Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
  • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B26/14—Polyepoxides
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/121—Amines, polyamines
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5026—Amines cycloaliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • E—FIXED CONSTRUCTIONS
  • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
  • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
  • E01C7/00—Coherent pavings made in situ
  • E01C7/08—Coherent pavings made in situ made of road-metal and binders
  • E01C7/30—Coherent pavings made in situ made of road-metal and binders of road-metal and other binders, e.g. synthetic material, i.e. resin
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction

Definitions

• the present invention relates to a paving material composition and a structure.
• Natural stone is used as aggregate in landscape paving materials. By using natural stone, paving materials that blend better with the landscape of parks, tourist spots, etc. than asphalt or concrete can be obtained. For landscape paving materials, in addition to the strength of the resulting structure, high water permeability is generally desired. In particular, high weather resistance is preferred for landscape paving materials.
• Patent Document 1 discloses that a paving material kneaded with a weather-resistant epoxy fiberized resin as a binder for aggregate, the weather-resistant epoxy fiberized resin being mainly composed of a mixture of an alicyclic epoxy resin in which an aromatic benzene ring has been substituted by a reduction reaction and fibers whose fiber diameter and fiber length are equal to or less than a predetermined value, is strong, permeable, and has excellent weather resistance.
• Patent Document 1 is a technology in which an epoxy resin, which is a binder resin, is kneaded with fibers to form fibers, and the process for obtaining a structure is complicated. Furthermore, since paving materials for scenic paving are usually used outdoors, it is important that not only the initial strength but also the strength does not decrease after exposure to rain, etc.
• An object of the present invention is to provide a paving material composition which can provide a structure having high water permeability, weather resistance and strength, and excellent strength retention even in a wet environment.
• a paving material composition containing an epoxy resin, a specified epoxy resin curing agent, and aggregate. That is, the present invention relates to the following.
• a paving material composition comprising an epoxy resin, an epoxy resin curing agent containing 50 mass% or more of a polyamine compound represented by the following general formula (1) or a modified product thereof (A), and an aggregate.
• (IV) A reaction product of a polyamine compound represented by the general formula (1) and an unsaturated carboxylic acid or a derivative thereof.
• a structure comprising a cured product of the paving material composition described in any one of [1] to [4] above.
• the present invention provides a paving material composition that can produce structures that have high water permeability, weather resistance, and strength, and that have excellent strength retention even in wet environments.
• pavement composition refers to a composition containing aggregate for pavement and used to form a pavement.
• the pavement composition of the present invention does not include a primer composition or the like used for pavement.
• the strength of the structure obtained by curing the paving material composition can be evaluated by the method described in the Examples using the maximum bending stress as an index.
• “strength of the structure” means the initial strength of the structure
• a high initial strength of the structure means that the value of the maximum bending stress before the structure is submerged in water is high.
• the strength retention rate of a structure in a wet environment is a value obtained by the ratio of the initial maximum bending stress of the obtained structure (before submersion in water) to the maximum bending stress after submersion in water for a predetermined period of time, and specifically, it can be calculated by the method described in the examples.
• the paving material composition of the present invention contains an epoxy resin, an epoxy resin curing agent containing 50 mass% or more of a polyamine compound (A) represented by the following general formula (1) or a modified product thereof, and an aggregate.
• a polyamine compound (A) represented by the following general formula (1) or a modified product thereof
• an aggregate H 2 N-CH 2 -X-CH 2 -NH 2 (1)
• X is a cyclohexylene group.
• the composition of the present invention having the above-mentioned configuration can form a structure having high water permeability, weather resistance, and strength, and excellent strength retention even in a wet environment.
• the reason why the composition of the present invention exhibits the above-mentioned effects is not clear, but is thought to be as follows.
• the polyamine compound represented by the general formula (1) is an aliphatic cyclic polyamine, and has moderate hydrophilicity, but is more hydrophobic than aliphatic chain polyamines.
• a cured product with a high glass transition temperature (Tg) can be obtained. Due to the above properties, it is believed that the cured product of the composition of the present invention using an epoxy resin curing agent containing the polyamine compound or its modified product in a predetermined amount or more has high water permeability, high strength, and high strength retention in a humid environment.
• the polyamine compound represented by the general formula (1) does not contain an aromatic ring and has a low ratio of nitrogen atoms in the molecule, it is believed that the cured product of the composition of the present invention exhibits high weather resistance.
• the epoxy resin is not particularly limited as long as it has two or more glycidyl groups capable of reacting with active hydrogen in the epoxy resin curing agent described below, and may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. From the viewpoint of improving the strength of the structure obtained by curing the paving material composition and the strength retention rate in a wet environment, the epoxy resin is preferably an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule.
• the epoxy resin include at least one resin selected from the group consisting of epoxy resins having a glycidylamino group derived from meta-xylylenediamine, epoxy resins having a glycidylamino group derived from para-xylylenediamine, epoxy resins having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having a glycidylamino group derived from diaminodiphenylmethane, epoxy resins having a glycidylamino group and/or a glycidyloxy group derived from para-aminophenol, epoxy resins having a glycidyloxy group derived from bisphenol A, epoxy resins having a glycidyloxy group derived from bisphenol F, epoxy
• main component means that other components may be contained within a range that does not deviate from the spirit of the present invention, and preferably means 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass of the total.
• the epoxy resin may be either a solid epoxy resin or a liquid epoxy resin, but from the viewpoint of improving the strength of the resulting structure and strength retention in a wet environment, a liquid epoxy resin is more preferable.
• solid epoxy resin means an epoxy resin that is solid at room temperature (25°C)
• liquid epoxy resin means an epoxy resin that is liquid at room temperature (25°C).
• the epoxy equivalent of the epoxy resin is preferably 80 g/equivalent or more, more preferably 100 g/equivalent or more, even more preferably 120 g/equivalent or more, and even more preferably 150 g/equivalent or more, from the viewpoint of improving the strength of the structure obtained by curing the paving material composition and the strength retention rate in a wet environment, and is preferably 1,000 g/equivalent or less, more preferably 800 g/equivalent or less, even more preferably 500 g/equivalent or less, even more preferably 300 g/equivalent or less, and even more preferably 200 g/equivalent or less, from the viewpoint of handleability.
• X is a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, or a 1,4-cyclohexylene group. From the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the structure obtained by curing the paving material composition, X is preferably a 1,3-cyclohexylene group or a 1,4-cyclohexylene group, and more preferably a 1,3-cyclohexylene group.
• the polyamine compound represented by the general formula (1) is one or more bis(aminomethyl)cyclohexanes selected from the group consisting of 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane, and is preferably one or more selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, and more preferably 1,3-bis(aminomethyl)cyclohexane.
• the modified polyamine compound represented by the general formula (1) is preferably at least one selected from the group consisting of the following (I) to (IV):
• IV A reaction product of a polyamine compound represented by the general formula (1) and an unsaturated carboxylic acid or a derivative thereof.
• the number of carbon atoms in the alkyl group in the alkylphenol is preferably 1 to 24, more preferably 1 to 18, and the number of carbon atoms in the alkenyl group in the alkenylphenol is preferably 2 to 24, more preferably 2 to 18.
• the phenol compound used in the modified product (I) is preferably at least one selected from the group consisting of phenol, cresol, p-tert-butylphenol, nonylphenol, and cardanol, and more preferably phenol.
• the aldehyde compound used in the modified product (I) may be formaldehyde; formaldehyde-releasing compounds such as trioxane and paraformaldehyde; and other aldehydes such as benzaldehyde.
• formaldehyde and formaldehyde-releasing compounds are preferred.
• the method for producing the modified product (I) is not particularly limited, and any known method can be used.
• an aldehyde compound or a solution thereof is added dropwise to a mixture of the polyamine compound and the phenol compound at preferably 80° C. or less, more preferably 60° C. or less, and after the addition is completed, the temperature is raised to preferably 80 to 180° C., more preferably 90 to 150° C., and the reaction is carried out for 1 to 10 hours while removing the distillate from the reaction system.
• the amounts of the polyamine compound, phenol compound, and aldehyde compound used in the Mannich reaction are not particularly limited as long as the ratio is such that the resulting modified product (I) contains an amino group having active hydrogen.
• the amounts are preferably within the following ranges.
• the aldehyde compound is used in an amount of preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per mol of the polyamine compound, and the phenol compound is used in an amount of preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per mol of the polyamine compound.
• the modified product (II) is a reaction product between the polyamine compound represented by the above general formula (1) and an unsaturated hydrocarbon compound.
• an unsaturated hydrocarbon compound having 2 to 10 carbon atoms is preferred.
• the unsaturated hydrocarbon compound examples include unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms, and aromatic hydrocarbon compounds having 2 to 10 carbon atoms and an ethylenically unsaturated bond, such as at least one selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, cyclohexene, cyclohexadiene, styrene, and divinylbenzene.
• unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms examples include unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms, and aromatic hydrocarbon compounds having 2 to 10 carbon atoms and an ethylenically unsaturated bond, such as at least one selected
• aromatic hydrocarbon compounds having an ethylenically unsaturated bond such as styrene and divinylbenzene are preferred, and styrene is more preferred.
• the method for producing the modified product (II) is not particularly limited, and a known method can be used.
• the modified product (II) can be obtained by subjecting the polyamine compound and the unsaturated hydrocarbon compound to an addition reaction under heating conditions.
• the amount of the unsaturated hydrocarbon compound used in the addition reaction is not particularly limited as long as the resulting modified product (II) contains an amino group having active hydrogen, but is preferably in the range of 0.1 to 5.0 mol, more preferably 0.4 to 3.0 mol, even more preferably 0.5 to 1.5 mol, and still more preferably 0.8 to 1.2 mol, per 1 mol of the polyamine compound.
• the modified product (III) is a reaction product of the polyamine compound represented by the above general formula (1) and an epoxy compound having at least one epoxy group.
• Examples of the epoxy compound used in the modified product (III) include epichlorohydrin, butyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, biphenol diglycidyl ether, dihydroxynaphthalene diglycidyl ether, dihydroxyanthracene diglycidyl ether, triglycidyl isocyanurate, tetraglycidyl glycoluril, and a polyfunctional epoxy resin having a glycidylamino group derived from metaxylylenediamine, and a polyfunctional epoxy resin derived from 1,3-bis(aminomethyl)cyclohexane.
• the epoxy resin examples include a polyfunctional epoxy resin having a glycidylamino group derived from diaminodiphenylmethane, a polyfunctional epoxy resin having a glycidylamino group and a glycidyloxy group derived from paraaminophenol, a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A, a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol F, a polyfunctional epoxy resin having a glycidyloxy group derived from phenol novolac, and a polyfunctional epoxy resin having a glycidyloxy group derived from resorcinol.
• a polyfunctional epoxy resin having a glycidylamino group derived from diaminodiphenylmethane examples include a polyfunctional epoxy resin having a glycidylamino group derived from diaminodiphenylmethane, a polyfunctional epoxy resin having
• the method for producing the modified product (III) is not particularly limited, and a known method can be used.
• the modified product (III) can be obtained by subjecting the polyamine compound and the epoxy compound to an addition reaction under heating conditions.
• the amounts of the polyamine compound and the epoxy compound used in the addition reaction are not particularly limited as long as the resulting modified product (III) contains an amino group having active hydrogen, but it is preferable to use an excess amount of the polyamine compound relative to the epoxy equivalent of the epoxy compound.
• the polyamine compound and the epoxy compound are reacted at a ratio such that the number of active hydrogen atoms in the polyamine compound/the number of epoxy groups in the epoxy compound is preferably 4 to 50, more preferably 8 to 20.
• the modified product (IV) is a reaction product of the polyamine compound represented by the above general formula (1) and an unsaturated carboxylic acid or a derivative thereof.
• Examples of the unsaturated carboxylic acid or a derivative thereof used in the modified product (IV) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, ⁇ -propylacrylic acid, ⁇ -isopropylacrylic acid, ⁇ -n-butylacrylic acid, ⁇ -t-butylacrylic acid, ⁇ -pentylacrylic acid, ⁇ -phenylacrylic acid, ⁇ -benzylacrylic acid, crotonic acid, 2-pentenoic acid, 2-hexenoic acid, 4-methyl-2-pentenoic acid, 2-heptenoic acid, 4-methyl-2-hexenoic acid, 5-methyl-2-hexenoic acid, 4,4-dimethyl-2-pentenoic acid, 4-phenyl-2-butenoic acid, cinnamic acid, o-methylcinnamic acid, m-methylcinnamic acid, p-methylcinn
• the unsaturated carboxylic acid or a derivative thereof is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and derivatives thereof, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, and alkyl esters thereof, still more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof, still more preferably an alkyl ester of acrylic acid, and still more preferably methyl acrylate.
• the method for producing the modified substance (IV) is not particularly limited, and a known method can be used.
• the modified substance (IV) can be obtained by reacting the polyamine compound with an unsaturated carboxylic acid or a derivative thereof under heating conditions.
• the reaction molar ratio of the polyamine compound to the unsaturated carboxylic acid or its derivative is not particularly limited as long as the resulting modified product (IV) contains an amino group having an active hydrogen, but is preferably in the range of 0.3 to 1.0, and more preferably in the range of 0.6 to 1.0.
• component (A) is at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, and more preferably 1,3-bis(aminomethyl)cyclohexane.
• the active hydrogen equivalent (AHEW) of component (A) is preferably 130 or less, more preferably 120 or less, and even more preferably 110 or less.
• AHEW of component (A) is 130 or less, good hardening performance is exhibited even when the amount of component (A) blended into the paving material composition is small.
• the AHEW of component (A) is 35.6 or more because it is equal to or greater than the AHEW of bis(aminomethyl)cyclohexane.
• the AHEW of component (A) can be determined, for example, by a titration method.
• the content of component (A) in the epoxy resin hardener is 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass or less, from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the structure obtained by curing the paving material composition.
• the epoxy resin curing agent may further contain another curing agent component other than the component (A).
• the "other curing agent component” may be a polyamine compound other than the component (A) or a modified product thereof.
• the polyamine compound include chain aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine; aliphatic polyamine compounds having an aromatic ring such as orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine; menthene diamine, isophorone diamine, norbornane diamine, tricyclodecane diamine, adamantane diamine, diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-d
• polyamine compounds having an alicyclic structure such as cyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (bis(4-amino-3-methylcyclohexyl)methane), 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, etc.; aromatic polyamine compounds, such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 2,2'-diethyl-4,4'-methylenedianiline, etc.; polyamine compounds having a heterocyclic structure, such as N-aminomethylpiperazine, N-aminoethylpiperazine, N,N'-bis(aminoethyl)piperazine, etc
• modified polyamine compound examples include Mannich modified products, epoxy modified products, Michael adducts, Michael adduct-polycondensates, styrene modified products, polyamide modified products, etc. These can be used alone or in combination of two or more.
• the content of hardener components other than component (A) in the epoxy resin hardener is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and may even be 0% by mass.
• the active hydrogen equivalent (AHEW) of the epoxy resin curing agent is preferably 150 or less, more preferably 140 or less, even more preferably 130 or less, and even more preferably 120 or less, from the viewpoint of exhibiting high curing properties even when the amount of the curing agent is small, while from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the structure obtained by curing the paving composition, the AHEW of the curing agent is preferably 30 or more, and more preferably 35 or more.
• the aggregate used in the present invention is preferably an inorganic granular aggregate for landscape paving.
• the aggregate may be either a natural aggregate or an artificial aggregate, but from the viewpoint of use as a paving material for landscape paving, natural aggregates such as natural stone are preferred.
• Specific examples of aggregates include pebbles, river gravel, crushed stone, silica stone, river sand, crushed sand, silica sand, slag, glass beads, crushed glass pieces, crushed pottery pieces, ceramic balls, processed industrial waste products, as well as powders or fine particles of alumina, clay, talc, glass, mica, calcium carbonate, barium sulfate, aluminum oxide, and aluminum hydroxide, and one or more of these can be used.
• At least one type selected from the group consisting of gravel and silica sand is preferred, and from the viewpoint of improving the water permeability of the structure obtained by hardening the paving material composition, gravel is more preferred.
• the particle size of the aggregate is not particularly limited, but is preferably 0.002 to 50 mm, more preferably 0.1 to 30 mm, even more preferably 0.5 to 20 mm, and even more preferably 0.5 to 10 mm. If the particle size of the aggregate is 0.002 mm or more, the water permeability, strength, and strength retention in a wet environment of the resulting structure are good. If the particle size is 50 mm or less, the strength of the resulting structure and the strength retention in a wet environment are good.
• the particle size of the aggregate can be determined by a method conforming to JIS A1204:2020 "Soil particle size testing method.”
• the particle size classification of silica sand is classified into No. 3 to No. 8 in JIS G 5901:2016.
• the particle size classification of the silica sand is preferably silica sand No. 3 to No. 7, more preferably silica sand No. 3 to No. 5, and even more preferably silica sand No. 3 to No. 4, from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the structure obtained by hardening the paving material composition.
• the particle shape of the aggregate is not particularly limited, and may be either spherical or non-spherical.
• Spherical also includes nearly spherical shapes, such as those with an elliptical cross section.
• Non-spherical particle shapes include plate-like, scale-like, chain-like, columnar, and fragmented shapes.
• the moisture content of the aggregate is not particularly limited, but from the viewpoint of improving the strength of the resulting structure and strength retention in a wet environment, it is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 5.0% by mass or less, and still more preferably 3.0% by mass or less.
• the lower limit may be 0% by mass, and is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more.
• the moisture content of the aggregate referred to here means the moisture content of the aggregate when it is mixed into the composition of the present invention. Specifically, the moisture content of the aggregate can be measured by the method described in the Examples.
• the paving material composition may further contain other components such as known modifying components such as plasticizers, flow adjusting components such as thixotropic agents, leveling agents, tackifiers, and hardening accelerators, within the scope of the invention.
• the content or content ratio of each component in the paving material composition is preferably within the following ranges.
• the ratio of the epoxy resin to the epoxy resin curing agent contained in the paving material composition is, from the viewpoints of curing property and of improving the water permeability, weather resistance, strength, and strength retention rate under humid environments of the resulting structure, such that the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin [number of active hydrogens/number of epoxy groups] is preferably 1/0.8 to 1/1.2, more preferably 1/0.9 to 1/1.1, and even more preferably 1/1.
• the mass ratio of the epoxy resin to the aggregate contained in the paving material composition [epoxy resin/aggregate] is preferably in the range of 0.005 to 0.5, more preferably 0.01 to 0.3, even more preferably 0.01 to 0.2, and even more preferably 0.01 to 0.1. If the [epoxy resin/aggregate] is 0.005 or more, it is easy to suppress the falling off of the aggregate in the obtained structure, and if it is 0.5 or less, the water permeability, strength, and strength retention rate in a wet environment of the obtained structure are further improved. When the aggregate used is a wet aggregate, the mass ratio of the epoxy resin to the dry mass of the aggregate is preferably within the above range.
• the content of the epoxy resin in the paving material composition is preferably 0.1 to 30% by mass, more preferably 0.2 to 25% by mass, even more preferably 0.5 to 20% by mass, even more preferably 1.0 to 15% by mass, and even more preferably 1.0 to 10% by mass, from the viewpoints of curability, water permeability, weather resistance, strength, and improved strength retention in a humid environment of the resulting structure.
• the content of the epoxy resin curing agent in the paving material composition is preferably 0.01 to 15 mass%, more preferably 0.05 to 10 mass%, and even more preferably 0.1 to 5.0 mass%, from the viewpoints of curing property, water permeability, weather resistance, strength, and improved strength retention in a humid environment of the resulting structure.
• the content of aggregate in the paving material composition is preferably 50 to 99.5% by mass, more preferably 55 to 99% by mass, even more preferably 60 to 99% by mass, still more preferably 70 to 99% by mass, even more preferably 80 to 99% by mass, even more preferably 85 to 99% by mass, and even more preferably 87 to 99% by mass, from the viewpoints of hardening property and of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the resulting structure.
• the "aggregate content” means the content based on the dry mass of the aggregate, even in the case where a wet aggregate is used.
• the total content of epoxy resin, epoxy resin hardener, and aggregate in the paving material composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less, from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a wet environment of the resulting structure.
• the water content in the paving material composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of improving the strength of the resulting structure and strength retention rate in a wet environment.
• the water content is the amount of water that is intentionally mixed, and does not exclude, for example, the content of water that is already contained in each compounding component.
• the content of organic solvents in the paving material composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of improving the strength of the resulting structure and strength retention in a wet environment, with the lower limit being 0% by mass.
• the method for producing the epoxy resin composition of the present invention can be produced by mixing the epoxy resin, epoxy resin hardener, aggregate, and other components as necessary using known methods and equipment.
• the structure of the present invention includes the cured product of the paving material composition of the present invention described above.
• the paving material composition can be cured by a known method.
• the curing conditions of the paving material composition are appropriately selected depending on the use environment, the shape of the structure, etc., and are not particularly limited, but it can be cured under room temperature conditions in the atmosphere.
• the structure of the present invention is suitably used as a paving material, particularly as a scenic paving material.
• the paving material composition of the present invention can provide a structure having high strength and high strength retention in a wet environment.
• a flat plate-shaped structure having dimensions of 16 cm x 16 cm x 4 cm obtained by curing the paving material composition of the present invention has a maximum bending stress of preferably 2.0 MPa or more, more preferably 2.5 MPa or more, and even more preferably 3.0 MPa or more, measured when a bending test is performed at a test speed of 1 mm/min according to a method conforming to JIS R 5201:2015.
• the retention of maximum bending stress after the structure is immersed in water at 23° C. for one week is preferably 90% or more, and more preferably 95% or more.
• the maximum bending stress and its retention rate can be determined by the method described in the examples.
• Moisture content of aggregate 100 to 150 g of aggregate stored under conditions of 23°C and 50% RH was weighed out and dried in a hot air dryer at 110°C. The weight was measured appropriately, and when no change in weight was observed, it was assumed that the moisture had completely dried, and the moisture content of the aggregate was calculated using the following formula.
• Moisture content of aggregate (mass%) [(mass of aggregate before drying (g))-(mass of aggregate after drying (g))]/(mass of aggregate before drying (g)) ⁇ 100
• Tg Glass Transition Temperature
• test piece was placed in a UV tester "Suntest XXL+" (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and irradiated with ultraviolet light having a wavelength of 300 to 400 nm at a temperature of 38°C with an intensity of 60 W/m 2 using a xenon lamp.
• the test piece was taken out, and the YI value was measured in the same manner as above, and is shown in Table 1.
• the smaller the increase in the YI value the better the weather resistance of the cured product. In particular, if the YI value is 15 or less at an integrated exposure of 35,449 kJ/ m2 , the weather resistance can be determined to be good.
• the paving material compositions shown in Tables 2 to 3 were placed in a mold measuring 16 cm x 16 cm x 4 cm, and cured for one week in an atmosphere of 23°C and 50% RH.
• the maximum bending stress was the average value of three measurements.
• the above cured product was also immersed in water at 23° C. for one week and subjected to a similar bending test.
• Bending stress retention rate (%) (maximum bending stress of cured product after immersion in water)/(maximum bending stress of cured product before immersion in water) ⁇ 100
• Examples 1 to 4 Comparative Examples 1 to 6 (Preparation of paving material composition and cured product, and evaluation (1)-water permeability and weather resistance)
• the epoxy resin, epoxy resin curing agent, and aggregate shown in Table 1 were weighed and mixed, and the mixture was stirred by hand for 4 minutes under conditions of 23° C. and 50% R.H. to prepare a paving material composition.
• the mixture was mixed so that the number of epoxy groups in the epoxy resin and the number of active hydrogens in the epoxy resin curing agent were equal.
• the composition was used to evaluate water permeability by the method described above.
• the weather resistance was evaluated by the method described above by using the epoxy resin and the epoxy resin curing agent shown in Table 1. The results are shown in Table 1.
• ⁇ Epoxy resin> jER828 liquid epoxy resin having a glycidyloxy group derived from bisphenol A (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g/equivalent, solid content: 100% by mass)
• ⁇ MXDA metaxylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Ltd.
• ⁇ IPDA isophoronediamine
• ⁇ DETA diethylenetriamine
• TETA triethylenetetramine ⁇ Aggregate> - Silica sand No.
• the cured product of the paving material composition of the present invention has high water permeability, and the cured product of the epoxy resin composition (epoxy resin + epoxy resin curing agent) used in the paving material composition has high Tg and weather resistance. Furthermore, as shown in Tables 2 and 3, the cured product of the paving material composition of the present invention has high initial strength (maximum bending stress before immersion in water) and bending stress retention after immersion in water, which shows that the cured product has high strength and excellent strength retention even in a wet environment.
• the cured products of the paving material compositions of Comparative Examples 1-2 and 5-6 had low water permeability
• the cured products of the epoxy resin compositions (epoxy resin + epoxy resin curing agent) used in the paving material compositions of Comparative Examples 1-6 had low Tg
• the cured products of the epoxy resin compositions used in the paving material compositions of Comparative Examples 1-2 and 4-6 had low weather resistance.
• the cured products of the paving material compositions of Comparative Examples 7-16 were inferior in at least one of the initial strength (maximum bending stress before immersion in water) and bending stress retention.
• the present invention provides a paving material composition that can produce structures that have high water permeability, weather resistance, and strength, and that have excellent strength retention even in wet environments.

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• 2024
  • 2024-02-07 WO PCT/JP2024/004213 patent/WO2024202567A1/ja not_active Ceased
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