JPH05262886A - Surface treating agent for powdered rubber and granular mass of powdered rubber prepared by using same - Google Patents

Abstract

PURPOSE:To obtain a surface treating agent for powdered rubber which gives a granular mass of powdered rubber, that is not disintegrated even when used outdoors and is excellent in water resistance and flexibility so that it can stand satisfactorily the use of spiked shoes, etc., thereon. CONSTITUTION:The title treating agent comprises at least an organic monocarboxylic acid, a metal salt of an organic monocarboxylic acid and a polyol compound such as a polyether compound. The granular mass of powdered rubber is obtained by mixing 0.5-30 pts.wt. surface treating agent with 100 pts.wt. powdered rubber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdered rubber surface treating agent and agglomerate agglomerates using the same, and in particular, a powdered rubber surface treatment for agglomerating powdery rubber powder to construct an elastic pavement. The agent relates to the aggregated mass.

[0002]

2. Description of the Related Art A method for constructing a pavement using powdery rubber is disclosed in JP-A-49-126777 and JP-A-50.
No. 34, Japanese Patent Publication No. 51-20233, Japanese Patent Publication No. 2-31165 and the like disclose methods using liquid polyurethane as a binder for powder rubber.

[0003] However, these methods have a drawback that although the aggregated mass obtained has a compression resistance, the flexibility due to bending is poor and cracks easily occur. Therefore, Japanese Patent Application Laid-Open No. 63-19303 proposes a method of pretreating powdery rubber with a polybutadiene-based polyol.

However, even if it is treated with the above-mentioned pretreatment agent, a sufficient solution to the flexibility and cracking of the agglomerate is not yet obtained. Further, as the conventional powdered rubber agglomerates, in addition to those obtained by treating powdered rubber with a pretreatment agent as described above, those obtained by using latex, resin emulsion, etc. have been proposed. The obtained agglomerates do not have enough water resistance, so they may collapse during outdoor use, and cannot be used as pavements. It is limited to use in a completely sealed condition by sealing the top and bottom. Further, the one using latex or the like has a problem that it requires high-temperature and high-pressure press molding for agglomeration of aggregates, and requires long-term curing.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a pavement which, even when it is used outdoors, has the ability to prevent collapse of aggregated aggregates, have flexibility, and prevent walking wear erosion especially by spikes. The present invention provides a powdered rubber surface treatment agent for obtaining a powdered rubber aggregated material having excellent water resistance during production, and a powdered rubber aggregated material using the same.

[0006]

The inventors of the present invention have completed the present invention as a result of earnest research in order to solve the above problems.

That is, the present invention is a powder rubber surface treating agent comprising at least an organic monocarboxylic acid, an organic monocarboxylic acid metal salt and a polyol compound, and is characterized in that a polyether compound is particularly used as the polyol compound. Further, the present invention provides a powdered rubber agglomerate comprising a powdered rubber surface treating agent, particularly 0.5 to 30 parts by weight based on powdered rubber.

The powdery rubber aggregate of the present invention is excellent in durability by pretreatment with the powdery rubber surface-treating agent having the specific composition of the present invention.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The organic monocarboxylic acid as a powdery rubber surface treating agent used in the present invention is selected from formic acid, acetic acid, propionic acid, octylic acid, lauric acid, stearic acid and the like at room temperature. It is preferable that the liquid has a low odor.

The organic monocarboxylic acid metal salt of the powdery rubber surface treating agent used in the present invention includes, for example, potassium formate, sodium acetate propionate, calcium octylate, lead octylate, dibutyltin dilaurate, stanna octate, Those selected from lauric acid, calcium stearate, etc.

The polyol compound of the powder rubber surface treating agent used in the present invention is, for example, polyester polyols, polyether polyols, polyester polyamide polyols, polycarbonate polyols, polycaprolactone polyester polyols, polybutadiene polyols, polybutadiene polyols, It is selected from pentadiene polyols, castor oil-based polyols, low molecular weight diols, trimethylolpropane, glycerin, sorbitol, mannitol, dulcitol and the like. Among these, preferably, the molecular weight is 200 to 10,000.
Polyether polyols of a degree, low molecular weight diol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol, ethylenediamine, tolylenediamine, diphenylmethanediamine, tetramethylolcyclohexane, methyl glucoside, 2,2,2. Alkylene oxide starting from 6,6-tetrakis (hydroxylmethyl) cyclohexanol, diethylenetriamine, sorbitol, mannitol, sucrose, etc.
It is the one to which ethylene oxide, propylene oxide, etc. are added.

The liquid polyurethane referred to in the present invention is an organic isocyanate compound such as 2,4-tolylene diisocyanate (abbreviated as TDI), 65 / 35-TDI, 8
0 / 20-TDI, 4,4'-diphenylmethane diisocyanate (abbreviated as MDI), dianisidine diisocyanate, tridene diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, Organic polyisocyanate compounds selected from aromatic diisocyanates and alicyclic diisocyanates such as 1,5 naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated MDI and hydrogenated TDI, or these Of the NCO group-containing prepolymers obtained by reacting a polyol alone or a mixture thereof with an NCO / OH equivalent ratio of 1.5 or more, more preferably from 1.5 to 20. Or the isocyanate Those of a two-part formed by combining an active hydrogen compound which reacts with bets compound.

The viscosity of the powdery rubber surface treating agent of the present invention is 3
00 to 20000 cps is preferable. The powdered rubber surface treating agent of the present invention is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the granular rubber. If it is less than this range, a sufficient bonding force of the rubber aggregate is not obtained, and if it is too large, the rubber aggregate shows foaming and the hardness is lowered, which is not preferable.

Known curing catalysts used in polyurethane resins and epoxy resins to accelerate the curing of the agglomerating agent used in the present invention can be used.

Examples of the curing catalyst include trimethylamine, triethylamine, tributylamine, N-dimethyllaurylamine, N-diethyllaurylamine,
N, N'-methylpiperazine, N, N'-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N-pentamethylethylenetriamine, N, N, N ', N'-tetramethylpropylene Any of diamines and tertiary amines such as N-polymethyl polyethylene polyamine may be used as long as they are composed of a single substance or a mixture thereof.

The amount of these curing catalysts used is preferably 0.01 to 1.0 part by weight, more preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the organic polyisocyanate compound.
0.50 parts by weight is used.

The powdered rubber powder used in the present invention includes natural rubber, polyisoprene rubber, styrene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile rubber, ethylene / propylene rubber, chlorosulfonated polyethylene, urethane rubber, acrylic rubber, and many other rubbers. A pulverized product of a rubber product such as a tire or a tube produced from a sulfide rubber, etc., and a pulverized product in the range of 0.001 to 20 mm can be used alone or in combination.

The powder rubber agglomerate of the present invention is a state in which a powdery granular material has voids without breaking the shape thereof, and powdery granular particles such as a columnar shape, a rectangular shape, a disk shape, and a plate shape are aggregated together. It is solidified. The size is 1 mm to 30 cm x 1
It is a molded product having a size of about mm to 30 cm x 1 mm to 30 cm, or a plate-like one in which the mixture is directly applied to the asphalt surface or the concrete surface. The surface-treating agent of the present invention is usually added to and mixed with a dry powdery or granular rubber material, but a powdery or granular rubber material containing moisture may be used.

The powdery rubber surface treating agent of the present invention may contain a plasticizer, a process oil, a stabilizer and an ultraviolet absorber in combination within a range not impairing the effects of the present invention. As a plasticizer,
Dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate,
Phthalic acid derivatives such as ditridecyl phthalate, diundecyl phthalate and benzyl phthalate; Isophthalic acid derivatives such as dimethyl isophthalate and di (2-ethylhexyl) isophthalate; Tetrahydro such as di (2-ethylhexyl) tetrahydrophthalate and dioctyl tetrahydrophthalate Phthalic acid derivatives; adipic acid derivatives such as dibutyl adipate, dioctyl adipate, diisodecyl adipate, diisononyl adipate; azelaic acid derivatives such as diisooctyl azelate, diisooctyl azelate; sebacic acid derivatives such as dibutyl sebacate and dioctyl sebacate Maleic acid derivatives such as dibutyl maleate, dimethyl maleate, dioctyl maleate; maleic acid derivatives such as dibutyl fumarate, dioctyl fumarate ; Citric acid derivatives; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; sulfonic acid derivatives, glycol derivatives; trimellitic acid derivatives such as trioctyl trimellitate glycerin derivatives.

The method for producing powdered rubber aggregates by the surface treatment agent of the present invention is as follows: 1) powder rubber is mortar mixer;
It is put in a disper, a kneader, etc., and the surface treatment agent of the present invention is added with stirring and mixed until the whole shows a wet state. 2) Add a prescribed amount of liquid polyurethane and mix until uniform. 3) The mixture is put into a mold having a predetermined shape, lightly pressed and statically cured by moisture, and taken out from the mold to produce an aggregated mass. 4) Alternatively, the mixture is put into a mold having a predetermined shape, lightly pressed and then water, warm water, steam or the like is poured into the molded product, and the mixture is allowed to stand and harden to be taken out from the mold to produce an aggregated mass. 5) Alternatively, the mixture is poured on a grooved belt conveyor provided in a direction perpendicular to the traveling direction, a wire mesh belt conveyor, or the like,
Water, warm water, water vapor and other water are poured into the mixture and cured on a belt conveyor to produce agglomerates. 6) Further, the powdery rubber is treated with a surface treatment agent and a binder is added, and the mixture is spread directly on the asphalt surface and / or concrete surface to a desired thickness, and then rolled into a plate shape by rolling with a roller, a metal iron, or the like.

[0021]

EXAMPLES The present invention will be described in detail with reference to Examples. The invention is not limited to these examples only. Also, "part" and "%" in the text are based on weight unless otherwise specified.

Example 1 Average molecular weight of 2 in a 1-liter flask
000 polyoxypropylene diol [Product name Hyprox DP-200 manufactured by Dainippon Ink and Chemicals, Inc.
0] 1000 g, stearic acid 50 g, and calcium octylate 30 g were weighed and mixed to prepare a treating agent A. Next, 20 g of treating agent A was added to 900 g of tire powder and uniformly mixed, and 120 g of polyoxypropylene diol having an average molecular weight of 1000 [Hyprox DP-1000 manufactured by Dainippon Ink and Chemicals, Inc.] and TDI [Mitsubishi] One-component type binder [Dainippon Ink and Chemicals, Inc.] synthesized from 80 g of Kasei Dow Co., Ltd. trade name TDI80 and MDI [Mitsubishi Kasei Dow Co., Ltd. trade name Isonate 143L].
225 g of trade name Pandex TP-1221] was added and uniformly mixed, and then applied on a release paper to a thickness of 15 mm. When this product was left as it was for 15 hours, elastic aggregates could be obtained. Even if this aggregated mass was bent, it was highly flexible and did not break into two from the center.

Example 2 Average molecular weight of 4 in a 1-liter flask
00 polyoxypropylene diol [Dainippon Ink and Chemicals, Inc., trade name Hyprox DP-400] 1
A treating agent B was prepared by weighing and mixing 000 g, 10 g of acetic acid and 5 g of stannous acetate. 20 g of the treating agent B was added to 900 g of rubber powder having a particle diameter of 1 mm and mixed for 3 minutes with a mixer, and then 225 g of the one-pack type binder of Example 1 was added and uniformly mixed, and then a JIS sidewalk plate (30 × 30 × 5 cm) was used. ) Was pressed to a thickness of 1.5 cm. This product was strong enough not to be damaged even when the end part was stepped on with spike shoes after 24 hours.

Example 3 Average molecular weight of 2 in a 1-liter flask
1,000 g of polybutadienediol (trade name: Poly bdG-2000 manufactured by Nippon Soda Chemical Co., Ltd.) and 400 g of process oil [Hizoru SAS-296] (Nippon Petroleum Industry Co., Ltd.), 10 g of octylic acid, 20 g of stannous octoate. , Lead octylate 30 g are weighed and mixed to prepare a treating agent C
Was prepared. Rubber powder 90 with a particle size of 1 mm
In addition to 0 g, the mixture was mixed for 3 minutes with a mixer, 125 g of the one-component binder of Example 1 was added and uniformly mixed, and 430 g was filled into a 300 × 150 × 10 mm mold and press-molded at 100 ° C. for 20 minutes. did. Although the molded product was taken out and bent to 180 degrees immediately, it was tough without breaking.

Example 4 Treatment Agent A used in Example 1
Was added to 900 g of rubber powder having a particle diameter of 1 mm and mixed for 3 minutes with a mixer, and 125 g of the one-pack binder of Example 1 was added and uniformly mixed to obtain 430 g.
It was filled in a mold of 0 × 150 × 10 mm and press-molded at 100 ° C. for 20 minutes. When the molded product was taken out and immediately bent at 180 degrees, a crack was slowly generated on the surface, but it was not damaged.

[Example 5] Treatment agent C used in Example 3
(120 g) was added to 900 g of rubber powder having a particle diameter of 1 mm and mixed for 3 minutes with a mixer, and then 225 g of the one-component binder of Example 1 was added and uniformly mixed to obtain 430 g.
It was filled in a mold of 0 × 150 × 10 mm and press-molded at 100 ° C. for 20 minutes. Although the molded product was to be taken out from the mold after a lapse of a predetermined time, it was in a weakly cured state such that the end of the molded product was missing. This was cured by allowing it to stand at room temperature until the next day. After standing, the molded body was bent at 180 degrees and a crack was generated in the central portion.

Comparative Example 1 900 g of tire powder of Example 1
90 g of polyoxypropylene diol having an average molecular weight of 2000 (trade name Hyprox DP-2000 manufactured by Dainippon Ink and Chemicals, Inc.) is added and mixed uniformly, and then 225 g of the one-pack type binder used in Example 1 is added. In addition, after uniformly mixing, it was spread evenly on a release paper to a thickness of 15 mm and cured.

Although the cured product had elasticity, when it was bent, a crack was generated in the surface portion. [Comparative Example 2] Polyoxypropylene diol [Hyprox DP-2000, trade name, manufactured by Dainippon Ink and Chemicals, Inc.] having an average molecular weight of 2000 in a 1-liter flask is 100
Processing agent D was prepared by weighing and mixing 0 g and 50 g of stearic acid. Next, 20 g of the treating agent D was added to 900 g of tire powder and uniformly mixed, and 225 g of the one-component binder of Example 1 was added and uniformly mixed, and the mixture was applied to a release paper having a thickness of 15 mm. This is as it is 15
After standing for a time, elastic aggregates could be obtained. This agglomerate was highly flexible, but when it was bent, a crack was generated in the center.

[Comparative Example 3] Average molecular weight of 4 in a 1-liter flask
00 polyoxypropylene diol [Dainippon Ink and Chemicals, Inc., trade name Hyprox DP-400] 1
A treating agent E was prepared by weighing and mixing 000 g and 5 g of stannous acetate. 900g of rubber powder with a particle size of 1mm
Was mixed for 3 minutes with a mixer, and then 225 g of the one-component binder of Example 1 was added and uniformly mixed.
JIS sidewalk board (30 x 30 x 5 cm) with a thickness of 1.5 cm
It was applied to the thickness of. This was an elastic body after 24 hours had passed, but when the end was stepped on with spike shoes, the heel part was missing.

[Comparative Example 4] Polybutadiene polyol having an average molecular weight of 2000 [trade name: po manufactured by Idemitsu Petrochemical Co., Ltd.]
lybdR-45HT] 18 g of rubber powder 9 mm in particle shape
In addition to 00g, after mixing for 3 minutes with a mixer, Example 1
225 g of the one-component binder was added and uniformly mixed, and the mixture was applied onto release paper having a thickness of 15 mm. When this product was left as it was for 15 hours, elastic aggregates could be obtained. This aggregate was highly flexible, but when it was bent, a crack was generated in the center.

From the above results, it was confirmed that the rubber powder surface-treating agent of the present invention imparts durability to the aggregate of rubber chips when used particularly in the aggregate of rubber chips.

[0032]

EFFECTS OF THE INVENTION The aggregates obtained by using the powdery rubber surface treating agent of the present invention have excellent water resistance, so that the aggregates do not disintegrate and need not be used indoors. Can have sufficient flexibility. In addition, such agglomeration of aggregates does not require a large amount of equipment and can be widely applied.

Claims (4)

[Claims] 1. A powder rubber surface treating agent comprising at least an organic monocarboxylic acid, an organic monocarboxylic acid metal salt and a polyol compound. 2. The powdery rubber surface treating agent according to claim 1, wherein a polyether compound is used as the polyol compound. 3. A powder rubber agglomerate obtained by treating powder rubber with the surface treatment agent for powder rubber. 4. A powdery rubber surface treating agent is powdery rubber 100.
The rubber powder agglomerate according to claim 3, which is obtained by using 0.5 to 30 parts by weight based on parts by weight.