JP3928626B2 - Flooring composition, consolidated lump and construction method using the same - Google Patents

Description

The present invention relates to a solid aggregate comprising a urethane prepolymer having a terminal isocyanate group containing 2,4′-diphenylmethane diisocyanate (abbreviated as 2,4′-MDI) excellent in flexibility, odor, curability and workability. excellent flooring composition caking strength consisting of a binding agent and the elastic granules, relates Katayuikatamari shaped flooring and construction method using it to cure it.

As a method of constructing a pavement using powdered rubber, JP-A-49-126777, JP-A-50-34, JP-B-51-20233, JP-B-2-31165, etc. There has been proposed a method using liquid polyurethane as a solidifying agent for powdered and granular rubber.

In these liquid polyurethanes, a prepolymer having an NCO group at the molecular end mainly composed of 4,4′-MDI is used. In addition, prepolymers with NCO groups at the molecular ends based on tolylene diisocyanate (abbreviated as TDI) are used less because of environmental problems, curability is slow, viscosity tends to increase, and NCO% cannot be increased. It has not been.
JP 49-126777 A, JP-A-50-34, Japanese Patent Publication No. 51-20233, Japanese Patent Publication No. 2-31165

The present invention relates to an aggregate, a flocculating agent excellent in workability, odor, curability and flexibility for producing elastic granular materials, in particular, powder / granular rubber consolidated bodies. It is an object of the present invention to provide a construction method which is excellent in flexibility and workability with an elastic flooring composition having a low viscosity of a caking agent and having good work efficiency.

In order to solve the above problems, the present inventors have completed the present invention as a result of intensive studies.

That is, the present invention relates to (a) a polyol and (b) a aggregate solidifying agent mainly composed of a urethane prepolymer having a terminal isocyanate group comprising a polyisocyanate compound.
The polyisocyanate compound (b) contains 1% by weight or more of 2,4′-diphenylmethane diisocyanate and 99% by weight or less of other organic polyisocyanate compounds (provided that 20% by weight of 2,4′-diphenylmethane diisocyanate, other The organic polyisocyanate compound is a polyisocyanate compound consisting of 80% by weight of 4,4′-diphenylmethane diisocyanate),
Other organic polyisocyanate compounds include 2,4-tolylene diisocyanate (abbreviated as TDI), 65 / 35-TDI, 80 / 20-TDI, 4,4′-diphenylmethane diisocyanate (4,4). 4'-MDI) and 2,2'-MDI alone or as a mixture, dianisidine diisocyanate, tridendiisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1,5- It is selected from aromatic diisocyanates such as naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated MDI, hydrogenated TDI, and alicyclic diisocyanates,
From the aggregate solidifying agent and the elastic granular material (c), characterized in that 2 to 25% by weight of 2,4′-diphenylmethane diisocyanate is used with respect to the urethane prepolymer of the aggregate solidifying agent. There is provided a flooring composition characterized by comprising: a flooring composition obtained by curing the flooring composition; and a floor construction method characterized by rolling the flooring composition onto a substrate.

The aggregate solidifying agent comprising the urethane prepolymer of the present invention can improve workability by including 2,4′-MDI in the polyisocyanate, thereby reducing the low odor and viscosity. Can be applied in a wide range without requiring a large amount of equipment. Moreover, since the obtained consolidated lump can maintain flexibility, it does not need to be used indoors without collapse of the consolidated lump, and has sufficient flexibility and curability to withstand use with spiked shoes. It is what you have.

(Constitution) The urethane prepolymer having a terminal isocyanate group of the present invention reacts with the polyol (a) and the organic polyisocyanate compound (b) containing 2,4′-diphenylmethane diisocyanate, and uses the isocyanate compound in excess. It is obtained by this. At this time, the amount of 2,4'-MDI, the organic polyisocyanate compound (b) 1 wt% or more in, preferably included 9.5% by weight or more. In the case of use of 1% by weight, the workability is slightly improved because the viscosity of the urethane prepolymer is lowered, but other physical properties do not change, so it is better to use 9.5% by weight or more if possible. Meanwhile, the amount of the other organic polyisocyanate compound, 99 wt% or less, preferably 90.5 wt% or less. 2,4′-MDI may be of high purity or a mixture with 4,4′-MDI, 2,2′-MDI or the like. Commercially available products include, for example, lupranate MI (2,4′-MDI 50% by weight, 4,4′-MDI 50% by weight product, manufactured by BASF Corporation).

Examples of other organic polyisocyanate compounds include 2,4-tolylene diisocyanate (abbreviated as TDI), 65 / 35-TDI, 80 / 20-TDI, 4,4′-diphenylmethane diisocyanate ( 4,4′-MDI) and 2,2′-MDI, alone or as a mixture, dianisidine diisocyanate, tridendiisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1, It is selected from aromatic diisocyanates and alicyclic diisocyanates such as 5-naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated MDI, and hydrogenated TDI.

In the production of the urethane prepolymer of the present invention, 2,4′-MDI alone or in a mixture of other organic polyisocyanate compound, polyol alone, polyol and low molecular weight diol, preferably NCO / OH equivalent ratio It is obtained by reacting at a ratio of 1.5 or more, more preferably from 1.5 to 20, and consists of an NCO group-containing urethane prepolymer alone or as a mixture. The amount of free isocyanate (NCO) groups in the urethane prepolymer thus obtained is preferably 3 to 30% by weight.

Examples of the polyol include polyester polyols, polyether polyols, polyester polyamide polyols, polycarbonate polyols, polycaprolactone polyester polyols, polybutadiene polyols, polypentadiene polyols, castor oil-based polyols, low molecular weight diols, and trimethylol. One selected from propane, glycerin, sorbitol, mannitol, dulcitol and the like. Preferred are polyether polyols and polybutadiene polyols, preferably those having a number average molecular weight of about 200 to 10,000.

Low molecular weight diols are those having a molecular weight of less than 200, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, bisphenol A, etc. is there.

Polyether polyols include the low molecular weight diol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol, ethylenediamine, tolylenediamine, diphenylmethanediamine, tetramethylolcyclohexane, methylglucoside, 2,2,6, An alkylene oxide such as ethylene oxide or propylene oxide is subjected to addition polymerization using 6-tetrakis (hydroxylmethyl) cyclohexanol, diethylenetriamine, sorbitol, mannitol, sucrose or the like as a starting material.

Examples of polybutadiene polyols include trade names polybd R-45HT, R-45M, R-15HT (Idemitsu Petrochemical Co., Ltd.), NISSO-PB G-1000, G-2000 (Nippon Soda Co., Ltd.), etc. .

The ratio is for the polyurethane prepolymers of the present invention 2,4'-diphenylmethane diisocyanate 2-25 wt%, preferably used 2 to 20 wt%.

The viscosity of the crumb consolidation agent of the present invention are preferably 300～8000Cps, particularly preferably 500~ 4 000cps.

The use amount of the aggregate-setting agent of the present invention is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the elastic granular material. When the amount is less than this range, a sufficient binding force of the rubber solid agglomerate as a flooring material cannot be obtained, and when it is too large, the rubber agglomerate agglomerate is not preferable.

In order to accelerate the curing of the aggregated caking agent of the present invention, known curing catalysts used for polyurethane resins and epoxy resins, for example, trimethylamine, triethylamine, tributylamine, N-dimethyllaurylamine, N -Diethyllaurylamine, NN'-methylpiperazine, N, N'-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N-pentamethylethylenetriamine, N, N, N'N'-tetra It is composed of tertiary amines such as methylpropylenediamine and N-polymethylpolyethylenepolyamine, and organic metal salts such as calcium octylate, lead octylate, dibutyltin dilaurate, stannous octate and the like alone or as a mixture. Any of them can be used.

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

The aggregated caking agent of the present invention can be used as an adhesive as it is, particularly as an adhesive for rubber. This rubber is a material used for the following elastic granular materials.

The aggregate solidifying agent of the present invention is used as a flooring composition by mixing elastic granules. Moreover, those curing the composition is Katayuikatamari shaped flooring.

Examples of the elastic granular material of the present invention include natural rubber, polyisoprene rubber, styrene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile rubber, ethylene / propylene rubber, chlorosulfonated polyethylene, urethane rubber, acrylic rubber, and polysulfide rubber. If the particle diameter is preferably in the range of 0.001 to 20 mm, it is used alone or in combination. be able to.

The consolidated lump of the present invention is a state in which powder particles such as a columnar shape, a square shape, a disk shape, and a plate shape are aggregated and consolidated in a state having voids without destroying the shape of the granular material. is there. The size is formed into a size of about 1 mm to 30 cm × 1 mm to 30 cm × 1 mm to 30 cm, or the mixture is directly applied to the asphalt surface or concrete surface in a plate shape. The caking aid of the present invention is usually used after being added to and mixed with a dry powdered rubber product, but it may also contain moisture.

The aggregated caking agent of the present invention can be used in combination with a plasticizer, a process oil, a stabilizer and an ultraviolet absorber as long as the effects of the present invention are not impaired.

Plasticizers include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, benzyl phthalate, and the like; dimethyl isophthalate, di ( Isophthalic acid derivatives such as 2-ethylhexyl) isophthalate; tetrahydrophthalic acid derivatives such as di (2-ethylhexyl) tetrahydrophthalate and dioctyltetrahydrophthalate; adipic acid derivatives such as dibutyl adipate, dioctyl adipate, diisodecyl adipate and diisononyl adipate; Azelaic acid derivatives such as octyl azelate and diisooctyl azelate; dibutyl sebacate, dioctyl seba Sebacic acid derivatives such as dibutyl malate, maleic acid derivatives such as dimethyl malate and dioctyl malate; maleic acid derivatives such as dibutyl fumarate and dioctyl fumarate; trimellitic acid derivatives such as trioctyl trimellitate; Examples thereof include citric acid derivatives; itaconic acid derivatives; oleic acid derivatives; ricinoleic acid derivatives; stearic acid derivatives; sulfonic acid derivatives, glycol derivatives;

The production method of the consolidated lump with the flooring composition of the present invention is as follows: 1) Put the granular rubber granules into a mortar mixer, disperser, kneader, etc., and add the aggregate solidifying agent of the present invention while stirring. Mix until the whole is wet. 2) The mixture is put into a mold (mold) having a predetermined shape, lightly pressed, allowed to stand and cure with moisture, and taken out from the mold to produce a solidified lump.

3) Or, after putting into a mold (mold) having a predetermined shape and lightly pressing it, water such as water, warm water, water vapor, etc. is poured into the molded product, left to cure, and taken out from the mold to produce a solidified lump. 4) Alternatively, the mixture is poured onto a grooved belt conveyor provided in a direction perpendicular to the traveling direction, a belt conveyor made of wire mesh, etc., and water, hot water, steam, etc. are poured onto the mixture while pouring water into the mixture. To produce a consolidated mass.

5) Further, for applying directly to the substrate indoors and outdoors, the mixture of the powder rubber granule and the aggregate solidifying agent of the present invention is directly applied to the substrate, for example, asphalt surface, wood surface or concrete surface. After spreading to thickness, it is rolled into a plate by rolling with a roller or a metal iron. If necessary, further urethane flooring may be applied.

The present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the text, “parts” and “%” are based on weight unless otherwise specified.

[Example 1]
Into 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400, 38.5 g of lupranate MI (product of Basf Co., Ltd.) was charged so that the equivalent ratio of NCO: OH was 2: 1. The reaction was carried out with stirring at 90 ° C. for 2 hours under a nitrogen stream to obtain an aggregate solidifying agent composed of a urethane prepolymer having a terminal isocyanate group having a free isocyanate group concentration of 4.5% and a viscosity at 25 ° C. of 2000 cps. .

[Example 2]
To 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400, 15.3 g of TDI and 16.3 g of lupranate MI were charged so that the equivalent ratio of NCO: OH was 2: 1. The reaction was carried out with stirring at 90 ° C. for 2 hours under an air stream to obtain an agglomerate solidifying agent composed of a urethane prepolymer having a terminal isocyanate group having a free isocyanate group concentration of 4.6% and a viscosity at 25 ° C. of 3000 cps.

Example 3
16.5 g of TDI and 6.0 g of Lupranate MI and 4,4 ′ so that the equivalent ratio of NCO: OH is 2: 1 to 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400 -Prepared with 9.0 g of MDI, reacted with stirring at 90 ° C for 2 hours under a nitrogen stream, and composed of a urethane prepolymer having a terminal isocyanate group with a free isocyanate group concentration of 4.7% and a viscosity at 25 ° C of 3500 cps. Aggregate caking agent was obtained.

[Examples 4 to 6]
Aggregate consolidation agent consisting of urethane prepolymer obtained in Examples 1 to 3 To 100 parts of each, 900 g of tire powder having a particle size of 0.1 to 3 mm was added and mixed uniformly for 5 minutes, and then the formwork Lightly tamped to 1 × 30 × 15 (cm). When it was solidified and demolded after 24 hours at 25 ° C., an elastic-like solidified lump having elasticity was obtained. This material was allowed to stand for 1 week, and the basic physical properties (hardness, tensile strength, elongation, tear strength) were measured. Table 2 shows the results.

[Comparative Example 1]
4,4′-diphenylmethane diisocyanate (Nippon Polyurethane Co., Ltd. product, MDI) so that the equivalent ratio of NCO: OH is 2: 1 to 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400 23.0 g and liquid 4,4′-diphenylmethane diisocyanate [Mitsubishi Chemical Corporation, trade name isonate 143 L] 18.0 g were charged, reacted under stirring at 90 ° C. for 2 hours under a nitrogen stream, and released. isocyanate group concentration of 4.5% to obtain a urethane prepolymer having a terminal isocyanate groups of 5 000Cps viscosity 25 ° C..

[Comparative Example 2]
Tolylene diisocyanate (Mitsubishi Chemical Corporation product, T-80, TDI) so that the equivalent ratio of NCO: OH is 2: 1 to 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400 26.7 g), and a urethane prepolymer having a terminal isocyanate group having a free isocyanate group concentration of 4.8% and a viscosity at 25 ° C. of 100,000 cps under stirring at 90 ° C. for 2 hours under a nitrogen stream. Got.

[Comparative Example 3]
7.4 g of TDI and liquid 4,4′-diphenylmethane diisocyanate [Mitsubishi] so that the equivalent ratio of NCO: OH is 2: 1 to 100 g of polyoxypropylene diol having an average molecular weight of 2000 and 10 g of polyoxypropylene diol having an average molecular weight of 400 Chemical Co., Ltd. trade name “Isonate 143L”] 30.0 g was charged and reacted with stirring at 90 ° C. for 2 hours under a nitrogen stream to obtain a free isocyanate group concentration of 4.6% and a terminal isocyanate group having a viscosity at 25 ° C. of 3400 cps. A urethane prepolymer having the following was obtained.

[Comparative Examples 4 to 6]
To 100 parts of the urethane prepolymer of Comparative Examples 1 to 3, after being added to 900 g of tire powder having a particle size of 0.1 to 3 mm and mixed uniformly for 5 minutes, the mold is lightly 1 × 30 × 15 (cm) Tamped. When it was solidified and demolded after 24 hours at 25 ° C., an elastic-like solidified lump having elasticity was obtained. This material was allowed to stand for 1 week, and the basic physical properties (hardness, tensile strength, elongation, tear strength) were measured. The results are shown in Tables 1-2.

［評価基準］
*柔軟性： ○：硬度／伸びが、２．５以下
×：〃 ２．５より、大きい 。

[Evaluation criteria]
* Flexibility: ○: Hardness / elongation is 2.5 or less
×: Larger than 〃2.5.

* Workability: ○: The viscosity of the caking agent is 4000 cps or less
Δ: Exceeding 4000 cps to 6000 cps or less
×: Over 6000 cps.

* Low odor
○: Three people do not smell.
Δ: One or two people smelled slightly.
X: All three smelled strongly.
* Curability: After standing at 23 ° C for 17 hours, bend and check for caking.

Claims (3)

(A) polyol, (b) a aggregate solidifying agent mainly composed of a urethane prepolymer having a terminal isocyanate group comprising a polyisocyanate compound,
The polyisocyanate compound (b) contains 1% by weight or more of 2,4′-diphenylmethane diisocyanate and 99% by weight or less of other organic polyisocyanate compounds (provided that 20% by weight of 2,4′-diphenylmethane diisocyanate, other The organic polyisocyanate compound is a polyisocyanate compound consisting of 80% by weight of 4,4′-diphenylmethane diisocyanate),
Other organic polyisocyanate compounds include 2,4-tolylene diisocyanate (abbreviated as TDI), 65 / 35-TDI, 80 / 20-TDI, 4,4′-diphenylmethane diisocyanate (4,4). 4'-MDI) and 2,2'-MDI alone or as a mixture, dianisidine diisocyanate, tridendiisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, 1,5- It is selected from aromatic diisocyanates such as naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, hydrogenated MDI, hydrogenated TDI, and alicyclic diisocyanates,
It consists of an aggregate granule and elastic granule (c) which use 2 to 25 weight% of 2,4'-diphenylmethane diisocyanate with respect to the urethane prepolymer of an aggregate binder. Flooring composition. Katayuikatamari Joyuka, characterized in that formed by curing the flooring sets composition as claimed in claim 1, wherein. A floor construction method comprising rolling and curing the flooring composition according to claim 1.