JPWO2015194239A1 - Civil engineering materials - Google Patents

Abstract

The problem to be solved by the present invention is to provide a civil engineering and building material that is excellent in storage stability and adhesiveness to wet concrete, and has excellent workability without causing a feeling of resistance and no unevenness on the coated surface. That is. The present invention provides a civil engineering and building material comprising a urethane resin (A) and cyclodextrin and / or a derivative (B) thereof. The civil engineering and building material of the present invention is excellent in storage stability and has excellent adhesion to not only dry concrete but also wet concrete. Also, since there is no resistance when coating and no unevenness occurs on the coated surface, the workability is excellent. Furthermore, the civil engineering and building materials of the present invention are excellent in mechanical strength such as workability and tensile properties.

Description

  The present invention relates to civil engineering and building materials that can be suitably used for concrete repair materials, road primers, and the like.

  In the civil engineering and construction industry, such as repairing concrete structures, attention has been focused on infrastructure repairs against the backdrop of the fall of the Isogo tunnel. Since concrete structures constructed after the period of high economic growth will exceed 50 years from the construction in the next 30 years, the demand for concrete repairs is increasing.

  As the concrete repair material, epoxy resin, which is superior in performance such as mechanical strength, occupies about 70% of the market, and acrylic resin, urethane resin, etc. occupy the remaining 30%.

  As demand for concrete repair materials increases in the future, further performance improvement and shortening of construction period will be required. In particular, good adhesion to concrete is required even in humid environments such as rainy weather and sewerage.

  As urethane resin which has favorable adhesiveness with respect to concrete also in the said humid environment, the composition containing a urethane resin and aluminum oxide powder is disclosed, for example (for example, refer patent document 1). However, since the composition has an inorganic powder dispersed in a urethane resin, there is a problem that there is a feeling of resistance or unevenness on the coated surface when applied to a substrate. In order to separate over time, improvement in storage stability is also required.

JP 2003-128479 A

  The problem to be solved by the present invention is to provide a civil engineering and building material that is excellent in storage stability and adhesiveness to wet concrete, and has excellent workability without causing a feeling of resistance and no unevenness on the coated surface. That is.

  The present invention provides a civil engineering and building material comprising a urethane resin (A) and cyclodextrin and / or a derivative (B) thereof.

  The civil engineering and building material of the present invention is excellent in storage stability and has excellent adhesion to not only dry concrete but also wet concrete (hereinafter abbreviated as “wet surface adhesion”). is there. Also, since there is no resistance when coating and no unevenness occurs on the coated surface, the workability is excellent. Furthermore, the civil engineering and building materials of the present invention are excellent in mechanical strength such as workability and tensile properties.

  Therefore, the civil engineering and building materials of the present invention can be suitably used as coating materials in the fields of civil engineering, architecture, railways, roads, bridges, primers, repair materials, etc., concrete repair materials, concrete waterproofing materials, road use It can be particularly suitably used as a primer and road paving material.

  The civil engineering and building material of the present invention contains urethane resin (A) and cyclodextrin and / or its derivative (B) as essential components.

  As said urethane resin (A), what is obtained by making a polyol (a1), a polyisocyanate (a2), and a chain extender (a3) react as needed can be used, for example.

  Examples of the polyol (a1) include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacryl polyol, polyisoprene polyol, dimer diol, and the like. These polyols may be used alone or in combination of two or more.

  The number average molecular weight of the polyol (a1) is preferably in the range of 700 to 5,000, more preferably in the range of 800 to 4,000, from the viewpoint of mechanical strength. In addition, the number average molecular weight of the said polyol (a1) shows the value measured 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

  Examples of the polyisocyanate (a2) include aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, carbodiimidized diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, and phenylene diisocyanate; hexamethylene diisocyanate, isophorone Aliphatic / or alicyclic polyisocyanates such as diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane diisocyanate; adducts thereof; nurate bodies; These polyisocyanates may be used alone or in combination of two or more.

Examples of the chain extender (a3) include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Aliphatic polyol compounds such as sucrose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Aromatic polyol compounds; water and the like can be used. These chain extenders may be used alone or in combination of two or more.

  As the method for producing the urethane resin (A), a known and commonly used method can be used. For example, the isocyanate group of the polyisocyanate (a2), the polyol (a1), and the chain extender (a3) The molar ratio [NCO / OH] to the total of hydroxyl groups possessed by is preferably in the range of 0.3 to 10, and preferably in the range of 0.5 to 8.

  When [NCO / OH] is less than 1, a urethane resin having a hydroxyl group is obtained. When [NCO / OH] is more than 1, a urethane resin having an isocyanate group is obtained. .

  The [NCO / OH] in obtaining the urethane resin having a hydroxyl group is preferably in the range of 0.3 to 0.99, and more preferably in the range of 0.5 to 0.95.

  As said [NCO / OH] at the time of obtaining the urethane resin which has the said isocyanate group, it is preferable that it is the range of 1.01-8, and the range of 1.05-5 is more preferable.

  As the urethane resin (A), it is preferable to use a urethane resin having an isocyanate group from the viewpoint that the mechanical strength is further improved by moisture crosslinking. In addition, in this invention, even if it uses the urethane resin which has the said isocyanate group, it is excellent in storage stability.

  The weight average molecular weight of the urethane resin (A) is preferably in the range of 1,000 to 1,000,000 from the viewpoint of workability, storage stability and mechanical strength, More preferably, it is in the range of 100,000. In addition, the weight average molecular weight of the said urethane resin (A) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a1).

  When manufacturing the said urethane resin (A), you may use a solvent as needed.

  Examples of the solvent include toluene, xylene, benzene, ethyl acetate, butyl acetate, cellosolve acetate, methyl cellosolve, carbitol acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, methanol, butanol, water, and the like. . These solvents may be used alone or in combination of two or more.

  When using the said solvent, it is preferable that it is the range of 10-1,000 mass parts with respect to 100 mass parts of said urethane resins, and it is more preferable that it is the range of 30-500 mass parts.

  The cyclodextrin and / or derivative (C) is an essential component for obtaining excellent storage stability, workability, and wet surface adhesion, such as cyclodextrin; alkylated cyclodextrin, acetylated cyclodextrin In addition, it is possible to use those obtained by substituting the hydrogen atom of the hydroxyl group of the glucose unit of cyclodextrin such as hydroxyalkylated cyclodextrin with other functional groups. The cyclodextrin skeleton in cyclodextrin and cyclodextrin derivatives includes α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. Any of these can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a cyclodextrin derivative from the viewpoint that the compatibility with the urethane resin (A) can be further improved and the wet surface adhesion can be further improved, and it is more preferable to use an alkylated cyclodextrin. preferable.

  The degree of substitution of other functional groups in the cyclodextrin derivative is preferably in the range of 0.3 to 14 / glucose from the viewpoint of compatibility with the urethane resin (A) and wet surface adhesion, A range of 0.5 to 8 / glucose is more preferable.

  Examples of the alkylated cyclodextrin include methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

  Examples of the acetylated cyclodextrin include monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin, and monoacetyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

  Examples of the hydroxyalkylated cyclodextrin include hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, and hydroxypropyl-γ-cyclodextrin. These compounds may be used alone or in combination of two or more.

  As content of the said cyclodextrin and / or its derivative (C), from the point which can further improve compatibility with the said urethane resin (A), workability | operativity, storage stability, mechanical strength, and wet surface adhesiveness. , Preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.3 to 15 parts by weight, with respect to 100 parts by weight of the urethane resin (A). A range is more preferred.

  The civil engineering and building material of the present invention contains the urethane resin (A) and cyclodextrin and / or its derivative (B) as essential components, but may contain other additives as necessary.

  Examples of the other additives include a curing agent, a curing accelerator, petroleum wax, a polymerization inhibitor, a pigment, a thixotropic agent, an antioxidant, a solvent, a filler, a reinforcing material, an aggregate, and a flame retardant. Can be used. These additives may be used alone or in combination of two or more.

  The civil engineering and building material of the present invention obtained by the above method is excellent in storage stability and has excellent wet surface adhesion as well as dry concrete. Also, since there is no resistance when coating and no unevenness occurs on the coated surface, the workability is excellent. Furthermore, the civil engineering and building materials of the present invention are excellent in mechanical strength such as workability and tensile properties.

  Accordingly, any of the civil engineering and building materials of the present invention can be suitably used as a covering material in the fields of civil engineering, architecture, railways, roads, bridges, primers, repair materials, etc., concrete repair materials, concrete waterproofing materials, roads It can be particularly suitably used as a primer for roads and a pavement material for roads.

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

[Synthesis Example 1] Synthesis of Urethane Resin (A-1) In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser, [NCO / OH] was 3.8. 322 parts by mass of polymeric diphenylmethane diisocyanate (“Millionate MR-200” manufactured by Nippon Polyurethane Co., Ltd.), 68 parts by mass of polypropylene glycol (number average molecular weight; 1,000), 362 parts by mass of toluene, and ethyl acetate 362 parts by mass, and reacted at 80 ° C. for 5 hours to obtain a urethane resin (A-1).

[Synthesis Example 2] Synthesis of Urethane Resin (A-2) [NCO / OH] is 1.6 in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser. 217 parts by mass of toluene diisocyanate (“Cosmonate T-80” manufactured by Mitsui Chemicals, Inc.), 156 parts by mass of polypropylene glycol (number average molecular weight; 1,000), and 56 of 1,3-butanediol The urethane resin (A-2) was obtained by adding mass part and making it react at 80 degreeC for 4 hours, and adding and mixing 285 mass parts of xylene and 285 mass parts of toluene after that.

[Example 1]
100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1 and 1 part by mass of methylated β-cyclodextrin (manufactured by Cyclochem Co., Ltd.) were mixed to obtain a civil engineering and building material.

[Examples 2-4, Comparative Examples 1-2]
Civil engineering and building materials were obtained in the same manner as in Example 1 except that the types and / or amounts of the urethane resin (A) and cyclodextrin and / or derivative (B) used were changed to Table 1.

[Comparative Example 3]
Civil engineering building materials were obtained by mixing 100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1 and 250 parts by mass of activated alumina.

[Comparative Example 4]
100 parts by mass of the urethane resin (A-2) obtained in Synthesis Example 1 and 250 parts by mass of Portland cement were mixed to obtain a civil engineering and building material.

[Comparative Example 5]
Civil engineering and building materials were obtained in the same manner as Comparative Example 3 except that the amount of activated alumina used was changed by 3 parts by mass.

[Comparative Example 6]
A civil engineering and building material was obtained in the same manner as in Comparative Example 4 except that the amount of Portland cement used was changed by 3 parts by mass.

[Method of evaluating workability]
Civil engineering and building materials obtained in Examples and Comparative Examples were applied on concrete pavement boards using rollers. At that time, “T” was evaluated when the coating was uniformly spread without resistance, and “F” was evaluated when there was a feeling of resistance or smear occurred.

[Method for evaluating storage stability]
The civil engineering and building materials obtained in Examples and Comparative Examples were filled in 350 g in a 500 mL can, sealed, and then left in a dryer maintained at 50 ° C. for 1 week. Thereafter, the can was opened and the presence or absence of sedimentation was visually observed. The case where no sedimentation separation occurred was evaluated as “T”, and the case where precipitation occurred was evaluated as “F”.

[Method for evaluating wet surface adhesion]
The concrete pavement board was immersed in water for 24 hours and taken out. Immediately after that, the surface was wiped with a waste cloth, and the civil engineering and building materials obtained in Examples and Comparative Examples were applied in an amount of 0.2 kg / mm ² , and then cured for 24 hours. Then, the Kenken type adhesive strength (N / 25 mm) was measured based on JISK6849-1994 using the Kenken type tensile tester ("LPT-1000" manufactured by Oxjack Co., Ltd.). Moreover, the destruction state of the base material after the measurement was also observed visually and evaluated as follows.
“T”; the adhesive strength is 2 N / 25 mm or more, and the substrate is broken.
“F”: Adhesive strength is less than 2 N / 25 mm, and interface peeling occurs.

  Examples 1 to 4, which are civil engineering and building materials of the present invention, are excellent in storage stability and adhesiveness to wet concrete, and excellent in workability without causing a sense of resistance and non-uniformity on the coated surface when applied. I understood.

  On the other hand, Comparative Examples 1 and 2 were embodiments that did not contain cyclodextrin and / or its derivative (B), but the wet surface adhesion was extremely poor.

  Comparative Examples 3 and 4 are embodiments using an inorganic powder such as activated alumina or Portland cement instead of cyclodextrin and / or its derivative (B). As a result, unevenness occurred and the workability was poor, and the storage stability was also poor.

  In Comparative Examples 5 and 6, the amount of inorganic powder used in Comparative Examples 3 and 4 was reduced, but the wet surface adhesion was poor.

Claims (4)

A civil engineering and building material comprising a urethane resin (A) and cyclodextrin and / or a derivative (B) thereof. The civil engineering and building material according to claim 1, wherein the cyclodextrin and / or derivative (B) thereof is an alkylated cyclodextrin. The civil engineering and building material according to claim 1, wherein a content of the cyclodextrin and / or a derivative thereof (B) is in a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the urethane resin (A). The civil engineering and building material according to claim 1, wherein the urethane resin (A) has an isocyanate group.