JPH1036660A - Binder composition for elastic paving material and elastic paving material prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a binder resin composition which can give a tough elastic paving material even when an un-pretreated ground material for an elastic paving material is used by using a binder composition prepared by adding a specified compound to a polyisocyanate compound. SOLUTION: This composition comprises either a modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen compound and an additive comprising a chlorosilane compound and/or a chlorophosphine compound or another modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen compound, an organic isocyanate, and an additive comprising a chlorosilane compound and/or a chlorophosphine compound. A preferable elastic paving material is one comprising the binder composition and a crushed material based on crushed rubber. Another preferable elastic paving material is one comprising the binder composition, a ground material based on a crushed rubber, and an active hydrogen compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a binder composition for an elastic pavement and an elastic pavement using the same.

[0002]

2. Description of the Related Art Elastic bodies in which rubber such as pulverized waste tires are fixed with a binder are widely used as flooring materials and pavement materials. Generally, a modified polyisocyanate compound is used as a binder composition for an elastic pavement. As a prior art, Japanese Patent Application Laid-Open No. 58-142,836 discloses an example in which an organic acid halogenite is added as a binder to an isocyanate group-terminated prepolymer of polypropylene glycol and diphenylmethane diisocyanate (hereinafter abbreviated as MDI). Is disclosed. JP-A-4-132788 discloses an example in which a mixture of a liquid isocyanate-terminated prepolymer of polypropylene glycol and MDI and liquid MDI to which benzoyl chloride and a pigment are added is used as a binder. Further, JP-A-4-239580
Japanese Patent Application Laid-Open Publication No. H11-157, discloses an example using a binder obtained by adding a halogenocarbonate to a polyether-based isocyanate-terminated prepolymer.

[0003]

However, the conventional binder composition for an elastic pavement has insufficient adhesion to rubber. For this reason, when the shape change of the elastic pavement becomes large, troubles such as peeling between the rubber and the binder often occur. In order to improve the adhesion between the rubber and the binder composition for elastic pavement, a method of washing the surface of the pulverized rubber with a solvent such as trichlene or treating the surface with an acid has been devised. However, the above-described method has problems such as insufficient adhesiveness, shortage of labor, increase in production cost, deterioration of the environment due to waste liquid, and a method of treating waste liquid.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that a binder for an elastic pavement obtained by adding a chlorosilane compound and / or a chlorophosphine compound to a polyisocyanate compound. The present inventors have found that a tough elastic pavement can be obtained from the composition even if the pretreatment step of the pulverized raw material for the elastic pavement is omitted, and the present invention has been completed.

That is, the present invention is as follows (1) to (4). (1) A binder composition for an elastic pavement, comprising a modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen-containing compound, and an additive of a chlorosilane-based compound and / or a chlorophosphine-based compound.

(2) An elastic pavement comprising an additive of a modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen-containing compound, an organic isocyanate, a chlorosilane compound and / or a chlorophosphine compound. Binder composition.

(3) An elastic pavement comprising the binder composition for an elastic pavement according to the above (1) or (2) and a pulverized raw material for an elastic pavement mainly composed of pulverized rubber.

(4) Elasticity characterized by comprising a binder composition for an elastic pavement according to the above (1) or (2), a pulverized raw material for an elastic pavement mainly composed of pulverized rubber, and an active hydrogen-containing compound. Pavement.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The modified polyisocyanate compound constituting the binder composition for paving an elastic body of the present invention is obtained by the reaction between an organic isocyanate and an active hydrogen-containing compound. The active hydrogen-containing compound comprises a long-chain polyol and optionally a chain extender.

The organic isocyanate used in the present invention is 4,4'-MDI, 2,4'-MDI, 2,2'-MDI.
MDI, polymeric MDI, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanate, para-xylylene diisocyanate, meta-xylylene diisocyanate,
Ortho-xylylene diisocyanate, 1,5-naphthylene diisocyanate, para-phenylene diisocyanate, meta-tetramethyl xylylene diisocyanate, para-tetramethyl xylylene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, 2,2
4-trimethylhexamethylene diisocyanate, 2,
4,4-trimethylhexamethylene diisocyanate,
There are various modified isocyanates such as a mixture of two or more kinds of the above-mentioned organic isocyanates, a carbodiimide-modified substance, a buret-modified substance, a uretdione-modified substance, and an isocyanurate-modified substance of the above-described organic isocyanate alone or as a mixture.

Among these various organic isocyanates, MDI-based polyisocyanates such as 4,4'-MDI, carbodiimide-modified MDI, and polymeric MDI are preferred from the viewpoints of vapor pressure, price and the like. Specific products include Millionate MT, Millionate MTL, Millionate MR-200, and Coronate 102 manufactured by Nippon Polyurethane Industry.
There are single products and mixtures such as 1.

The long-chain polyol used in the present invention includes:
Polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, acrylic polyols, polyolefin polyols and the like having a number average molecular weight of 500 to 5,000 and an average number of functional groups of 2 to 3 are used. A polyether polyol is preferred in consideration of the viscosity, price, and the like of the obtained modified polyisocyanate compound, and polypropylene glycol is most preferred.

When the molecular weight of the long-chain polyol is less than 500, the resulting elastic pavement is hard and brittle because the urethane group concentration becomes too large. Conversely, the molecular weight is 5,000
If it exceeds 0, the urethane group concentration becomes too small, and the strength of the elastic pavement decreases.

When the number of functional groups of the polyol is less than 2,
A molecule that is not an isocyanate group will be present at the terminal of the obtained compound, and during the production of an elastic pavement,
Sufficient crosslinking reaction does not occur, and the strength of the resulting elastic pavement decreases. If the number of functional groups exceeds 3, gelation is likely to occur, and it is difficult to obtain the desired modified polyisocyanate compound itself.

In the production of the modified polyisocyanate compound, a chain extender having a molecular weight of 18 to 500 can be used, if necessary, for adjusting the isocyanate content and adjusting the hardness of the elastic pavement.

Specific examples of the chain extender include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. There are low molecular polyols and low molecular polyamines such as diol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerin, ethylenediamine, hexamethylenediamine, diaminodiphenylmethane, isophoronediamine and diethylenetriamine, and water can be used as another.

In the synthesis of the modified polyisocyanate compound of the present invention, the ratio of isocyanate groups / active hydrogen groups, the so-called isocyanate index, is 2 to 10, preferably 3 to 6. As the reaction method, any conventionally known method can be used. The reaction temperature is 10 to 100 ° C,
Preferably, it is 50 to 80 ° C. Examples of the urethanization catalyst include organometallic compounds such as dibutyltin dilaurate, and amine compounds such as triethylenediamine and salts thereof. Such a catalyst can be used as needed. Furthermore, after the reaction with the active hydrogen-containing compound, various organic isocyanates can be added as necessary, for example, by adjusting the isocyanate content and the viscosity.

With respect to the isocyanate index, when the index is less than 2, a modified polyisocyanate compound having a sufficient isocyanate content cannot be obtained, and the strength of the elastic pavement is low. When the index exceeds 10, most of the components of the modified polyisocyanate compound are organic isocyanates themselves, and the elastic pavement obtained has poor flexibility. When the reaction temperature is lower than 10 ° C., the reaction rate is low, so that the synthesis time becomes long and the economic efficiency is poor. 100 ° C
When the ratio exceeds the above, a side reaction of the isocyanate group tends to occur.

The polyisocyanate compound of the present invention thus obtained has an isocyanate group content of 3
-18% by weight, preferably 5-15% by weight.

When the isocyanate content is less than 3% by weight, a sufficient crosslink density cannot be obtained even if the isocyanate group reacts, and the strength of the elastic pavement and the adhesiveness between the elastic pavement raw material and the binder composition are reduced. bad. Isocyanate content is 1
If it exceeds 8% by weight, the crosslinking density becomes too high,
The elastic pavement is hard and brittle.

The binder composition for an elastic body of the present invention uses a chlorosilane-based compound and / or a chlorophosphine-based compound as an additive in a modified polyisocyanate compound. Specific chlorosilane-based compounds include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, etc. Specific chlorophosphine-based compounds include trichlorophosphine, pentachlorophosphine, phenyl Dichlorophosphine and the like. As the chlorosilane compound, phenyltrichlorosilane or diphenyldichlorosilane having a low odor is preferable, and as the chlorophosphine compound, phenyldichlorophosphine having a low odor is preferable. These chlorosilane-based compounds and chlorophosphine-based compounds may be used alone or in a mixture of two or more kinds at an arbitrary ratio to the modified polyisocyanate.

The amount of the chlorosilane-based compound or chlorophosphine-based compound to be added is preferably 0.01 to 2.0 parts by weight, more preferably 0.03 to 1.0 part by weight, based on 100 parts by weight of the modified polyisocyanate compound. Is most preferred.
When the addition amount is less than 0.01 part by weight, the adhesiveness between the binder and the crushed rubber becomes insufficient. If the amount exceeds 2.0 parts by weight, odor problems are likely to occur, and chlorosilane-based compounds and chlorophosphine-based compounds are expensive.
Inferior in cost.

The chlorosilane-based compound or the chlorophosphine-based compound is added to the elastic pavement of the present invention immediately after the synthesis of the modified polyisocyanate compound, using a kneader such as a mortar mixer. It does not matter as long as it is during the mixing of the raw material for body use. However, when additives are added before to during the synthesis of the modified polyisocyanate compound,
A side reaction of the isocyanate group such as carbodiimidization occurs, and it is difficult to obtain a desired modified polyisocyanate compound.

The pulverized raw material for the elastic pavement in the elastic pavement of the present invention contains pulverized rubber as an essential component. Other usable raw materials include wood chips, sand, crushed stone, crushed waste concrete and waste plastic.

As the pulverized rubber in the pulverized raw material for an elastic pavement of the present invention, any pulverized organic polymer exhibiting elastic behavior can be used regardless of the type. For example, natural rubbers, synthetic rubbers such as NBR and SBR, urethane elastomers and the like can be mentioned. this house,
In consideration of economy, pulverized old tires as industrial waste are preferable. In addition, the elastic pavement using the elastic body pavement binder composition of the present invention does not require a pretreatment step such as surface treatment with an acid or a solvent for the pulverized rubber, but the pretreated one can be used naturally. is there.

The proportion of the crushed rubber in the crushed raw material for the elastic pavement is 30 to 100% by weight, preferably 35 to 100% by weight.
100% by weight. If it is less than 30% by weight, the pavement obtained will have low elasticity and lack flexibility.

The average particle size of the pulverized rubber used for the elastic pavement of the present invention is 0.1 mm to 10 mm, preferably 1 to 10 mm.
7 mm. When the average particle size is less than 0.1 mm, the total surface area of the pulverized rubber increases, the required amount of binder increases, and the price of the pulverized rubber increases, which is economically disadvantageous. When the average particle size exceeds 10 mm, the surface of the elastic pavement becomes rough.

As the pulverizing raw material for the elastic pavement of the elastic pavement of the present invention, pulverized wood, sand, crushed stone, pulverized waste concrete or pulverized plastic, or the like can be used as necessary. The average particle size of this material may be appropriately selected depending on the thickness of the elastic pavement.

In the elastic pavement of the present invention, the weight ratio of the pulverized raw material for the elastic pavement to the binder composition for the elastic pavement is 100/5 to 100/40, preferably 100/100.
10 to 100/30. If the amount of the binder is less than 5 parts, the strength of the obtained elastic body is not high. Also, 4
If it is added in an amount of 0 part or more, excessive carbon dioxide gas is generated due to the reaction between the excess isocyanate groups and the moisture in the air, and blisters and bubbles are generated in the elastic pavement, and the strength of the elastic pavement decreases.

Since the binder composition for an elastic pavement of the present invention contains an isocyanate group, it can be cured by moisture, and is usually used as a one-pack type binder. Furthermore, it is also possible to use the binder composition for elastic pavement of the present invention as a two-pack type binder in which part or all of the isocyanate groups contained are cured with an active hydrogen-containing compound such as a polyol or polyamine. .

The method for producing the elastic pavement includes a method of curing at room temperature (such as an on-site construction type) and a method of curing for a short time by hot pressing. The binder composition for an elastic pavement of the present invention can be applied to both methods.

[0032]

The binder composition for an elastic pavement of the present invention is excellent in productivity in that a pretreatment step of a pulverized raw material for an elastic pavement is omitted, and no waste liquid generated in the pretreatment step is produced. It is a so-called "people and earth-friendly" binder that does not affect the working environment or the global environment. Also,
Adhesion with the pulverized raw material for elastic pavement and durability of the obtained elastic pavement are improved. Further, the binder composition of the present invention is also effective as a binder for solidifying not only pulverized rubber but also pulverized wood, sand, crushed stone, pulverized concrete waste material, pulverized waste plastic, and the like.

[0033]

EXAMPLES Hereinafter, the binder composition for an elastic pavement, the method for producing an elastic pavement, and the elastic pavement of the present invention will be described with reference to examples, but the present invention is not limited thereto. Note that “parts” and “%” in Synthesis Examples, Examples and Comparative Examples indicate “parts by weight” and “% by weight” unless otherwise specified.

[Synthesis of Modified Polyisocyanate Compound] Synthesis Example 1 360 parts of 4,4′-MDI (Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) was placed in a synthesizer equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas inlet pipe. And 640 parts (isocyanate group / hydroxyl group = 4.5 / 1) of polypropylene glycol having a number average molecular weight of 2,000 and a number average molecular weight of 2,000 are reacted under a nitrogen stream at 75 to 85 ° C. for 3 hours to form a molecular end. Modified polyisocyanate compound P having isocyanate group
-1 was obtained. The isocyanate content of P-1 is 9.4%,
The viscosity was 3,200 cP / 25 ° C.

Synthesis Example 2 In an apparatus similar to that of Synthesis Example 1, an isocyanate content of 30 was used.
% Of polymeric MDI (manufactured by Nippon Polyurethane Industry, Millionate MR-200), 107 parts of Millionate M
T is 285 parts, the number of average functional groups is 2, and the number average molecular weight is 2,000.
0 to 608 parts (isocyanate group / hydroxyl group = 5/1) of 75 to 85 parts under a nitrogen stream.
C. for 3 hours to obtain a modified polyisocyanate compound P-2 having an isocyanate group at a molecular terminal. P-
2 has an isocyanate content of 10.4% and a viscosity of 4,50.
It was 0 cP / 25 ° C.

Synthesis Example 3 In a device similar to that of Synthesis Example 1, 54 million of MT was added.
0 parts, 10 parts of neopentyl glycol, 450 parts of polypropylene glycol having an average functional group number of 2 and a number average molecular weight of 1,000 (isocyanate group / hydroxyl group = 4/1) under a nitrogen stream at 75 to 85 ° C. The reaction was carried out for an hour to obtain a modified polyisocyanate compound P-3 having an isocyanate group at a molecular terminal. The isocyanate content of P-3 was 6.8%, and the viscosity was 4,500 cP / 25 ° C.

Example 4 A modified polyisocyanate compound P-4 was obtained by mixing 80 parts of P-2 synthesized in Synthesis Example 2 and 20 parts of millionate MR-200. The isocyanate content of P-4 was 13.4%, and the viscosity was 2,360 cP / 25 ° C.

[Blending of Binder Composition] Synthesis Examples 1-4
A chlorosilane-based compound and a chlorophosphine-based compound were added to the modified polyisocyanate compounds P-1 to P-4 obtained in the above at the ratios shown in Table 1 to obtain binder compositions B-1 to B-9 for elastic pavement. Further, comparative binder compositions R-1 to 5 for an elastic pavement were also prepared with the formulations shown in Table 2.

[0039]

[Table 1]

[0040]

[Table 2]

In Tables 1 and 2, PTCS: phenyltrichlorosilane DPDCS: diphenyltrichlorosilane PDCP: phenyldichlorophosphine ECC: ethyl chlorocarbonate BZC: benzoyl chloride

[Preparation of Elastic Pavement] Example 1 An untreated old tire pulverized to an average particle diameter of 3 mm
Part, B-1 mixed with 20 parts, length 5cm, width 10cm,
The mixture was poured into a mold having a thickness of 1 cm, formed so as to have a specific gravity of 0.7, and cured at 25 ° C./50% RH for 10 days to obtain an elastic pavement BS-1.

Examples 2 to 9 and Comparative Examples 1 to 5 In the same manner as in Example 1, B-2 to 1 were used in place of B-1.
0, R-1-5, elastic pavement BS-2-9, BR
-1 to 5 were obtained.

Example 10 An untreated old tire pulverized to an average particle size of 3 mm was mixed with 80
Part, 20 parts of P-1 and 0.1 part of phenyltrichlorosilane.
One part is mixed, poured into a mold having a length of 5 cm, a width of 10 cm, and a thickness of 1 cm, formed so as to have a specific gravity of 0.7, and cured at 25 ° C./50% RH for 10 days. BS-10 was obtained.

Example 11 An untreated old tire pulverized to an average particle size of 3 mm was mixed with 80
Parts, 19 parts of B-1 and 1 part of ethylene glycol were mixed, poured into a mold having a length of 5 cm, a width of 10 cm and a thickness of 1 cm, and formed so as to have a specific gravity of 0.7.
Cured at / 50% RH for 10 days, elastic pavement BS-
11 was obtained.

Examples 12 to 19, Comparative Examples 6 to 10 In the same manner as in Example 11, B-2 to B-2 were used instead of B-1.
8, BS-12-1 of elastic pavement using R-1 to 5
9, BR-6 to 10 were obtained.

A mixture of 80 parts of an untreated old tire pulverized to an average particle size of 3 mm, 19 parts of P-1, 0.1 part of phenyltrichlorosilane, and 1 part of ethylene glycol, is 5 cm long and 10 cm wide. , Poured into a mold having a thickness of 1 cm, and formed so as to have a specific gravity of 0.7.
Cured at / 50% RH for 10 days, elastic pavement BS-
20 was obtained.

Example 21 10 parts of crushed stone having an average particle size of 2.5 to 5 mm, 40 parts of sand,
30 untreated old tires pulverized to an average particle size of 3 mm
Part and B-1 were mixed in 20 parts, length 5 cm, width 20 c
m, forming into a mold having a thickness of 2 cm, forming so that the specific gravity becomes 1.45, and 10% at 25 ° C./50% RH.
After curing for days, an elastic pavement BS-21 was obtained.

Examples 22 to 29 and Comparative Examples 11 to 15 In the same manner as in Example 21, B-2 to B-2 were used instead of B-1.
8, using R-1 to 5 elastic pavement BS-22 to 29,
BR-11 to BR-15 were obtained.

Example 30 10 parts of crushed stone having an average particle size of 2.5 to 5 mm, 40 parts of sand,
30 untreated old tires pulverized to an average particle size of 3 mm
Parts, 20 parts of P-1 and 0.1 part of phenyltrichlorosilane were mixed, poured into a mold having a length of 5 cm, a width of 20 cm, and a thickness of 2 cm, and formed so as to have a specific gravity of 1.45. Cured at / 50% RH for 10 days to obtain an elastic pavement BS-30.

Example 31 An untreated old tire pulverized to an average particle diameter of 3 mm was 75
Parts, 10 parts of wood chips crushed to an average particle size of 3 mm, B
-15, 15 cm × 15 at a specific gravity of 0.8
Forming in an aluminum mold coated with a release agent with a thickness of 3 mm and a thickness of 3 mm, 150 ° C., surface pressure of 100 kgf / cm
^After hot curing at 25 ° C./50% RH for 10 days, an elastic pavement BS-31 was obtained.

Examples 32-39, Comparative Examples 16-20 In the same manner as in Example 31, B-2 to B-2 were used instead of B-1.
8, using R-1 to 5 elastic pavement BS-32 to 39,
BR-16 to 20 were obtained.

Example 40 An untreated old tire pulverized to an average particle diameter of 3 mm was 75
Parts, 10 parts of wood chips pulverized to an average particle size of 3 mm, P
15 parts of -1 and 0.1 parts of phenyltrichlorosilane are mixed, and the specific gravity is 0.8, 15 cm × 15 cm, thickness 3 m
m in an aluminum mold coated with a mold release agent, hot-pressed at 150 ° C. and a surface pressure of 100 kgf / cm ² for 5 minutes, cured at 25 ° C./50% RH for 10 days, and then subjected to elastic pavement BS- 40 was obtained.

[Evaluation of Physical Properties of Elastic Pavement] Examples 1-2
0, BS-1 to 20 obtained in Comparative Examples 1 to 10, BR-
180 ° bending test of 1-20 and JIS K-630
The tensile strength was measured by the method described in 1. Table 3 shows the results
Are shown in FIGS.

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

In Tables 3 to 5, ◎: No crack was observed at all. ：: Some cracks were observed. ×: Large crack was generated and divided into two.

The BS-21 to 30 and BR-11 to 15 obtained in Examples 21 to 30 and Comparative Examples 11 to 15 were JIS
The bending strength was measured by the method described in A-5908. Table 6 shows the results.

[0060]

[Table 6]

The BS-31 to 40 and BR-16 to 20 obtained in Examples 31 to 40 and Comparative Examples 16 to 20 were subjected to JIS.
The tensile strength was measured by the method described in K-6301.
The results are shown in Tables 7 and 8.

[0062]

[Table 7]

[0063]

[Table 8]

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Claims (4)

[Claims] 1. A binder composition for an elastic pavement, comprising a modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen-containing compound, an additive of a chlorosilane compound and / or a chlorophosphine compound. . 2. A modified polyisocyanate compound obtained by reacting an organic isocyanate with an active hydrogen-containing compound, an organic isocyanate, a chlorosilane compound and / or
Or a binder composition for an elastic pavement, comprising an additive of a chlorophosphine compound. 3. An elastic pavement comprising the binder composition for an elastic pavement according to claim 1 or 2 and a pulverized raw material for an elastic pavement mainly comprising ground rubber. 4. An elastic pavement comprising the binder composition for an elastic pavement according to claim 1 or 2, a pulverized raw material for an elastic pavement mainly composed of pulverized rubber, and an active hydrogen-containing compound.