JP2002121395A - Pavement material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pavement material which is easy to recycle and excels in mechanical properties. SOLUTION: The pavement material is obtained by consolidating an organic aggregate and/or an inorganic aggregate with a resin binder containing a thermally reversible crosslinkable resin which can form a hydrogen bond and contains (i) a carbonyl group-containing group and (ii) a heterocyclic amine containing group in the side chain at a volume ratio of the above thermally reversible crosslinkable resin to the organic aggregate and the inorganic aggregate of 20-50%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pavement material, and more particularly to a pavement material which is easy to recycle and has excellent mechanical properties.

[0002]

2. Description of the Related Art Conventionally, as a pavement material for a sidewalk or the like, a material produced by consolidating an organic aggregate or an inorganic aggregate with a resin binder has been widely used. As the resin binder, a polyurethane resin, an epoxy resin, an acrylic resin, or the like is generally used. Although these resins are thermosetting resins having excellent mechanical properties and workability, they have the problem that once cured, they cannot be reused as a resin binder again. In response to the problem, a material that can be recycled as a resin binder has been demanded.

Therefore, if a thermoplastic resin is used as a resin binder, it can be reused by heating after use, but there is a problem that mechanical properties are inferior to thermosetting resins.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a pavement material which is easy to recycle and has excellent mechanical properties.

[0005]

According to the present invention, an organic aggregate and / or an inorganic aggregate have (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain. It is solidified with a resin binder containing a hydrogen bonding thermoreversible crosslinkable resin (hereinafter, also referred to as the thermoreversible crosslinkable resin of the present invention), and the volume of the thermoreversible crosslinkable resin with respect to the organic and inorganic aggregates A paving material having a ratio of 20 to 50% is provided.

Further, according to the present invention, there is provided the pavement material wherein the (i) carbonyl group-containing group is at least one of amide, ester, imide and carboxyl.

According to the present invention, the following formula (1):
The paving material having at least one group of (2), (3), (4), and (5) is provided.

[0008]

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The thermoreversible crosslinkable resin of the present invention has a structure capable of self-crosslinking by having a group which can be a donor and a group which can be an acceptor at the time of hydrogen bonding in a molecule.
In addition to being able to repeat thermotropic crosslinking and de-crosslinking repeatedly, it forms extremely stable and stable hydrogen bonds, and exhibits sufficient mechanical properties that can be used as a resin binder. It indicates fluidity.

Therefore, by using the thermoreversible crosslinkable resin of the present invention as a resin binder, the resin binder is melted and fluidized by heating, and hydrogen bonds are generated by cooling, whereby the resin binder is solidified. In addition, recycling by heating becomes possible. Further, it is firmly consolidated by hydrogen bonding, exhibits excellent mechanical properties, and has excellent durability and heat resistance.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention includes the following two embodiments. The first aspect of the present invention: the side chain (including the molecular terminal) has
A thermoreversible crosslinkable resin comprising an elastomeric polymer having hydrogen bonding (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group. Second embodiment of the present invention: Thermo-reversible cross-linking composed of a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain (including a molecular terminal). Resin.

Here, "having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group" in the side chain means that the atom (usually carbon) forming the main chain of the elastomeric polymer or the plastic polymer is replaced by (I) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group have a chemically stable bond (covalent bond). On the other hand, a “hydrogen bond” is one in which atoms having high electronegativity are physically bonded via hydrogen, for example, and the bond energy is usually about 1 to 8 kcal / mol, and Lower than that.

[0013] In the first embodiment of the present invention, the elastomeric polymer serving as the main chain is generally vulcanized (crosslinked, cured).
Is a natural polymer or a synthetic polymer known as a rubber elastic material. Specific examples of such elastomeric polymers include diene rubbers such as natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene- Examples include propylene rubbers (EPDM, EPM), chlorosulfonated polyethylene, olefin rubbers such as acrylic rubber and fluorine rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber and the like.

A thermoreversible crosslinkable resin containing a resin component (T
PE), for example, a polystyrene-based TPE (SBS, SIS, SEBS) which may be hydrogenated,
Polyolefin-based TPE, polyvinyl chloride-based TPE, polyurethane-based TPE, polyester-based TPE, polyamide-based TPE, and the like may be used.

[0015] The elastomeric polymer as described above is
It may be liquid or solid. The molecular weight is not particularly limited and can be appropriately selected depending on the purpose of use, crosslink density, and the like. However, convenience in producing a thermoreversible crosslinkable resin, and heating of a thermoreversible crosslinkable resin (decrosslinking) When importance is placed on fluidity at the time, liquid rubber is preferable. It is desirable that the molecular weight is such that it shows a liquid state. For example, in a diene rubber such as isoprene rubber and butadiene rubber, the weight average molecular weight is 1,000 to 300,000,
Preferably, it is about 1,000 to 100,000. On the other hand, when importance is attached to mechanical properties, it is preferably a solid rubber, and the weight average molecular weight is 100,000 to 200,000.
It is desirably about 10,000, preferably about 500,000 to 1,000,000.

In the first embodiment of the present invention, the (i) carbonyl group-containing group bonded to the side chain of the elastomeric polymer as described above is hydrogen-bonding, and is specifically a carbonyl group or a carboxyl group (OH ), An amide group, an ester group, an imide group and the like. Examples of the compound into which such a group can be introduced include a carboxylic acid and a derivative thereof without particular limitation. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Examples of the carboxylic acid derivatives include carboxylic acid anhydrides, esters, ketones, amino acids, amides, imides, and thiocarboxylic acids (carboxylic acids containing a mercapto group).

Specifically, malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, mercaptoacetic acid, etc. Acid anhydrides such as carboxylic acids and substituent-containing carboxylic acids, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride, maleic esters, malonic esters, succinic esters , Glutarate, aliphatic esters such as ethyl acetate, phthalates, isophthalates, terephthalates, aromatic esters such as ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate, quinones, anthraquinones, naphthoquinones, etc. Ketone, glycine, Shin, bicine, alanine, valine,
Amino acids such as leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- (p-aminobenzoyl) -β-alanine, maleamide, maleamic acid (maleic monoamide), succinic acid monoamide; 5-hydroxyvaleramide, N-acetylethanolamine, N,
N'-hexamethylenebisacetamide, malonamide, cycloserine, 4-acetamidophenol, p-
Examples include amides such as acetamidobenzoic acid and imides such as maleimide and succinimide.

(Ii) The heterocyclic amine-containing group is introduced from a nitrogen-containing heterocyclic ring or a compound containing the heterocyclic ring. The nitrogen-containing heterocyclic ring may be any structure that contains or generates a hydrogen-bonding amino group in the heterocyclic ring. Examples of such a nitrogen-containing heterocyclic ring include pyrrololin, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxindole, isatin, indolyl, phthalimidine, β-isoindigo, and monoporphyrin. , Diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyroerythrin, imidazole, pyrazole, triazole, tetrazole, penzoimidazole, penzopyrazole, penzotriazole, imidazoline, imidazolone, imidazolidone, hydazolidone , Pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, pyrrole, pyrroline, indole, ind Phosphorus, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazoles, thiazoles, isoxazoles, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, benzoxazine, phthalazine, pteridine ,
Pyrazine, phenazine, tetrazine, benzoxazole, benzoisoxazole, anthranyl, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazoline, naphthyridine, thiazine, pyridazine, pyrimidine, quinazoline, quinoxaline, triazine and the like. Can be The nitrogen-containing heterocyclic ring may include another hetero atom in the ring.

The compound containing a nitrogen-containing heterocyclic ring is not particularly limited as long as it has the above-mentioned heterocyclic skeleton. For example, a compound capable of chemically (covalently) bonding to the main chain carbon of the elastomeric polymer. May be provided. Examples of such a group include an amino group, a hydroxyl group, an alkyl group, a carboxyl group, and a mercapto group.
Specific examples of such a compound containing a nitrogen-containing heterocyclic ring include dipyridylamine, 1,2-dimethylimidazole, 2-benzimidazoleurea, pyrrole-2-carboxylic acid, 3-methyl-pyrazole, and 4 (or2 ) -Hydroxymethylpyridine, 2 (or4)-(β-hydroxyethyl) -pyridine, 2 (or4)-(2-aminoethyl) -pyridine, 2 (or4) -aminopyridine,
2,6-diaminopyridine, 2-amino-6-hydroxypyridine, 6-azathymine, acetoguanamine, benzoguanamine, citrazinic acid, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3- Aminomethyl-1,2,4-triazole, 3-methylamino-1,2,4-triazole, 3-methylol-1,
2,4-triazole, 3-hydroxy-1,2,4-
Triazole, 2-hydroxytriazine, 2-aminotriazine, 2-hydroxy-5-methyltriazine,
2-amino-5-methyltriazine, 2-hydroxypyrimidine, 2-aminopyrimidine, 2-aminopyrazine, 2-hydroxypyrazine, 6-aminopurine, 6-
Hydroxypurine, 2-amino-1,3,4-thiadiazole, 2-amino-5-ethyl-1,3,4-thiadiazole and the like.

The thermoreversible crosslinkable resin of the present invention is an elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain and in one molecule. Consists of (I) a carbonyl group-containing group and (i)
i) The heterocyclic amine-containing group is pendant to the side chain of the elastomeric polymer and has a chemically stable bond as described above. At this time, (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group may be bonded to the polymer main chain as mutually independent side chains, or may be bonded to the main chain via different groups. Thereby, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group may form one side chain. Thus, when one side chain is formed by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, not only the bond with the main chain but also the (i) carbonyl group-containing group (ii) it is also chemically bonded to the heterocyclic amine-containing group. This (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group may be bonded via some kind of bond.

As an example of a thermoreversible crosslinkable resin in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are independently bonded to the main chain of an elastomeric polymer, (i) ) The structure of the thermoreversible crosslinkable resin (A) in which a carboxyl group as a carbonyl group-containing group and (ii) 1,2,4-triazole as a heterocyclic amine-containing group are schematically shown below.

[0022]

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A thermoreversible crosslinkable resin having one side chain formed by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group by bonding to the main chain via different groups. As an example, the elastomeric polymer is isoprene rubber, (i) the carbonyl group-containing group is a group derived from maleic anhydride, and (ii) the heterocyclic amine is from 3-amino-1,2,4-triazole. The structure of the thermoreversible crosslinkable resin (B), which is a derived group, is schematically shown below. The thermoreversible crosslinkable resin (B) is a 3-amino-1,2,4
-Having a carboxyl group and an amide-bonding group formed by the ring-opening of maleic anhydride by the reaction of triazole and maleic anhydride in one side chain.

[0024]

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In the first aspect of the present invention, among the above, (i) the carbonyl group-containing group includes succinic anhydride,
Cyclic acid anhydrides such as maleic anhydride, glutaric anhydride, and phthalic anhydride, particularly groups derived from maleic anhydride are preferred.

(Ii) The heterocyclic amine-containing group includes a heterocyclic ring having one or more nitrogen atoms in the skeleton, a heterocyclic ring having three or more nitrogen atoms, and a 5-membered heterocyclic ring represented by the following formula: And a group derived from a 6-membered heterocyclic ring, particularly a triazole ring, is preferred. Specifically, 3-amino-1,2,4-
Triazole, 3-hydroxy-1,2,4-triazole, 3-aminomethyl-1,2,4-triazole,
A group derived from 3-methylamino-1,2,4-triazole, 3-methylol-1,2,4-triazole or the like is preferable.

[0027]

Embedded image

Further, those obtained by condensing a benzene ring with the above-mentioned heterocyclic ring and those obtained by condensing the above-mentioned monocyclic heterocyclic rings can be used. For example, a condensed ring represented by the following formula is preferable.

[0029]

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Further, as shown above as the thermoreversible crosslinkable resin (B), the main chain is linked with (ii) a heterocyclic amine-containing group via a carbonyl group-containing group to form one side chain. A structure having a modified structure is preferred. (i) a carbonyl group-containing group and (ii)
In a structure in which a heterocyclic amine-containing group forms one side chain, (i
i) a heterocyclic amine-containing group and a carbonyl group in the (i) carbonyl group-containing group form at least one kind of bond of amide, ester, and imide, or at least one kind of bond and a carboxyl group; Is preferred. In particular, the side chain formed by the bond between the cyclic acid anhydride and (ii) the heterocyclic amine-containing group has a carboxyl group together with an amide, ester or imide. Specific examples of the side chain having such a bond, amide, ester, or imide are shown below (amide: the following formula (1),
(2), ester: following formula (3), (4), imide: following formula (5)).

[0031]

Embedded image

The heterocyclic amine represented by R is not particularly limited, but may be, for example,

Embedded image And the like.

When (i) the carbonyl group-containing group is a group derived from a cyclic acid anhydride, and / or (ii) the heterocyclic amine-containing group is a group derived from a triazole compound, these groups are Those independently bonded to the main chain are also preferred.

The thermoreversible crosslinkable resin of the present invention as described above can have a structure having the above-mentioned (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in the side chain of the elastomeric polymer. The production method is not particularly limited.
For example, during the production of an elastomeric polymer, a monomer capable of forming the main chain of the polymer and a copolymerizable monomer capable of introducing the above group are copolymerized to form (i) a carbonyl group-containing group and (ii) a heterocyclic group on the side chain. A thermoreversible crosslinkable resin having a structure having a cyclic amine-containing group may be directly produced, or a main chain (elastomeric polymer) is formed in advance by polymerization or the like,
Then, it may be graft-modified with a compound capable of introducing (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group.

Among the thermoreversible crosslinkable resins of the present invention,
Those having both (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in one side chain include, for example, (i) an elastomer modified with a carbonyl group-containing group, Reacting with a compound capable of introducing an amine-containing group,
It can be obtained by bonding (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group. (i) The modified elastomer having a carbonyl group-containing group is obtained by, for example, stirring a diene rubber such as butadiene rubber and a toluene solution containing mercaptoacetic acid at room temperature under a nitrogen atmosphere for 1 hour to precipitate the reaction mixture in methanol. And dried under reduced pressure.

Commercially available modified elastomers can be used. For example, LIR-410M is an elastomer having a carbonyl group-containing group in the side chain.
Maleic anhydride-modified isoprene rubber such as (Kuraray), carboxyl-modified isoprene rubber such as LIR-410 (Kuraray), Clinac 110, -221,-
Carboxyl-modified nitrile rubber such as 231 (manufactured by Policer); carboxyl-modified polybutene such as CPIB (manufactured by Nisseki Chemical Co., Ltd.); HRPIB (produced by Nisseki Chemical Lab.);
And Yucaron (manufactured by Mitsubishi Chemical Corporation).

Further, (i) a carbonyl group-containing group and (i)
i) The compounds capable of introducing a heterocyclic amine-containing group may be bonded to each other, and then bonded to a side chain of the elastomeric polymer. In each of the above-described production methods, whether each group of the side chain of the elastomeric polymer is independently bonded or bonded to each other can be confirmed by conventional analysis means such as an NMR spectrum. it can.

In the first embodiment of the present invention, among the above, the groups of (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are added to the side chain of the preformed elastomeric polymer (main chain). Preferably, the modified elastomer having a cyclic acid anhydride group in the side chain and the heterocyclic amine-containing compound are combined at a temperature at which the heterocyclic amine-containing compound can chemically bind to the cyclic acid anhydride group. Is preferably reacted. By this reaction, the acid anhydride may be opened.

The temperature at which the heterocyclic amine-containing compound can chemically bond varies depending on the type of the compound, but is usually about room temperature to about 200 ° C. More specifically, for example, in the reaction between maleic anhydride-modified isoprene rubber and 3-amino-1,2,4-triazole as a heterocyclic amine-containing compound, if the reaction temperature is about 150 ° C., maleic anhydride And 3-amino-1,2,4-triazole are chemically bonded to form a side chain having an amide bond as shown in the above formula (A), but when the carbonyl group is a carboxyl group However, 3-amino-1,2,4-triazole requires a dehydration catalyst even though the reaction temperature is the same. The reaction time is usually about 3 to 5 hours.

Next, a second embodiment of the present invention will be described. A second aspect of the present invention is a hydrogen-bonding thermoreversible crosslinkable resin comprising a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain. In the second embodiment of the present invention, the plastic polymer serving as the main chain is a synthetic polymer generally known as a thermoplastic resin. Specific examples of such a plastic polymer include a homopolymer of ethylene (branched or linear) such as low-, medium-, or high-density polyethylene, ethylene, propylene, butene-1, 3- Methylbutene-1, pentene-1, 3-methylpentene-
Copolymers with α-olefins such as 1,4-methylpentene-1, hexene-1, octene-1, and decene-1, ethylene, vinyl esters such as vinyl acetate, acrylic acid, methacrylic acid, and the like Ethylene resins such as copolymers with other monomers such as esters, propylene homopolymers (polypropylene, PP), propylene, ethylene, butene-1, 3-methylbutene-1, pentene-
1,3-methylpentene-1,4-methylpentene-
Α- such as 1, hexene-1, octene-1, and decene-1
Copolymer with olefin, propylene, isoprene,
1,3-butadiene, 1,3-pentadiene, 1,4-
Propylene resins such as copolymers with other monomers such as diene compounds such as hexadiene, 1,5-hexadiene and 1,9-decadiene; butene-1,4-methylpentene-
1. Homopolymers and copolymers of α-olefins such as hexene-1, graft polymers with acrylonitrile, butadiene, and styrene (ABS resin), copolymers with acrylonitrile and styrene (AS resin), general-purpose polystyrene Styrene resin such as polystyrene for impact resistance, vinyl chloride resin, acrylic resin, polycarbonate, polyamide resin and the like. Among these, an olefin resin such as an ethylene resin or a propylene resin is particularly preferable because it is excellent in heat resistance, mechanical strength, and adhesion.

The plastic polymer as described above is
The molecular weight is not particularly limited, and can be appropriately selected depending on the purpose of use, crosslink density, and the like. However, convenience in producing a thermoreversible crosslinkable resin, and heating during thermoreversible crosslinkable resin (decrosslinking) From the viewpoint of fluidity, the molecular weight is, for example, in the case of polypropylene, the number average molecular weight is 1,000 to 500,000.
Is preferable.

In the second embodiment of the present invention, the (i) carbonyl group-containing group bonded to the side chain of the plastic polymer as described above is hydrogen-bonding, and specifically includes a carbonyl group, a carboxyl group and an amide group. Groups, ester groups, imide groups and the like. Examples of the compound into which such a group can be introduced include a carboxylic acid and a derivative thereof without particular limitation. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Further, as the carboxylic acid derivative, carboxylic anhydride, ester, ketone, amino acid,
Examples include amides, imides, and thiocarboxylic acids (carboxylic acids containing a mercapto group).

Specific examples of the carboxylic acid compound and the carboxylic acid derivative include the same compounds as the compounds exemplified as the specific examples of the carboxylic acid compound and the carboxylic acid derivative in the first embodiment of the present invention.

Further, (ii) the heterocyclic amine-containing group is introduced from a nitrogen-containing heterocyclic ring or a compound containing the heterocyclic ring. The nitrogen-containing heterocyclic ring may be any structure that contains or generates a hydrogen-bonding amino group in the heterocyclic ring. Examples of such a nitrogen-containing heterocyclic ring include the same compounds as the compounds exemplified as the nitrogen-containing heterocyclic ring in the first embodiment of the present invention. The nitrogen-containing heterocyclic ring may include another hetero atom in the ring.

The compound containing a nitrogen-containing heterocyclic ring is not particularly limited as long as it has a heterocyclic skeleton as exemplified as the above-described nitrogen-containing heterocyclic ring. It may have a (covalent) bondable group. Examples of such a group include an amino group, a hydroxyl group, a methylene group, an ethylene group, a carboxyl group, a mercapto group, and the like. Examples of such a compound containing a nitrogen-containing heterocyclic ring include the same compounds as the compounds exemplified as specific examples of the compound containing a nitrogen-containing heterocyclic ring in the first embodiment of the present invention.

The thermoreversible crosslinkable resin of the present invention is a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain and in one molecule. Consists of (I) a carbonyl group-containing group and (i)
i) The heterocyclic amine-containing group is pendant to the side chain of the plastic polymer and has a chemically stable bond as described above. In this case, (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group may be bonded to the polymer main chain as independent side chains, and (i) the carbonyl group-containing group and (ii) ) The heterocyclic amine-containing group may form one side chain. Thus, when one side chain is formed by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, not only the bond with the main chain but also the (i) carbonyl group-containing group (ii) it is also chemically bonded to the heterocyclic amine-containing group. This (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group may be bonded via some kind of bond.

As an example of a thermoreversible crosslinkable resin in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are independently bonded to the main chain of a plastic polymer, (i) The structure of a thermoreversible crosslinkable resin (C) in which a carboxyl group as a carbonyl group-containing group and (ii) 1,2,4-triazole as a heterocyclic amine-containing group are schematically shown below.

[0048]

Embedded image (Where x = 40-99.8, y = 0.1-30, z =
0.1 to 30. )

As one example of the thermoreversible crosslinkable resin in which (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group form one side chain, the plastic polymer is polypropylene, i) the carbonyl group-containing group is a group derived from maleic anhydride, and (ii) the heterocyclic amine is 3-
The structure of the thermoreversible crosslinkable resin (D), which is a group derived from amino-1,2,4-triazole, is schematically shown below. This thermoreversible crosslinkable resin (D) is 3-amino-1,
The 2,4-triazole has a carboxyl group and a carboxyl group in one side chain formed by the reaction of maleic anhydride with maleic anhydride to form a ring by opening maleic anhydride.

[0050]

Embedded image (Where x = 70 to 99.9 and y = 0.1 to 30)

Further, as a further example of the thermoreversible crosslinkable resin forming one side chain with (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, the plastic polymer is polypropylene, The structure of a thermoreversible crosslinkable resin (E) in which (i) the carbonyl group-containing group is derived from maleic anhydride and (ii) the heterocyclic amine is a group derived from aminopyridine (γ-form) is shown. It is shown below. This thermoreversible crosslinkable resin (E) is an aminopyridine (γ-form)
Has a carboxyl group and an amide-bonding group formed by ring-opening of maleic anhydride by a reaction with maleic anhydride in one side chain.

[0052]

Embedded image (Where x = 70 to 99.9 and y = 0.1 to 30)

In the second embodiment of the present invention, among the above, (i) the carbonyl group-containing group includes succinic anhydride,
Cyclic acid anhydrides such as maleic anhydride, glutaric anhydride, and phthalic anhydride, particularly groups derived from maleic anhydride are preferred.

(Ii) The heterocyclic amine-containing group is preferably a heterocyclic ring having two or more nitrogen atoms in the skeleton, more preferably a heterocyclic ring having three or more nitrogen atoms, particularly preferably a group derived from a triazole ring. preferable. Specifically 3-
Amino-1,2,4-triazole, 3-hydroxy-
1,2,4-triazole, 3-aminomethyl-1,
2,4-triazole, 3-methylamino-1,2,4
Preferred are groups derived from -triazole, 3-methylol-1,2,4-triazole and the like.

Further, the thermoreversible crosslinkable resin (D)
As shown in (E), those having a structure in which (i) a heterocyclic amine-containing group is bonded to a main chain via (i) a carbonyl group-containing group to form a side chain are preferable. In a structure in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain, (ii) a heterocyclic amine-containing group and a carbonyl group in the (i) carbonyl group-containing group , Amides, esters,
It is preferable that at least one bond between imide and imide, or at least one bond and a carboxyl group are formed. In particular, the side chain formed by the bond between the cyclic acid anhydride and (ii) the heterocyclic amine-containing group is an amide,
It has a carboxyl group together with an ester or imide. As a specific example of such a side chain having a bond, an amide, an ester, or an imide, in the first embodiment of the present invention, as a specific example of a side chain having an amide, an ester, or an imide, (amide: the following formula (1) ), (2), ester: the following formulas (3), (4), and imide: the following formula (5)). Specific examples are shown below.

[0056]

Embedded image

The heterocyclic amine represented by R is not particularly limited, but is exemplified by the heterocyclic amine represented by R in formulas (1) to (5) in the first embodiment of the present invention. And the same groups as those described above.

When (i) the carbonyl group-containing group is a group derived from a cyclic acid anhydride, and / or (ii) the heterocyclic amine-containing group is a group derived from a triazole compound, these groups are Those independently bonded to the main chain are also preferred.

The thermoreversible crosslinkable resin of the present invention as described above can have a structure having the above-mentioned (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in the side chain of the plastic polymer. The production method is not particularly limited.
For example, during the production of a plastic polymer, a monomer capable of forming the main chain of the polymer and a copolymerizable monomer capable of introducing the above group are copolymerized to form (i) a carbonyl group-containing group and (ii) a heterocyclic group on the side chain. A thermoreversible crosslinkable resin having a structure having a cyclic amine-containing group may be directly produced, or a main chain (plastic polymer) is formed in advance by polymerization or the like,
Then, it may be graft-modified with a compound capable of introducing (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group.

Among the thermoreversible crosslinkable resins of the present invention,
Those having both (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in one side chain include, for example, (i) a plastic polymer modified with a carbonyl group-containing group, (ii) It can be obtained by reacting with a compound into which a heterocyclic amine-containing group can be introduced, and bonding (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group.
(i) The modified plastic polymer having a carbonyl group-containing group is, for example, an α-olefin such as polypropylene and a toluene solution containing mercaptoacetic acid are stirred at room temperature under a nitrogen atmosphere for 1 hour, and the reaction mixture is dissolved in methanol. It can be obtained by precipitating and drying under reduced pressure.

Further, (i) a carbonyl group-containing group and (i)
i) Compounds capable of introducing a heterocyclic amine-containing group may be bonded to each other, and then bonded to a side chain of a plastic polymer. In each of the above-mentioned production methods, whether each group of the side chain of the plastic polymer is independently bonded or bonded to each other can be confirmed by conventional analysis means such as an NMR spectrum. it can.

In the second embodiment of the present invention, among the above, the groups of (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are added to a side chain of a preformed plastic polymer (main chain). It is preferable to bond, in particular, a plastic polymer having a cyclic acid anhydride group in a side chain and a heterocyclic amine-containing compound at a temperature at which the heterocyclic amine-containing compound can chemically bond to the cyclic acid anhydride group. It is preferred to react below. By this reaction, the acid anhydride may be opened. The temperature at which the heterocyclic amine-containing compound can chemically bond varies depending on the type of the compound, but is usually from room temperature to 2 ° C.
It is about 00 ° C.

As such a modified plastic polymer, a commercially available product can be used. For example, as a plastic polymer having a carbonyl group-containing group in the side chain, a maleic anhydride-modified product such as Eumex 1010 (manufactured by Sanyo Chemical Industries, Ltd.) can be used. Polyethylene, maleic anhydride-modified ethylene ethyl acrylate resin such as AR201 (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.), and ethylene acrylate ester / maleic anhydride such as Bondyne TX8030 (manufactured by Sumitomo Chemical Co., Ltd.) And the like.

More specifically, for example, in the reaction of maleic anhydride-modified polypropylene with 3-amino-1,2,4-triazole as a heterocyclic amine-containing compound,
When the reaction temperature is about 150 to 180 ° C., maleic anhydride and 3-amino-1,2,4-triazole are chemically bonded to form an amide bond as shown in the above formula (D). To form side chains. The reaction time is usually 0.5
About 2 hours. In the reaction of maleic anhydride-modified polypropylene with aminopyridine (γ-form) as a heterocyclic amine-containing compound, the reaction temperature is 150 to 1
At about 80 ° C., maleic anhydride and aminopyridine chemically bond to form a side chain having an amide bond as shown in the above formula (E). The reaction time is usually about 0.5 to 2 hours.

Next, the thermoreversible crosslinkable resin of the present invention, and
The self-crosslinking of the thermoreversible crosslinkable resin of the present invention by hydrogen bonding will be described. The thermoreversible crosslinkable resin of the present invention as described above can be self-crosslinked by hydrogen bonding. At the time of hydrogen bonding, (i) carbonyl group-containing group and
Any of the (ii) heterocyclic amine-containing groups may act as a donor (proton donor) or an acceptor (proton acceptor), but usually (ii) a tertiary amino group or ( i) The carbonyl group in the carboxyl group-containing group serves as an acceptor, and (ii) the tertiary amino group (NH) in the heterocyclic amine-containing group or (i) the OH in the carboxyl group-containing group.
The group acts as a donor and hydrogen bonds between the acceptor and the donor. In such a thermoreversible crosslinkable resin having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain, the main chain of the elastomeric polymer or the plastic polymer further participates in hydrogen bonding. Sometimes.

Specifically, (i) a carbonyl group-containing group,
(ii) In the thermoreversible crosslinkable resin of the present invention having a heterocyclic amine-containing group, when a hydrogen bond is represented by (donor) -H ... (acceptor), at least OH ... O, NH ... O,
Hydrogen bonds represented by OH ... N and NH ... N are possible. Such a hydrogen bond may occur between molecules or within a molecule. For example, in the thermoreversible crosslinkable resin represented by the structure (B) and the thermoreversible crosslinkable resin represented by the structures (D) and (E), (ii) the intracyclic amino group of the heterocyclic amine-containing group or (i) ) It is presumed that the carbonyl group in the carboxyl group-containing group and the amino group in the ring of the other side chain (ii) heterocyclic amine-containing group or (i) the OH group in the carboxyl group-containing group are hydrogen-bonded.

The hydrogen bond of the thermoreversible crosslinkable resin of the present invention having the above-mentioned (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group is thermotropic and forms a crosslinked structure when used at room temperature. However, when heated at a high temperature, it delinks and exhibits fluidity. Moreover, it is possible to repeatedly reproduce this crosslinking / decrosslinking. Therefore, with the thermoreversible crosslinkable resin of the present invention, it is possible to easily perform recycling by melting of rubber, which was practically impossible with a conventional chemically vulcanized rubber made of sulfur or peroxide. In addition, the cold flow property of the elastomeric polymer can be prevented. Further, with the thermoreversible crosslinkable resin of the present invention, it is practically impossible with a crosslinked body which has been subjected to a crosslinking treatment by conventional blending of sulfur or an organic peroxide, irradiation of radiation, or utilization of a silanol condensation reaction. Further, the resin can be easily recycled by melting.

The thermoreversible crosslinkable resin of the present invention has a specific group
By having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain, the crosslinkability is high, the crosslinked product exhibits excellent heat resistance, and can maintain a stable hydrogen bond during use. it can. That is, the hydrogen bond is maintained up to a high temperature that can be used. Specifically, for example, in a thermoreversible crosslinkable resin as shown in the above (B), the collapse temperature of hydrogen bond is 100 ° C. or more, and hydrogen bond is formed extremely stably at room temperature. In the thermoreversible crosslinkable resin as shown in the above (D), the collapse temperature of hydrogen bond is 110 to 1
At 50 ° C., hydrogen bonds are formed very stably at room temperature, and the hydrogen bonds are maintained up to a high temperature that can be used.
The effective formation of hydrogen bonds can be confirmed by observing the gelation phenomenon (increase in viscosity), and the collapse of hydrogen bonds is observed as a decrease in viscosity (increase in fluidity) or a decrease in hardness. .

The thermoreversible crosslinkable resin of the present invention has a specific group as described above, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, so that the curability during hydrogen bonding (crosslinking) can be improved. And a decrease in viscosity at the time of hydrogen bond collapse (decrosslinking) at a high temperature. That is, it becomes extremely soft at the time of high-temperature heating exceeding the heat-resistant temperature, and at about 150 ° C. or more, the fluidity becomes remarkably large, and recycling and use becomes easy. In particular, in the case of the plastic polymer which is the main chain of the thermoreversible crosslinkable resin of the present invention, good melt fluidity can be easily exhibited at a temperature around the molding temperature when it has no side chain and is not modified. Therefore, reshaping and recycling are easy. Also,
It has a group capable of hydrogen bonding, and has a feature of high adhesion to various adherends.

The effect of the thermoreversible crosslinkable resin of the present invention is exhibited by having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain, This is considered to be because the cyclic amine is more easily hydrogen-bonded than the amine which does not form a ring structure.

In the thermoreversible crosslinkable resin according to the first aspect of the present invention, when (ii) a group derived from an amine compound other than the heterocyclic structure is used instead of the heterocyclic amine-containing group, hydrogen The bond is weak and the thermoreversible crosslinkable resin remains liquid. Further, in the thermoreversible crosslinkable resin of the present invention, by appropriately selecting a specific group, (i) a carbonyl group-containing group and (ii) a crosslink density by a heterocyclic amine-containing group,
Sufficient mechanical strength and rubber elasticity comparable to those of conventional vulcanized rubber made of peroxide or the like can be exhibited. The crosslink density varies depending on the purpose of use, application, molecular weight of the main chain, etc., and cannot be determined unconditionally. However, it is desirable that the crosslink density at the time of crosslinking be sufficient rubber elasticity and excellent mechanical strength. For example, when the main chain is a conjugated diene rubber such as isoprene and butadiene, the side chain groups (i) and (ii)
About 0.1 to 30% by weight, preferably 1 to 1
Desirably, it is contained in an amount of about 0% by weight. (i) and (ii) usually need only be about 0.5 to 2 in a (i) / (ii) molar ratio.

Further, in the thermoreversible crosslinkable resin according to the second aspect of the present invention, (ii) a heterocyclic amine-containing group is
When the resin has a group derived from an amine compound other than the heterocyclic structure, the hydrogen bond is weak, and the heat resistance and strength are equal to or lower than those of the unmodified resin. In the thermoreversible crosslinkable resin of the present invention, a specific group, (i) a carbonyl group-containing group and (ii)
By appropriately selecting the crosslinking density and the like by the heterocyclic amine-containing group, it is possible to have excellent mechanical strength.
The crosslink density varies depending on the purpose of use, application, molecular weight of the main chain and the like, and cannot be determined unconditionally. However, it is desirable that the crosslink density exhibit excellent mechanical strength at the time of crosslinking. For example, when the main chain is polypropylene, the side chain group (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group are each about 0.1 to 30 mol%, based on the monomer unit,
Preferably, it is contained in an amount of about 1 to 10 mol%. The (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group may usually be about 0.5 to 2 in (i) / (ii) molar ratio.

The organic aggregate of the present invention includes powdery rubber,
Examples include crushed products of various resin waste products (such as bumper chips obtained by crushing automobile bumpers), resin chips, wood chips, and plant chips such as walnuts. As the granular rubber, a pulverized product of a rubber compound (including waste products such as waste tires) and a product obtained by molding a rubber compound and then crushing or cutting the same can be used. As the form of the powdery rubber, the average particle diameter is 0.3
~ 50mm granular, average maximum length 0.3 ~ 50mm hijiki (fibrous elongated shape), average particle size 0.3
There is a fixed shape composed of a polyhedron or a curved surface having a size of up to 50 mm, and any one of these or a combination of a plurality of them can be used.

Examples of the inorganic aggregate of the present invention include artificial stone, natural stone, quartz sand, crushed natural stone, crushed artificial stone, and metal powder.

The pavement material of the present invention is produced by consolidating the above-mentioned organic aggregate and inorganic aggregate with a resin binder containing the thermoreversible crosslinkable resin of the present invention. That is, in a state where the thermoreversible crosslinkable resin of the present invention is heated and melted, mixed with an organic aggregate or an inorganic aggregate and cooled, the thermoreversible crosslinkable resin of the present invention is crosslinked by hydrogen bonding and solidified. Thereby, the aggregate is consolidated. The pavement material may be solidified after being directly arranged at the construction site in a molten state, or may be solidified in blocks of a predetermined size in advance and arranged in the construction site.

The amount of the thermoreversible crosslinkable resin of the present invention is 20 to 50%, preferably 30 to 40%, as a volume ratio of the thermoreversible crosslinkable resin to the organic aggregate and the inorganic aggregate. If the amount is less than 20%, the physical properties such as strength become insufficient, and if it exceeds 50%, the porosity becomes small and the drainage property becomes poor.

The pavement material of the present invention can be used for various purposes and is not particularly limited. For example, the pavement material can be used for a sidewalk, an athletic stadium, a footpath of a golf course, a pavement of a park, a road, and the like. it can.

[0078]

EXAMPLES The present invention will be further described below with reference to examples, but the scope of the present invention is not limited to these examples. Examples 1 to 6 and Comparative Examples 1 and 4 As shown in the following formulas, a maleic anhydride-modified liquid isoprene rubber (1) having a modification ratio of 4% by weight (Kuraray, LIR-
410M), 3-amino-1,2,4-triazole (2) was added thereto such that the mole number of (1) in terms of the maleic anhydride skeleton and the mole number of (2) became the same, and 120 ° C. For 3 hours. After confirming that the solution became a homogeneous solution, the solution was allowed to stand overnight to obtain a thermoreversible crosslinkable resin of the present invention as a gelled reactant (3).

[0079]

Embedded image

The temperature (outflow starting temperature) showing the fluidity of the obtained thermoreversible crosslinkable resin (3) was measured to be 110 ° C.
Met. The outflow starting temperature was measured using a Koka type flow tester. Capillary (D = 1mm, length = 10
mm) and the sample is packed at 1 ° C / m under a pressure of 10 MPa.
The temperature was increased in and the temperature at which the sample began to flow from the capillary was measured.

Next, the pellets of the thermoreversible crosslinkable resin (3) and various types of aggregates were heated and mixed at a weight ratio and a mixing temperature shown in Table 1 below by using a heating mixer. After the molten state, a dumbbell No. 1 test piece having a thickness of 10 mm was prepared, and a tensile test was performed at a tensile speed of 10 mm / min. The results are shown in Table 1. Table 1 also shows the volume ratio of the thermoreversible crosslinkable resin to the aggregate and the recyclability (○ or ×).

Comparative Examples 1 and 2 Specimens were prepared in the same manner as in Example except that a room temperature-curable polyurethane resin (Comparative Example 1) and a thermoplastic resin (thermoplastic elastomer, Comparative Example 2) were used as binder resins. Was prepared and a tensile test was conducted.

[0083]

[Table 1]

The following components were used in Table 1 above. Thermoplastic resin: Thermoplastic polyurethane resin, Pandex T1000, Dainippon Ink & Chemicals, Inc. Room temperature curing type polyurethane resin: F3S, Sumitomo Bayer Urethane Co., Ltd.

As shown in Table 1 above, in Comparative Example 1 in which a room temperature-curable polyurethane resin was used as the resin binder, it was impossible to reuse the resin. In Comparative Example 2 in which a thermoplastic resin was used as the resin binder, the values of the tensile strength and the elongation at break were small, and the mechanical properties were poor. On the other hand, the embodiment in which the thermoreversible crosslinkable resin of the present invention is blended so that the volume ratio of the thermoreversible crosslinkable resin to the aggregate is 20 to 50% is melted by heating, so that recycling is easy. In addition, a good result that the mechanical properties were also excellent was obtained.

[0086]

According to the present invention, by using a hydrogen-bonding thermoreversible crosslinkable resin having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain of the resin binder, A pavement material that is easy to recycle and has excellent mechanical properties can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 17/48 C09K 17/48 P C09K 103: 00 C09K 103: 00 F term (reference) 4H026 CA06 CB08 CB09 CC05 CC06 4J002 AA00X AC00X AC01W AC03W AC04W AC06W AC07W AC08W AC09W AC10W AC11W AC12W AC13X AH00X BB04W BB07W BB08W BB09W BB10W BB11W BB15W BB17W BB18W BB20W BB21W BB27W BD03W WB04W BN04W WB04W BN04W BN04W BB04W

Claims (3)

[Claims] 1. An organic aggregate and / or an inorganic aggregate are prepared by adding a hydrogen-bonding thermoreversible crosslinkable resin having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group to a side chain. And a volume ratio of the thermoreversible crosslinkable resin to the organic aggregate and the inorganic aggregate is 20%.
Paving material that is ~ 50%. 2. The pavement material according to claim 1, wherein the (i) carbonyl group-containing group is at least one of amide, ester, imide and carboxyl. 3. The following formulas (1), (2), (3),
2. The method according to claim 1, which has at least one group of (4) and (5).
Or the pavement material according to 2. Embedded image