JP7299139B2 - Method for manufacturing elastic paving material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an elastic pavement material, and more particularly to a method for producing an elastic pavement material used for elastic pavement of outdoor stadiums, indoor stadiums, playground paths, grounds, courts, and the like.

Currently, in elastic pavement such as outdoor stadiums, indoor stadiums, playground passages, grounds, and courts, it is known to pave the surface to be paved, such as concrete, with an elastic pavement material containing aggregate and elastic resin. It is

As such an elastic pavement material, for example, an elastic pavement material formed by mixing an aggregate and an aromatic amine compound in advance and then mixing a urethane prepolymer has been proposed (see, for example, Patent Document 1).

JP 2013-138508 A

On the other hand, as an elastic pavement material, improvements in various physical properties such as mechanical properties (tensile strength, elongation) and workability (pot life) are required depending on the application.

INDUSTRIAL APPLICABILITY The present invention is a method for producing an elastic pavement material that can obtain an elastic pavement material having excellent mechanical properties (tensile strength and elongation) with good workability.

The present invention [1] comprises a first mixing step of first mixing a pretreatment agent containing polyetheramine and an aggregate to prepare a first composition, A second mixing step of second mixing with a binder containing a polymer to prepare a second composition, and an application step of applying the second composition to form an elastic pavement material. contains a method.

The present invention [2] includes the method for producing an elastic pavement material according to [1] above, wherein the polyetheramine has a number average molecular weight of 500 or more.

The present invention [3] is the elastic pavement according to [1] or [2] above, wherein the ratio of amino groups in the pretreatment agent to isocyanate groups in the binder is 1 equivalent % or more and 30 equivalent % or less. Includes methods of making lumber.

The present invention [4] includes the method for producing an elastic pavement material according to any one of the above [1] to [3], wherein the binder further contains a xylylene diisocyanate monomer. .

In the method for producing an elastic pavement material of the present invention, first, a pretreatment agent containing polyetheramine and an aggregate are first mixed (first mixing step), and then the obtained first composition and isocyanate group It is second mixed with a binder containing a terminated urethane prepolymer (second mixing step), and then the resulting second composition is applied to form a resilient pavement material (application step).

According to such a method for producing an elastic pavement material, the isocyanate group of the isocyanate group-terminated urethane prepolymer first reacts with polyetheramine in the pretreatment agent, then reacts with moisture in the air, and hardens. do. As a result, the second composition containing the isocyanate group-terminated urethane prepolymer has a relatively long pot life, is excellent in workability, and provides an elastic pavement material excellent in mechanical properties (tensile strength, elongation). can be done.

In the method for producing an elastic pavement material of the present invention, first, a pretreatment agent and an aggregate are first mixed to prepare a first composition (first mixing step).

The pretreatment agent contains polyetheramine as an essential component.

A polyetheramine is a polyether having one or more amino groups (primary amino group and/or secondary amino group) capable of reacting with an isocyanate group, preferably a polyether having a primary amino group.

Examples of polyether amines include polyether polyamines having two or more amino groups and polyether monoamines having one amino group.

Examples of polyether polyamines include polyether polyols in which terminal hydroxyl groups are substituted with terminal amino groups, and more specifically, for example, polyoxyalkylene (carbon number (C) 2-3) polyamines. more specifically, for example, polyoxyalkylene (C2-3) diamines such as polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene/polyoxypropylene (random and/or block) copolymerized diamine, Polyoxyalkylene (C2-3) triamines such as polyoxyethylene triamine, polyoxypropylene triamine, polyoxyethylene/polyoxypropylene (random and/or block) copolymerized triamine, and the like. These polyether polyamines can be used alone or in combination of two or more.

Polyether polyamines are also commercially available, and include NOF's PEG#1000 diamine, Huntsman's Jeffamine series, and BASF's Baxxodur series.

Examples of the polyether monoamine include one-end-blocked polyoxyalkylene (C2-3) diamine obtained by blocking one end of the above polyoxyalkylene (C2-3) diamine with an alkyl group having 1 to 20 carbon atoms. is mentioned.

These polyetheramines can be used alone or in combination of two or more.

From the viewpoint of improving workability (pot life) and mechanical properties (tensile strength, elongation), polyether amines are preferably polyether amines, more preferably polyoxyalkylene (C2-3) polyamines. and more preferably polyoxyalkylene (C2-3) diamine, and particularly preferably polyoxypropylene diamine.

The number average molecular weight (polystyrene equivalent molecular weight by GPC measurement) of polyetheramine is, for example, 300 or more, preferably 400 or more, from the viewpoint of improving workability (pot life) and mechanical properties (tensile strength, elongation). More preferably 500 or more, still more preferably 1000 or more, particularly preferably 1500 or more, for example, 10000 or less, preferably 8000 or less, more preferably 6000 or less, still more preferably 5000 or less, especially preferably is 3000 or less.

Moreover, the pretreatment agent can contain a plasticizer and/or a polyether polyol as an optional component from the viewpoint of improving uniform adhesion to the aggregate (described later).

From the viewpoint of improving mechanical properties (tensile strength, elongation), the pretreatment agent preferably contains a plasticizer and/or polyether polyol.

Examples of plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, dinonyl phthalate, and phthalate. phthalate plasticizers such as diisononyl acid, diisodecyl phthalate, ditridecyl phthalate, dibutylpentyl phthalate, and dicyclohexyl phthalate; Aliphatic dibasic acid ester plasticizers such as dioctyl sebacate, glycol ester plasticizers such as diethylene glycol benzoate and dipentaerythritol hexaester, and phosphate ester plasticizers such as tricresyl phosphate and trioctyl phosphate agents, for example, epoxy-based plasticizers such as epoxidized soybean oil, butyl epoxystearate, and octyl epoxystearate. These plasticizers can be used alone or in combination of two or more.

The plasticizer preferably includes a phthalate plasticizer, more preferably diisononyl phthalate.

Examples of polyether polyols include polyoxy(C2-3) alkylene polyols and polytetramethylene ether polyols.

Polyoxy(C2-3) alkylene polyols include, for example, addition polymers of alkylene oxides having 2 to 3 carbon atoms with known initiators such as low-molecular-weight polyols and polyamine compounds.

The low-molecular-weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of less than 300, preferably less than 400, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl pentanediol, 3,3-dimethylolheptane, alkane (C7-20) diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and their Dihydric alcohols such as mixtures, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol , trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine; tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin; pentahydric alcohols such as xylitol; , allitol, iditol, dulcitol, altritol, inositol and dipentaerythritol; heptahydric alcohols such as perseitol; and octahydric alcohols such as sucrose. These low-molecular-weight polyols can be used alone or in combination of two or more.

Examples of alkylene oxides having 2 to 3 carbon atoms include propylene oxide and ethylene oxide. Moreover, these alkylene oxides can be used alone or in combination of two or more. The polyoxy(C2-3)alkylene polyols include, for example, random and/or block copolymers of propylene oxide and ethylene oxide.

More specific examples of polyoxy(C2-3)alkylene polyols include polyoxyethylene polyols, polyoxypropylene polyols, polyoxyethylene/polyoxypropylene (random and/or block) copolymers, and the like.

Polytetramethylene ether polyols include, for example, ring-opening polymers obtained by cationic polymerization of tetrahydrofuran, and amorphous (non-crystalline nature) polytetramethylene ether glycol and the like.

Amorphous (non-crystalline) means liquid at room temperature (25° C.).

Amorphous polytetramethylene ether glycol is, for example, a copolymer of tetrahydrofuran and alkyl-substituted tetrahydrofuran (eg, 3-methyltetrahydrofuran) (tetrahydrofuran/alkyl-substituted tetrahydrofuran (molar ratio) = 15/85 to 85/ 15, a number average molecular weight of 500 to 4000, preferably 800 to 2500) or, for example, a copolymer of tetrahydrofuran and a branched glycol (e.g., neopentyl glycol) (tetrahydrofuran/branched glycol (molar ratio) = 15/85 to 85/15, number average molecular weight 500 to 4000, preferably 800 to 2500).

These polyether polyols can be used alone or in combination of two or more.

Polyether polyols preferably include polyoxy(C2-3) alkylene polyols, more preferably polyoxypropylene polyols, and still more preferably polyoxypropylene diols.

The number average molecular weight (polystyrene equivalent molecular weight by GPC measurement) of the polyether polyol is, for example, 300 or more, preferably 400 or more, more preferably 500 or more, still more preferably 1000 or more, and particularly preferably 1500 or more. , for example, 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less.

The pretreatment agent preferably contains a plasticizer or polyether polyol, and more preferably contains a plasticizer from the viewpoint of improving uniform adhesion to the aggregate (described later).

When the pretreatment agent contains a polyetheramine, a plasticizer and/or a polyether polyol, the polyetheramine is, for example, 30 parts by mass or more, preferably 40 parts by mass, relative to the total amount of 100 parts by mass. It is at least 90 parts by mass, preferably 80 parts by mass or less. Further, the plasticizer and/or polyether polyol is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 70 parts by mass or less, preferably 60 parts by mass or less.

Further, the plasticizer and the polyether polyol (when used together, the total amount thereof) is, for example, 10 parts by mass or more, preferably 50 parts by mass or more, with respect to 100 parts by mass of the total amount of polyetheramine. , 500 parts by mass or less, preferably 200 parts by mass or less.

Examples of aggregates include inorganic aggregates, organic aggregates, rubber chips, foam chips, and the like.

Examples of inorganic aggregates include natural silicic substances (eg, river sand, silica sand, etc.). Moreover, as an inorganic aggregate, the ground material of an inorganic material is also mentioned, for example. Examples of such inorganic materials include glass, ceramics, mullite, electrode alumina, and silicon carbide. Furthermore, examples of inorganic aggregates include sawdust, wood chips, pumice stone, vermiculite, and glass fiber.

These inorganic aggregates can be used alone or in combination of two or more.

Organic aggregates include, for example, pulverized plastics. Examples of such plastics include nylon (registered trademark) resin, vinyl chloride resin, urea resin, phenol resin, melamine resin, acetal resin, acrylic resin, acrylonitrile-butadiene-styrene (ABS) resin, cellulose acetate resin, and polycarbonate. resins, polyethylene terephthalate (PET) resins, polystyrene resins, polyurethane resins, polyethylene resins, polypropylene resins, and the like. Examples of organic aggregates include cotton, wool, polyamide fibers, polyester fibers, and polyacrylonitrile fibers.

These organic aggregates can be used alone or in combination of two or more.

Examples of rubber chips include known rubber chips such as natural rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyurethane rubber, and ethylene-propylene-diene rubber (EPDM).

These rubber chips can be used alone or in combination of two or more.

Examples of foam chips include polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer (ABS), ethylene-vinyl acetate copolymer (EVA), polyurethane, polyvinyl chloride, polyethylene, and polypropylene. resin foam chips such as glass foam chips and cork chips. The foam chips are preferably resin foam chips, more preferably ethylene-vinyl acetate copolymer (EVA) resin foam chips.

These foam chips can be used alone or in combination of two or more.

These aggregates can be used singly or in combination of two or more.

Aggregates preferably include rubber chips.

In the first mixing step, the method of mixing the pretreatment agent and the aggregate is not particularly limited, and a known method is employed.

The mixing ratio of the pretreatment agent and the aggregate is not particularly limited as long as the surface of the aggregate can be coated with the pretreatment agent. 01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, for example, 30 parts by mass or less, preferably 20 It is not more than 10 parts by mass, more preferably not more than 5 parts by mass.

Further, when the pretreatment agent contains polyetheramine and a plasticizer and/or polyether polyol, the polyetheramine is, for example, 0.005 parts by mass or more with respect to 100 parts by mass of the aggregate, Preferably 0.025 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.25 parts by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass or less, or more It is preferably 5 parts by mass or less, more preferably 2.5 parts by mass or less. In addition, the plasticizer and polyether polyol (the total amount thereof when used together) is, for example, 0.005 parts by mass or more, preferably 0.025 parts by mass or more, with respect to 100 parts by mass of the aggregate, More preferably 0.05 parts by mass or more, still more preferably 0.25 parts by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably is 2.5 parts by mass or less.

By mixing the pretreatment agent and the aggregate, a first composition including the pretreatment agent and the aggregate is obtained.

The first composition further comprises, as optional components, fillers, pigments, plasticizers, antifoaming agents, antiblocking agents, heat stabilizers, light stabilizers, antioxidants, release agents, catalysts, dyes, lubricants, Additives such as hydrolysis inhibitors can be included.

The additive may be, for example, premixed with the pretreatment agent, premixed with the aggregate, or added at the same time as the pretreatment agent and aggregate are mixed. It may also be added to the mixture (first composition) of the pretreatment agent and the aggregate.

The proportion of the additive is appropriately set according to the purpose and application.

Next, in this method, the first composition obtained above and a binder are secondly mixed to prepare a second composition (second mixing step).

The binder contains an isocyanate group-terminated urethane prepolymer as an essential component.

The isocyanate group-terminated urethane prepolymer is a urethane prepolymer having at least two isocyanate groups at the molecular ends, and can be obtained by reacting a raw material isocyanate and a raw material polyol in a predetermined ratio.

Examples of raw material polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives.

Polyisocyanate monomers include, for example, aromatic polyisocyanates, araliphatic polyisocyanates, and aliphatic polyisocyanates.

Examples of aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof), 4, 4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) (MDI), aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenylether diisocyanate;

Examples of araliphatic polyisocyanates include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra araliphatic diisocyanates such as methylxylylene diisocyanate (or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 ,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc. and aliphatic diisocyanates.

Aliphatic polyisocyanates also include alicyclic polyisocyanates. Examples of alicyclic polyisocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3 ,5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis(cyclohexylisocyanate) (4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexylisocyanate), trans, trans -, Trans, Cis-, Cis, Cis-, or mixtures thereof)) (H ₁₂ MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane Alicyclics such as diisocyanates (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H ₆ XDI) group diisocyanates.

These polyisocyanate monomers can be used singly or in combination of two or more.

Polyisocyanate derivatives include, for example, multimers (e.g., dimers, trimers (e.g., isocyanurate modified products, iminooxadiazinedione modified products), pentamers, 7 polymer, etc.), allophanate modified products (e.g., allophanate modified products produced by the reaction of the above-described polyisocyanate monomers and low-molecular-weight polyols described later), polyol modified products (e.g., polyisocyanate monomers and later described polyol modified product (alcohol adduct) produced by reaction with a low molecular weight polyol), biuret modified product (for example, the above-mentioned polyisocyanate monomer, biuret modified product produced by reaction with water or amines, etc. ), modified urea (for example, modified urea produced by the reaction of the above-mentioned polyisocyanate monomer and diamine), modified oxadiazinetrione (for example, the above-mentioned polyisocyanate monomer and carbon dioxide gas oxadiazinetrione produced by the reaction), modified carbodiimide (modified carbodiimide produced by the decarboxylation condensation reaction of the above-mentioned polyisocyanate monomer, etc.), modified uretdione, modified uretonimine, and the like.

Furthermore, polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear substance-containing diphenylmethane diisocyanate) and the like.

These polyisocyanate derivatives can be used alone or in combination of two or more.

These raw material polyisocyanates can be used alone or in combination of two or more.

The starting polyisocyanate preferably includes a polyisocyanate monomer, more preferably an aromatic polyisocyanate, still more preferably tolylene diisocyanate and/or diphenylmethane diisocyanate, and particularly preferably tri Diisocyanates are mentioned.

Further, as tolylene diisocyanate, a combination of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate is preferably used. These combined ratios are appropriately set according to the purpose and application.

Examples of raw material polyols include high-molecular-weight polyols.

The high-molecular-weight polyol is a compound having a number average molecular weight of 300 or more, preferably 400 or more, for example, 10000 or less, having two or more hydroxyl groups, such as polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, and epoxy polyol. , vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols.

These high molecular weight polyols can be used alone or in combination of two or more.

Polyether polyols, polyester polyols, and polycarbonate polyols are preferred as high-molecular-weight polyols, and polyether polyols are more preferred.

Examples of the polyether polyol include the polyether polyols described above, more specifically, the polyoxy (C2-3) alkylene polyols described above, the polytetramethylene ether polyols described above, and the like. (C2-3) Alkylene polyols, more preferably polyoxypropylene polyols.

The average number of hydroxyl groups of the high molecular weight polyol is, for example, 1.8 or more, preferably 2 or more, and is, for example, 6 or less, preferably 4 or less, more preferably 3 or less.

The number average molecular weight (polystyrene equivalent molecular weight by GPC measurement) of the high molecular weight polyol is, for example, 300 or more, preferably 400 or more, from the viewpoint of improving workability (pot life) and mechanical properties (tensile strength, elongation). More preferably 500 or more, still more preferably 700 or more, particularly preferably 800 or more, for example, 10000 or less, preferably 8000 or less, more preferably 5000 or less, still more preferably 3000 or less, particularly preferably is 2000 or less.

Moreover, the raw material polyol can contain a low-molecular-weight polyol as needed.

The content of the low-molecular-weight polyol in the raw material polyol is appropriately set according to the purpose and application. The feedstock polyol is preferably free of low molecular weight polyols.

The starting polyol preferably includes a high-molecular-weight polyol, more preferably a polyether polyol, still more preferably a polyoxypropylene polyol, and particularly preferably a polyoxypropylene glycol.

Then, the isocyanate group-terminated urethane prepolymer is obtained by combining the raw material isocyanate and the raw material polyol so that the equivalent ratio (NCO/OH) of the raw material isocyanate to the hydroxyl group of the raw material polyol is greater than 1, preferably 1.3 to 50, More preferably, it can be obtained by a urethanization reaction at a ratio of 1.5 to 2.

The urethanization reaction can conform to known methods. The reaction temperature in the urethanization reaction is, for example, 50° C. or higher, and for example, 120° C. or lower, preferably 100° C. or lower. The reaction time is, for example, 0.5 hours or longer, preferably 1 hour or longer, and for example, 15 hours or shorter, preferably 10 hours or shorter.

In addition, in the urethanization reaction, if necessary, a known organic solvent can be added to prepare an isocyanate group-terminated urethane prepolymer in the presence thereof (solution polymerization).

In addition, in the solution polymerization, the blending ratio of the organic solvent is appropriately set according to the purpose and application.

In addition, in the above urethanization reaction, a known urethanization catalyst such as amines or organometallic compounds can be added in an appropriate proportion, if necessary.

In the case of preparing the isocyanate group-terminated urethane prepolymer by solution polymerization, if an organic solvent is used, the organic solvent can be removed by a known removing means, if necessary.

If necessary, free (unreacted) polyisocyanate may be removed from the obtained isocyanate group-terminated urethane prepolymer by known removal means such as distillation or extraction.

The average number of isocyanate groups in the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 1.2 or more, preferably 1.5 or more, more preferably 2 or more, and for example, 4 or less, preferably 3 or less. , more preferably 2.5 or less, and particularly preferably 2.

The isocyanate group equivalent weight of the isocyanate group-terminated urethane prepolymer (solid content) is, for example, 84-3500, preferably 150-2800, more preferably 168-2335. The isocyanate group equivalent has the same meaning as the amine equivalent, and can be determined by Method A or Method B of JIS K 1603-1 (2007).

The isocyanate group content (isocyanate group content, NCO %) of such an isocyanate group-terminated urethane prepolymer (solid content) is, for example, 1.2% by mass or more, preferably 1.5% by mass or more, More preferably 1.8% by mass or more, still more preferably 2.0% by mass or more, particularly preferably 3.0% by mass or more, for example, 50% by mass or less, preferably 28% by mass or less, More preferably, it is 25% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

The isocyanate group-terminated urethane prepolymers may be used alone or in combination of two or more.

The isocyanate group-terminated urethane prepolymer preferably includes an isocyanate group-terminated urethane prepolymer that is a reaction product of an aromatic polyisocyanate and a polyether polyol, more preferably tolylene diisocyanate and/or diphenylmethane diisocyanate and a polyether polyol. Examples include isocyanate group-terminated urethane prepolymers that are reaction products with ether polyols, more preferably isocyanate group-terminated urethane prepolymers that are reaction products of tolylene diisocyanate and polyether polyol, and particularly preferably and an isocyanate group-terminated urethane prepolymer which is a reaction product of tolylene diisocyanate and polyoxypropylene glycol.

Moreover, the binder can contain a polyisocyanate monomer and/or a polyisocyanate derivative as an optional component.

From the viewpoint of improving mechanical properties (especially tensile strength), the binder preferably contains a plasticizer and/or polyether polyol.

Examples of polyisocyanate monomers include the above-described polyisocyanate monomers. Polyisocyanate monomers can be used singly or in combination of two or more.

Examples of the polyisocyanate derivative include the polyisocyanate derivatives described above. Polyisocyanate derivatives can be used alone or in combination of two or more.

From the viewpoint of improving workability (pot life) and mechanical properties (tensile strength, elongation), the binder preferably contains an araliphatic polyisocyanate monomer and/or derivative thereof, more preferably It contains a xylylene diisocyanate monomer and/or a derivative thereof, more preferably a xylylene diisocyanate monomer.

In the binder, the polyisocyanate monomer and/or polyisocyanate derivative (when used in combination, the total amount) is, for example, 1 part by mass or more, preferably 5 parts by mass with respect to 100 parts by mass of the total amount of the binder. or more, for example, less than 50 parts by mass, preferably 30 parts by mass or less.

Further, the isocyanate group-terminated urethane prepolymer is, for example, more than 50 parts by mass, preferably 70 parts by mass or more, for example, 99 parts by mass or less, preferably 95 parts by mass, relative to the total amount of 100 parts by mass of the binder. It is below the department.

Moreover, in the second mixing step, the mixing ratio of the first composition and the binder is appropriately set according to the purpose and application.

For example, the ratio of amino groups in the pretreatment agent to isocyanate groups in the binder is, from the viewpoint of improving mechanical properties (especially elongation), for example, 0.1 equivalent % or more, preferably 0.2 equivalents. % or more, more preferably 0.3 equivalent % or more, still more preferably 0.5 equivalent % or more, particularly preferably 1 equivalent % or more, and from the viewpoint of improving workability (pot life), for example , 30 equivalent % or less, preferably 25 equivalent % or less, more preferably 20 equivalent % or less, still more preferably 10 equivalent % or less, particularly preferably 5 equivalent % or less.

Also, on a mass basis, the mass ratio of polyetheramine to 100 parts by mass of the binder is, for example, 0.1 parts by mass or more, preferably 1 mass, from the viewpoint of improving mechanical properties (especially elongation). parts or more, more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, and particularly preferably 2.5 parts by mass or more. , 70 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.

By mixing the first composition and the binder in this manner, the second composition containing the first composition (pretreatment agent and aggregate) and the binder is obtained.

The second composition is an uncured resin composition (curable resin composition) that forms an elastic resin upon curing.

In addition, the second composition further includes, as optional components, a filler, a pigment, a plasticizer, an antifoaming agent, an antiblocking agent, a heat stabilizer, a light stabilizer, an antioxidant, a release agent, a catalyst, a dye, Additives such as lubricants, anti-hydrolysis agents and the like can be included.

The additive may be, for example, pre-mixed with the first composition or pre-mixed with the binder, or may be added at the same time as the first composition and the binder are mixed. may be added to the mixture of the first composition and the binder (second composition).

The proportion of the additive is appropriately set according to the purpose and application.

Thereafter, in this method, the second composition obtained above is applied to form an elastic pavement material (application step).

More specifically, in this step, the second composition is applied to the surface to be paved.

The surface to be paved is a surface to be elastically paved with an elastic pavement material, and examples thereof include concrete floor surfaces in outdoor stadiums, indoor stadiums, playground paths, grounds, courts, and the like. Further, for example, a guide frame is provided on the surface to be paved. The guide frame is a member that guides the second composition so that it falls within a predetermined range, and consists of a removable frame.

The method of applying the second composition to the surface to be paved is not particularly limited. Spread it evenly using, etc., harden it, and if necessary, cure it.

The curing conditions are not particularly limited, but the curing temperature is, for example, 0° C. or higher, preferably 5° C. or higher, for example, 50° C. or lower, preferably 40° C. or lower, and the curing time is, for example, 5 hours or longer. , preferably 8 hours or more, for example 24 hours or less, preferably 18 hours or less.

The curing conditions are not particularly limited, but the curing temperature is, for example, 5° C. or higher, preferably 10° C. or higher, for example, 50° C. or lower, preferably 40° C. or lower, and the curing time is, for example, 1 day or more. , preferably 3 days or more, for example 30 days or less, preferably 15 days or less.

As a result, a urethanization reaction of the isocyanate group-terminated urethane prepolymer and the polyether amine and a moisture curing reaction of the isocyanate group-terminated urethane prepolymer occur to obtain a polyurethane elastic resin (paving resin).

As a result, the surface to be paved is paved with an elastic layer containing polyurethane elastic resin (pavement resin).

The elastic layer that paves the surface to be paved may be a single layer or multiple layers. The elastic layer may contain only the above elastic resin (cured product of the second composition), or may contain other resins. Furthermore, an elastic layer such as a durable layer or an embossed layer may be laminated on the elastic layer.

In the above method for producing an elastic pavement material, first, a pretreatment agent containing polyetheramine and an aggregate are first mixed (first mixing step), and then the obtained first composition and isocyanate A binder containing a terminal urethane prepolymer is second mixed (second mixing step), and then the resulting second composition is applied to form a resilient pavement material (application step).

According to such a method for producing an elastic pavement material, the isocyanate group of the isocyanate group-terminated urethane prepolymer first reacts with polyetheramine in the pretreatment agent, then reacts with moisture in the air, and hardens. do. As a result, the second composition containing the isocyanate group-terminated urethane prepolymer has a relatively long pot life, is excellent in workability, and provides an elastic pavement material excellent in mechanical properties (tensile strength, elongation). can be done.

Therefore, the resulting elastic pavement material is suitably used for elastically paving surfaces to be paved in various facilities, such as concrete floors in outdoor stadiums, indoor stadiums, playground paths, grounds, courts, and the like.

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. "Parts" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.

<Pretreatment agent>
Preparation Examples 1 to 7 (Pretreatment agents (PT-1 to PT-7))
As shown in Table 1, Jeffamine D-400 (polyoxypropylene diamine having an average molecular weight of 400, manufactured by Huntsman), D-700 (polyoxypropylene diamine having an average molecular weight of 700, manufactured by Huntsman), D-2000 (average molecular weight) 2000 polyoxypropylene diamine, manufactured by Huntsman), hexamethylene diamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), or Lonzacure DETDA80 (diethyltoluene diamine with a ratio of 2,4 to 2,6 of 80/20, Lonza Japan Co., Ltd.) was mixed with polyoxypropylene glycol (PPG, Actcol D-2000, average molecular weight 2000, Mitsui Chemicals SKC Polyurethane) or DINP (plasticizer, diisononyl phthalate, Shin Nippon Rika Co., Ltd.). Thus, a pretreatment agent was obtained.

<Isocyanate group-terminated urethane prepolymer>
Preparation example 1 (TDI-based prepolymer (P-1))
Polyoxypropylene glycol (PPG, Actcol D-1000, average molecular weight 1000, manufactured by Mitsui Chemicals SKC Polyurethane) 742 parts by mass, toluene diisocyanate (T-80/20, Cosmonate T-80, 2,4-isomer and 258 parts by mass of TDI having a 2,6-isomer ratio of 80/20 (manufactured by Mitsui Chemicals SKC Polyurethane) was charged into a separable flask and reacted at 90° C. for 3 hours.

As a result, a TDI-based prepolymer (P-1) was obtained as an isocyanate group-terminated urethane prepolymer.

The TDI prepolymer (P-1) had an isocyanate group concentration (NCO %) of 6.1% and a viscosity (25° C.) of 17,000 mPa·s.

<Binder>
Production Example 1 (binder (B-1))
As shown in Table 2, 15 parts by mass of m-xylylene diisocyanate (XDI monomer, Takenate 500, manufactured by Mitsui Chemicals) was added to 85 parts by mass of the TDI prepolymer (P-1), and the binder (B -1) was obtained.

Production Example 2 (Binder (B-2))
As shown in Table 2, 15 parts by mass of carbodiimide-modified diphenylmethane diisocyanate (MDI derivative, Cosmonate LK, manufactured by Mitsui Chemicals SKC Polyurethane) was added to 85 parts by mass of TDI-based prepolymer (P-1), and a binder was added. (B-2) was obtained.

Production Example 3 (Binder (B-3))
As shown in Table 2, 100 parts by mass of TDI prepolymer (P-1) was used as binder (B-3).

<Manufacturing elastic paving materials>
Examples 1 to 5, 7 to 10, Reference Example 6 and Comparative Examples 1 to 4
According to the formulations shown in Tables 3 to 5, a pretreatment agent was added to red colored rubber chips (particle size: about 3 mm, manufactured by Toyo Rubber Chip Co., Ltd.) as aggregate, and the mixture was thoroughly mixed by pre-stirring for 3 minutes (first mixing step). After that, a binder was added to the obtained first composition and mixed well for an additional 3 minutes (second mixing step). A second composition was thus obtained.

Thereafter, the obtained second composition was poured into a mold having a thickness of 10 mm so as to have an apparent specific gravity of 0.98, and was evenly spread with a trowel so that the surface was smooth (application step). Thus, a rubber mat as an elastic pavement material was obtained.

Tables 3 to 5 also show the ratio of the amino groups in the pretreatment agent to the isocyanate groups in the binder (amino groups in the pretreatment agent/isocyanate groups in the binder (% by equivalent)).

In Comparative Examples 1 and 2, no polyetheramine was used as the pretreatment agent.

Moreover, in Comparative Example 3, the aggregate and the binder were first mixed, and then the pretreatment agent was added to the mixture.

Moreover, in Comparative Example 4, no pretreatment agent was used.

<Evaluation>
(1) Workability In the production of the elastic pavement material, the workability at the time of application of the second composition was evaluated as ◯. Also, when the viscosity of the second composition was excessively high and/or there was much adhesion of rubber chips to the trowel, the workability was poor. And the middle of them was made into (triangle|delta).

Thirty minutes after the start of the preparation (mixing) of the second composition, ◯ was given when the rubber chips could be spread evenly with a trowel. In addition, X was given to those in which such spreading was impossible. And the middle of them was made into (triangle|delta).

(2) Tensile Strength and Elongation Properties The rubber mats of each example , reference example and each comparative example were aged for one week under the conditions of 23° C. and 50% relative humidity.

Thereafter, the obtained rubber mat was punched into a dumbbell shape with a JIS No. 1 dumbbell, and the tensile strength and elongation at break were measured with a universal tensile tester (model number Autograph AGS-5kNX, manufactured by Shimadzu Corporation). The tensile speed was 300 mm, and the distance between the marked lines was 40 mm.

The details of the abbreviations in the table are described below.
Jeffamine D-400: polyoxypropylene diamine having an average molecular weight of 400, Huntsman Jeffamine D-700: polyoxypropylene diamine having an average molecular weight of 700, Huntsman Jeffamine D-2000: polyoxypropylene diamine having an average molecular weight of 2000. , Huntsman Co., Ltd. Hexamethylenediamine: Tokyo Chemical Industry Co., Ltd. Lonsacure DETDA 80: Diethyl toluenediamine with a ratio of 2,4 and 2,6 of 80/20, Lonza Japan PPG: Polyoxypropylene glycol, Actcole D -2000, average molecular weight 2000, Mitsui Chemicals SKC polyurethane DINP: plasticizer, diisononyl phthalate, Shin Nippon Rika Co., Ltd. TDI-based prepolymer: TDI-based prepolymer obtained in Preparation Example 1 XDI monomer: m-xyl Diisocyanate, Takenate 500, Mitsui Chemicals MDI derivative: carbodiimide modified diphenylmethane diisocyanate, Cosmonate LK, Mitsui Chemicals SKC Polyurethane

Claims (3)

a first mixing step of first mixing a pretreatment agent containing polyetheramine and an aggregate to prepare a first composition;
A second mixing step of second mixing the first composition and a binder containing an isocyanate group-terminated urethane prepolymer to prepare a second composition;
A construction step of applying the second composition to form an elastic pavement material ,
The ratio of amino groups in the pretreatment agent to the isocyanate groups in the binder is 1% by equivalent or more and 30% by equivalent or less.
A method for producing an elastic pavement material, characterized by: 2. The method for producing an elastic pavement material according to claim 1, wherein the polyetheramine has a number average molecular weight of 500 or more. 3. The method for producing an elastic pavement material according to claim 1, wherein the binder further contains a monomer of xylylene diisocyanate.