JP2018076662A - Displacement isolation material composition, hardening body, method of displacement isolation for drainage facility and drainage facility - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a displacement isolation material composition capable of forming a thick hardening body which is light in weight, excellent in workability, less likely to be running even in a case of an application on a vertical wall, and excellent in displacement isolation property comparing to tar urethane resin-based seal material and bitumen joint sealant.SOLUTION: A displacement isolation material composition including a bifunctional or higher polyfunctional polyol, isocyanate, and organic fiber is applied to at least a part of a drainage facility and is cured so that the drainage facility has a displacement isolation property.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a displacement insulating material composition, a cured body, a displacement insulation method for water control equipment, and water control equipment.

  In dams, weirs, sluices, etc., sluice gates are provided as water control facilities such as water control gates or emergency spillway gates. As the sluice gate, a radial gate is widely adopted because of the stability of flow conditions, the height of the concrete pier at the time of installation is not limited, and the low opening / closing resistance.

  FIG. 1 is a schematic cross-sectional view showing an example of the structure of a radial gate. In this radial gate, the level of water existing in front of the door body can be adjusted by moving the door body up and down using a wire rope or the like around the support portion.

  FIG. 2 is a schematic cross-sectional view showing an example of the structure of the support portion. The bearing part is composed of a trunnion pin (shaft) that becomes the center of rotation, and a pedestal, trunnion girder, tension beam, bearing plate, etc. for holding the shaft and transmitting hydraulic load to the concrete pier of the dam, etc. . Furthermore, a radial bearing, a thrust bearing, or the like is attached to the trunnion pin that generates friction so that the door body rotates smoothly.

As shown in FIG. 2, anchor metal such as a tension beam is embedded in a concrete pier. However, when an external force is applied through the pedestal due to water pressure, etc., the tension beam extends through the trunnion girder, and if the tension beam is not insulated from the concrete pier, excessive stress is generated between the concrete pier and the tension beam. However, cracks and the like may occur in the concrete pier. Therefore, it is necessary that the anchor hardware such as the tension beam is insulated from the concrete pier.
A displacement insulating material is formed on the surface of the tension beam for insulation from the concrete pier.

  Further, the anchor hardware is required to have a displacement insulation enough to cope with a displacement in a shear direction that occurs when a huge earthquake or the like occurs. In recent years, the scale of enormous earthquakes is increasing. For example, a displacement insulating material having a certain sluice door structure is required to be able to follow a displacement of 12 mm in the shear direction.

  As a composition for forming such a displacement insulating material, for example, Patent Document 1 describes the use of biturer (tar urethane resin-based sealing material).

JP 47-21907 A

  When insulating water control equipment members such as anchor hardware from surrounding structures (eg concrete piers), it is possible to fully follow the entire circumference of the anchor hardware when displacement in the shear direction occurs. Thus, it is necessary to form a displacement insulating material having a sufficient thickness (for example, a thickness of 2 mm or more). Furthermore, since anchor metal such as a tension beam has a vertical surface, it is necessary that the composition forming the displacement insulating material does not sag even when applied to the vertical surface (suppression of slump).

  However, since the biturer described in Patent Document 1 and the conventionally used history joint material have high consistency (high viscosity), it is very burdensome for an operator to apply a sufficient thickness. Met. Further, since the scale of large earthquakes that can be assumed in recent years has increased, the required displacement insulation is also high, and for example, it is required to be able to follow a displacement of 12 mm in the shear direction. Insulating material compositions and hysteretic joint materials have not been able to follow the shearing direction sufficiently because of the insufficient elongation of the cured body, even if applied to a sufficient thickness, and recently demanded It was not possible to form a cured body satisfying the high displacement insulation properties. Furthermore, when these materials are applied to a vertical surface or the like, there is a risk of dripping due to high specific gravity.

  The present invention has been made in view of such circumstances, and is lighter than conventional tar-urethane resin-based sealing materials and historical joint materials, has excellent workability, and is applied to a vertical surface or the like. Even if it exists, it aims at providing the displacement insulation material composition which can form the thick hardening body which is hard to drip and is excellent in displacement insulation.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by a specific displacement insulating material composition, and the present invention has been completed. Examples of embodiments of the present invention are as follows.

  [1] A displacement insulating material composition containing a bifunctional or higher polyfunctional polyol (A), an isocyanate (B), and an organic fiber (C).

  [2] The composition according to [1], wherein the content of the organic fiber (C) is 10 parts by mass or more with respect to a total of 100 parts by mass of the polyol (A) and the isocyanate (B).

[3] The composition according to [1] or [2], wherein the organic fiber (C) is a polyethylene fiber.
[4] The composition according to any one of [1] to [3], wherein the fiber length of the organic fiber (C) is 3 mm or less.

[5] The composition according to any one of [1] to [4], wherein a slump measured according to JIS A 5758: 2010 (however, the measurement temperature is 23 ° C.) is 3 mm or less.
[6] The composition according to any one of [1] to [5], which satisfies the following requirement (I).
Requirement (I): Using the above composition, the elongation measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 150% or more. [7] The following requirement (II) is satisfied [1 ] The composition in any one of [6].
Requirement (II): Using the composition, the tensile strength measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 1 MPa or less.

  [8] The composition according to any one of [1] to [7], comprising an amine (D).

  [9] The composition according to any one of [1] to [8], which is a displacement insulating material composition for water control equipment.

  [10] A cured product of the composition according to any one of [1] to [9].

  [11] A displacement insulation method for water control equipment, comprising a step of applying the composition according to any one of [1] to [9] to at least a part of the water control equipment and curing the composition.

  [12] A water control facility having a cured film of the composition according to any one of [1] to [9] at least in part.

  According to the present invention, it is lighter (smaller in density) than conventional tar urethane resin-based sealing materials and historical joint materials, has excellent workability, and is difficult to sag even when applied to a vertical surface or the like. A composition (in which slump is suppressed) can be provided, and according to the composition, a thick cured body excellent in displacement insulation can be formed.

FIG. 1 is a schematic cross-sectional view showing an example of the structure of a radial gate. FIG. 2 is a schematic cross-sectional view showing an example of the structure of the support portion of FIG.

≪Displacement insulation composition≫
The displacement insulating material composition (hereinafter also referred to as “the present composition”) according to the present invention includes a bifunctional or higher polyfunctional polyol (A), an isocyanate (B), and an organic fiber (C).
In the present invention, the displacement insulating material composition means that even when a member having a cured body formed from the composition is displaced, the cured body is deformed by the displacement, and is generated by the displacement. It refers to a composition that can form a cured body that does not propagate shearing stress to the periphery of the member (that can insulate the propagation of displacement of the member).

  The composition may be a one-component composition, but from the viewpoint of excellent storage stability, the main component containing the polyol (A) and the curing agent component containing the isocyanate (B). A two-component (or more) type is preferred. In this case, the organic fiber (C) is contained in one of the main agent component and the hardener component, or is contained in both, or is prepared separately, and added when mixing the main agent component and the hardener component. May be.

<Bifunctional or higher polyfunctional polyol (A)>
The bifunctional or higher polyfunctional polyol (A) (hereinafter also referred to as “component (A)”) is not particularly limited as long as it is a polyol having two or more hydroxyl groups in one molecule. Polyol polyols, polycarbonate polyols, polyolefin polyols, lactone polyols, castor oil polyols, and the like can be used. Of these, polyether polyols are preferred because they are inexpensive and can easily provide a cured product having excellent water resistance.
Only 1 type may be used for a component (A), and 2 or more types may be used for it.

  Although it does not specifically limit as a polyether-type polyol, For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol , Neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Fats such as diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol Group diol, 1,4- Cyclohexanediol, cycloaliphatic diols such as 1,4-cyclohexanedimethanol, xylene glycol, bishydroxyethoxybenzene, bishydroxyethyl terephthalate, aromatic diols such as bisphenol A, glycerin, diglycerin, trimethylolpropane, pentaerythritol Starting with compounds having at least two active hydrogen groups, such as polyols such as polyhydric alcohols such as sorbitol and sucrose, which are trifunctional or higher, and amine compounds such as ethylenediamine, diethylenetriamine, triethanolamine and aromatic diamine Polyethers obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, polyoxytetramethylene oxide as raw materials. System polyols.

  The polyester-based polyol is not particularly limited. For example, the polyol and the oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, isophthalic acid, azelaic acid, sebacic acid And polyester polyols obtained by reacting polybasic acids such as the above and / or caprolactone.

  The polycarbonate polyol is not particularly limited. For example, a polycarbonate polyol obtained by a deethanol condensation reaction between the polyols and diethyl carbonate, a polycarbonate polyol obtained by a dephenol condensation reaction between the polyols and diphenyl carbonate, The polycarbonate polyol obtained by the deethylene glycol condensation reaction of polyols and ethylene carbonate is mentioned.

  Although it does not specifically limit as a polyolefin-type polyol, For example, the polybutadiene-type polyol which introduce | transduced the hydroxyl group into the terminal of the copolymer of polybutadiene or a butadiene, and styrene or acrylonitrile, and its hydrogenated substance are mentioned.

  The lactone-based polyol is not particularly limited, and examples thereof include polymerization initiators such as glycols and triols, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, β-methyl-δ. -Polyols obtained by addition polymerization of lactones such as valerolactone in the presence of a catalyst such as an organometallic compound, a metal chelate compound, or a fatty acid metal acyl compound.

  The castor oil-based polyol is not particularly limited, but, for example, a transesterification product of at least one of castor oil and an alkylene oxide adduct of castor oil and at least one of alcohol, polyester-based polyol and polyether-based polyol. An ester compound of castor oil fatty acid (a fatty acid obtained from castor oil, usually a mixture of ricinoleic acid and oleic acid, etc.) and at least one of alcohol, polyester polyol and polyether polyol; Castor oil diol-type partially dehydrated or partially acylated product; transesterified product, ester compound and hydrogenated product of each of the partially dehydrated product or partially acylated compound; castor oil polymerized to obtain polymerized castor oil , Obtained heavy The compounds of two or more functional groups which is obtained by reacting the transesterification reaction products and caprolactone of castor oil and the like.

  As the component (A), it is preferable to use a bifunctional polyol and a trifunctional or higher functional polyol in combination from the viewpoint that a three-dimensional network structure can be efficiently formed.

  The hydroxyl value of the component (A) is not particularly limited, but a composition having an appropriate consistency and viscosity, excellent in workability can be obtained, and a cured product having excellent elongation characteristics can be easily obtained. From the viewpoint, it is preferably 14 to 400 mgKOH / g, more preferably 25 to 160 mgKOH / g.

  The viscosity of the component (A) is not particularly limited, but is a viscosity measured at 25 ° C. using an Ubbelohde viscometer in accordance with JIS Z 8803: 2011 because a composition having excellent workability can be obtained. However, it is preferably 70 to 3,000 mPa · s, more preferably 250 to 2,000 mPa · s.

  Although the number average molecular weight (Mn) of the component (A) is not particularly limited, it is preferable from the viewpoint that a composition having an appropriate consistency and viscosity, excellent workability, and excellent low-temperature curability can be obtained. Is preferably from 1,000 to 10,000, more preferably from 1,500 to 8,000, and particularly preferably from 4,000 to 7,000, from the viewpoint that a cured product excellent in elongation characteristics can be easily obtained. It is.

Component (A) may be synthesized according to a conventionally known method, or a commercially available product may be used.
Commercially available products include “Excenol 3030” (manufactured by Asahi Glass Co., Ltd., trifunctional polyether polyol), “Excenol 5030” (manufactured by Asahi Glass Co., Ltd., trifunctional polyether polyol), “Boranol 3022J” (Dow Chemical Japan) Co., Ltd., trifunctional polyether polyol), “Excenol 805” (Asahi Glass Co., Ltd., bifunctional polyether polyol), and the like.

  The content of the component (A) is such that a composition having an appropriate consistency and viscosity can be obtained with respect to the total amount (solid content) of the present composition, and a cured product having excellent elongation characteristics can be easily obtained. From the point, it is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and particularly preferably 17 to 22% by mass.

<Isocyanate (B)>
The isocyanate (B) (hereinafter also referred to as “component (B)”) may be any compound that can react with the component (A) and can be cured.
Only 1 type may be used for a component (B), and 2 or more types may be used for it.

As the component (B), diphenylmethane diisocyanate (hereinafter abbreviated as “MDI” [Example: 2,2′-MDI, 2,4′-MDI, 4,4′-MDI]), polymeric MDI (crude MDI) , Tolylene diisocyanate (hereinafter abbreviated as “TDI” [Example: 2,4-TDI, 2,6-TDI]), aromatic isocyanates such as naphthalene diisocyanate, and araliphatic isocyanates such as xylylene diisocyanate. And aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, carbodiimide-modified products of the isocyanate, and polyurethane-based prepolymers obtained by reacting an isocyanate compound with a low molecular polyol and the like.
Among these, it is possible to appropriately adjust the pot life of the present composition, and to obtain a cured product having excellent flexibility. Thus, the composition can be obtained using aromatic isocyanate or araliphatic isocyanate and the isocyanate. A polyurethane-based prepolymer is preferred, and a TDI prepolymer is more preferred.

Component (B) may be synthesized according to a conventionally known method, or a commercially available product may be used.
As a commercial item of a component (B), "Takenate L-1028" (Mitsui Chemicals make, bifunctional TDI prepolymer which has an isocyanate group in both ends), "Lupranate M20S" (BASF INOAC polyurethane make) , Crude MDI), “Millionate MR-200” (manufactured by Tosoh Corporation, Crude MDI), “Millionate MTL” (manufactured by Tosoh Corporation, carbodiimide-modified MDI), and the like.

Component (B) is preferably blended so that the equivalent ratio of the isocyanate group of the component to the hydroxyl group of component (A) is NCO / OH = 0.5 to 1.5, more preferably Is 0.8 to 1.2.
It is preferable for the equivalence ratio to fall within this range since it is difficult to cause poor curing and foaming.

  The content of the component (B) is preferably 20 to 55% by mass with respect to the total amount (solid content) of the present composition from the viewpoint that a composition having an appropriate consistency and viscosity can be easily obtained. More preferably, it is 30-45 mass%.

<Organic fiber (C)>
The organic fiber (C) (hereinafter also referred to as “component (C)”) has a role as a thickener. By using the component (C) together with the components (A) and (B), the density is small, and even when it is applied to a vertical surface or the like with a sufficient thickness (for example, a thickness of 2 mm or more), At the same time, a composition having excellent workability (paintability) can be easily obtained.
Only 1 type may be used for a component (C), and 2 or more types may be used for it.

  The component (C) is not particularly limited as long as it is a fiber mainly composed of an organic substance. For example, polyethylene fiber, polypropylene fiber, polyolefin fiber such as polystyrene fiber, polyvinyl alcohol fiber such as vinylon fiber, nylon fiber, Polyamide fibers such as aramid fibers, acrylic fibers, polyacrylonitrile fibers, polyester fibers, polyurethane fibers, polyvinylidene chloride fibers, polyvinyl chloride fibers, and cellulose fibers can be used. Among these, it is possible to easily obtain a composition that does not sag even when applied to a vertical surface or the like with a sufficient thickness, and further, it is possible to easily obtain a cured body having excellent elongation characteristics. Polyolefin fibers are preferable, and polyethylene fibers are more preferable.

  The fiber length of the component (C) is not particularly limited, but a composition that does not easily sag even when applied to a vertical surface or the like with a sufficient thickness can be easily obtained, and a cured product having excellent elongation characteristics can be obtained. From the viewpoint that it can be easily obtained, it is preferably 3 mm or less, more preferably 1 mm or less, and the lower limit is preferably 0.001 mm.

  The fiber diameter of the component (C) is not particularly limited, but is preferably 20 μm or less from the viewpoint that a composition that does not sag easily can be obtained even when applied to a vertical surface with a sufficient thickness. More preferably, it is 5 μm or less.

  Commercially available components (C) include “Chemibest FDSS-2”, “Chemibest FDSS-5” (manufactured by Mitsui Chemicals, polyethylene fiber), “Izanus Cyber Chop” (manufactured by Toyobo Co., Ltd., polyethylene fiber) Etc.

  The content of the component (C) is less likely to sag even when applied to a vertical surface or the like with a sufficient thickness with respect to a total of 100 parts by mass of the components (A) and (B). From the point that a composition excellent in paintability) can be easily obtained, it is 10 parts by mass or more, more preferably 10 to 50 parts by mass, and a composition excellent in workability is easily obtained. It is particularly preferably from 20 to 20 parts by mass from the standpoint that it can be obtained and a cured product having better elongation characteristics can be easily obtained.

<Amine (D)>
The amine (D) (hereinafter also referred to as “component (D)”) can be used arbitrarily, and forms a urea bond with the isocyanate group of the component (B) at the time of curing, whereby a cured product having high fracture toughness. Can be easily formed.
Only 1 type may be used for a component (D), and 2 or more types may be used for it.
Moreover, a component (D) is normally mix | blended with a main ingredient component in this 2 component type composition.

  Although it does not restrict | limit especially as a component (D), Among these, amines, such as an aliphatic type, an alicyclic type, an aromatic type, and a heterocyclic type, are preferable.

Examples of the aliphatic amine include alkylene polyamines and polyalkylene polyamines. Examples of the alkylene polyamine include a compound represented by the formula: H ₂ N—R—NH ₂ . In the above formula, R is a divalent hydrocarbon group having 1 to 30 carbon atoms and may have a branch. Specifically, methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2,2-dimethyl-1,3-propanediamine, 1,4-diaminobutane, 1,3-diaminopentane 1,5-diaminopentane, 2-methyl-1,5-pentanediamine, 1,6-diaminohexane, 2,2,4- or 2,4,4-trimethylhexanediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2-methylpentamethylenediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 2,2,4- or 2 4,4-trimethylhexamethylenediamine and the like.

Examples of the polyalkylene polyamine include a compound represented by the formula: H ₂ N— (C _m H _2m NH) _n H. In the above formula, m is an integer of 1 to 10, and n is an integer of 2 to 10, preferably 2 to 6. Specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis (hexamethylene) triamine, and the like.

  Other aliphatic amines include o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1, Examples include 3-bis (2′-aminoethylamino) propane, triethylene-bis (trimethylene) hexamine, tris (2-aminoethyl) amine, bis (cyanoethyl) diethylenetriamine, and diethylaminopropylamine.

  Specific examples of the alicyclic amine include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebis (cyclohexylamine), and norbornane. Examples thereof include diamine, bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, isophoronediamine (IPDA), mensendiamine (MDA), and the like.

  Examples of the aromatic amine include bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, and aromatic polyamine compounds having two or more primary amino groups bonded to the benzene ring. More specifically, examples of the aromatic amine include tolylenediamine, phenylenediamine, naphthalenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, and 4,4 ′. -Diamino-3,3'-dichlorodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl -4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis (amino Methyl) naphthalene and bis (aminoethyl) naphthalene. It is.

  Specific examples of the heterocyclic amine system include piperazine, N-methylpiperazine, morpholine, 1,4-bis- (3-aminopropyl) piperazine, 1,4-diazacycloheptane, 1- (2 ′ -Aminoethylpiperazine), 1- [2 ′-(2 ″ -aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane and the like.

  Examples of other amines include polyether diamines and amines (amine compounds) described in JP-A-47-30799. Further, modified products of the compounds mentioned as the amines, for example, polyamidoamines, amine adducts of the compounds and epoxy compounds, Mannich compounds (for example, Mannich-modified polyamidoamines, phenalkamines), Michael adducts, ketimines, aldimines, and the like. .

  Among these, aromatic amines are preferable from the viewpoint that a composition having a long pot life can be easily obtained, and a cured product having high fracture toughness can be easily obtained, and 4,4′-diamino is preferred. -3,3'-dichlorodiphenylmethane and its modified products are more preferred.

  Component (D) may be synthesized by a conventionally known method or may be a commercially available product. Examples of commercially available products include “Iharacamine ML-520E” and “Iharacamine ML-620E” (both manufactured by Ihara Chemical Industry Co., Ltd.), which are aromatic amines, and “ACI Hardener, which is an aliphatic polyamine. K-39 "(manufactured by PTI Japan), polyamidoamines" PA-66 "," PA-23 "and" PA-290 (A) "(all manufactured by Akira Ohtake Shin Chemical Co., Ltd.) “MAD-204 (A)” (modified by Otake Ashin Shin Chemical Co., Ltd.), a modified polyamine, “Adeka Hardener EH-342W3” (produced by ADEKA), Mannich modified aliphatic polyamine "Sanmide CX-1154" (manufactured by Sanwa Chemical Co., Ltd.) and "Cardlight NC556x80" which is a phenalkamine adduct ( Doraito Co., Ltd.) and the like.

  Content of a component (D) becomes like this. Preferably it is 0-10 mass% with respect to this composition whole quantity (solid content), More preferably, it is 0.5-5 mass%.

<Plasticizer>
It is preferable that this composition contains a plasticizer from the point that the hardened | cured material which is more excellent in an elongation characteristic can be obtained easily.
When the present composition is a two-component composition, the plasticizer may be blended in the curing agent component, but the main component is from the standpoint that a cured product having uniform physical properties can be easily obtained. It is preferable to mix in.

  Examples of plasticizers include 2-ethylhexyl phthalate, dibutyl phthalate, dioctyl phthalate, diundecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, diisodecyl phthalate, dibutyl adipate, dioctyl adipate, diisononyl adipate, dioctyl azelate, dioctyl sebacate, Trioctyl phosphate, triphenyl phosphate, process oil and the like can be mentioned.

  The content in the case of using the plasticizer is preferably 1 to 50% by mass from the viewpoint of easily obtaining a cured product having excellent elongation characteristics with respect to the total amount (solid content) of the present composition. More preferably, it is 10-30 mass%, More preferably, it is 13-27 mass%, Most preferably, it is 20-27 mass%.

<Other ingredients>
This composition may contain other components other than the said components (A)-(D) and a plasticizer in the range which does not impair the objective of this invention. Examples of other components include pigments, antifoaming agents, dispersants, catalysts, moisture adsorbents, surface conditioners, rheology control agents, leveling agents, thickeners, solvents, and the like.
Each of the other components may be used alone or in combination of two or more.
When this composition is a two-component composition, other components may be blended in the curing agent component, but the main component is from the standpoint that a cured product having uniform physical properties can be easily obtained. It is preferable to mix in.

[Pigment]
The present composition may contain a pigment for coloring, reduction of curing shrinkage, cost reduction, etc., depending on the desired application.
Examples of pigments include carbon black, titanium white, bengara, black dial, barite powder, silica, talc, chalk, iron oxide powder, diatomaceous earth, alumina, mica, calcium carbonate, magnesium carbonate, zinc carbonate, asbestos, Examples thereof include glass fiber, quartz powder, aluminum hydroxide, gold powder, silver powder, glass balloon, and barium sulfate. Moreover, you may use what surface-treated these surfaces with the silane compound etc.
The content when the pigment is used is preferably 1 to 30% by mass, more preferably 2 to 10% by mass, based on the total amount (solid content) of the present composition.

[Defoamer]
From the viewpoint of the strength and quality of the cured product, it is preferable that no bubbles are present in the cured product of the present composition. For this reason, it is preferable to mix | blend an antifoamer with this composition.
Examples of the antifoaming agent include silicone-based antifoaming agents and mineral oil-based antifoaming agents.
As the antifoaming agent, any of water-based, solvent-based, and solvent-free types can be used, but a solventless silicone-based antifoaming agent is preferable in order to suppress curing shrinkage when forming a cured product. Examples of the commercially available solventless silicone antifoaming agent include “Dow Corning Toray SAG-47” (manufactured by Toray Dow Corning Co., Ltd.).
The content in the case of using the antifoaming agent is preferably 0.01 to 1% by mass with respect to the total amount (solid content) of the present composition.

[Dispersant]
The present composition is preferably cured in a state where the component (C) and the pigment are uniformly dispersed. For this reason, you may mix | blend a dispersing agent with this composition.
Although it does not restrict | limit especially as a kind of dispersing agent, A phosphate ester type dispersing agent etc. are mentioned.
Examples of commercially available phosphate ester dispersants include “Efka 5220” (manufactured by BASF Japan) and “BYK W972” (manufactured by Big Chemie Japan).
The content when the dispersant is used is preferably 0.1 to 2% by mass relative to the total amount of the present composition (solid content).

[Moisture adsorption agent]
When a cured product is formed from the present composition in which moisture that can be contained in the component (A), component (C), and pigment is taken into the system, the component (B) reacts with moisture to foam. there is a possibility. In order to suppress this foaming, it is preferable to remove the water in the system, and for this reason, it is preferable to add a water adsorbent to the present composition.
The water adsorbent is not particularly limited as long as it has water adsorbing ability, and a conventionally known substance can be used. As a commercial product, “Molecular Sieve 4A” (manufactured by Union Showa Co., Ltd.) and the like can be mentioned. .
The content when the moisture adsorbent is used is preferably 0.1 to 3% by mass with respect to the total amount of the present composition (solid content).

[catalyst]
This composition may contain the catalyst which accelerates | stimulates reaction with a component (A) and a component (B).
Examples of such catalysts include tin carboxylates, amine catalysts, metal carboxylates other than tin, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) salts, organic acids, and the like.
Examples of tin carboxylates include dibutyltin dilaurate, dibutyltin diacetate, and tin octylate. Examples of amine catalysts include triethylamine, triethylenediamine, and tetramethylbutanediamine. Examples of metal carboxylates other than tin include , Cobalt octylate, manganese octylate and zinc octylate, and the DBU salts include DBU-stearate, DBU-oleate and DBU-formate. Examples of organic acids are 2 -Ethylhexylic acid, octylic acid and the like.

  Commercially available products of these catalysts include “Grec TL” (manufactured by Nippon Steel Trading Co., Ltd.), “DABCO 33-LV” (manufactured by Air Products Japan Co., Ltd.), and “Neostan U-28” (Nitto Kasei Co., Ltd.). )) And "triethylamine" (manufactured by Daicel Corporation), "octylic acid" (manufactured by KH Neochem), "K-KAT XK-627" (manufactured by Enomoto Kasei Co., Ltd.), and the like.

  The content when the catalyst is used is preferably 0.01 to 5% by mass with respect to the total amount of the present composition (solid content).

<Physical properties of the composition>
The density (23 ° C.) measured based on JIS K 5600-2-4: 1999 of this composition is light and does not sag even when applied to a vertical surface with sufficient thickness (suppression of slump) In view of being able to easily obtain a composition, it is preferably 1.00 to 1.20 g / cm ³ , more preferably 1.02 to 1.10 g / cm ³ .

  The slump (23 ° C.) measured based on JIS A 5758: 2010 of the present composition is less likely to sag even when applied to a vertical surface or the like with a sufficient thickness (the composition can be easily obtained). From such points, it is preferably 3 mm or less, more preferably 2 mm or less, and particularly preferably 1 mm or less.

The consistency (23 ° C.) measured based on JIS K 2220: 2013 of the present composition is preferably 40 to 500, more preferably from the viewpoint of obtaining a composition that can be applied to a vertical surface. 50-300.
The present composition has such a consistency, and is a composition that hardly drips (slump is suppressed) even when applied to a vertical surface with a sufficient thickness.

The present composition can be suitably used as a displacement insulating material composition, and preferably satisfies the following requirements (I) and (II) from the viewpoint that the obtained cured product is more excellent in displacement insulation. .
Requirement (I): Using this composition, the elongation (elongation at yield point) measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 150% or more. More preferably, it is 200% or more, particularly preferably 300% or more, and the upper limit is preferably 1,000%.
Requirement (II): Using this composition, the tensile strength measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 1 MPa or less. The tensile strength is more excellent in displacement insulation. From the point of becoming a cured body, it is more preferably 0.5 MPa or less, and the lower limit is preferably 0.01 MPa, more preferably 0.05 MPa.
It can be said that the composition capable of forming a cured body having an elongation and a tensile strength within the above ranges is a displacement insulating material composition.

<Preparation method of this composition>
The present composition can be prepared by mixing the components (A) to (C) and, if necessary, the component (D), a plasticizer and other components.
The method of mixing is not particularly limited, but if air is taken in at the time of preparing the main agent component or at the time of mixing the main agent component and the curing agent component, bubbles remain in the resulting cured body and the displacement insulation effect cannot be exhibited. As a result, the amount of air taken into the composition can be reduced by performing a defoaming step when preparing the main component, or by stirring at a low speed when mixing the main component and the curing agent component. Is preferred.

When the present composition is a two-component (or more) type, the components used immediately before use may be mixed. Preferred methods for preparing the present composition include the following methods.
First, the main component and the curing agent component are put into a container and stirred by a stirring means such as an electric stirrer. At this time, a component (D), a plasticizer and other components may be optionally added.
The container used is preferably a container that is about twice or more the volume of the resulting composition. Moreover, as a stirring blade of an electric stirrer, a stirring blade for mortar can be used.
Next, the component (C) is added little by little to a container in which the main component and the curing agent component are mixed and mixed. The component (C) may be previously contained in either the main agent component or the curing agent component as described above, or may be contained in both the main agent component and the curing agent component.

≪Hardened body≫
The cured body according to the present invention can be formed by curing the present composition.
According to the present composition, a cured product having high elongation (elongation at yield point) can be obtained. Therefore, by forming the cured body in a place or member where displacement insulation is required, such as water control equipment, the place or member can be displaced and insulated. For this reason, this composition can be used conveniently as a displacement insulation material composition for water control equipment.

  The cured body is usually formed as a cured coating on a member or place where displacement insulation is required. The thickness of the cured film may be appropriately selected according to the desired application, but is usually 2 mm or more, preferably 6 mm or more, more preferably 6 to 6 from the viewpoint of obtaining a cured film having sufficient displacement insulation. 10 mm. For example, in order to form a cured film capable of following a displacement of 12 mm or more in the shear direction, the thickness of the cured film may be 2 mm or more, but in consideration of errors during construction and safety and corrosion resistance, The thickness of the cured film is preferably 6 mm or more.

When the composition is cured, it may be heated from the viewpoint of shortening the curing time, but it is usually sufficient to leave it at room temperature for about 20 minutes to 1 hour without heating.
Since this composition is also excellent in curability at room temperature, it can be cured in a short time at room temperature.

The hardness of the cured body measured using durometer type E based on JIS K 6253: 2012 is preferably 5 to 70, more preferably 10 to 10 from the viewpoint that the cured body is more excellent in displacement insulation. 60, particularly preferably 40-50.
It can be said that the composition capable of forming a cured body having a hardness in the above range is a displacement insulating material composition.

≪Displacement insulation method for water control equipment and water control equipment≫
The displacement insulation method for water control equipment according to the present invention (hereinafter also referred to as “the present method”) includes a step of applying the composition to at least a part of the water control equipment and curing the composition.
The water control equipment according to the present invention is not particularly limited as long as it has at least a part of the cured film of the present composition. Specifically, it is formed by the present method.

  Examples of the water control equipment in the present invention include dams, weirs, sluices, and the like. Specifically, these water control members, discharge members, water intake members and the like can be mentioned. In particular, a tension beam, a trunnion girder, a bearing plate, or the like embedded in or in contact with a concrete member (eg, concrete pier) constituting a dam, dam, sluice, or the like.

  In this method, when constructing these water control equipment, it may be constructed while applying the present composition, the composition is applied in advance to a member constituting the water control equipment, such as a tension beam, You may build a water control installation using what formed the hardened film. In many cases, the latter method is used.

Examples of the material of the member to be coated with the composition include steel and stainless steel.
For example, H steel is usually used as the tension beam. In order to displace and insulate the H steel, it is necessary to cover the entire surface with a cured film of the present composition, and the cured film has a sufficient thickness (for example, 2 mm or more) according to the required displacement insulation. There is a need to. Because of the shape of such H steel, it is necessary to coat the composition on a vertical surface with respect to the ground and also on the ceiling surface, and suppression of slump (sagging) is highly desired. On the other hand, the tension beam is considerably large and needs to form a thick film, so that it is required to have excellent workability (paintability). Usually, a composition that easily sags is excellent in paintability, and a composition that is excellent in paintability easily sags. However, according to the present invention, a composition that can simultaneously achieve the above requirements can be obtained.

  The method of applying the present composition to at least a part of the water control equipment is not particularly limited, and a conventionally known method can be adopted. For example, a cured film that can follow a displacement of 12 mm or more in the shear direction is formed. For this purpose, the thickness of the cured film may be 2 mm or more, but the thickness of the cured film is preferably 6 mm or more in consideration of errors during construction, safety factor, and corrosion resistance. In order to form a film having such a thickness, it is usually preferable to apply a coating or the like, and more specifically, it is preferable to apply the coating using a coating or the like.

When this composition is applied to at least a part of the water control facility, a primer is usually applied to the construction site in advance to improve adhesion. Examples of the primer include modified epoxy resin-based paint “Uniban NT-100K” (manufactured by China Paint Co., Ltd.).
In addition, before apply | coating a primer, a construction location surface may be processed by a conventionally well-known method, and dust etc. may be removed.

After applying the primer, the primer is confirmed to be cured, and if there is something that inhibits adhesion of dust or the like, it is removed. Next, after thoroughly mixing this composition, apply it on the primer so that it is pressed with a scissors, etc., apply it to a certain level, and then apply thinner to the scissors to smooth the surface of this composition. And finishing method.
In this way, after applying the composition or forming a cured film, if the object is a metal, measure the film thickness with an eddy current film thickness meter or the like to adjust the thickness of the cured film. May be.

The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
The materials used in Examples and Comparative Examples are as follows.

<Bifunctional or higher polyfunctional polyol (A)>
"Excenol 5030" (manufactured by Asahi Glass Co., Ltd., trifunctional polyether polyol, hydroxyl value: 33 mgKOH / g, Mn = 5,100, viscosity (25 ° C.): 910 mPa · s)
"Boranol 3022J" (manufactured by Dow Chemical Japan Co., Ltd., trifunctional polyether polyol, hydroxyl value: 56 mgKOH / g, Mn = 3,000, viscosity (25 ° C.): 485 mPa · s)
"Excenol 805" (Asahi Glass Co., Ltd. bifunctional polyether polyol, hydroxyl value: 26 mgKOH / g, Mn = 6,500, viscosity (25 ° C.): 1,200 mPa · s)

<Isocyanate (B)>
"Takenate L-1028" (manufactured by Mitsui Chemicals, Inc., bifunctional TDI prepolymer having isocyanate groups at both ends, NCO%: 2.9 wt%, viscosity (25 ° C): 8,000 mPa · s)

<Organic fiber (C)>
・ "Chemibest FDSS-2" (Mitsui Chemicals, polyethylene fiber, fiber length 0.6 mm)
・ "Chemibest FDSS-5" (Mitsui Chemicals, polyethylene fiber, fiber length 0.1 mm or less)

<Amine (D)>
"ML-520E" (Iharacamine ML-520E, manufactured by Ihara Chemical Industry Co., Ltd., condensate of o-chloroaniline and formaldehyde (4,4'-diamino-3,3'dichlorodiphenylmethane) and polypropylene glycol di 50:50 mixture with benzoate)
"ML-620E" (Iharacamine ML-620E, manufactured by Ihara Chemical Industry Co., Ltd., 50:50 mixture of 4,4'-diamino-3,3'dichlorodiphenylmethane and polypropylene glycol)

<Plasticizer>
・ "DOP" (manufactured by Jay Plus Co., Ltd., dioctyl phthalate)
・ "Diana Oil E-900" (manufactured by Idemitsu Kosan Co., Ltd., petroleum hydrocarbon)

<Other ingredients>
[Thickener]
・ "BYK-410" (Big Chemie Japan Co., Ltd., urea urethane)
・ "Galamite 1958" (BYK Additives, organically modified clay)
[Pigment]
・ "Silica TK-1" (manufactured by Tono Coffee Co., Ltd., silica)
[Defoamer]
・ "SAG-47" (Toray Dow Corning Co., Ltd., dimethylpolysiloxane antifoaming agent)
[catalyst]
・ "K-KAT XK-627" (manufactured by Enomoto Kasei Co., Ltd., carboxylic acid mixed metal)
・ "Octylic acid"
・ "DABCO 33-LV" (Air Products Japan Co., Ltd., tertiary amine)
・ "Grec TL" (manufactured by Nippon Steel & Trade Co., Ltd., butyltin carboxylate)
[Moisture adsorption agent]
・ "Molecular sieve 4A" (Union Showa Co., Ltd.)

[Examples 1-14 and Comparative Examples 1-3]
A bifunctional or higher polyfunctional polyol (A), an amine (D), a plasticizer and other components described in Table 1 were mixed and stirred in the amounts described in Table 1 to prepare a main component. In addition, the numerical value of the column of the raw material in Table 1 shows a mass part.
The prepared main ingredient component was mixed with the kinds and amounts of isocyanate (B) and organic fiber (C) shown in Table 1 to prepare a composition.

[density]
Based on JIS K 5600-2-4: 1999, the density (23 degreeC) of the obtained composition was measured. A composition having a density of 1.00 to 1.20 was defined as a preferred composition.
The results are shown in Table 1.

[Slump test]
A slump test was conducted based on JIS A 5758: 2010 except that the obtained composition was used and the measurement temperature was 23 ° C.
Each composition was tested three times. The results (average slump) are shown in Table 1. When the average slump was 3 mm or less, it was judged as acceptable.

[Consistency]
Based on JIS K 2220: 2013, the consistency (23 degreeC) of the obtained composition was measured. A composition having a consistency of 40 to 500 was defined as a preferred composition. The results are shown in Table 1.

[Foaming]
A polypropylene container having a capacity of about 100 ml was flatly filled with the resulting composition using a spatula to the same height as the edge of the container. After 1 hour from filling, it was confirmed that the composition was sufficiently cured, and then the difference between the height of the surface of the cured body and the height of the container was visually confirmed with calipers to confirm the presence or absence of foaming. Since this composition shrinks when cured, the surface of the cured product is less than the height of the container if there is no foaming. On the other hand, when foaming occurs, volume expansion of the cured body occurs, so that the surface becomes higher than the container height. The case where the surface of the cured body was less than the height of the container was evaluated as “no foaming”, and the case where the surface of the cured body was equal to or higher than the container height was evaluated as “present”. And the case where foaming was not able to be confirmed was made into the pass. The results are shown in Table 1.

[Elongation]
Using the obtained composition, based on JIS K 6251: 2010, three test pieces (dumbbell-shaped test pieces using dumbbell-shaped No. 3) were prepared for each composition, and a tensile tester (automatic Yield point elongation was measured using a graph AGS-10KNX (manufactured by Shimadzu Corporation) (test speed: 500 ± 50 mm, test temperature: 23 ± 1 ° C.), and the average value of yield point elongation of each test piece was calculated. did. The results are shown in Table 1.

[Tensile strength]
Using the obtained composition, based on JIS K 6251: 2010, three test pieces (dumbbell-shaped test pieces using dumbbell-shaped No. 3) were prepared for each composition, and a tensile tester (automatic The tensile strength was measured using a graph AGS-10KNX (manufactured by Shimadzu Corporation) (test speed: 500 ± 50 mm, test temperature: 23 ± 1 ° C.), and the average value of the tensile strength of each test piece was calculated. did. The results are shown in Table 1.

<Evaluation>
The compositions obtained in Examples 1 to 14 had a small slump and did not sag when applied to a vertical surface. In addition, it has excellent elongation characteristics, so it can be used suitably as a displacement insulating material composition. By applying it to the structure of water control equipment, the surrounding concrete structure that occurs when a huge earthquake occurs, etc. It is also possible to deal with displacement in the shear direction with an object.
In addition, the compositions obtained in Examples 1 to 14 are small in density and light, and excellent in workability when applied to a thick film.
When the compositions obtained in Examples 1 to 11 are used, it is possible to obtain cured bodies that are particularly excellent in elongation characteristics, and in the case of using the compositions obtained in Examples 12 to 14, crosslinking is performed. A cured product having a high density can be obtained.

  On the other hand, since the composition of Comparative Examples 1-3 did not use a component (C), it was unsatisfactory with a large slump or foaming. Urea urethane is known as a general thickener, but when comparing Comparative Examples 1 and 2, when urea urethane is used as a thickener, slump is not increased even if the amount added is increased. It was not improved. Organic modified clay is also known as a general thickening agent, but the composition of Comparative Example 3 was not only slump large but also foamed during curing and could not be used.

Claims (12)

  A displacement insulating material composition comprising a bifunctional or higher polyfunctional polyol (A), an isocyanate (B) and an organic fiber (C).   The composition of Claim 1 whose content of the said organic fiber (C) is 10 mass parts or more with respect to a total of 100 mass parts of the said polyol (A) and isocyanate (B).   The composition according to claim 1 or 2, wherein the organic fiber (C) is a polyethylene fiber.   The composition of any one of Claims 1-3 whose fiber length of the said organic fiber (C) is 3 mm or less.   The composition according to any one of claims 1 to 4, wherein a slump measured according to JIS A 5758: 2010 (however, the measurement temperature is 23 ° C) is 3 mm or less. The composition according to any one of claims 1 to 5, which satisfies the following requirement (I).
Requirement (I): Elongation measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 150% or more using the composition. The composition according to any one of claims 1 to 6, which satisfies the following requirement (II).
Requirement (II): Using the composition, the tensile strength measured based on JIS K 6251: 2010 (dumbbell shape No. 3) is 1 MPa or less.   The composition according to any one of claims 1 to 7, comprising an amine (D).   The composition according to any one of claims 1 to 8, which is a displacement insulating material composition for water control equipment.   The hardened | cured material of the composition of any one of Claims 1-9.   A displacement insulation method for water control equipment, comprising the step of applying the composition according to any one of claims 1 to 9 to at least a part of the water control equipment and curing the composition.   The water control equipment which has the cured film of the composition of any one of Claims 1-9 in at least one part.

Images