TWI491632B - Aminoacrylate elastomer filler - Google Patents

Description

Urethane elastomer filler

The present invention relates to a urethane elastomer filler which can be used as a water stop material for a structure such as civil engineering or construction, particularly a structure for concrete.

Conventionally, in the structure of civil engineering or construction, a method of filling a water stop material with a structure gap is used for the purpose of repairing a gap caused by water leakage or vibration of a structure.

In the case of the water-stopping material used in the method, for example, JP-A-2007-197534 (Patent Document 1) discloses a foaming urethane-based waterstop. However, in the case of the foamed urethane-based water-stopping material of the patent document 1, the crack is liable to be cracked by vibration such as an earthquake due to lack of flexibility, and the crack is a cause of water leakage. Further, as the water-stopping material used in the method, a water-repellent material in the form of a lance injection is generally used. For example, in JP-A-2005-350893 (Patent Document 2), a modified anthrone or a modified amine group is disclosed. Formate, anthrone, urethane, acrylic acid, etc. are materials for the water stop. However, in Patent Document 2, it is conventionally known that the water-stopping material has a high viscosity at a normal temperature (for example, 15 to 30 ° C), and can be used for a short period of time, is easy to be thickened, has a problem that the injection operation cannot be performed for a long period of time, or takes time for soaking. The fine gap has a problem that it is difficult to inject the water stop material. Further, when the water-repellent material is used for a concrete structure, it is required to have alkali resistance from the viewpoint of concrete resistance. However, the above-mentioned Patent Documents 1 to 2 are not sufficient from the viewpoint of alkali resistance.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2007-197534

[Patent Document 2] JP-A-2005-350893

The present invention has been made in view of the problems of the prior art described above, and it is an object of the invention to provide a molded article for a filler which has excellent impact resistance and alkali resistance, and which can be used for a long period of time (for example, 15 to 30 ° C). Since the viscosity is low enough, it is possible to perform a long-time injection operation and a urethane elastomer filling material which can be injected in a fine gap.

The inventors of the present invention have diligently studied the results for achieving the above object, and the urethane-filled material containing a specific polyol and containing a specific amount of an aromatic hydrocarbon-based plasticizer can be formed to have excellent impact resistance and resistance. The alkaline filler material molded body is long enough to be used, and the viscosity at a normal temperature (for example, 15 to 30 ° C) is sufficiently low, so that the injection operation can be performed for a long period of time and the injection can be performed in a fine gap, and the present invention has been completed.

The urethane elastomer filler of the present invention contains an organic polyisocyanate (A) and a polyether polyol (b1) having an average functional group number of 2 to 4 and a number average molecular weight of 1,000 or less as a main component. The alcohol (B) and the aromatic hydrocarbon-based plasticizer (C) containing the aromatic hydrocarbon (c1) as a main component, and the content of the aromatic hydrocarbon-based plasticizer (C) relative to 100 parts by mass of the organic polyisocyanate (A) , in the range of 10 to 100 parts by mass.

Further, in the urethane elastomer filler of the present invention, the polyol (B) is preferably a castor oil-based polyol.

Further, the urethane elastomer filler of the present invention is a secondary overfill concrete formed on the inner surface side of the primary overlying concrete layer as a primary concrete layer formed on the inner surface of the tunnel floor. The layer and the filler material for the tunnel waterproof structure formed of the waterproof sheet layer and the overlaid water stop layer formed between the primary overlaid concrete layer and the secondary overworked concrete layer are particularly suitable.

According to the present invention, it is possible to form a molded body of a filler material having excellent impact resistance and alkali resistance, and the use time is long enough, and the viscosity at a normal temperature (for example, 15 to 30 ° C) is sufficiently low, so that it can be injected for a long time. A urethane elastomer filler that can be injected and can be injected in a fine gap.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

The urethane elastomer filler of the present invention contains an organic polyisocyanate (A) and a polyether polyol (b1) having an average functional group number of 2 to 4 and a number average molecular weight of 1,000 or less as a main component. The alcohol (B) and the aromatic hydrocarbon-based plasticizer (C) containing the aromatic hydrocarbon (c1) as a main component, and the content of the aromatic hydrocarbon-based plasticizer (C) relative to 100 parts by mass of the organic polyisocyanate (A) , in the range of 10 to 100 parts by mass.

The organic polyisocyanate (A) of the present invention is not particularly limited, and a known organic polyisocyanate can be used. Such organic polyisocyanates (A), such as aromatic, alicyclic, aliphatic polyisocyanates, and their urethane modified, urea modified, URETEDIONE modified A modified polyisocyanate such as a body, an isocyanurate modified product, a carbodiimide modified product, a URETONIMINE modified product, a urea modified product, or a biuret modified body.

The aromatic polyisocyanate is, for example, toluene diisocyanate (hereinafter, referred to as "TDI" as the case may be), diphenylmethane diisocyanate (hereinafter, referred to as "MDI" as the case may be), naphthalene diisocyanate, triphenyl Methane triisocyanate, xylene diisocyanate (hereinafter referred to as "XDI" by way of example), tetramethyl xylene diisocyanate (hereinafter referred to as "TMXDI" as the case may be), polymethylene polyphenyl poly Isocyanate (hereinafter, referred to simply as "P-MDI" as the case may be). Moreover, these aromatic polyisocyanates are a single product and a mixture containing individual various isomers. Further, examples of the alicyclic polyisocyanate include cyclohexylmethane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated TDI, hydrogenated XDI, and hydrogenated TMXDI. Further, examples of such an aliphatic polyisocyanate include hexamethylene diisocyanate and isocyanuric acid diisocyanate. Among these organic polyisocyanates (A), from the viewpoint of low viscosity and environmental influence, an aromatic polyisocyanate is preferred, and MDI is more preferable. Further, these organic polyisocyanates (A) may be used singly or in combination of two or more kinds.

The polyol (B) of the present invention is a polyether polyol (b1) described below as a main component.

The polyether polyol (b1) of the present invention has an average functional group number of 2 to 4 and a number average molecular weight of 1,000 or less. In such a polyether polyol (b1), it is necessary to have an average number of functional groups of 2 to 4. When the average number of functional groups is less than 2, the mechanical strength (tensile strength, elongation, etc.) of the filler formed by the obtained filler is insufficient, and when the average number of functional groups exceeds 4, the viscosity of the obtained filler becomes When the height is too high, the softness of the molded body of the filler formed using the obtained filler material is insufficient.

Further, in the polyether polyol (b1), the number average molecular weight needs to be 1,000 or less, more preferably 200 to 1,000. When the number average molecular weight exceeds 1,000, the viscosity of the obtained filler becomes too high, and the mechanical strength (tensile strength, elongation, etc.) of the filler molded body formed using the obtained filler becomes insufficient. On the other hand, if the number average molecular weight is less than 200, the reactivity becomes too high, and the usable time of the obtained filler tends to be shortened.

The polyether polyol (b1) is obtained by adding a hydroxy group-containing compound having 1 to 4 hydroxyl groups in one molecule to an alkylene oxide such as ethylene oxide or propylene oxide. . Such a hydroxyl group-containing compound, for example, an alcohol such as methanol, ethanol or propanol; an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; toluenediamine, vinyldiamine, divinyltriamine, ammonia, An amine compound such as polyamines such as aniline, xylene diamine or diaminodiphenylmethane; ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, and the like. Methylene glycol, hexamethylene diterpene alcohol, fluorene methylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, pentaerythritol, etc. Polyol. These hydroxyl group-containing compounds may be used singly or in combination of two or more kinds. Further, among these polyether polyols (b1), a propylene oxide adduct having propylene glycol as a starting agent is preferred from the viewpoint of having a low viscosity and a large amount of hydrophobic components and being less susceptible to water.

In the polyol (B), the content of the polyether polyol (b1) is preferably 70% by mass or more based on the total mass of the polyol (B), and more preferably 80% by mass or more. When the content of the polyether polyol (b1) in the polyol (B) is less than the above lower limit, the reactivity becomes too slow, and the mechanical strength of the filler formed from the obtained filler is insufficient. The tendency.

Moreover, it is preferable that the content of the above-mentioned polyol (B) in the urethane elastomer filler of the present invention is such that the equivalent ratio of the isocyanate group to the active hydrogen group is within the range described later.

Further, the polyol (B) of the present invention is preferably one containing a castor oil-based polyol in addition to the above-mentioned polyether polyol (b1). Thus, the JIS-A hardness of the filler body formed using the obtained filler material by the castor oil-containing polyol tends to be high. Such castor oil is a polyhydric alcohol such as castor oil and modified castor oil (castor oil modified with a polyol such as trimethylolpropane or pentaerythritol). Moreover, when such a castor oil-based polyol is used, the content of the castor oil-based polyol is preferably in the range of 5 to 30% by mass based on the total mass of the polyol (B).

Further, the polyhydric alcohol (B1) to be used in the polyol (B) of the present invention and the polyhydric alcohol other than the castor oil-based polyol may, for example, be a polyester polyol, a polycarbonate polyol, or a polybutane. Alkenyl polyol.

The aromatic hydrocarbon-based plasticizer (C) of the present invention is mainly composed of an aromatic hydrocarbon (c1). Further, the aromatic hydrocarbon (c1) of the present invention means a monocyclic ring having an aromaticity or a hydrocarbon compound composed of a plurality of rings. Next, the aromatic hydrocarbon (c1) is not particularly limited, but preferably has a boiling point of 150 ° C or higher. Such aromatic hydrocarbons (c1) are, for example, SAS-296 manufactured by Nippon Oil Corporation, Ipzole 150 manufactured by Idemitsu Kosan Co., Ltd., Rudajopu DI manufactured by Rutgers Kureha Solvents GmbH, and Swazol 1800 manufactured by Maruzen Petrochemical Co., Ltd. .

In the present invention, the aromatic hydrocarbon-based plasticizer (C) is used as the plasticizer component, and the alkali resistance of the filler molded body formed using the obtained filler is not adversely affected, and the viscosity of the filler can be adjusted. Or the mechanical strength of the filler shaped body.

Such an aromatic hydrocarbon-based plasticizer (C) may contain an aliphatic hydrocarbon in addition to the aromatic hydrocarbon (c1), but in the aromatic hydrocarbon-based plasticizer (C), the aromatic hydrocarbon (c1) The content of the aromatic hydrocarbon-based plasticizer (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. When the content of the aromatic hydrocarbon (c1) in the aromatic hydrocarbon-based plasticizer (C) is less than the above lower limit, the obtained filler tends to be easily leaked.

Further, as such an aromatic hydrocarbon-based plasticizer (C), a commercially available product such as SAS-296 manufactured by Nippon Oil Co., Ltd., Mineral spirits A, etc.; Solvesso 100 manufactured by Exxon Chemical Co., Ltd.; and Swazol manufactured by Maruzen Petrochemical Co., Ltd. can be used. 1800, etc.; Ipzole 150, etc., manufactured by Idemitsu Kosan Co., Ltd.; Rudadoop DI, manufactured by Rutgers Kureha Solvents GmbH.

Furthermore, in the present invention, the content of the aromatic hydrocarbon-based plasticizer (C) is in the range of 10 to 100 parts by mass, and 10 to 50 parts by mass based on 100 parts by mass of the organic polyisocyanate (A). Better inside. When the content of the aromatic hydrocarbon-based plasticizer (C) is less than 10 parts by mass, the viscosity of the obtained filler becomes too high, and the flexibility or elongation of the filler formed from the obtained filler is insufficient. In addition, when the content of the aromatic hydrocarbon-based plasticizer (C) exceeds 100 parts by mass, the tensile strength of the filler molded body formed using the obtained filler is insufficient.

The urethane elastomer filler of the present invention contains the organic polyisocyanate (A), the polyol (B), and the aromatic hydrocarbon plasticizer (C). Such a urethane elastomer filler can be, for example, a premix of the above-mentioned organic polyisocyanate (A) and a polyol containing the aforementioned polyol (B) and the aforementioned aromatic hydrocarbon-based plasticizer (C). Mixed. The method of mixing the above-mentioned organic polyisocyanate (A) with the above-described polyol premix is not particularly limited, and for example, a method of mixing at a temperature of 15 to 30 ° C for 0.5 to 5 minutes in a stirrer can be employed. Moreover, such a urethane elastomer filler may further contain other additive components such as an antioxidant, a UV absorber, a heat resistance enhancer, an antifoaming agent, a leveling agent, a colorant, an inorganic and an organic filler, as necessary. Materials, lubricants, antistatic agents, reinforcing materials.

Further, the equivalent ratio (NCO/OH) of the isocyanate group of the active hydrogen group (the total active hydrogen group of the polyol) in the urethane elastomer filler of the present invention is from 0.50/1.00 to 2.00/1.00. The range is better, and the range of 0.80/1.00 to 1.50/1.00 is better. When the equivalent ratio of the isocyanate group to the active hydrogen group is less than the above lower limit, the obtained filler material tends to be uncured, and the mechanical strength (tensile strength) of the filler body formed using the obtained filler material becomes In addition, when it exceeds the said upper limit, the softness of the filler molding formed using the obtained filler material will become inadequate.

In the urethane elastomer filling material of the present invention, the mixing viscosity at an ambient temperature of 20 ° C is preferably 1000 mPa ‧ or less, more preferably 500 mPa ‧ s or less. If the viscosity exceeds the above upper limit, it is difficult to inject the obtained filler into the fine gap. Further, in the present invention, even after the organic polyisocyanate (A) and the polyol premix are mixed, the mixture is allowed to stand in an environment of a temperature of 20 ° C for 1 hour, and the mixed viscosity at an ambient temperature of 20 ° C is 1000 mPa·s or less. For better, 500mPa‧s or less is better. As described above, in the present invention, when the organic polyisocyanate (A) is mixed with the above-described polyol premix and then placed in an environment at a temperature of 20 ° C, the time for using the urethane elastomer filler can be used, that is, The usable time can be more than 1 hour, and more than 2 hours is possible. Since the urethane elastomer filler of the present invention has a long enough use time and a low mixing viscosity, it can be implanted for a long period of time, and the filler can be injected into the fine gap.

Further, the filler of the filler is obtained by curing the urethane elastomer filler of the present invention at a temperature of 0 to 40 ° C for 24 to 168 hours. The JIS-A hardness of the molded material of such a filler is preferably in the range of 30 to 90, and more preferably in the range of 40 to 70, from the viewpoint of flexibility and impact resistance. Such a JIS-A hardness can be measured by a method according to the method described in JIS K6253 using a type A hardness tester (JIS-A hardness meter).

The urethane elastomer filler of the present invention described above can form a filler body molded article having excellent impact resistance and alkali resistance, and can be used for a long time, and has a viscosity at a normal temperature (for example, 15 to 30 ° C). Since it is low enough, it becomes possible to perform an injection operation for a long time and to perform injection in a fine gap. Therefore, the urethane elastomer filler of the present invention is suitably used as a water stop material for structures such as civil engineering or construction, and is used as a tunnel for forming a watertight sheet waterproofer (watertight sheet waterproofer) using a mountain tunnel or the like. Waterproof materials for waterproof construction are particularly suitable.

Next, the urethane elastomer filling material of the present invention is used as a secondary overlying concrete formed on the inner surface side of the primary overlying concrete layer as a primary concrete layer formed on the inner surface of the tunnel floor. The layer and the filler material for the tunnel waterproof structure formed by the waterproof sheet layer and the overlaid water stop layer formed between the primary overlaid concrete layer and the secondary overworked concrete layer are particularly suitable for use, for example, by inclusion a step of forming the primary overlying concrete layer, the waterproof sheet layer and the secondary overworked concrete layer (first step), and between the waterproof sheet layer and the secondary overworked concrete layer and/or the waterproof sheet a step of forming the aforementioned layer of the water-repellent material layer after injecting the urethane elastomer filler of the present invention between the layer and the primary-coated concrete layer (second step), and the tunnel can be more reliably suppressed over a long period of time Construction of a leaky tunnel waterproof structure.

Hereinafter, a method of constructing a tunnel waterproof structure using the urethane elastomer filler of the present invention will be described with reference to the drawings. In the following description and the drawings, the same reference numerals are used for the same or corresponding elements, and the description thereof will be omitted.

Fig. 1 is a schematic side cross-sectional view showing an example of a tunnel (one part of the upper side) in which a tunnel waterproof structure is formed using the urethane elastomer filler of the present invention. The tunnel of Fig. 1 is provided with a primary concrete layer 2 formed on the inner surface of the tunnel site 1, a waterproof sheet layer 3 formed on the inner surface of the primary concrete layer 2, and an inner surface formed by the waterproof sheet layer 3. The secondary concrete layer 5 formed by the inner surface of the water layer 4 and the overburden water layer 4 is formed.

In the first step of the tunnel waterproof structure construction method, the primary concrete layer 2, the waterproof sheet layer 3, and the secondary concrete layer 5 are formed. The method of forming the primary-coated concrete layer 2, the waterproof sheet layer 3, and the secondary-covered concrete layer 5 is not particularly limited, and for example, the method of JP-A-2000-337096 can be employed.

That is, first, on the inner surface of the tunnel site 1, a covered concrete layer 2 is formed. The method is not particularly limited. For example, a method of forming a molding frame on the inner surface side of the tunnel floor 1 and pouring concrete into the molding frame may be employed.

Next, a water repellent layer 3 is formed on the inner surface side of the primary concrete layer 2. Although the method is not particularly limited, for example, a method of laying a conventional waterproof seal on the inner surface of the primary concrete layer 2 can be employed. Moreover, the size or thickness of such a waterproof seal is not particularly limited. Further, the material for such waterproof sealing is not particularly limited as long as it is water-repellent and can be joined by fusion or the like. Further, a non-woven fabric or the like may be provided as a cushioning material between the primary concrete layer 2 and the waterproof sheet layer 3 as needed.

Next, a secondary overlaid concrete layer 5 is formed on the inner surface side of the waterproof sheet layer 3. The method is not particularly limited. For example, a method of forming a molding frame on the inner surface side of the waterproof sheet layer 3 and pouring the concrete into the molding frame can be employed. Further, in the method of JP-A-2000-337096, a water-stopping for injecting the urethane elastomer filler of the present invention is formed between the waterproof sheet layer 3 and the secondary-coated concrete layer 5. The material is injected into the hole 6. The method is also not particularly limited. For example, a method in which a rod-shaped heart material is inserted into a tube, and the tube and the heart material are embedded in the secondary overworked concrete, and only the heart material is removed.

In the second step of the method for implementing the tunnel waterproof structure, the urethane elastomer filling material of the present invention is injected between the waterproof sheet layer 3 and the secondary overlaid concrete layer 5 to form a covering water stop material. Layer 4. The method of forming the overburden water stop layer 4 in this manner is not particularly limited, and for example, the urethane elastomer of the present invention may be injected from the water stop injection hole 6 formed in the secondary overlaid concrete layer 5. The method of filling the material. Further, the urethane elastomer filling material of the present invention can be used for a long period of time and can be used for a long time because the usable time is long enough and the viscosity at room temperature (for example, 15 to 30 ° C) is sufficiently low. Pu et al. easily inject the filler material.

Further, in the tunnel waterproof structure construction method described above, the overlay water stop layer 4 is formed only between the waterproof sheet layer 3 and the secondary overlaid concrete layer 5, and the waterproof sheet layer 3 and the primary overlying concrete layer are formed. A cover water stop layer 4 may also be formed between the two, between the waterproof sheet layer 3 and the secondary overlaid concrete layer 5, and between the waterproof sheet layer 3 and the primary overlying concrete layer 2, Overlay water stop layer 4.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. Also, in the case of no special statement, the "parts" and "%" in the text are based on quality. Moreover, the raw materials used in the examples and the comparative examples are as follows.

(using raw materials) <Organic Polyisocyanate>

MR-200: Polymeric MDI, manufactured by Japan Polyurethane Industrial Co., Ltd., trade name "MR-200".

<polyol>

PP-400: polyether polyol, hydroxyl group 280 mgKOH/g, average functional group number 2, number average molecular weight 400, manufactured by Sanyo Chemical Industries, Ltd., trade name "PP-400".

H-24: Castor oil, polyol, hydroxyl group 160 mgKOH/g, number average molecular weight 932, manufactured by Ito Oil Co., Ltd., trade name "URIC H-24".

GP-1000: a castor oil-based polyol, a hydroxyl group of 160 mgKOH/g, a number average molecular weight of 1,000, manufactured by Sanyo Chemical Industry Co., Ltd., and a trade name "Sannicks GP-1000".

<plasticizer>

SAS-296: an aromatic hydrocarbon-based plasticizer, an aromatic component of 100%, manufactured by Nippon Oil Corporation, and trade name "SAS-296".

Solvesso 100: an aromatic hydrocarbon-based plasticizer, an aromatic component of 99%, and a product name "Solvesso 100" manufactured by Exxon Chemical Co., Ltd.

Mineral spirits A: Aromatic hydrocarbon-based plasticizer, aromatics, about 20%, manufactured by Nippon Oil Corporation, trade name "Mineral spirits A".

Swazol 1800: Aromatic hydrocarbon-based plasticizer, aromatics 99%, manufactured by Maruzen Petrochemical Co., Ltd., trade name "Swazol 1800".

Non-hydrocarbon plasticizer 1: ester-based plasticizer, manufactured by Asahi Kasei Corporation, trade name "Alice M9020".

Non-hydrocarbon plasticizer 2: a carbonate-based plasticizer, manufactured by Asahi Glass Co., Ltd., and trade name "Asahinate".

Non-hydrocarbon plasticizer 3: an ether-based plasticizer, manufactured by Sanyo Chemical Industries, Ltd., trade name "SK-500".

Mobile paraffin: an aliphatic hydrocarbon-based plasticizer, manufactured by KISHIDA Chemical Co., Ltd.

(Examples 1 to 8 and Comparative Examples 1 to 7) <Preparation of a urethane elastomer filler and a filler molded body>

In Example 1, a urethane elastomer filler and a filler sheet-like molded article were obtained as follows. That is, a reactor equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer is substituted with nitrogen, and then PP-400: 800 parts, H-24: 50 parts, and SAS-296: 150 parts are added, and the temperature is 20 ° C. A polyol premix was obtained after 1 hour of mixing. Thereafter, the obtained polyol premix was adjusted to a temperature of 20 °C.

Next, 300 parts of the obtained polyol premix and 150 parts of organic polyisocyanate (MR-200) were placed in a container, and the mixture was mixed at a temperature of 20 ° C for 1 minute, and then subjected to a vacuum defoaming treatment for 30 minutes to obtain an amine. Carbamate elastomer filler (polyurethane resin composition: PU-1). Then, the obtained filler was placed in a mold for sheet molding (thickness: 2 mm), and cured at a temperature of 45 ° C for one day, and then released to obtain a sheet-like molded body of a filler.

In addition, in the examples 2 to 8, the urethane elastomer filler (PU-2) to (PU-2) was obtained in the same manner as in Example 1 except that the composition of the polyol premix was changed as shown in Table 1. PU-8) and a sheet-like molded body of a filler. Further, in Comparative Examples 1 to 6, the urethane elastomer filler (PU-9) to (PU) was obtained in the same manner as in Example 1 except that the composition of the polyol premix was changed as shown in Table 2. -14) and a sheet-like formed body of a filler. Further, in Comparative Example 7, except that the composition of the polyol premix was changed as shown in Table 2, a urethane elastomer filler (PU-15) was produced in the same manner as in Example 1, and an attempt was made to fill the material. In the production of the sheet-like formed body, the plasticizer on the surface of the sheet leaked, and the sheet-like molded body of the filler was not produced.

<Evaluation of urethane elastomer filler and filler molded body>

The urethane elastomer filler and the filler molded article obtained in Examples 1 to 8 and Comparative Examples 1 to 6 were subjected to the following methods to carry out the viscosity of the urethane elastomer filler and the filler. Evaluation or measurement of JIS-A hardness, alkali resistance, tensile strength (TB) and elongation (EB) of the molded body. The results obtained are shown in Table 3.

(i) Determination of viscosity of urethane elastomer filling materials

The urethane elastomer filler obtained in the examples and the comparative examples was measured for viscosity at 20 ° C using a B-type rotational viscometer. Further, regarding the viscosity, the viscosity after mixing and the viscosity after leaving for 1 hour at 20 ° C in the mixture were measured.

(ii) Determination and evaluation of JIS-A hardness of shaped body of filler

100 g of the urethane elastomer filler obtained in the examples and the comparative examples was placed in a cup for molding, and cured at a temperature of 45 ° C for one day, and then released to obtain a filler molded body. Next, the JIS-A hardness of the obtained filler material molded body was measured by a method of JIS K6253 using a type A hardness meter (JIS-A hardness meter). In addition, the JIS-A hardness evaluation of the filler material molded body is judged as "A" when the JIS-A hardness (unit: Hs) is in the range of 30 to 90, and is determined to be "C".

(iii) Evaluation of alkali resistance of shaped bodies of filler materials

The alkali resistance of the filler-like sheet-like formed body obtained in the examples and the comparative examples was evaluated in accordance with the method of JIS K7312. In other words, the filler-shaped sheet-like molded body was used as a sample (size: 100 mm × 25 mm × 2 mm), and the sample was immersed in a saturated calcium hydroxide aqueous solution having a temperature of 70 ° C and pH 13 for 28 days. Next, the mass ratio of the extract to the saturated calcium hydroxide aqueous solution was calculated from the mass (m _b ) of the sample before the impregnation and the mass (m _a ) of the sample after the immersion [ΔE={(m _b -m _a )/m _b } × 100], when the extract mass ratio (ΔE) is less than 3%, it is judged as "A", and the other is judged as "C".

(iv) Determination and evaluation of tensile strength and elongation of shaped bodies of fillers

The tensile strength and elongation of the filler sheet-like molded article obtained in the examples and the comparative examples were measured in accordance with the method of JIS K7312. In addition, the tensile strength of the filler-like sheet-like molded article was evaluated as "A" when the tensile strength was 2 MPa or more, and was determined to be "C". Moreover, the evaluation of the extension of the sheet-like formed body was judged as "A" when it was extended to 120% or more, and was determined to be "C".

From the results of Table 3, it was confirmed that the urethane elastomer filler of the present invention (Examples 1 to 8) had a sufficiently low viscosity at 20 ° C and was long enough to be used. Further, it was confirmed that the filler molded article obtained by using the urethane elastomer filler of the present invention (Examples 1 to 8) has excellent alkali resistance. Further, such a filler material molded body has excellent JIS-A hardness and is excellent in flexibility and has excellent impact resistance. Moreover, such a filler molded body also has excellent mechanical strength (tensile strength and elongation).

[Industrial use]

As described above, according to the present invention, it is possible to provide a molded article of a filler material which can have excellent impact resistance and alkali resistance, and can be used for a long time, and the viscosity at a normal temperature (for example, 15 to 30 ° C) is sufficiently low, so that it becomes A urethane elastomer filler which can be injected in a fine gap for a long time.

Therefore, the urethane elastomer filler of the present invention can be used for a water stop material of a structure such as civil engineering or construction, especially a concrete structure, because of its excellent impact resistance and alkali resistance.

1. . . Site

2. . . One-time concrete layer

3. . . Waterproof sheet

4. . . Overlay water stop layer

5. . . Secondary overlying concrete layer

6. . . Water stop injection hole

Fig. 1 is a schematic side cross-sectional view showing an example of a tunnel (an upper portion) in which a tunnel waterproof structure is formed using the urethane elastomer filler of the present invention.

Claims (4)

A urethane elastomer filling material characterized by comprising an organic polyisocyanate (A) and a polyether polyol (b1) having an average functional group number of 2 to 4 and a number average molecular weight of 1000 or less as a main component The polyol (B) and the aromatic hydrocarbon-based plasticizer (C) containing the aromatic hydrocarbon (c1) as a main component, and the content of the aromatic hydrocarbon-based plasticizer (C) relative to the organic polyisocyanate (A) 100 parts by mass, in the range of 10 to 100 parts by mass. The urethane elastomer filler according to claim 1, wherein the polyol (B) is a castor oil-based polyol. A urethane elastomer filling material for forming a secondary concrete layer formed on the inner surface side of the primary overlying concrete layer by forming a primary concrete layer formed on the inner surface of the tunnel floor a layer, and a filler material for the tunnel waterproof structure of the waterproof sheet layer and the overlaid water stop layer formed between the primary overlaid concrete layer and the secondary overworked concrete layer, characterized in that the organic polyisocyanate is contained (A) And a polyhydric alcohol (B) having a polyether polyol (b1) having an average functional group number of 2 to 4 and a number average molecular weight of 1,000 or less as a main component, and an aromatic component containing an aromatic hydrocarbon (c1) as a main component The hydrocarbon-based plasticizer (C), and the content of the aromatic hydrocarbon-based plasticizer (C) is in the range of 10 to 100 parts by mass based on 100 parts by mass of the organic polyisocyanate (A). The urethane elastomer filler according to claim 3, wherein the polyol (B) is a castor oil-based polyol.