Composition for paving material and structure

Abstract

A composition for a paving material, which contains an epoxy resin, an epoxy resin curing agent and an aggregate, and wherein the epoxy resin curing agent contains 50 mass% or more of a polyamine compound represented by general formula (1) or a modified product (A) thereof. H2N-CH2-X-CH2-NH2 (1) (In formula (1), X represents a cyclohexylidene group. ).

Description

Technical Field

[0001] The present invention relates to a composition and a structure for paving materials. Background Art

[0002] Natural stone is used as an aggregate in landscape paving materials. Using natural stone allows for a paving material that blends better with the scenery of parks, tourist spots, and the like, compared to asphalt and concrete.

[0003] For landscape paving materials, in addition to the strength of the structure required, high water permeability is usually also desired. In addition, as landscape paving materials, high weather resistance is particularly preferred.

[0004] Paving material compositions with excellent weather resistance that use epoxy resins as binder resins are known. For example, Patent Document 1 discloses a paving material that is strong, water-permeable, and has excellent weather resistance, and is kneaded using a weather-resistant epoxy-based fiberized resin as a binder for aggregates. The weather-resistant epoxy-based fiberized resin comprises, as its main component, a mixture of an alicyclic epoxy resin in which aromatic benzene rings have been substituted by a reduction reaction and fibers having a fiber diameter and fiber length that are below specified values.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-294616 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, the technology disclosed in Patent Document 1 uses an epoxy resin as a binder resin, kneaded with fibers, and then fiberized. This results in complex processes leading to the production of the structure. Furthermore, landscape paving materials are often used outdoors, making it crucial that their initial strength not be compromised, and that their strength not be compromised even after exposure to rain or other factors.

[0010] An object of the present invention is to provide a paving composition capable of obtaining a structure having high water permeability, weather resistance, and strength, and having an excellent strength retention rate even in a humid environment.

[0011] Solutions for solving problems

[0012] The present inventors have found that the above-mentioned problems can be solved by a paving material composition containing an epoxy resin, a predetermined epoxy resin curing agent, and aggregate.

[0013] That is, the present invention relates to the following.

[0014] [1] A composition for a paving material comprising: an epoxy resin, an epoxy resin curing agent, and an aggregate, wherein the epoxy resin curing agent contains 50% by mass or more of a polyamine compound represented by the following general formula (1) or a modified form thereof (A).

[0015] H2N-CH2-X-CH2-NH2(1)

[0016] (In formula (1), X is a cyclohexylene group.)

[0017] [2] The pavement composition according to [1] above, wherein the modified form of the polyamine compound is at least one selected from the group consisting of the following (I) to (IV).

[0018] (I) Mannich reaction product of a polyamine compound represented by the aforementioned general formula (1), a phenol compound and an aldehyde compound

[0019] (II) Reaction product of the polyamine compound represented by the above general formula (1) and the unsaturated hydrocarbon compound

[0020] (III) a reaction product of a polyamine compound represented by the aforementioned general formula (1) and an epoxy compound having at least one epoxy group

[0021] (IV) Reaction product of the polyamine compound represented by the above general formula (1) and an unsaturated carboxylic acid or a derivative thereof

[0022] [3] The pavement composition according to [1] or [2] above, wherein the mass ratio of the epoxy resin to the aggregate [epoxy resin / aggregate] is in the range of 0.005 to 0.5.

[0023] [4] The paving material composition according to any one of [1] to [3] above, wherein the aggregate has a particle size of 0.002 to 50 mm.

[0024] [5] A structure comprising a cured product of the pavement composition according to any one of [1] to [4] above.

[0025] Effects of the Invention

[0026] According to the present invention, there can be provided a paving composition capable of obtaining a structure having high water permeability, weather resistance, and strength, and excellent strength retention in a humid environment. DETAILED DESCRIPTION

[0027] [definition]

[0028] In this specification, the term "paving material composition" refers to a composition containing a paving material aggregate and used for forming a paving material. The paving material composition of the present invention does not include a primer composition used for a paving material.

[0029] In this specification, the strength of a structure obtained by curing a paving material composition uses maximum bending stress as an indicator and can be evaluated using the methods described in the Examples. Unless otherwise specified, "strength of a structure" refers to the initial strength of the structure. A high initial strength of a structure means a high maximum bending stress value before the structure is immersed in water.

[0030] The strength retention rate of a structure in a wet environment is a value obtained from the ratio of the maximum bending stress after immersion in water for a predetermined time to the initial maximum bending stress of the obtained structure (before immersion in water), and can be specifically calculated by the method described in the Examples.

[0031] [Paving material composition]

[0032] The paving material composition of the present invention (hereinafter also referred to as "the composition (of the present invention)") contains: an epoxy resin, an epoxy resin curing agent and aggregate, wherein the epoxy resin curing agent contains 50% by mass or more of a polyamine compound represented by the following general formula (1) or a modified form thereof (A).

[0033] H2N-CH2-X-CH2-NH2(1)

[0034] (In formula (1), X is a cyclohexylene group.)

[0035] The composition of the present invention, having the above-mentioned structure, can form a structure having high water permeability, weather resistance, and strength, and excellent strength retention even in a humid environment.

[0036] The reason why the composition of the present invention exhibits the above-mentioned effects is not clear, but is considered as follows.

[0037] The polyamine compound represented by the general formula (1) is an aliphatic cyclic polyamine, which has moderate hydrophilicity, but is more hydrophobic than aliphatic chain polyamines. In addition, if the polyamine compound represented by the general formula (1) is used as an epoxy resin curing agent, a cured product with a high glass transition temperature (Tg) can be obtained. It is believed that due to the above properties, the cured product of the composition of the present invention using an epoxy resin curing agent containing more than a specified amount of the polyamine compound or its modified form has high water permeability, high strength, and a higher strength retention rate in a humid environment. In addition, the polyamine compound represented by the general formula (1) does not contain an aromatic ring, and the ratio of nitrogen atoms in the molecule is also low. Therefore, it is believed that the cured product of the composition of the present invention shows high weather resistance.

[0038] Hereinafter, each component used in the composition of the present invention will be described.

[0039] Epoxy resin

[0040] The epoxy resin is not particularly limited as long as it has two or more glycidyl groups reactive with the active hydrogen in the epoxy resin curing agent described below. It may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. From the perspective of improving the strength of the structure obtained by curing the paving material composition and the strength retention in a humid environment, the epoxy resin preferably contains an aromatic ring or alicyclic structure in the molecule.

[0041] Specific examples of the epoxy resin include epoxy resins having a glycidyl amino group derived from m-xylylenediamine, epoxy resins having a glycidyl amino group derived from p-xylylenediamine, epoxy resins having a glycidyl amino group derived from 1,3-bis(aminomethyl)cyclohexane, epoxy resins having a glycidyl amino group derived from 1,4-bis(aminomethyl)cyclohexane, epoxy resins having a glycidyl amino group derived from diaminodiphenylmethane, epoxy resins having a glycidyl amino group derived from p-aminophenol, and epoxy resins having a glycidyl amino group derived from diaminodiphenylmethane. At least one resin selected from the group consisting of an epoxy resin having a glycidylamino group and / or a glycidyloxy group, an epoxy resin having a glycidyloxy group derived from bisphenol A, an epoxy resin having a glycidyloxy group derived from bisphenol F, an epoxy resin having a glycidyloxy group derived from hydrogenated bisphenol A, an epoxy resin having a glycidyloxy group derived from hydrogenated bisphenol F, an epoxy resin having a glycidyloxy group derived from phenol novolac, and an epoxy resin having a glycidyloxy group derived from resorcinol. Two or more of these epoxy resins may be used in combination.

[0042] Among the above, 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 preferably contains as the main component at least one selected from the group consisting of an epoxy resin having a glycidyl amino group derived from m-xylylenediamine, an epoxy resin having a glycidyl amino group derived from p-xylylenediamine, an epoxy resin having a glycidyloxy group derived from bisphenol A, an epoxy resin having a glycidyloxy group derived from bisphenol F, an epoxy resin having a glycidyloxy group derived from hydrogenated bisphenol A, and an epoxy resin having a glycidyloxy group derived from hydrogenated bisphenol F. From the viewpoint of the strength of the structure obtained by curing the paving material composition, the strength retention rate in a wet environment, availability, and cost-effectiveness, it is more preferable to use as the main component an epoxy resin having a glycidyloxy group derived from bisphenol A.

[0043] It should be noted that the "main component" herein means that other components may be included within the scope of the present invention, and preferably accounts for 50 to 100 mass %, more preferably 70 to 100 mass %, and even more preferably 90 to 100 mass % of the total.

[0044] The epoxy resin may be either a solid epoxy resin or a liquid epoxy resin. However, from the perspective of improving the strength of the resulting structure and the strength retention in a wet environment, a liquid epoxy resin is more preferred. In the present invention, a "solid epoxy resin" refers to an epoxy resin that is solid at room temperature (25°C), and a "liquid epoxy resin" refers to an epoxy resin that is liquid at room temperature (25°C).

[0045] From the perspective of improving workability, the epoxy resin may contain a reactive diluent in addition to the epoxy resin as a main component. Examples of such reactive diluents 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-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0046] The above-mentioned reactive diluents can be used alone or in combination of two or more.

[0047] The epoxy equivalent of the epoxy resin is preferably 80 g / equivalent or more, more preferably 100 g / equivalent or more, further 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. From the viewpoint of workability, it is preferably 1000 g / equivalent or less, more preferably 800 g / equivalent or less, further preferably 500 g / equivalent or less, further preferably 300 g / equivalent or less, and even more preferably 200 g / equivalent or less.

[0048] Commercially available epoxy resins may be used. Examples of commercially available epoxy resins include "jER825," "jER827," "jER828," "jER801N," "jER801PN," "jER802," "jER811," "jER813," "jER819," "jER806," "jER806H," and "jER807" manufactured by Mitsubishi Chemical Corporation.

[0049] <Epoxy resin curing agent>

[0050] The epoxy resin curing agent contains 50% by mass or more of a polyamine compound represented by the following general formula (1) or a modified form thereof (A). When an epoxy resin curing agent containing 50% by mass or more of component (A) is used, a structure having high water permeability, weather resistance, and strength, and excellent strength retention in a humid environment can be formed.

[0051] H2N-CH2-X-CH2-NH2(1)

[0052] (In formula (1), X is a cyclohexylene group.)

[0053] In the aforementioned formula (1), X is a 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene group. From the viewpoint of improving the water permeability, weather resistance, strength, and strength retention in a humid environment of a structure obtained by curing the pavement composition, 1,3-cyclohexylene or 1,4-cyclohexylene is preferred, and 1,3-cyclohexylene is more preferred. That is, the polyamine compound represented by the aforementioned 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, preferably one or more bis(aminomethyl)cyclohexane 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.

[0054] Preferred examples of the modified form of the polyamine compound represented by the general formula (1) include at least one selected from the group consisting of the following (I) to (IV).

[0055] (I) Mannich reaction product of a polyamine compound represented by the aforementioned general formula (1), a phenol compound and an aldehyde compound

[0056] (II) Reaction product of the polyamine compound represented by the above general formula (1) and the unsaturated hydrocarbon compound

[0057] (III) a reaction product of a polyamine compound represented by the aforementioned general formula (1) and an epoxy compound having at least one epoxy group

[0058] (IV) Reaction product of the polyamine compound represented by the above general formula (1) and an unsaturated carboxylic acid or a derivative thereof

[0059] ((I) Mannich reaction product of a polyamine compound represented by the aforementioned general formula (1), a phenol compound, and an aldehyde compound)

[0060] The modified product (I) is a Mannich reaction product of a polyamine compound represented by the aforementioned general formula (1), a phenol compound, and an aldehyde compound.

[0061] Examples of the phenolic compound used in the modified product (I) include naturally occurring phenolic compounds such as phenol, alkylphenol, alkenylphenol, terpenephenol, and cardanol. From the perspective of improving the water permeability, weather resistance, strength, and strength retention in a wet environment of the structure obtained by curing the paving material composition, the alkyl group in the alkylphenol preferably has 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, and the alkenyl group in the alkenylphenol preferably has 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms.

[0062] Specific examples of the phenolic compound include phenol, cresol, ethylphenol (p-ethylphenol, etc.), isopropylphenol (o-isopropylphenol, p-isopropylphenol, etc.), butylphenol (p-tert-butylphenol, p-sec-butylphenol, o-tert-butylphenol, o-sec-butylphenol, etc.), amylphenol (p-tert-amylphenol, o-tert-amylphenol, etc.), p-octylphenol, nonylphenol, p-cumylphenol, decylphenol, undecylphenol, p-dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, pentadecenylphenol, pentadecadienylphenol, pentadecatrienylphenol, hexadecylphenol, heptadecylphenol, octadecylphenol, octadecenylphenol, terpene phenols, and cardanol. These can be used alone or in combination of two or more.

[0063] Among the above, from the viewpoint of reactivity with the polyamine compound represented by the aforementioned general formula (1) and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention in a humid environment of the structure obtained by curing the paving material composition, 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 phenol is more preferred.

[0064] Examples of the aldehyde compound used in modified product (I) include formaldehyde; formaldehyde-releasing compounds such as trioxane and paraformaldehyde; and other aldehydes such as benzaldehyde. Of these, at least one selected from the group consisting of formaldehyde and formaldehyde-releasing compounds is preferred. Among these, aqueous formaldehyde solutions are more preferred from the perspective of workability in the Mannich reaction.

[0065] The method for producing the modified product (I) is not particularly limited, and a known method can be used. For example, the following 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, preferably at 80°C or lower, more preferably at 60°C or lower. After the addition, the temperature is raised to preferably 80 to 180°C, more preferably 90 to 150°C, and the mixture is reacted for 1 to 10 hours while removing distillates from the reaction system.

[0066] 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 obtained modified product (I) contains an amino group having active hydrogen. However, from the viewpoint of reactivity with the polyamine compound represented by the aforementioned general formula (1), and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a humid environment of the structure obtained by curing the paving material composition, the following ranges are preferred.

[0067] The aldehyde compound is preferably used in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per mol of the polyamine compound. The phenol compound is preferably used in an amount of 0.3 to 2 mol, more preferably 0.5 to 1.5 mol, per mol of the polyamine compound.

[0068] ((II) Reaction product of the polyamine compound represented by the aforementioned general formula (1) and the unsaturated hydrocarbon compound)

[0069] The modified product (II) is a reaction product of the polyamine compound represented by the aforementioned general formula (1) and an unsaturated hydrocarbon compound.

[0070] As the unsaturated hydrocarbon compound used in the modified product (II), an unsaturated hydrocarbon compound having 2 to 10 carbon atoms is preferred from the viewpoint of reactivity with the polyamine compound represented by the aforementioned general formula (1) and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a humid environment of the structure obtained by curing the paving material composition.

[0071] Examples of the unsaturated hydrocarbon compound include unsaturated aliphatic hydrocarbon compounds having 2 to 10 carbon atoms and aromatic hydrocarbon compounds having 2 to 10 carbon atoms and having an olefinically unsaturated bond, for example, 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.

[0072] Among these, from the viewpoint of reactivity with the polyamine compound represented by the aforementioned general formula (1) and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a humid environment of the structure obtained by curing the paving material composition, aromatic hydrocarbon compounds having an ethylenically unsaturated bond such as styrene and divinylbenzene are preferred, and styrene is more preferred.

[0073] The method for producing the modified product (II) is not particularly limited, and a known method can be used. For example, the modified product (II) can be obtained by subjecting the aforementioned polyamine compound to an addition reaction with an unsaturated hydrocarbon compound under heating conditions.

[0074] The amount of the unsaturated hydrocarbon compound used in the addition reaction is not particularly limited as long as the obtained modified product (II) contains amino groups having active hydrogen. However, it is preferably in the range of 0.1 to 5.0 mol, more preferably 0.4 to 3.0 mol, further preferably 0.5 to 1.5 mol, and even more preferably 0.8 to 1.2 mol per 1 mol of the polyamine compound.

[0075] ((III) Reaction product of a polyamine compound represented by the aforementioned general formula (1) and an epoxy compound having at least one epoxy group)

[0076] The modified product (III) is a reaction product of the polyamine compound represented by the aforementioned general formula (1) and an epoxy compound having at least one epoxy group.

[0077] Examples of the epoxy compound used in the modified product (III) include epichlorohydrin, butyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, biphenyl diglycidyl ether, dihydroxynaphthalene diglycidyl ether, dihydroxyanthracene diglycidyl ether, triglycidyl isocyanurate, tetraglycidyl glycoluril, a polyfunctional epoxy resin having a glycidylamino group derived from m-xylylenediamine, and a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane. Polyfunctional epoxy resins having oleylamino groups, polyfunctional epoxy resins having glycidylamino groups derived from diaminodiphenylmethane, polyfunctional epoxy resins having glycidylamino groups and glycidyloxy groups derived from p-aminophenol, polyfunctional epoxy resins having glycidyloxy groups derived from bisphenol A, polyfunctional epoxy resins having glycidyloxy groups derived from bisphenol F, polyfunctional epoxy resins having glycidyloxy groups derived from phenol novolac, and polyfunctional epoxy resins having glycidyloxy groups derived from resorcinol, etc., can be used alone or in combination.

[0078] The method for producing the modified product (III) is not particularly limited, and a known method can be used. For example, the modified product (III) can be obtained by subjecting the aforementioned polyamine compound and epoxy compound to an addition reaction under heating conditions.

[0079] The amounts of the polyamine compound and the epoxy compound used in the addition reaction are not particularly limited as long as the ratio is such that the resulting modified product (III) contains amino groups having active hydrogen. However, it is preferred to use an excess of the polyamine compound relative to the epoxy equivalent of the epoxy compound. Specifically, the polyamine compound and the epoxy compound are reacted at a ratio of preferably 4 to 50, more preferably 8 to 20, of the number of active hydrogen atoms in the polyamine compound to the number of epoxy groups in the epoxy compound.

[0080] ((IV) Reaction product of the polyamine compound represented by the aforementioned general formula (1) and an unsaturated carboxylic acid or a derivative thereof)

[0081] 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.

[0082] Examples of the unsaturated carboxylic acid or its derivative used in the modified product (IV) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, α-propylacrylic acid, α-isopropylacrylic acid, α-n-butylacrylic acid, α-tert-butylacrylic acid, α-pentylacrylic acid, α-phenylacrylic acid, α-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-methylcinnamic acid, and 2-octenoic acid, as well as esters, amides, anhydrides, and acid chlorides thereof.

[0083] Among the above, the unsaturated carboxylic acid or its derivative 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, further preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and alkyl esters thereof, further preferably an alkyl ester of acrylic acid, and further preferably methyl acrylate.

[0084] The method for producing the modified product (IV) is not particularly limited, and a known method can be used. For example, the modified product (IV) can be obtained by reacting the aforementioned polyamine compound with an unsaturated carboxylic acid or a derivative thereof under heating conditions.

[0085] The reaction molar ratio of the polyamine compound to the unsaturated carboxylic acid or its derivative (polyamine compound / unsaturated carboxylic acid or its derivative) is not particularly limited as long as the obtained modified product (IV) contains an amino group having active hydrogen, but is preferably in the range of 0.3 to 1.0, more preferably in the range of 0.6 to 1.0.

[0086] The aforementioned polyamine compounds and modified products thereof may be used alone or in combination of two or more.

[0087] In the above, the component (A) is at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, and 1,3-bis(aminomethyl)cyclohexane is more preferable.

[0088] The active hydrogen equivalent weight (AHEW) of component (A) is preferably 130 or less, more preferably 120 or less, and even more preferably 110 or less. When the AHEW of component (A) is 130 or less, good curing performance is achieved even when the amount of component (A) added to the pavement composition is small. Furthermore, the AHEW of component (A) is a value greater than or equal to that of bis(aminomethyl)cyclohexane, and therefore is 35.6 or greater.

[0089] The AHEW of the component (A) can be determined by, for example, titration.

[0090] The content of component (A) in the epoxy resin curing agent is 50% by mass or more, preferably 70% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more, and is 100% by mass or less, from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention in a humid environment of a structure obtained by curing the paving material composition.

[0091] (Other curing agent ingredients)

[0092] The epoxy resin curing agent may further contain other curing agent components in addition to the component (A). Examples of such "other curing agent components" include polyamine compounds other than the component (A) or modified forms thereof.

[0093] Examples of 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 o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine; menthanediamine, isophoronediamine, norbornanediamine, tricyclodecanediamine, adamantanediamine, diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, diaminodiethylmethylcyclohexane, 3,3'-diamino-1,4-diamino-2-methylcyclohexane, 1,4-diamino-3,6-diethyl ... -dimethyl-4,4'-diaminodicyclohexylmethane (bis(4-amino-3-methylcyclohexyl)methane), 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane and other polyamine compounds with an alicyclic structure; phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diethyltoluenediamine, 2,2'-diethyl-4,4'-methylenedianiline and other aromatic polyamine compounds; N-aminomethylpiperazine, N-aminoethylpiperazine, N,N'-bis(aminoethyl)piperazine and other polyamine compounds with a heterocyclic structure; polyether polyamine compounds, etc.

[0094] Examples of modified polyamine compounds include Mannich-modified products, epoxy-modified products, Michael adducts, Michael adduct / polycondensates, styrene-modified products, and polyamide-modified products of the above-mentioned compounds. These may be used alone or in combination of two or more.

[0095] However, the content of curing agent components other than component (A) in the epoxy resin curing agent is 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of more effectively achieving the effects of the present invention. It may also be 0% by mass.

[0096] The active hydrogen equivalent weight (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 perspective of achieving high curability even with a small amount of the paving composition. On the other hand, from the perspective of improving the water permeability, weather resistance, strength, and strength retention in a humid environment of a structure obtained by curing the paving composition, the AHEW of the curing agent is preferably 30 or more, more preferably 35 or more.

[0097] Aggregates

[0098] As the aggregate used in the present invention, inorganic granular aggregate for landscape paving is preferred. The aggregate may be natural aggregate or artificial aggregate, but from the perspective of being used as a paving material for landscape paving, natural aggregate such as natural stone is preferred.

[0099] Specific examples of aggregates include coarse gravel, river gravel, crushed stone, silica, river sand, crushed sand, silica sand, slag, glass beads, broken glass pieces, broken pottery pieces, ceramic balls, processed industrial waste, and powders or granules of alumina, clay, talc, glass, mica, calcium carbonate, barium sulfate, aluminum oxide, and aluminum hydroxide. One or more of these can be used.

[0100] Among the above, as the aggregate, from the viewpoint of use for landscape paving and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention rate in a humid environment of the structure obtained by curing the paving material composition, it is preferred to select at least one type from the group consisting of coarse gravel and silica sand. From the viewpoint of improving the water permeability of the structure obtained by curing the paving material composition, coarse gravel is more preferred.

[0101] 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. Aggregate particle sizes of 0.002 mm or greater improve the water permeability, strength, and strength retention in a humid environment of the resulting structure. Aggregate particle sizes of 50 mm or less improve the strength and strength retention in a humid environment of the resulting structure.

[0102] The particle size of the aggregate can be determined by a method in accordance with JIS A1204:2020 “Test method for particle size of soil”.

[0103] The particle size of silica sand is classified as No. 3 to No. 8 in JIS G 5901:2016. When the aggregate is silica sand, the particle size classification of the silica sand is preferably No. 3 to No. 7, more preferably No. 3 to No. 5, and even more preferably No. 3 to No. 4, from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention in a wet environment of the structure obtained by curing the paving material composition.

[0104] The particle shape of the aggregate is not particularly limited and may be spherical or non-spherical. Spherical also includes roughly spherical shapes such as those with elliptical cross-sections. Non-spherical particle shapes include plate-like, flaky, chain-like, columnar, and crushed flake shapes.

[0105] The moisture content of the aggregate is not particularly limited. However, from the perspective of improving the strength of the resulting structure and the 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, even more preferably 10% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 3.0% by mass or less. The lower limit may be 0% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.

[0106] The moisture content of the aggregate referred to herein refers to the moisture content of the aggregate when mixed with the composition of the present invention. Specifically, the moisture content of the aggregate can be measured by the method described in the Examples.

[0107] <Other ingredients>

[0108] The paving material composition may further contain other components such as known modifying components such as plasticizers, flow control components such as thixotropic agents, leveling agents, thickeners, and curing accelerators, within the range not impairing the effects of the present invention.

[0109] <Content>

[0110] The content or content ratio of each component in the pavement composition is preferably within the following ranges.

[0111] From the viewpoint of curing properties, and the improvement of the water permeability, weather resistance, strength, and strength retention of the obtained structure in a humid environment, the ratio of the epoxy resin to the epoxy resin curing agent contained in the paving material composition is 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], preferably 1 / 0.8 to 1 / 1.2, more preferably 1 / 0.9 to 1 / 1.1, and still more preferably 1 / 1.

[0112] The mass ratio of the epoxy resin to the aggregate in the paving 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. When the [epoxy resin / aggregate] ratio is 0.005 or greater, aggregate shedding in the resulting structure is easily suppressed, while when it is 0.5 or less, the water permeability, strength, and strength retention in a wet environment of the resulting structure are further improved.

[0113] In addition, when the aggregate used is a hydrous aggregate, it is preferable that the mass ratio of the epoxy resin with respect to the dry mass of the aggregate is within the above-mentioned range.

[0114] From the viewpoint of curing properties, and the improvement of the water permeability, weather resistance, strength, and strength retention in a humid environment of the obtained structure, 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%, further preferably 0.5 to 20 mass%, further preferably 1.0 to 15 mass%, and further preferably 1.0 to 10 mass%.

[0115] From the viewpoint of curing properties, and from the viewpoint of improving the water permeability, weather resistance, strength, and strength retention of the resulting structure in a humid environment, 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 %.

[0116] From the viewpoint of curing properties, and the improvement of the water permeability, weather resistance, strength, and strength retention of the obtained structure in a humid environment, the content of aggregate in the paving material composition is preferably 50 to 99.5% by mass, more preferably 55 to 99% by mass, further preferably 60 to 99% by mass, further preferably 70 to 99% by mass, further preferably 80 to 99% by mass, further preferably 85 to 99% by mass, and further preferably 87 to 99% by mass.

[0117] In addition, the "aggregate content" in this specification means the content based on the dry mass of the aggregate even when a hydrous aggregate is used.

[0118] The total content of the epoxy resin, epoxy resin curing agent and aggregate in the paving material composition is preferably 50% by mass or more, more preferably 60% by mass or more, further 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 is 100% by mass or less, from the viewpoint of improving the water permeability, weather resistance, strength and strength retention rate of the resulting structure in a humid environment.

[0119] 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 perspective of improving the strength of the resulting structure and the strength retention rate in a wet environment. The water content described above is the amount of water intended to be blended, and does not exclude the inclusion of water previously contained in the blended components.

[0120] The content of the organic solvent 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 the strength retention rate in a wet environment. The lower limit is 0% by mass.

[0121] The method for producing the epoxy resin composition of the present invention is not particularly limited, and the epoxy resin composition can be produced by mixing an epoxy resin, an epoxy resin curing agent, an aggregate, and other components as needed using a known method and apparatus.

[0122] [Structure]

[0123] The structure of the present invention comprises a cured product of the paving composition of the present invention. The paving composition can be cured by known methods. Curing conditions for the paving composition are appropriately selected based on the usage environment, the structure's morphology, and other factors, and are not particularly limited. The paving composition can be cured at room temperature in the atmosphere.

[0124] The structure of the present invention is suitable for use as a paving material, particularly suitable for use as a landscape paving material.

[0125] <Characteristics of the structure>

[0126] The paving composition of the present invention provides a structure with high strength and strength retention in a wet environment. For example, a 16 cm × 16 cm × 4 cm flat plate structure obtained by curing the paving composition of the present invention exhibits a maximum bending stress of preferably 2.0 MPa or greater, more preferably 2.5 MPa or greater, and even more preferably 3.0 MPa or greater, when subjected to a bending test in accordance with JIS R 5201:2015 at a test speed of 1 mm / min.

[0127] Furthermore, the retention rate of the maximum bending stress after immersing the structure in water at 23° C. for one week is preferably 90% or more, more preferably 95% or more.

[0128] Specifically, the maximum bending stress and its retention rate can be determined according to the method described in the Examples.

[0129] Example

[0130] The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. It should be noted that various measurements in the Examples were performed by the following methods.

[0131] (Moisture content of aggregate)

[0132] Weigh 100-150g of aggregate, previously stored at 23°C and 50% RH, and dry in a hot air dryer at 110°C. Measure the weight appropriately. When no weight change is observed, assume complete drying. Calculate the moisture content of the aggregate using the following formula.

[0133] Moisture content of aggregate (mass %) = [(mass of aggregate before drying (g)) - (mass of aggregate after drying (g))] / (mass of aggregate before drying (g)) × 100

[0134] (Water permeability)

[0135] The paving material composition obtained in each example was placed in a mold of 11 cm × 11 cm × 2 cm and aged for 1 week in an atmosphere of 23°C and 50% RH to solidify. A 50 mL screw-capped tube filled with water was inverted and placed on the obtained flat plate-shaped solidified material, and the time until the water in the screw-capped tube fell was measured. Here, in the first test, the water was discharged slowly, but if the test was repeated, the time until the water fell gradually became faster and eventually reached a stable state. Therefore, the test was repeated with the same solidified material, and the test was terminated when the speed of water falling became constant. The time taken for water to fall when the speed of water falling became constant is shown in Table 1. If the time until water falls is less than 2 minutes, it can be judged that the water permeability is good.

[0136] (Glass transition temperature (Tg))

[0137] The epoxy resin and epoxy resin curing agent listed in Table 1 were mixed so that the number of epoxy groups in the epoxy resin and the number of active hydrogen atoms in the epoxy resin curing agent were equal. The resulting mixture was aged and cured for 7 days at 23°C and 50% RH to prepare a sample. This sample was subjected to differential scanning calorimetry analysis from 35°C to 225°C using a differential scanning calorimeter "TA DSC-25" (manufactured by OMRON Corporation) at a heating rate of 10°C / min to determine its Tg.

[0138] (Weather resistance (YI))

[0139] Weather resistance tests were conducted according to ISO4982 Part 3 Method A.

[0140] The epoxy resin and epoxy resin curing agent listed in Table 1 were mixed in such a manner that the number of epoxy groups in the epoxy resin and the number of active hydrogens in the epoxy resin curing agent became equal. The obtained mixture was placed in a mold of 5 cm×5 cm×2 mm and aged for 1 week in an atmosphere of 23°C and 50% RH to cure. The obtained flat cured product (test piece) was measured for its YI value (accumulated exposure 0 kJ / m2) using a colorimeter ("COH400" manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7373:2006. 2 Then, the test piece was placed in a UV tester "Santest XXL+" (manufactured by Toyo Seiki Co., Ltd.) and the temperature was 38°C and the illumination was 60 W / m 2 The specimen was irradiated with ultraviolet light of wavelength 300-400nm at an intensity of 1000 nm. After the cumulative exposure reached the prescribed amount, the specimen was taken out and the YI value was measured in the same manner as above, as shown in Table 1. The smaller the increase in the YI value, the better the weather resistance of the cured product. In particular, the cumulative exposure of 35449 kJ / m 2 If the YI value at this time is 15 or less, it can be judged that the weather resistance is good.

[0141] (Maximum bending stress)

[0142] The paving material compositions listed in Tables 2 and 3 were placed in a 16 cm × 16 cm × 4 cm mold and cured for one week in an atmosphere at 23°C and 50% RH. The resulting cured product was subjected to a bending test (N = 3) using a precision universal testing machine ("Autograp AG-Xplus 100 kN" manufactured by Shimadzu Corporation) at a test speed of 1 mm / min according to JIS R 5201:2015. The maximum bending stress before immersion in water was measured. The maximum bending stress was recorded as the average of three measurements.

[0143] The above-mentioned cured product was immersed in water at 23° C. for one week, and a bending test was performed in the same manner. The bending stress retention rate of the cured product after immersion in water was calculated based on the following formula.

[0144] Bending stress retention (%) = (maximum bending stress of the cured product after immersion in water) / (maximum bending stress of the cured product before immersion in water) × 100

[0145] Examples 1 to 4, Comparative Examples 1 to 6 (Preparation and Evaluation of Paving Material Compositions and Cured Products (1) - Water Permeability and Weather Resistance)

[0146] The epoxy resin, epoxy resin curing agent, and aggregate listed in Table 1 were measured and mixed, and then stirred by hand for 4 minutes at 23°C and 50% RH 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 hydrogen atoms in the epoxy resin curing agent were equal.

[0147] This composition was used to evaluate water permeability by the aforementioned method. Furthermore, weather resistance was evaluated by the aforementioned method using the epoxy resins and epoxy resin curing agents listed in Table 1. The results are shown in Table 1.

[0148] Examples 2, 4, and Comparative Examples 7 to 16 (Preparation and Evaluation of Paving Material Compositions and Cured Products (2) - Cured Product Strength Before and After Water Immersion)

[0149] The epoxy resin, epoxy resin curing agent, and aggregate listed in Tables 2 and 3 were measured and mixed. The mixture was then stirred by hand for 4 minutes at 23°C and 50% RH 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 hydrogen atoms in the epoxy resin curing agent were equal.

[0150] Using this composition, a cured product was prepared and its strength was evaluated (measurement of maximum bending stress and bending stress retention) by the above-mentioned method. The results are shown in Tables 2 and 3.

[0151] [Table 1]

[0152] Table 1

[0153]

[0154] [Table 2]

[0155] Table 2

[0156]

[0157] [Table 3]

[0158] Table 3

[0159]

[0160] The components used in Tables 1 to 3 are as follows.

[0161] Epoxy resin

[0162] jER828: Liquid epoxy resin having a glycidyl group derived from bisphenol A (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / equivalent, solid content: 100% by mass)

[0163] <Epoxy resin curing agent>

[0164] 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0165] ·MXDA: m-xylylenediamine, manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0166] IPDA: Isophorone diamine

[0167] DETA: diethylenetriamine

[0168] TETA: triethylenetetramine

[0169] Aggregates

[0170] Silica sand No. 4: JFE Minerals Ltd. "Nikko Silica Sand No. 4", particle size 0.6-1.2 mm, moisture content 0.2% by mass

[0171] Coarse gravel: KAMIHATA FISH INDUSTRY GROUP "aquatic plant and fish-friendly coarse gravel", particle size 1-5mm, water content 1.3% by mass

[0172] As shown in Table 1, the cured product of the paving composition of the present invention exhibits high water permeability, and the cured product of the epoxy resin composition (epoxy resin + epoxy resin curing agent) used in the paving composition exhibits high Tg and weather resistance. Furthermore, as shown in Tables 2 and 3, the cured product of the paving composition of the present invention exhibits high initial strength (maximum flexural stress before immersion in water) and high flexural stress retention after immersion in water, demonstrating high strength and excellent strength retention even in a humid environment.

[0173] In contrast, as shown in Table 1, the cured products of the paving compositions of Comparative Examples 1-2 and 5-6 exhibited lower water permeability than those of the Examples, the cured products of the epoxy resin compositions (epoxy resin + epoxy resin curing agent) used in the paving compositions of Comparative Examples 1-6 exhibited lower Tg, and the cured products of the epoxy resin compositions used in the paving compositions of Comparative Examples 1-2 and 4-6 exhibited lower weather resistance. Furthermore, as shown in Tables 2-3, the cured products of the paving compositions of Comparative Examples 7-16 exhibited inferior initial strength (maximum flexural stress before immersion in water) or flexural stress retention compared to the Examples.

[0174] Industrial applicability

[0175] According to the present invention, there can be provided a paving composition that can produce a structure having high water permeability, weather resistance, and strength, and excellent strength retention in a humid environment.

Claims

1. A paving material composition comprising: an epoxy resin, an epoxy resin curing agent, and aggregate, wherein the epoxy resin curing agent contains 50% by mass or more of a polyamine compound represented by the following general formula (1) or a modified form thereof (A), H2N-CH2-X-CH2-NH2(1) In formula (1), X is a cyclohexylene group.

2. The paving material composition according to claim 1, wherein The modified form of the polyamine compound is at least one selected from the group consisting of the following (I) to (IV), (I) a Mannich reaction product of a polyamine compound represented by the general formula (1), a phenol compound and an aldehyde compound, (II) a reaction product of a polyamine compound represented by the general formula (1) and an unsaturated hydrocarbon compound, (III) a reaction product of a polyamine compound represented by the general formula (1) and an epoxy compound having at least one epoxy group, (IV) A reaction product of the polyamine compound represented by the general formula (1) and an unsaturated carboxylic acid or a derivative thereof.

3. The paving material composition according to claim 1 or 2, wherein The mass ratio of the epoxy resin to the aggregate, ie, epoxy resin / aggregate, is in the range of 0.005 to 0.

5.

4. The pavement composition according to any one of claims 1 to 3, wherein The particle size of the aggregate is 0.002-50 mm. 5 . A structure comprising a cured product of the paving material composition according to claim 1 .

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