultraviolet absorbers, anti-aging agents, dyes / pigments, adhesion agents, dehydrating agents, and the like can be blended in appropriate amounts.
- the one-component thermosetting composition of the present invention can be produced by batch-mixing the above components by a conventionally known method.
- the one-component thermosetting composition of the present invention can be cured at a curing temperature of 50 ° C. to 150 ° C., preferably 60 ° C. to 120 ° C. for 3 minutes to 30 minutes, preferably 5 minutes to 20 minutes.
- the fine powder-coated amine according to the present invention is preferably used as a curing agent for a one-pack thermosetting composition because the surface of the solid amine is coated with fine powder without the amino group of the solid amine being carbonated. Can do.
- the one-component thermosetting composition comprising the fine powder coating amine of the present invention can be cured sufficiently even when the curing temperature is low or the central particle size of the solid amine of the fine powder coating amine is small.
- Adhesives, sealing materials, coating materials, underfill materials and the like are examples of the fine powder coating amine according to the present invention.
- the second absorption peak calorific value was measured with a differential scanning calorimeter (DSC).
- DSC used Q2000 manufactured by TA Instruments Japan. In the temperature program, the temperature was raised from room temperature to 200 ° C. at a rate of 5 ° C./min, and the second absorption peak was measured in the course of the temperature rise.
- the test composition was applied to a release paper at a film thickness of 2 mm and cured by heating at 100 ° C. for 10 minutes, and then the state of the cured product surface was confirmed by finger touch and evaluated according to the following criteria.
- ⁇ The component of the cured product does not adhere to the finger.
- X The component of hardened
- Example 1 (Production of Fine Powder Coated Amine According to the Present Invention)
- a jet amine milled solid amine (76.9 g of 1,12-dodecanediamine, melting point of 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m.
- the solid amine was pulverized so that the center particle size was 13 ⁇ m.
- a fine powder coated amine having a second absorption peak calorific value of 71 J / g was obtained.
- Example 2 (Production of Fine Powder Coated Amine According to the Present Invention)
- a jet mill containing solid amine (76.9 g of 1,12-dodecanediamine, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m in an atmosphere of 28 ° C. and 65% relative humidity was crushed and coated.
- the solid amine was pulverized so that the center particle size was 8 ⁇ m.
- a fine powder coated amine having a second absorption peak calorific value of 120 J / g was obtained.
- Example 3 (Production of a finely divided coating amine according to the invention) Under an atmosphere of a temperature of 28 ° C. and a relative humidity of 68%, 76.9 g of a solid amine (1,12-dodecanediamine, melting point 71 ° C.) was charged into a jet mill (counter jet mill manufactured by Hosokawa Micron Corporation), and a center particle size of 4 ⁇ m. To grind. Subsequently, the pulverized solid amine and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m were put into a Henschel mixer (FM20 type manufactured by Nippon Coke Co., Ltd.). After mixing for 5 minutes, a fine powder coated amine was obtained. The resulting fine powder coated amine had a second absorption peak heat value of 187 J / g.
- Example 4 (Production of Fine Powder Coated Amine According to the Present Invention)
- a jet amine was used to mix a solid amine (1,12-dodecanediamine 76.9 g, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m.
- the solid amine was pulverized so that the center particle size was 5 ⁇ m.
- a fine powder coated amine having a second absorption peak calorific value of 120 J / g was obtained.
- Example 5 Preparation of finely coated amine according to the present invention
- a jet mill was used to mix a solid amine (1,12-dodecanediamine 76.9 g, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m.
- the solid amine was pulverized so that the center particle size was 15 ⁇ m.
- a fine powder coated amine having a second absorption peak heat value of 37 J / g was obtained.
- Example 6 (Preparation of finely coated amine according to the present invention) In an atmosphere of a temperature of 15 ° C. and a relative humidity of 52%, a jet amine milled solid amine (1,12-dodecanediamine 76.9 g, melting point 71 ° C.) and fine titanium oxide powder 23.1 g with a center particle size of about 0.02 ⁇ m. Was crushed and coated. The solid amine was pulverized so that the center particle size was 4 ⁇ m. A fine powder coated amine having a second absorption peak heat value of 63 J / g was obtained.
- Example 7 (Production of a finely divided coating amine according to the invention) In an atmosphere of a temperature of 28 ° C. and a relative humidity of 72%, a jet mill was used to mix a solid amine (1,12-dodecanediamine 76.9 g, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m. Was crushed and coated. The solid amine was pulverized so that the center particle size was 10 ⁇ m. A fine powder coated amine having a second absorption peak heat value of 209 J / g was obtained.
- Comparative Example 1 (Production of fine powder coated amine not according to the present invention) In an atmosphere of a temperature of 35 ° C. and a relative humidity of 85%, a jet mill was used to add 76.9 g of solid amine (1,12-dodecanediamine, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m. Was crushed and coated. The solid amine was pulverized so that the center particle size was 15 ⁇ m. A fine powder coated amine having a second absorption peak heat value of 263 J / g was obtained.
- Comparative Example 2 (Production of fine powder coated amine not according to the present invention) Under an atmosphere of a temperature of 32 ° C. and a relative humidity of 73%, 76.9 g of a solid amine (1,12-dodecanediamine, melting point 71 ° C.) was charged into a jet mill (a counter jet mill manufactured by Hosokawa Micron Corporation), and the center particle diameter Grind to 5 ⁇ m. Next, the pulverized solid amine and 23.1 g of titanium oxide fine powder having a center particle size of about 0.02 ⁇ m are put into a Henschel mixer (FM20 type, manufactured by Nippon Coke Co., Ltd.) and mixed for 5 minutes. Obtained. A fine powder coated amine having a second absorption peak heat value of 374 J / g was obtained.
- a Henschel mixer FM20 type, manufactured by Nippon Coke Co., Ltd.
- Comparative Example 3 (Production of fine powder coated amine not according to the present invention) In an atmosphere at a temperature of 31 ° C. and a relative humidity of 71%, a jet amine was used to mix a solid amine (1,12-dodecanediamine 76.9 g, melting point 71 ° C.) and 23.1 g of fine titanium oxide powder having a center particle size of about 0.02 ⁇ m. Was crushed and coated. The solid amine was pulverized so that the center particle size was 4 ⁇ m. A fine powder coated amine having a second absorption peak heat value of 275 J / g was obtained.
- Fine powder coating amines 1 to 7 are fine powder coating amines obtained in Examples 1 to 7, respectively.
- Fine powder coating amine 8-10 Fine powder coating amines 8 to 10 are fine powder coating amines obtained in Comparative Examples 1 to 3, respectively.
- [Isocyanate component] A terminal NCO prepolymer having a terminal NCO content of 3.5% and a viscosity at 20 ° C. of 20000 mPa ⁇ s.
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Abstract
Description
本発明は、微粉体コーティングアミン、および微粉体コーティングアミンを硬化剤成分として含有する一液型加熱硬化性組成物に関する。
本発明は、微紛体コーティングアミンを硬化剤成分として含む一液型加熱硬化性組成物を、比較的低い温度において硬化させた場合でも、優れた硬化性および物性、とりわけ良好な破断強度が得られる微粉体コーティングアミンを含有する一液型加熱硬化性組成物を提供する。
すなわち、本発明には、以下のものが含まれる。
[1]50℃以上の融点および20μm以下の中心粒径を有する固形アミンの表面が、2μm以下の中心粒径を有する微粉体で被覆された微紛体コーティングアミンであって、示差走査熱量計により測定される第2吸収ピークにおける熱量が220J/g以下である、微紛体コーティングアミン。
[2]固形アミンは、芳香族アミンまたは脂肪族アミンである、[1]に記載の微紛体コーティングアミン。
[3]固形アミンは、中心粒径が1μm~20μmである、[1]または[2]に記載の微紛体コーティングアミン。
[4]固形アミンに対する微粉体の重量比は、1/0.001~1/0.5である、[1]~[3]のいずれかに記載の微紛体コーティングアミン。
[5]微紛体は、ポリ塩化ビニル、酸化チタン、炭酸カルシウム、クレー、カーボン、アルミナ、タルク、酸化亜鉛およびシリカからなる群から選択される少なくとも1種である、[1]~[4]のいずれかに記載の微紛体コーティングアミン。
[6][1]~[5]のいずれかに記載の微紛体コーティングアミンを含んでなる、一液型加熱硬化性組成物。
[7]イソシアネート成分を含んでなる、[6]に記載の一液型加熱硬化性組成物。
RNH2+CO2+H2O → RNH3 +CO3H-
で示される反応により炭酸塩化されたアミノ基に起因するものと推測され、微紛体コーティングアミンは、第2吸収ピーク熱量が低いほど、炭酸塩化されていない活性アミノ基(NH2)を多く含有し、硬化剤として高い活性を有することとなる。したがって、本発明の微紛体コーティングアミンは、第2吸収ピーク熱量が220J/g以下であり、200J/g以下が好ましく、150J/g以下がより好ましい。第2吸収ピーク熱量の下限値は、特に限定されないが、例えば0J/g以上である。第2吸収ピーク熱量が220J/gを超える場合には、比較的低い硬化温度、例えば100℃等において十分に活性化されず、一液型加熱硬化性組成物において硬化剤として高い活性が得られない。本発明において、第2吸収ピーク熱量は、特記のない限り、本明細書の実施例に記載の第2吸収ピークの測定方法に従って測定された値である。
1)50℃以上の融点を有する固形アミンを、粉砕機を用いることにより20μm以下の中心粒径を有する固形アミンに粉砕する工程、および
2)工程1)において得られた固形アミンと、2μm以下の中心粒径を有する微紛体とを混合撹拌機を用いて混合し、前記固形アミンの表面を微粉体で被覆する工程
を含み、工程1)および2)を温度30℃以下および/または相対湿度70%以下の雰囲気下で行う製造方法により得られる。
(i)特公平3-80829号公報に開示の、(a)アクリル酸アルキルエステル(アルキル炭素数は好ましくは2~4)(例えばエチルアクリレート、プロピルアクリレート、n-ブチルアクリレート、イソブチルアクリレート、アミルアクリレート、ヘキシルアクリレート、2-エチルヘキシルアクリレート、シクロヘキシルアクリレート、n-オクチルアクリレート等)と、(b)ビニルアルコキシシラン(例えばビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルトリエトキシシラン、ビニルジメチルメトキシシラン等)および(メタ)アクリロキシアルコキシシラン(例えばγ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン等)の群から選ばれる1種または2種以上の混合物とを、連鎖移動剤としてメルカプトアルコキシラン(c)(例えばγ-メルカプトプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリメトキシシラン等)の存在下で、ラジカル共重合[通常、α,α’-アゾビスイソブチロニトリル(AIBN)、α,α’-アゾビスイソバレロニトリル、過酸化ベンゾイル、メチルエチルケトンパーオキシドなど重合開始剤を用いて公知の塊状重合、溶液重合などの手法;あるいはレドックス触媒、例えば、遷移金属塩、アミン等と過酸化物系開始剤を組合せたレドックス重合法により]させることによって製造されるもの(通常、数平均分子量3000~100000、1分子中の平均アルコキシシリル基数1.5~3個);および
(ii)特公平4-69667号公報に開示の、ビニル系モノマー[例えばエチルアクリレート、ブチルアクリレート、2-エチルヘキシルアクレート、プロピルアクリレート、ペンチルアクリレート、ステアリルアクリレートなどのアクリレート;メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、2-エチルヘキシルメタクリレート、ラウリルメタクリレート、ベンジルメタクリレート、シクロヘキシルメタクリレートなどのメタクリレート;スチレンもしくはその誘導体(α-メチルスチレン、クロルメチルスチレンなど);ジエチルフマレート、ジブチルフマレート、ジプロピルフマレートなどのフマル酸ジエステル;塩化ビニル、塩化ビニリデン、フッ化エチレン、フッ化ビニリデン、フッ化ビニレンなどのハロゲン化ビニル類等]100部(重量部、以下同様)に、アルコキシシリル基含有ジスルフィド化合物[例えばビス(トリメトキシシリルメチル)ジスルフィド、ビス(トリエトキシシリルメチル)ジスルフィド、ビス(トリメトキシシリルプロピル)ジスルフィド、ビス(トリエトキシシリルプロピル)ジスルフィド、ビス(メチルジメトキシシリルメチル)ジスルフィド、ビス(メチルジエトキシシリルメチル)ジスルフィド、ビス(プロピルジメトキシシリルメチル)ジスルフィド、ビス(プロピルジエトキシシリルメチル)ジスルフィド、ビス(ジメチルメトキシシリルプロピル)ジスルフィド、ビス(ジメチルエトキシシリルプロピル)ジスルフィド等]0.05~50部を加え、必要に応じて有機溶媒(トルエン、キシレン、ヘキサン、酢酸エチル、ジオクチルフタレートなど)中で光重合(常温乃至50~60℃で、4~30時間の光照射)に付すことによって製造されるものが挙げられる。
の化学構造を有する、株式会社カネカ製の「エピオン」(登録商標)シリーズが例示される。
第2吸収ピーク熱量は、示差走査熱量計(DSC)により測定した。DSCはティー・エイ・インスツルメント・ジャパン株式会社製Q2000を用いた。温度プログラムは、室温より5℃/分の速度で200℃まで昇温し、第2吸収ピークの測定は昇温の過程で行った。
固形アミンおよび微粉体の粒子径および粒度分布の測定には、株式会社堀場製作所製レーザー回折/散乱式粒子径分布測定装置LA-950V2を用いて、乾式法にて測定した。求められる通過分積算分布が50%になる粒径を中心粒径とした。
供試組成物をそれぞれ剥離紙上に膜厚2mmにて塗布し、100℃で10分間加熱硬化を行った後、JIS K 6251「加硫ゴムおよび熱可塑性ゴム-引張特性の求め方」に従って破断強度を求め、測定結果を以下の基準で判定した。
○:破断強度2MPa以上
×:破断強度2MPa未満
供試組成物を剥離紙上に膜厚2mmにて塗布し、100℃で10分加熱硬化させた後に、指触により硬化物表面の状態を確認し、以下の基準で評価した。
○:硬化物の成分が指に付着しない。
×:硬化物の成分が指に付着する。
一液型加熱硬化性組成物の硬化性について評価を行うために、FT-IR(サーモフィッシャーサイエンテフィック社製Nicolet iS10)を用いて硬化後の一液型加熱硬化性組成物中に残存するイソシアネート基の吸収ピーク(2260cm-1)の有無について確認した。
温度29℃および相対湿度69%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が13μmとなるように粉砕した。第2吸収ピーク熱量が71J/gの微粉体コーティングアミンを得た。
温度28℃および相対湿度65%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が8μmとなるように粉砕した。第2吸収ピーク熱量が120J/gの微粉体コーティングアミンを得た。
温度28℃および相対湿度68%の雰囲気下で、固形アミン(1,12-ドデカンジアミン、融点71℃)76.9gをジェットミル(ホソカワミクロン株式会社製カウンタジェットミル)に投入し、中心粒径4μmに粉砕した。次いで粉砕した固形アミンと、中心粒径約0.02μmの酸化チタン微粉体23.1gとをヘンシェルミキサー(日本コークス株式会社製FM20型)中に投入した。5分間混合した後、微粉体コーティングアミンを得た。得られた微粉体コーティングアミンは、第2吸収ピーク熱量が187J/gであった。
温度23℃および相対湿度63%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が5μmとなるように粉砕した。第2吸収ピーク熱量が120J/gの微粉体コーティングアミンを得た。
温度25℃および相対湿度63%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が15μmとなるように粉砕した。第2吸収ピーク熱量が37J/gの微粉体コーティングアミンを得た。
温度15℃および相対湿度52%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が4μmとなるように粉砕した。第2吸収ピーク熱量が63J/gの微粉体コーティングアミンを得た。
温度28℃および相対湿度72%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が10μmとなるように粉砕した。第2吸収ピーク熱量が209J/gの微粉体コーティングアミンを得た。
温度35℃および相対湿度85%の雰囲気下で、固形アミン(1,12-ドデカンジアミン、融点71℃)76.9gと中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が15μmとなるように粉砕した。第2吸収ピーク熱量が263J/gの微粉体コーティングアミンを得た。
温度32℃および相対湿度73%の雰囲気下で、固形アミン(1,12-ドデカンジアミン、融点71℃)76.9gを、ジェットミル(ホソカワミクロン株式会社製カウンタジェットミル)に投入し、中心粒径5μmに粉砕した。次いで粉砕した固形アミンと、中心粒径約0.02μmの酸化チタン微粉体23.1gとをヘンシェルミキサー(日本コークス株式会社製FM20型)中に投入し、5分間混合し、微粉体コーティングアミンを得た。第2吸収ピーク熱量が374J/gの微粉体コーティングアミンを得た。
温度31℃および相対湿度71%の雰囲気下で、固形アミン(1,12-ドデカンジアミン76.9g、融点71℃)と中心粒径約0.02μmの酸化チタン微粉体23.1gとをジェットミルに投入し、粉砕およびコーティングを行った。尚、固形アミンは中心粒径が4μmとなるように粉砕した。第2吸収ピーク熱量が275J/gの微粉体コーティングアミンを得た。
以下の表1に示す組成にて、各成分を、混合攪拌機を用いて室温において混合し及び分散することにより、一液型加熱硬化性組成物を得た。得られた一液型加熱硬化性組成物を100℃にて10分間硬化させた。硬化後の一液型加熱硬化性組成物の破断強度、タック性および反応性について、上記評価方法に従って評価を行った。結果を表2に示す。
微粉体コーティングアミン1~7は、それぞれ実施例1~7において得られた微紛体コーティングアミンである。
〔微紛体コーティングアミン8~10〕
微粉体コーティングアミン8~10は、それぞれ比較例1~3において得られた微紛体コーティングアミンである。
〔イソシアネート成分〕
末端NCO含有率3.5%および20℃における粘度20000mPa・sを有する末端NCOプレポリマー。平均分子量2000のポリエーテルポリオール(旭硝子株式会社製エクセノール2020)79.3gとジフェニルメタンジイソシアネート20.7gとを反応温度80℃にて2時間反応させることにより得られる。
Claims (7)
- 50℃以上の融点および20μm以下の中心粒径を有する固形アミンの表面が、2μm以下の中心粒径を有する微粉体で被覆された微紛体コーティングアミンであって、示差走査熱量計により測定される第2吸収ピークにおける熱量が220J/g以下である、微紛体コーティングアミン。
- 固形アミンは、芳香族アミンまたは脂肪族アミンである、請求項1に記載の微紛体コーティングアミン。
- 固形アミンは、中心粒径が1μm~20μmである、請求項1または2に記載の微紛体コーティングアミン。
- 固形アミンに対する微粉体の重量比は、1/0.001~1/0.5である、請求項1~3のいずれかに記載の微紛体コーティングアミン。
- 微紛体は、ポリ塩化ビニル、酸化チタン、炭酸カルシウム、クレー、カーボン、アルミナ、タルク、酸化亜鉛およびシリカからなる群から選択される少なくとも1種である、請求項1~4のいずれかに記載の微紛体コーティングアミン。
- 請求項1~5のいずれかに記載の微紛体コーティングアミンを含んでなる、一液型加熱硬化性組成物。
- イソシアネート成分を含んでなる、請求項6に記載の一液型加熱硬化性組成物。
Priority Applications (9)
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EP16775447.2A EP3181605B1 (en) | 2015-11-05 | 2016-03-29 | Fine powder-coated amine and composition containing same |
JP2017509790A JP6297209B2 (ja) | 2015-11-05 | 2016-03-29 | 微紛体コーティングアミンおよびそれを含有する組成物 |
SI201630478T SI3181605T1 (sl) | 2015-11-05 | 2016-03-29 | S finim praškom oplaščen amin in sestavki, ki ga vsebujejo |
ES16775447T ES2751764T3 (es) | 2015-11-05 | 2016-03-29 | Amina recubierta con polvo fino y composición que contiene la misma |
SG11201704184UA SG11201704184UA (en) | 2015-11-05 | 2016-03-29 | Fine powder-coated amine and composition containing same |
CN201680003559.7A CN107108834B (zh) | 2015-11-05 | 2016-03-29 | 经微粉体包覆的胺和含有该经微粉体包覆的胺的组合物 |
EP19195849.5A EP3617245B1 (en) | 2015-11-05 | 2016-03-29 | A fine particles-coated amine and a composition containing the same |
PL16775447T PL3181605T3 (pl) | 2015-11-05 | 2016-03-29 | Amina powlekana drobnym proszkiem i jej kompozycja |
US15/542,775 US10189937B2 (en) | 2015-11-05 | 2016-03-29 | Fine powder-coated amine and composition containing same |
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US (1) | US10189937B2 (ja) |
EP (2) | EP3181605B1 (ja) |
JP (2) | JP6297209B2 (ja) |
CN (1) | CN107108834B (ja) |
ES (1) | ES2751764T3 (ja) |
PL (1) | PL3181605T3 (ja) |
SG (1) | SG11201704184UA (ja) |
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2016
- 2016-03-29 WO PCT/JP2016/060104 patent/WO2017077722A1/ja active Application Filing
- 2016-03-29 JP JP2017509790A patent/JP6297209B2/ja active Active
- 2016-03-29 SI SI201630478T patent/SI3181605T1/sl unknown
- 2016-03-29 EP EP16775447.2A patent/EP3181605B1/en active Active
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- 2016-03-29 ES ES16775447T patent/ES2751764T3/es active Active
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- 2016-03-29 CN CN201680003559.7A patent/CN107108834B/zh active Active
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Also Published As
Publication number | Publication date |
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EP3181605B1 (en) | 2019-10-23 |
EP3181605A1 (en) | 2017-06-21 |
EP3617245B1 (en) | 2021-11-10 |
SI3181605T1 (sl) | 2019-12-31 |
US10189937B2 (en) | 2019-01-29 |
EP3181605A4 (en) | 2017-09-13 |
US20180237575A1 (en) | 2018-08-23 |
CN107108834A (zh) | 2017-08-29 |
ES2751764T3 (es) | 2020-04-01 |
JPWO2017077722A1 (ja) | 2017-11-02 |
SG11201704184UA (en) | 2017-06-29 |
JP6297209B2 (ja) | 2018-03-20 |
JP6638007B2 (ja) | 2020-01-29 |
CN107108834B (zh) | 2019-09-24 |
PL3181605T3 (pl) | 2020-05-18 |
EP3617245A1 (en) | 2020-03-04 |
JP2018141144A (ja) | 2018-09-13 |
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