JP2003137941A - Binder composition for colored pavement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a binder composition which satisfies coating workability and durability, has excellent safety, can uniformly be cured, and is used for colored pavements, to provide a self dispersing type aqueous resin dispersion which is suitably used for preparing the composition, and to provide a colored pavement which is prepared by applying the composition and has excellent durability. SOLUTION: This binder composition for the colored pavements comprises a condensation polymerization type resin (resin A) containing a curing agent and having radically polymerizable unsaturated bonds, a colorant, a curing agent and/or a curing accelerator, and water. The self dispersing type aqueous resin dispersion used for preparing the binder composition for the colored pavements is prepared by dispersing a condensation polymerization type resin (resin B) containing a curing accelerator and having radically polymerizable unsaturated bonds in water. The self dispersing type aqueous resin dispersion used for preparing the binder composition for the colored pavements is prepared by dispersing a condensation polymerization type resin (resin A) containing a curing agent and having radically polymerizable unsaturated bonds in water. The colored pavement is prepared by applying the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored pavement binder composition, a self-dispersible water-based resin dispersion used for preparing the composition, and a colored pavement constructed by using the composition. Regarding

[0002]

2. Description of the Related Art Asphalt and modified asphalt are not used for colored pavement, colored pavement, and non-slip pavement for roads, sidewalks, amusement parks, playgrounds, parks and plazas, and a binder composition for colored pavement is used. It is used. An example of such a colored pavement binder composition is, for example, JP-A-4-1-1.
JP-A-06262 discloses a composition containing a C4 to C9 petroleum resin, a petroleum resin such as a terpene and / or a phenol resin, a coumarone indene resin, a coal resin such as a xylene resin, a petroleum solvent extracted oil and a thermoplastic rubber Is disclosed. Further, JP-A-11-21385 discloses a composition containing an isoprene-based carbonized resin and the like.

A conventional colored binder composition for pavement is heated and melt-mixed with an aggregate as in the case of using asphalt or modified asphalt, and is applied in a thin layer at a construction site. Therefore, there are problems in terms of danger and odor during heating, melting and mixing.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a binder composition for a colored pavement which does not require heat-melt mixing and is excellent in safety and capable of causing a uniform curing reaction. A self-dispersible water-based resin dispersion that is preferably used for
Another object of the present invention is to provide a colored pavement body constructed by using the composition.

[0005]

The summary of the present invention is as follows.
(1) Colored pavement containing a condensation-polymerized resin (resin A) having a radical-polymerizable unsaturated bond internally added with a curing agent, a colorant, a curing agent and / or a curing accelerator, and water. (2) A colored pavement containing a polycondensation resin (resin B) having a radical-polymerizable unsaturated bond internally added with a curing accelerator, a colorant, a curing agent, and water. (3) A polycondensation resin having a radically polymerizable unsaturated bond, which is internally added with a curing agent (resin A), and a radically polymerizable unsaturated, which is internally added with a curing accelerator. A polycondensation resin having a bond (resin B),
A colored pavement binder composition containing a colorant and water, (4) Radical-polymerizable unsaturation used for preparing a colored pavement binder composition, internally added with a curing accelerator A self-dispersion type water-based resin dispersion obtained by dispersing a polycondensation resin having a bond (resin B) in water, (5) a hardener used for preparing a colored pavement binder composition is added internally. A self-dispersible water-based resin dispersion obtained by dispersing a polycondensation resin having a radically polymerizable unsaturated bond (resin A) in water, and (6) above (1) to
(5) A colored pavement constructed by using the binder composition for colored pavement according to any one of the above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The colored pavement binder composition of the present invention (hereinafter referred to as the binder composition) comprises a polycondensation resin, a colorant, a curing agent, a curing accelerator and water. It is a stable resin water dispersion in which a polycondensation resin is uniformly dispersed in water, and a curing agent and a curing accelerator are uniformly dispersed and / or dissolved (however, in the first embodiment of the present invention described below. Includes the case where the curing accelerator is not included). The condensed resin is preferably in the form of fine particles. A curing agent or a curing accelerator is internally added to the polycondensation resin, and therefore, the curing agent or the curing accelerator constituting the binder composition of the present invention is dispersed and / or dissolved in water. In the open state,
And a state of being internally added to the polycondensation resin.
That is, the first embodiment of the binder composition of the present invention contains a polycondensation resin (resin A) containing a curing agent internally, a colorant, a curing agent and / or a curing accelerator, and water. It is a binder composition. The second aspect of the binder composition of the present invention is a binder composition containing a polycondensation resin (resin B) containing a curing accelerator internally, a colorant, a curing agent, and water. A third aspect of the binder composition of the present invention is a binder composition containing resin A, resin B, a colorant, and water.

The binder composition of the present invention contains a polycondensation resin and a curing agent, and the curing reaction proceeds by heating. However, when the curing reaction proceeds at room temperature, it contains a curing accelerator. It is preferable. Further, in order to avoid direct contact between the curing agent and the curing accelerator, the resin A and the resin B in which the curing agent and the curing accelerator are internally added to the polycondensation resin independently are used. It has a relatively high storage stability without causing In addition, when a polycondensation resin obtained by internally adding a curing agent and a curing accelerator, or a condensation polymerization resin obtained by internally adding a curing accelerator and a curing agent, is contained in water, a binder It is preferable to prevent them from coming into direct contact with each other during storage of the composition, and for example, it is preferable to add a curing agent or a curing accelerator to the aqueous dispersion of the polycondensation resin immediately before coating. Further, the binder composition of the present invention is excellent in coating workability, and when applied uniformly on the pavement, the unsaturated bond present in the polycondensation resin at room temperature due to the action of the curing agent and the curing accelerator. The involved polymerization reaction proceeds uniformly, curing is efficiently performed over the whole, and a colored pavement having excellent durability can be obtained. Also, the time required for curing is within a range that causes no problem in ordinary coating. further,
The binder composition of the present invention is made of a raw material having no odor and no risk of fire, etc., and the conventional problems concerning the risk etc. have been greatly improved.

The polycondensation resin contained in the binder composition of the present invention is a resin containing an unsaturated dicarboxylic acid having a radical-polymerizable unsaturated bond or its acid anhydride as at least one of the constituent monomers, The acid value is preferably 3 to
100 mg KOH / g, more preferably 10-70 mg
It is KOH / g. The polycondensation resin is in the form of fine particles, and the average particle diameter thereof is preferably 0.01 to 10 μm, more preferably 0.02 to 10 μm from the viewpoint of dispersibility.
It is 5 μm.

The acid value of the polycondensation resin is preferably 3 mgKOH / g or more from the viewpoint of obtaining a stable aqueous dispersion. For example, when an oil-soluble curing agent or curing accelerator is internally added to the resin. , 100mgKOH from the viewpoint of compatibility
/ G or less is preferable.

The acid value is measured according to JIS K 0070, and the average particle diameter is, for example, a laser diffraction particle size distribution measuring device, SALD-2000J (manufactured by Shimadzu Corporation).
To measure.

As the polycondensation resin used in the present invention, specifically, polyester or polyester polyamide is preferable from the viewpoint of exhibiting the desired effects of the present invention.

The polycondensation resin used in the present invention, such as the polyester, can be produced, for example, by polycondensing an acid component shown below as a constituent monomer with a polyol component.

The unsaturated dicarboxylic acid having a radical-polymerizable unsaturated bond or its acid anhydride as an acid component includes maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and their acid anhydrides. And maleic acid, fumaric acid, maleic anhydride and tetrahydrophthalic anhydride are preferred. These may be used alone or in combination of two or more. The content of these acid components is preferably 20 to 100 mol% and more preferably 50 to 100 mol% in the total acid components.

The acid components other than the above-mentioned acid components that can be used in the present invention are not particularly limited, and for example, the following polyvalent carboxylic acids or derivatives thereof can be used.

The polyvalent carboxylic acid or its derivative is not particularly limited, but divalent and trivalent non-radical reactive carboxylic acids having 4 to 40 carbon atoms are preferably used, and examples thereof include phthalic acid and isophthalic acid. Terephthalic acid, succinic acid, dimer acid, alkenyl succinic acid (C4 to C2
0), divalent carboxylic acids such as cyclohexanedicarboxylic acid and naphthalene dicarboxylic acid, and trivalent carboxylic acids such as 1,2,4-benzenetricarboxylic acid, their anhydrides and their lower alkyl esters (C1 to C4). .
When a non-radical-reactive acid component is used as the other acid component, the unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or the acid anhydride thereof should be used within the range specifically exemplified above. Is preferred.

On the other hand, the polyol component is not particularly limited, and preferably ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, 1,6-hexane. An aliphatic polyol having 2 to 10 carbon atoms such as a diol or an aromatic polyol such as bisphenol A and hydrogenated bisphenol A, and an alkylene (C2-C3) oxide adduct thereof (addition mole number: n = 2 to 20) are used. Among them, propylene oxide adducts and ethylene oxide adducts of bisphenol A are particularly preferable from the viewpoint of heat resistance and water resistance.

The polycondensation of the polyol component and the acid component can be carried out by a known method, for example, by reacting the polyol component and the acid component at a temperature of 180 to 250 ° C. in an inert gas atmosphere, The end point may be determined by tracing the softening point (Tm), which is an index of the molecular weight, and the acid value.

The molar ratio of the polyol component and the acid component may be appropriately determined depending on the acid value, the number average molecular weight, the glass transition point (Tg) and the like of the obtained polyester. It is preferably 1: 1.5 (polyol component: acid component).

During the condensation polymerization, additives such as an esterification catalyst such as dibutyltin oxide and a polymerization inhibitor such as hydroquinone and t-butylcatechol can be appropriately used.

On the other hand, the above-mentioned polyester polyamide, which is one of the preferable embodiments of the polycondensation resin used in the present invention, is prepared by a known method, for example, in the component containing the acid component and the polyol used in the production of the polyester. It can be produced by adding an amine derivative and polycondensation. The amine derivative is not particularly limited, and polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and xylylenediamine; aminocarboxylic acids such as methylglycine, trimethylglycine, 6-aminocaproic acid, δ-aminocaprylic acid and ε-caprolactam. And amino alcohols such as ethanolamine and propanolamine, and methylglycine, trimethylglycine and 6-aminocaproic acid are preferable from the viewpoint of solubility in organic solvents.

The molar ratio of the polyol component, the acid component and the amine derivative during the synthesis of the polyester polyamide is
As in the case of the polyester, it may be appropriately determined depending on the acid value, the number average molecular weight, the glass transition point and the like of the polyester polyamide.

The acid value of the polycondensation resin obtained can be adjusted, for example, by adjusting the raw materials thereof, for example, the molar ratio of the acid component / polyol component, the reaction time and the like.

The average particle size can be adjusted, for example, by adjusting the molecular weight, acid value, degree of neutralization, etc. of the polycondensation resin to be obtained, and dissolving the resin in an organic solvent to prepare water and, if necessary, water. A step of adding a surfactant or the like and distilling off the organic solvent to invert the phase into an aqueous system is carried out, and at that time, the phase inversion emulsification conditions and the like can be appropriately adjusted.

The polycondensation resin used in the present invention has a glass transition point (Tg) (measured by a differential scanning calorimeter) of -50 to 100 ° C. and a softening point (Tm).
It is preferable that (measured by the flow tester method) is 180 ° C. or lower and the number average molecular weight (value converted into polystyrene by the GPC method) is 1,000 to 50,000. When the resin is polyester polyamide, the amine value of the resin based on ASTM D2073 is 10 mg.
It is preferably KOH / g or less.

Further, at least a part of the carboxyl groups present in the polycondensation resin must be neutralized. For example, a neutralizing agent before or during the preparation of the binder composition of the present invention. Neutralization may be performed using, and the neutralization method is not particularly limited.

The neutralizing agent is not particularly limited as long as it can ionize a carboxyl group, but preferably,
Hydroxides of alkali metals, alkaline earth metals and the like and various amines, particularly alkali metal hydroxides, the amount of which is 0.8 relative to 1 equivalent of the carboxyl group in the polycondensation resin. ~ 1.4 equivalents are preferred. The neutralizing agent may be used as it is, or may be diluted and dissolved in a very small amount of water before use.

The content of the polycondensation resin in the binder composition of the present invention varies depending on the method of using the binder composition, but is preferably 10 to 10 from the balance of required strength and stability of the dispersion. 70% by weight, more preferably 30
-60% by weight.

Further, in the binder composition of the present invention, in addition to the polycondensation resin, it is also possible to appropriately use other resins as long as the desired effects of the present invention are not impaired.

The curing agent used in the binder composition of the present invention may be an oil-soluble curing agent or a water-soluble curing agent. When the curing agent is dissolved or dispersed in water, it is preferable to dissolve it by using a water-soluble curing agent from the viewpoints of curing speed and workability. Examples of the oil-soluble curing agent include organic peroxides and azo-based polymerization initiators, and organic peroxides having high reactivity are preferable. On the other hand, examples of the water-soluble curing agent include persulfate, hydrogen peroxide, and water-soluble peroxide.

Examples of the organic peroxide include diacyl peroxides, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxydicarbonates, peroxyesters and the like. . Diacyl peroxides, hydroperoxides and ketone peroxides are preferable from the viewpoint of having a large amount of active oxygen and a small activation energy. Specific preferred examples include diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, stearoyl peroxide, and the like, and as ketone peroxides,
Methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide and the like can be mentioned. Hydroperoxides include t-amyl hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. , Cumene hydroperoxide and the like. In addition, as peroxyketals,
1,1-di (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) 3,3 , 5-trimethylcyclohexane,
1,1-di (t-butylperoxy) cyclohexane,
1,1-di (t-amylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-amylperoxy) cyclohexane, n-butyl-4,4-di (t-
Butyl peroxy) valerate and the like, and as dialkyl peroxides, dicumyl peroxide,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-
t-Butyl peroxide, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3,1,3-
Examples of the peroxydicarbonates include di (2-t-butylperoxyisopropyl) benzene and the like, examples of the peroxydicarbonates include bis (4-t-butylcyclohexyl) peroxydicarbonate, and the peroxyesters.
t-butylperoxy-2-ethylhexanoate, t
-Hexyl peroxyisopropyl monocarbonate,
t-butyl peroxyisopropyl monocarbonate,
t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, bis (t
-Butylperoxy) isophthalate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate and the like.

As the azo-based polymerization initiator, 2,2 '
-Azobis-isobutyronitrile [1 minute half-life temperature (hereinafter, the same): 116.0 ° C], 2,2'-azobis-2
-Methylbutyronitrile [119.0 ° C], 2,2'-
Azobis-2,4-dimethylvaleronitrile [104.
0 ° C.], 1,1′-azobis-1-cyclohexanecarbonitrile [141.0 ° C.], dimethyl-2,2′-azobisisobutyrate [119.0 ° C.], 1,1′-azobis- ( 1-acetoxy-1-phenylethane) [1
11.0 ° C.] and the like. These curing agents may be used alone or in admixture of two or more. Of these curing agents, diacyl peroxides and ketone peroxides are particularly preferable.

As the water-soluble curing agent, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate,
2,2-azobis (2-amidinopropane) dihydrochloride,
Examples thereof include water-soluble azo compounds such as 4,4-azobis (4-cyanovaleric acid) and hydrogen peroxide. These curing agents may be used alone or in admixture of two or more.

The content of the curing agent in the binder composition of the present invention is from the viewpoint of the required curing rate and the balance between the strength of the colored pavement and the storage stability of the binder composition. It is preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 15 parts by weight, relative to 100 parts by weight of the polycondensation resin contained in (1). The curing agent may be internally added to the polycondensation resin so that the content of the curing agent in the binder composition agent is preferably within the above range. As the internal addition method, for example, a polycondensation resin and a curing agent are dissolved in an organic solvent, water and, if necessary, a surfactant and the like are added and the organic solvent is distilled off to invert the phase to an aqueous system. Methods and the like. Further, the curing agent may be further added in water, if desired. When a curing accelerator is present in water, it is preferable to add it immediately before coating from the viewpoint of storage stability of the binder composition.

The curing accelerator used in the binder composition of the present invention may be an oil-soluble curing accelerator or a water-soluble curing accelerator. When the curing accelerator is dissolved or dispersed in water, it is preferable to use a water-soluble curing agent to dissolve it from the viewpoint of curing speed and workability. The oil-soluble curing accelerator is not particularly limited as long as it does not inhibit the desired effects of the present invention, and examples thereof include aniline derivatives, toluidine derivatives, metal soaps, thiourea derivatives and the like. Examples of the water-soluble curing accelerator include sulfites such as sodium sulfite and sodium hydrogen sulfite, divalent iron salts, L-ascorbic acid, and sodium L-ascorbate.

Preferred specific examples of the oil-soluble curing accelerator include N, N-dimethylaniline as the aniline derivative, p-toluidine as the toluidine derivative, and naphthene as the metal soap. Examples thereof include cobalt acid, and examples of the thiourea derivative include Rongalit. These curing accelerators can be used alone or in admixture of two or more.

The content of the curing accelerator in the binder composition of the present invention is determined from the viewpoint of the required curing rate and the balance between the strength of the colored pavement and the storage stability of the binder composition. The amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the polycondensation resin contained in the product. The curing accelerator may be internally added to the polycondensation resin so that the content of the curing accelerator in the binder composition is preferably within the above range. The method of internal addition may be the same method as in the case of the curing agent. Further, the curing accelerator may be further added in water, if desired. When a curing agent is present in water, it is preferable to add it just before coating from the viewpoint of storage stability of the binder composition.

When the curing agent and / or the curing accelerator is added to the binder composition of the present invention immediately before coating, it is preferably dissolved in water or a water-soluble solvent in advance. Examples of the water-soluble solvent include acetone, methyl ethyl ketone (MEK), ethanol, isopropanol and the like.

Examples of the colorant used in the present invention include color pigments such as red iron oxide, carbon black, titanium oxide, and phthalocyanine blue, which may be used depending on the application. Regarding black color, India ink in which carbon black is dispersed is desirable from the viewpoint of weather resistance. The content of the colorant in the binder composition is 0.1 to 50% by weight, more preferably 0.5 to 50% by weight from the viewpoint of the curing rate and the physical properties of the pavement.
It is 30% by weight.

From the viewpoint of increasing the crosslink density of the resin after curing, the binder composition of the present invention comprises a compound having two or more radically polymerizable unsaturated bonds (hereinafter referred to as unsaturated bond
It is preferable to further include a compound having one or more).

The compound having two or more unsaturated bonds used in the present invention is selected from the group consisting of compounds having an allyl group, compounds having a (meth) acryl group at both ends and a compound having a divinyl group. One or more compounds may be mentioned. Among these, when the binder composition of the present invention is applied to pavement, for example, when the binder composition is heated and used, in a heated molten state before curing, a polycondensation resin is used. Has a function of reducing the melt viscosity of the resin, and has a high reactivity with the decrease of the melt viscosity of the resin, and the amount of unsaturated bonds is improved, and as a result, the crosslink density is improved. From the viewpoints of improving the strength of the colored pavement after curing, storage stability of the binder composition, odor during coating, etc., a compound containing an allyl group is preferable. Specifically, diallyl compounds such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl itaconate, diallyl hexahydrophthalate, diallyl phthalate prepolymer, diallyl isophthalate prepolymer and 1,
More preferred are triallyl compounds such as triallyl 2,4-benzenetricarboxylate.

The compounds having both-end (meth) acrylic groups include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butylene glycol. Dimethacrylate, 1,6-hexanediol dimethacrylate, etc., triethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate and the like are preferable. As the compound having a divinyl group, divinylbenzene, divinylnaphthalene and the like are preferable. These compounds having two or more unsaturated bonds may be used alone or in combination of two or more.

The content of the compound having two or more unsaturated bonds in the binder composition of the present invention is from the viewpoint of increasing the strength of the colored pavement and improving the heat resistance and water resistance of the polycondensation resin 100. The amount is preferably 0.5 to 80 parts by weight, more preferably 1 to 60 parts by weight, based on parts by weight. The compound having two or more unsaturated bonds is preferably used by being internally added to the polycondensation resin from the viewpoint of further increasing the participation in the crosslinking reaction. In such a case, the content of the compound having two or more unsaturated bonds in the binder composition may be internally added so that it is preferably within the above range. The method of internal addition may be the same method as in the case of the curing agent. A compound having two or more unsaturated bonds may be added just before coating.

Further, in the binder composition of the present invention, in addition to the above-mentioned components, various known additives such as UV absorbers such as benzotriazole and benzophenone, antifungal agents such as chloromethylphenol, EDTA and the like. Chelating agent,
Fillers such as sulfite, calcium carbonate and talc, oxygen absorbers and the like may be added within a range that does not impair the effects of the present invention.

Further, isocyanates such as MDI can be added to further increase the crosslink density of the resin after curing.

Examples of water used in the binder composition of the present invention include tap water, ion-exchanged water and distilled water, but are not particularly limited as long as the desired effects of the present invention are not impaired. Absent. The content is adjusted so that the total amount becomes 100% by weight when the components other than water are contained.

The self-dispersible water-based resin dispersion of the present invention (hereinafter referred to as "resin dispersion") is specifically the resin A described above.
Is an aqueous dispersion of a resin, which is an aqueous dispersion of a resin obtained by dispersing the resin B in water or the resin B in water, and is suitable for preparing the binder composition of the present invention. Used.

The polycondensation resin contained in the resin dispersion is the same as the polycondensation resin described above. The content thereof in the resin dispersion is preferably 10 to 60% by weight, more preferably 20 to 50% by weight. The amount of the internally added curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 100 parts by weight of the polycondensation resin.
~ 15 parts by weight. On the other hand, the amount of the curing accelerator internally added is preferably 0. 0, based on 100 parts by weight of the polycondensation resin.
The amount is 01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight. Further, if desired, a hardening agent and / or a hardening accelerator may be contained in water. When both the curing agent and the curing accelerator are contained in water, it is preferable not to contact them directly during storage of the resin dispersion. For example, it is preferable that either one of the curing agent and the curing accelerator be added and used immediately before coating.
The mode of addition at that time is preferably the same as in the case of the binder composition. Further, other components than the curing agent and the curing accelerator, for example, a compound having two or more of the above unsaturated bonds may be contained in water and / or may be internally added to the polycondensation resin. The water used for the resin dispersion is also the same as above, and its content is adjusted so that the total amount of the water and the components other than water in the resin dispersion is 100% by weight.

Next, a method for producing the binder composition of the present invention will be described. The binder composition is, for example, the following component: (1) A self-dispersion type resin obtained by dispersing a condensation-polymerized resin (resin A) having a radical-polymerizable unsaturated bond internally added with a curing agent in water. Water-based resin dispersion, (2) self-dispersible water-based resin dispersion obtained by dispersing a polycondensation resin (resin B) having a radical-polymerizable unsaturated bond internally added with a curing accelerator in water, 3) Colorant (4) A curing agent, and (5) A curing accelerator can be produced by mixing all components or appropriate components by selecting and combining them by a conventional method.

Preferably, the self-dispersion type aqueous resin dispersion of (1) and (2), the colorant, the curing agent and the curing accelerator are appropriately combined and mixed by a conventional method. Other components than the polycondensation resin, the colorant, the curing agent, and the curing accelerator may be appropriately added at the time of the mixing and mixed together.

The binder composition of the present invention comprises the above (1) to (1).
All of (5) or appropriately selected components can be mixed in advance to prepare a preparation (aspect A), or they can be mixed immediately before use to form a preparation (aspect B). . Further, other components than the polycondensation resin, the colorant, the curing agent and the curing accelerator can be used in the same manner.

The resin dispersion is produced by phase inversion emulsification or the like. For example, when the polycondensation resin and the colorant, the curing agent or the curing accelerator are internally added to the polycondensation resin, other components such as a compound having two or more unsaturated bonds are further added. It is manufactured by dissolving the component of (1) in an organic solvent, adding the above-mentioned water and, if desired, a surfactant and the like, distilling off the organic solvent, and inverting the phase to an aqueous system. The phase inversion is
It may occur when water is added, but from the viewpoint of obtaining a stable resin water dispersion, it is preferable that it occurs during the distillation of the organic solvent. Incidentally, in the case of containing a colorant, a curing agent, a curing accelerator, and other components in water,
It may be appropriately mixed during or after the production of the resin dispersion containing the polycondensation resin and water.

Examples of the organic solvent include a ketone solvent having 3 to 8 carbon atoms such as acetone, methyl ethyl ketone, and diethyl ketone, and a carbon atom having 4 carbon atoms such as tetrahydrofuran (THF).
The ether solvents of 8 to 8 are preferable, and acetone, methyl ethyl ketone and THF are more preferable. The amount of the organic solvent used is preferably 100 to 600 parts by weight of the organic solvent with respect to 100 parts by weight of the polycondensation resin used in the resin dispersion of the present invention.

The amount of water used is preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the polycondensation resin used in the resin dispersion of the present invention. In this case, acetylene glycol compounds in water, various anions, surfactants such as nonions, particularly higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, dialkyl sulfosuccinates, β-naphthalene sulfonic acid formalin condensate salts, etc. It is preferable to add about 1 to 20 parts by weight to 100 parts by weight of the polycondensation resin, because the average particle size of the resin fine particles can be reduced and the resin concentration can be increased.

The organic solvent is preferably distilled off under reduced pressure at 25 to 70 ° C., and the content of the organic solvent is preferably 1% by weight or less, more preferably 0.1% by weight or less.
It is desirable to adjust the amount to be less than or equal to weight%. Further, it is more preferable to adjust the pH of the obtained treatment liquid to be 6 to 10. The above-mentioned neutralizing agent and the like can be used to adjust the pH.

The average particle size of the polycondensation resin contained in the resin dispersion can be adjusted by changing the molecular weight, acid value, degree of neutralization, phase inversion emulsification conditions, etc. of the polycondensation resin used. Can be adjusted.

The binder composition of the present invention is excellent in coating workability and safety, and also excellent in curability and storage stability. Heating may be performed to increase the curing speed. By uniformly coating the binder composition of the present invention on pavement, a colored pavement colored with the binder composition of the present invention can be obtained. Further, if desired, a colored pavement can be obtained by applying a composition obtained by adding an aggregate or other additives to the binder composition. Examples of other additives include fillers, peeling preventing agents, antioxidants and the like. Examples of aggregates include sand, crushed stone, crushed stone, gravel, recycled aggregate, and ceramics. When the aggregate is added, the content of the aggregate is preferably 5 to 90% by weight, and more preferably 20 to 85% by weight.

[0057]

EXAMPLES Resin Production Example 1 Preparation of Polyester Resin 3500 g of bisphenol A propylene oxide adduct (average number of moles added: 2.2 moles), fumaric acid 1160
g (100 mol% in all acid components), hydroquinone 0.3
g and 8.4 g of dibutyltin oxide under nitrogen stream 16
The reaction was carried out at 0 ° C for 4 hours. Then, the temperature was raised to 200 ° C., and the reaction was carried out under normal pressure for 1 hour and under reduced pressure of 9.33 kPa for 1 hour. The physical properties of the obtained polyester resin are acid values.
The solid (AV) was 23.0 mgKOH / g, the softening point (Tm) was 95.1 ° C, and the glass transition point (Tg) was 81.3 ° C. This is referred to as resin (1). For the softening point, use a Koka type flow tester (manufactured by Shimadzu Corporation) and load 20 kg.
f (196N), orifice diameter 10 mm, orifice length 1 mm, the temperature was measured at a temperature rising condition of 3 ° C./min. Further, the glass transition point is 1 by a differential scanning calorimeter, DSC200 (manufactured by Seiko Denshi KK).
The measurement was performed under the temperature rising condition of 0 ° C./min, and the value was obtained by the tangent method.

Resin Production Example 2 Preparation of Polyester Polyamide Resin Bisphenol A-ethylene oxide adduct (average addition mole number: 2.1) 650 g (2 mole), ethylene glycol 217 g (3.5 mole), hydrogenated bisphenol A 840 g ( 3.5 mol), meta-xylene diamine 1
36 g (1 mol), 1009 g of maleic anhydride (10.
3 mol) and 0.4 g of hydroquinone were reacted at 160 ° C. for 4 hours under a nitrogen atmosphere. Then, after raising the temperature to 200 ° C., the reaction was carried out at normal pressure for 1 hour, and further under reduced pressure of 9.33 kPa for 1 hour. The physical properties of the obtained resin are: AV 25 mgKOH / g, iodine value 78.6, Tm 105.
C., Tg was 55.degree. C. solid. This is referred to as resin (2).

Example 1 (1) Preparation of Resin Dispersion (A-1) 300 g of the above resin (1), 15 g of benzoyl peroxide (trade name: Niper BW, manufactured by NOF CORPORATION), and 45 g of diallyl phthalate were added to 540 g of methyl ethyl ketone.
Dissolved in. Then 30% sodium hydroxide 16.
Neutralize by adding 4 g, and ion-exchanged water 750 g under stirring
Then, methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure to adjust the water content, and then a thermosetting self-dispersible water-based polyester resin dispersion (average particle diameter: 0.52 μm, solid content: 3) was added.
5% by weight) was obtained [resin dispersion (A-1)].

(2) Preparation of Resin Dispersion (A-2) 300 g of the above resin (1), 15 g of methyl ethyl ketone peroxide (trade name: Permec N, manufactured by NOF CORPORATION),
And diallyl phthalate (45 g) with methyl ethyl ketone (5)
It was dissolved in 40 g to obtain a thermosetting self-dispersible aqueous polyester resin dispersion (average particle diameter: 0.52 μm, solid content: 35% by weight) in the same manner as the resin dispersion (A-1). Resin dispersion (A-2)].

(3) Preparation of Resin Dispersion (A-3) 300 g of the above resin (2), 15 g of methyl ethyl ketone peroxide (trade name: Permec N, manufactured by NOF CORPORATION),
And diallyl phthalate (45 g) with methyl ethyl ketone (5)
It was dissolved in 40 g to obtain a thermosetting self-dispersible aqueous polyester resin dispersion (average particle size: 0.64 μm, solid content: 35% by weight) in the same manner as the resin dispersion (A-1). Resin dispersion (A-3)].

(4) Preparation of Resin Dispersion (B-1) 300 g of the above resin (1), 6 g of dimethylaniline, and 30 g of diallyl phthalate were added to methyl ethyl ketone 540.
g, and 16.4 g of 30% sodium hydroxide was added for neutralization, 750 g of ion-exchanged water was added under stirring, and then methyl ethyl ketone was distilled off at 40 ° C. under reduced pressure to adjust the water content. A thermosetting self-dispersible aqueous polyester resin dispersion (average particle diameter: 0.55 μm, solid content: 35% by weight) was obtained [resin dispersion (B-1)].

Examples 2 to 9 The resin dispersion, colorant, curing agent, curing accelerator and aggregate prepared in Example 1 were mixed according to the formulation (parts by weight) of Table 1,
A binder composition was prepared. Next, after pouring the binder composition into an aluminum cup, the mixture was left at room temperature, and the time until it did not stick to the finger even when touched with the finger was measured as the curing time (minutes). If the curing time is within 30 minutes, ◎, 30
If more than 1 minute and less than 1 hour, it was rated as ◯.

The binder composition was coated on pavement, and the coating workability was evaluated by the presence or absence of unpleasant odor at that time. The above results are also shown in Table 1.

[0065]

[Table 1]

From Table 1, it is understood that the curing time of the binder composition of the present invention is within a time that does not cause a problem in the usual coating, and the coating workability is excellent.

[0067]

EFFECTS OF THE INVENTION According to the present invention, a colored paving binder composition having excellent coating workability and safety and capable of causing a uniform curing reaction can be obtained, and the composition can be applied to paving. Thereby, a colored pavement having practically sufficient strength can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2D051 AB03 AB04 AD01 AE01 AF01                       AG11 AG16 AH02 EA01 EA06                       EB06                 4J027 AB06 AB07 AB08 AB10 AB15                       AB16 AB18 AB19 AB23 AB25                       AB26 AC03 AC06 AD04 AJ05                       AJ08 BA03 BA18 BA19 BA20                       BA22 BA23 CA34 CB02 CB03                       CB06 CB07 CB09 CC01 CC02                       CD09

Claims (9)

[Claims] 1. A polycondensation resin (resin A) having a radical-polymerizable unsaturated bond formed by internally adding a curing agent, a colorant, a curing agent and / or a curing accelerator, and water. Binder composition for colored pavement. 2. A colored pavement binder composition comprising a polycondensation resin (resin B) having a radical-polymerizable unsaturated bond internally added with a curing accelerator, a colorant, a curing agent and water. object. 3. The colored pavement binder composition according to claim 2, further comprising a curing accelerator. 4. A condensation-polymerized resin (resin A) having a radical-polymerizable unsaturated bond internally added with a curing agent, and a condensation-polymerized resin having a radical-polymerizable unsaturated bond internally added with a curing accelerator. A colored pavement binder composition comprising a polymeric resin (resin B), a colorant and water. 5. The colored pavement binder composition according to claim 1, further comprising a compound having two or more radically polymerizable unsaturated bonds. 6. The colored pavement binder composition according to claim 1, wherein the polycondensation resin is polyester or polyester polyamide. 7. A polycondensation resin (resin B) having a radical-polymerizable unsaturated bond, which is used for preparing a colored pavement binder composition and internally added with a curing accelerator, is dispersed in water. A self-dispersion type water-based resin dispersion obtained. 8. A polycondensation resin (resin A) having a radical-polymerizable unsaturated bond, which is used for preparing a colored pavement binder composition and internally added with a curing agent, is dispersed in water. A self-dispersible aqueous resin dispersion comprising 9. A colored pavement constructed by using the binder composition for colored pavement according to claim 1.