JP5299072B2 - Two-component room temperature curable urethane film waterproofing material composition - Google Patents

Description

  The present invention relates to a two-component room temperature curable urethane coating film waterproofing material composition.

Conventionally, a composition containing a urethane prepolymer and a resin-based hollow body has been proposed as a waterproofing material composition.
For example, Patent Document 1 states that “a room-temperature-curing polyurethane elastomer composed of a urethane prepolymer having an isocyanate group at the molecular end, an active hydrogen compound, a urethanization catalyst, and other auxiliaries, and an organic micro-hollow in the polyurethane elastomer. Describes a room temperature curing polyurethane elastomer characterized by containing 0.2 to 2.0% by weight of a sphere. "

  In addition, the present applicant described in Patent Document 2 that “a two-component room temperature curable urethane coating waterproofing material composition having a main component containing a urethane prepolymer and a curing agent containing a polypropylene polyol to which ethylene oxide is added. The balloon having a maximum particle size of 280 μm or less, in which the main agent and / or the curing agent is coated with an inorganic filler, is 0.5% by mass or more based on the total amount of the main agent and the curing agent. It contains a two-component room-temperature curable urethane coating film waterproof material composition ".

Japanese Patent No. 2575776 JP 2006-232971 A

However, the present inventor has developed a coating film obtained from a room temperature curable polyurethane elastomer described in Patent Document 1 and a urethane obtained from a two-component room temperature curable urethane coating waterproof material composition described in Patent Document 2. Examination of the waterproof coating material revealed that the defoaming properties were all inferior.
Therefore, an object of the present invention is to provide a two-component room temperature curable urethane coating film waterproofing material composition that can be a urethane coating film waterproofing material having excellent defoaming properties.

As a result of earnest research to solve the above problems, the present inventor has a main agent containing a urethane prepolymer and a curing agent containing a compound having an active hydrogen group, and has a predetermined molecular weight together with the resin-based hollow body. The present inventors have found that a composition containing a specific amount of a castor oil-based polyol can be a waterproofing film composition having excellent antifoaming properties, and completed the present invention.
That is, the present invention provides the following (1) to (3).

Two-component room temperature curing type having a main agent containing a urethane prepolymer and a curing agent containing a compound having an active hydrogen group in a ratio of NCO group / OH group (equivalent ratio) of 1.2 to 2.5 A urethane film waterproofing material composition comprising:
The main agent and / or the curing agent contains 0.5% by mass to 10% by mass of a resin-based hollow body in the curing agent ,
The curing agent contains a castor oil-based polyol in an amount of 2% by mass or more based on the total mass of the compound having an active hydrogen group as the compound having the active hydrogen group,
A two-component room-temperature-curing urethane coating film waterproofing material composition, wherein the castor oil-based polyol has a weight average molecular weight of less than 3000.

  (2) The two-component room temperature curable urethane coating film waterproofing material composition according to (1), wherein the castor oil-based polyol is contained in an amount of 55% by mass or less based on the total mass of the compound having the active hydrogen group.

  (3) The two-component room temperature curable urethane coating film waterproofing material composition according to the above (1) or (2), wherein the castor oil-based polyol has a weight average molecular weight of 500 or more.

  As will be described below, according to the present invention, it is possible to provide a two-component room-temperature-curing urethane coating film waterproofing material composition that can be a urethane coating film waterproofing material having excellent defoaming properties.

The present invention will be described in detail below.
The two-component room temperature curable urethane coating waterproof material composition of the present invention (hereinafter also referred to as “waterproofing composition of the present invention”) contains a main ingredient containing a urethane prepolymer and a compound having an active hydrogen group. A two-component room temperature curing urethane coating film waterproofing material composition having a curing agent,
The main agent and / or the curing agent contains a resin-based hollow body,
The curing agent contains a castor oil-based polyol in an amount of 2% by mass or more based on the total mass of the compound having an active hydrogen group as the compound having the active hydrogen group,
The castor oil-based polyol has a two-component room temperature curable urethane coating film waterproofing material composition having a weight average molecular weight of less than 3000.
Next, the urethane prepolymer, the compound having an active hydrogen group, the resin-based hollow body, and the like contained in the waterproof material composition of the present invention will be described in detail.

<Urethane prepolymer>
The urethane prepolymer contained in the main agent is not particularly limited, and conventionally known ones can be used. For example, a reaction product obtained by reacting a polyol compound and a polyisocyanate compound so that an isocyanate group (NCO group) is excessive with respect to a hydroxy group (OH group) can be used.
The urethane prepolymer can contain 0.5 to 5% by mass of NCO groups at the molecular ends.

(Polyisocyanate compound)
The polyisocyanate compound used in the production of the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule.
Specific examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI ( For example, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diene Aromatic polyisocyanates such as isocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as socyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); carbodiimide-modified polyisocyanates; isocyanurate-modified polyisocyanates; and the like.

Such polyisocyanate compounds can be used alone or in combination of two or more.
Among these, tolylene diisocyanate (TDI) is preferable because the resulting urethane prepolymer has a low viscosity and the main agent containing this urethane prepolymer can be easily handled.

(Polyol compound)
The polyol compound used in the production of the urethane prepolymer is not particularly limited as long as it has two or more hydroxy groups.
Examples of the polyol compound include polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1, Polyols obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to at least one selected from the group consisting of 4-butanediol and pentaerythritol, etc. Is mentioned. Specifically, polypropylene ether diol and polypropylene ether triol are preferably exemplified.

  Specifically, the polyester polyol is selected from the group consisting of, for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane, and other low molecular polyols. And at least one selected from the group consisting of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid and other aliphatic carboxylic acids, castor oil and other hydroxycarboxylic acids and oligomeric acids Examples thereof include condensation polymers with seeds; ring-opening polymers such as propionlactone and valerolactone; and the like.

  Specific examples of other polyols include, for example, polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, And low molecular weight polyols such as hexanediol.

Such polyol compounds can be used alone or in combination of two or more.
Of these, polypropylene ether polyols, in particular, polypropylene ether diols and polypropylene ether triols, are suitable for the viscosity of the urethane prepolymer obtained, and the main agent containing this urethane prepolymer is easy to handle. This is preferable because the tensile properties of the urethane coating film waterproofing material comprising the waterproofing material composition of the present invention are suitable.

  In the present invention, the combination of the polyol compound and the polyisocyanate compound in producing the urethane prepolymer is selected from the group consisting of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI) and diphenylmethane diisocyanate (MDI). A combination of at least one of the above and polypropylene ether diol and / or polypropylene ether triol is preferably exemplified.

  In the present invention, the amount of the polyisocyanate compound and the polyol compound when producing the urethane prepolymer is preferably such that the NCO group / OH group (equivalent ratio) is 1.2 to 2.5, More preferably, it is 1.5 to 2.2. When the equivalence ratio is in such a range, the viscosity of the obtained urethane prepolymer becomes appropriate, and the storage stability of the main agent containing this urethane prepolymer becomes good.

  In this invention, the manufacturing method of a urethane prepolymer is not specifically limited, For example, it can manufacture by heating and stirring the polyol compound and polyisocyanate compound of the above-mentioned equivalent ratio at 50-130 degreeC. Moreover, if necessary, for example, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

  Such urethane prepolymers can be used alone or in combination of two or more.

<Compound with active hydrogen group>
The compound having an active hydrogen group contained in the curing agent is a compound having in the molecule two or more substituents selected from the group consisting of a hydroxy group, a mercapto group and an amino group (including an imino group, the same shall apply hereinafter). It is.
Examples of such a compound include a polyol compound having two or more hydroxy groups, a polythiol compound having two or more mercapto groups, and a polyamine compound having two or more amino groups.

(Polyol compound)
Specific examples of the polyol compound include, for example, polyol compounds used in the production of the urethane prepolymer described above, and these may be used alone or in combination of two or more.
In the present invention, at least a castor oil-based polyol is used as the compound having an active hydrogen group.

  Here, as the castor oil-based polyol, specifically, for example, castor oil represented by the following structural formula, its alkylene oxide adduct, its epoxy compound, its halide, and castor oil are used as raw materials. Derivatives such as a transesterified product with a polyhydric alcohol having a valency or higher are listed.

  Moreover, the said castor oil-type polyol may be manufactured in accordance with a conventional method, or a commercial item may be used.

In the present invention, if a castor oil-based polyol having a weight average molecular weight of less than 3000 is used in an amount of 2% by mass or more based on the total mass of the compound having active hydrogen groups, the cured product comprising the waterproofing material composition of the present invention. The defoaming property of (urethane film waterproofing material) becomes good.
This is considered to be because the compatibility between the compound having an active hydrogen group containing a castor oil-based polyol and the resin-based hollow body is improved, and the resin hollow body is prevented from being lifted and arranged on the coating film surface during construction. .
In the present invention, the weight average molecular weight is a weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC). For the measurement, tetrahydrofuran (THF) is preferably used as a solvent.

  In the present invention, the castor oil-based polyol is 55% by mass with respect to the total mass of the compound having an active hydrogen group, because the tensile strength of the urethane coating film waterproof material comprising the waterproof material composition of the present invention is good. % Is preferably used in an amount of not more than%, more preferably 3 to 53% by mass.

  Furthermore, in the present invention, it is preferable that the weight average molecular weight of the castor oil-based polyol is 500 or more from the viewpoint of suppressing the occurrence of bleeding on the surface of the urethane coating waterproof material made of the waterproofing material composition of the present invention. 2500 is more preferable.

(Polythiol compound)
Specific examples of the polythiol compound include methanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, and 1,3-benzenedithiol. 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, 1,8-octanedithiol, 1,5-pentanedithiol, 1,2-propanedithiol, 1,3-propadithiol, toluene-3,4-dithiol, 3,6-dichloro-1,2-benzenedithiol, 1,5-naphthalenedithiol, 1,2-benzenedimethanethiol 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 4,4 ′ Thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, 1,8-dimercapto-3,6-dioxaoctane, 1,5-dimercapto-3-thiapentane, 2-di-n-butyl Examples include amino-4,6-dimercapto-s-triazine, thiol group-terminated polymers (for example, polysulfide polymer (thiocol LP, manufactured by Toray Fine Chemical Co., Ltd.), etc.), and these may be used alone. More than one species may be used in combination.

(Polyamine compound)
Specific examples of the polyamine compound include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, hexamethylene Diamine, trimethylhexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 1,5-diamino-2-methylpentane, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane , 3-aminomethyl Aliphatic polyamines such as 3,3,5-trimethyl-cyclohexylamine, dimethyleneamine with norbornane skeleton, metaxylylenediamine (MXDA), hexamethylenediamine carbamate, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylene Aromatic polyamines such as amine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3,4-tolylenediamine, diethyltoluenediamine Etc., and these may be used alone or in combination of two or more.

Among these, as the compound having an active hydrogen group other than the castor oil-based polyol, it is preferable to use polypropylene ether polyol, particularly polypropylene ether diol or polypropylene ether triol. The tensile property of the urethane coating film waterproofing material comprising the waterproofing material composition of the present invention obtained using the above is suitable, and it is preferable for the reason that there is little decrease in physical properties due to swelling after water immersion.
The use of an aromatic polyamine such as 3,3′-dichloro-4,4′-diaminodiphenylmethane provides good workability and tensile properties of the resulting urethane coating waterproof material comprising the waterproof composition of the present invention. It is preferable for the reason.

  In the present invention, the compound having an active hydrogen group is such that the equivalent ratio of the active hydrogen group to the isocyanate group of the urethane prepolymer (isocyanate group / active hydrogen group) is 0.8 to 2.0. It is preferable to mix | blend, and it is more preferable to mix | blend so that it may become 0.9-1.5.

<Resin hollow body>
The resin-based hollow body contained in the waterproof material composition of the present invention is such that the outer shell of the hollow sphere is made of resin. For example, a heat-expandable resin-based hollow body obtained by encapsulating a liquid in a resin-based hollow body and heating it to expand the resin-based hollow body serving as an outer shell and vaporize the internal liquid Is mentioned.

Examples of the material constituting the outer shell of the resin hollow body include phenol resin, urea resin, polystyrene resin, polyvinylidene chloride, and thermoplastic resin.
Of these, at least one selected from the group consisting of phenol resin, urea resin, polystyrene, polyvinylidene chloride and thermoplastic resin is preferable.

Specific examples of the thermoplastic resin constituting the outer shell of the thermoplastic resin hollow body include, for example, vinyl chloride, vinylidene chloride; acrylonitrile, methacrylonitrile; acrylate compounds such as benzyl acrylate and norbornane acrylate; methyl methacrylate And methacrylate compounds such as norbornane methacrylate and trimethylolpropane trimethacrylate; styrenic monomers; vinyl acetate; butadiene; vinyl pyridine; chloroprene homopolymers;
Among these, from the viewpoint of weather resistance and heat resistance, an acrylonitrile copolymer (for example, a copolymer of acrylonitrile and methacrylonitrile, a butadiene copolymerizable with acrylonitrile and acrylonitrile, a vinyl monomer such as styrene, etc.) Copolymers) and vinylidene chloride polymers are preferred.

  On the other hand, examples of the liquid encapsulated in the resin-based hollow body include hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, and petroleum ether; methyl chloride, methylene chloride, dichloroethylene, trichloroethane, and trichloro. Examples include chlorinated hydrocarbons such as ethylene.

  The manufacturing method of the resin-based hollow body is not particularly limited, and can be manufactured by a conventionally known method.

In the waterproof material composition of the present invention, the content of the resin-based hollow body is preferably 0.5% by mass or more of the curing agent.
Here, when the content of the resin-based hollow body is an amount of 0.5% by mass or more of the curing agent, the specific gravity of the urethane coating waterproof material made of the waterproofing material composition of the present invention is reduced, and the weight is reduced. Can be achieved.
Moreover, from a viewpoint that durability and weight reduction of the urethane coating-film waterproof material which consists of the waterproof material composition of this invention obtained improve more, content of a resin-type hollow body is 0.5-10 mass of a hardening | curing agent. %, Preferably 0.5 to 6% by weight.

  In the waterproof material composition of the present invention, the resin-based hollow body can be contained in either or both of the main agent and the curing agent, but the main agent and the curing agent of the waterproof material composition of the present invention to be obtained. From the reason that workability at the time of mixing is improved, it is more preferable to be contained only in the curing agent.

In the present invention, the resin hollow body includes a resin hollow body having a particle diameter of 70 μm or less in more than 20% of the total volume of the resin hollow body, and a resin hollow body having a particle diameter of 110 μm or less. It is preferable to contain more than 80% of the product.
Here, including over 20% means including over 20%, and the same applies to including over 80% (the same applies hereinafter).
The resin-based hollow body contains a resin-based hollow body having a particle diameter of 70 μm or less in more than 20% of the total volume of the resin-based hollow body, and a resin-based hollow body having a particle diameter of 110 μm or less is 80% of the total volume of the resin-based hollow body. By containing more than%, it becomes possible to make the resin-based hollow body finely packed in the urethane coating film waterproof material made of the waterproof material composition of the present invention to be obtained.

The maximum particle diameter of the resin-based hollow body is not particularly limited as long as the resin-based hollow body is used for general purposes, and is preferably 600 μm or less, more preferably 500 μm or less.
Here, the particle diameter of the resin hollow body is measured using a Microtrac particle size distribution meter (manufactured by Nikkiso Co., Ltd.) as a measuring device based on the laser diffraction method.

  In the present invention, the resin-based hollow body is preferably coated with an inorganic filler from the viewpoint of excellent handling during production of the curing agent.

The inorganic filler used for coating the resin hollow body is not particularly limited, and specific examples thereof include calcium carbonate, titanium oxide, silicon oxide, talc, clay, carbon black and the like.
Among these, from the viewpoint of excellent coating of the resin-based hollow body, at least one selected from the group consisting of calcium carbonate, titanium oxide, silicon oxide, talc, clay and carbon black is preferable.
Such inorganic fillers can be used alone or in combination of two or more.

  The method for coating the resin-based hollow body with an inorganic filler is not particularly limited, and can be coated by a conventionally known method.

The waterproof material composition of the present invention can contain additives other than the urethane prepolymer, the compound having an active hydrogen group and the resin-based hollow body described above, as long as the object of the present invention is not impaired.
Examples of the additive include a reinforcing agent, a curing catalyst, a plasticizer, a dispersant, a solvent, an antioxidant, an antiaging agent, and a pigment. The additive can be added to the main agent and / or the curing agent.

  A reinforcing agent will not be specifically limited if it can reinforce the tensile physical property of the urethane-film waterproof material which consists of a waterproof material composition of this invention obtained, A conventionally well-known thing can be used.

Specific examples of the reinforcing agent include titanium oxide, silicon oxide, talc, clay, quicklime, kaolin, zeolite, diatomaceous earth, fine powder silica, hydrophobic silica, and carbon black.
Of these, titanium oxide, hydrophobic silica, and carbon black are preferred from the viewpoint of wettability with polypropylene ether hydroxide and plasticizer.
The reinforcing agents can be used alone or in combination of two or more.

  The content of the reinforcing agent is 40 to 400 parts by mass with respect to 100 parts by mass of the urethane prepolymer, from the viewpoint of excellent elongation at break of the urethane coating film waterproofing material comprising the waterproofing material composition of the present invention obtained and supplementing the breaking strength. The amount is preferably 160 parts by mass, and more preferably 50 to 150 parts by mass.

Examples of the curing catalyst include an organometallic catalyst.
Specific examples of organometallic catalysts include lead-based catalysts such as lead octenoate and lead octylate; organozinc compounds such as zinc octylate; organotins such as dibutyltin dilaurate and dioctyltin laurate. Compound; Organic calcium compound such as calcium octylate and calcium neodecanoate; Organic barium compound; Organic bismuth compound;
The curing catalysts can be used alone or in combination of two or more.

It is preferable that the usage-amount of a curing catalyst is 0.2-5 mass% with respect to the mass of the whole hardening | curing agent.
In addition, a curing catalyst may be mix | blended in a hardening | curing agent with the compound which has the said active hydrogen group, and may be added at the time of mixing of a main ingredient and a hardening | curing agent.

Specific examples of the plasticizer include diisononyl adipate (DINA), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), and dibutyl benzyl phthalate (BBP). ), Dioctyl adipate (DOA), diisodecyl adipate (DIDA), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate (TDCPP), propylene glycol polyester adipate, adipine Examples include acid butylene glycol polyester.
The plasticizers can be used alone or in combination of two or more.
It is preferable that the usage-amount of a plasticizer is 20 mass parts or less with respect to 100 mass parts of said urethane prepolymers.

A dispersing agent will not be specifically limited if solid can be disperse | distributed in a liquid.
The amount of the dispersant used is preferably 0.01 to 5% by mass and more preferably 0.05 to 5% by mass with respect to the mass of the entire curing agent.

  Specific examples of the solvent include hydrocarbon compounds such as hexane and toluene; halogenated hydrocarbon compounds such as tetrachloromethane; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; And esters such as ethyl acetate; mineral spirits;

  Specific examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxytolueneanisole (BHA), diphenylamine, phenylenediamine, and triphenyl phosphite.

Pigments are roughly classified into inorganic pigments and organic pigments.
Specific examples of inorganic pigments include metal oxides such as titanium dioxide, carbon black, zinc oxide, ultramarine, and bengara; lithopone, lead, cadmium, iron, cobalt, aluminum sulfide, and hydrochlorides thereof. Or these sulfates etc. are mentioned.
Specific examples of organic pigments include azo pigments and copper phthalocyanine pigments.

The method for producing the waterproof material composition of the present invention is not particularly limited. For example, the main agent containing a urethane prepolymer, and the curing agent containing a compound having an active hydrogen group and a resin-based hollow body are separately supplied with nitrogen gas. It can be prepared by a method of thoroughly mixing in an atmosphere.
Further, in the present invention, the prepared main agent can be filled and stored in a container in which the prepared main agent is replaced with nitrogen gas or the like, and the prepared hardener can be stored in another container. It is also possible to prepare a mixture.

The waterproofing material composition of the present invention can be used by sufficiently mixing the main agent and the curing agent.
The waterproof material composition of the present invention can be used for new construction or renovation of buildings such as concrete, mortar, metal roof, and urethane coating coated with a top coat.
A primer can be used before constructing the waterproof material composition of the present invention.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Preparation of Urethane Prepolymer First, 1500 g of polypropylene ether triol having a number average molecular weight of 4000 (EXCENOL 4030, manufactured by Asahi Glass Co., Ltd.) and 1400 g of polypropylene ether diol having a number average molecular weight of 2000 (EXCENOL 2020, manufactured by Asahi Glass Co., Ltd.) are placed in a reaction vessel. The mixture was heated to 110 ° C. under reduced pressure and dehydrated for 6 hours.
Next, tolylene diisocyanate (Cosmonate T80, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added to the reaction vessel after the dehydration treatment while stirring so that the equivalent ratio of NCO group / OH group was 1.95.
Thereafter, the inside of the reaction vessel was heated to 80 ° C., and further mixed and stirred for 24 hours under a nitrogen atmosphere to prepare a urethane prepolymer.
The content (NCO%) of the NCO group in the obtained urethane prepolymer was 3.0% by mass relative to the total mass of the urethane prepolymer.

2. Preparation of two-component room temperature curable urethane film waterproofing material composition (Examples 1-6, Comparative Examples 1-3)
The components shown in Table 1 below were used in the quantitative ratios (parts by mass) shown in Table 1, and these were sufficiently mixed using an electric stirrer or the like to prepare a curing agent.
A two-component room temperature curable urethane coating waterproof material composition by sufficiently mixing 100 parts by mass of the above urethane prepolymer with 100 parts by mass of the curing agent in Table 1 using an electric stirrer or the like. Got.

3. Evaluation The defoaming property, surface state, and tensile properties of the obtained two-component room temperature curable urethane coating film waterproofing material composition were measured and evaluated by the following methods. These results are shown in Table 1 below.

(1) Antifoaming property The obtained two-component room temperature curable urethane film waterproofing material composition was applied to the surface of a slate plate (20 cm × 30 cm) at a rate of ² kg / m ² , and then 23 ° C., 50% relative A specimen was prepared by curing for 24 hours under the condition of humidity.
The surface condition of the coating film of the test body is confirmed by visual observation, those having less than 10 pinholes are evaluated as “◯” as having excellent defoaming properties, and those having 10 or more pinholes are made defoaming. “X” was evaluated as inferior.

(2) Surface condition Check the surface condition of the test specimen similar to the above by touching it, evaluate the non-sticky one as being excellent in bleed resistance, and evaluate the one with stickiness as inferior in bleed resistance. It was evaluated as “×”.

(3) Tensile properties For each of the two-component room temperature curable urethane film waterproofing material composition obtained, the tensile strength (breaking strength) was determined according to the test method specified in “Building film waterproofing material” of JIS A6021: 2000. It was measured.

Each component shown in Table 1 is as follows.
Active hydrogen group-containing compound 1: Polypropylene ether triol having a number average molecular weight of 5000 (EXCENOL 5030, manufactured by Asahi Glass Co., Ltd.)
・ Calcium carbonate: Heavy calcium carbonate (Super SS, manufactured by Maruo Calcium)
Active hydrogen group-containing compound 2: 3,3'-dichloro-4,4'-diaminodiphenylmethane (manufactured by Ihara Chemical Industry Co., Ltd.)
・ Titanium oxide: Ishihara Sangyo Co., Ltd. ・ Carbon black: Mitsubishi Carbon Black MA220 (Mitsubishi Chemical Corporation)
Hydrophobic silica: AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.)
・ Plasticizer: Diisononyl phthalate (DINP, manufactured by Jay Plus)
・ Curing catalyst: Lead catalyst (Minico P-30, manufactured by Active Materials Chemicals)
・ Solvent: Mineral Spirit (manufactured by Nippon Oil Corporation)

  Resin-based hollow body: MFL-60CAS (specific gravity: 0.15, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)

Active hydrogen group-containing compound 3: castor oil-based polyol (URIC H-30, weight average molecular weight: 1000, manufactured by Ito Oil Co., Ltd.)
Active hydrogen group-containing compound 4: castor oil (URIC H-62, weight average molecular weight: 400, manufactured by Ito Oil Co., Ltd.)
Active hydrogen group-containing compound 5: castor oil-based polyol (URIC SE-3506, weight average molecular weight: 3500, manufactured by Ito Oil Co., Ltd.)
Active hydrogen group-containing compound 6: castor oil-based polyol (URIC POLYCASTOR # 30, weight average molecular weight: 2000, manufactured by Ito Oil Co., Ltd.)

As is apparent from the results shown in Table 1, the two-component room temperature curable urethane coating film of Comparative Example 1 in which the content of castor oil-based polyol is less than 2% by mass and Comparative Example 3 prepared without using castor oil-based polyol. It was found that the waterproof material composition is inferior in antifoaming properties.
Moreover, it turned out that the anti-foaming property is also inferior in the two-component room-temperature-curing urethane paint waterproofing material composition of Comparative Example 2 prepared using a castor oil-based polyol having a weight average molecular weight of 3000 or more.
On the other hand, the two-component room temperature curable urethane coating waterproof material composition of Examples 1 to 6 prepared using a specific amount of castor oil-based polyol having a specific weight average molecular weight is a urethane coating waterproof material excellent in defoaming properties. I found out that
In particular, the two-component room temperature curable urethane coating waterproofing compositions of Examples 1 to 3 and 6 prepared so as to contain a castor oil-based polyol having a weight average molecular weight of 500 or more in an amount of 55% by mass or less include bleed. It was also found that the urethane film waterproofing material is excellent in tensile strength.

Claims (3)

Two-component room temperature curing type having a main agent containing a urethane prepolymer and a curing agent containing a compound having an active hydrogen group in a ratio of NCO group / OH group (equivalent ratio) of 1.2 to 2.5 A urethane film waterproofing material composition comprising:
The main agent and / or the curing agent contains 0.5% by mass to 10% by mass of a resin-based hollow body in the curing agent ,
The curing agent contains a castor oil-based polyol in an amount of 2% by mass or more based on the total mass of the compound having an active hydrogen group as the compound having the active hydrogen group,
A two-component room-temperature-curing urethane coating film waterproofing material composition, wherein the castor oil-based polyol has a weight average molecular weight of less than 3000.   The two-component room temperature curable urethane coating film waterproofing material composition according to claim 1, comprising the castor oil-based polyol in an amount of 55% by mass or less based on the total mass of the compound having an active hydrogen group.   The two-component room temperature curing urethane coating film waterproofing material composition according to claim 1 or 2, wherein the castor oil-based polyol has a weight average molecular weight of 500 or more.