JP7208050B2 - civil engineering building materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to civil engineering and construction materials that can be suitably used as concrete repair materials, road primers, and the like.

In the civil engineering and construction industry, which repairs concrete structures, etc., attention is focused on infrastructure repair against the background of the collapse of the Sasago Tunnel. Concrete structures constructed after the high economic growth period will exceed 50 years of construction in the next 30 years, so the demand for concrete repair is increasing.

As repair materials for concrete, epoxy resins, which are superior in performance such as mechanical strength, occupy about 70% of the market share, and acrylic resins, urethane resins, etc. occupy the remaining nearly 30% of the market.

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

As a urethane resin having good adhesion to concrete even in a humid environment, for example, a composition containing a urethane resin and aluminum oxide powder is disclosed (see, for example, Patent Document 1). However, since the composition contains inorganic powder dispersed in urethane resin, there are problems such as a feeling of resistance when applied to a substrate and unevenness in the coated surface. Since it separates over time, it is also required to improve its storage stability.

JP-A-2003-128479

The problem to be solved by the present invention is to provide a civil engineering and construction material which is excellent in storage stability and adhesion to wet concrete, has excellent workability, does not cause resistance when applied, and does not cause unevenness on the applied surface. That is.

In order to solve the above problems, the civil engineering and construction material according to the present invention contains a urethane resin (A) and a cyclic oligosaccharide (B) represented by the following general formula (1). However, in general formula (1), R represents a hydrogen atom or a substituent thereof, a plurality of R may be the same or different, and n represents an integer of 0-3.

The civil engineering and construction material of the present invention has excellent storage stability and excellent adhesion not only to dry concrete but also to wet concrete (hereinafter abbreviated as "wet surface adhesion"). be. In addition, since there is no sense of resistance during application and no unevenness occurs on the coated surface, the workability is also excellent. Furthermore, the civil engineering and construction material of the present invention is excellent in mechanical strength such as workability and tensile properties.

Therefore, the civil engineering and construction material of the present invention can be suitably used as a coating material in the fields of civil engineering, construction, railways, roads, bridges, etc.; primer, repair material, etc.; It can be particularly suitably used as a primer and road pavement material.

FIG. 2 shows steps for synthesizing cyclic oligosaccharides according to one embodiment. FIG. 2 shows steps for synthesizing cyclic oligosaccharides according to another embodiment. 1 is a photograph of a molecular model showing the molecular structure of a cyclic oligosaccharide according to one embodiment. 1 is a photograph of a molecular model showing the molecular structure of cyclodextrin. 1 is an FT-IR spectrum diagram of fully methylated cellulose and partially methylated cellulose in Synthesis Example 1. FIG. 1 is a 1H-NMR spectrum diagram of fully methylated cellulose in Synthesis Example 1. FIG. 1 is a MALDI-TOF MS spectrum diagram of a crude product before hexamer isolation in Synthesis Example 1. FIG. 1 is a 1H-NMR spectrum diagram of a methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a NOESY spectrum diagram of a methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. FIG. 10 is a partially enlarged view of FIG. 9; 13 is a 13C-NMR spectrum diagram of the methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a MALDI-TOF MS spectrum diagram of the methylated cyclic cellooligosaccharide (hexamer) of Synthesis Example 1. FIG. 1 is a HPLC chromatogram of methylated cyclic cellooligosaccharide (hexamer) and fully methylated α-cyclodextrin of Synthesis Example 1. FIG. 2 is a MALDI-TOF MS spectrum diagram of partially acetylated cellooligosaccharide in Synthesis Example 2. FIG. 2 is a MALDI-TOF MS spectrum diagram of a crude product containing acetylated cyclic cellooligosaccharides in Synthesis Example 2. FIG. 1 is a MALDI-TOF MS spectrum diagram of a crude product containing cyclic cellooligosaccharides in Synthesis Example 2. FIG.

[Cyclic cellooligosaccharide]
First, the cyclic oligosaccharide (also referred to as cyclic cellooligosaccharide) represented by the general formula (1) according to the present embodiment will be described in detail.

Cyclodextrin is conventionally known as a cyclic oligosaccharide. Cyclodextrin has a cyclic structure in which glucose is linked by α-1,4 glucosidic bonds, as represented by the following general formula (x) (where m is an integer of 1 to 3), Generally, there are α-cyclodextrins with 6 glucose linkages, β-cyclodextrins with 7 glucose linkages, and γ-cyclodextrins with 8 glucose linkages.

On the other hand, the cyclic cellooligosaccharide according to the present embodiment is a compound represented by the general formula (1), and is a cyclic cello-oligosaccharide in which structural units that are glucose or a derivative thereof are linked by a β-1,4 glucosidic bond. have structure. n in formula (1) represents an integer of 0 to 3, and therefore the cyclic oligosaccharide represented by formula (1) is composed of pentamers, hexamers, heptamers and octamers of the above structural units. , or a mixture of two or more thereof.

The cyclic cellooligosaccharide according to the embodiment of the present invention can be obtained, for example, by bonding terminal hydroxyl groups of an oligosaccharide represented by the following general formula (2) to cyclize it, as described later. However, in formula (2), R represents a hydrogen atom or a substituent thereof, a plurality of R may be the same or different, and k represents an integer of 3-6.

When all R in formula (1) are hydrogen atoms, it is a chemically unmodified (i.e., unsubstituted) cyclic oligosaccharide represented by the following formula (3) (here, in formula (3) n represents an integer of 0 to 3.).

The cyclic oligosaccharide of the formula (3) differs from the cyclodextrin of the above formula (x) only in that the linking structure between glucose is β-1,4 bond and α-1,4 bond. Generally, substituents can be introduced using known chemical modification methods applied to cyclodextrins. Therefore, the cyclic oligosaccharide of formula (1) can have substituents similar to those of known cyclodextrins.

As described above, R in formula (1) may be all hydrogen atoms, all may be substituents, or hydrogen atoms and substituents may coexist. When coexisting, the ratio of both is not particularly limited. For example, OR is divided into a group corresponding to a primary hydroxy group (OR ¹ ) and a group corresponding to a secondary hydroxy group (OR ² ) of a glucose constitutional unit, and formula (1) is replaced by the following general formula (1-1 ), all of R ¹ may be substituents and all of R ² may be hydrogen atoms, some of R ¹ may be substituents and the remainder of R ¹ and all of R ² may be hydrogen atoms, All of R ¹ and part of R ² may be substituents and the rest of R ² may be hydrogen atoms. Further, all of R ² may be substituents and all of R ¹ may be hydrogen atoms, some of R ² may be substituents and the remainder of R ² and all of R ¹ may be hydrogen atoms, all of R ² and R A part of ¹ may be a substituent and the remainder of R ¹ may be a hydrogen atom. Furthermore, both R ¹ and R ² may be partly substituted and the remainder may be hydrogen atoms.

The substituent represented by R in formula (1) is a group that substitutes the hydroxy hydrogen of glucose, and includes various groups that can be derived from the hydroxy hydrogen of glucose through one or more reactions.

Specifically, the substituent represented by R (hereinafter referred to as substituent R) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group (e.g., phenyl group, tolyl group, etc.), substituted or unsubstituted aralkyl group (e.g., benzyl group, phenethyl group, trityl group, etc.), acyl group, silyl groups, sulfonyl groups, sugar residues, substituted or unsubstituted polyoxyalkylene groups, and the like. The number of carbon atoms in the substituent R is not particularly limited, and may be, for example, 1-40, 1-30, or 1-20.

The substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted cycloalkenyl group, substituted aryl group, and substituted aralkyl group, which are examples of the substituent R, include, for example, a hydroxy group as a substituent such as a hydroxyalkyl group. Those having a sulfo group or a derivative group thereof as a substituent such as a sulfoalkyl group or a salt or ester group thereof, a carboxy group or a derivative group thereof as a substituent such as a carboxymethyl group or a salt or ester group thereof and the like. The hydrocarbon group constituting the ester group here includes, for example, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.

Examples of the acyl group, which is an example of the substituent R, include monocarboxylic acid residues that form an ester bond with the oxygen atom in -OR such as an acetyl group and a benzoyl group (for example, R: -CO-Q ¹ ), or a residue of a dicarboxylic acid such as succinic acid. In the case of a dicarboxylic acid residue, the carboxy group that is not ester-bonded to glucose forms an ester group in either an acid form or a metal salt. (eg, R: -CO-Q ² -COO-Q ³ ). Here, Q ¹ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms (preferably 1 to 6), and the organic group includes an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, An aralkyl group is mentioned. ^Q2 represents a hydrocarbon group having 1 to 6 carbon atoms (such as an alkanediyl group). Q ³ represents a hydrogen atom, an alkali metal, or an organic group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and examples of the organic group include alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, An aralkyl group is mentioned.

Examples of the silyl group, which is an example of the substituent R, include trialkylsilyl groups such as a tert-butyldimethylsilyl group. Examples of the sulfonyl group include arylsulfonyl groups such as p-toluenesulfonyl group. Furthermore, examples of sugar residues include glucosyl groups, mantosyl groups, and the like.

Examples of the substituted or unsubstituted polyoxyalkylene group, which is an example of the substituent R, include groups having repeating units of oxyalkylene having 1 to 4 carbon atoms such as a polyoxyethylene group, and the terminal OH is amino may be substituted with a substituent such as a group, an azide group, or a trityl group. The number of repetitions of the oxyalkylene group is not particularly limited, and may be, for example, 2-20.

As for the substituents R listed above, only one of the plurality of Rs in the formula (1) may be introduced, or two or more of them may be introduced in combination.

The cyclic oligosaccharide having a β-1,4 glucosidic bond according to the present embodiment is produced through a step of cyclizing by bonding the terminal hydroxyl groups of the oligosaccharide represented by the general formula (2). can be done. R in Formula (2) represents a hydrogen atom or a substituent thereof. Examples of the substituent represented by R in formula (2) include the same substituents as in formula (1) described above, preferably R is an alkyl group or an acyl group, for example, the formula OR in (2) is an acylated (more preferably acetylated) hydroxy group of glucose (that is, an acyloxy group, preferably an acetyloxy group), an alkylated (more preferably methylated) hydroxy group of glucose ) (ie, an alkoxy group, preferably a methoxy group).

A method for producing a cellulose-derived cyclic cellooligosaccharide as a cyclic oligosaccharide according to one embodiment will be described with reference to FIG.

In the production method shown in FIG. 1, first, cellulose represented by formula (4) is acetylated (here, p in the formula is a number corresponding to the number of repetitions of two molecules of glucose in cellulose). Cellulose has a structure in which glucose units are linked by β-1,4 glucosidic bonds, and adjacent glucose units are turned inside out and arranged in a line to form a linear structure. Therefore, cellulose has strong intramolecular and intermolecular hydrogen bonds and is insoluble in water. By acetylating the hydroxy groups of cellulose to eliminate hydrogen bonds, flexibility is imparted to the molecular chain. Note that partially acetylated cellulose may be used as a starting material.

Acetylation can be performed, for example, by reacting cellulose with acetic anhydride in the presence of perchloric acid (see, for example, P. Arndt et al., Cellulose, 2005, 12, 317). Acetylation yields cellulose triacetate (completely acetylated cellulose) represented by formula (5) in which all three hydroxy groups of each structural unit of cellulose are acetylated.

Then, the glucosidic bond is cleaved from the cellulose triacetate to synthesize the partially acetylated cellooligosaccharide represented by the formula (6). Cleavage of glucosidic bonds can be performed by adding concentrated sulfuric acid to cellulose triacetate (for example, H. Namazi et al., J. Appl. Polym. Sci., 2008, 110, 4034. and T. Kondo, D. G. Gray, J. Appl. Polym. Sci. 1992, 45, 417). Then, by separating and purifying after cleavage, it has 5 to 8 glucose units as shown in formula (6), and has hydroxy groups at positions 1 and 4 of the glucose units at both ends, A chain-shaped partially acetylated cellooligosaccharide having a structure in which all other hydroxy groups are acetylated is obtained. The cellooligosaccharide of formula (6) is an oligosaccharide represented by formula (2) above in which -OR is -O-Ac (where Ac is an acetyl group).

Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by formula (6) are bonded together to cyclize it. The cyclization method is not particularly limited, and for example, the terminal 1-hydroxy group of the partially acetylated cellooligosaccharide represented by formula (6) may be trichloroacetimidated and then cyclized. Trichloroacetimidation can be performed by reacting the partially acetylated cellooligosaccharide with trichloroacetonitrile, and then adding a boron trifluoride diethyl ether complex to the partially acetylated cellooligosaccharide that has been trichloroacetimidated. By reacting, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a ring.

By adding a boron trifluoride diethyl ether complex to the partially acetylated cellooligosaccharide without converting it to trichloroacetimidate, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a cyclic structure. can be

As a result, an acetylated cyclic cellooligosaccharide represented by formula (7) is obtained. The acetylated cyclic cellooligosaccharide of formula (7) is a cyclic oligosaccharide represented by formula (1) above in which all —ORs are —O—Ac.

Then, the acetyloxy group of the acetylated cyclic cellooligosaccharide represented by the formula (7) is hydrolyzed using, for example, a base catalyst (sodium hydroxide, triethylamine, etc.) to obtain the compound represented by the above formula (3). cyclic oligosaccharides are obtained.

FIG. 2 is a diagram showing steps of synthesizing a cyclic oligosaccharide according to another embodiment. In the example of FIG. 2, a partially methylated cellulose represented by the formula (10), in which the hydroxy groups of the cellulose are partially methylated, was used as a starting material to obtain a methylated cyclic cellooligot represented by the formula (13). Synthesize sugar.

In the production method shown in FIG. 2, first, partially methylated cellulose is methylated to synthesize fully methylated cellulose. Methylation can be carried out, for example, by reacting partially methylated cellulose with sodium hydride and iodomethane (see, for example, J. N. Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133.). As a result, a fully methylated cellulose represented by formula (11) in which all three hydroxy groups of each structural unit of cellulose are methylated is obtained.

Then, the partially methylated cellooligosaccharide represented by the formula (12) is synthesized by cleaving the glucosidic bond of the fully methylated cellulose. Glucosidic bond cleavage is the same as in FIG. Then, by separating and purifying after cleavage, it has 5 to 8 glucose units as shown in formula (12), and has hydroxyl groups at positions 1 and 4 of the glucose units at both ends, A chain-shaped partially methylated cellooligosaccharide having a structure in which all other hydroxy groups are methylated is obtained. The cellooligosaccharide of formula (12) is an oligosaccharide represented by formula (2) above in which —OR is —O—Me (where Me represents a methyl group).

Next, the hydroxy groups at both ends of the partially acetylated cellooligosaccharide represented by formula (12) are combined to cyclize. The cyclization method is not particularly limited, and for example, the partially methylated cellooligosaccharide may be reacted with trifluoromethanesulfonic anhydride (Tf ₂ O) and 2,6-di-tert-butylpyridine (DBP). can be done. As a result, the glucose units at both ends are linked by β-1,4 glucosidic bonds to form a cyclic structure, and the methylated cyclic cellooligosaccharide represented by the formula (13) is obtained. This methylated cyclic cellooligosaccharide is a cyclic oligosaccharide represented by the above formula (1) in which all —ORs are —O—Me.

In the cyclic oligosaccharide represented by the formula (1), the substituent for R in the formula can be introduced using a known chemical modification method basically applied to cyclodextrins, as described above. . For example, to introduce an alkoxy group such as a methoxy group as —OR, a method of alkylating a hydroxy group described in JP-A-61-200101 may be used. In addition, in the case where R is a substituted alkyl group, a sulfoalkyl group or a carboxymethyl ester group can be introduced via an ether oxygen by the methods described in JP-A-11-60610 and JP-A-2013-28744. may be used. When R is an acyl group, the method described in JP-A-4-81403 may be used to introduce a dicarboxylic acid residue such as succinic acid. In addition, when R is a sulfonyl group, the method described in JP-A-2016-69652 may be used to introduce a tosyl group via an ether oxygen.

As a method for introducing a substituent, it is not always necessary to first synthesize an acetylated cyclic cellooligosaccharide as described above, and then hydrolyze it into a cyclic oligosaccharide of formula (3) before introducing a substituent. Instead, after cyclization, it may be directly converted to other substituents.

As described above, the cyclic oligosaccharide according to the present embodiment can be synthesized from cellulose, which is the most abundant organic compound on earth and is a renewable non-edible plant resource. can be achieved.

Further, when the molecular structures of the cyclic oligosaccharide according to the present embodiment and cyclodextrin are compared, the cyclic oligosaccharide according to the present embodiment has higher hydrophobicity in the pores than cyclodextrin. Specifically, the molecular structure of the cyclodextrin represented by the formula (x) is as shown in FIG. 4, whereas the molecular structure of the cyclic oligosaccharide represented by the formula (3) is as shown in FIG. be. 3 and 4, white atoms are hydrogen atoms, black atoms are carbon atoms, and gray atoms therebetween are oxygen atoms.

As shown in FIG. 4, in cyclodextrin, the glucoside oxygen linking the glucose units faces the inside of the pore, so the interior of the pore is in a hydrophobic environment similar to ether. In contrast, as shown in FIG. 3, in the cyclic oligosaccharide according to the present embodiment, the glucoside oxygen faces outward, and the oxygen atoms do not face the inside of the vacancy. Therefore, in the cyclic oligosaccharide according to the present embodiment, the inside of the pore is in a more hydrophobic environment than cyclodextrin, and it is possible to take in highly hydrophobic substances. As a result, it can be expected to have higher guest inclusion ability and higher guest selectivity, for example, in water.

Since the cyclic oligosaccharide according to the present embodiment has the property of enclosing a hydrophobic guest molecule or a part thereof in the pore, similarly to cyclodextrin, volatile substances are nonvolatile and sustained release, nonvolatile. For the purpose of stabilizing stable substances and solubilizing poorly soluble substances, it can be used for applications such as foods, cosmetics, toiletry products, and pharmaceuticals.

[Civil engineering and building materials]

The civil engineering and construction material of the present embodiment contains the urethane resin (A) and the above-described cyclic cellooligosaccharide (B) as essential components.

As the urethane resin (A), for example, one obtained by reacting a polyol (a1), a polyisocyanate (a2), and optionally a chain extender (a3) can be used.

As the polyol (a1), for example, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacryl polyol, polyisoprene polyol, dimer diol and the like can be used. 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.

Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, carbodiimidated diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, and phenylene diisocyanate; hexamethylene diisocyanate, isophorone; Aliphatic/alicyclic polyisocyanates such as diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and cyclohexane diisocyanate; their adducts; nurates; burettes and the like can be used. These polyisocyanates may be used alone or in combination of two or more.

Examples of the chain extender (a3) include ethylene glycol, diethylene glycol, 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. of 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 a method for producing the urethane resin (A), a known and commonly used method can be used. is preferably in the range of 0.3 to 10, more preferably in the range of 0.5 to 8.

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

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

The [NCO/OH] when obtaining the urethane resin having the isocyanate group is preferably in the range of 1.01 to 8, more preferably in the range of 1.05 to 5.

As the urethane resin (A), it is preferable to use a urethane resin having an isocyanate group, since the mechanical strength is further improved by moisture crosslinking. In addition, in this embodiment, even if the urethane resin having the isocyanate group is used, the storage stability is excellent.

From the viewpoint of workability, storage stability and mechanical strength, the weight average molecular weight of the urethane resin (A) is preferably in the range of 1,000 to 1,000,000, preferably 1,500 to 1,500. More preferably in the range of 100,000. The weight average molecular weight of the urethane resin (A) is the value obtained by measuring in the same manner as the number average molecular weight of the polyol (a1).

If necessary, a solvent may be used when producing the urethane resin (A).

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 the solvent is used, the amount used is preferably in the range of 10 to 1,000 parts by mass, more preferably in the range of 30 to 500 parts by mass, based on 100 parts by mass of the urethane resin.

The aforementioned cyclic cellooligosaccharide (B) is an essential component for obtaining excellent storage stability, workability and wet surface adhesion.

The content of the cyclic cellooligosaccharide (B) is the urethane resin ( A) With respect to 100 parts by mass, it is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 0.3 to 15 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass.

The civil engineering and construction material of the present embodiment may contain other additives as necessary.

Examples of other additives include curing agents, curing accelerators, petroleum wax, polymerization inhibitors, pigments, thixotropic agents, antioxidants, solvents, fillers, reinforcing materials, aggregates, flame retardants, and the like. can be used. These additives may be used alone or in combination of two or more. Examples of the flame retardant include conventionally known general flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants. Phosphorus-based flame retardants include phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Halogenated flame retardants include bromine-containing compounds such as tetrabromobisphenol A epoxy oligomers. Also, as a flame retardant, ADEKA's Adekastab FP-2600U or the like can be used. Known fillers such as aluminum hydroxide, magnesium oxide, calcium carbide and talc can be used as fillers. For example, thermally conductive MgO filler manufactured by Ube Industries, Ltd. may be used depending on the usage of civil engineering and construction materials. As talc, for example, ultrafine talc of Nippon Talc Co., Ltd. having a particle size of about 0.6 μm may be used.

The civil engineering and construction material of the present embodiment obtained by the above method has excellent storage stability and excellent wet surface adhesion as well as dry concrete. In addition, since there is no sense of resistance during application and no unevenness occurs on the coated surface, the workability is also excellent. Furthermore, the civil engineering and construction material of the present embodiment is excellent in mechanical strength such as workability and tensile properties.

Therefore, the civil engineering and building material of the present embodiment can be suitably used as a covering material; It can be particularly suitably used as a road primer and a road pavement material.

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the following examples, "%" means "% by mass" unless otherwise specified.

[Cyclic cellooligosaccharide]
Synthesis of cyclic cellooligosaccharides used in this example and the like are described below. Analysis and measurement methods are as follows.

(Infrared absorption spectrum (FT-IR))
Measured with a Fourier transform infrared spectrophotometer (“FT/IR4700ST model” manufactured by JASCO Corporation) (ATR method).

(NMR)
Measured with "JNM-ECS400" manufactured by JEOL Ltd.

(mass spectrometry)
Measured with a matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF MS) ("Voyager ^TM RP" manufactured by Nippon Perceptive Limited).

(HPLC)
Column: ODS ("Wakosil 5C18 AR" manufactured by Wako Pure Chemical Industries, Ltd., inner diameter 4.6 mm, length 150 mm)
Mobile phase: acetonitrile/water = 8/2 (volume ratio)
Flow rate: 1.0 mL/min Temperature: 30°C
Detection: ELSD (“Model400 ELSD” manufactured by SoftTA, USA).

(TLC)
Developing solvent: methanol/chloroform=1/40 (volume ratio).

<Synthesis Example 1. Synthesis of methylated cyclic cellooligosaccharide>
First, synthesis of a methylated cyclic cellooligosaccharide, which is one aspect of the cyclic cellooligosaccharide according to the present embodiment, will be described.

(1-1 Synthesis of fully methylated cellulose from partially methylated cellulose)
JN Bemiller, Earle E. Allen, JR., J. Polym. Sci. 1967, 5, 2133. The details of the reaction formula and synthesis method are as follows.

Partially methylated cellulose (2.01 g, 5.03×10 ⁻⁵ mol, Sigma-Aldrich “cellulose acetate (Mn~30,000)”) vacuum-dried at 80° C. overnight was dried in DMSO under a nitrogen atmosphere. (110 mL). This solution was added to sodium hydride (content: 60%, 1.81 g, 4.53×10 ⁻² mol) and stirred at 50° C. for 16 hours. Iodomethane (2.95 mL, 4.74×10 ⁻² mol) was added dropwise thereto over 30 minutes and stirred at 50° C. for 24 hours. Methanol (3.85 mL) was added to the system to deactivate unreacted sodium hydride, and the resulting solution was added to water (350 mL) for reprecipitation. The resulting solid was separated by centrifugation and vacuum dried at 60° C. to obtain the product (white powdery solid) (1.90 g, 95% yield).

The FT-IR spectrum of the product is shown in FIG. 5 together with the FT-IR spectrum of the starting partially methylated cellulose. In partially methylated cellulose as a raw material, an absorption peak based on OH stretching vibration was observed near 3400 cm ⁻¹ as shown in FIG. 5(a). In contrast, in the FT ^- IR spectrum of the product, absorption peaks were observed at 2915, 1455, and 1050 cm ⁻¹ as shown in FIG. Absorption peaks disappeared, confirming that all hydroxy groups were methylated.

The results of ¹ H-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
¹ H-NMR (400MHz, chloroform-d): δ 2.92 (t, 1H), 3.19 (t, 1H), 3.27(m,1H), 3.37 (s, 3H), 3.52 (s,3H), 3.56 ( s, 3H), 3.69-3.61 (m, 2H), 3.75 (m, 1H), 4.31 (d, 1H).

From the above, it was confirmed that the product was fully methylated cellulose.

(1-2 Synthesis of partially methylated cellooligosaccharides from fully methylated cellulose)
With reference to the method described in T. Kondo, DG Gray, J. Appl. Polym. Sci. 1992, 45, 417, partially methylated cellooligosaccharides (5-8 glucose units) were synthesized from fully methylated cellulose. rice field. The details of the reaction formula and synthesis method are as follows.

Permethylated cellulose (0.55 g, 1.2×10 ⁻² mmol) vacuum-dried at 80° C. was dissolved in dehydrated dichloromethane (30 mL) under a nitrogen atmosphere. Boron trifluoride diethyl etherate (7.2 mL, 56 mmol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0 to 49.0% (BF ₃ )) was added thereto and stirred at room temperature for 6 hours. . A saturated aqueous sodium bicarbonate solution (15 mL) was added to the resulting solution to terminate the reaction. After extraction with dichloromethane (30 mL) twice, the collected dichloromethane solutions were dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a brown viscous liquid (crude yield: 0.52 g, crude yield: 93%).

MALDI-TOF-MS measurements revealed that the resulting product was a mixture of partially methylated cellooligosaccharides consisting of 2-11 glucose units. This was subjected to size exclusion chromatography to separate partially methylated cellooligosaccharides consisting of 5-8 glucose units (88 mg, 16% yield).

Size exclusion chromatography used the following as a separation device.
Apparatus: Recycle preparative HPLC LC-9210 NE×T manufactured by Nippon Analytical Industry Co., Ltd. Column: JAIGEL-2HR (exclusion limit molecular weight 5,000) x 2 manufactured by Nippon Analytical Industry Co., Ltd. Flow rate: 9 .5 mL/min Eluent: chloroform Injection volume per injection: 67 mg (1 mL of chloroform)
・Detector: RI-700 II NE×T manufactured by Nippon Analytical Industry Co., Ltd.

(1-3 Synthesis of methylated cyclic cellooligosaccharide from partially methylated cellooligosaccharide)

Under a nitrogen atmosphere, the partially methylated cellooligosaccharide (75 mg, 5.2×10 ⁻⁵ mol) obtained in 1-2 above was dissolved in toluene (18 mL). Trifluoromethanesulfonic anhydride (Tf ₂ O) (15 μL, 9.0×10 ⁻⁵ mol) dissolved in toluene (3 mL) was added dropwise thereto and stirred at room temperature for 1 hour. After that, 2,6-di-tert-butylpyridine (DBP) (185 μL, 8.4×10 ⁻⁴ mol) dissolved in toluene (3 mL) was added dropwise and stirred at room temperature for 17 hours. After that, a saturated aqueous sodium hydrogencarbonate solution (50 mL) was added, and the mixture was extracted with toluene (100 mL). The toluene layer was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the resulting crude product (white solid) was subjected to size exclusion chromatography and medium-pressure column chromatography to purify the methylated cyclic cellooligosaccharide (hexamer ) was obtained (1 mg, 1.5% yield, white solid). The reaction formula is as described above.

Size exclusion chromatography was performed in the same manner as in 1-2 above. The separation conditions by medium pressure column chromatography are as follows.
・Column: ODS (“Universal Column ODS” manufactured by Yamazen Co., Ltd., inner diameter 20 mm, length 84 mm)
- Mobile phase: acetonitrile/water = 8/2 (volume ratio).

Mass spectrometry (MALDI-TOF MS) results for the crude product prior to hexamer purification are shown in FIG. As shown in FIG. 7, peaks corresponding to 5- to 8-mer methylated cyclic cellooligosaccharides were observed.

The results of ¹ H-NMR analysis of the purified product (hexamer) are shown below, and the NMR spectrum is shown in FIG.
¹ H NMR (400 MHz, chloroform-d): 5.08 (d, J = 2.3 Hz, 6H), 4.33 (dd, J = 2.3, 7.7 Hz, 6H), 4.20 (ddd, J = 2.3, 4.5, 7.3 Hz , 6H), 4.03 (dd,J = 2.3, 6.8 Hz, 6H), 3.96 (dd, J = 6.8, 7.7 Hz, 6H), 3.67 (dd, J = 8.2, 9.9Hz, 6H), 3.50 (dd, J = 4.5, 9.5 Hz, 6H), 3.42 (s, 18H), 3.40 (s, 18H), 3.32 (s, 18H) ppm.

FIG. 9 shows the NOESY spectrum of the product, and FIG. 10 shows an enlarged view near the hydrogen (H ₁ ) bonded to the 1-position carbon of the glucose unit.

The results of ¹³ C-NMR analysis of the product are shown below, and the NMR spectrum is shown in FIG.
^13C NMR (400 MHz, chloroform-d): 105.38, 90.72, 87.34, 79.27, 74.20, 72.59, 59.11, 58.86, 57.69 ppm.

The results of mass spectrometry (MALDI-TOF MS) of the product are shown below, and the spectrum is shown in FIG.
MALDI-TOF MS (m/z): 1246 [M+Na] ⁺ .

TLC of the product gave an Rf value of 0.48.

The HPLC results of the product (FIG. 13(a)) are shown in FIG. shown in

From the results of MS spectrum and HPLC, this product has the same molecular weight as permethylated α-cyclodextrin, but it is found to be a different compound. Moreover, from the ¹ H-NMR spectrum and ¹³ C-NMR spectrum, this product is a highly symmetrical compound composed of glucose units in which the hydroxyl groups at the 2-, 3-, and 6-positions are methylated. Conceivable. Furthermore, from the NOESY spectrum (FIGS. 9 and 10), the 1-position proton of the glucose unit shows correlation with the 2-, 3-, 5-, and 6-position protons, while the 4-position proton shows correlation. Therefore, it is considered that the 1-position proton and the 4-position proton are separated from each other, and the glucose units are connected by a β-1,4 bond. From these facts, it can be identified that the chemical structure of the methylated cyclic cellooligosaccharide is represented by the formula (1) (R=methyl group, n=1).

Hereinafter, the methylated cyclic cellooligosaccharide thus obtained is also referred to as "cyclic cellooligosaccharide 1".

<Synthesis Example 2. Synthesis of cyclic cellooligosaccharide>
Next, synthesis of cyclic cellooligosaccharide (R=hydrogen atom in formula (1)), which is another aspect of the cyclic cellooligosaccharide according to the present embodiment, will be described.

(2-1 Synthesis of fully acetylated cellulose from partially acetylated cellulose)
Fully acetylated cellulose was synthesized according to the method described by P. Arndt et al., Cellulose, 2005, 12, 317. The details of the reaction formula and synthesis method are as follows.

Partially acetylated cellulose (manufactured by Sigma-Aldrich, Mn=30000, degree of acetylation=1.48) (4.0 g, 9.3×10 ⁻⁵ mol) was dissolved in acetic acid (80 mL), and acetic anhydride (26 mL, 2.7×10 ⁻¹ mol) and perchloric acid (1.6 mL, 2.8×10 ⁻² mol) were added and stirred at room temperature for 2 hours. The reaction mixture was poured into water (100 mL) and the resulting solid was collected by suction filtration. This was washed with a saturated aqueous sodium bicarbonate solution (500 mL) and then with water (500 mL), and after this washing operation was carried out once more, the solid was vacuum dried at 70° C. to give a white powdery solid (yield: 3.9 g, 80% yield).

The infrared absorption spectrum of the obtained solid confirmed the presence of a carbonyl group absorption peak (1735 cm ⁻¹ ) and the disappearance of a hydroxy group absorption peak (around 3400 cm ⁻¹ ) observed in the raw material.

(2-2 Synthesis of partially acetylated cellooligosaccharides from fully acetylated cellulose)
Partially acetylated cellooligosaccharides were synthesized from fully acetylated cellulose with reference to the method described in T. Kondo, DG Gray, J. Appl. Polym. The details of the reaction formula and synthesis method are as follows.

The fully acetylated cellulose (0.45 g, 8.3×10 ⁻⁶ mol) synthesized in 2-1 above was dissolved in acetic acid (9.0 mL) at 80° C., and acetic anhydride (150 μL, 1.6×10 ⁻³ mol), concentrated sulfuric acid (35 μL, 6.5×10 ⁻⁴ mol) and water (54 μL, 3.0×10 ⁻³ mol) were sequentially added and stirred at 80° C. for 16 hours. The reaction solution was allowed to cool to room temperature, 20% aqueous magnesium acetate solution (70 μL) was added, the reaction mixture was poured into diethyl ether (100 mL), the resulting solid was collected by suction filtration, and washed with water (100 mL). Vacuum dried (yield 0.16 g).

MALDI-TOF-MS measurements revealed that the resulting product was a mixture of partially acetylated cellooligosaccharides consisting of 2-13 glucose units (see Figure 14).

(2-3 Synthesis of acetylated cyclic cellooligosaccharide from partially acetylated cellooligosaccharide)

The partially acetylated cellooligosaccharide (500 mg, 2.0×10 ⁻⁴ mol) obtained in 2-2 above was dissolved in a mixed solution of dehydrated dichloromethane (27 mL) and dehydrated toluene (3.0 mL). Boron trifluoride diethyl ether complex (800 μL, 7.0×10 ⁻³ mol, manufactured by Wako Pure Chemical Industries, Ltd., content: 46.0 to 49.0% (BF ₃ )) was added thereto and heated to 40° C. and stirred for 15 hours. After that, a saturated aqueous sodium hydrogencarbonate solution (50 mL) was added, and after extraction with 100 mL of chloroform, the solvent was distilled off to obtain a brownish yellowish white solid (200 mg). This was dissolved in dehydrated pyridine (3.0 mL), acetic anhydride (1.5 mL, 1.5×10 ⁻² mol) was added, and the mixture was stirred at room temperature for 24 hours to acetylate the liberated hydroxyl groups. Extraction was performed with saturated saline (100 mL) and chloroform (100 mL), and the solvent was distilled off from the chloroform layer to obtain a brownish yellowish white solid (250 mg). Silica gel column chromatography was performed twice (first mobile phase: methanol/chloroform (1/99), second mobile phase: methanol/chloroform (1/150)) to obtain a crude product (6 mg). The reaction formula is as described above.

The obtained crude product was subjected to MALDI-TOF-MS measurement. The results are shown in FIG. As shown in FIG. 15, similarly to the case of the methylated product of Synthesis Example 1, peaks corresponding to 5- to 8-mer cyclic products were observed. Specifically, in Synthesis Example 2, peaks corresponding to 5- to 8-mer acetylated cyclic cellooligosaccharides were observed together with peaks corresponding to non-cyclized linear 6- to 8-mers.

(2-4 Synthesis of cyclic cellooligosaccharide from acetylated cyclic cellooligosaccharide)

Acetylated cyclic cellooligosaccharide (4.0 mg) was dissolved in methanol (1.2 mL), and water (0.8 mL) was added thereto. Further triethylamine (0.8 mL, 5.5×10 ⁻³ mol) was added and stirred at 40° C. for 24 hours. Evaporation of the solvent gave the crude product (4 mg). The reaction formula is as described above.

The obtained crude product was subjected to MALDI-TOF-MS measurement. The results are shown in FIG. As shown in FIG. 16, a peak corresponding to a 6- to 8-mer cyclic cellooligosaccharide was observed together with a peak corresponding to a 6- to 8-mer linear cellooligosaccharide.

The cyclic cellooligosaccharide thus obtained is hereinafter referred to as "cyclic cellooligosaccharide 2".

[Civil engineering and building materials]
Hereinafter, the synthesis of the urethane resin used in this example and the preparation and evaluation of civil engineering and construction materials will be described.

[Synthesis Example 1] Synthesis of urethane resin (A-1) A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser was charged with [NCO/OH] of 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, ethyl acetate and reacted at 80° C. for 5 hours to obtain a urethane resin (A-1).

[Synthesis Example 2] Synthesis of urethane resin (A-2) A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser was charged with [NCO/OH] of 1.6. 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), 56 parts by mass of 1,3-butanediol 285 parts by mass of xylene and 285 parts by mass of toluene were added and mixed to obtain a urethane resin (A-2).

Table 1 shows the compounding amounts (parts by mass) of raw materials for civil engineering and construction materials according to each example and each comparative example, and the evaluation results thereof.

[Example 1]
100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1 and 1 part by mass of cyclic cellooligosaccharide 1 were mixed to obtain a civil engineering and construction material.

[Examples 2-5, Comparative Examples 1-2]
A civil engineering and construction material was obtained in the same manner as in Example 1, except that the types and/or amounts of the urethane resin (A) and cyclic cellooligosaccharide used were changed as shown in Table 1.

[Comparative Example 3]
100 parts by mass of the urethane resin (A-1) obtained in Synthesis Example 1 and 250 parts by mass of activated alumina were mixed to obtain a civil engineering and construction material.

[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 construction material.

[Comparative Example 5]
A civil engineering and construction material was obtained in the same manner as in Comparative Example 3, except that the amount of activated alumina used was changed to 3 parts by mass.

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

[Evaluation method for workability]
The civil engineering and construction materials obtained in Examples and Comparative Examples were applied onto a concrete paving board using a roller. At that time, it was evaluated as "O" when it spreads evenly without resistance, and as "X" when there was resistance or unevenness in application.

[Method for evaluating storage stability]
350 g of the civil engineering and construction materials obtained in Examples and Comparative Examples were filled in a 500 mL can, sealed, and left in a dryer maintained at 50° C. for one week. After that, the can was opened and the presence or absence of sedimentation separation was visually observed. In addition, those in which sedimentation separation did not occur were evaluated as "◯", and those in which sedimentation separation occurred were evaluated as "x".

[Evaluation method for wet surface adhesion]
The concrete paving board was immersed in water for 24 hours and taken out. Immediately after that, the surface was wiped with a rag, and the civil engineering and construction materials obtained in Examples and Comparative Examples were applied in an amount of 0.2 kg/mm ² and then cured for 24 hours. After that, the Kenken-type adhesive strength (N/25 mm) was measured according to JISK6849-1994 using a Kenken-type tensile tester ("LPT-1000" manufactured by Oxjack Co., Ltd.). Moreover, the broken state of the base material after the measurement was visually observed and evaluated as follows.
"O"; Adhesive strength is 2 N/25 mm or more, and the substrate is destroyed.
"x"; the adhesive strength is less than 2 N/25 mm, and interfacial peeling occurs.

Examples 1 to 5, which are the civil engineering and construction materials of the present embodiment, have excellent storage stability and adhesion to wet concrete, and have good workability that does not cause resistance when applied and does not cause unevenness on the applied surface. I found it to be excellent.

On the other hand, Comparative Examples 1 and 2, in which the cyclic cellooligosaccharide (B) was not contained, were remarkably poor in wet surface adhesion.

In Comparative Examples 3 and 4, instead of the cyclic cellooligosaccharide (B), an inorganic powder such as activated alumina or Portland cement was used. The workability was poor, and the storage stability was also poor.

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

Claims (2)

A civil engineering and construction material containing a urethane resin (A) and a cyclic oligosaccharide (B) represented by the following general formula (1). However, in formula (1), R represents a hydrogen atom or a substituent that substitutes the hydrogen atom, and the substituent is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, acyl group, silyl group, sulfonyl group, sugar residue, or substituted or unsubstituted poly It is an oxyalkylene group, the substituent R has 1 to 40 carbon atoms, a plurality of R may be the same or different, and n represents an integer of 0 to 3.

A road primer comprising the civil engineering and building material according to claim 1 .

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