JP6442638B1 - Two-component mixed room temperature curing pavement and elastic pavement method - Google Patents

Abstract

The present invention provides a two-component mixed room temperature curing pavement that exhibits excellent cured material properties and workability without applying specific chemical substance prevention rules, and sufficiently suppresses foaming during curing.
The two-component mixed room temperature curing pavement material of the present invention includes an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate and a polyol compound, and 1.0 mass of unreacted diphenylmethane diisocyanate. The main component is less than 90% and 90% by mass or more of dimethylthiotoluenediamine, the remainder is a polyol compound, and the remainder is a polyamine compound other than 3,3′-dichloro-4-4′-diaminodiphenylamine. And a curing agent comprising an active hydrogen-containing compound.
[Selection figure] None

Description

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

  An isocyanate group-terminated prepolymer obtained by reacting tolylene diisocyanate and a polyol as a two-component mixed room temperature curing type paving material used for elastic paving of pavement surfaces such as stadiums, grounds, runways or walking paths. There is known a paving material containing a main component as a main component and a curing agent mainly composed of a mixture of 3,3′-dichloro-4-4′-diaminodiphenylamine (MOCA) and a polyol. The main agent and the curing agent were mixed at the construction site to prepare a two-component mixed room temperature curing pavement, and the pavement was applied to the pavement and cured.

  However, MOCA used as a main component in a curing agent is considered to be carcinogenic to humans (International Agency for Research on Cancer), and in the production of a curing agent containing MOCA and on-site construction, Protective measures against this are required.

  Therefore, Patent Document 1 discloses tolylene diisocyanate (TDI) as a two-component mixed room temperature curable pavement 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 with a polyol, dimethylthiotoluenediamine (DMTDA), which is a room temperature liquid aromatic diamine containing no chlorine as a curing agent, and a polyoxyalkylene polyol. And a curing agent comprising a mixture used in proportions.

JP 2001-139654 A

  In the paving material described in Patent Document 1, regarding the polyamine compound as the main component of the curing agent, by using DMTDA instead of MOCA, there is no carcinogenicity to humans, it has excellent mechanical properties, and is moderate. The pot life and curing time are shown. However, according to the study by the present inventors, it has been found that the pavement material of Patent Document 1 has the following problems.

  In the paving material of Patent Document 1, 65% by mass or more of tolylene diisocyanate (TDI) is said to be 2,4-tolylene diisocyanate, and in the examples, 2,4-tolylene diisocyanate (2,4 -TDI) and 2,6-tolylene diisocyanate (2,6-TDI) are used in an 80:20 mixture. However, it has been found that when such tolylene diisocyanate and polyol are reacted, 1% by mass or more of unreacted TDI remains. Unreacted TDI not only causes allergies, but paving material containing 1% by mass or more becomes a target product for specific chemical substances, and the specific chemical substance prevention rules are applied. This rule has been applied to pavement construction not only indoors but also outdoors due to recent revisions.

  Moreover, although it is supposed that the pavement material of patent document 1 shows moderate pot life and hardening time, according to examination of the present inventors, in this pavement material, the viscosity increase after mixing with a main ingredient and a hardening | curing agent is carried out. It turns out that it is not fast enough from the viewpoint of workability in actual construction. Furthermore, in the pavement material of patent document 1, foaming is recognized in the process of hardening depending on the working environment, and it is thought that it is not suitable as a pavement material.

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

When the present inventors diligently studied to solve the above problems, the following knowledge was obtained.
First, regarding the main agent, diphenylmethane diisocyanate (MDI), which is not a specific chemical substance, is 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. . Further, as the active hydrogen group-containing compound serving as a curing agent, DMTDA is used instead of MOCA as in Patent Document 1.

  However, by simply using MDI as the polyisocyanate compound on the main agent side and using DMTDA as the curing agent, it was not possible to obtain excellent cured product properties and workability. In addition, unreacted in the main agent It was found that by setting the MDI to less than 1.0% by mass, excellent cured product properties and workability can be obtained. That is, since MDI is not a specific chemical substance, unreacted MDI does not necessarily have to be less than 1.0% by mass from the viewpoint of avoiding application of the specific chemical substance prevention rules. However, the speed of increase in viscosity after mixing the main agent and the curing agent by combining unreacted MDI in the main agent with less than 1.0% by mass and using DMTDA as the active hydrogen group-containing compound as the curing agent. As a result, it was found that workability can be significantly improved during actual construction.

  It was also found that foaming during curing was sufficiently suppressed by not using a polyol compound as the active hydrogen group-containing compound serving as a curing agent.

This invention is completed based on said knowledge, The summary structure is as follows.
(1) a main agent containing an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate and a polyol compound, wherein unreacted diphenylmethane diisocyanate is less than 1.0% by mass;
It contains 90% by mass or more of dimethylthiotoluenediamine, the remainder does not contain a polyol compound, and the remainder consists of an active hydrogen group-containing compound that is a polyamine compound other than 3,3′-dichloro-4-4′-diaminodiphenylamine. A curing agent;
A two-component mixed room temperature curing pavement characterized in that the equivalent ratio of isocyanate groups in the main agent and amino groups in the curing agent is 0.8 to 1.5.

  (2) The two-component mixed room temperature curing pavement according to (1) above, containing a curing accelerator containing an organic acid in an amount of 0.01 to 3% by mass relative to the total amount of the main agent and the curing agent.

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

(4) The two-component mixed room temperature curing pavement according to any one of (1) to (3) above is spread on a pavement surface to form an application layer made of the pavement,
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 (4), wherein an elastic chip is mixed in advance with the two-component mixed room temperature curing pavement and then spread on the pavement surface.

(6) Before the coating layer is cured, an excessive amount of elastic tip is sprayed on the coating layer,
The elastic coating method according to (4), wherein after the coating layer is cured, surplus elastic chips that are not fixed to the coating layer are collected.

  According to the two-component mixed room temperature curing type paving material and the elastic paving method of the present invention, excellent cured material properties and workability are exhibited without applying specific chemical substance prevention rules, and foaming during curing is sufficient. To be suppressed.

It is a schematic cross section of the elastic pavement structure 100 obtained by the elastic pavement method by one Embodiment of this invention. It is a schematic cross section of the elastic pavement structure 100 obtained by the elastic pavement method by other embodiment of this invention. It is a graph which shows the viscosity rise curve of the pavement material in Experimental example 2.

(Two-component mixed room temperature curing pavement)
The two-component mixed room temperature curing pavement according to an 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 agent in this embodiment contains, as a main component, an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound containing diphenylmethane diisocyanate (MDI) and a polyol compound.

<Polyisocyanate compound>
In this 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 isomers of MDI: 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI. As existing products of MDI, products with 99% by mass or more composed of 4,4'-MDI (product example, Cosmonate PH manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) and 50% by mass of 2,4'-MDI And 50% by mass of 4,4′-MDI (product example, Lupranate MI manufactured by BASF INOAC Polyurethane Co., Ltd.).

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

<Polyol compound>
In general, examples of the active hydrogen group-containing compound used as a raw material for synthesizing the isocyanate group-terminated prepolymer include any or known polyol compounds, polythiol compounds, and polyamine compounds. A polyol compound is used.

  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, 1, Polyols 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, etc. Is mentioned. Specifically, polypropylene ether diol and polypropylene ether triol are preferably exemplified.

  Specifically, the polyester polyol is selected from the group consisting of, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. And 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 Examples thereof include condensation polymers with seeds; ring-opening polymers such as propionlactone and valerolactone; and the like.

  Specific examples of other polyols include, for example, polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, And 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 main agent in the present embodiment has an unreacted MDI of less than 1.0% by mass. In combination with the fact that the unreacted MDI is 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 remarkably improved.

<Blending ratio of polyisocyanate compound and polyol compound and reaction conditions>
The compounding ratio of the polyisocyanate compound and the polyol compound is not particularly limited, but the equivalent ratio (NCO / H) of the isocyanate group (NCO group) in the polyisocyanate compound and the active hydrogen (H) in the polyol compound is the polyol compound. It is preferable to set appropriately so that unreacted MDI may become 1.0 mass% or less according to the molecular weight. As one embodiment, the equivalent ratio (NCO / H) can be 2.0 / 1.0 or less, which is not a theoretically excessive isocyanate group, but even a value slightly exceeding 2.0 / 1.0 is appropriate depending on the molecular weight of the polyol compound. By setting it as such an upper limit, unreacted MDI can be made less than 1.0 mass%. With respect to a preferred lower limit of the equivalent ratio (NCO / H), from the viewpoint of avoiding excessive polymerization of the polyol compound and a product viscosity that impairs workability, the equivalent ratio (NCO / H) is 1.7 / It is preferably 1.0 or more.

  In the present embodiment, the reaction temperature is particularly important among the reaction conditions for the polyisocyanate compound and the polyol compound. Specifically, the reaction temperature is preferably 60 ° C. or lower. Generally, the reaction temperature between the polyisocyanate compound and the polyol compound is set to 100 ° C. or higher. On the other hand, in this embodiment, unreacted MDI can be made less than 1.0 mass% by making MDI and a polyol compound react at the reaction temperature of 60 degrees C or less. In addition, the reaction temperature needs to be 50 degreeC or more from a viewpoint of advancing reaction with MDI and a polyol compound reliably.

  In addition, although the main ingredient in this embodiment contains the isocyanate group terminal prepolymer obtained by said reaction as a main component, you may also contain other isocyanate group terminal prepolymer as the remainder in a main ingredient. However, from the viewpoint of sufficiently obtaining the effects of the present invention, the isocyanate group-terminated prepolymer obtained by the above reaction is preferably 90% by mass or more in the main agent. Further, other isocyanate group-terminated prepolymers are not particularly limited, and have lower reactivity than MDI, tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), norbornane diisocyanate (NBDI). Urethane prepolymers using etc. can be used.

[Curing agent]
In a general two-component mixed room temperature curing type paving material, the active hydrogen group-containing compound constituting the curing agent has two or more substituents selected from the group consisting of hydroxy group, mercapto group and amino group in the molecule. A 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 includes 90% by mass or more of dimethylthiotoluenediamine (DMTDA), which is a kind of polyamine compound, and is also 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 specific chemical substance prevention rules are not applied by not containing MOCA. Then, by using DMTDA instead of MOCA, it is possible to obtain a cured product property equivalent to a curing agent using MOCA. Furthermore, by using DMTDA as an active hydrogen group-containing compound to be a curing agent, and combining the unreacted MDI in the above-mentioned main agent with less than 1.0% by mass, after mixing the main agent and the curing agent, The speed of viscosity increase can be remarkably suppressed, and workability can be remarkably improved during actual construction.

  In the present embodiment, the active hydrogen group-containing compound is substantially composed of DMTDA, but the balance (that is, 10% by mass or less) may be a polyamine compound other than MOCA. Examples of polyamine compounds other than MOCA include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 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 , 3,5-trimethyl-cyclohexylamine, dimethyleneamine having a norbornane skeleton, metaxylylenediamine (MXDA), hexamethylenediamine carbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like; 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- And aromatic polyamines such as 2,6-tolylenediamine, 3,4-tolylenediamine, diethyltoluenediamine, and the like. These may be used alone or in combination of two or more. Also good.

  However, the remainder of the active hydrogen group-containing compound does not include a polyol compound. This significantly reduces foaming due to moisture in the curing process of the mixture of the main agent and the curing agent. This is because amine is much more nucleophilic with respect to the isocyanate contained in the main agent than the hydroxyl group, and the reaction between the isocyanate and the amine is selectively carried out in a system in which the main agent and the curing agent are mixed. This is thought to be because it does not react.

[Mixing ratio of main agent and curing agent]
Regarding the mixing ratio of the main agent and the curing agent, the equivalent ratio of the isocyanate group in the main agent to the amino group in the curing agent is set to 0.8 to 1.5. When the equivalence ratio is less than 0.8, the isocyanate is insufficient, resulting in poor curing, and the target cured product properties are not produced.When the equivalence ratio is more than 1.5, the isocyanate after mixing becomes excessive, and moisture in the air There is a high possibility of foaming due to the reaction. A more preferred equivalent ratio is 1.0 to 1.3.

[Filler]
In addition to the main agent and the curing agent, the two-component mixed room temperature curing pavement material of the present embodiment may include a filler (filler). 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, fine 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 with respect to the total amount of the main agent and the curing agent.

[Plasticizer]
In addition to the main agent and the curing agent, the two-component mixed room temperature curing pavement material of the present embodiment may include a plasticizer. The plasticizer can be added to the main agent and / or the curing agent. The plasticizer may be any one used in a two-component 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) Examples thereof include phosphate (TDCPP), propylene glycol polyester adipate, butylene glycol polyester adipate, 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. Further, 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 curing pavement of the present embodiment. Examples of other additives include a curing accelerator, a dispersant, a solvent, an antioxidant, a colorant, 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 at 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 organometallic catalyst or an amine catalyst can be used. As organometallic catalysts, bell catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate; lead catalysts such as lead octylate, lead octenoate, lead naphthenate; bismuth octylate, bismuth neodecanoate, etc. Bismuth catalyst; and the like. It is preferable not to use a tin or lead catalyst in terms of safety to the environment and the human body. Examples of the amine catalyst include tertiary amine compounds such as triethylenediamine. However, amine-based catalysts may cause allergies such as rashes by humans. These may be used alone or in combination.

  Furthermore, in this embodiment, an organic acid can be used as a catalyst. In general, organic acids have no effect on the reaction between isocyanate and polyol. However, in this embodiment, since the curing agent does not contain a polyol and contains only DMTDA, an organic acid can be used as a curing catalyst and can be made 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 preferable from the viewpoints of good compatibility with the main agent and the curing agent, and being liquid and excellent in workability.

  In this embodiment, it is preferable to add a hardening accelerator in 0.01-3 mass% with respect to the total amount of a main ingredient and a hardening | curing agent.

  A dispersing agent will not be specifically limited if solid can be disperse | distributed in a 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; ethyl acetate and dimethyl carbonate and the like. And the like; mineral spirits;

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

  The colorant 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 elastic paving a base such as a stadium, a ground, a runway or a walking path, and the two-component mixed room temperature curing pavement described above is spread on the pavement surface, A coating layer made of the paving material is formed, the coating layer is cured, and a cured resin layer is formed on the paving surface. In this method, the specific chemical substance prevention rules are not applied, and excellent cured material properties and workability are exhibited, and foaming during curing is sufficiently suppressed.

  Although the example of the concrete construction method is shown below, this invention is not limited to these.

  First, the process of the elastic pavement method by one Embodiment of this invention is demonstrated, referring FIG. The surface of the asphalt concrete layer (hereinafter simply referred to as “ascon layer”) 10 of FIG. 1 is cleaned. Next, cement, a cement-based solidifying agent and water are mixed with a high-speed mixer, and this mixture can be uniformly spread and applied with a rubber lake. The surface treatment layer 12 in which the mixture is solidified can reinforce and smooth the surface of the ascon layer 10, can block the rising moisture from the ascon layer 10, and enhance the moisture-proof effect. Next, a primer coating is uniformly applied on the base treatment layer 12 to form the adhesive layer 14. In addition, these processes are examples of this invention, and this invention is not limited to these.

  Next, an elastic chip is mixed in advance with the two-component mixed room temperature curing pavement of the present embodiment. The elastic tip can have a particle size of about 1 to 3 mm. The material constituting the elastic chip is not particularly limited, and any one or more of thermosetting elastomers such as vulcanized rubber (including natural rubber and synthetic rubber) and thermosetting resin-based elastomers, and thermoplastic elastomers may be used. Can be used. The elastic tip may be non-foaming or foaming elastic tip, or a combination of both. Examples of the non-foaming elastic chip include a chip obtained by pulverizing a removed urethane pavement material generated in the repair work of an existing urethane pavement, a chip obtained by pulverizing 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, for example, by pulverizing foamed EPDM rubber such as a surplus portion when a car window frame, a handle, a seat cushion material or the like is molded.

  Then, within a predetermined time from the application of the primer paint, the surface of the adhesive layer 14 as a pavement surface is spread with the two-component mixed room temperature curing type pavement material of this embodiment in which an elastic chip is mixed in advance, and the pavement material is The coating layer to be formed is formed, and the coating layer is cured to form the cured resin layer 20 on the paved surface. The cured resin layer 20 includes the elastic chip 22. In this way, the elastic pavement structure 100 can be obtained.

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

  Next, within a predetermined time after application of the primer paint, the surface of the adhesive layer 14 as a pavement surface is spread with the two-component mixed room temperature curing type pavement material to form an application layer made of the pavement material. (First step) Subsequently, before the coating layer is cured, an excessive amount of elastic tip is sprayed on the coating layer (second step). After the coating layer is cured, excess elastic chips that are not fixed to the coating layer are collected (third step). In this way, the base layer 16 including the elastic tip 22 is formed as shown in FIG.

  Next, in this embodiment, the 1st-3rd process is repeated twice or more, and the 1st resin hardening layer 20 containing an elastic chip is formed. In the example shown in FIG. 2, the process of the previous paragraph is repeated twice to form a similar base layer 18 on the base layer 16, and the base layers 16 and 18 constitute the first resin cured layer 20. Each base layer may be adhered via an adhesive layer formed by uniformly applying the primer paint 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. This is because if the thickness is less than 6.0 mm, the first cured resin layer as the elastic layer is too thin to obtain excellent impact absorbability. If this thickness is achieved by applying the first curable resin composition only once, the mixing amount of the foamed elastic chip in the first resin cured layer 20 tends to be uneven depending on the location, and flatness Tend to be damaged. Therefore, in this embodiment, it is preferable to apply the first curable resin composition in two or more steps. However, the present invention is not limited to this, and may be used when an appropriate cured resin layer can be formed by one application. When the first to third steps are repeated twice or more, the thickness of each base layer is preferably 4 to 7 mm. In addition, although the upper limit of the thickness of the 1st resin cured layer 20 is not specifically limited, What is necessary is just to be about 13 mm.

  With reference to FIG. 1, in the present embodiment, a step of forming a second resin cured layer 24 by spreading and curing a second curable resin composition on the first resin cured layer 20 is performed. Preferably, the method further includes a step of forming the uppermost layer 26 on the second cured resin layer 24 with a mixture obtained by mixing the third curable resin composition and the elastic chip 28.

  As the second and third curable resin compositions, a conventional or arbitrary one-component curable polyurethane composition or two-component 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.

  As the elastic tip 28 included in the uppermost layer, an EPDM tip or a urethane tip can be cited, and the particle size can be 5.0 mm or less.

  In addition, you may adhere the 1st resin cured layer 20 and the 2nd resin cured layer 24 through the contact bonding layer formed by apply | coating the primer coating as described above uniformly. The same applies between the second cured resin layer 24 and the uppermost layer 26.

  As a method for forming the uppermost layer 26, there is a method of spraying the mixture with a spraying machine to form a spray embossed layer. Alternatively, after the mixture is spread with a squeegee and leveled, the mixture layer is pressed with a sand-bone roller to form an embossed shape (that is, a roller embossed layer is obtained).

<Preparation of main agent>
The main agent was prepared by the following procedure. In addition, diisononyl phthalate as a plasticizer is added to the main agent below. Moreover, the content rate of unreacted diphenylmethane diisocyanate in each main ingredient was measured by gas chromatograph mass spectrometer GC-MS (made by Shimadzu Corporation).

[Main agent A-1]
756 g of polypropylene ether diol having a number average molecular weight of 2,000 (Actol D-2000, Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Monomeric MDI (Cosmonate PH made by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so that it might become NCO% 3.5 (equivalent ratio (NCO / H) = 2.05), and stirred for 48 hours at 60 ° C. in a nitrogen atmosphere, and urethane. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol 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. Monomeric MDI (Cosmonate PH, Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so that it might become NCO% 2.3 (equivalent ratio (NCO / H) = 2.05), and stirred at 60 ° C. for 48 hours in a nitrogen atmosphere, and urethane. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol D-2000, Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so that the NCO% was 3.8 (equivalent ratio (NCO / H) = 2.15), and stirred at 60 ° C. for 48 hours in a nitrogen atmosphere. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol 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. Monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so that NCO% 2.6 (equivalent ratio (NCO / H) = 2.20) was obtained, and the mixture was stirred at 60 ° C. for 48 hours in a nitrogen atmosphere. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol D-2000, Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so as to be NCO% 3.5 (equivalent ratio (NCO / H) = 2.05), and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere, and urethane. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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. Monomeric MDI (Cosmonate PH made by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so that it might become NCO% 3.5 (equivalent ratio (NCO / H) = 2.05), and stirred for 48 hours at 60 ° C. in a nitrogen atmosphere, and urethane. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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, and dehydrated by heating to 110 ° C. under reduced pressure for 5 hours. Monomeric MDI (Cosmonate PH, manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd.) was added here so as to be NCO% 3.0 (equivalent ratio (NCO / H) = 2.05), and stirred at 60 ° C. for 48 hours in a nitrogen atmosphere to obtain urethane. A prepolymer was obtained. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol D-2000, Mitsui Chemicals SKC Polyurethane Co., Ltd.) was placed in a reactor, heated to 110 ° C. under reduced pressure, and dehydrated for 5 hours. Monomeric MDI (manufactured by Lupranate MI BASF INOAC Polyurethane Co., Ltd.) is placed here so as to be NCO% 3.5 (equivalent ratio (NCO / H) = 2.05), and stirred at 60 ° C. for 48 hours in a nitrogen atmosphere, urethane prepolymer Got. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. 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 (Actol D-2000, 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 monomeric MDI, Cosmonate PH (Mitsui Chemicals SKC Polyurethane Co., Ltd.) and Lupronate MI (BASF INOAC Polyurethane Co., Ltd.) NCO% 3.5 (equivalent ratio ( NCO / H) = 2.05) and stirred at 60 ° C. for 48 hours under a nitrogen atmosphere to obtain a urethane prepolymer. The main component was prepared by mixing 95 parts by mass of the urethane prepolymer thus obtained and 5 parts by mass of diisononyl phthalate as a plasticizer. The unreacted monomeric MDI content was 0.5%.

<Production of curing agent>
A curing agent was prepared by the following procedure. In addition, to the following curing agents, calcium carbonate as a filler (filler), diisononyl phthalate as a plasticizer, and other additives are also added.

[Curing agent B-1 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 6.8 parts by mass (ETHACURE300 made by Albemarle Japan), diisononyl phthalate as plasticizer 29.4 parts by mass (Sanso Sizer DINP made by Nippon Nippon Chemical Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-1-1 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 4.5 parts by mass (ETHACURE300 Albemarle made in Japan), diisononyl phthalate as plasticizer 31.7 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-1-2 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 7.4 parts by mass (ETHACURE300 Albemarle made in Japan), diisononyl phthalate as plasticizer 23.8 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate as filler 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-1-3 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 5.1 parts by mass (ETHACURE300 made by Albemarle Japan), 31.1 parts by mass diisononyl phthalate as a plasticizer (Sanso Sizer DINP made by Shin Nippon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-1-4 (DMTDA)]
Dimethylthiotoluenediamine (DMTDA) 5.9 parts by mass (ETHACURE300 Albemarle made in Japan), diisononyl phthalate as plasticizer 30.3 parts by mass (Sanso Sizer DINP made by Shin Nippon Chemical Co., Ltd.), calcium carbonate as filler 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-2 (DBADPM)]
N, N'-dibutylaminodiphenylmethane (DBADPM) 9.8 parts by mass (ETHACURE420 Albemarle made in Japan), diisononyl phthalate as plasticizer 26.4 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate as filler 60.0 parts by mass Part (LW-350 manufactured by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer 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 (Sanso Sizer DINP made by Shin Nippon Rika Co., Ltd.), calcium carbonate as a filler 60.0 parts by mass Part (LW-350 manufactured by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer 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 made by Nippon Nippon Chemical Co., Ltd.), calcium carbonate as a filler 60.0 masses Part (LW-350 manufactured by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-3 (MOCA + polyol)]
3,3'-Dichloro-4,4'diaminodiphenylamine (MOCA) 7.7 parts by mass (Bisamine A Wakayama Seika Kogyo Co., Ltd.), number average molecular weight 2,000 polypropylene ether diol 5.8 parts by mass (Actol D-2000 Mitsui Chemicals) SKC Polyurethane Co., Ltd.), 22.7 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 manufactured by Shimizu Kogyo Co., Ltd.), and others A curing agent was obtained by uniformly mixing 3.8 parts by mass of the additive. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-3-1 (MOCA + polyol)]
3,3'-Dichloro-4,4'diaminodiphenylamine (MOCA) 4.8 parts by mass (Bisamine A Wakayama Seika Kogyo Co., Ltd.), number average molecular weight 2,000 polypropylene ether diol 5.8 parts by mass (Actol D-2000 Mitsui Chemicals) SKC Polyurethane Co., Ltd.), 25.6 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 manufactured by Shimizu Kogyo Co., Ltd.), and others A curing agent was obtained by uniformly mixing 3.8 parts by mass of the additive. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-3-2 (MOCA + polyol)]
3,3'-dichloro-4,4'diaminodiphenylamine (MOCA) 6.6 parts by mass (Bisamine A Wakayama Seika Kogyo Co., Ltd.), number average molecular weight 2,000 polypropylene ether diol 5.8 parts by mass (Actol D-2000 Mitsui Chemicals) SKC Polyurethane Co., Ltd.), 23.9 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 others A curing agent was obtained by uniformly mixing 3.8 parts by mass of the additive. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-4 (DMTDA + polyol)]
Dimethylthiotoluenediamine (DMTDA) 6.2 parts by mass (ETHACURE300 made by Albemarle Japan), 5.7 parts by mass of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 made by Mitsui Chemicals SKC Polyurethanes), diisononyl phthalate as a plasticizer 24.3 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate as filler 60.0 parts by mass (LW-350 Shimizu Kogyo Co., Ltd.) and other additives 3.8 parts by mass are mixed uniformly to hardener It was. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-4-1 (DMTDA + polyol)]
Dimethylthiotoluenediamine (DMTDA) 3.9 parts by mass (ETHACURE300 made by Albemarle Japan), 5.7 parts by weight of polypropylene ether diol having a number average molecular weight of 2,000 (Actocol D-2000 made by Mitsui Chemicals SKC Polyurethane Co., Ltd.), diisononyl phthalate as a plasticizer 26.6 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate as filler 60.0 parts by mass (LW-350 Shimizu Kogyo Co., Ltd.) and other additives 3.8 parts by mass are mixed uniformly to hardener It was. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-4-2 (DMTDA + polyol)]
Dimethylthiotoluenediamine (DMTDA) 5.3 parts by mass (ETHACURE300 manufactured by Albemarle Japan), number average molecular weight 2,000 polypropylene ether diol 5.7 parts by mass (Accor D-2000, Mitsui Chemicals SKC Polyurethane Co., Ltd.), diisononyl phthalate as a plasticizer 25.2 parts by mass (Sansocizer DINP made by Shin Nippon Rika Co., Ltd.), 60.0 parts by mass of calcium carbonate as filler (LW-350 made by Shimizu Kogyo Co., Ltd.), and 3.8 parts by mass of other additives are uniformly mixed and hardened. It was. Other additives include ASA DS525 (wet dispersant) manufactured by Ito Oil Co., Ltd., octyl acid (catalyst) manufactured by KH Neochem Co., Ltd., NBK-1202 (colorant) manufactured by Nihongo Bix Co., Ltd., Enomoto Kasei Co., Ltd. DISPARLON P-450 (antifoaming agent) manufactured by the manufacturer was used.

[Curing agent B-5 (DMTDA, no catalyst added)]
Dimethylthiotoluenediamine (DMTDA) 6.8 parts by mass (ETHACURE300 made by Albemarle Japan), diisononyl phthalate as plasticizer 29.4 parts by mass (Sanso Sizer DINP made by Nippon Nippon Chemical Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., NBK-1202 (colorant) manufactured by Nichihiro Bix Co., Ltd., and DISPARLON P-450 (antifoaming agent) manufactured by Enomoto Kasei Co., Ltd. Using.

[Curing agent B-5-1 (DMTDA, no catalyst added)]
Dimethylthiotoluenediamine (DMTDA) 3.9 parts by mass (ETHACURE300 Albemarle made in Japan), diisononyl phthalate as plasticizer 26.6 parts by mass (Sanso Sizer DINP Shin Nippon Rika Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., NBK-1202 (colorant) manufactured by Nichihiro Bix Co., Ltd., and DISPARLON P-450 (antifoaming agent) manufactured by Enomoto Kasei Co., Ltd. Using.

[Curing agent B-5-2 (DMTDA, no catalyst added)]
Dimethylthiotoluenediamine (DMTDA) 5.3 parts by mass (ETHACURE300 made by Albemarle Japan), diisononyl phthalate as plasticizer 25.2 parts by mass (Sanso Sizer DINP made by Nippon Nippon Chemical Co., Ltd.), calcium carbonate 60.0 parts by mass (LW- 350 made by 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 (wet dispersant) manufactured by Ito Oil Co., Ltd., NBK-1202 (colorant) manufactured by Nichihiro Bix Co., Ltd., and DISPARLON P-450 (antifoaming agent) manufactured by Enomoto 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 a mass ratio shown in Table 1 to obtain various two-component mixed room temperature curing pavement materials. As shown in Table 1, when 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed, the equivalent ratio of isocyanate group to amino group is 1.25. About the obtained pavement material, the hardened | cured material physical property and workability | operativity were evaluated with the following method. The evaluation results are also shown in Table 1.

(1) Evaluation of physical properties of cured product (1-1) Evaluation of tensile strength and elongation A test piece was prepared by punching out a fully cured 2mm thick sheet with dumbbell-shaped No. 3, and compliant with JISK6251 Went. 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 sheet with a thickness of 2 mm is punched out with an angle die to produce a test piece, which is tested in accordance with JIS K6252, and the tear strength is 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 paving material, the viscosity (25 ° C.) after mixing the main agent and the curing agent was measured over time, and a viscosity increase curve was prepared. When the viscosity exceeds 50000 mPa · s, workability becomes insufficient. Therefore, the time until the viscosity reaches 50000 mPa · s after mixing the two liquids was defined as “pot life”.

(2-2) Evaluation of hardness on the next day Each pavement was poured into a container to a depth of 1 cm, and after 18 hours, Shore A hardness was measured in accordance with JISK6253. When the hardness of the next day is less than 30, it is difficult for a person to get on and work.

  As is clear from Table 1, in the levels 1 to 6 (invention examples) using the main agent and the curing agent within the scope of the present invention, excellent cured product properties and workability could be exhibited. On the other hand, in levels 7 to 12 (comparative examples) using DBADPM as a curing agent, the cured product properties are inferior and the pot life is not a problem, but the curing is too slow and inferior to the next day curability. The nature is bad. Moreover, in the level 13-18 (comparative example) using MOCA + polyol as a hardening | curing agent, although cured | curing material physical property is equivalent to the level 1-6, since a specific chemical substance disorder prevention rule is applied. It is not preferable. As is clear from the levels 1, 5, and 6, even if the isomer ratio of the monomeric MDI is changed, if the curing agent is the same, excellent physical properties and workability can be exhibited.

[Experiment 2: Comparative workability test]
The main agent and the curing agent were mixed at a mass ratio shown in Table 2 to obtain various two-component mixed room temperature curing 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 of isocyanate group to amino group is 1.25. About the obtained pavement material, the viscosity (25 degreeC) after mixing of a main ingredient and a hardening | curing agent was measured with time similarly to Experimental example 1. FIG. The obtained viscosity increase curve is shown in FIG. 3, and the time until the viscosity reaches 50000 mPa · s after mixing the two liquids is shown in Table 2 as “pot life”.

  As is apparent from Table 2 and FIG. 3, in the levels 1, 2, 6 to 9 (invention examples) using the main agent having an unreacted MDI of less than 1.0% by mass and the curing agent within the scope of the present invention, the increase in the viscosity It was very gentle and was able to maintain a viscosity of 50,000 mPa · s or less for good workability for about 60 to 70 minutes. On the other hand, as shown in levels 3 to 5 (comparative examples), when an unreacted MDI is used in an amount of 1.0% by mass or more, the viscosity immediately after mixing, even if a curing agent within the scope of the present invention is used. As a result, the viscosity of 50000 mPa · s or less, which provides good workability, can only be maintained for about 20 minutes from 5 minutes, and the workability is poor.

[Experimental Example 3: Foaming test]
The main agent, curing agent and water were mixed at a mass ratio shown in Table 3 to obtain various two-component mixed room temperature curing pavement materials. In addition, as shown in Table 3, when 50 parts by mass of the main agent and 50 parts by mass of the curing agent are mixed, the equivalent ratio of isocyanate group to amino group is 1.25. About the obtained pavement material, the foamability during hardening was observed visually. The results are shown in Table 3 with “x” when foaming is observed and “◯” when no foaming is observed.

  As is clear from Table 3, foaming was observed during curing in levels 7 to 18 (comparative examples) using a curing agent containing polyol. On the other hand, in levels 1 to 6 (invention examples) using a curing agent not containing a polyol, foaming was not recognized during curing.

[Experimental Example 4: Catalyst Comparison Test]
The main agent, curing agent, and various curing catalysts were mixed at a mass ratio shown in Table 4 to obtain various two-component mixed room temperature curing 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 of isocyanate group to amino group is 1.25. In Table 4, “lead” is Nikka Octix 24% (made by Nippon Chemical Industry Co., Ltd.), and “tin” is Neostan U-100 (made by Nitto Kasei Co., Ltd.) As the “organic acid”, octylic acid (manufactured by KH Neochem) was used. About the obtained pavement material, the same hardened | cured material property and workability | operativity as shown in Experimental example 1 were evaluated. The evaluation results are also shown in Table 4.

  As is clear from Table 4, the deterioration of workability and the decrease in cured properties due to the catalyst change were not 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 a mass ratio shown in Table 5 to obtain various two-component mixed room temperature curing pavement materials. In addition, the curing agent B-1-α in Table 5 was changed in each level 1 to 9 as appropriate so that the mass part of DMTDA was appropriately changed so that the equivalent ratio of isocyanate group and amino group was 0.90. It is the same as said hardening | curing agent B-1. About the obtained pavement material, the viscosity (25 degreeC) after mixing of a main ingredient and a hardening | curing agent was measured with time similarly to Experimental example 1. FIG. The time required for the viscosity to reach 50000 mPa · s after mixing the two liquids is shown in Table 5 as “pot life”.

  Moreover, the main agent and the curing agent were mixed at a mass ratio shown in Table 6 to obtain various two-component mixed room temperature curing pavement materials. In addition, the curing agent B-1-β in Table 6 was appropriately changed in the weight part of DMTDA in each level 1 to 9, and the equivalent ratio of isocyanate group and amino group was 1.50, It is the same as said hardening | curing agent B-1. About the obtained pavement material, the viscosity (25 degreeC) after mixing of a main ingredient and a hardening | curing agent was measured with time similarly to Experimental example 1. FIG. The time until the viscosity reaches 50000 mPa · s after mixing the two liquids is shown in Table 6 as “pot life”.

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

  The present invention is used when elastically paving various pavement surfaces such as various stadiums such as athletic stadiums, various grounds such as schoolyards, playgrounds, and tennis courts, runways such as jogging courses, and walking paths such as promenades. It can be used suitably.

DESCRIPTION OF SYMBOLS 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 and a polyol compound, wherein the unreacted diphenylmethane diisocyanate is less than 1.0% by mass;
It contains 90% by mass or more of dimethylthiotoluenediamine, the remainder does not contain a polyol compound, and the remainder consists of an active hydrogen group-containing compound that is a polyamine compound other than 3,3′-dichloro-4-4′-diaminodiphenylamine. A curing agent;
A two-component mixed room temperature curing pavement characterized in that the equivalent ratio of isocyanate groups in the main agent and amino groups in the curing agent is 0.8 to 1.5.   The two-component mixed room temperature curable pavement according to claim 1, comprising a curing accelerator containing an organic acid in an amount of 0.01 to 3% by mass based on the total amount of the main agent and the curing agent.   The two-component mixed room temperature curing pavement according to claim 1 or 2, further comprising 10 to 50% by mass of a filler based on a total amount of the main agent and the curing agent. Spread the two-component mixed room temperature curing pavement according to any one of claims 1 to 3 on a pavement surface to form an application 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 and then spread on the pavement surface. Before the coating layer is cured, an excessive amount of elastic tip is sprayed on the coating layer,
The elastic coating method of Claim 4 which collect | recovers the surplus elastic chips which were not fixed to the said application layer after hardening of the said application layer.

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