JP2015038190A - Two-liquid curable polyurethane-based sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-liquid curable polyurethane-based sealing material composition which can obtain suitable durability even though the specific gravity is reduced and can also suppress the occurrence of springback after the use of a caulking gun.SOLUTION: There is provided a two-liquid curable polyurethane-based sealing material composition which comprises a first liquid containing a urethane prepolymer and a second liquid containing a polyol, wherein the first liquid and/or the second liquid contain a polyaldimine, the second liquid contains 10 to 20 mass% of a resin-based fine hollow body having an average particle diameter of 10 to 40 μm based on the total mass of the second liquid, the thixotropic index [(the viscosity of the second liquid at 1 rpm)/(the viscosity of the second liquid at 10 rpm)] calculated by a ratio of the viscosity (Pas) of the second liquid measured at 23°C, a relative humidity of 50% and a rotation speed of 1 rpm and 10 rpm using a BS type viscometer No. 7 rotor is 2.9 or more.

Description

  The present invention relates to a two-component curable polyurethane sealant composition.

  2. Description of the Related Art Conventionally, as a building sealing material, a two-component curable polyurethane sealing material composition comprising a first liquid containing a urethane prepolymer and a second liquid containing a polyol has been used. In this composition, it is known that a resin-based hollow body is blended with the second liquid from the viewpoint of weight reduction (see Patent Document 1). According to the invention described in Patent Document 1, it is possible to provide a sealing material composition that is excellent in durability, has a small specific gravity, can be reduced in weight, and is excellent in all of elastic recovery, modulus, and elongation.

  It has also been proposed to contain 10 to 17% by weight of a microballoon having an average particle size of 10 to 100 μm based on a room temperature curable resin (see Patent Document 2).

JP 2008-297473 A JP 2011-68764 A

  By the way, when constructing various joints using the sealing material composition, first, the operator mixes the first liquid and the second liquid, and the mixed sealing material composition is an instrument such as a caulking gun. Inhale and fill. Then, the operator operates the lever of the instrument to fill the joint with the sealing material composition. And if an operator stops operation of a lever, the filling to the joint of a sealing material composition will stop.

  However, when the sealing material composition described in Patent Documents 1 and 2 is used, the sealing material composition is discharged from the tip of an instrument such as a caulking gun even after the operator has finished operating the lever. Sometimes. This phenomenon is called springback by those skilled in the art.

  The present invention has been made in view of the above circumstances, and it is possible to suppress the phenomenon of springback while reducing the specific gravity and even after the operator has finished operating the lever. It is to provide a liquid curable polyurethane-based sealant composition.

  In order to solve the above-mentioned problems, the present inventor has conducted extensive research. As a result, the first liquid contains a urethane prepolymer, and at least one of the first liquid and the second liquid contains polyaldimine. In addition to the polyol, the second liquid contains a resin-based fine hollow body having an average particle diameter of 10 μm or more and 40 μm or less at a certain ratio, and the thixotropic index of the second liquid is set within a certain range. Even if the specific gravity is reduced, a suitable durability can be obtained in the sealing material after the first liquid and the second liquid are mixed and the composition is cured. As a result, the inventors have found that the present invention has an extraordinary effect of suppressing the occurrence of the occurrence of the problem. Specifically, the present invention provides the following.

  (1) The present invention comprises a first liquid containing a urethane prepolymer and a second liquid containing a polyol, wherein the first liquid and / or the second liquid contains a polyaldimine, and the second liquid The liquid contains a resin-based fine hollow body having an average particle diameter of 10 μm or more and 40 μm or less in an amount of 10% by mass or more and 20% by mass or less based on the total mass of the second liquid. Thixotropic index [(viscosity of the second liquid at 1 rpm) / calculated from the ratio of the viscosity (Pa · s) of the second liquid measured at a rotational speed of 1 rpm and 10 rpm at 23 ° C. and 50% relative humidity / (Viscosity of the second liquid at 10 rpm) is a two-component curable polyurethane-based sealing material composition having a viscosity of 2.9 or more.

  (2) Moreover, this invention contains 30 mass% or more of surface treatment calcium carbonate with respect to the mass of the whole said 2nd liquid, and 80 mass% or more of calcium carbonate, the said 2nd liquid, (1) The two-component curable polyurethane sealant composition described in 1.

(3) Further, the present invention provides an equivalent ratio (R value) of an isocyanate group contained in the urethane prepolymer with respect to a total equivalent of an amino group generated by hydrolysis of the polyaldimine and a hydroxyl group of a polyol in the second liquid. ) The first liquid and the second liquid were mixed so that [NCO / (OH + NH ₂ )] was 1.08, and the No. 7 rotor of the BS type viscometer was used for the mixture stirred for 15 minutes. The thixotropy index of the mixture calculated from the ratio of the viscosity (Pa · s) of the mixture measured at a rotation speed of 1 rpm and 10 rpm at 23 ° C. and 50% relative humidity [(viscosity of the mixture at 1 rpm) / (Viscosity of the mixture at 10 rpm)] is 6.1 or more, is a two-component curable polyurethane sealant composition according to (1) or (2)

  According to the present invention, even if the specific gravity is reduced, a suitable durability can be obtained in the sealing material after the first liquid and the second liquid are mixed and the composition is cured. It is possible to provide a two-component curable polyurethane-based sealing material composition that can suppress the occurrence of springback after use.

It is the schematic of the aluminum channel 1 for evaluating the non-sagging property of the sealing material which concerns on this invention. It is the schematic for demonstrating the evaluation method of the sagging amount after hardening of the sealing material which concerns on this invention.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. can do.

<Two-component curable polyurethane-based sealing material composition>
The two-component curable polyurethane-based sealing material composition of the present invention (hereinafter also referred to as “sealing material composition”) includes a first liquid containing a urethane prepolymer and a second liquid containing a polyol.

[First liquid]
The first liquid mainly contains a urethane prepolymer. It is called a base or a main agent among those skilled in the art.

[Urethane prepolymer]
The kind of urethane prepolymer is not specifically limited, A conventionally well-known thing 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 (H6XDI), alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate (H12MDI); carbodiimide-modified polyisocyanates; isocyanurate-modified polyisocyanates; and the like.

  Such polyisocyanate compounds can be used alone or in combination of two or more.

  Of these, tolylene diisocyanate (TDI) is preferable because the urethane prepolymer obtained has a low viscosity and the first liquid containing the 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. A condensation polymer of at least one selected from the group consisting of glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid, other aliphatic carboxylic acids and oligomeric acids; Ring-opening polymers such as lactone 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. Among these, polypropylene ether diol and polypropylene ether triol are suitable for the viscosity of the curing agent, and the elongation and strength of the cured product obtained from the sealing material composition of the present invention obtained using this curing agent are It is suitable because it is suitable and there is little decrease in physical properties due to swelling after immersion in water.

  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 within such a range, the viscosity of the obtained urethane prepolymer becomes appropriate, and the remaining amount of the unreacted polyisocyanate compound in the urethane prepolymer can be reduced.

  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.

[Polyaldimine]
At least one of the first liquid and the second liquid further contains polyaldimine. As a curing catalyst, it is known to use an organometallic catalyst (a lead catalyst, an organic tin compound, or an organic bismuth compound). When at least one of the first liquid and the second liquid contains polyaldimine, it is possible to suppress a foaming phenomenon that may occur when curing is performed using the curing catalyst. When the second liquid contains a resin-based hollow body, the physical properties (durability, elongation at breakage, etc.) of the sealing material after the first liquid and the second liquid are mixed to cure the composition Tends to decline. However, at least one of the first liquid and the second liquid contains polyaldimine, and the second liquid contains the organometallic catalyst so that the second liquid contains a resin hollow body. Even when the specific gravity is reduced, suitable physical properties as a sealing material can be maintained.

  The polyaldimine is not particularly limited as long as it is a compound capable of generating an amine by hydrolysis. Conventionally known polyaldimines can be widely used, but because of their good storage stability, polyaldimines are aromatic. A polyaldimine obtained by reacting an aldehyde and a polyamine is more preferred, a polyaldimine obtained by reacting an aromatic aldehyde and an alicyclic diamine is more preferred, and a polyaldimine represented by the following general formula (1): Aldimine is particularly preferred. These polyaldimines may be used alone or in combination of two or more.

In Formula (1), R ¹ is an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group and a substituted phenyl group substituted with one or more substituents. As a substituent, a C1-C9 alkyl group, a C1-C9 alkoxy group, etc. are preferable. The number of substituents of the aryl group is preferably 1 to 3. Specific examples of suitable R ¹ include phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, dimethylphenyl, methoxyphenyl, ethoxyphenyl, and propoxyphenyl groups. Can be mentioned. R ¹ may be the same or different in one molecule.

In the formula (1), R ² is a divalent or trivalent hydrocarbon group having 2 to 15 carbon atoms, a divalent or trivalent polyoxyalkylene group having a molecular weight of 70 to 6,000, and an amino residue of isophoronediamine. Or an amino residue of an amine represented by the following general formula (2). In formulas (1) and (2), n represents 2 or 3.

In the formula (2), R ³ is a hydrocarbon group having 6 to 13 carbon atoms and comprising a divalent or trivalent monocyclo ring, bicyclo ring, or tricyclo ring. The ring has preferably 5 to 12 carbon atoms. Furthermore, the cyclo ring may have a substituent. As the substituent, an alkyl group such as a methyl group, an ethyl group, or a propyl group is preferable.

  The production method of polyaldimine is not particularly limited, and can be easily produced by a known method such as reacting an amine and an aldehyde. For example, amine and aldehyde are heated in an acid catalyst in a solvent such as toluene, xylene, methylcyclohexane or butyl acetate to perform an azeotropic dehydration reaction, and the distillation of water stops in the water droplet separator. The polyaldimine is obtained by continuing the reaction until. The mixing ratio of amine and aldehyde is suitably 1 to 2 equivalents of aldehyde with respect to 1 equivalent of amine. The reaction is usually complete in a few hours. After completion of the reaction, polyaldimine can be obtained by distilling off the aldehyde, the solvent and the like by reducing the reaction mixture under reduced pressure.

As the amine, polyamine is suitable, for example, (a) aliphatic diamine such as ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, 4 , 4'-diaminodicyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2.2.1] heptane, diaminocyclohexane, 3 (4), 8 (9)- Alicyclic diamines such as bis (aminomethyl) -tricyclo [5.2.1.0 ^2.6 ] decane, diaminodiphenylmethane, diaminodiphenyl ether, xylylenediamine, phenylenediamine, 3,5-diethyltoluene-2,4 -Or 2,6-diamy Polyoxyalkylene diamine obtained by converting the hydroxyl group of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc. to amino groups And (b) 1,3,5-tris (aminomethyl) benzene, triamines such as 1,3,5-tris (aminomethyl) cyclohexane, glycerin, trimethylolpropane and the like, propylene oxide and / or ethylene Examples include triamines such as polyoxyalkylene triamines obtained by converting hydroxyl groups of polyoxyalkylene triols obtained by addition polymerization of oxides to amino groups, and alicyclics such as alicyclic diamines or alicyclic triamines. Polyamine Preferably, in particular melting point 50 ° C. or lower melting polyamines are preferred.

  Examples of the aldehyde include benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5 -Trimethylbenzaldehyde, p-anisaldehyde, p-ethoxybenzaldehyde, etc. are mentioned, Aromatic aldehyde is suitable.

The blending ratio of polyaldimine is not particularly limited, but it is preferably 0.5 to 10 parts by weight, more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the urethane prepolymer. In particular, the equivalent ratio (NCO / NH ₂ ) of isocyanate groups contained in the urethane prepolymer to amino groups generated by hydrolysis of polyaldimine is preferably 1.4 to 28, and preferably 2.8 to 7.0. It is more preferable that Polyaldimine may be used alone or in combination of two or more.

  The polyaldimine may be contained in either the first liquid or the second liquid, but considering the hydrolyzability of the polyaldimine, the polyaldimine is preferably contained in the first liquid.

[Second liquid]
The second liquid mainly contains a polyol. The second liquid contains various components such as an anti-aging agent and a plasticizer in addition to the polyol, but is referred to as a curing agent by those skilled in the art.

[Polyol]
The second liquid mainly contains a polyol. As the polyol, polyether polyols such as polypropylene polyol (PPG) and polyethylene polyol (PEG) and the same polyols used as raw materials for the above-mentioned urethane prepolymer can be used. Among them, the polyol is preferably a polyether polyol because the viscosity of the composition can be lowered (workability is good) even in a relatively low temperature region (5 ° C. or lower). (PPG) is more preferable. The number average molecular weight of such a polyol is preferably from 400 to 12,000, particularly from 3,000 to 7,000, since balanced physical properties can be obtained.

  In addition, a polyol may be used only by 1 type and may be used together 2 or more types.

[Resin micro hollow body]
The second liquid contains a resin-based fine hollow body having an average particle diameter of 10 μm or more and 40 μm or less. In the resin-based fine hollow body, the outer shell of the hollow sphere is made of resin. For example, a heat-expandable resin system obtained by encapsulating a liquid inside a resin-based fine hollow body and heating it to expand the resin-based fine hollow body serving as an outer shell and vaporizing the liquid inside A fine hollow body is mentioned.

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

  Specific examples of the thermoplastic resin constituting the outer shell of the thermoplastic fine hollow body include, for example, vinyl chloride, vinylidene chloride; acrylonitrile, methacrylonitrile; acrylate compounds such as benzyl acrylate and norbornane acrylate; methyl Methacrylate compounds such as methacrylate, norbornane methacrylate, 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, a copolymer of a vinyl monomer such as styrene). A vinylidene chloride polymer).

  On the other hand, as the liquid contained in the resin fine hollow body, for example, hydrocarbons such as n-pentane, isopentane, neopentane, butane, isobutane, hexane, petroleum ether; methyl chloride, methylene chloride, dichloroethylene, trichloroethane, Mention may be made of chlorinated hydrocarbons such as trichloroethylene.

  In order to improve the handling property when producing the second liquid, the resin-based fine hollow body is preferably coated with an inorganic filler. In this case, the kind of the inorganic filler 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 fine hollow body, at least one selected from the group consisting of calcium carbonate, titanium oxide, silicon oxide, talc, clay and carbon black is preferable. In addition, an inorganic filler can be used individually or in combination of 2 or more types, respectively. Moreover, the method for coating the resin-based fine hollow body with an inorganic filler is not particularly limited, and it can be coated by a conventionally known method.

  In the sealing material composition of the present invention, the resin-based fine hollow body is 10% by mass or more and 20% by mass with respect to the total mass of the second liquid in order to suppress the specific gravity and suppress the phenomenon of springback. Contains the following. The resin-based fine hollow body is more preferably contained in an amount of 10% by mass to 15% by mass with respect to the mass of the entire second liquid. If the content of the resin fine hollow body is too small, it is not preferable because the second liquid cannot be reduced in specific gravity. If the content of the resin-based fine hollow body of the second liquid is too large, the viscosity of the second liquid becomes too high, which is not preferable in terms of reducing workability.

  The resin-based fine hollow body may be contained in the first liquid in addition to the second liquid, but considering the storage stability of the first liquid, the resin-based fine hollow body is included only in the second liquid. It is preferable that

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

[Surface treatment calcium carbonate]
The second liquid preferably contains surface-treated calcium carbonate. Since the surface-treated calcium carbonate functions as a thixotropic agent, the second liquid contains the surface-treated calcium carbonate, so that the springback, that is, even after the operator has finished the operation of the caulking gun, The phenomenon that the sealing material composition is discharged from the tip can be suppressed.

  In the surface-treated calcium carbonate, the surface treatment agent used is not particularly limited, and a wide variety of known surface treatment agents can be used. Examples of the surface treatment agent include higher fatty acid compounds, higher fatty acid ester compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, and nonionic surfactants. , Paraffin, titanate coupling agent and silane coupling agent. These surface treatment agents may be used alone or in combination of two or more.

  As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used and is not particularly limited. For example, Vigot 15 (manufactured by Shiroishi Calcium Co., Ltd., light calcium carbonate surface-treated with fatty acid) Surface treated light calcium carbonate such as, primary particle diameter 0.15 μm; Vigot 10 (manufactured by Shiraishi Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle diameter 0.10 μm), white glaze CCR-B (Shiraishi Colloidal calcium carbonate surface-treated with fatty acid, primary particle size 0.08 μm, Calfine N-350 (manufactured by Maruo Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle size) 0.04μm), Sealets 200 (Maruo Calcium Co., Ltd., fatty acid ester) Surface-treated colloidal calcium carbonate, primary particle diameter 0.05 μm), Sealets 500 (manufactured by Maruo Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid ester, primary particle diameter 0.05 μm), Sealets 700 (Maruo calcium Co., Ltd., colloidal calcium carbonate surface-treated with a fatty acid ester, primary particle diameter 0.05 μm), Shiraka Hana DD (manufactured by Shiraishi Calcium Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, primary particle diameter 0. 05 μm), Carlex 300 (manufactured by Maruo Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle size 0.05 μm), Neolite SS (manufactured by Takehara Chemical Industries, Ltd., colloidal surface-treated with fatty acid) Calcium carbonate, average particle size 0.04 μm), Neolite GP- 0 (manufactured by Takehara Chemical Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, average particle size 0.03 μm), Calsees P (manufactured by Kamishima Chemical Industries, Ltd., colloidal calcium carbonate surface-treated with fatty acid, Surface-treated colloidal calcium carbonate such as average particle size 0.15 μm; Ryton A-5 (manufactured by Bihoku Flour & Chemical Co., Ltd., heavy calcium carbonate surface-treated with fatty acid, average particle size 3.6 μm), MC coating P1 (manufactured by Maruo Calcium Co., Ltd., heavy calcium carbonate surface-treated with paraffin, primary particle size 3.3 μm), AFF-95 (manufactured by Pfematotech Co., Ltd., heavy calcium carbonate surfaced with a cationic polymer, Primary particle size 0.9 μm), AFF-Z (manufactured by Pfematech Co., Ltd., heavy calcium carbonate surfaced with cationic polymer and antistatic agent, Surface treated calcium carbonate of the following particle size 1.0 .mu.m), and the like. Among these, calcium carbonate surface-treated with a fatty acid ester is more preferable from the viewpoint that the storage stability of the curable composition is good.

  The content of the surface-treated calcium carbonate is preferably 30% by mass or more and more preferably 40% by mass or more with respect to the mass of the entire second liquid. If the content of the surface-treated calcium carbonate is too small, thixotropy is not sufficiently imparted, and as a result, springback may occur.

  Further, the content of the surface-treated calcium carbonate with respect to calcium carbonate is preferably 80% by mass or more, and more preferably 90% by mass or more of calcium carbonate. If the ratio of the surface-treated calcium carbonate to the calcium carbonate is too small, thixotropy is not sufficiently imparted, and as a result, springback may occur.

[Urethane plasticizer]
Although not an essential component, the second liquid may contain a urethane plasticizer, that is, a reaction product of a polyalkylene ether monool and hexamethylene diisocyanate in order to keep the viscosity low and improve the workability of the composition. preferable.

  The production method of the polyalkylene ether monool is not particularly limited and can be obtained by a known production method. For example, a compound having a hydroxyl group as one active hydrogen group at the molecular end can be obtained by adding ethylene oxide, propylene oxide, butylene oxide. Further, those obtained by polymerizing alkylene oxides such as styrene oxide alone, those obtained by copolymerization, or mixtures of these polymers can be used.

  Examples of the compound having a hydroxyl group as one active hydrogen group at the molecular end include aliphatic monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; cyclopentanol, dimethylcyclohexanol and the like. And alicyclic monoalcohols; araliphatic monoalcohols such as benzyl alcohol; aromatic (phenolic) monoalcohols such as phenol and cresol;

  These polyalkylene ether monools may be used alone or in combination of two or more. The OH value of the polyalkylene ether monool is preferably 5.5 to 281.0 [mg KOH / g], more preferably 11.0 to 140.3 [mg KOH / g], and 24.0 to 125.0 [mg KOH]. / G] is more preferable. As the polyalkylene ether monool, polyoxypropylene monool (including those containing a polyoxyethylene unit) is preferable.

  The reaction between the polyalkylene ether monool and hexamethylene diisocyanate is preferably performed under reaction conditions of 40 ° C to 100 ° C. In this reaction, the equivalent ratio of NCO / OH is preferably 1.1 / 1.0 to 1.0 / 1.1. By reacting the hydroxyl group of the polyalkylene ether monool with an isocyanate group, not only the hydroxyl group is blocked, but also all the isocyanate groups are blocked. It is preferable that the content of the isocyanate group remaining in the urethane-based plasticizer is 0.1% by mass or less in terms of suppressing foaming. In order to shorten the reaction time between the polyalkylene ether monool and hexamethylene diisocyanate, it is preferable to use a catalyst such as a tertiary amine, a tin catalyst, or a bismuth catalyst.

  The urethane plasticizer preferably has a viscosity at 25 ° C. of 10,000 mPa · s or less, and more preferably 500 mPa · s or more and 7,000 mPa · s or less.

  The blending ratio of the urethane plasticizer is not particularly limited, but it is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the urethane prepolymer contained in the first liquid. preferable.

  A urethane type plasticizer may be used by 1 type and may be used in combination of 2 or more type.

[Other ingredients (additives)]
The sealing material composition of the present invention can contain additives in addition to the urethane prepolymer, polyol, and resin fine hollow body 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 first liquid or can be added to the second liquid.

(Reinforcing agent)
The reinforcing agent is not particularly limited as long as it can reinforce the cured product properties (for example, elongation, tensile strength, etc.) of the cured product comprising the sealing material composition of the present invention to be obtained, and a conventionally known one may be used. Can do.

  Examples of the reinforcing agent include titanium oxide, silicon oxide, talc, clay, quicklime, kaolin, zeolite, diatomaceous earth, fine powder silica, hydrophobic silica, carbon black and the like. Of these, titanium oxide, hydrophobic silica, and carbon black are preferred from the viewpoint of wettability with polypropylene ether hydroxide and plasticizer. In addition, a reinforcing agent can be used individually or in combination of 2 or more types, respectively.

  The content of the reinforcing agent is excellent in the elongation at break of the cured product made of the sealing material composition of the present invention obtained, and from the viewpoint of supplementing the breaking strength, with respect to 100 parts by mass of the urethane prepolymer contained in the first liquid, It is preferable that it is 40-160 mass parts, and it is more preferable that it is 50-150 mass parts.

(Curing catalyst)
An example of the curing catalyst is an organometallic catalyst. Examples of organometallic catalysts include lead catalysts such as lead octenoate and lead octylate; organozinc compounds such as zinc octylate; organotin compounds such as dibutyltin dilaurate and dioctyltin laurate; calcium octylate; Organic calcium compounds such as calcium neodecanoate; organic barium compounds; organic bismuth compounds; 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 2nd liquid. In addition, a curing catalyst may be mix | blended in a hardening | curing agent with a polypropylene ether hydroxide, and may be added at the time of mixing of a main ingredient and a hardening | curing agent.

(Plasticizer)
Examples of the plasticizer include diisononyl adipate (DINA), diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), dibutyl benzyl phthalate (BBP), dioctyl adipate (DOA) ), Diisodecyl adipate (DIDA), trioctyl phosphate (TOP), tris (chloroethyl) phosphate (TCEP), tris (dichloropropyl) phosphate (TDCPP), propylene glycol adipate polyester, butylene glycol polyester adipate, terminal Examples include esterified polyfunctional polyether, acetic acid ester of polyoxyalkylene monoalkyl ether, polyethylene glycol dibenzoate, and the like. The plasticizers can be used alone or in combination of two or more.

  The amount of the plasticizer used is preferably 20 parts by mass or less with respect to 100 parts by mass of the urethane prepolymer.

(Dispersant)
A dispersing agent will not be specifically limited if solid can be disperse | distributed in a liquid. The amount of the dispersing agent used is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, based on the entire second liquid.

(solvent)
Solvents such as 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; esters such as ethyl acetate Mineral spirit; and the like.

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

(Pigment)
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.

〔density〕
The density of the second liquid is preferably 1.10 g / cm ³ or less. If the density is 1.10 g / cm ³ or less, it can be said that the specific gravity of the cured sealing material composition is sufficiently reduced.

[Thixotropic Index]
In the present invention, in order to suppress the phenomenon of springback, the thixotropy index is suppressed within a certain range. In the present invention, the thixotropy index is the ratio of the viscosity (Pa · s) of an object when measured at a rotational speed of 1 rpm and 10 rpm at 23 ° C. and 50% relative humidity using a No. 7 rotor of a BS viscometer. The thixotropy index [(viscosity of the object at 1 rpm) / (viscosity of the object at 10 rpm)] calculated from the above. In the present invention, the thixotropic index of the second liquid is preferably 2.9 or more, and more preferably 3.1 or more. If the thixotropy index is too low, a springback phenomenon may occur after using a sealing material composition obtained by mixing the first liquid and the second liquid, which is not preferable.

[Mixing of first liquid and second liquid]
The mixing ratio of the first liquid and the second liquid is not particularly limited, but the urethane prepolymer with respect to the total equivalent of amino groups generated by hydrolysis of the polyaldimine and hydroxyl groups of the polyol in the second liquid. The equivalent ratio (R value) [NCO / (OH + NH ₂ )] of isocyanate groups contained in is preferably 0.5 to 2.0, and more preferably 0.7 to 1.5.

〔density〕
The density after mixing is preferably 1.10 g / cm ³ or less. If the density is 1.10 g / cm ³ or less, it can be said that the specific gravity of the cured sealing material composition is sufficiently reduced.

[Thixotropic Index]
Further, the equivalent ratio (R value) of isocyanate groups contained in the urethane prepolymer to the total equivalents of amino groups generated by hydrolysis of the polyaldimine and hydroxyl groups of the polyol in the second liquid [NCO / (OH + NH ₂ ) ] The thixotropic index of the mixture obtained by mixing the first liquid and the second liquid so as to be 1.08 and stirring for 15 minutes using a light-weight Mikista (Mikista Kogyo Co., Ltd.) is 6.1 or more. Is preferable, and it is more preferable that it is 6.4 or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all in these description.

<Preparation of two-component curable polyurethane sealant composition>
[Preparation of the first liquid]

[Examples 1-5, Comparative Examples 1-3]
80 ° C of 748 parts by mass of 2,4-tolylene diisocyanate, 2600 parts by mass of polyoxypropylene glycol (OH value 55.6 mgKOH / g), and 1802 parts by mass of polyoxypropylene triol (OH value 56.1 mgKOH / g) For 7 hours to obtain a urethane prepolymer terminated with an isocyanate group. The terminal NCO group was 3.49 mass%, and the viscosity was 7,500 mPa · s / 25 ° C.

  And 2.5 mass parts of polyaldimine was mixed with 100 mass parts of said urethane prepolymer, and the 1st liquid which concerns on Examples 1-5 and Comparative Examples 1-3 was prepared.

[Comparative Example 4]
A first liquid according to Comparative Example 4 was prepared in the same manner as in Example 1 except that the liquid was composed of the urethane prepolymer and did not contain polyaldimine.

The density of the first liquid at 23 ° C. was measured according to JIS K6833-1.5.2.1 “specific gravity cup method”. As a result of the measurement, the first liquid according to Examples 1 to 5 and Comparative Examples 1 to 3 was 1.02 g / cm ³ , and the first liquid according to Comparative Example 4 was 1.03 g / cm ³ . .

[Preparation of second liquid]

In Tables 2 and 3, the various materials are as follows.
(A) Curing component (polyol)
Polypropylene ether triol (Product name: Actol T-5000, number average molecular weight: 5000, manufactured by Mitsui Chemicals)
Polypropylene ether diol (Product name: Actol D-3000, Number average molecular weight: 3000, manufactured by Mitsui Chemicals)
(B) Resin-based fine hollow body resin having an average particle diameter of 20 to 40 μm (product name: MFL-SEVEN, an average particle diameter of 20 to 40 μm, and a true specific gravity of 0.14 ± 0.03 (g / cc)) Hollow body, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
A resin-based hollow body having an average particle size of 10 to 30 μm (product name: MFL-81GCA, an average particle size of 10 to 30 μm and a true specific gravity of 0.23 ± 0.03 (g / cc), Matsumoto Yushi Seiyaku Co., Ltd. Made)
(B ′) Resin-based hollow body: average particle diameter of 60 to 70 μm (product name: MFL-100MCA, average particle diameter of 60 to 70 μm, true specific gravity of 0.12 ± 0.02 (g / cc)) Hollow body, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.
(C) Surface-treated calcium carbonate Fatty acid-treated calcium carbonate (Product name: Calfine 200, manufactured by Maruo Calcium Co., Ltd.)
(C ′) Untreated surface calcium carbonate Heavy calcium carbonate (Product name: Super # 1500, manufactured by Maruo Calcium Co., Ltd.)
(D) Urethane plasticizer Polyalkylene ether monool (product name: Actol EH-25, polyoxypropylene monool, manufactured by Mitsui Chemicals) 200 g and hexamethylene diisocyanate (product name: HDI, manufactured by Nippon Polyurethane) 9 The urethane plasticizer was synthesized by reacting with .05 g. The viscosity of the urethane plasticizer was 6,400 mPa · s / 25 ° C., and the number average molecular weight was 4,268.
(E) Additives Titanium oxide (Product name: Taipei P820, manufactured by Ishihara Sangyo Co., Ltd.)
Antioxidant (Product name: Irganox 1010, hindered phenol antioxidant, manufactured by BASF)
Curing catalyst A (Product name: Puccat 25, Bismuth octylate, manufactured by Nippon Chemical Industry Co., Ltd.)
Curing catalyst B (Product name: Nikka Octix Lead 17% (DINP), Lead Octylate, manufactured by Nippon Chemical Industry Co., Ltd.)
Plasticizer (Product name: TXIB, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, manufactured by Eastman Chemical Company)
Petroleum hydrocarbons (Product name: Exol D-80, manufactured by ExxonMobil Chemical)
Octyl acid (Toyo Gosei Co., Ltd.)

  All materials other than petroleum hydrocarbons and octylic acid were charged into a planetary mixer at a mass ratio shown in Table 1, and the mixture was heated and mixed under stirring at 90 ° C. for 1 hour to dehydrate the blend. And after cooling to 20 degreeC, petroleum-type hydrocarbon and octylic acid were added, and the 2nd liquid was obtained by carrying out the vacuum pressure reduction mixing for further 10 minutes.

[Mixing of first liquid and second liquid]

The equivalent ratio (R value) [NCO / (OH + NH ₂ )] of the isocyanate group contained in the urethane prepolymer with respect to the total equivalent of the amino group generated by hydrolysis of the polyaldimine and the hydroxyl group of the polyol in the second liquid is The 1st liquid and the 2nd liquid were mixed so that it might be set to 1.08, and it stirred for 15 minutes using the lightweight type MIKISTA (made by MIKISTA KOGYO). By doing in this way, the sealing material composition which concerns on an Example and a comparative example was obtained. The weight ratio between the first liquid and the second liquid was as shown in Tables 4 and 5.

<Evaluation>
First, the density, viscosity, and thixotropy index of the second liquid were measured by the following methods. Moreover, about the sealing material composition which concerns on an Example and a comparative example, the viscosity, a thixotropy index, durability, a tensile physical property, springback property, mixing property, and non-sagging property were evaluated by the method shown below.

(1) Density (g / cm ³ )
The density of the second liquid and the sealing material composition was measured based on JIS K6833-1.5.2.1 “specific gravity cup method”. The results for the second liquid are shown in Table 6, and the results for the sealing material composition are shown in Table 7. In addition, if the density of a 2nd liquid is 1.10 g / cm < ³ > or less, it can be evaluated that the specific gravity of the sealing material composition after hardening is also small enough.

(2) Viscosity (Pa · s)
About the 2nd liquid and the sealing material composition, the viscosity (Pa * s) measured by rotational speed 1rpm and 10rpm in 23 degreeC and 50% relative humidity was measured using the No. 7 rotor of a BS type | mold viscosity meter. The results for the second liquid are shown in Table 6, and the results for the sealing material composition are shown in Table 7.

(3) Thixotropic index (TI)
The thixotropy index [(viscosity at 1 rpm) / (viscosity at 10 rpm)] was calculated from the ratio of the viscosity (Pa · s) measured at a rotational speed of 1 rpm and 10 rpm. The results for the second liquid are shown in Table 6, and the results for the sealing material composition are shown in Table 7. In the present specification, the thixotropy index of the sealing material composition is an isocyanate group contained in the urethane prepolymer with respect to the total equivalent of the amino group generated by hydrolysis of the polyaldimine and the hydroxyl group of the polyol in the second liquid. The first liquid and the second liquid are mixed so that the equivalent ratio (R value) of [NCO / (OH + NH ₂ )] is 1.08, and the mixture is stirred for 15 minutes using a light-weight mister (Mikista Kogyo Co., Ltd.). It is calculated from the ratio of the viscosity (Pa · s) of the mixture measured at a rotational speed of 1 rpm and 10 rpm at 23 ° C. and 50% relative humidity using a BS type viscometer No. 7 rotor. The thixotropic index of the mixture [(viscosity of the mixture at 1 rpm) / (viscosity of the mixture at 10 rpm)].

(4) Durability Tests specified in JIS A5758: 2010 were performed on the obtained two-pack curable polyurethane sealant composition, and durability category 8020 was evaluated. The results are shown in Table 7. Clear abnormalities such as dissolution, swelling, cracking, peeling from the adherend, etc. were visually confirmed, and those without these abnormalities were evaluated as “Excellent” as those with excellent durability. The case where there was was evaluated as “x” as being inferior in durability.

(5) Tensile properties Each of the two-component curable polyurethane-based sealing material compositions obtained was evaluated based on “5.3 Tensile property test” defined in “Testing method for architectural sealing material” of JIS A1439: 2010. Tensile stress at% elongation (N / mm ² ), tensile stress at 100% elongation (N / mm ² ), tensile stress at break (N / mm ² ), and elongation at break (%) were measured. . In addition, the anodized aluminum substrate was used for the adherend, and curing was performed for 28 days under conditions of 23 ° C. and 50% relative humidity. The test was performed under conditions of 23 ° C. and 50% relative humidity. The results are shown in Table 7.

(6) Springback property First, a nozzle having an inner diameter of about 8 mm was attached to a 320 ml paper tube cartridge, and the sealing material compositions according to Examples and Comparative Examples were filled. Subsequently, about 100 g of the above sealing material composition was discharged using a cartridge gun. Subsequently, the paper tube cartridge was removed from the cartridge gun, and the cartridge gun was left on the desk so that the nozzle of the paper tube cartridge faced upward. Then, after 1 hour had passed after standing, the amount of the composition discharged (naturally) from the tip of the nozzle was measured. A composition having a discharge amount of 1 g or less was evaluated as “◯”, and a composition exceeding 1 g was evaluated as “x”. The results are shown in Table 7.

(7) Mixability For the obtained sealing material, the mass of the first and second liquids was adjusted to 6 L at a ratio shown in Tables 4 and 5 under an atmosphere of 40 ° C. and RH 75%, and the diameter was 229 mm. In the metal round can, the second liquid, the first liquid, and the pigment (3 g with respect to the second liquid 100 g) are put in this order, and with a dedicated stirrer (lightweight type MIKISTA, manufactured by MIKISTA KOGYO), using a mountain-shaped paddle, Stir for 15 minutes. Thereafter, the sealing material was smoothed on a glass plate with a metal spatula to a thickness of about 5 mm, and the mixed state was visually observed. And, the case where it becomes uniform after 3 minutes from the start of stirring is evaluated as “◯”, the case where it becomes uniform after 5 minutes from the start of stirring is evaluated as “△”, and even after 5 minutes from the start of stirring, The case of being in a fooled state or mottled state was evaluated as “x”. In addition, a dull state means that the spherical poor mixing part has generate | occur | produced, and a mottled state means the color spot state which is not fully mixed. The results are shown in Table 7.

(8) Non-sagging FIG. 1A is a schematic overall view of an aluminum channel 1 used for evaluating the non-sagging of a sealing material, where x is 20 mm, y is 25 mm, and L is 1000 mm. . The back surface and the bottom of the aluminum channel 1 were loaded with foamed polyethylene backup materials 2 and 3 having the same width as the joint width and thicknesses of 3 mm and 10 mm, respectively, as shown in FIG. The sealing material according to the comparative example was placed using a caulking gun. The sealing material was filled into the aluminum channel 1 and finished using a spatula, and then suspended vertically in an oven at 50 ° C. FIG. 1 (B) is a diagram showing a state after the aluminum channel 1 after filling and placing the sealing material is suspended vertically in an oven at 50 ° C. and the sealing material is cured.

  2 is an SS cross-sectional view of the aluminum channel 1 shown in FIG. In particular, FIG. 2A is a diagram showing a state before the sealing material is filled into the aluminum channel 1, and FIG. 2B is a diagram of the aluminum channel 1 after the sealing material is filled. It is a figure which shows the state after hanging vertically in 50 degreeC oven and sealing material hardened | cured.

  Evaluation of non-sagging was performed by measuring the sagging amount after curing the sealing material by measuring the maximum bulging amount a (mm) in the hatched area A shown in FIG. The case where a (mm) is less than 0.5 mm is evaluated as “◯”, the case where it is 0.5 to 2.0 mm is evaluated as “Δ”, and the case where it is 2.0 mm or more is indicated as “×”. evaluated. The results are shown in Table 7.

In Table 7, M50, M100, TB and EB are as follows.
M50: Tensile stress at 50% elongation (N / mm ² )
M100: Tensile stress at 100% elongation (N / mm ² )
TB: Tensile stress at break (N / mm ² )
EB: Elongation at break (%)

According to the example, the first liquid contains a urethane prepolymer, at least one of the first liquid and the second liquid contains polyaldimine, and the second liquid has a density of 1.10 g / cm ³ or less. Yes, the thixotropy index is 2.9 or higher. As a result, the sealing material composition obtained by mixing the first liquid and the second liquid has sufficient durability and tensile properties despite the low specific gravity of the cured sealing material composition. Moreover, a springback can be prevented by using the sealing material composition of an Example. Moreover, according to the Example, even when the amount of the plasticizer is increased and the viscosity of the second liquid is lowered, the mixing property at a high temperature becomes good.

On the other hand, in Comparative Example 1, since the proportion of the resin-based fine hollow body having an average particle diameter of 10 μm or more and 40 μm or less is not within the range of 10% by mass or more and 20% by mass or less of the second liquid, the density of the second liquid is 1.10 g / cm ³ is exceeded. As a result, also in the sealing material composition obtained by mixing the first liquid and the second liquid, the density exceeds 1.10 g / cm ³ , and as a result, the cured sealing material composition is sufficiently low. There is a possibility that the specific gravity cannot be achieved.

  In Comparative Example 2, since the average particle diameter of the resin-based hollow body exceeds 40 μm, the thixotropy index is within an appropriate range in the sealing material composition obtained by mixing the first liquid and the second liquid. Even if this occurs, the occurrence of springback cannot be prevented appropriately. The non-sagging property was 2.0 mm or more.

  In Comparative Example 3, the surface-treated calcium carbonate is less than 80% by mass of calcium carbonate, and the thixotropy index of the second liquid is less than 2.9, so that it is obtained by mixing the first liquid and the second liquid. Also in the sealing material composition to be obtained, the thixotropy index is less than 6.1, and as a result, it may not be possible to appropriately prevent the occurrence of springback. It tends to be inferior in terms of mixing and non-sagging.

  In Comparative Example 4, since the first liquid does not contain polyaldimine, even if the specific gravity can be reduced, the durability and tensile properties can be insufficient.

1 Aluminum channel 2, 3 Backup material

Claims (3)

A first liquid containing a urethane prepolymer and a second liquid containing a polyol;
The first liquid and / or the second liquid contains polyaldimine,
The second liquid is
Containing 10% by mass or more and 20% by mass or less of a resin-based fine hollow body having an average particle size of 10 μm or more and 40 μm or less, based on the mass of the entire second liquid,
Using a No. 7 rotor of a BS viscometer, a thixotropy index calculated from the ratio of the viscosity (Pa · s) of the second liquid measured at a rotational speed of 1 rpm and 10 rpm at 23 ° C. and 50% relative humidity. The two-component curable polyurethane-based sealing material composition, wherein the viscosity of the second liquid at 1 rpm / (the viscosity of the second liquid at 10 rpm)] is 2.9 or more.   2. The two-component curable polyurethane system according to claim 1, wherein the second liquid contains 30% by mass or more of surface-treated calcium carbonate with respect to the total mass of the second liquid and 80% by mass or more of calcium carbonate. Sealant composition. Equivalent ratio (R value) of isocyanate groups contained in the urethane prepolymer with respect to the total equivalents of amino groups generated by hydrolysis of the polyaldimine and hydroxyl groups of the polyol in the second liquid [NCO / (OH + NH ₂ )] The first liquid and the second liquid were mixed so that the ratio was 1.08, and the mixture stirred for 15 minutes was subjected to a BS viscometer No. 7 rotor at 23 ° C. and 50% relative humidity. The thixotropy index of the mixture ((viscosity of the mixture at 1 rpm) / (viscosity of the mixture at 10 rpm) calculated from the ratio of the viscosity (Pa · s) of the mixture measured at a rotational speed of 1 rpm and 10 rpm) ] Is 6.1 or more, The two-component curable polyurethane-type sealing material composition of Claim 1 or 2.

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