JP6589093B2 - Urethane cement composition and repair material - Google Patents

Description

  The present invention relates to a urethane cement composition that can be suitably used as a road repair material.

  In the civil engineering and construction industry, such as repairing concrete structures, attention has been paid to infrastructure reinforcement against the backdrop of the fallen tunnel accident. Since concrete structures constructed after the period of high economic growth are 50 years old in the next 30 years, the demand for concrete repairs is increasing.

  As current concrete repair materials, epoxy resin-based repair materials and (meth) acrylic-based repair materials occupy the majority (see, for example, Patent Document 1). However, the adhesive strength to cement concrete is still weak and further improvement is required.

JP 2002-201802 A

  The problem to be solved by the present invention is to provide a urethane cement composition having excellent adhesion to cement concrete.

  The present invention relates to a urethane prepolymer (A) having an isocyanate group obtained by reacting a polyol (a1) containing a polyol (a1-1) having an oxyethylene group and a polyisocyanate (a2), a non-containing glycidyl group. Polymer obtained by polymerizing compound (b1) obtained by reacting saturated monomer (b1-1) and aliphatic tertiary amine (b1-2) with unsaturated monomer (b2) ( B), a urethane cement composition containing polyisocyanate compound (C), cement (D), water (E), and aggregate (F), and a repair comprising the urethane cement composition The material is provided.

  The urethane cement composition of the present invention exhibits excellent adhesiveness to cement concrete and is excellent in fast curability. In addition, the urethane cement composition of the present invention prevents an increase in viscosity over time and is excellent in storage stability. Therefore, the urethane cement composition of the present invention can be suitably used as a repair material, and can be particularly suitably used as a road repair material.

  The urethane cement composition of the present invention is a urethane prepolymer (A) having an isocyanate group obtained by reacting a polyol (a1) containing a polyol (a1-1) having an oxyethylene group with a polyisocyanate (a2), A compound (b1) obtained by reacting an unsaturated monomer (b1-1) having a glycidyl group and an aliphatic tertiary amine (b1-2) and an unsaturated monomer (b2) are polymerized. The resultant polymer (B), polyisocyanate compound (C), cement (D), water (E), and aggregate (F) are contained.

  The urethane prepolymer (A) is an essential component for obtaining good hydrophilicity and adhesion, and is obtained by reacting a polyol (a1) containing (a1-1) with a polyisocyanate (a2). It has an isocyanate group.

  The polyol (a1-1) having an oxyethylene group imparts hydrophilicity and expresses good affinity with cement (D) and water (E), and has excellent adhesion to cement concrete as a substrate. It is an essential ingredient for obtaining. Examples of the polyol (a1) include polyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and the like. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use polyoxyethylene polyoxypropylene glycol because it is easy to adjust the curing rate of the urethane cement composition. Moreover, it is preferable that it is the range of 50 / 50-90 / 10 as molar ratio [EO / PO] of the oxyethylene group and oxypropylene group in the said polyoxyethylene polyoxypropylene glycol.

  The number average molecular weight of the polyol (a1-1) is preferably in the range of 500 to 7,000, more preferably in the range of 800 to 5,000, from the viewpoint that good hydrophilicity can be imparted. In addition, the number average molecular weight of the said polyol (a1-1) shows the value obtained by measuring on condition of the following by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

  As the usage-amount of the said polyol (a1-1), it is preferable that it is 50 mass% or more in a polyol (a1) from the point which can provide favorable hydrophilicity, and it is more preferable that it is the range of 60-80 mass%. preferable.

  As the polyol (a1), other polyols can be used in addition to the polyol (a1-1). Examples of the other polyol include polypropylene triol, polyester polyol, polycarbonate polyol, polyacryl polyol, and chain extender having a number average molecular weight in the range of 50 to 300. These polyols may be used alone or in combination of two or more. Among these, polypropylene triol is preferably used from the viewpoint that high strength can be imparted without impairing hydrophilicity, and the amount used is preferably in the range of 20 to 40% by mass in the polyol (a1). . The number average molecular weight of the polypropylene triol is preferably in the range of 300 to 5,000 from the viewpoint of high strength. In addition, the number average molecular weight of the said polypropylene triol shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1-1).

  Examples of the polyisocyanate (a2) include phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, and 1-methyl. -3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4 , 6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzene diisocyanate, 3-methyl 1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene -1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2′-diisocyanate, biphenyl-2,4′-diisocyanate, biphenyl-4,4 Aromatic polyisocyanates such as' -diisocyanate, 3-3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, diphenylmethane-2,4-diisocyanate; Ramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3- Di (isocyanatemethyl) cyclohexane, 1,4-di (isocyanatemethyl) cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate , 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate or other aliphatic or alicyclic polyiso Cyanate, carbodiimide-modified isocyanate, polymethylene polyphenyl polyisocyanate, and the like can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use aromatic polyisocyanate from the viewpoint of mechanical strength and adhesiveness, and it is more preferable to use toluene diisocyanate.

  The urethane prepolymer (A) is obtained by a known urethanization reaction of the polyol (a1) and the polyisocyanate (a2), and has an isocyanate group that imparts excellent adhesion to cement concrete. It is.

  The molar ratio [NCO / OH] in the reaction of the polyol (a1) and the polyisocyanate (a2) is preferably in the range of 1.01 to 10 from the viewpoint of adhesiveness and high strength. 1.1 to 8 is more preferable.

  The polymer (B) is an essential component for obtaining excellent adhesion to cement concrete, and an unsaturated monomer (b1-1) having a glycidyl group and an aliphatic tertiary amine (b1-2). It is obtained by polymerizing the compound (b1) obtained by reacting with the unsaturated monomer (b2).

  The glass transition temperature of the polymer (B) is preferably 50 ° C. or less, more preferably in the range of −10 to 20 ° C., because the adhesion to the cement concrete of the base material is facilitated. It is more preferable. The glass transition temperature of the polymer (B) is a value measured by DSC in accordance with JISK7121-1987. Specifically, the polymer (B) is placed in a differential scanning calorimeter. , (Tmg + 50 ° C.), heated at a rate of temperature increase of 10 ° C./min, held for 3 minutes, then rapidly cooled, and the midpoint glass transition temperature (Tmg) read from the obtained differential heat curve is shown.

  As the usage-amount of the said polymer (B), it is preferable that it is the range of 50-500 mass parts with respect to 100 mass parts of said urethane prepolymers (A) from the adhesive point with respect to cement concrete, 100- The range of 400 parts by mass is more preferable.

  As the unsaturated monomer (b1-1) having a glycidyl group, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, or the like can be used. These monomers may be used alone or in combination of two or more.

  Since the aliphatic tertiary amine (b1-2) can impart a cationic group to the urethane cement composition, it does not react with an isocyanate group present in the urethane cement composition and does not cause gelation, and It can be adsorbed to cement concrete as a substrate and exhibit excellent adhesiveness.

  As the aliphatic tertiary amine (b1-2), for example, an amine compound having three alkyl groups having 1 to 20 carbon atoms can be used. Among these, the polymer (B) has one or two alkyl groups having 1 to 2 carbon atoms, and the remaining is an alkyl group having 6 to 20 carbon atoms in that good stability of the polymer (B) can be obtained. A certain amine compound is preferably used, and it is more preferable to use an amine compound having two methyl groups and the remaining alkyl group having 6 to 20 carbon atoms.

  Examples of the unsaturated monomer (b2) to be reacted with the compound (b1) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) ) (Meth) acrylic acid alkyl esters such as acrylate; ester compounds such as maleic acid, fumaric acid and itaconic acid; monobasic acids such as (meth) acrylic acid and vinylsulfonic acid; (meth) acrylamide, maleic acid amide, N -Amide compounds such as methylol acrylamide and diacetone acrylamide; vinyl compounds such as vinyl acetate, vinyl propionate, styrene, vinyl toluene, vinyl ether, acrylonitrile; diallyl phthalate, allyl acrylate, trimethylol propane chicken methacrylate, etc. It can be used. These monomers may be used alone or in combination of two or more.

  As a reaction of the compound (b1) and the unsaturated monomer (b2), for example, the compound (b1) is preferably 0.2 by 100 parts by mass of the unsaturated monomer (b2). Performing a known radical polymerization method with an amount of use in the range of 10 to 10 parts by mass. Specifically, after stirring and mixing the compound (b1), water and, if necessary, an emulsifier and an initiator, for example, at a temperature of 0 to 100 ° C., the unsaturated monomer (b2) is batched. Or the method of carrying out radical polymerization at the temperature of 30-90 degreeC, for example dripping continuously is mentioned.

  Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts It is possible to have. These emulsifiers may be used alone or in combination of two or more.

  Examples of the initiator include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide; 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2- An azo initiator such as amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid.

  Examples of the persulfate that is a representative of the polymerization initiator include potassium persulfate, sodium persulfate, ammonium persulfate, and the like. Specific examples of the organic peroxide include benzoyl peroxide. , Diacyl peroxides such as lauroyl peroxide and decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Peroxyesters such as laurate and t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, paramentane hydroperoxide, and t-butyl hydroperoxide can be used.

  The polymerization initiator may be used in such an amount that the polymerization proceeds smoothly, but 10% by mass or less based on the total mass of the compound (a1) and the unsaturated monomer (a2). It is preferable that

  The polyisocyanate compound (C) is for diluting the urethane prepolymer (A) to suppress an abrupt or temporal increase in viscosity of the urethane cement composition, and the polyisocyanate (a2) Similar compounds can be used. Among these, from the viewpoint of mechanical strength and suppression of thickening, it is preferable to use an aromatic polyisocyanate, more preferably 4,4′-diphenylmethane diisocyanate, and 4,4′-diphenylmethane diisocyanate and 4,4 ′. It is more preferable to use C-MDI which is a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate.

  The amount of the polyisocyanate compound (C) used is preferably in the range of 50 to 400 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A) from the viewpoint of obtaining good suppression of thickening. , More preferably in the range of 80 to 300 parts by mass.

  As the cement (D), for example, ordinary Portland cement, early-strength Portland cement, ultra-early strong Portland cement, moderately hot Portland cement, low heat Portland cement, blast furnace cement, silica cement, fly ash cement and the like can be used. These cements may be used alone or in combination of two or more. Although the usage-amount of the said cement (D) is suitably determined according to the use used, For example, it is the range of 300-1,000 mass parts with respect to 100 mass parts of said urethane prepolymers (A). .

  As said water (E), ion-exchange water, distilled water, tap water etc. can be used, for example. The amount of water (E) used is preferably in the range of 100 to 800 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A) from the viewpoint of obtaining good workability.

  As the aggregate (F), silica sand, gravel, crushed glass, or the like can be used. As the usage-amount of the said aggregate, it is the range of 20-60 mass% in a urethane cement composition, for example.

  The urethane cement composition of the present invention includes the urethane prepolymer (A), the polymer (B), the polyisocyanate compound (C), the cement (D), the water (E), and the aggregate (F). As an essential component, but may contain other additives as necessary.

  As said other additive, a pigment, a flame retardant, a plasticizer, a wax, an antifoamer, antioxidant, a thickener etc. can be used, for example. These additives may be used alone or in combination of two or more.

  As described above, the urethane cement composition of the present invention exhibits excellent adhesiveness to cement concrete and is excellent in fast curability. In addition, the urethane cement composition of the present invention prevents an increase in viscosity over time and is excellent in storage stability. Therefore, the urethane cement composition of the present invention can be suitably used as a repair material, and can be particularly suitably used as a road repair material.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1] Synthesis of urethane prepolymer (A-1) In a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen stream tube, polyoxyethylene polyoxypropylene glycol (number average molecular weight; 3,000, oxyethylene) 251 parts by mass of a molar ratio of a group to an oxypropylene group of 50/50, hereinafter abbreviated as “EOPO”), and polypropylene triol (number average molecular weight: 3,000, hereinafter abbreviated as “PPT3000”). 7 parts by mass and 5.3 parts by mass of polypropylene triol (number average molecular weight; 400, hereinafter abbreviated as “PPT400”) were added and mixed with stirring. Next, 56.4 parts by mass of toluene diisocyanate (hereinafter abbreviated as “TDI”) was added and reacted at 80 ° C. for 3 hours to obtain a urethane prepolymer (A-1) having an isocyanate group.

[Synthesis Example 2] Synthesis of Polymer (B-1) In a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen stream tube, 119 parts by mass of ion-exchanged water, “Latemul K-120” manufactured by Kao Corporation ( 10 parts by mass of an addition reaction product of allyl glycidyl ether (hereinafter referred to as “AGE”) and N, N-dimethyllaurylamine (hereinafter referred to as “DMLA”), and “Emulgen 920” manufactured by Kao Corporation as an emulsifier ( Polyoxyethylene nonylphenyl ether) 0.5 part by mass was charged, and the mixture was heated to 50 ° C. and stirred under a nitrogen stream.
Next, the mixture was heated to 80 ° C., 0.5 parts by mass of cumene hydroperoxide was added, and a mixture of 55 parts by mass of butyl acrylate (hereinafter abbreviated as “BA”) and 45 parts by mass of methyl methacrylate was required for 180 minutes. Then, the solution was added dropwise, and the polymerization was carried out by further maintaining for 30 minutes. Next, the mixture was cooled to 30 ° C., adjusted to pH 205.0 with 1 part by mass of 2% hydrochloric acid, non-volatile content: 45% by mass, viscosity: 120 mPa · s, glass transition temperature: 5 ° C. polymer (B-1) Got.

[Example 1]
14.8 parts by mass of the urethane prepolymer obtained in Synthesis Example 1 and 36 parts by mass of the polymer (B-1) obtained in Synthesis Example 2 are abbreviated as 4,4′-diphenylmethane diisocyanate (hereinafter “MDI”). 21.2 parts by mass, ordinary Portland cement (hereinafter abbreviated as “P cement”) manufactured by Sumitomo Osaka Cement Co., Ltd., 100 parts by mass, tap water (hereinafter abbreviated as “water”), 60 parts by mass, Inc. 200 parts by mass of Sanei Silica No. 6 silica sand (hereinafter abbreviated as “No. 6 silica sand”) was mixed to obtain a urethane cement composition.

[Comparative Example 1]
A urethane cement composition was obtained in the same manner as in Example 1 except that the polymer (B-1) was not blended.

[Evaluation of adhesion]
The evaluation of adhesiveness was performed in accordance with JIS R5201-1997 “(5) (a) Bending strength” by performing an alternative evaluation based on adhesiveness to mortar. Specifically, a mixture of P cement, No. 6 silica sand and city water mixed at a mass ratio of 100/200/60 was poured into a mold, cured, and cured for 28 days. Next, this was cut into 40 mm × 40 mm × 80 mm. This was also fitted into a mold, and the urethane cement composition obtained in Examples or Comparative Examples was filled thereon and cured. The specimen was cured for 14 days under the conditions of 20 ° C. and 65% humidity. The test specimen was visually checked for bending strength (N / 25 mm ² ) and fracture state.

  It has been found that the urethane cement composition of the present invention is excellent in adhesiveness to cement concrete.

  On the other hand, although the comparative example 1 is an aspect which does not use a polymer (B), the adhesiveness with respect to cement concrete was inadequate.

Claims (3)

A urethane prepolymer (A) having an isocyanate group obtained by reacting a polyol (a1) containing a polyol (a1-1) having an oxyethylene group with a polyisocyanate (a2),
A compound (b1) obtained by reacting an unsaturated monomer (b1-1) having a glycidyl group and an aliphatic tertiary amine (b1-2) and an unsaturated monomer (b2) are polymerized. The resulting polymer (B),
Polyisocyanate compound (C), cement (D), water (E), and, a urethane cement composition you containing <br/> aggregate the (F),
The amount of the polymer (B) is, the urethane the prepolymer (A) 100 parts by mass of a urethane cement composition, wherein the range der Rukoto 50-500 parts by weight. The urethane cement composition according to claim 1, wherein the polymer (B) has a glass transition temperature of 50 ° C. or lower. Repair material made according to claim 1 or 2 urethane cement composition.