JP2007099889A - Primer composition for aggregate, aggregate for pavement material and pavement material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pavement material hardly causing the separation of a hard aggregate and having excellent crack resistance, and to provide a primer composition for aggregates excellent in adhesion with the hard aggregate. <P>SOLUTION: The primer composition for aggregates contains a urethane prepolymer, a latent hardener and a solvent. The pavement material comprises an aggregate for the pavement material, which is obtained by treating an aggregate containing the hard aggregate with the above primer composition, and a resin binder. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aggregate primer composition, an aggregate for a paving material, and a paving material using the same.

2. Description of the Related Art Conventionally, an elastic pavement material in which an elastic aggregate such as a rubber chip obtained by mechanically grinding a waste tire and a hard aggregate are bonded with a urethane binder is used for a sidewalk, a roadway, and the like. In such an elastic pavement, Patent Document 1 describes that a hard aggregate is surface-treated with a silane coupling agent.
That is, in Patent Document 1, for the purpose of providing an elastic pavement excellent in durability against external environmental degradation, “in an elastic pavement formed by bonding a hard aggregate and an elastic aggregate with a urethane binder, the hard bone The material is a surface-treated hard aggregate pretreated with a silane coupling agent, and contains an antioxidant and an ultraviolet absorber. "

JP 2003-342906 A

  However, the present inventor has found that the slip resistance when wet for the elastic pavement material described in Patent Document 1 decreases with time. The present inventors have found that such a decrease in slip resistance is caused by the separation of the hard aggregate from the elastic pavement or the occurrence of cracks at the interface between the hard aggregate and the urethane binder.

  Accordingly, an object of the present invention is to provide a paving material that is hard to remove hard aggregates and has excellent crack resistance and an aggregate primer composition that is excellent in adhesion to hard aggregates.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a urethane prepolymer, a latent curing agent, and a solvent has excellent adhesion to a hard aggregate, and such The paving material composed of the hard aggregate treated with the composition and the resin binder has been found to be hard to be detached from the paving material and has excellent crack resistance, and the present invention has been completed based on these findings. It was.

That is, the present invention provides the following (1) to (11).
(1) An aggregate primer composition containing a urethane prepolymer, a latent curing agent, and a solvent.
(2) The primer composition for aggregates according to (1), wherein the urethane prepolymer has a polycarbonate structure in the skeleton.
(3) The aggregate primer composition according to (1) or (2), wherein all of the isocyanate groups of the urethane prepolymer are bonded to an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom. .
(4) The urethane prepolymer contains a urethane prepolymer having a weight average molecular weight of 1500 or less and having 3 or more functional groups, and the amount of the urethane prepolymer having a weight average molecular weight of 1500 or less and having 3 or more functional groups is the urethane prepolymer. The primer composition for aggregates according to any one of (1) to (3), wherein the primer composition is 10 to 90% by mass in the polymer.
(5) The aggregate primer composition according to any one of (1) to (4), wherein the latent curing agent is an imine compound derived from a ketone or an aldehyde and an amine.
(6) The aggregate primer composition according to (5), wherein the imine compound is a ketimine represented by the following formula (I) or formula (II).

[In Formula (I), R ¹ and R ³ each independently represents a methyl group, an ethyl group or a hydrogen atom, R ² represents a methyl group or an ethyl group, and R ⁴ has 1 to 6 carbon atoms. Represents an alkyl group, and R ⁴ may combine with R ¹ or R ² to form a ring. Provided that when R ⁴ is bonded to R ² to form a ring and the carbon atom in the α-position of the carbonyl group is bonded to R ² or R ^{4 through} a double bond, R ³ does not exist. In formula (II), R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ may be bonded to each other to form a ring. ]
(7) The primer composition for aggregate according to any one of (1) to (6), further comprising an epoxy resin.
(8) The primer composition for aggregates according to (7), wherein the content of the epoxy resin is 10 to 90% by mass of the total amount of the urethane prepolymer and the epoxy resin.
(9) An aggregate for pavement that can be obtained by treating an aggregate containing hard aggregate with the aggregate primer composition described in any one of (1) to (8) above.
(10) The aggregate for pavement according to (9), wherein the aggregate further includes an elastic aggregate.
(11) A paving material comprising the aggregate for paving materials according to (9) or (10) above and a resin binder.

The primer composition for aggregates of the present invention is excellent in adhesiveness with hard aggregates.
Moreover, the pavement material of the present invention is excellent in crack resistance because hard aggregates are not easily detached.

Hereinafter, the present invention will be described in more detail.
First, the aggregate primer composition of the present invention will be described.
The primer composition for aggregate of the present invention is a composition containing a urethane prepolymer, a latent curing agent, and a solvent.

  The urethane prepolymer used in the aggregate primer composition of the present invention can be obtained by reacting a polyol compound and a polyisocyanate compound in an amount ratio in which an isocyanate group is excessive with respect to a hydroxy group. There is no particular restriction.

The polyisocyanate compound used in the production of the urethane prepolymer is not particularly limited as long as it is a compound having two or more isocyanate groups in the molecule. For example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2, 4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate ( NDI), aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane di Aliphatic polyisocyanates such as Socia diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI), H ₁₂ MDI (hydrogenated MDI), H ₆ TDI And alicyclic polyisocyanates such as (hydrogenated TDI); carbodiimide-modified polyisocyanates of these polyisocyanate compounds; and isocyanurate-modified polyisocyanates of these polyisocyanate compounds.

Among these, the polyisocyanate compound is superior in adhesion to a hard aggregate, and is excellent in heat resistance and water resistance, so that the isocyanate group of the polyisocyanate compound is an aliphatic secondary carbon atom or an aliphatic tertiary carbon. Those bonded to atoms are preferred. Such a polyisocyanate compound is a compound represented by the following formula (1).

In the formula, R ^a represents an organic group that can contain at least one hetero atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and R ^b consists of an oxygen atom, a sulfur atom, and a nitrogen atom. Represents an organic group or a hydrogen atom that can contain at least one heteroatom selected from the group, R ^a and R ^b may be the same or different, p is an integer of 2 or more, and R ^c is Represents a divalent or higher valent hydrocarbon group that can include at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and R ^a is a part of R ^c or bonded to R ^b To form a ring.

  Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. The organic group can contain at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, and specifically includes, for example, a carbonyl group, a urea group (carbamide group), and an isocyanate group. Functional groups; such bonds as ether bonds, ester bonds, amide bonds, and urethane bonds.

As the alkyl group, for example, an alkyl group having 1 to 5 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group include a phenyl group; a group obtained by removing at least one hydrogen atom from a condensed polycyclic hydrocarbon such as naphthalene and anthracene; and at least one hydrogen atom from a heterocyclic ring such as furan, thiophene, pyrrole, and pyridine. Examples include groups that have been removed. The aryl group is a phenyl group, which is one of preferred embodiments from the viewpoint of strength and adhesiveness.
When R ^a is bonded to R ^b to form a ring, examples of the ring that can be formed include an alicyclic hydrocarbon group such as a cyclopentyl group and a cyclohexyl group.

The isocyanate group bonded to the aliphatic secondary carbon atom or the aliphatic tertiary carbon atom is bonded to the aliphatic tertiary carbon atom from the viewpoint of storage stability, curability, adhesion, and workability. It is preferably an isocyanate group. One preferred embodiment is that R ^a and R ^{b in} formula (1) are both methyl groups.

The divalent or higher valent hydrocarbon group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group such as a benzene ring. The divalent or higher valent hydrocarbon group can be used alone or in combination of two or more.
When R ^a is bonded to a part of R ^c or R ^b to form a ring, the ring that can be formed includes, for example, a divalent or higher alicyclic hydrocarbon such as a cyclopentylene group or a cyclohexylene group Groups.
p is an integer of 2 or more, and is preferably an integer of 2 to 4 from the viewpoint of adhesion to the substrate.

  Examples of the compound represented by the formula (1) include isocyanates such as hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), lysine diisocyanate, lysine ester triisocyanate, and hydrogenated toluene diisocyanate (hydrogenated TDI). A polyisocyanate compound in which a group is bonded to an aliphatic secondary carbon atom; m- or p-tetramethylxylylene diisocyanate (TMXDI) represented by formula (2), an isocyanate compound having an α-methylstyrene skeleton (TMI) And the like, and polyisocyanate compounds in which an isocyanate group is bonded to an aliphatic tertiary carbon atom, such as polyisocyanate compounds obtained by polymerizing ()); isocyanurate bodies, burette bodies, and adduct bodies of these polyisocyanate compounds. It is done.

  Among these, m- or p-tetramethylxylylene diisocyanate (TMXDI) represented by the formula (2) is preferable from the viewpoint of excellent adhesion to a hard aggregate and excellent elasticity of the resulting primer layer.

The polyisocyanate compound can be used in combination with a monoisocyanate compound having only one isocyanate group in the molecule.
A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  The polyol compound used in the production of the urethane prepolymer is not particularly limited as long as it is a compound having two or more hydroxy groups. Examples thereof include low molecular weight polyhydric alcohols, polycarbonate polyols, polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Examples of low molecular weight polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, butanediol, pentanediol, neopentylglycol, hexanediol, and cyclohexanedimethanol. Alcohols having three or more hydroxy groups; glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, alcohols having three or more hydroxy groups such as pentaerythritol; Such sugars.

The polycarbonate polyol is not particularly limited as long as it has a carbonate bond (—O—CO—O—) and two or more hydroxy groups. For example, what can be obtained by transesterification with the alkoxy group of a dialkyl carbonate and the group which remove | excluded the hydrogen atom from the hydroxyl group of a polyol compound is mentioned.
Examples of the polyol compound that can be used in the production of the polycarbonate polyol include 1,6-hexanediol, 1,4-butanediol, and 1,5-pentanediol.
Examples of the dialkyl carbonate that can be used in the production of the polycarbonate polyol include dialkyl carbonates represented by the following formula (3).

In the formula, R ⁷ and R ⁸ each independently represents an alkyl group having 12 or less carbon atoms. Among these, alkyl groups having 12 or less carbon atoms are methyl, ethyl, propyl, and isopropyl from the viewpoints of adhesion to a substrate, storage stability, wettability, workability, and availability of raw materials. The group is preferably an isobutyl group.

  Examples of the dialkyl carbonate represented by the formula (3) include dimethyl carbonate and diethyl carbonate.

  The polycarbonate polyol is not particularly limited for its production. For example, it can be performed according to a conventionally known method. When the polycarbonate polyol is produced by the transesterification reaction as described above, the transesterification reaction can be performed in the presence of a catalyst. Examples of the catalyst that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as potassium hydroxide; sodium methylate, potassium methylate, and titanium. Examples thereof include metal alcoholates such as tetraisopropylate and zirconium tetraisopropylate.

  Examples of the polycarbonate polyol include polycarbonate polyols that can be obtained from diols of chain aliphatic hydrocarbon compounds having 2 to 10 carbon atoms such as ethylene glycol and 1,6-hexanediol, and those having 3 carbon atoms such as cyclohexanediol. The polycarbonate polyol which can be obtained from the diol body of 10 alicyclic hydrocarbon compounds is mentioned. Especially, it is preferable that it is a polycarbonate polyol derived | led-out from the diol body of a C2-C10 aliphatic hydrocarbon compound from a viewpoint of adhesiveness, wettability, and the availability of a raw material.

The polycarbonate polyol preferably has a weight average molecular weight of 1000 or more from the viewpoint of adhesion and wettability.
The polycarbonate polyol is more preferably derived from a diol body of a chain aliphatic hydrocarbon compound having 6 or more carbon atoms and having a molecular weight of 1000 or more from the viewpoint of denseness and wettability.
Specific polycarbonate polyols include, for example, HO [(CH ₂ ) ₆ —O—C (═O) —O] _m (CH ₂ ) ₆ —OH (m is an integer of 2 to 50). Can be mentioned.
Polycarbonate polyols can be used alone or in combination of two or more.

  Polyether polyols and polyester polyols can usually be derived from the low molecular weight polyhydric alcohols described above. In the present invention, those derived from aromatic diols can also be used. Examples of aromatic diols include xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; bisphenol A structure (4,4′-dihydroxyphenylpropane) shown below. , A bisphenol F structure (4,4'-dihydroxyphenylmethane), a brominated bisphenol A structure, a hydrogenated bisphenol A structure, a bisphenol S structure, and a bisphenol AF structure.

Examples of polyether polyols derived from low molecular weight polyhydric alcohols and / or aromatic diols include ethylene oxide, propylene oxide, and butylene at least one selected from low molecular weight polyhydric alcohols and aromatic diols. Examples include polyols obtained by adding at least one selected from alkylene oxides such as oxide (tetramethylene oxide) and styrene oxide.
Examples of such polyether polyols include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol.
Examples of polyether polyols having a bisphenol skeleton include polyether polyols obtained by adding ethylene oxide and / or propylene oxide to bisphenol A (4,4′-dihydroxyphenylpropane).

Examples of the polyester polyol include condensates (condensed polyester polyols) of the above low molecular weight polyhydric alcohols and / or aromatic diols and polybasic carboxylic acids, and lactone polyols.
Examples of the polybasic carboxylic acid used in the production of the condensed polyester polyol include glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and others. And low molecular weight carboxylic acids, oligomeric acids, castor oil, and hydroxycarboxylic acids such as the reaction product of castor oil and ethylene glycol.
Examples of the lactone-based polyol include ring-opening polymers such as propionlactone and valerolactone.
Examples of the polyester polyol having a bisphenol skeleton include condensed polyester polyols obtained by using a diol having a bisphenol skeleton instead of the low molecular weight polyhydric alcohols or together with the low molecular weight polyhydric alcohols. . Specific examples include polyester polyols obtained from bisphenol A and castor oil, and polyester polyols obtained from bisphenol A, castor oil, ethylene glycol and propylene glycol.

  Examples of other polyols include polymer polyols having a carbon-carbon bond in the main chain skeleton such as acrylic polyols; polybutadiene polyols; and hydrogenated polybutadiene polyols.

The polyol compound is preferably a polycarbonate polyol from the viewpoint of excellent mechanical strength of the resulting primer layer. In addition, alcohols having three or more hydroxy groups are preferable, and 1,1,1-trimethylolpropane is more preferable from the viewpoint of being superior in adhesiveness to hard aggregates.
A polyol compound can be used individually or in combination of 2 types or more, respectively.

  From the viewpoint that the urethane prepolymer contained in the primer composition for aggregates of the present invention has a polycarbonate structure in the skeleton, is superior in adhesion between the primer and the hard aggregate, and is excellent in the mechanical properties of the primer. preferable. For this reason, it is preferable that the polyol compound used in the production of such a urethane prepolymer is a polycarbonate polyol.

  In addition, the urethane prepolymer has all of the isocyanate groups of the urethane prepolymer bonded to an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom. It is preferable from the viewpoint that it is excellent in properties and is superior in adhesiveness to hard aggregates. Therefore, as a polyisocyanate compound used in the production of such a urethane prepolymer, a polyisocyanate in which all of the isocyanate groups are bonded to an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom. Compounds are preferred, compounds represented by formula (1) are more preferred, hydrogenated MDI, hydrogenated TDI, and m- or p-tetramethylxylylene diisocyanate (TMXDI) represented by formula (2) are even more preferred.

A urethane prepolymer can be used individually or in combination of 2 types or more, respectively.
When two or more kinds of urethane prepolymers are used in combination, the urethane prepolymer preferably includes a urethane prepolymer having three or more functional groups and having a weight average molecular weight of 1500 or less. When the urethane prepolymer includes a urethane prepolymer having 3 or more functional groups and a weight average molecular weight of 1500 or less, the urethane prepolymer is superior in adhesiveness to a hard aggregate and excellent in the elasticity of the resulting primer layer.

Examples of the urethane prepolymer having 3 or more functional groups and a weight average molecular weight of 1500 or less include, for example, alcohols having 3 or more hydroxy groups, and an isocyanate group having an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom. And adducts with a diisocyanate compound bonded to the above. Specifically, for example, a TMXDI / TMP adduct synthesized from 1,1,1-trimethylolpropane (TMP) and tetramethylxylylene diisocyanate (TMXDI) is one preferred embodiment.
As a commercial product of such an adduct, for example, Seicen 3174 manufactured by Nippon Cytec Industries, Inc. can be used. The adduct may contain unreacted raw materials.

  The amount of the urethane prepolymer having 3 or more functional groups and a weight average molecular weight of 1500 or less is 10 to 90% by mass in the urethane prepolymer to be used, so that the crosslinking density is increased and the elasticity of the primer layer is excellent. From the viewpoint of superior adhesion to the hard aggregate, 20 to 70% by mass is more preferable.

  The urethane prepolymer other than the urethane prepolymer having 3 or more functional groups and having a weight average molecular weight of 1500 or less, which can be combined with the urethane prepolymer having 3 or more functional groups and having a weight average molecular weight of 1500 or less, is not particularly limited. . For example, a urethane prepolymer having a weight average molecular weight exceeding 1500, which can be obtained from a polycarbonate polyol and a polyisocyanate compound in which an isocyanate group is bonded to an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom. It is done. Specifically, for example, a urethane prepolymer having a weight average molecular weight exceeding 1500, which can be obtained from polycarbonate polyol and tetramethylxylylene diisocyanate (TMXDI), is mentioned as one of preferable embodiments.

  The amount of the urethane prepolymer other than the urethane prepolymer having 3 or more functional groups and a weight average molecular weight of 1500 or less is 10 to 90% by mass in the urethane prepolymer used, and the adhesiveness to the hard aggregate It is preferable from a viewpoint of being excellent, and it is more preferable that it is 30-80 mass%.

  The urethane prepolymer is not particularly limited for its production. For example, it can be produced according to a conventionally known method.

The latent curing agent contained in the aggregate primer composition of the present invention will be described below. The latent curing agent is not particularly limited as long as it is a compound that can be a curing agent for the urethane prepolymer. For example, an imine compound is mentioned.
An imine compound is a compound having an imino bond (> C═N—). Examples of the imine compound include compounds derived from ketones or aldehydes and amines. Specific examples include ketimines derived from ketones and amines and aldimines derived from aldehydes and amines.

  Examples of the ketone or aldehyde used in the production of the imine compound include compounds represented by the following formula (I) or formula (II). Among them, it is represented by the following formula (I) in which at least one α-position carbon atom of the ketone carbonyl group or the α-position carbon of the aldehyde carbonyl group is a secondary carbon atom or a tertiary carbon atom. It is preferable that it is a compound.

In formula (I), R ¹ and R ³ each independently represents a methyl group, an ethyl group or a hydrogen atom, R ² represents a methyl group or an ethyl group, and R ⁴ represents an alkyl having 1 to 6 carbon atoms. Represents a group, and R ⁴ may combine with R ¹ or R ² to form a ring. However, R ⁴ is bonded to R ² to form a ring, and among the carbon atoms at the α-position of the carbonyl group, the carbon atom contained in the ring is bonded to R ² or R ⁴ with a double bond. If R ³ is not present. When R ⁴ is bonded to R ¹ or R ² to form a ring, examples of the formed cyclic hydrocarbon include aliphatic hydrocarbons and aromatic hydrocarbons.

In formula (II), R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ may be bonded to each other to form a ring. In the case where R ⁵ and R ⁶ are combined to form a ring, examples of the cyclic hydrocarbon consisting formed, for example, alicyclic hydrocarbons, and aromatic hydrocarbons.

  As described above, in the compound represented by the formula (I), one of the carbon atoms at the α-position of the carbon atom (hereinafter also referred to as “imine carbon atom”) that forms an imino bond when iminized is formed. It has 2 or 3 substituents, so to speak a branched carbon atom. As described above, since the imine carbon atom has a bulky group and a relatively bulky group, the compound represented by the formula (I) has both curability and pot life within a suitable range.

  In the compound represented by the formula (II), both of the α-position carbon atoms of the imine carbon atom are bonded to an alkyl group having 1 to 6 carbon atoms. Two alkyl groups having 1 to 6 carbon atoms can be bonded to each other to form a ring. Thus, since the imine carbon atom has 2 alkyl groups having 2 to 7 carbon atoms, the compound represented by the formula (II) has both curability and pot life within suitable ranges.

Specific examples of the compound represented by the formula (I) include methyl isobutyl ketone (MIBK), methyl t-butyl ketone (MTBK), methyl isopropyl ketone (MIPK), pivalaldehyde (trimethylacetaldehyde), Examples include isobutyraldehyde ((CH ₃ ) ₂ CHCHO) in which a branched carbon is bonded to a carbonyl group, methylcyclohexanone, ethylcyclohexanone, methylcyclohexyl ketone, acetophenone, and propiophenone. May be used in combination. Of these, MTBK and MIPK are preferred.

  Specific examples of the compound represented by the formula (II) include diethyl ketone, dipropyl ketone, dibutyl ketone, ethyl propyl ketone, ethyl butyl ketone, butyl propyl ketone, ethyl isopropyl ketone, and ethyl amyl ketone. And cyclohexanone. These may be used alone or in combination of two or more. Of these, diethyl ketone, dipropyl ketone, and dibutyl ketone are preferred.

  On the other hand, the amine compound used in the production of the imine compound includes, for example, a polyamine having two or more amino groups in the molecule. Of these, aliphatic polyamines and / or alicyclic polyamines are preferred. Moreover, from the viewpoint that reaction adjustment is easy, ethylenediamine and a polyamine represented by the following formula (4) are preferable.

In the formula, R ⁹ represents a divalent to hexavalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 2 to 6.
The divalent to hexavalent hydrocarbon group having 1 to 20 carbon atoms is not particularly limited. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The hydrocarbon group can be bonded to the nitrogen atom of the amino group in formula (4) to form a ring structure.

  Specific examples of the polyamine represented by the formula (4) include propylenediamine, butylenediamine, diethylenetriamine, triethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, and trimethylhexa. Methylenediamine, 1,2-propanediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane (MPMD, manufactured by DuPont Japan), norbornanediamine (NBDA, manufactured by Mitsui Chemicals) ) And other aliphatic polyamines such as diamines having norbornane skeletons and diamines having dicyclopentadiene skeletons; metaphenylene diamines, orthophenylene diamines, paraphenylene diamines, m-xyliles Aromatic polyamines such as diamine (MXDA), diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane; N-aminoethylpiperazine; diamine having a polyether skeleton represented by Jeffamine EDR148 manufactured by Sun Techno Chemical Co .; isophorone diamine, 1 , 3-bisaminomethylcyclohexane (1,3BAC, manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine Polyamine; polyamide amine having an amino group at the molecular end of polyamide; 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, Sun Techno Chemical Co. JEFFAMINE D230 having polypropylene glycol (PPG) to the backbone, include JEFFAMINE D400.

Examples of the diamine having a dicyclopentadiene skeleton include 3 (4), 8 (9) -bis- (aminomethyl) -tricyclo [5.2.1.0 ^2,6 ] decane represented by the following formula (III): (Isomers, TCD diamine) and mixtures thereof.
Examples of commercially available mixtures of isomers of TCD diamine include those manufactured by Celanese Chemical Company.

Among these, hexamethylenediamine, 1,3-bisaminomethylcyclohexane (1,3BAC), norbornanediamine (NBDA), m-xylylenediamine (MXDA), dicyclopentadiene skeleton diamine, Jeffamine EDR148 (trade name) And polyamidoamines are preferred.
An amine compound can be used individually or in combination of 2 types or more, respectively.

Examples of the imine compound include those that can be obtained by a combination of the various ketones or aldehydes described above and the various amines described above.
For example, obtained from MIBK and propylene diamine; obtained from MIPK and / or MTBK and hexamethylene diamine; obtained from MIPK and / or MTBK and Jeffamine EDR148; and MIPK and / or MTBK and 1, Obtained from 3BAC; obtained from MIPK and / or MTBK and NBDA; obtained from MIPK and / or MTBK and MXDA; obtained from MIPK and / or MTBK and polyamidoamine; and diethylketone Those obtained from MXDA; those obtained from MIPK and / or MTBK and a diamine having a dicyclopentadiene skeleton.
Of these, obtained from MIPK or MTBK and hexamethylenediamine; obtained from MIPK or MTBK and 1,3BAC; obtained from MIPK or MTBK and NBDA; obtained from MIPK or MTBK and MXDA Those obtained from MIPK and / or MTBK and a diamine having a dicyclopentadiene skeleton are preferred from the viewpoint of better adhesion to hard aggregates.

  Examples of the imine compound obtained from a combination of an aldehyde and a polyamine include, for example, at least one aldehyde selected from the group consisting of pivalaldehyde, isobutyraldehyde and cyclohexanecarboxaldehyde, NBDA, 1,3BAC, Jeffer And those obtained from a combination with at least one amine selected from the group consisting of Min EDR148 and MXDA.

  The imine compound is not particularly limited for its production. For example, it can be obtained by heating and refluxing a ketone or aldehyde and an amine in the absence of a solvent or in a solvent such as benzene, toluene, xylene, and the like, and reacting while removing azeotropic water.

  The aggregate primer composition of the present invention is excellent in adhesion, drying property, and mechanical properties by using an imine compound. The present inventor believes that this is because the imine compound is easily hydrolyzed by moisture or the like in the air to produce an amine, and the produced amine rapidly proceeds with the curing reaction with the urethane prepolymer.

  The content of the imine compound is preferably an equivalent ratio represented by (isocyanate group in the urethane prepolymer) / (imino bond in the imine compound), and is preferably 0.5 to 1.5, and preferably 0.95 to More preferably, it is 1.05. When the content of the imine compound is in such a range, the adhesion with the hard aggregate is excellent.

In the primer composition of the present invention, when the latent curing agent is an imine compound, it is one of preferred embodiments that further contains a hydrolysis catalyst.
The hydrolysis catalyst is not particularly limited, and specific examples thereof include carboxylic acids such as 2-ethylhexanoic acid and oleic acid; phosphoric acids such as polyphosphoric acid, ethyl acid phosphate and butyl acid phosphate; dibutyltin dilaurate, dioctyl Organic metals such as tin dilaurate can be mentioned.
When such a hydrolysis catalyst is contained, when the aggregate is treated with the primer composition, hydrolysis due to moisture or the like is promoted, and the balance between workability and adhesion is improved.

  The content of the hydrolysis catalyst is preferably 0.01 to 30 parts by mass and more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the imine compound.

The solvent contained in the aggregate primer composition of the present invention will be described below.
A solvent will not be restrict | limited especially if it is inactive with respect to a urethane prepolymer and a latent hardener. For example, aromatic hydrocarbons such as benzene, xylene and toluene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran and dioxane And ethers. Of these, ethyl acetate and toluene are preferable from the viewpoint of low boiling point and quick drying.
A solvent can be used individually or in combination of 2 types or more, respectively.
The solvent is preferably used after being sufficiently dried or dehydrated.

  The content of the solvent is preferably 50 to 99% by mass and more preferably 80 to 98% by mass in the total amount of the primer composition for aggregate of the present invention. In such a range, the resulting primer composition for aggregate is excellent in applicability and drying properties.

The primer composition for an aggregate of the present invention further preferably contains an epoxy resin from the viewpoint of being superior in adhesiveness to a hard aggregate.
An epoxy resin will not be specifically limited if it consists of a compound which has a 2 or more oxirane ring (epoxy group) in 1 molecule. Those having an epoxy equivalent of 90 to 2000 can be used.
Examples of the epoxy resin include bisphenol A-type, bisphenol F-type, brominated bisphenol A-type, hydrogenated bisphenol A-type, bisphenol S-type, bisphenol AF-type and biphenyl-type epoxy compounds, Bifunctional glycidyl ether type epoxy resin such as polyalkylene glycol type, alkylene glycol type epoxy compound, epoxy compound having naphthalene ring, epoxy compound having fluorene group; phenol novolak type, orthocresol novolak type, DPP novolak type Type, tris-hydroxyphenylmethane type, trifunctional type, polyfunctional type such as tetraphenylolethane type glycidyl ether type epoxy resin; synthetic fatty acid glycidyl ester such as dimer acid Type epoxy resin; N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane (TGDDM) represented by the following formula (5), tetraglycidyl-m-xylylenediamine, triglycidyl-p-aminophenol, N , N-diglycidylaniline, an aromatic epoxy resin having a glycidylamino group; an epoxy compound having a tricyclo [5.2.1.0 ^2,6 ] decane ring represented by the following formula (6), For example, an epoxy compound obtainable by a known production method of reacting epichlorohydrin after polymerizing cresols or phenols such as dicyclopentadiene and methacresol; alicyclic epoxy resin; Epoxy resin having sulfur atom in the main chain of epoxy resin represented by FLEP 10 A urethane-modified epoxy resin having a urethane bond; a rubber-modified epoxy resin containing polybutadiene, liquid polyacrylonitrile-butadiene rubber or acrylonitrile butadiene rubber (NBR).

In formula (6), m is an integer of 0-15.
Especially, the epoxy resin which has an aromatic ring in frame | skeleton is preferable from a viewpoint that it is excellent by the adhesiveness with respect to a hard aggregate, and is excellent in heat resistance and mechanical strength.
An epoxy resin can be used individually or in combination of 2 types or more, respectively.

  The content of the epoxy resin is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass, based on the total amount of the urethane prepolymer and the epoxy resin. In the case of such a range, it is excellent by adhesiveness with a hard aggregate.

  The aggregate primer composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of the additive include a filler, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesiveness imparting agent, a dispersant, and a solvent.

  Examples of the filler include wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, oxidized Magnesium; calcium carbonate, magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
An additive can be used individually or in combination of 2 types or more, respectively.

The aggregate primer composition of the present invention is not particularly limited for its production. For example, a method of mixing a urethane prepolymer, a latent curing agent, and an epoxy resin and additives in a solvent with a roll, a kneader, an extruder, a universal agitator, etc. It is done.
The aggregate primer composition of the present invention can be used to treat aggregates (eg, for paving materials).

In the aggregate primer composition of the present invention, a latent curing agent is hydrolyzed by moisture or the like to generate a curing agent, and the generated curing agent is cured by reacting with a urethane prepolymer to form a primer layer. . The primer layer obtained from the aggregate primer composition of the present invention is superior in adhesion to a hard aggregate, adhesion to a resin binder, and elasticity compared to a conventional primer composition.
Moreover, the aggregate primer composition of the present invention contains a latent curing agent, so that the curing reaction is faster and the drying property and mechanical properties are superior compared to the conventional primer composition.

Next, the aggregate for paving material of the present invention will be described.
The aggregate for paving materials of the present invention can be obtained by treating an aggregate containing hard aggregates with the primer composition for aggregates of the present invention.

The aggregate primer composition used in the aggregate for pavement of the present invention is not particularly limited as long as it is an aggregate primer composition of the present invention.
The aggregate used for the aggregate for paving materials of the present invention will be described below.
Aggregates include hard aggregates. All of the aggregates may be hard aggregates.

The hard aggregate is not particularly limited. For example, natural aggregates composed of natural stones such as mountain gravel and river gravel; artificial aggregates such as crushed stone, cryogenic stone, quartz sand, artificial stone, slag and ceramics; and metal particulates such as metal powder. Among these, crushed stone and silica sand are preferable from the viewpoint of cost.
The hard aggregate can be excellent in the strength and wear resistance of the paving material. Further, the hard aggregate can be prevented from being exposed to the surface of the pavement material and slipping of the tire or the like, and is excellent in slip resistance. Since it is excellent from such a viewpoint, it is preferable that the average particle diameter of a hard aggregate is 1 mm or more, and 1-4 mm is more preferable. Moreover, it is preferable from the same viewpoint that the hard aggregate contains 10% by volume or more of fine aggregate having an average particle diameter of 4 mm or less.

In the aggregate for paving material of the present invention, the aggregate further includes an elastic aggregate as one of preferred embodiments.
Examples of the elastic aggregate include various rubbers, synthetic resins, wood chips, and cork chips. Of these, rubber and synthetic resin are preferable from the viewpoint of excellent elasticity of the paving material.
Examples of the rubber chip include natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, polyurethane rubber, and EPDM. From the viewpoint of economy, it is preferable to grind waste tires as industrial waste.

Examples of the rubber chip include a granular shape and a hijiki shape.
The average particle size of the granular rubber chips is preferably 1 mm or more, and more preferably 1 to 4 mm from the viewpoint that the paving material is excellent in elasticity and the paving material tends to have a porous structure.
The elbow-shaped rubber chip is not particularly limited as long as its shape is a elbow-shaped. The average length of the elbow-shaped rubber chip is preferably 0.5 to 6 mm from the viewpoint that the paving material is excellent in elasticity and the paving material tends to have a porous structure.

  The synthetic resin chip is not particularly limited as long as it is a granular material obtained from various synthetic resin materials other than rubber chips. For example, a bumper of an automobile or a pulverized product of a golf ball can be mentioned.

  In this specification, hard aggregates and elastic aggregates are classified according to their hardness. That is, the hard aggregate has a hardness larger than A90 in the type A durometer hardness of JIS K 6253-1997. The elastic aggregate has a hardness of A90 or less.

In the aggregate for pavement of the present invention, the aggregate used includes a case where only the hard aggregate is included and a case where the aggregate includes a hard aggregate and an elastic aggregate.
When the aggregate includes a hard aggregate and an elastic aggregate, the combination of the hard aggregate and the elastic aggregate is not particularly limited. A combination of a rubber chip and crushed stone is mentioned as one of the preferred embodiments.

Moreover, when an aggregate contains a hard aggregate and an elastic aggregate, the mixing ratio of a hard aggregate and an elastic aggregate can be suitably changed according to various uses. For example, when used for a sidewalk, the volume ratio of elastic aggregate / hard aggregate is suitably 10 / 0.1 to 5/5. In such a range, the shock absorption is sufficient and the safety at the time of falling is excellent. In particular, 10 / 0.1 to 7/3 is preferable, and 10 / 0.1 to 8/2 is more preferable when safety with respect to impact at the time of falling is emphasized.
When used for various stadiums, the volume ratio of elastic aggregate / hard aggregate is 10 / 0.1 to 6/4 for track stadiums and 10/0. 1/6/4, 10 / 0.1-7 / 3 for tennis courts, 9 / 1-5 / 5 for soccer fields, 10 / 0.1-5 / 5 for other multipurpose grounds Is suitable.

  When used in a roadway, the volume ratio of elastic aggregate / hard aggregate is preferably 6/4 to 1/9. In such a range, there is no problem in the steering stability of the vehicle such that the tires are slippery when wet, and the noise reduction effect is excellent. In particular, when wear resistance such as an expressway is particularly required, the volume ratio of the elastic aggregate / hard aggregate is preferably 4/6 to 1/9, and more preferably 3/7 to 1/9. .

  The use amount of the primer composition for aggregate is preferably 0.5 to 15 g with respect to 100 g of aggregate from the viewpoint of superior adhesion to the hard aggregate.

In the aggregate for paving material of the present invention, the method for treating the aggregate with the primer composition for aggregate of the present invention is not particularly limited. Examples thereof include a method of spraying and applying the aggregate primer composition of the present invention to the aggregate, and a method of dipping the aggregate into the aggregate primer composition of the present invention.
The aggregate treated with the aggregate primer composition of the present invention only needs to be at least partially coated with the aggregate primer composition of the present invention. From the viewpoint of adhesion, the entire surface is coated. It is preferable.
Moreover, in order to dry a solvent after such a primer treatment process, a drying process can be provided. The drying temperature is preferably 60 to 80 ° C. from the viewpoint that the drying time can be shortened and the adhesiveness with the hard aggregate is excellent.

  The aggregate for paving materials of the present invention is excellent in the adhesion between the primer and the hard aggregate, the elasticity of the primer layer, and the adhesion between the primer and the resin binder. Therefore, using the aggregate for pavement of the present invention, the pavement obtained by mixing this with a resin binder is such that the hard aggregate is detached from the elastic pavement or the hard aggregate and the resin binder. Less likely to crack at the interface.

Next, the pavement material of the present invention will be described.
The paving material of the present invention comprises the aggregate for paving material of the present invention and a resin binder.
The aggregate for paving materials used in the paving material of the present invention is not particularly limited as long as it is an aggregate for paving materials of the present invention. The aggregate for paving materials of the present invention is as described above.

The resin binder will be described below.
The resin binder used in the pavement material of the present invention is not particularly limited as long as it can fix the aggregate and form the pavement material. For example, urethane resin is mentioned.
The urethane resin as the resin binder is not particularly limited, and for example, a conventionally known one can be used.

  The resin binder can contain an additive as needed. Examples of the additive include a filler, a plasticizer, a thixotropy imparting agent, a pigment, a dye, an antiaging agent, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersant, and a solvent. As each additive, a conventionally well-known thing is mentioned, for example. An additive can be used individually or in combination of 2 types or more, respectively. The amount of additive used is not particularly limited.

When the paving material is required to be colored, it can be colored by adding a pigment to the resin binder. It is preferable that the addition amount of a pigment is 1.5-8 volume parts with respect to 100 volume parts of resin binders. Moreover, a colored material can also be used as an aggregate. For example, color chips such as rubber such as EPDM, synthetic resin, and artificial stone can be used.
In the case of further improving the curing speed, a conventionally known curing agent such as an amine curing agent, an acid curing agent, an acid anhydride curing agent, a basic active hydrogen compound, a polythiol curing agent, or water is used at the time of construction. Can be added.

In the paving material of the present invention, the blending ratio of the aggregate for paving material and the resin binder (indicated by the volume ratio of the aggregate for paving material / resin binder) can be appropriately selected according to the application. For example, 9/1 to 6/4 is suitable for sidewalks, and 9/1 to 7/3 is particularly suitable. Also, 9 / 1-6 / 4 for track and field, 9 / 1-6 / 4 for jogging track, 9 / 1-7 / 3 for tennis court, 9/1 for soccer field -5/5, 9 / 1-5 / 5 are suitable for other multipurpose grounds.
When used for a roadway, the blending ratio of the aggregate for paving material and the resin binder (indicated by the volume ratio in the aggregate for paving material / resin binder) is suitably 9/1 to 6/4. / 2 to 6/4 is particularly suitable. For example, 8/2 to 6/4 is suitable for use on a highway.

The paving material of the present invention will be described with reference to the accompanying drawings.
2 to 3 are cross-sectional views schematically showing examples of paved roads on which the paving material of the present invention is laid.
In FIG. 2, 20 is a pavement material of the present invention. A base 24 is laid under the pavement 20. The base 24 is provided on the ground 22.
The pavement material 20 is a one-layer pavement material. When the pavement material is composed of one layer as described above, it is preferable that the aggregate in the pavement material includes a hard aggregate and an elastic aggregate because the pavement material has both sliding characteristics and elasticity.

The construction method of the pavement 20 will be described below.
The construction method of the pavement 20 includes a mixing step of mixing a pavement aggregate and a resin binder to form a pavement composition, and a laying step of laying the pavement composition on the base 24. Is mentioned.

First, the aggregate for paving materials and the resin binder are mixed in the mixing step. Specifically, for example, the aggregate for paving material of the present invention is put into an agitating apparatus such as a mixer and stirred, and a resin binder and an additive used as necessary are added thereto for paving material. A composition is prepared. The quantitative ratio between the aggregate for paving material and the resin binder is as described above.
As another method, for example, an aggregate containing hard aggregate is put into a stirring apparatus, and the aggregate composition of the present invention is added to the stirring apparatus by a method such as spraying or dripping to sufficiently stir these. After that, a resin binder and an additive used as necessary can be added here to prepare a composition for paving material.

  The addition method of the resin binder is not particularly limited as long as the resin binder can be uniformly attached to the aggregate for paving material. For example, a spray method and a dropping method can be mentioned.

Next, in the laying step, this is laid on the base 24 using the paving material composition prepared as described above.
A base 24 is provided on the ground 22 in advance. Examples of the base include various pavements such as concrete pavement, mortar pavement, asphalt concrete pavement, and semi-flexible pavement, and a roadbed layer such as a wood board, a synthetic resin, a crushed stone layer, and a chestnut layer.
The paving material composition has a predetermined thickness on the base 24 using, for example, a smoother or finisher (for example, about 1 to 2 cm for sidewalks, about 2 to 3 cm for roadways, and for stadiums). 1-5 cm), and in some cases, it is compacted with a tandem roller or the like, and then solidified at room temperature to become a paving material 20.
If necessary, the base 24 can be subjected to a primer treatment (not shown) before laying the paving material composition. Examples of the primer include those obtained by diluting a TMXDI prepolymer, an MDI prepolymer, a TDI prepolymer, or the like with a solvent (such as ethyl acetate or toluene) or water.

  In FIG. 3, 30 is a pavement of the present invention (hereinafter referred to as “upper pavement 30”). A lower pavement material 36 is laid under the upper pavement material 30. A base 34 is provided under the lower pavement material 36, and the base 34 is provided on the ground 32.

The lower pavement material 36 is a pavement material made of an aggregate including an elastic aggregate and a resin binder. The aggregate contained in the lower pavement material 36 can further include a hard aggregate. Moreover, the aggregate contained in the lower layer pavement material 36 can be substantially made of only the elastic aggregate.
Aggregates containing elastic aggregates can be treated with the aggregate primer composition of the present invention. Further, the elastic aggregate can be processed by other methods (for example, a conventionally known method).
When the aggregate contained in the lower layer pavement material 36 is substantially only the elastic aggregate, the aggregate used for the production of the aggregate for the pavement material contained in the upper layer pavement material 30 is substantially reduced. Only hard aggregates can be used.
Thus, the pavement material 38 is formed by the lower layer pavement material 36 having elasticity and the upper layer pavement material 30 having sliding characteristics.

  As a construction method of the pavement material 38, for example, a mixing step in which an aggregate containing an elastic aggregate and a resin binder are mixed to form a lower layer pavement composition (hereinafter, this mixing step is referred to as “mixing step 1”). A laying step of laying the lower pavement composition on the base 34 to form the lower pavement 36 (hereinafter, this laying step is referred to as “laying step 1”), and the aggregate and resin for pavement of the present invention. A mixing step (hereinafter, this mixing step is referred to as “mixing step 2”) by mixing the binder with the upper pavement composition, and the upper pavement composition is laid on the lower pavement material 36. And a laying step (hereinafter, this laying step is referred to as “laying step 2”) as the material 30. The mixing step 1 may be performed before the laying step 1. Moreover, the mixing process 2 should just be performed before the laying process 2. FIG.

  First, in the mixing step 1, an aggregate including an elastic aggregate and a resin binder are mixed to obtain a lower layer pavement composition. The amount ratio of the aggregate including the elastic aggregate and the resin binder is not particularly limited, and for example, it can be mixed in a conventionally known amount. The mixing method is not particularly limited, and for example, a stirring device such as a mixer may be used.

  In the laying step 1, the obtained lower pavement composition is laid on the base 34 to obtain a lower pavement 36. The base 34 is previously provided on the ground 32. Examples of the base are the same as described above. The base 34 can be subjected to the same primer treatment as described above. The method for laying the pavement composition is the same as described above. The thickness of the laid lower pavement 36 is about 0.5 to 2 cm for sidewalks, about 1 to 3 cm for roadways, and about 1 to 3 cm for stadiums. Primers and / or adhesives can be applied on the lower pavement material 36.

  In the mixing step 2, the aggregate for a pavement of the present invention and a resin binder are mixed to obtain an upper pavement composition. The quantitative ratio between the aggregate for paving material and the resin binder is as described above. The mixing method is the same as above.

In the laying step 2, the obtained upper pavement composition is laid on the lower pavement 36 to obtain an upper pavement 30. The laying method is the same as above. The thickness of the laid upper pavement 30 is about 0.5 to 2 cm for sidewalks, about 1 to 3 cm for roadways, and about 0.5 to 2 cm for stadiums. The thickness of the paving material 38 is about 0.5 to 3 cm for sidewalks, about 1.5 to 4 cm for roadways, and about 1 to 5 cm for stadiums.
The pavement material 38 is obtained as described above.

  In addition to the on-site construction type as described above, the pavement construction method of the present invention, for example, in advance with a mold, the composition of the aggregate for pavement and the resin binder in a predetermined shape (for example, There is a method in which a molded body is formed into a panel shape to form a molded body, and the obtained molded body is laid on a base and a pavement material as shown in FIG. The base and paving material composition used for laying such a single layer of paving material are the same as described above. The thickness of the pavement is about 0.5 to 3 cm for sidewalks, about 1.5 to 4 cm for roadways, and about 1 to 5 cm for stadiums.

  Moreover, the method of laying the obtained molded object on a lower-layer pavement material and constructing a pavement material like FIG. 3 is mentioned. The base, lower pavement composition, and upper pavement composition used for such a two-layer pavement are the same as described above. The method of laying the lower pavement material 36 is not limited, and the lower pavement material composition can be laid on the base 34 to a predetermined thickness using, for example, a smoother or finisher, or molded using a mold. And it can also lay using the obtained molded object. A primer and / or an adhesive can be applied on the lower pavement material 36. The thickness of the lower pavement material 36 is about 0.5 to 2 cm for a sidewalk, about 1 to 3 cm for a roadway, and about 1 to 3 cm for a stadium. The thickness of the upper pavement 30 is about 0.5 to 2 cm for sidewalks, about 1 to 3 cm for roadways, and about 0.5 to 2 cm for stadiums. The thickness of the paving material 38 is about 0.5 to 3 cm for sidewalks, about 1.5 to 4 cm for roadways, and about 1 to 5 cm for stadiums.

In the pavement of the present invention, the hard aggregate is less likely to be detached from the elastic pavement and cracks are not generated at the interface between the hard aggregate and the resin binder. This can prevent the slip resistance when wet in the pavement material from decreasing with time. This is because the paving material of the present invention is obtained by treating an aggregate containing hard aggregate with the aggregate primer composition of the present invention, adhesiveness with hard aggregate, adhesiveness with resin binder. It uses aggregates for paving materials that have a primer layer with excellent elasticity, and such a primer layer can microscopically disperse stress concentrated on the interface of hard aggregates in paving materials containing hard aggregates. According to the present inventors.
Note that the mechanism as described above is only an estimation of the present inventor, and even if the mechanism is different, it is within the scope of the present invention.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Preparation of urethane prepolymer (1) Preparation of urethane prepolymer 1 Polycarbonate polyol (Placcel CD220, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight 2000) and tetramethylxylylene diisocyanate (TMXDI, manufactured by Nihon Cytec Industries, Inc.) Isocyanate group / hydroxy group (number of isocyanate groups per hydroxy group) (hereinafter simply referred to as “NCO / OH”) = 2.0, and mixed in an equivalent ratio of 2.0 in a nitrogen stream in the presence of a tin catalyst. By reacting at 80 ° C. for 8 hours with stirring, a polycarbonate / TMXDI urethane prepolymer containing 3.3% by mass of NCO groups was obtained. The obtained urethane prepolymer is referred to as urethane prepolymer 1.

(2) Urethane prepolymer 2
As urethane prepolymer 2, a reaction product (NCO / OH = 2.0) of 1,1,1-trimethylolpropane (TMP) and tetramethylxylylene diisocyanate (TMXDI) is diluted in butyl acetate. (Solid content: 75% by mass) Seicen 3174 (manufactured by Nippon Cytec Industries, Inc.) was used.

2. Preparation of latent curing agent As a latent curing agent, 100 g of norbornanediamine (NBDA, Mitsui Chemicals) and 200 g of methyl isopropyl ketone (MIPK) are placed in a flask together with 200 g of toluene, and water formed is removed by azeotropic distillation. However, ketimine represented by the following formula (7) obtained by reacting for 20 hours was used.

3. Example 1
(1) Preparation of Primer Composition 1 for Aggregate 50 parts by mass of urethane prepolymer 1 obtained as described above, 30 parts by mass of urethane prepolymer 2, and 20 parts by mass of epoxy resin [general-purpose bisphenol A type epoxy EP4100E (Asahi Denka Kogyo Co., Ltd., epoxy equivalent 190)], latent curing agent 25.2 parts by weight obtained as described above, 1 part by weight of 2-ethylhexanoic acid, and methyl ethyl ketone as a solvent 900 parts by mass was mixed to prepare an aggregate primer composition. The obtained primer composition for aggregates is referred to as an aggregate primer composition 1. In the primer composition 1 for aggregates, the content of the urethane prepolymer 2 was 31% by mass in the total of the urethane prepolymer 1 and the urethane prepolymer 2.

(2) Preparation of aggregate 1 for paving material 3 kg of hard aggregate (No. 7 crushed stone, particle size: 5 mm>, average particle size: 3.8 mm) was put into a mixer, and the primer composition for aggregate was added to this while stirring. Product 1 (40 g) was sprayed in the form of a mist. After spraying, the hard aggregate on which the primer composition for aggregate 1 was sprayed was dried at 80 ° C. for 30 minutes to obtain an aggregate for paving. The obtained paving aggregate is designated as paving aggregate 1.

(3) Production of pavement material First, the components for the lower layer shown in Table 1 are mixed at the composition ratio (unit: volume) shown in Table 1 to form a mixture for the lower layer, and the lower layer mixture is injected into the mold. Then, a lower layer portion having a thickness of 15 mm was formed.
Subsequently, each component for the upper layer shown in Table 1 is mixed at a composition ratio (unit: volume part) shown in Table 1 to obtain a mixture for the upper layer, and the mixture for the upper layer is further injected into the mold. It was spread on the lower layer, formed and cured at room temperature, and a panel having a length of 300 mm, a width of 300 mm, and a thickness of 30 mm (upper layer thickness of 15 mm, lower layer thickness of 15 mm) was obtained.

4). Comparative Example 1
An experiment was performed in the same manner as in Example 1 except that a hard aggregate that was not treated with the aggregate primer composition was used to obtain a pavement material. In addition, the hard aggregate which is not processed with the primer composition for aggregates is set as the aggregate 2 for pavement materials.
5. Comparative Example 2
The 1% acetic acid solution of γ-glycidoxypropylmethyldiethoxysilane (hereinafter referred to as “aggregate primer composition 2”) prepared while adjusting the aggregate primer composition 1 to pH 4. Except for the change, the experiment was performed in the same manner as in Example 1 to obtain a paving material. In addition, the aggregate for pavement materials obtained by processing a hard aggregate with the primer composition 2 for aggregates is set as the aggregate 3 for pavement materials.

6). Evaluation of pavement material The repeated loading test of the pavement material was performed as follows.
The repeated loading running test for pavement materials will be described with reference to the accompanying drawings. FIG. 1 illustrates a repeated loading travel test employed as an evaluation method in the present invention, and the present invention is not limited to the attached drawings.

FIG. 1 is a schematic view schematically showing a repeated loading traveling test of a pavement material.
In FIG. 1, 1 is a paving material, and 10 is a repeated loading test machine. The paving material 1 is a panel having a length of 300 mm, a width of 300 mm, an upper layer thickness of 15 mm, and a lower layer thickness of 15 mm produced as described above. The repeated loading test machine 10 includes two tires 12 and a shaft portion 14. For example, tires may be used for trucks and buses. The tire size used in this test is as follows: rim diameter: 22.5 inches, radial structure, tire cross-section width: 12 inches, Intensity: 16. The tires 12 are respectively attached to the end portions of the shaft portion 14. The axial load of the repeated loading test machine 10 is 2.1 t. The length W of the shaft portion 14 is 6 m. The repeated loading test machine 10 can be rotated at a constant speed around the central axis 16 of the shaft portion 14 in either the left or right direction by a driving device (not shown). In FIG. It rotates counterclockwise about the central axis 16. With such rotation, the tire 12 travels on the dotted line portion 2 at a speed of 12.5 km / hr. A pavement material 1 is disposed in the dotted line portion 2. The pavement material 1 is fixed to the dotted line portion 2 with an epoxy resin adhesive. In FIG. 1, five pavement materials 1 are arranged on the dotted line portion 2 and are evaluated at the same time. However, the number of pavement materials 1 can be evaluated by one. Further, a counter (not shown) counts the number of times (unit: wheel) that the tire 12 has passed through one paving material 1 on the dotted line portion 2. When the shaft portion 14 makes one rotation, the tire 12 passes two wheels on one pavement material 1.

  In the present invention, the number of times that the tire 12 passed over the pavement 1 when the pavement was crushed, cracked, dug, or rubbed was evaluated by the repeated loading running test of the pavement. The results are shown in Table 1.

The evaluation standard for grain removal is that one hard aggregate is missing from the surface of the pavement.
The evaluation criteria for the cracks are such that minute cracks are visually confirmed on the surface of the pavement material.
The evaluation criteria for digging and rubbing is a state in which wrinkles of 1 mm or more are generated on the surface of the pavement material.
In addition, the number of passes (number of wheels) of the tire 12 until the pavement becomes difficult to travel is described.

The details of each component shown in Table 1 are as follows.
-Aggregate for paving material 1, 3: Aggregate for paving material obtained as described above-Aggregate for paving material 2: No. 7 crushed stone (particle size: 5mm>, average particle size: 3.8mm, aggregate Not treated with primer composition for use)
Resin binder: Polyurethane resin [Modified product of urethane prepolymer of diphenylmethane diisocyanate (MDI), trade name: PPU16, manufactured by Yokohama Rubber Co., Ltd.]
・ Carbon black: HTC # G (particle size: 64 nm, oil absorption: 80 ml / 100 g), manufactured by Nikka Chemicals Co., Ltd. ・ Elastic aggregate: Hijiki rubber chips (95% or more of Hikiki rubber chips with a length of 3.36-1-1 mm) Contained)

  As is clear from the results shown in Table 1, the pavement material of Example 1 is harder to detach the hard aggregate, has excellent crack resistance, and has dramatic durability compared to Comparative Examples 1 and 2. Excellent. From this, it can be seen that the pavement material of the present invention hardly deteriorates in slip characteristics with time. Moreover, it turns out that the primer layer obtained from the primer composition for aggregates of Example 1 has high adhesiveness with a hard aggregate and a resin binder.

FIG. 1 is a schematic view schematically showing a repeated loading traveling test of a pavement material. FIG. 2 is a cross-sectional view schematically showing an example of a paved road on which the paving material of the present invention is laid. FIG. 3 is a cross-sectional view schematically showing an example of a paved road on which the paving material of the present invention is laid.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pavement material 2 Dotted line part 10 Repeated load running test machine 12 Tire 14 Axle part 16 Central axis 20, 38 Pavement material 22, 32 Ground 24, 34 Base 30 Upper pavement material 36 Lower pavement material

Claims (11)

  An aggregate primer composition containing a urethane prepolymer, a latent curing agent, and a solvent.   The primer composition for aggregate according to claim 1, wherein the urethane prepolymer has a polycarbonate structure in a skeleton.   The aggregate primer composition according to claim 1 or 2, wherein all of the isocyanate groups of the urethane prepolymer are bonded to an aliphatic secondary carbon atom or an aliphatic tertiary carbon atom.   The urethane prepolymer contains a urethane prepolymer having a weight average molecular weight of 1500 or less and having 3 or more functional groups, and the amount of the urethane prepolymer having a weight average molecular weight of 1500 or less and having 3 or more functional groups in the urethane prepolymer It is 10-90 mass%, The primer composition for aggregates in any one of Claims 1-3.   The aggregate primer composition according to any one of claims 1 to 4, wherein the latent curing agent is an imine compound derived from a ketone or an aldehyde and an amine. The aggregate composition for primer according to claim 5, wherein the imine compound is a ketimine represented by the following formula (I) or formula (II).

[In formula (I), R ¹ and R ³ each independently represents a methyl group, an ethyl group or a hydrogen atom, R ² represents a methyl group or an ethyl group, and R ⁴ has 1 to 6 carbon atoms. Represents an alkyl group, and R ⁴ may combine with R ¹ or R ² to form a ring. Provided that when R ⁴ is bonded to R ² to form a ring and the carbon atom in the α-position of the carbonyl group is bonded to R ² or R ^{4 through} a double bond, R ³ does not exist. In formula (II), R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms, and R ⁵ and R ⁶ may be bonded to each other to form a ring. ]   Furthermore, the primer composition for aggregates in any one of Claims 1-6 containing an epoxy resin.   The aggregate composition for primer according to claim 7, wherein the content of the epoxy resin is 10 to 90 mass% of the total amount of the urethane prepolymer and the epoxy resin.   An aggregate for a paving material obtainable by treating an aggregate containing a hard aggregate with the aggregate primer composition according to any one of claims 1 to 8.   The aggregate for pavement according to claim 9, wherein the aggregate further includes an elastic aggregate.   A paving material comprising the aggregate for paving material according to claim 9 or 10, and a resin binder.

Images