JP2020002574A - Two-part mixed cold-cure type pavement material and elastic pavement method - Google Patents

Abstract

To provide a two-part mixed cold-cure type pavement material which exhibits excellent physical properties of the cured product and workability without being subject to specific chemical substance failure prevention regulations, and which sufficiently suppresses foaming during curing.SOLUTION: A two-part mixed cold-cure type pavement material 100 includes: a main agent comprising an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate and a polyol compound, in which unreacted diphenylmethane diisocyanate is less than 1.0 mass%; and a curing agent comprising an active hydrogen-containing compound which is a polyamine compound other than 3,3'-dichloro-4-4'-diaminodiphenylamine, which contains 90 mass% or more of dimethylthiotoluenediamine and does not contain a polyol compound as the balance.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a two-component mixed-room-temperature-curable pavement material and an elastic pavement method using the same.

  Conventionally, as a two-part mixed-room-temperature-curable pavement material for elastically paving a pavement surface such as a stadium, a ground, a runway or a walking path, an isocyanate group-terminated prepolymer obtained by reacting tolylene diisocyanate with a polyol is conventionally used. BACKGROUND ART A pavement material including a main agent as a main component and a hardener mainly containing a mixture of 3,3′-dichloro-4-4′-diaminodiphenylamine (MOCA) and a polyol is known. The main agent and the curing agent were mixed at a construction site to produce a two-part mixed room temperature-curable pavement material, and the pavement material was applied to a pavement surface and cured.

  However, MOCA used as a main component in the curing agent is considered to be probably carcinogenic to humans (International Agency for Research on Cancer). Protective measures are required.

  Therefore, Patent Document 1 discloses tolylene diisocyanate (TDI) as a two-part mixed room temperature-curable pavement material that has no carcinogenicity to humans, has excellent mechanical properties, and exhibits an appropriate pot life and curing time. A main component comprising an isocyanate group-terminated prepolymer obtained by reacting a polyol with dimethylthiotoluenediamine (DMTDA) and a polyoxyalkylene polyol which are liquid-state aromatic diamines containing no chlorine as curing agents. And a hardener consisting of a mixture used in proportions.

JP 2001-139654 A

  In the pavement material described in Patent Literature 1, the use of DMTDA instead of MOCA for the polyamine compound as a main component of the curing agent has no carcinogenicity to humans, has excellent mechanical properties, and is moderate. It shows that the pot life and the curing time are high. However, according to studies by the present inventors, it has been found that the pavement material of Patent Document 1 has the following problems.

  In the pavement material of Patent Document 1, 65% by mass or more of tolylene diisocyanate (TDI) is said to be 2,4-tolylene diisocyanate. In Examples, 2,4-tolylene diisocyanate (2,4 An 80:20 mixture of -TDI) and 2,6-tolylene diisocyanate (2,6-TDI) has been used. However, it has been found that when such a tolylene diisocyanate is reacted with a polyol, 1% by mass or more of unreacted TDI remains. Unreacted TDI causes not only allergy, but also paving materials containing 1% by mass or more are products targeted for specific chemical substances, and the regulations for the prevention of specific chemical substance disorders are applied. The regulations have been revised in recent years to apply to paving work both indoors and outdoors.

  Further, although it is said that the pavement material of Patent Document 1 exhibits an appropriate pot life and curing time, according to the study of the present inventors, in this pavement material, the viscosity increase after mixing the main agent and the curing agent is observed. It turned out that it was not fast enough in terms of workability in actual construction. Furthermore, in the pavement material of Patent Document 1, foaming is recognized during the curing process depending on the working environment, and is considered to be inappropriate as a pavement material.

  In view of the above-mentioned problems, the present invention provides a two-component mixed-room-temperature-curable pavement that exhibits excellent cured physical properties and workability without applying specific chemical substance prevention rules, and that foaming during curing is sufficiently suppressed. It is an object of the present invention to provide a material and an elastic pavement method using the same.

The present inventors have conducted intensive studies in order to solve the above problems, and obtained the following knowledge.
First, regarding the main agent, diphenylmethane diisocyanate (MDI), which is not a specific chemical substance, was used in place of TDI, which is a specific chemical substance, as a polyisocyanate compound used as a raw material for synthesizing an isocyanate group-terminated prepolymer. . Also, as in the case of Patent Document 1, DMTDA was used instead of MOCA as the active hydrogen group-containing compound serving as a curing agent.

  However, simply using MDI as a polyisocyanate compound on the main agent side and using DMTDA as a curing agent could not obtain excellent cured material properties and workability. In addition, unreacted components in the main agent were added. By setting the MDI to less than 1.0% by mass, it was found that excellent cured material properties and workability could be obtained. That is, since MDI is not a specific chemical substance in the first place, it is not always necessary to make unreacted MDI less than 1.0% by mass from the viewpoint of avoiding application of the specific chemical substance failure prevention rule. However, the combination of reducing the amount of unreacted MDI in the main component to less than 1.0% by mass and using DMTDA as the active hydrogen group-containing compound serving as a curing agent allows the speed of viscosity increase after mixing of the main component and the curing agent. It can be seen that the workability can be significantly improved in actual construction.

  Further, it was found that foaming during curing was sufficiently suppressed by not using a polyol compound as an active hydrogen group-containing compound serving as a curing agent.

The present invention has been completed based on the above findings, and the gist configuration thereof is as follows.
(1) a base agent comprising an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate with a polyol compound, wherein unreacted diphenylmethane diisocyanate is less than 1.0% by mass;
It contains 90% by mass or more of dimethylthiotoluenediamine, does not contain a polyol compound as the balance, and the balance consists of an active hydrogen group-containing compound that is a polyamine compound other than 3,3′-dichloro-4-4′-diaminodiphenylamine. A curing agent,
Wherein the equivalent ratio of the isocyanate group in the main agent to the amino group in the curing agent is 0.8 to 1.5.

  (2) The two-component mixed cold-setting pavement material according to the above (1), wherein a hardening accelerator containing an organic acid is contained in an amount of 0.01 to 3% by mass based on the total amount of the main agent and the hardening agent.

  (3) The two-part cold-setting pavement material according to the above (1) or (2), further comprising a filler of 10 to 50% by mass based on the total amount of the main agent and the curing agent.

(4) The two-component mixed cold-setting pavement material according to any one of (1) to (3) is spread on a pavement surface to form a coating layer made of the pavement material,
An elastic pavement method comprising curing the coating layer to form a cured resin layer on the pavement surface.

  (5) The elastic pavement method according to the above (4), wherein an elastic chip is mixed in advance with the two-component mixed room-temperature-curable pavement material and then spread on the pavement surface.

(6) spraying an excessive amount of elastic chips on the coating layer before the coating layer is cured;
The elastic coating method according to the above (4), wherein after the application layer is cured, excess elastic chips not fixed to the application layer are collected.

  ADVANTAGE OF THE INVENTION According to the two-part mixed room temperature hardening type pavement material and the elastic pavement method of the present invention, excellent physical properties and workability of the hardened material are exhibited and foaming during hardening is sufficiently performed without applying the specific chemical substance obstacle prevention rule. Is suppressed.

1 is a schematic sectional view of an elastic pavement structure 100 obtained by an elastic pavement method according to an embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of an elastic pavement structure 100 obtained by an elastic pavement method according to another embodiment of the present invention. 7 is a graph showing a viscosity increase curve of a pavement material in Experimental Example 2.

(Two-component mixed room-temperature-curable pavement material)
The two-part cold-setting pavement material according to one embodiment of the present invention includes a main agent and a curing agent as main components, and may further include a filler, a plasticizer, and other additives. .

[Main agent]
The main component in the present embodiment contains, as a main component, an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate (MDI) with a polyol compound.

<Polyisocyanate compound>
In the present embodiment, diphenylmethane diisocyanate (MDI) is used as a polyisocyanate compound used as a raw material for synthesizing an isocyanate group-terminated prepolymer.

  There are three kinds of isomers of MDI, 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI. Existing products of MDI include products in which 99% by mass or more are composed of 4,4'-MDI (product examples, Cosmonate PH manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.), and 50% by mass of 2,4'-MDI And a product (product example, Lupranate MI manufactured by BASF INOAC Polyurethane Co., Ltd.) composed of 4,4'-MDI and 50% by mass.

  In the present embodiment, the ratio of isomers in MDI used as a raw material for synthesizing the isocyanate group-terminated prepolymer is not particularly limited. When tolylene diisocyanate (TDI) is used instead of MDI, the ratio of 2,4 and 2,6 isomers affects the mass ratio of unreacted TDI in the base material. However, since MDI has higher activity than TDI, it does not significantly affect the mass ratio of unreacted MDI in the base material, and depends on the isomer ratio by adopting the predetermined reaction conditions described later. Without this, unreacted MDI can be reduced to less than 1.0% by mass.

<Polyol compound>
Generally, as the active hydrogen group-containing compound used as a raw material for synthesizing an isocyanate group-terminated prepolymer, any or a known polyol compound, a polythiol compound, and a polyamine compound can be given. And a polyol compound.

  The polyol compound is not particularly limited as long as it has two or more hydroxy groups, and examples thereof include polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, Polyol obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to at least one selected from the group consisting of 4-butanediol and pentaerythritol Is mentioned. Specifically, polypropylene ether diol and polypropylene ether triol are preferably exemplified.

  As the polyester polyol, specifically, for example, selected from the group consisting of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane and other low-molecular polyols At least one selected from the group consisting of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid and other aliphatic carboxylic acids, castor oil and other hydroxycarboxylic acids and oligomeric acids. Condensed polymers with species; ring-opened polymers such as propionlactone and valerolactone; and the like.

  As other polyols, specifically, for example, polymer polyols, polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, Low molecular weight polyols such as hexanediol; polytetramethylene ether glycol; and the like.

  Such polyol compounds can be used alone or in combination of two or more.

<Unreacted MDI in main agent>
It is important that the unreacted MDI of the main agent in the present embodiment is less than 1.0% by mass. Due to the combination of the unreacted MDI of less than 1.0% by mass and the characteristics of the curing agent described later, the speed of viscosity increase after mixing the main agent and the curing agent can be remarkably suppressed. Workability can be significantly improved.

<Blending ratio of polyisocyanate compound and polyol compound and reaction conditions>
The mixing ratio of the polyisocyanate compound and the polyol compound is not particularly limited, but the equivalent ratio (NCO / H) between the isocyanate group (NCO group) in the polyisocyanate compound and the active hydrogen (H) in the polyol compound is determined by the polyol compound It is preferable to set appropriately so that the unreacted MDI can be 1.0% by mass or less depending on the molecular weight of the compound. In one embodiment, the equivalent ratio (NCO / H) can be 2.0 / 1.0 or less, in which isocyanate groups are theoretically not excessive. However, even if the value slightly exceeds 2.0 / 1.0, it is appropriate according to the molecular weight of the polyol compound. By setting the upper limit, unreacted MDI can be less than 1.0% by mass. With respect to a preferable lower limit of the equivalent ratio (NCO / H), the equivalent ratio (NCO / H) is 1.7 / from the viewpoint of avoiding excessive polymerization of the polyol compound and resulting in a product viscosity that impairs workability. It is preferably 1.0 or more.

  In the present embodiment, the reaction temperature is particularly important among the reaction conditions of the polyisocyanate compound and the polyol compound. Specifically, the reaction temperature is preferably set to 60 ° C. or lower. Generally, the reaction temperature between the polyisocyanate compound and the polyol compound was 100 ° C. or higher. On the other hand, in the present embodiment, the unreacted MDI can be reduced to less than 1.0% by mass by reacting the MDI with the polyol compound at a reaction temperature of 60 ° C. or lower. The reaction temperature needs to be 50 ° C. or higher from the viewpoint of reliably proceeding the reaction between the MDI and the polyol compound.

  In addition, although the main component in this embodiment contains the isocyanate group-terminated prepolymer obtained by the above-mentioned reaction as a main component, other isocyanate group-terminated prepolymers may be included as the balance in the main component. However, from the viewpoint of sufficiently obtaining the effects of the present invention, it is preferable that the isocyanate group-terminated prepolymer obtained by the above reaction be 90% by mass or more in the main agent. The other isocyanate group-terminated prepolymer is not particularly limited, and is less reactive than MDI, such as tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate (NBDI). A urethane prepolymer using such as above can be used.

[Curing agent]
In a general two-component mixed cold curing pavement material, the active hydrogen group-containing compound constituting the curing agent has at least two substituents in a molecule selected from the group consisting of a hydroxy group, a mercapto group and an amino group. Compound. Examples of such a compound include a polyol compound having two or more hydroxy groups, a polythiol compound having two or more mercapto groups, and a polyamine compound having two or more amino groups.

  However, in the present embodiment, the active hydrogen group-containing compound constituting the curing agent contains 90% by mass or more of dimethylthiotoluenediamine (DMTDA), which is a kind of polyamine compound. Certain 3,3'-dichloro-4-4'-diaminodiphenylamine (MOCA) shall not be contained. Since MOCA is also a specific chemical substance, the absence of MOCA does not apply the specific chemical substance failure prevention rule. Then, by using DMTDA instead of MOCA, it is possible to obtain cured material properties equivalent to those of a curing agent using MOCA. Further, by combining DMTDA as an active hydrogen group-containing compound serving as a curing agent and reducing the unreacted MDI in the main component to less than 1.0% by mass, the main component and the curing agent after mixing are mixed. The speed of viscosity increase can be significantly suppressed, and workability during actual construction can be significantly improved.

  In this embodiment, the active hydrogen group-containing compound is substantially composed of DMTDA, but the remainder (ie, 10% by mass or less) may be a polyamine compound other than MOCA. As polyamine compounds other than MOCA, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7 -Heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylenediamine, trimethyl Hexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3- Aminomethyl- Aliphatic polyamines such as 3,3,5-trimethyl-cyclohexylamine, dimethyleneamine having a norbornane skeleton, metaxylylenediamine (MXDA), hexamethylenediaminecarbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2, 4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5- Aromatic polyamines such as lylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, diethyltoluenediamine; and the like, and these may be used alone or in combination of two or more. Is also good.

  However, the remainder of the active hydrogen group-containing compound does not include a polyol compound. As a result, foaming due to moisture during the curing process of the mixture of the main agent and the curing agent is greatly reduced. This is because amines have a much higher nucleophilicity to isocyanates contained in the main agent than hydroxyl groups, and the reaction between the isocyanate and the amine is selectively performed in a system in which the main agent and the curing agent are mixed, and almost water Is not considered to be a reaction.

[Mixing ratio of main agent and curing agent]
As for the mixing ratio between the main agent and the curing agent, the equivalent ratio between the isocyanate group in the main agent and the amino group in the curing agent is set to 0.8 to 1.5. If the equivalent ratio is less than 0.8, the isocyanate is insufficient, curing failure occurs, and the target cured material properties are not obtained.If the equivalent ratio is more than 1.5, the isocyanate after mixing becomes excessive, and the moisture in the air and The possibility of foaming is increased by the reaction of A more suitable equivalent ratio is 1.0 to 1.3.

[Filling material]
The two-component mixed cold-setting pavement material of the present embodiment may include a filler in addition to the main agent and the curing agent. The filler is preferably added to the curing agent, and powders such as calcium carbonate, titanium oxide, silicon oxide, talc, clay, quicklime, kaolin, zeolite, diatomaceous earth, finely divided silica, hydrophobic silica, carbon black, etc. One or more of these can be used. The filler is preferably added in the range of 10 to 50% by mass based on the total amount of the main agent and the curing agent.

[Plasticizer]
The two-part mixed room temperature curable pavement material of the present embodiment may contain a plasticizer in addition to the main agent and the curing agent. The plasticizer can be added to the base and / or the curing agent. The plasticizer may be any one used for the two-part curable polyurethane composition. For example, diisononyl adipate (DINA), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP) , Dilauryl phthalate (DLP), dibutyl benzyl phthalate (BBP), dioctyl adipate (DOA), diisodecyl adipate (DIDA), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) Phosphate (TDCPP), propylene glycol adipate polyester, butylene glycol adipate polyester, and the like can be used, and these can be used alone or in combination of two or more. The plasticizer is preferably added in an amount of 5% by mass or more based on the total amount of the main agent and the curing agent from the viewpoint of obtaining the effect of addition, and from the viewpoint of preventing the plasticizer from causing bleed out due to excessive addition. It is preferably added in a range of 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the main agent and the curing agent.

[Other additives]
In addition to the main agent and the curing agent, other additives may be added to the two-component mixed room temperature-curable pavement material of the present embodiment. Other additives include a curing accelerator, a dispersant, a solvent, an antioxidant, a coloring agent, and an antifoaming agent, and can be added to the main agent and / or the curing agent. Other additives are added within a range that does not impair the object of the present invention, and are usually added in an amount of 5% by mass or less based on the total amount of the main agent and the curing agent.

  As the curing accelerator, for example, an organic metal catalyst or an amine catalyst can be used. Examples of the organic metal catalyst include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctate; lead catalysts such as lead octylate, lead octenoate, and lead naphthenate; bismuth octylate, bismuth neodecanoate, and the like. Bismuth catalyst; and the like. It is preferable not to use a tin or lead catalyst from the viewpoint of safety to the environment and the human body. Examples of the amine-based catalyst include tertiary amine compounds such as triethylenediamine. However, amine catalysts may cause allergies such as rashes by humans. These are used alone or in combination.

  Further, in the present embodiment, an organic acid can be used as a catalyst. Generally, organic acids have no effect on the reaction between isocyanate and polyol. However, in the present embodiment, the curing agent does not contain a polyol, but contains only DMTDA, so that an organic acid can be used as a curing catalyst and metal-free. Examples of the organic acid include stearic acid, phthalic acid, caprylic acid, lauric acid, oleic acid, naphthenic acid, octylic acid, and the like. In the present embodiment, octylic acid is preferred from the viewpoint that the compatibility with the main agent and the curing agent is good, the liquid is excellent and the workability is excellent.

  In the present embodiment, the curing accelerator is preferably added in the range of 0.01 to 3% by mass based on the total amount of the main agent and the curing agent.

  The dispersant is not particularly limited as long as the solid can be dispersed in the liquid.

  Examples of the solvent include hydrocarbon compounds such as hexane; halogenated hydrocarbon compounds such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; Esters; mineral spirits; and the like.

  Specific examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxytolueneanisole (BHA), diphenylamine, phenylenediamine, and triphenyl phosphite.

  The coloring agent and the antifoaming agent are not particularly limited as long as they have the function.

(Elastic coating method)
The elastic coating method of the present embodiment is a method of elastically paving a base such as a stadium, a ground, a runway or a walkway, and laying the two-liquid mixed cold-curable pavement material described above on a pavement surface, The method is characterized in that a coating layer made of the pavement material is formed, and the coating layer is cured to form a cured resin layer on the pavement surface. In this method, excellent cured physical properties and workability are exhibited without applying the specific chemical substance failure prevention rule, and foaming during curing is sufficiently suppressed.

  Two specific examples of the construction method are shown below, but the present invention is not limited to these.

  First, the steps of an elastic pavement method according to an embodiment of the present invention will be described with reference to FIG. The surface of the asphalt concrete layer (hereinafter, simply referred to as “ascon layer”) 10 in FIG. 1 is cleaned or the like. Next, the cement, the cement-based solidifying agent, and water are mixed by a high-speed mixer, and the mixture can be evenly spread with a rubber lake and applied. The ground treatment layer 12 in which the mixture is solidified can strengthen and smooth the surface of the ascon layer 10, block moisture rising from the ascon layer 10, and enhance the moisture-proof effect. Next, a primer paint is uniformly applied on the base treatment layer 12 to form an adhesive layer 14. Note that these steps are examples of the present invention, and the present invention is not limited thereto.

  Next, an elastic chip is mixed in advance with the two-component mixed room-temperature-curable pavement material of the present embodiment. The elastic tip may have a particle size of about 1 to 3 mm. The material constituting the elastic chip is not particularly limited, and may be any one or more of thermosetting elastomers such as vulcanized rubber (including natural rubber and synthetic rubber) and thermosetting resin-based elastomer, and thermoplastic elastomers. Can be used. The elastic tip may be a non-foamable or foamed elastic tip, or a combination of both. Examples of the non-foamable elastic chip include a chip obtained by crushing a removed urethane pavement material generated in a repair work of an existing urethane pavement, a chip obtained by crushing a waste tire, and a vulcanized rubber chip. A foamed elastic chip having a specific gravity of less than 1 and a porosity of about 20 to 50% can be used. The foamed elastic chip can be obtained by, for example, crushing foamed EPDM rubber, such as a surplus portion when a vehicle window frame, a handle, a cushion material for a seat, or the like is formed.

  Then, within a predetermined time after the application of the primer paint, the two-component mixed-room-temperature-curable pavement material of the present embodiment in which an elastic chip is mixed in advance is spread on the surface of the adhesive layer 14 as a pavement surface, and the pavement material is removed. A coated layer is formed, and the coated layer is cured to form a cured resin layer 20 on the pavement surface. The cured resin layer 20 includes the elastic chip 22. Thus, the elastic pavement structure 100 can be obtained.

  Next, the steps of an elastic pavement method according to another embodiment of the present invention will be described with reference to FIG. Also in the present embodiment, the formation of the base treatment layer 12 and the adhesive layer 14 on the ascon layer 10 is similar to the embodiment shown in FIG.

  Next, within a predetermined time after the application of the primer paint, the two-liquid mixed cold curing pavement material of the present embodiment is spread over the surface of the adhesive layer 14 as a pavement surface to form an application layer composed of the pavement material. Then, before the coating layer is cured, an excessive amount of elastic chips is sprayed on the coating layer (second step). After the coating layer is cured, the excess elastic chips that are not fixed to the coating layer are collected (third step). Thus, the base layer 16 including the elastic tip 22 is formed as shown in FIG.

  Next, in the present embodiment, the first to third steps are repeated two or more times to form the first resin cured layer 20 including the elastic chip. In the example shown in FIG. 2, the steps in the preceding paragraph are repeated twice to form a similar base layer 18 on the base layer 16, and the base layers 16 and 18 constitute the first cured resin layer 20. In addition, each base layer may be bonded via an adhesive layer formed by uniformly applying the primer coating as described above.

  The thickness of the first cured resin layer 20 is preferably 6.0 mm or more, and more preferably 9.0 mm or more. When the thickness is less than 6.0 mm, the first cured resin layer as the elastic layer is too thin, so that it is difficult to obtain excellent shock absorption. If the thickness is to be realized by applying the first curable resin composition only once, the mixing amount of the foamed elastic chips in the first cured resin layer 20 tends to be non-uniform depending on the location, and the flatness is poor. Tends to be impaired. Therefore, in the present embodiment, it is preferable to apply the first curable resin composition in two or more portions. However, the present invention is not limited to this, and if an appropriate resin cured layer can be formed by a single application, that may be the case. When the first to third steps are repeated two or more times, the thickness of each base layer is preferably 4 to 7 mm. The upper limit of the thickness of the first cured resin layer 20 is not particularly limited, but may be about 13 mm.

  Referring to FIG. 1, in the present embodiment, a step of spreading a second curable resin composition on first cured resin layer 20 and curing the same to form second cured resin layer 24; And a step of forming the uppermost layer 26 by using a mixture obtained by mixing the third curable resin composition and the elastic chip 28 on the second resin cured layer 24.

  As the second and third curable resin compositions, a conventional or arbitrary one-part curable polyurethane composition or two-part curable polyurethane composition may be used. The thickness of the second cured resin layer 24 can be about 2 to 7 mm, and the thickness of the uppermost layer 26 can be about 0.5 to 1.5 mm.

  Examples of the elastic chip 28 included in the uppermost layer include an EPDM chip or a urethane chip, and may have a particle size of 5.0 mm or less.

  The first cured resin layer 20 and the second cured resin layer 24 may be bonded to each other via an adhesive layer formed by uniformly applying a primer coating as described above. The same applies between the second cured resin layer 24 and the uppermost layer 26.

  As a method of forming the uppermost layer 26, there is a method of spraying the mixture with a sprayer to form a spray embossed layer. Alternatively, a method may be used in which the mixture is spread with a squeegee, and then, when the mixture layer is leveled, the mixture is pressed with a sand roller to form an embossed shape (that is, a roller embossed layer is obtained).

<Preparation of main agent>
A main agent was prepared according to the following procedure. In addition, diisononyl phthalate as a plasticizer is also added to the following main ingredients. In addition, the content of unreacted diphenylmethane diisocyanate in each main agent was measured by gas chromatography mass spectrometer GC-MS (manufactured by Shimadzu Corporation).

[Main agent A-1]
756 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added so as to have an NCO% of 3.5 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane was added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.5%.

[Main agent A-2]
822 g of polypropylene ether triol having a number average molecular weight of 5,000 (Actocol T-5000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added so as to have an NCO% of 2.3 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane was added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.3%.

[Main agent A-3]
749 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) is added so as to have an NCO% of 3.8 (equivalent ratio (NCO / H) = 2.15), and the mixture is stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane is added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 1.4%.

[Main agent A-4]
814 g of polypropylene ether triol having a number average molecular weight of 5,000 (Actocol T-5000 manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) is added so as to have an NCO% of 2.6 (equivalent ratio (NCO / H) = 2.20), and the mixture is stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane is added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 1.2%.

[Main agent A-5]
756 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added so as to have an NCO% of 3.5 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 100 ° C. for 3 hours under a nitrogen atmosphere, and urethane was added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 1.8%.

[Main agent A-6]
756 g of a polyester polyol (diol) having a number average molecular weight of 2,000 (Kuraray polyol P-2010, manufactured by Kuraray Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added so as to have an NCO% of 3.5 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane was added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.5%.

[Main agent A-7]
783 g of polybutadiene polyol (diol) having a number average molecular weight of 2,400 (poly bd R-45HT manufactured by Idemitsu Kosan Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added so as to have an NCO% of 3.0 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere, and urethane was added. A prepolymer was obtained. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.4%.

[Main agent A-8]
756 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, monomeric MDI (Lupranate MI BASF INOAC Polyurethane Co., Ltd.) was added so as to have an NCO% of 3.5 (equivalent ratio (NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours in a nitrogen atmosphere to obtain a urethane prepolymer. Got. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.5%.

[Main agent A-9]
756 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Here, as a monomeric MDI, NCO% 3.5 (equivalent ratio (Equivalent ratio (%)) is used so that the mass ratio of Cosmonate PH (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) and Lupranate MI (BASF INOAC Polyurethane Co., Ltd.) becomes 80:20. NCO / H) = 2.05), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere to obtain a urethane prepolymer. 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer were mixed to prepare a main component. The unreacted monomeric MDI content was 0.5%.

<Preparation of curing agent>
A curing agent was prepared according to the following procedure. In addition, the following hardening agents also include calcium carbonate as a filler, diisononyl phthalate as a plasticizer, and other additives.

[Curing agent B-1 (DMTDA)]
6.8 parts by mass of dimethylthiotoluenediamine (DMTDA) (ETHACURE300 Albemarle Japan), 29.4 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as a filler (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-1-1 (DMTDA)]
4.5 parts by mass of dimethylthiotoluenediamine (DMTDA) (ETHACURE300 Albemarle Japan), 31.7 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as a filler (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-1-2 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 7.4 parts by mass (ETHACURE300 Albemarle Japan), 23.8 parts by mass of diisononyl phthalate as plasticizer (Sanso Sizer DINP manufactured by Shin Nippon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-1-3 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 5.1 parts by mass (ETHACURE300 Albemarle Japan), 31.1 parts by mass of diisononyl phthalate as plasticizer (Sanso Sizer DINP Shin Nihon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-1-4 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 5.9 parts by mass (ETHACURE300 Albemarle Japan), 30.3 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP Shin Nihon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-2 (DBADPM)]
9.8 parts by mass of N, N'-dibutylaminodiphenylmethane (DBADPM) (ETHACURE420 Albemarle Japan), 26.4 parts by mass of diisononyl phthalate as plasticizer (Sanso Sizer DINP manufactured by Shin Nihon Rika Co., Ltd.), 60.0 mass of calcium carbonate as filler (LW-350 manufactured by Shimizu Corporation) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-2-1 (DBADPM)]
6.5 parts by mass of N, N'-dibutylaminodiphenylmethane (DBADPM) (ETHACURE420 made by Albemarle Japan), 29.7 parts by mass of diisononyl phthalate as a plasticizer (Sansosizer DINP manufactured by Shin Nippon Rika Co., Ltd.), and 60.0 parts by mass of calcium carbonate as a filler (LW-350 manufactured by Shimizu Corporation) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-2-2 (DBADPM)]
8.5 parts by mass of N, N'-dibutylaminodiphenylmethane (DBADPM) (ETHACURE420 made by Albemarle Japan), 27.7 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP manufactured by Shin Nihon Rika Co., Ltd.), and 60.0 parts by mass of calcium carbonate as a filler (LW-350 manufactured by Shimizu Corporation) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-3 (MOCA + polyol)]
7.7 parts by mass of 3,3'-dichloro-4,4'diaminodiphenylamine (MOCA) (bisamine A manufactured by Wakayama Seika Kogyo Co., Ltd.), 5.8 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 Mitsui Chemicals, Inc.) SKC Polyurethane Co., Ltd.), 22.7 parts by mass of diisononyl phthalate as plasticizer (manufactured by Sansosizer DINP Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350 manufactured by Shimizu Corporation), and others The curing agent was uniformly mixed with 3.8 parts by mass of the additive. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-3-1 (MOCA + polyol)]
4.8 parts by mass of 3,3'-dichloro-4,4 'diaminodiphenylamine (MOCA) (bisamine A manufactured by Wakayama Seika Kogyo Co., Ltd.), 5.8 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 Mitsui Chemicals, Inc.) SKC Polyurethane Co., Ltd.), 25.6 parts by mass of diisononyl phthalate as plasticizer (Sanso Sizer DINP, manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350, manufactured by Shimizu Corporation) and others The curing agent was uniformly mixed with 3.8 parts by mass of the additive. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-3-2 (MOCA + polyol)]
6.6 parts by mass of 3,3'-dichloro-4,4'diaminodiphenylamine (MOCA) (bisamine A manufactured by Wakayama Seika Kogyo Co., Ltd.), 5.8 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 Mitsui Chemicals, Inc.) SKC Polyurethane Co., Ltd.), 23.9 parts by mass of diisononyl phthalate as plasticizer (Sanso Sizer DINP, manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350, manufactured by Shimizu Corporation) and others The curing agent was uniformly mixed with 3.8 parts by mass of the additive. Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-4 (DMTDA + polyol)]
Dimethylthiotoluenediamine (DMTDA) 6.2 parts by mass (ETHACURE300 Albemarl Japan), 5.7 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.), diisononyl phthalate as a plasticizer 24.3 parts by mass (SANSOSIZER DINP, manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as a filler (LW-350, manufactured by Shimizu Industry Co., Ltd.) and 3.8 parts by mass of other additives are uniformly mixed and cured. And Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-4-1 (DMTDA + polyol)]
3.9 parts by mass of dimethylthiotoluenediamine (DMTDA) (ETHACURE300 Albemarl Japan), 5.7 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.), diisononyl phthalate as a plasticizer 26.6 parts by mass (SansoSizer DINP manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350 manufactured by Shimizu Industry Co., Ltd.), and 3.8 parts by mass of other additives are uniformly mixed and hardener And Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-4-2 (DMTDA + polyol)]
Dimethylthiotoluenediamine (DMTDA) 5.3 parts by mass (ETHACURE300 Albemarle Japan), 5.7 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.), diisononyl phthalate as a plasticizer 25.2 parts by mass (SansoSizer DINP, manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350, manufactured by Shimizu Industry Co., Ltd.) and 3.8 parts by mass of other additives are uniformly mixed and cured. And Other additives include ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., octylic acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (coloring agent) manufactured by Nichibox Co., Ltd., Kusumoto Chemicals Co., Ltd. DISPARLON P-450 (defoaming agent) was used.

[Curing agent B-5 (DMTDA, no catalyst added)]
6.8 parts by mass of dimethylthiotoluenediamine (DMTDA) (ETHACURE300 Albemarle Japan), 29.4 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP manufactured by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as a filler (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. As other additives, ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., NBK-1202 (coloring agent) manufactured by Nihon Bix Co., Ltd., and DISPARLON P-450 (defoaming agent) manufactured by Kusumoto Kasei Co., Ltd. Using.

[Curing agent B-5-1 (DMTDA, no catalyst added)]
3.9 parts by mass of dimethylthiotoluenediamine (DMTDA) (ETHACURE300 Albemarl Japan), 26.6 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as a filler (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. As other additives, ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., NBK-1202 (coloring agent) manufactured by Nihon Bix Co., Ltd., and DISPARLON P-450 (defoaming agent) manufactured by Kusumoto Kasei Co., Ltd. Using.

[Curing agent B-5-2 (DMTDA, no catalyst added)]
Dimethylthiotoluenediamine (DMTDA) 5.3 parts by mass (ETHACURE300 Albemarle Japan), 25.2 parts by mass of diisononyl phthalate as a plasticizer (Sanso Sizer DINP Shin Nihon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 Shimizu Kogyo Co., Ltd.) and 3.8 parts by mass of other additives were uniformly mixed to obtain a curing agent. As other additives, ASA DS525 (wetting and dispersing agent) manufactured by Ito Oil Co., Ltd., NBK-1202 (coloring agent) manufactured by Nihon Bix Co., Ltd., and DISPARLON P-450 (defoaming agent) manufactured by Kusumoto Kasei Co., Ltd. Using.

[Experimental example 1: Comparative test of workability and physical properties of cured product]
The main agent and the curing agent were mixed at the mass ratios shown in Table 1 to obtain various two-part mixed room temperature curable pavement materials. When 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed as shown in Table 1, the equivalent ratio of the isocyanate group to the amino group is 1.25. About the obtained pavement material, the physical properties of cured product and workability were evaluated by the following methods. Table 1 also shows the evaluation results.

(1) Evaluation of physical properties of cured product (1-1) Evaluation of tensile strength and elongation A fully cured 2 mm thick sheet was punched out with a dumbbell-shaped No. 3 to prepare a test piece, and a test in accordance with JISK6251 Was done. The tensile speed was 500 mm / min. Tensile strength and elongation were calculated by the following calculation methods.
Tensile strength (MPa) = Tensile strength (N) / width (mm) x thickness (mm)
Elongation (%) = Elongation (cm) / Distance between marked lines

(1-2) Evaluation of tear strength A fully cured 2 mm thick sheet was punched out with an angle mold to prepare a test piece, which was tested in accordance with JISK6252, and the tear strength was calculated by the following calculation method. Calculated.
Tear strength (N / mm) = Tear strength (N) / Thickness (mm)

(2) Evaluation of workability (2-1) Evaluation of pot life For each pavement material, the viscosity (25 ° C.) after mixing the main agent and the curing agent was measured over time, and a viscosity rise curve was created. If the viscosity exceeds 50,000 mPa · s, the workability becomes insufficient. Therefore, the time required for the viscosity to reach 50,000 mPa · s after mixing the two liquids was defined as “working time”.

(2-2) Evaluation of hardness the next day Each pavement material was poured into a container so as to have a depth of 1 cm, and 18 hours later, Shore A hardness was measured in accordance with JISK6253. If the hardness is less than 30 the next day, it is difficult for a person to get on and work, and therefore, it is described as “x” in Table 1.

  As is evident from Table 1, in the levels 1 to 6 (inventive examples) using the main agent and the curing agent in the range of the present invention, excellent cured material properties and workability could be exhibited. On the other hand, in the case of the level 7 to 12 (comparative example) using DBADPM as a curing agent, the cured material properties are inferior and the pot life is not a problem. Poor sex. In addition, in the levels 13 to 18 (comparative examples) using MOCA + polyol as the curing agent, the properties of the cured product are the same as those in the levels 1 to 6, but the specific chemical substance failure prevention rule is applied. Not preferred. As is clear from the levels 1, 5, and 6, even if the isomer ratio of the monomeric MDI changes, excellent curing physical properties and workability can be exhibited as long as the curing agent is the same.

[Experimental example 2: Workability comparison test]
The main agent and the curing agent were mixed at the mass ratios shown in Table 2 to obtain various two-part mixed room-temperature-curable pavement materials. As shown in Table 2, when 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed, the equivalent ratio between the isocyanate group and the amino group is 1.25. About the obtained paving material, the viscosity (25 degreeC) after mixing of the main agent and the hardening | curing agent was measured over time similarly to Experimental example 1. The obtained viscosity increase curve is shown in FIG. 3, and the time required for the viscosity to reach 50,000 mPa · s after mixing the two liquids is shown in Table 2 as “working time”.

  As is clear from Table 2 and FIG. 3, when the unreacted MDI is less than 1.0% by mass and the level is 1, 2, 6 to 9 (invention examples) using the curing agent in the range of the present invention, the increase in the viscosity is small. It was very gradual and could maintain a state of a viscosity of 50,000 mPa · s or less at which good workability was obtained for about 60 to 70 minutes. On the other hand, as shown in Levels 3 to 5 (Comparative Example), when the unreacted MDI uses a main component of 1.0% by mass or more, even if the curing agent in the range of the present invention is used, the viscosity immediately after mixing is reduced. And the state of viscosity of 50,000 mPa · s or less, at which good workability can be obtained, can be maintained from 5 minutes to about 20 minutes for a long time, resulting in poor workability.

[Experimental example 3: Foaming test]
The main agent, the curing agent and the water were mixed at the mass ratios shown in Table 3 to obtain various two-part mixed room temperature curable pavement materials. When 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed as shown in Table 3, the equivalent ratio of the isocyanate group to the amino group is 1.25. About the obtained pavement material, the foaming property during curing was visually observed. The results are shown in Table 3, where "X" indicates that foaming was observed and "O" indicates that foaming was not observed.

  As is clear from Table 3, foaming was observed during curing at levels 7 to 18 (comparative examples) using a curing agent containing a polyol. In contrast, foaming was not observed during curing at levels 1 to 6 (inventive examples) using a curing agent containing no polyol.

[Experimental example 4: catalyst comparison test]
The main agent, the curing agent, and the various curing catalysts were mixed at the mass ratios shown in Table 4 to obtain various two-part mixed room temperature-curable pavement materials. As shown in Table 4, when 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed, the equivalent ratio between the isocyanate group and the amino group is 1.25. In Table 4, as the “lead”, Nikka Octic Lead 24% (manufactured by Nippon Chemical Industry Co., Ltd.) was used, and as the “tin”, Neostan U-100 (manufactured by Nitto Kasei Co., Ltd.) was used. Octyl acid (manufactured by KH Neochem Corporation) was used as the "organic acid". About the obtained pavement material, the same cured material properties and workability evaluation as shown in Experimental Example 1 were performed. Table 4 also shows the evaluation results.

  As is clear from Table 4, no deterioration in workability and no deterioration in cured physical properties due to catalyst change were observed. That is, octylic acid could be used as a curing catalyst.

[Experimental Example 5: Workability comparison test (equivalent ratio change)]
The main agent and the curing agent were mixed at the mass ratios shown in Table 5 to obtain various two-part mixed room temperature curable pavement materials. In addition, the hardening | curing agent B-1-alpha of Table 5 changed the mass part of DMTDA suitably in each level 1-9, except having made the equivalent ratio of an isocyanate group and an amino group 0.90, It is the same as the above-mentioned curing agent B-1. About the obtained paving material, the viscosity (25 degreeC) after mixing of the main agent and the hardening | curing agent was measured over time similarly to Experimental example 1. The time required for the viscosity to reach 50,000 mPa · s after mixing the two liquids is shown in Table 5 as “working time”.

  In addition, the main agent and the curing agent were mixed at the mass ratio shown in Table 6 to obtain various two-part mixed room temperature curable pavement materials. In addition, the hardening | curing agent B-1-beta in Table 6 changed the mass part of DMTDA suitably in each level 1-9, except that the equivalent ratio of the isocyanate group and the amino group was set to 1.50. It is the same as the above-mentioned curing agent B-1. About the obtained paving material, the viscosity (25 degreeC) after mixing of the main agent and the hardening | curing agent was measured over time similarly to Experimental example 1. Table 6 shows the time required for the viscosity to reach 50,000 mPa · s after mixing the two liquids, as “pot life”.

  As is clear from Tables 5 and 6, even when the equivalent ratio between the isocyanate group and the amino group was 0.90 and 1.50, the same tendency as in Experimental Example 2 in which the equivalent ratio was 1.25 could be obtained.

  The present invention is applicable when elastically paving various pavement surfaces such as various stadiums such as athletics stadiums, various grounds such as school yards / playgrounds and tennis courts, running paths such as jogging courses, and walking paths such as promenades. It can be suitably used.

100,200 Elastic pavement structure 10 Asphalt concrete layer 12 Ground treatment layer 14 Adhesive layer 16 Base layer 18 Base layer 20 First resin cured layer 22 Elastic chip 24 Second resin cured layer 26 Top layer (spray embossed layer or roller Embossed layer)
28 elastic tip

Claims (6)

A main agent comprising an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate with a polyol compound, wherein unreacted diphenylmethane diisocyanate is less than 1.0% by mass;
It contains 90% by mass or more of dimethylthiotoluenediamine, does not contain a polyol compound as the balance, and the balance consists of an active hydrogen group-containing compound that is a polyamine compound other than 3,3′-dichloro-4-4′-diaminodiphenylamine. A curing agent,
Wherein the equivalent ratio of the isocyanate group in the main agent to the amino group in the curing agent is 0.8 to 1.5.   The two-part mixed-room-temperature-curable pavement material according to claim 1, wherein a hardening accelerator containing an organic acid is contained in an amount of 0.01 to 3% by mass based on the total amount of the main agent and the hardening agent.   The two-component mixed cold-setting pavement material according to claim 1 or 2, further comprising a filler of 10 to 50% by mass based on the total amount of the main agent and the curing agent. A two-component mixed cold-setting pavement according to any one of claims 1 to 3 is spread over a pavement surface to form a coating layer made of the pavement,
An elastic pavement method comprising curing the coating layer to form a cured resin layer on the pavement surface.   The elastic pavement method according to claim 4, wherein an elastic chip is mixed in advance with the two-component mixed room-temperature-curable pavement material, and then spread on the pavement surface. Before curing of the coating layer, spray an excessive amount of elastic chips on the coating layer,
5. The elastic coating method according to claim 4, wherein after the application layer is cured, excess elastic chips not fixed to the application layer are collected.

Images