JPH1129741A - Resin-based self-emulsifiable primer for pavement and execution using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the generation of odor, the danger of solvent intoxication, and the risk of fire due to ignition by using a self-emulsifiable primer contg. a hydrophilic isocyanate-terminated compd. obtd. by the reaction of an org. polyisocyanate with an alkoxy(polyoxyalkylene) glycol. SOLUTION: This self-emulsifiable primer contains a high-boiling thinner in addition to a hydrophilic isocyanate-terminated compd. which is obtd. by reacting an org. polyisocyanate with an alkoxy(polyoxyalkylene) glycol obtd. by the addition reaction a 1-6C monohydric alcohol with ethylene oxide alone or together with propylene oxide (provided the number of moles of ethylene oxide alone or together with propylene oxide is 5 or higher, and the number of moles of ethylene oxide is higher than that of propylene oxide) and an active hydrogen compd. having an average functionality of 2-3 and a number average mol.wt. of 62-5,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-emulsifying primer containing an isocyanate group-terminated compound for resin-based pavement and a method of using the same.

[0002]

2. Description of the Related Art Conventionally, resin-based pavements have been used in athletics stadiums, tennis courts, promenades, etc., mainly for absorbing shock. A typical example is a pavement material in which rubber chips are consolidated with urethane resin. On the other hand, recently, on the road, low noise, mirror burn countermeasures, rut prevention, etc.
A resin-based pavement using a urethane resin, an epoxy resin, an acrylic resin, or the like has been devised.

[0003] The lower ground of the resin-based pavement is made of concrete, asphalt concrete, or the like. In general, a primer is used to improve the adhesion to the ground surface. As the primer, those obtained by diluting an isocyanate-terminated prepolymer with a volatile solvent such as toluene or ethyl acetate to reduce the viscosity are often used, and a strong adhesive force is obtained. For example, Japanese Patent Application Laid-Open No. 55-98504 discloses T
A primer comprising 20 parts of a prepolymer having an NCO group content of 7.5% obtained by reacting a DI isocyanate with polyoxypropylene glycol and 50 parts of toluene, and a primer comprising a 50% xylene solution of crude MDI are described. After applying the primer of
A method of paving with a paving material mainly composed of a synthetic resin emulsion is described.

[0004]

However, since these primers contain volatile solvents, they have an odor, and workers are always at risk of poisoning with organic solvents. In addition, a fire may be caused by ignition. JP 5
Toluene and xylene used in JP-A-5-98504 are all second-class organic solvents regulated by the Organic Solvent Regulations of the Industrial Safety and Health Act. The boiling point is about 140 ° C and the flash point is about 24 ° C. Therefore, it is difficult to use it in an urban area or a densely populated residential area, and it is extremely difficult to use it in a place where solvent vapor is likely to stay, such as in a tunnel.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the problem can be solved by using a primer containing a self-emulsifying isocyanate compound. Reached.

That is, the present invention relates to a resin-based pavement primer, comprising an alkoxy (poly) obtained by adding ethylene oxide or ethylene oxide or propylene oxide to an organic polyisocyanate and a monoalcohol having 1 to 6 carbon atoms. (Oxyalkylene) glycol (provided that ethylene oxide or the total added mole number of ethylene oxide and propylene oxide is 5 or more, and the added mole number of ethylene oxide> the added mole number of propylene oxide) is reacted with a hydrophilic isocyanate group terminal. A self-emulsifying primer characterized by containing a compound.

Invention 2: A resin-based pavement primer comprising an organic polyisocyanate and a monoalcohol having 1 to 6 carbon atoms, ethylene oxide or ethylene oxide;
Alkoxy (polyoxyalkylene) glycol obtained by adding propylene oxide (provided that ethylene oxide or the total added mole number of ethylene oxide and propylene oxide is 5 or more, and the added mole number of ethylene oxide> the added mole number of propylene oxide) And number of average functional groups 2-3, number average molecular weight 62-5000
A self-emulsifying primer comprising a hydrophilic isocyanate group-terminated compound obtained by reacting an active hydrogen group-containing compound according to (1).

Invention 3: The self-emulsifying primer for resin-based pavement according to invention 1 or 2, further comprising a high-boiling-point thickener.

Invention 4: The resin-based pavement self-emulsifying primer described in Invention 1, 2, or 3 is mixed at a construction site with the primer / water at a weight ratio of 20/80 to 80/20 to form an emulsion. An application method characterized by applying to a base surface. It is.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The organic polyisocyanate used in the present invention includes 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4'-MDI,
2,2'-MDI, polymethylene polyphenylene polyisocyanate (hereinafter abbreviated as polymeric MDI),
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude tolylene diisocyanate, para-xylylene diisocyanate, meta-xylylene diisocyanate, ortho-xylylene diisocyanate, 1,5-naphthylene diisocyanate, para-
Phenylene diisocyanate, meta-tetramethyl xylylene diisocyanate, para-tetramethyl xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, , 4,4-trimethylhexamethylene diisocyanate, a mixture of two or more of the above-mentioned polyisocyanates, and various modified isocyanates such as carbodiimide-modified, buret-modified, uretdione-modified and isocyanurate-modified polyisocyanates.

Among these various organic polyisocyanates, MDI such as 4,4'-MDI, carbodiimide-modified N4DI, and polymeric MDI are selected from the viewpoints of vapor pressure, price and the like.
Polyisocyanates are preferred. Specific products include Millionate MT, Millionate MTL, Millionate MR100, and Coronate 1107 manufactured by Nippon Polyurethane Industry.

The self-emulsifying property is imparted to an alkoxy (polyoxyalkylene) glycol obtained by adding ethylene oxide or ethylene oxide or propylene oxide to a monoalcohol having 1 to 6 carbon atoms to an organic polyisocyanate (however, ethylene oxide Alternatively, the total added mole number of ethylene oxide and propylene oxide is 5 or more, and the self-emulsifying property is obtained by adding the added mole number of ethylene oxide> the added mole number of propylene oxide. The sequence of the ethylene oxide unit and the propylene oxide unit in the glycol may be random or block, and the unit bonded to the alkoxy group may be an ethylene oxide unit or a propylene oxide unit. The alkoxy (polyoxyalkylene) glycol may have a number average molecular weight of 250 to 5000, and from the viewpoint of versatility, is preferably methoxypolyethylene glycol having a number average molecular weight of 300 to 600. The amount of glycol is 100 parts of organic polyisocyanate.
2.5 to 25 parts by weight with respect to parts by weight.

The active hydrogen group-containing compound used in the second invention has a number average molecular weight of 62 to 5000 and an average number of functional groups of 2 to 3, and is a polyether polyol, a polyester polyol, a polycarbonate polyol,
Castor oil, modified castor oil-based polyols, etc.
From the viewpoint of the viscosity of the composition to be obtained, polyether polyol is preferred, and polypropylene glycol is most preferred.

Further, low molecular weight polyols and polyamines having a number average molecular weight of less than 500, which are generally called chain extenders, are also included in the active hydrogen group-containing compound. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, ethylenediamine, hexamethylenediamine, isophoronediamine, and the like.

The active hydrogen group-containing compound has the effect of improving the adhesion and flexibility to the pavement and the ground surface. The amount used is based on 100 parts by weight of the organic polyisocyanate.
It is 10 to 300 parts by weight.

The hydrophilic isocyanate group-terminated compound in the present invention has an average number of functional groups of 1.8 to 3.5, preferably 2.0 to 3.0. In the synthesis, isocyanate groups /
The ratio of active hydrogen groups, the so-called isocyanate index, is 2 or more, preferably 3 or more. The isocyanate group content of the obtained reactant is preferably 10 to 30% when the raw material organic polyisocyanate is polymeric MDI. The reaction method is a nitrogen atmosphere, and the reaction temperature is 20 to 120.
C, preferably at 50-90C.

When the average number of functional groups is 1.8 or less, the resulting primer has a low adhesive strength and easily peels off. When the average number of functional groups is 3.5 or more, the obtained primer is hard and brittle, and easily peels off due to vibration or the like. When the isocyanate index is 2 or less, the obtained primer has low adhesive strength and generally becomes a high-viscosity product, resulting in poor workability.

It is also effective to add a high-boiling point thinner such as an alkylene carbonate immediately after the synthesis or immediately before the emulsification in order to improve the emulsification workability during construction.
The addition amount is desirably 50 parts by weight or less, more preferably 20% by weight or less, based on 100 parts by weight of the prepolymer. The viscosity after mixing is 200 to 2500 mPa · s / 2.
At 5 ° C., workability is good. A preferred high boiling thinner is propylene carbonate. Propylene carbonate has a boiling point of 242 ° C and a flash point of 132 ° C.

The isocyanate group-terminated self-emulsifying primer of the present invention has a weight ratio of isocyanate group-terminated self-emulsifying primer / water of 20% immediately before the application of the primer.
/ 80 to 80/20 to form an emulsion. On this occasion,
As described above, a viscosity reducing agent may be added to reduce the viscosity and improve the emulsifying property, or a primer to which a viscosity reducing agent has been added may be used. The emulsion is applied to the base using a known tool such as roller coating or rubber lake.
The coating amount varies depending on the type and condition of the base surface, but is generally 50 to 300 g / m ² in terms of solid content.

The primer coated with the primer is preferably cured at room temperature for about 1 hour. As a pavement method after curing, for example, there is the following method. A method in which crushed synthetic resin such as a rubber chip or a mixture of crushed resin and inorganic particles such as sand is mixed with a binder such as a moisture-curable urethane resin and spread on the primer surface. A method of spray-coating a two-part urethane elastomer on the primer surface. A method of bonding a primer-coated surface and a resin-based pavement material that has already been molded using an appropriate adhesive. The curing time of the surface coated with the primer is
It is preferable to adjust the lipophilicity, humidity at the time of enforcement, and the like.

[0021]

The self-emulsifying primer containing an isocyanate group-terminated compound according to the present invention does not contain a volatile solvent, so that there is no concern that a worker may cause solvent poisoning and the problem of odor is low. In addition, there is no possibility of ignition at room temperature, and it is a highly safe primer. This has made it easier to use in densely populated residential areas and tunnels, which were difficult to use in the past. In addition, since it contains a hydrophilic isocyanate group-terminated prepolymer, it exhibits the same or better adhesive strength than conventional solvent-diluted types, not only on dry substrates but also when wet after rain. I do.

[0022]

EXAMPLES The self-emulsifying primer for resin-based pavement of the present invention and the method of using the same will be described below with reference to examples, but the present invention is not limited thereto. Note that “parts” and “%” in Synthesis Examples, Examples and Comparative Examples are
Unless otherwise specified, "parts by weight" and "% by weight" are indicated.

Example 1 950 parts of Polymeric MDI (Millionate MR100, manufactured by Nippon Polyurethane Industry Co., Ltd.) were stirred at 45 ° C. in a synthesizer equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas inlet pipe. After gradually adding 50 parts of methoxypolyethylene glycol, the mixture is reacted at 75 to 85 ° C. for 3 hours, and isocyanate group-terminated prepolymer (P-1)
I got The isocyanate content of P-1 was 28.8%, and the viscosity was 300 mPa · s / 25 ° C.

Example 2 A 4,4'-MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., comprising a stirrer, thermometer, cooling pipe and nitrogen gas introducing pipe)
100 parts of Millionate MT), Polymeric MDI (Millionate MR100, manufactured by Nippon Polyurethane Industry) 35
After stirring 0 parts at 45 ° C., gradually adding 400 parts of polypropylene glycol having an average functional group number of 2, and a number average molecular weight of 2,200, and 50 parts of methoxypolyethylene glycol having a number average molecular weight of 400, and then reacting at 75 to 85 ° C. for 3 hours. And 5
After cooling to 0 ° C., 100 parts of propylene carbonate was added to obtain an isocyanate group-terminated prepolymer-containing primer (P-2). The isocyanate content of P-2 is 1
The viscosity was 2.1% and the viscosity was 1400 mPa · s / 25 ° C.

Comparative Example 1 An isocyanate-terminated prepolymer (P-2) was prepared in the same manner as in Synthesis Example 1 except that polyethylene glycol having a number average molecular weight of 800 and a functional group number of 2 was used instead of methoxypolyethylene glycol having a number average molecular weight of 400. Obtained.
P-2 has an isocyanate content of 12.1% and a viscosity of 17
It was 00 mPa · s / 25 ° C.

Application Example 1 50 parts of the primer (P-2) of Example 2 and 50 parts of water
After mixing for 0 seconds, a yellow-white emulsion was obtained. The viscosity of this emulsion is 30 mPa · s / 25
° C and low viscosity.

Application Comparative Example 1 50 parts of the composition (P-2) of Comparative Example 1 and 50 parts of water were mixed for 30 seconds, but did not disperse. When the stirring was stopped, phase separation occurred.

Example 3 50 parts of the primer (P-1) of Example 1 and 50 parts of water
After mixing for 0 seconds, a yellow-white emulsion was obtained. The emulsion was applied on a slate plate by roller coating at a rate of 80 g / m ² (in terms of solid content). One hour later, using a mold, a mixture of 50 parts of waste tire rubber chips, 30 parts of No. 5 silica sand, and 20 parts of an isocyanate-terminated moisture-curing binder (Coronate 4569, manufactured by Nippon Polyurethane Industry Co., Ltd.) was reduced to 4 cm × 4 cm and 1.5 cm in thickness. Homing. After curing in a constant temperature room at 25 ° C for 2 weeks, JIS A59
When the peel strength of the primer surface was measured in accordance with No. 08, the peel strength was 1.0 MPa, which was equivalent to that of Application Comparative Example 2 shown below.

Example 4 50 parts of the primer (P-2) of Example 2 and 50 parts of water
After mixing for 0 seconds, a yellow-white emulsion was obtained. The emulsion was applied on a slate plate by roller coating at a rate of 80 g / m ² (in terms of solid content). One hour later, using a mold, a mixture of 50 parts of waste tire rubber chips, 30 parts of No. 5 silica sand, and 20 parts of an isocyanate-terminated moisture-curing binder (Coronate 4569, manufactured by Nippon Polyurethane Industry Co., Ltd., 4 cm x 4 cm) was formed to a thickness of 1.5 cm Homing. After curing in a constant temperature room at 25 ° C for 2 weeks, JIS A59
When the peel strength of the primer surface was measured according to No. 08, the peel strength was 1.3 MPa, which was equivalent to that of Application Comparative Example 2 shown below.

Application Comparative Example 2 Polymeric MDI / castor oil-based isocyanate-terminated prepolymer (toluene / ethyl acetate = 50/50, solids = 50%, NCO content = 6%, viscosity = 50 mPa ·
s / 25 ° C) by roller coating on a slate plate 80 g
/ M ² (solid content conversion). One hour later, a mixture of 50 parts of waste tire rubber chips, 30 parts of No. 5 silica sand, and 20 parts of an isocyanate-terminated moisture-curable binder (Coronate 4569, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to a mold using a mold.
It was homed to a size of cm × 4 cm and thickness of 1.5 cm. 25
After curing for 2 weeks in a constant temperature chamber at ℃, the peel strength of the primer surface was measured according to JIS A5908, and the peel strength was 1.2 MPa. The solvent smelled during application. The flash point of the primer was 1 ° C.

Example 5 50 parts of the primer (P-2) of Example 2 and 50 parts of water
After mixing for 0 seconds, a yellow-white emulsion was obtained. This emulsion was applied by a roller brush onto a wet concrete plate by roller application at a rate equivalent to 150 g / m ² (in terms of solid content). One hour later, using the formwork, EP
A mixture of 40 parts of a DM rubber chip, 35 parts of No. 7 silica sand, and 25 parts of an isocyanate group-terminated moisture-curing binder (Coronate 4569, manufactured by Nippon Polyurethane Industry Co., Ltd.) was 4 cm × 4.
cm and a thickness of 1.5 cm. After curing for 10 days in a constant temperature room at 25 ° C, a Kenken-type small adhesive peel tester (B
When the peel strength was measured by A-400), the peel strength was 1.3 MPa, which was larger than the following applied comparative example 3.

Application Comparative Example 3 Isocyanate group terminal solvent dilution type primer (manufactured by Nippon Polyurethane Industry, Coronate 2460, toluene /
(Ethyl acetate) was applied to the same wet concrete plate as in Example 5 by roller coating at a rate of 150 g / m ² (equivalent to solid content). One hour later, use an EPDM rubber chip 4
0 parts, 7 parts of silica sand, 35 parts of isocyanate group terminal moisture curing binder (manufactured by Nippon Polyurethane Industry, Coronate 456)
9) 25 parts of the mixture is 4 cm × 4 cm, thickness 1.5 cm
Homed. After curing in a 25 ° C constant temperature room for 10 days,
When the peel strength was measured with a Kenken-type small adhesive peel tester (BA-400), the peel strength was 0.9 MPa. The solvent smelled during application. The flash point of the primer was 1 ° C.

Claims (4)

[Claims] Claims: 1. A resin-based pavement primer comprising an alkoxy (polyoxyalkylene) glycol obtained by adding ethylene oxide or ethylene oxide or propylene oxide to an organic polyisocyanate and a monoalcohol having 1 to 6 carbon atoms, provided that , The total number of moles of ethylene oxide or ethylene oxide and propylene oxide is 5 or more, and the number of moles of ethylene oxide added> the number of moles of propylene oxide added) contains a hydrophilic isocyanate group-terminated compound. Features a self-emulsifying primer. 2. A resin-based paving primer, which is obtained by adding ethylene oxide, ethene oxide, or propylene oxide to an organic polyisocyanate and a monoalcohol having 1 to 6 carbon atoms, and obtaining an alkoxy (polyoxyalkylene) glycol ( However, the total added mole number of ethylene oxide or ethylene oxide and propylene oxide is 5 or more, and the added mole number of ethylene oxide> the added mole number of propylene oxide) and the average number of functional groups is 2 to 3, and the number average molecular weight is 62 to 5000. A self-emulsifying primer comprising a hydrophilic isocyanate group-terminated compound obtained by reacting an active hydrogen group-containing compound. 3. The primer according to claim 1, wherein the self-emulsifying primer for resin-based pavement further contains a high-boiling-point viscosity reducing agent. 4. A self-emulsifying primer for resin-based pavement according to claim 1, 2 or 3 at a construction site, wherein said primer / water is mixed at a weight ratio of 20/80 to 80/20 to form an emulsion. An application method characterized by applying to a base surface.