Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G59/5006—Amines aliphatic
  • C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
• • 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
  • 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
  • C08G59/5033—Amines aromatic
• • 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. Pavement materials for scenic paving are required to have high strength in the resulting structure, and are generally also desired to have high water permeability.
• Patent Document 1 describes that a resin composition for water-permeable paving materials that is composed of a liquid epoxy resin, an amine-based curing agent such as m-xylylenediamine or an acrylonitrile-modified m-xylylenediamine, and a xylene formaldehyde resin can reduce chipping of aggregate and the occurrence of cracks.
• Patent Document 2 discloses that a resin composition for water-permeable paving materials, which comprises an amine-based curing agent such as an epoxy resin, m-xylylenediamine or an acrylonitrile-modified m-xylylenediamine, an adhesion promoter, and a xylene formaldehyde resin, is less susceptible to deterioration due to contact with water and hot water, has high initial tensile strength and tensile elongation at break, is excellent in chemical resistance, and further has excellent adhesion to aggregate particles.
• an amine-based curing agent such as an epoxy resin, m-xylylenediamine or an acrylonitrile-modified m-xylylenediamine, an adhesion promoter, and a xylene formaldehyde resin
• Patent Document 3 discloses that a paving resin composition containing at least an epoxy resin and a diluent and consisting of an epoxy resin base having a viscosity of 10 poise or less at 25°C and a Mannich-modified metaxylylenediamine as a curing agent has excellent workability, can be applied at low temperatures, and provides a robust water-permeable pavement structure with excellent aggregate adhesion.
• the object of the present invention is to provide a paving material composition which can provide a structure having high strength and excellent strength retention even in a wet environment, and in particular, which has good hardening properties even when a water-containing aggregate is used, and can form a structure having high strength.
• a paving material composition comprising an epoxy resin, an epoxy resin curing agent containing a reaction composition (A) containing a reaction product of styrene and a polyamine compound represented by the following general formula (1), and an aggregate.
• a reaction composition A containing a reaction product of styrene and a polyamine compound represented by the following general formula (1), and an aggregate.
• a reaction composition A containing a reaction product of styrene and a polyamine compound represented by the following general formula (1), and an aggregate.
• H 2 N-CH 2 -X-CH 2 -NH 2 (1) In formula (1), X is a phenylene group.
• the present invention provides a paving material composition that can produce structures that are strong and have excellent strength retention even in wet environments, and that can form structures that have good hardening properties and high strength even when using wet aggregate.
• the term "pavement composition” refers to a composition containing aggregate for pavement and used to form pavement.
• the pavement composition of the present invention does not include compositions that do not contain aggregate, such as primers used for pavement.
• reaction composition containing a reaction product of styrene and a polyamine compound represented by general formula (1) means a product obtained by reacting styrene with the polyamine compound, and a composition containing not only the reaction product (adduct) of styrene and the polyamine compound, but also by-products other than the reaction product, unreacted raw materials, etc.
• the term “water-containing aggregate” refers to aggregate having a moisture content of 3% by mass or more, preferably 5% by mass or more.
• 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 a reaction composition (A) containing a reaction product of styrene and a polyamine compound represented by the following general formula (1), and an aggregate.
• composition of the present invention has the above-mentioned configuration, it is possible to obtain a structure that is strong and has excellent strength retention even in a wet environment, and in particular, even when a water-containing aggregate is used, it is possible to form a structure that has good hardening properties and high strength.
• composition of the present invention exhibits the above-mentioned effects.
• Polyamine compounds generally used as amine-based curing agents are water-soluble, and therefore dissolve in water in the presence of water, and the reactivity with epoxy resins, which are usually hydrophobic, decreases.
• epoxy resins which are usually hydrophobic
• polyamine compounds dissolved in water react with carbon dioxide in the atmosphere to convert to carbonates, and are inactivated as epoxy resin curing agents. Therefore, it is believed that the reactivity of the polyamine compound with epoxy resins decreases even if the water is volatilized after dissolving in water, and the crosslink density of the resulting cured product decreases.
• the reactive composition (A) used as the epoxy resin curing agent in the present invention is hydrophobic, so that it does not dissolve in water even in the presence of water, and can fully react with the hydrophobic epoxy resin.
• the reactive composition (A) is not only hydrophobic but also has low viscosity, it can drain water while impregnating the aggregate surface in the composition.
• the adhesion between the aggregate and the epoxy resin composition components epoxy resin + epoxy resin curing agent
• the adhesion between the aggregates is also strengthened.
• the drained water also contributes to the promotion of the epoxy ring-opening reaction of the epoxy resin. Therefore, it is considered that a structure with good curability and high strength can be formed even when a water-containing aggregate is used.
• 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.
• 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
• the epoxy resin is preferably one having as its main component at least one selected from the group consisting of epoxy resins having a glycidylamino group derived from metaxylylenediamine, epoxy resins having a glycidylamino group derived from paraxylylenediamine, epoxy resins having a glycidyloxy group derived from bisphenol A, and epoxy resins having a glycidyloxy group derived from bisphenol F, and from the viewpoints of the strength of the structure obtained, the strength retention rate in a wet environment, the improved curing properties when a hydrous aggregate is used, and from the viewpoints of availability and economy, one having as its main component an epoxy resin having a glycidyloxy group derived from bisphenol A is more preferable.
• 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 resin may contain a reactive diluent in addition to the epoxy resin that may be contained as a main component.
• the reactive diluent include low molecular weight compounds having at least one epoxy group, such as aromatic monoglycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, alkyl monoglycidyl ethers such as butyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether and tetradecyl glycidyl ether, and diglycidyl ethers of aliphatic diols such as 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, n
• 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 the strength of the structure obtained by curing the paving material composition, the strength retention rate in a wet environment, and the improvement of the curing property when a water-containing aggregate is used, 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 handling.
• the epoxy resin curing agent contains a reaction composition (A) containing a reaction product of styrene and a polyamine compound represented by the following general formula (1).
• A a reaction composition containing a reaction product of styrene and a polyamine compound represented by the following general formula (1).
• H 2 N-CH 2 -X-CH 2 -NH 2 (1) (In formula (1), X is a phenylene group.)
• the epoxy resin curing agent contains a reaction composition (A) containing a reaction product of styrene and a polyamine compound represented by the general formula (1).
• a reaction composition (A) containing a reaction product of styrene and a polyamine compound represented by the general formula (1).
• X is a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group, preferably a 1,3-phenylene group or a 1,4-phenylene group, and more preferably a 1,3-phenylene group.
• the polyamine compound represented by the general formula (1) is one or more xylylenediamines selected from the group consisting of o-xylylenediamine, m-xylylenediamine (meta-xylylenediamine; MXDA), and p-xylylenediamine (para-xylylenediamine; PXDA), preferably one or more selected from the group consisting of meta-xylylenediamine and para-xylylenediamine, and more preferably meta-xylylenediamine.
• the reaction composition (A) contains the reaction product of styrene and the polyamine compound represented by the general formula (1) preferably at 95% by mass or more, more preferably at 98% by mass or more, and even more preferably at 99% by mass or more, the upper limit being 100% by mass.
• the reaction composition (A) preferably contains 10% by mass or more of a compound represented by the following general formula (2).
• the compound represented by the above general formula (2) is a reaction product of styrene and the polyamine compound represented by the above general formula (1) (hereinafter also referred to as the "raw material polyamine"), in which 1 mole of styrene is added to 1 mole of the raw material polyamine (hereinafter also referred to as the "1:1 adduct").
• the reaction composition (A) may contain a 1:1 adduct of styrene and raw material polyamine, which is a compound represented by the above general formula (2), as well as multiple adducts such as a 2:1 adduct, a 3:1 adduct, and a 4:1 adduct of styrene and raw material polyamine, but among the above adducts, the 1:1 adduct of styrene and raw material polyamine has the lowest active hydrogen equivalent.
• the active hydrogen equivalent hereinafter also referred to as "AHEW" is the molecular weight per equivalent of active hydrogen that can react with the epoxy resin. Therefore, the epoxy resin curing agent using the reaction composition (A) containing a large amount of the compound represented by the above general formula (2) can exhibit good curing performance even if the amount of the epoxy resin curing agent mixed into the paving material composition is small.
• the content of the compound represented by the above-mentioned general formula (2) in the reaction composition (A) is more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 45% by mass or more, and 100% by mass or less.
• the content of the compound represented by the above general formula (2) in the reaction composition (A) can be determined by gas chromatography (GC) analysis.
• the active hydrogen equivalent (AHEW) of the reaction composition (A) is preferably 130 or less, more preferably 120 or less, and even more preferably 110 or less.
• AHEW of the reaction composition (A) is 130 or less, good hardening performance is exhibited even when the amount of the composition mixed into the paving material composition is small.
• the AHEW of the reaction composition (A) is preferably 80 or more, more preferably 90 or more.
• the AHEW of the reaction composition (A) can be determined, for example, by a titration method.
• the content of the polyamine compound represented by the general formula (1) in the reaction composition (A) is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, from the viewpoints of the strength of the structure obtained by hardening the paving material composition, the strength retention rate in a wet environment, and the improvement of hardening properties when using a water-containing aggregate.
• the reaction composition (A) is obtained by reacting styrene with the polyamine compound represented by the general formula (1) by a known method. More specifically, it is obtained by subjecting styrene to an addition reaction with a raw material polyamine in the presence of a basic catalyst such as an alkali metal, an alkali metal amide (represented by the general formula MNRR', where M is an alkali metal, N is nitrogen, and R and R' are each independently hydrogen or an alkyl group), or an alkylated alkali metal, at a temperature of preferably 50 to 120°C, more preferably 70 to 100°C.
• a basic catalyst such as an alkali metal, an alkali metal amide (represented by the general formula MNRR', where M is an alkali metal, N is nitrogen, and R and R' are each independently hydrogen or an alkyl group), or an alkylated alkali metal, at a temperature of preferably 50 to 120°C, more preferably 70 to 100°C.
• the amount of the basic catalyst used is preferably 0.1 to 20 mol %, more preferably 0.5 to 15 mol %, even more preferably 1.0 to 12 mol %, and still more preferably 1.5 to 10 mol %, based on 100 mol % of the total amount of the raw material polyamine and styrene used.
• the amounts of styrene and raw material polyamine used in the addition reaction are 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, such that the molar ratio of styrene to 1 mol of raw material polyamine is 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.
• the content of the reactive composition (A) in the epoxy resin hardener is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 85% 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 viewpoints of the strength of the structure obtained by hardening the paving material composition, the strength retention rate in a wet environment, and the improvement of hardening properties when using a water-containing aggregate.
• the epoxy resin curing agent may further contain another curing agent component other than the reaction composition (A).
• the "other curing agent component” may be a polyamine compound other than the reaction composition (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 the polyamine compound represented by the general formula (1); menthene diamine, isophorone diamine, norbornane diamine, tricyclodecane diamine, adamantane diamine, diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-
• modified polyamine compound examples include Mannich modified products, epoxy modified products, Michael adducts, Michael adduct-polycondensates, styrene modified products (excluding styrene modified products of the polyamine compound represented by the general formula (1)), polyamide modified products, etc. These may be used alone or in combination of two or more.
• the content of hardener components other than the reactive composition (A) in the epoxy resin hardener is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even 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 be 0% by mass.
• the active hydrogen equivalent (AHEW) of the epoxy resin hardener 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 hardener blended in the paving material composition is small.
• the AHEW of the hardener is preferably 80 or more, and more preferably 90 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.
• the particle size of the aggregate is not particularly limited, but is preferably 0.002 to 50 mm, more preferably 0.01 to 30 mm, even more preferably 0.1 to 20 mm, even more preferably 0.2 to 10 mm, even more preferably 0.5 to 5 mm, and even more preferably 0.5 to 3 mm. If the particle size of the aggregate is 0.002 mm or more, the strength of the resulting structure, the strength retention rate in a wet environment, and the effect of improving hardening properties when using water-containing aggregate are good. Also, if the particle size is 50 mm or less, the effect of improving the water-proofing of the resulting structure is 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. 4 to No. 5, from the viewpoints of the strength of the structure obtained by hardening the paving material composition, the strength retention rate in a wet environment, and the improvement of hardening properties when using a water-containing aggregate.
• 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 0.1 to 30% by mass, even more preferably 0.1 to 25% by mass, still more preferably 0.2 to 25% by mass, still more preferably 0.5 to 25% by mass, still more preferably 1.0 to 25% by mass, still more preferably 3.0 to 25% by mass, and still more preferably 5.0 to 25% by mass.
• the paving material composition of the present invention has the effect of being able to form a hardened product (structure) that is excellent in hardening property and has high strength even when aggregate with a high moisture content is used.
• 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, strength of the resulting structure, strength retention rate in a wet environment, and improved curing property when a water-containing aggregate is used, 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, falling off of the aggregate in the resulting structure is easily suppressed, and if it is 0.5 or less, the strength of the resulting structure, the strength retention rate in a wet environment, and the hardening property when using a water-containing aggregate 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 mass%, more preferably 0.2 to 25 mass%, even more preferably 0.5 to 20 mass%, even more preferably 1.0 to 15 mass%, even more preferably 1.0 to 10 mass%, and even more preferably 1.5 to 7.0 mass%, from the viewpoints of hardening property, strength of the resulting structure, strength retention rate in a wet environment, and improved hardening property when using a water-containing aggregate.
• 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, strength of the resulting structure, strength retention rate in a wet environment, and improvement of curing property when using a water-containing aggregate.
• 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 90 to 99% by mass, from the viewpoints of hardening property, strength of the resulting structure, strength retention rate in a wet environment, and improved hardening property when a water-containing aggregate is used.
• 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 viewpoints of the strength of the resulting structure, strength retention rate in a wet environment, and improved hardening properties when using wet aggregate.
• the water content in the paving material composition is preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, even 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.
• 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 of the mixed components.
• 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, with the lower limit being 0% by mass, from the viewpoint of improving the strength of the resulting structure and strength retention in a wet environment.
• 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.
• the maximum compressive stress of a 16 cm x 16 cm x 4 cm plate-shaped structure obtained by curing the paving material composition of the present invention, measured in a compression test at a test speed of 1 mm/min according to a method in accordance with JIS R 5201:2015, is preferably 5.0 MPa or more, more preferably 5.5 MPa or more, and even more preferably 6.0 MPa or more.
• the retention of maximum compressive stress after the structure is immersed in water at 23° C. for one week is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more.
• the maximum compressive stress and its retention rate can be determined specifically by the method described in the Examples. The larger the maximum compressive stress value of the structure, the higher the initial strength, and the higher the retention rate of the maximum compressive stress, the higher the strength retention rate of the structure in a wet environment.
• the moisture content of the wet aggregates (silica sand No. 4 with moisture contents of 5% and 10% by mass) used in Table 3 was calculated from the amounts of water and silica sand No. 4 charged before soaking.
• the moisture content of the wet aggregate (silica sand No. 4 with a moisture content of 20.8% by mass) used in Table 3 was measured by the following method: Silica sand No. 4 before submersion was immersed in water at 23° C. and left to stand overnight, and then filtered to recover silica sand No. 4. This silica sand No. 4 was weighed and dried in a hot air dryer at 110° C., and the moisture content was calculated in the same manner as above.
• Example 1-1 Comparative Examples 1-1 to 1-8 (Preparation and Evaluation of Composition for Paving Material and Cured Product (1) - Strength of Cured Product Before and After Immersion in Water)
• the epoxy resin, epoxy resin curing agent, and aggregate (silica sand No. 4, moisture content 0.2% by mass) shown in Table 1 were mixed and stirred by hand for 4 minutes under conditions of 23°C and 50% R.H. to prepare a paving material composition.
• the epoxy resin 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. Using this composition, a cured product was produced and its strength was evaluated by the following method. The results are shown in Table 1.
• the above cured products were also immersed in water at 23° C. for a predetermined period of time and subjected to similar bending and compression tests.
• Example 1-2, Comparative Examples 1-9 to 1-16 The epoxy resin, epoxy resin curing agent, and aggregate (gravel, moisture content 1.3% by mass) shown in Table 2 were mixed and stirred by hand for 4 minutes under conditions of 23° C. and 50% R.H. to prepare a paving material composition.
• the epoxy resin 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.
• a cured product was produced and its strength was evaluated (measurement of maximum bending stress and bending stress retention) in the same manner as in Example 1-1 and Comparative Examples 1-1 to 1-8. The results are shown in Table 2.
• Example 2-1 Comparative Examples 2-1 to 2-8 (Preparation and Evaluation of Composition for Paving Material and Hardened Product (2) - Hardening Property and Hardened Product Strength When Using Water-Containing Aggregate)
• Silica sand No. 4 with a moisture content of 5% by mass and 10% by mass was prepared in the following manner: A specified amount of water was added to silica sand No. 4 before soaking in water to achieve the target moisture content, and the sand was stirred until the color was visually uniform.
• Silica sand No. 4 with a water content of 20.8% by mass was prepared by the following method: 31 g of silica sand No. 4 before soaking was weighed, 50 g of pure water was added, and the mixture was allowed to stand for one day at 23° C. After standing, the water was removed by decantation.
• ⁇ 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)
• G-240 A reaction composition containing a reaction product of styrene and metaxylylenediamine ("Gaskamine 240" manufactured by Mitsubishi Gas Chemical Co., Ltd., AHEW: 103)
• MXDA meta-xylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Ltd.
• 1,3-BAC 1,3-bis(aminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.
• IPDA isophoronediamine
• DETA diethylenetriamine
• TETA triethylenetetramine
• MXDA-AN1 acrylonitrile-1 mole adduct of meta-xylylenediamine obtained in Production Example 1
• MXDA Mannich Mannich reaction product of meta-xylylenediamine obtained in Production Example 2
• AEP N-aminoethylpiperazine ⁇ Aggregate> ⁇ Silica sand No. 4: "Nikko Silica Sand No. 4" manufactured by JFE Mineral Co., Ltd., particle size 0.6 to 1.2 mm - Gravel: "Gravel that is kind to aquatic plants and fish" manufactured by Kamihata Fish Farming Co., Ltd., particle size 1 to 5 mm
• the hardened product of the paving material composition of the present invention has high strength and retains a high degree of strength even after being submerged in water. Also, as shown in Table 3, the paving material composition of the present invention has excellent hardening properties even when aggregate with a high moisture content is used, and a hardened product with high strength can be obtained.
• the present invention provides a paving material composition that can produce structures that are strong and have excellent strength retention even in wet environments, and that can form structures that have good hardening properties and high strength even when using wet aggregate.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Ceramic Engineering (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Civil Engineering (AREA)
• Architecture (AREA)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Road Paving Structures (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92904073

Family Applications (1)

Country Status (6)

Citations (16)

• 2024
  • 2024-02-07 CN CN202480008594.2A patent/CN120584143A/zh active Pending
  • 2024-02-07 KR KR1020257020137A patent/KR20250164148A/ko active Pending
  • 2024-02-07 EP EP24778711.2A patent/EP4692156A1/en active Pending
  • 2024-02-07 WO PCT/JP2024/004212 patent/WO2024202566A1/ja not_active Ceased
  • 2024-02-07 JP JP2025509846A patent/JPWO2024202566A1/ja active Pending
  • 2024-02-16 TW TW113105405A patent/TW202442740A/zh unknown

Patent Citations (16)

Also Published As

Similar Documents

Legal Events