JP2001247644A - Polyurethane binder and elastic pavement material prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane binder composition and the elastic pavement material prepared therewith which is obtained by mixing the polyurethane binder with tips, being filled in a mold, and molded by heating and pressuring the elastic pavement material having a sufficient long allowable time, being excellent in heat-curing performance, and showing an excellent mat strength. SOLUTION: The polyurethane binder is a one-liquid curing polyurethane binder comprising a urethane prepolymer and a curing agent, wherein said urethane propolymer is obtained by reacting an organic polyisocyanate with an active hydrogen compound, having the isocyanate group at the molecular terminal; and said polyurethane binder contains 0.05 to 1.5% by mass of lead. The polyurethane binder can be used to produce the elastic pavement material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane binder. Elastic pavement members obtained by using waste rubber, granular rubber obtained by pulverizing colored synthetic rubber, hijiki rubber, granular natural stone, wood chips, hard plastic, soft plastic, foamed plastic, etc. and a specific polyurethane binder, and production thereof About the law.

[0002]

2. Description of the Related Art Conventionally, a polyurethane binder is used by mixing waste tires or colored synthetic rubber with crushed granular rubber, hiji-like rubber, granular natural stone, wood chips, hard plastic, soft plastic, foamed plastic, etc. (hereinafter referred to as chips). Elastic pavement members such as golf course walking paths, promenades, jogging courses, etc. Has been used as an adhesive for

[0003]

There is a need for a quick-curing type which can obtain a molded product in a short press time when performing heat molding with a mold. For example, JP-A-6-23496
No. 3 discloses a method using a metal catalyst to promote curing. However, according to this method,
The mixture of chips and polyurethane binder tends to solidify in a short time before filling the mold,
Frequent mixing of the chips and the binder in small amounts is required, and there is a problem in the balance between workability and productivity. Therefore, it is strongly required that the pot life after mixing the chips and the binder is sufficiently long and that the curability (heat curability) after pressurization and molding in the mold is sufficiently fast. As means for solving this, for example, Japanese Unexamined Patent Publication No.
No. 53846 discloses a method of compounding a strong acid salt of diazabicycloalkenes. In this method, when a strong acid salt of a diazabicycloalkene is added to the urethane prepolymer, skinning or aggregation tends to occur. Even at room temperature, the reaction proceeds to some extent,
The pot life is not long enough. Further, from the viewpoint of improving product quality, a cured product having higher physical strength is required.

[0004]

In order to solve the above-mentioned problems, the present inventors have proposed a one-component curable polyurethane binder having a sufficiently long pot life, a fast heat-curing property in a mold, and a high rubber mat. As a result of earnestly examining a polyurethane binder having physical properties, a one-part curing type polyurethane binder obtained by reacting an organic polyisocyanate with an active hydrogen compound, comprising a urethane prepolymer having a molecular terminal of an isocyanate group and a curing accelerator, And the polyurethane binder contains 0.05% lead.
It has been found that an elastic pavement member using a polyurethane binder characterized by being contained in an amount of not less than 1.5% by mass and not less than 1.5% by mass maintains sufficient pot life, fast heat curability, and excellent rubber mat strength, and completed the present invention. I came to. That is, the present invention provides the following (1) to (11). (1) A one-pack curable polyurethane binder obtained by reacting an organic polyisocyanate with an active hydrogen compound and comprising a urethane prepolymer having a molecular terminal of an isocyanate group and a curing accelerator, wherein the polyurethane binder contains no lead. A polyurethane binder containing 0.05% by mass or more and 1.5% by mass or less. (2) The polyurethane binder according to (1), wherein the curing accelerator contains at least one of an amine and a polyol and a catalyst, and the used amount thereof is 5 to 50 parts by weight based on 100 parts by weight of the urethane prepolymer. . (3) As the active hydrogen compound, two to six in the molecule
The polyurethane binder according to (1) or (2), which is a polyoxyalkylene polyol obtained by addition polymerization of at least one of propylene oxide and ethylene oxide to a compound having a single hydroxyl group. (4) The polyol of the curing accelerator is divalent or 3 having an average molecular weight of 75 to 10,000 per active hydrogen.
The polyurethane binder according to (2), comprising a polyvalent polyether polyol. (5) The polyurethane binder according to (2), wherein the curing accelerator comprises an amine and a polyol, and the equivalent ratio (amine / polyol) is more than 0/10 and 9/1 or less. (6) The polyurethane binder according to (2), wherein the catalyst contained in the curing accelerator contains lead. (7) The polyurethane binder according to (6), wherein the catalyst contains tin. (8) 5 to 30 parts by weight of the polyurethane binder described in (1) is added to and mixed with 100 parts by weight of the filler.
An elastic pavement member obtained by filling a mold, pressing and molding. (9) The elasticity according to (8), wherein the filler is selected from the group consisting of granular rubber, hijiki rubber, granular natural stone, wood chips, hard plastic chips, soft plastic chips, foamed plastic chips and the like, alone or in combination. Paving members. (10) A method for producing an elastic pavement member obtained by adding and mixing 5 to 30 parts by weight of the polyurethane binder described in (1) with respect to 100 parts by weight of a filler, filling the mixture into a mold, and pressing and molding. (11) The elastic pavement according to (10), wherein the filler is selected from the group consisting of granular rubber, hijiki rubber, granular natural stone, wood chips, hard plastic chips, soft plastic chips, foamed plastic chips and the like, alone or in combination. The method of manufacturing the material.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The one-component curable polyurethane binder of the present invention is a one-component curable polyurethane binder obtained by reacting an organic polyisocyanate with an active hydrogen compound and comprising a urethane prepolymer having a molecular terminal of an isocyanate group and a curing accelerator. A curable polyurethane binder, wherein the polyurethane binder contains 0.05% by mass or more and 1.5% by mass of lead.
It contains below. In particular, it relates to a moisture-curable binder. The details will be described below.

[Polyurethane Binder] The polyurethane binder used in the present invention is a one-part curable type comprising a urethane prepolymer having an isocyanate group at the molecular terminal and a curing accelerator, obtained by reacting an organic polyisocyanate with an active hydrogen compound. A polyurethane binder, wherein the polyurethane binder contains 0.05% by mass or more and 1.5% by mass or less of lead. Lead content is 0.0
When the content is 5% by mass or more, the heat curability during molding is improved, and
When the amount is less than mass%, the pot life is short, and the workability can be improved. Further, the polyurethane binder of the present invention may contain a coloring agent, a plasticizer, a solvent, an ultraviolet absorber, an antioxidant, and the like, if necessary.

<Urethane Prepolymer> The urethane prepolymer of the present invention is produced by reacting an organic polyisocyanate with an active hydrogen compound in the presence of a catalyst. The molar ratio of active hydrogen of the active hydrogen compound used in the production of the polyurethane binder to the organic polyisocyanate (NCO /
OH) is preferably 1.5 to 10.0. When the molar ratio (NCO / OH) is 1.5 or more, the bonding force between the rubber chips becomes strong, and the chips tend not to fall off when the elastic pavement member is used. Further, when it is 10.0 or less, foaming of the polyurethane binder can be suppressed or prevented at the time of molding, and flexibility and toughness can be imparted to the elastic pavement member, which is preferable. Further, the viscosity of the obtained urethane prepolymer is 1000 to 20,000 mPa · s (25
° C) is preferable, and especially 2,000 to 10,000 mPa · s
(25 ° C.) is preferred. When mixed with chips at a viscosity of 2,000 mPa · s or more, it is possible to prevent the polyurethane binder from accumulating below the mixture before heating and curing to form an uneven mixture.
-It can be prevented that mixing with chips and the like becomes difficult at s or less.

(Organic isocyanate) The organic polyisocyanate used in the present invention may be any organic polyisocyanate as long as it does not impair the effects of the present invention. Examples thereof include tolylene diisocyanate (TDI) and diphenylmethane-4,4-diisocyanate ( MDI), diphenylmethane-2,4-diisocyanate (2,4-MDI), naphthalene-1,5-diisocyanate (ND
I), 3,3-dimethyl-4,4-biphenylenediisocyanate
(TODI), liquid diphenylmethane diisocyanate (liquid M) liquefied by a conventionally known method described in JP-B-38-4576 and the like.
DI), crude tolylene diisocyanate (Crude TD
I), aromatic isocyanates such as polymethylene polyphenyl polyisocyanate (crude MDI), norbornane diisocyanate methyl (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, xylylene diisocyanate (XDI), Known aliphatic and / or cycloaliphatic isocyanates such as tetramethyl xylylene diisocyanate (TMXDI), hydrogenated MDI, hydrogenated XDI, and hydrogenated tetramethyl XDI. These may be used alone or in combination of two or more.

(Active Hydrogen Compound) The active hydrogen compound used in the present invention is water or a polyhydric alcohol having 2 to 6 hydroxyl groups, for example, ethylene glycol, propylene glycol, glycerin, diglycerin, trimethylolpropane, pentaerythritol. Sorbitol and the like and mixtures thereof. Further, polyoxyalkylene polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to these polyhydric alcohols and water, esters of higher fatty acids containing hydroxyl groups such as castor oil, A polyether polyol such as (caprolactone) polyol, polybutadiene polyol, poly (butylene carbonate) polyol, poly (hexamethylene carbonate) polyol, poly (ethylene adipate) diol, poly (propylene adipate) diol, and poly (butylene adipate) diol; Polymer polyols obtained by graft polymerization of acrylonitrile and styrene monomer to polyester polyol are exemplified. These may be used alone or in combination of two or more. Particularly preferred are poly (oxypropylene) polyol, poly (oxyethylene propylene) polyol, and polybutadiene polyol.

[Curing accelerator] The curing accelerator of the present invention is not particularly limited as long as it promotes the curing of the polyurethane binder. Preferably, it contains at least one of an amine or a polyol and a catalyst, and the amount thereof is 5 to 100 parts by weight of the urethane prepolymer.
５０50 parts by weight. It also consists of amine and polyol,
When the equivalent ratio (amine / polyol) is more than 0/10 and 9
/ L or less, and more preferably at least one of amine or polyol or a mixture thereof. When the ratio is 9/1 or less, the reaction is quick and a sufficient pot life can be secured. In addition, a catalyst is essential, and if necessary, a colorant, a plasticizer, a solvent, an ultraviolet absorber, an antioxidant, an inorganic filler, and the like may be used. Although the optimum value of the catalyst varies depending on the reaction activity, it is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the curing accelerator. In particular, when the amount is 10 parts by weight or less, the reaction is too fast, and it is possible to prevent the pot life from being shortened. Further, it is particularly preferable that the catalyst contained in the curing accelerator contains a lead compound. Further, a tin compound may be used in combination as a catalyst.

(Polyol) The polyol used as the curing accelerator in the present invention may be water or hydroxyl group.
Polyhydric alcohols having up to six such as ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, sorbitol and the like, and mixtures thereof. Further, polyoxyalkylene polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to these polyhydric alcohols and water, esters of higher fatty acids containing hydroxyl groups such as castor oil, (Caprolactone) polyol, polybutadiene polyol, poly (butylene carbonate) polyol, poly (hexamethylene carbonate) polyol,
Examples thereof include poly (ethylene adipate) diol, poly (propylene adipate) diol, and poly (butylene adipate) diol, and polymer polyols obtained by graft polymerization of acrylonitrile and styrene monomer to polyether polyol or polyester polyol. These can be used alone or in combination of two or more. Particularly preferred are poly (oxypropylene) polyol, poly (oxyethylene propylene) polyol, and polybutadiene polyol. In particular, the polyol has an average molecular weight of 75 to 75 per active hydrogen.
10,000 divalent or trivalent polyether polyols are preferred.

(Amine) The amine used as the curing accelerator in the present invention includes 3,3'-dichloro-4,
4′-diaminodiphenylmethane (MBOCA), an aromatic polyamine obtained by condensing aniline and 2-chloroaniline with formaldehyde in the presence of a mineral acid;
4,4'-diaminodiphenylmethane, o- or p-
Phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenyl, 1,5-naphthylenediamine, tris (4-
Aminophenyl) methane, trimethylene glycol-p
-Aminobenzoate, 2,6-dichloro-p-phenylenediamine, 4,4'-diamino-3,3'-dimethoxycarbonyldiphenylmethane, 2,2'-diaminodiphenyldithioethane, and 3,5-diethyltoluene-2 , 4- or -2,6-diamine, mixtures thereof, bis (methylthio) -2,4- or -2,6-
Examples include toluenediamine, methylthiotoluenediamine, and mixtures thereof.

(Catalyst) As a catalyst used for the curing accelerator in the present invention, a known urethanization catalyst is used. The catalyst is preferably an organometallic compound, more preferably a catalyst containing lead and / or tin. Examples include lead octoate, lead naphthoate, dibutyltin dilaurate, dimethyltin dilaurate, and the like.

[Chips] The chips used in the present invention include granular rubber, hijiki rubber, granular natural stone,
Examples include wood chips, hard, soft and foamed plastic chips. These can be used alone or in combination. Particularly preferred are granular rubber, hijiki rubber and wood chips. Butyl rubber, acrylic rubber, ethylene
It is appropriately selected from propylene rubber, chlorosulfonated rubber, chloroprene rubber, SBR, butadiene and other synthetic rubbers, or a mixture of these materials and a compounded product such as ethylene vinyl acetate. Although the shape of the synthetic rubber is not particularly specified, it is preferably used in the form of a dent or a granule. The average particle size of the granules is from 10 mm to 0.5 mm, more preferably from 7-1 mm.

[Elastic Pavement Member] The method for forming an elastic pavement member according to the present invention comprises:
It is obtained by adding and mixing at least one selected from granular rubber, granular natural stone, wood chips, hard, soft and foamed plastic chips, and the method of curing using a hot press is suitably used. I have. The mixing ratio of the polyurethane binder and the chips should be determined in consideration of the type and shape of the chips.
The polyurethane binder is preferably 5 to 30 parts by weight based on 00 parts by weight. When the amount of the polyurethane binder is 5 parts by weight or more, the bonding between the chips can be prevented from being weakened, and the phenomenon of chips falling off at the time of use after construction of the elastic pavement member can be prevented. The phenomenon that the polyurethane binder flows down to the lower part of the molded article at the time of hot press molding within 30 parts by weight, the porosity at the lower part of the molded article is reduced, and a phenomenon that appropriate elasticity cannot be obtained can be avoided.

(Method of Forming Elastic Pavement Member) As a specific forming method when using the above-mentioned polyurethane binder and chips, a urethane prepolymer and a curing accelerator are mixed in advance, and a urethane prepolymer and a curing accelerator are mixed. And adjust the polyurethane binder. Usually, after the chips are charged into a stirrer such as a cement mixer, a polyurethane binder mixed with a curing accelerator in advance is charged and stirred and mixed. After stirring, a mold or the like is filled with an appropriate amount and hot pressing is performed to obtain a target elastic pavement member.

[0017]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts in the examples represent parts by weight.

(Conditions for forming elastic pavement members and measuring physical properties) A color chip 3010, a gray color, and an average particle diameter of 3 mm from Nissei Sangyo Co., Ltd. was used as the synthetic rubber. Press (manufactured by Toho Kogyo Co., Ltd.) was performed under the conditions of a press temperature of 130 ° C.
The pressing was performed at a pressure of 100 kgf / cm2. The pot life is 2
Leave the mixture of polyurethane binder and chips in an atmosphere of 5 ° C and 60% RH, and use the time until a viscosity that is considered to be difficult to fill in the mold due to resistance when loosened with a small hand Was. Regarding the heat curability, the rubber mat taken out immediately after the press under the above conditions is sufficiently hardened, and the rubber mat that can be taken out of the mold but is insufficiently hardened is evaluated as △. And those that could not be taken out of the mold were marked as x. After taking out from the mold, it was cured for 7 days in an atmosphere of 23 ° C. and a relative humidity of 55% to obtain an elastic body. The physical properties are measured according to JIS K6301 (Physical test method for vulcanized rubber), and the tensile strength (Ts)
JIS dumbbell No. 2 and JIS tear (B) type test piece for tear strength (Tr) were used for the test piece for the elongation and elongation (El) in a constant temperature and humidity room at 23 ° C. and 50% RH. Tensile speed is 3
The test was performed at 00 mm / min. (Production of urethane prepolymer) 292 parts of purified MDI (MDI-PH, manufactured by Mitsui Chemicals), 73 parts of liquid MDI (MDI-LK, manufactured by Mitsui Chemicals) and PPG DIOL-200
0 (manufactured by Mitsui Chemicals, Inc., polyoxypropylene glycol, molecular weight: 2,000) was uniformly mixed, and reacted at 80 ° C. for 2 hours in a nitrogen stream to obtain a terminal isocyanate content of 9.0% by weight and a viscosity of 3,000 mPa. A s (25 ° C.) urethane prepolymer was obtained.

(Production Example 1) 10.99 parts of dissolved MBOCA (3,3'-dichloro-4,4'-diaminodiphenylmethane manufactured by Wakayama Seika) and PPG DIOL-300
0 (polyoxypropylene glycol, manufactured by Mitsui Chemicals, molecular weight 3000) 87.11 parts and 1.90 parts of P-25 (active material chemical, lead aliphatic monocarboxylate content 62%) are uniformly stirred and mixed by a dissolver. Thus, a curing accelerator was obtained.

[Production Examples 2 to 5] A curing accelerator was produced in the same manner as in Production Example 1 except that the composition was changed to Table 1.

[0021]

[Table 1]

Example 1 An elastic pavement member was produced using the curing accelerator of Production Example 1 at the compounding ratio shown in Table 2 according to the above-mentioned molding method. Table 2 shows the results.

[0023]

[Table 2]

[Examples 2 to 3] Elastic pavement members were manufactured in the same manner as in Example 1 except that the mixing ratio was changed to Table 2. The result
It is shown in Table 2.

(Comparative Examples 1 to 5) Elastic pavement members were manufactured in the same manner as in Example 1 except that the formulations were as shown in Table 3. The result
It is shown in Table 3.

[0026]

[Table 3]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kaoru Ueno 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture F-term (reference) 4F071 AA01 AA10 AA53 AA81 AC09 AC18 AE02 AH03 BA07 BB01 BB03 BC01 4J002 AA002 AC002 CK021 CK031 CK041 DM006 FD012 FD016 4J034 BA08 CA01 CA12 CB02 CB03 CC03 DB03 DB04 DG02 DG03 DG04 DH05 GA06 HA07 HC03 HC12 HC22 JA42 KA01 KC17 KC18 KD03

Claims (11)

[Claims] 1. A one-pack curable polyurethane binder obtained by reacting an organic polyisocyanate with an active hydrogen compound and comprising a urethane prepolymer having a molecular terminal of an isocyanate group and a curing accelerator, wherein the polyurethane binder contains lead. Is contained in an amount of 0.05% by mass or more and 1.5% by mass or less. 2. The curing accelerator contains at least one of an amine and a polyol and a catalyst, and the amount thereof is 5 to 50 parts by weight based on 100 parts by weight of the urethane prepolymer.
The polyurethane binder according to claim 1, wherein the amount is part by weight. 3. The method as claimed in claim 2, wherein the active hydrogen compound has 2
3. The polyurethane binder according to claim 1, which is a polyoxyalkylene polyol obtained by addition-polymerizing at least one of propylene oxide and ethylene oxide to a compound having from 1 to 6 hydroxyl groups. 4. The polyurethane binder according to claim 2, wherein the polyol of the curing accelerator comprises a divalent or trivalent polyether polyol having an average molecular weight of 75 to 10,000 per active hydrogen. 5. The curing accelerator comprises an amine and a polyol, and the equivalent ratio (amine / polyol) is 0/10.
3. The polyurethane binder according to claim 2, wherein the ratio is more than 9/1. 6. The polyurethane binder according to claim 2, wherein the catalyst contained in the curing accelerator contains lead. 7. The polyurethane binder according to claim 6, wherein the catalyst contains tin. 8. The method according to claim 1, wherein the amount of the filler is 100 parts by weight.
Addition of 5 to 30 parts by weight of the described polyurethane binder,
An elastic pavement member obtained by mixing, filling in a mold, pressing and molding. 9. The method according to claim 1, wherein the filler is selected from the group consisting of granular rubber, hijiki rubber, granular natural stone, wood chips, hard plastic chips, soft plastic chips, and foamed plastic chips. The elastic pavement member according to claim 8, wherein 10. Claim based on 100 parts by weight of filler
5. A method for producing an elastic pavement member, which is obtained by adding and mixing 5 to 30 parts by weight of the polyurethane binder according to 1 and filling the mixture into a mold, followed by pressing and molding. 11. A filler, wherein the filler is granular rubber, hijiki rubber,
11. The method for producing an elastic pavement material according to claim 10, wherein one selected from granular natural stone, wood chips, hard plastic chips, soft plastic chips, foamed plastic chips and the like is used alone or in combination.