JP6115474B2 - 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.

  Polyurethane is widely used in various applications such as architecture and automobiles. For example, it is used as a waterproof coating material for coating outer walls of buildings as a waterproofing material composition. Urethane-based waterproofing membranes are, for example, urethane-based compositions (urethane coatings) on the entire surface of a building, such as a flat surface such as a floor surface of a building and a flat surface such as a veranda or a vertical surface such as an outer wall surface of a building. It is a waterproofing material that prevents the penetration and penetration of water into the building by coating and curing the membrane waterproofing material composition).

  Conventionally, as a waterproofing material composition, a mixture of a main agent containing a urethane prepolymer and a curing agent containing a compound having an active hydrogen group has been proposed (for example, see Patent Document 1). For example, Patent Document 1 includes a main agent containing a urethane prepolymer and a compound having an active hydrogen group as a compound having an active hydrogen group in a specific diamine compound in an amount of 1% by mass or more based on the total mass of the compound having an active hydrogen group. In addition, there is described a two-component room temperature curable urethane coating waterproofing material composition having a curing agent containing 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. By using this two-component room temperature curing urethane waterproof membrane composition, a waterproof membrane composition having excellent defoaming properties can be obtained.

JP 2010-260988 A

  However, the urethane waterproof material obtained by curing the urethane composition described in Patent Document 1 seems to be exposed and exposed on the surface without allowing air from the base to enter the urethane waterproof material and be removed. Pinholes may occur and the appearance may be impaired.

  Therefore, a two-component room-temperature curable urethane coating film waterproofing material composition capable of suppressing the generation of pinholes is desired.

  In view of the above problems, an object of the present invention is to provide a two-component room temperature curable urethane coating film waterproofing material composition capable of suppressing the generation of pinholes.

The present invention is as follows (1).
(1) a main agent containing a urethane prepolymer and dimer acid;
A curing agent containing polypropylene glycol and a wetting and dispersing agent including at least one selected from the group consisting of an unsaturated polycarboxylic acid polymer solution and an alkylammonium salt solution of polycarboxylic acid ,
The content of the dimer acid is 0.15 parts by mass or more with respect to 100 parts by mass of the urethane prepolymer,
Content of the said wet dispersing agent is 0.15 mass part or more with respect to 100 mass parts of said urethane prepolymers, The two-component room temperature curing type urethane coating waterproof material composition characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the urethane coating-film waterproof material composition which can suppress generation | occurrence | production of a pinhole can be obtained.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The two-component room temperature curable urethane coating film waterproofing material composition (hereinafter referred to as “the composition of the present embodiment”) according to the present embodiment includes a main agent containing a urethane prepolymer and dimer acid, polypropylene glycol, and wet. A curing agent containing a dispersant, the content of the dimer acid is 0.15 parts by mass or more with respect to 100 parts by mass of the urethane prepolymer, and the content of the wet dispersant is the urethane prepolymer 100. It is a composition characterized by being 0.15 parts by mass or more with respect to parts by mass.

<Main agent>
The main agent used for the composition of this embodiment contains a urethane prepolymer and a dimer acid.

[Urethane prepolymer]
The urethane prepolymer contained in the main agent is not particularly limited. For example, a conventionally well-known thing is mentioned. Specifically, 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 can be mentioned. The urethane prepolymer can contain 0.5% by mass or more and 5% by mass or less of NCO groups at the molecular ends.

(Polyol compound)
A polyol compound is a general term for polyhydroxyl compounds having a structure in which a plurality of hydrogen atoms in a hydrocarbon are substituted with hydroxyl groups. 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. For example, polyether polyol, polyester polyol, other polyols, and mixed polyols thereof can be used.

  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, 1,4 -Polyol 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 butanediol and pentaerythritol. .

  As the polyester polyol, for example, at least one selected from the group consisting of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin, 1,1,1-trimethylolpropane and other low molecular polyols, and glutar A condensation polymer with at least one selected from the group consisting of acids, adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid, other aliphatic carboxylic acids and oligomeric acids; ring-opening weight of propionlactone, valerolactone Coalescence is mentioned.

  Other polyols include, for example, polymer polyols, polycarbonate polyols; polybutadiene polyols; hydrogenated polybutadiene polyols; acrylic polyols; A molecular weight polyol may be mentioned.

  A polyol compound can be used individually or in combination of 2 types or more, respectively.

(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. 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 diisocyanate (XDI), tetra Aromatic polyisocyanates such as methylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene diisocyanate (H DI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), aliphatic polyisocyanates such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate; transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI) ), Alicyclic polyisocyanates such as bis (isocyanatomethyl) cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); these carbodiimide-modified polyisocyanates; and these isocyanurate-modified polyisocyanates.

  A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  Examples of the combination of the polyol compound and the polyisocyanate compound include at least one selected from the group consisting of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI), polypropylene ether diol, and / or A combination with polypropylene ether triol is mentioned.

  The amount of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer is such that the equivalent ratio of isocyanate group to hydroxyl group (isocyanate group (NCO group) / hydroxyl group (OH group)) is 1.2 or more. 0.5 or less is preferable, and 1.5 or more and 2.0 or less is more preferable. The equivalent ratio refers to the ratio of isocyanate groups in the polyisocyanate compound per hydroxyl group in the polyol compound. When the equivalence ratio is in such a range, the viscosity of the obtained urethane prepolymer becomes appropriate, and the composition becomes more difficult to foam.

  The number average molecular weight of the urethane prepolymer is 2000 or more, preferably 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.

  The method for producing the urethane prepolymer is not particularly limited. The urethane prepolymer can be produced by reacting the polyol compound and the polyisocyanate compound having the above-described equivalent ratio with heating and stirring at 50 ° C to 130 ° C. Further, if necessary, for example, a urethanization catalyst such as an organic tin compound, an organic bismuth, or an amine can be used.

  A urethane prepolymer can be used individually or in combination of 2 types or more, respectively.

[Dimer acid]
The dimer acid is not particularly limited as long as it is a polybasic carboxylic acid. Examples of the polybasic carboxylic acid include saturated dicarboxylic acid, unsaturated dicarboxylic acid, and aromatic dicarboxylic acid. Examples of the saturated dicarboxylic acid include glutaric acid, adipic acid, azelaic acid and the like. Examples of the unsaturated dicarboxylic acid include fumaric acid and maleic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and the like.

  As the dicarboxylic acid, at least one dicarboxylic acid selected from aliphatic, alicyclic and aromatic dicarboxylic acids or derivatives thereof can be used. Specific examples of the dicarboxylic acid include, for example, linear aliphatic dicarboxylic acids having 2 to 25 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. Alternatively, a dimerized aliphatic dicarboxylic acid having 14 to 48 carbon atoms (hereinafter also referred to as dimer acid) obtained by dimerizing an unsaturated fatty acid obtained by fractional distillation of triglyceride and a hydrogenated product thereof (hereinafter referred to as hydrogenated dimer). And aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Of these, dimer acid is preferably used.

  A commercial item can be used as a dimer acid. Specific examples of commercially available dimer acids include long-chain aliphatic dicarboxylic acids having 22 carbon atoms (IPU-22, manufactured by Okamura Seiyaku Co., Ltd.), long-chain aliphatic dicarboxylic acids having 20 carbon atoms (UL-). 20, Okamura Essential Oil Co., Ltd.).

  The content of the dimer acid is 0.15 parts by mass or more, preferably 0.15 parts by mass or more and 10 parts by mass or less, more preferably 0.15 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer. Or less, more preferably 0.15 parts by mass or more and 3 parts by mass or less. When the content of the dimer acid is within the above range, the composition of the present embodiment can grow bubbles of air that has entered from the base and destroy the foam film, thereby suppressing the generation of pinholes. can do.

<Curing agent>
The curing agent used in the composition of this embodiment contains polypropylene glycol and a wetting and dispersing agent.

(Polypropylene glycol)
The curing agent includes polypropylene glycol. The curing agent can contain a polyol compound other than polypropylene glycol. Polyol compounds other than polypropylene glycol have two or more hydroxy groups, and examples thereof include polyether polyols, polyester polyols, other polyols, and mixed polyols thereof. Specifically as a polyol compound, it is the same as that of the polyol compound used for the urethane prepolymer mentioned above.

(Wet dispersant)
Examples of the wetting and dispersing agent include compounds having a polar group such as a carboxyl group, a hydroxyl group, and an acid ester, and polymer compounds such as acid-containing compounds such as phosphate esters, copolymers containing acid groups, and hydroxyl group-containing polycarboxylic acids. Examples include esters, polysiloxanes, salts of long-chain polyaminoamides and acid esters.

  The wetting and dispersing agent is preferably a compound having a structure having both a hydrophilic group and a hydrophobic group in one molecule. It is preferable that each of the hydrophilic group and the hydrophobic group has at least one in one molecule.

As the hydrophilic group, eg, carboxy group, a carbonyl group, hydroxy group, amino _{group, -C (= O) O -} , - NHCONH 2, - (OCH 2 CH 2) n -, - SO 3 H, -SO 3 _{M, -OSO 3 H, -OSO 3} M, -COOM, -NR 3 X , and the like. Examples of M include alkali metals such as sodium and potassium, and —NH ₄ . Examples of R include alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of X include halogen such as chlorine atom and bromine atom.

Among them, a carboxy group, a carbonyl group, —C (═O) O—, a hydroxy group, — (OCH ₂ CH ₂ ) _n — (n = 3 to 20), —C (═O) O— (OCH ₂ CH _{2 ) n -CH 3 (n = 5~15} ) are preferred. The hydrophilic groups can be used alone or in combination of two or more.

Examples of the hydrophobic group include an alicyclic hydrocarbon group such as a chain hydrocarbon group, a cyclopentyl group, a cyclohexyl group, and a cyclohexenyl group; a phenyl group, a tolyl group, a xylyl group, a benzyl group, a styryl group, and a naphthyl group. An aromatic hydrocarbon group such as: a halogenated alkyl group such as a chloromethyl group, a chloroethyl group, or a bromomethyl group, or an organosilicon group (-SiR ₃ (R is, for example, a methyl group, an ethyl group, or a phenyl group)). Can be mentioned.

Examples of the chain hydrocarbon group include a chain saturated hydrocarbon group having 5 to 15 carbon atoms. Specifically, for _{example, -C n H 2n + 1 (n} = 10~13). The chain hydrocarbon group may be branched. Hydrophobic groups can be used alone or in combination of two or more.

  The wetting and dispersing agent is not particularly limited with respect to its skeleton. Examples of the skeleton of the compound having a hydrophilic group and a hydrophobic group include those having a carbon atom. When the compound having a hydrophilic group and a hydrophobic group is an oligomer or a polymer, examples of the skeleton (main chain) include hydrocarbons. The skeleton of the compound having a hydrophilic group and a hydrophobic group can contain a double bond.

  The wetting and dispersing agent may contain, for example, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom in the skeleton of the compound (main chain in the case of an oligomer or polymer).

  In this embodiment, the wetting and dispersing agent has an effect that dimer acid can be uniformly dispersed.

  It is preferable that the wetting and dispersing agent contains an unsaturated polycarboxylic acid polymer solution from the viewpoint that air bubbles entering from the base can be grown to break the foam film.

  Moreover, it is more preferable that the wetting and dispersing agent contains a basic group from the viewpoint that air bubbles entering from the base can be grown to break the foam film. Suitable examples of the basic group include alkyl ammonium salts. Preferable examples of the wetting and dispersing agent containing an alkyl ammonium salt include a solution of an alkyl ammonium salt of a polycarboxylic acid.

  A commercially available product can be used as the wetting and dispersing agent. Specific examples of commercially available wetting and dispersing agents include BYK-W961, BYK-W935 (manufactured by Big Chemie Japan Co., Ltd.) and the like.

  The content of the wetting and dispersing agent is 0.15 parts by mass or more, preferably 0.15 parts by mass or more and 10 parts by mass or less, more preferably 0.15 parts by mass or more with respect to 100 parts by mass of the urethane prepolymer. 5 parts by mass or less, more preferably 0.15 parts by mass or more and 1 part by mass or less. When the content of the wetting and dispersing agent is within the above range, the composition of the present embodiment can grow bubbles of air that has entered from the base and destroy the foam film, thereby suppressing the generation of pinholes. can do. Further, the content of the wetting and dispersing agent is preferably increased or decreased in proportion to the content of the dimer acid from the viewpoint of uniformly dispersing the dimer acid.

  The main agent and the curing agent contained in the composition of the present embodiment can contain various additives as necessary within a range not impairing the purpose of the present embodiment. Examples of the additive include a filler, a catalyst, a plasticizer, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion promoter, a stabilizer, a dispersant, a solvent, a pigment, and a dye. Each additive can be used in combination as appropriate. The blending amounts of these additives can be conventional conventional blending amounts as long as the object of the present embodiment is not violated.

  Examples of the filler include organic or inorganic materials having various shapes. For example, calcium carbonate, wax stone clay, kaolin clay, calcined clay; silica sand, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide Magnesium carbonate, zinc carbonate; organic or inorganic fillers such as carbon black; and these fatty acids, resin acids, fatty acid ester-treated products, and fatty acid ester urethane compound-treated products. These may be used alone or in combination of two or more.

  Examples of calcium carbonate include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate. Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Calcium carbonate may be used alone or in combination of two or more.

  Examples of the catalyst include organometallic catalysts. Examples of the organometallic catalyst include lead catalysts such as lead octenoate and lead octylate; dibutyltin dilaurate, dioctyltin laurate, zinc octylate, and organic bismuth compounds. A catalyst may be used individually by 1 type and may use 2 or more types together.

  It does not specifically limit about the manufacturing method of the composition of this embodiment. For example, a main agent containing a urethane prepolymer and dimer acid and a curing agent containing polypropylene glycol and a wetting and dispersing agent can be separately mixed and prepared under a nitrogen gas atmosphere. The composition of this embodiment can store a main ingredient and a hardening | curing agent separately in a container, and can mix and use a main ingredient and a hardening | curing agent at the time of use.

  In order to improve the adhesiveness between the coated surface and the cured product obtained by curing the composition of the present embodiment before applying the composition of the present embodiment, a primer may be used.

  Thus, the composition of this embodiment has a main agent containing a urethane prepolymer and dimer acid, and a curing agent containing polypropylene glycol and a wetting and dispersing agent, and the content of dimer acid is urethane. The composition is 0.15 parts by mass or more with respect to 100 parts by mass of the prepolymer, and the content of the wetting and dispersing agent is 0.15 parts by mass or more with respect to 100 parts by mass of the urethane prepolymer. If the composition of this embodiment is used, the bubble produced | generated by the air which approached in the composition can be grown, and the film | membrane of a bubble can be destroyed. Therefore, if the composition of this embodiment is used, since the generation | occurrence | production of a pinhole can be suppressed and it is excellent in pinhole resistance, the urethane coating-film waterproof material which does not impair an external appearance can be obtained.

  In this embodiment, the pinhole resistance refers to the presence or absence of pinholes when the urethane coating surface is visually observed. If pinholes are not confirmed on the surface of the urethane coating obtained by curing the composition of the present embodiment, or if the number of pinholes confirmed on the surface of the urethane coating is less than a predetermined number, the pinhole resistance It is excellent. Moreover, if the number of pinholes confirmed on the surface of the urethane coating film is a predetermined number or more, the pinhole resistance is inferior.

  Although the use, application conditions, etc. of the composition of this embodiment are not specifically limited, As a use, a coating material, a waterproofing material, a flooring etc. are mentioned, for example. Examples of the application surface on which the composition of the present embodiment is applied include surfaces such as concrete, mortar, metal, and a urethane coating film to which a top coat is applied. The composition of the present embodiment can be suitably used for a flat surface such as a floor surface of a building roof and a horizontal surface such as a veranda or a vertical surface such as an outer wall surface of a building.

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

<Preparation of urethane prepolymer>
100 g of polypropylene ether triol having a number average molecular weight of 4000 (G-4000, manufactured by Asahi Glass Co., Ltd.) and 150 g of polypropylene ether diol having a number average molecular weight of 2000 (D-2000, manufactured by Asahi Glass Co., Ltd.) are placed in a reaction vessel to adjust the viscosity. Therefore, 15 g of diisononyl phthalate (DINP, manufactured by J Plus Co., Ltd.) was added as a plasticizer, heated to 110 ° C., and dehydrated for 6 hours. Next, tolylene diisocyanate (Cosmonate T80, manufactured by Mitsui Takeda Chemical Co., Ltd.) was added thereto so that the equivalent ratio of NCO group / OH group was 1.98, and this was heated to 80 ° C. under a nitrogen atmosphere. The mixture was stirred and stirred for 12 hours to prepare a urethane prepolymer. The content of NCO groups in the obtained urethane prepolymer was 3.0% by mass in the total amount of the urethane prepolymer.

<Preparation of two-component room temperature curable urethane film waterproofing material composition>
Each component used as the main agent and the curing agent shown in Tables 1 to 3 below is blended in the addition amount (parts by mass) shown in Tables 1 to 3, and these are sufficiently mixed using an electric stirrer etc. Prepared. Thoroughly mix 100 parts by mass of the main agents of each Example and Comparative Examples in Tables 1 to 3 and 100 parts by mass of the curing agent of each Example and Comparative Examples of Tables 1 to 3 using an electric stirrer or the like. Thus, the two-component room temperature curable urethane coating film waterproofing material composition of each example and each comparative example was obtained.

<Evaluation>
[Evaluation of pinhole resistance]
Using the obtained two-component room temperature curable urethane coating film waterproof material composition, the pinhole resistance was evaluated as follows. The results are shown in Tables 1-3.

(Pinhole resistance)
Applying the two-component room-temperature-curing urethane coating waterproofing composition of each Example and each Comparative Example prepared above on the surface of a concrete piece (7 cm × 7 cm), conditions of 40 ° C. and 90% RH Under curing in an autoclave for 24 hours. After curing, the surface state of each cured product was visually confirmed, and pinhole resistance was evaluated based on the following evaluation criteria. The results are shown in Tables 1-3.
(Evaluation criteria)
○: The number of pinholes was confirmed to be less than 10 on the surface of the urethane coating film, or no pinholes were confirmed ×: The number of pinholes was confirmed to be 10 or more on the surface of the urethane coating film

Each component shown in Tables 1-3 is as follows.
Urethane prepolymer: trade name “U-8000A”, manufactured by Yokohama Rubber Co., Ltd. • dimer acid 1: aliphatic dicarboxylic acid, trade name “IPU-22”, manufactured by Okamura Seiyaku Co., Ltd. • dimer acid 2: aliphatic dicarboxylic acid , Trade name "UL-20", manufactured by Okamura Seiyaku Co., Ltd., heavy calcium carbonate: trade name "Super SS", manufactured by Maruo Calcium Co., Ltd., polypropylene glycol: trade name "EXCENOL 2020", manufactured by Asahi Glass Co., Ltd., catalyst: Lead catalyst, Minico P-30, manufactured by Active Materials Chemical Co., Ltd./wet dispersant 1: solution of alkylammonium salt of polycarboxylic acid, trade name “BYK-W961”, manufactured by Big Chemie Japan Co., Ltd./wet dispersant 2: Unsaturated polycarboxylic acid polymer solution, trade name “BYK-W935”, manufactured by Big Chemie Japan

  As is clear from the results shown in Tables 1 to 3, it was confirmed that each of the urethane coating film waterproof materials of Examples 1 to 22 had good pinhole resistance and excellent pinhole resistance. On the other hand, it was confirmed that each urethane-based coating film waterproof material of Comparative Examples 1 to 7 is inferior in pinhole resistance.

  Therefore, it turned out that each urethane type waterproofing membrane waterproof material of Examples 1-22 is excellent in pinhole resistance compared with each urethane type waterproofing membrane waterproofing material of Comparative Examples 1-7.

  Thus, a urethane-based coating film waterproofing having a main agent containing a urethane prepolymer and a dimer acid, a curing agent containing a polypropylene glycol and a wetting and dispersing agent, and a specific amount of the dimer acid and the wetting and dispersing agent. The material composition can be suitably used as a waterproof material that has excellent pinhole resistance and does not impair the appearance.

Claims (1)

A main agent containing a urethane prepolymer and dimer acid;
A curing agent containing polypropylene glycol and a wetting and dispersing agent including at least one selected from the group consisting of an unsaturated polycarboxylic acid polymer solution and an alkylammonium salt solution of polycarboxylic acid ,
The content of the dimer acid is 0.15 parts by mass or more with respect to 100 parts by mass of the urethane prepolymer,
Content of the said wet dispersing agent is 0.15 mass part or more with respect to 100 mass parts of said urethane prepolymers, The two-component room temperature curing type urethane coating waterproof material composition characterized by the above-mentioned.