Waterproofing material composition, waterproofing material spray composition and waterproofing material

Abstract

The present invention provides a waterproofing material composition capable of forming a coating film with excellent tensile strength and elongation at break, a waterproofing material spray composition containing the composition, and a waterproofing material. [Solution] The present invention relates to a waterproofing composition for use as a waterproofing material, wherein the waterproofing material is urethane or urea, and contains at least one component A selected from the group consisting of polyols and polyamines, a crosslinking agent, and a curing catalyst, wherein the curing catalyst contains dimethyltin dilaurate.

Description

Technical Field

[0001] The present invention relates to a composition for waterproofing materials, a spray composition for waterproofing materials, and a waterproofing material.

Background Art

[0002] Spray urethane waterproofing materials or spray urea waterproofing materials (quick-curing spray urethane waterproofing materials) can quickly cure by spray spraying onto an object to form a waterproof coating film (urethane coating film or urea coating film). Such quick-curing spray urethane waterproofing materials are widely used, for example, in waterproof applications of buildings and are extremely useful functional materials. Quick-curing spray urethane waterproofing materials are known to be formed, for example, by mixing a composition containing a polyol or polyamine component as a main component and a catalyst, and a composition having a polyisocyanate as a main component, and curing the mixed composition.

[0003] For example, Patent Document 1 discloses a two-component diphenylmethane diisocyanate-based urethane waterproofing material composition. Such a composition includes a main agent containing an isocyanate group-terminated prepolymer obtained by the reaction of diphenylmethane diisocyanate and a polyol, a curing agent containing a polyol as a reaction component, and a curing accelerator such as an imidazole compound, and is said to be suitable as an environmentally friendly waterproofing material.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, the properties of the coating film formed by applying a fast-curing spray urethane waterproofing material are greatly affected by the environment during application (e.g., temperature, humidity). In particular, the inventors have found that, for example, when the catalyst (curing catalyst) contained in the fast-curing spray urethane waterproofing material is the most common tin-based catalyst (e.g., dibutylsulata laurate, DBTDL), the tensile strength and elongation at break of the coating film are insufficient, and further decrease in high-humidity environments.

[0006] In this regard, when a lead-based catalyst is used, the coating film properties (tensile strength and elongation at break) are good, and deterioration of properties is less likely to occur even in high-humidity environments. However, lead compounds are listed as one of the hazardous metals whose concentration in water is strictly regulated by environmental standards for water quality stipulated in the Environmental Standards Law, etc. Therefore, there is a risk that hazardous metals such as lead may leach from polyurethane waterproofing materials, and the use of lead compounds is undesirable from the standpoint of water pollution. From these perspectives, there has been a strong demand for the development of a material that can form a coating film with excellent tensile strength and elongation at break, and that can be suitably used in spray compositions for waterproofing materials.

[0007] The present invention has been made in view of the above, and aims to provide a waterproofing material composition that can form a coating film with excellent tensile strength and elongation at break, a waterproofing material spray composition containing the composition, and a waterproofing material. [Means for solving the problem]

[0008] The inventors of this invention conducted extensive research to achieve the above objectives and, as a result, discovered that these objectives can be achieved by using dimethyltin dilaurate as an essential component, thus completing the present invention.

[0009] In other words, the present invention encompasses, for example, the subject matter described in the following sections. Item 1 A composition for use as a waterproofing material, The aforementioned waterproofing material is urethane or urea. At least one component A selected from the group consisting of polyols and polyamines, Crosslinking agent and Curing catalyst and It contains at least the following: The curing catalyst is a waterproofing material composition containing dimethyltin dilaurate. Section 2 The waterproofing material composition according to claim 1, wherein component A is at least one selected from the group consisting of polyether polyols, polycarbonate polyols, and polyether polyamines. Section 3 The waterproofing composition according to claim 1 or 2, wherein the crosslinking agent is at least one selected from the group consisting of aromatic primary amines, aliphatic primary amines, and aliphatic secondary amines. Section 4 A spray composition for waterproofing materials containing the waterproofing material composition described in any one of items 1 to 3 and an isocyanate composition. Section 5 A waterproofing material containing a cured product of the waterproofing spray composition described in item 4. [Effects of the Invention]

[0010] The waterproofing composition of the present invention can form a coating film with excellent tensile strength and elongation at break, and can be suitably used in waterproofing spray compositions. [Modes for carrying out the invention]

[0011] As mentioned above, when urethane or urea coatings are formed using DBTDL as a curing catalyst, such coatings have insufficient tensile strength and elongation at break, and further decrease in humid environments. On the other hand, in order to form urethane or urea coatings, it is necessary to use a metal catalyst as a curing catalyst, and among them, tin-based catalysts are indispensable because they offer a good balance between curability and the physical properties of the coating.

[0012] From this perspective, the inventors have diligently studied and have succeeded in completing a waterproofing material composition that can form a coating film with excellent tensile strength and elongation at break, even when using a tin catalyst. Embodiments of the present invention will be described in detail below.

[0013] In this specification, the expressions "contains" and "include" include the concepts of "contains," "includes," "substantially consists of," and "consists solely of."

[0014] Furthermore, in the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Also, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0015] 1. Composition for waterproofing materials The waterproofing material composition of the present invention is for use as a waterproofing material, wherein the waterproofing material is urethane or urea and contains at least one component A selected from the group consisting of polyols and polyamines, a crosslinking agent, and a curing catalyst, wherein the curing catalyst contains dimethyltin dilaurate.

[0016] Using the waterproofing composition of the present invention, for example, a waterproofing spray composition can be prepared by mixing it with the polyisocyanate composition described later, and a waterproof coating can be formed by curing this composition. The waterproofing composition of the present invention can form a coating with excellent tensile strength and elongation at break, and is suitable for use in waterproofing spray compositions. The coating formed from the waterproofing composition of the present invention is urethane or urea, and therefore, the waterproofing composition can form a urethane waterproofing material or a urea waterproofing material.

[0017] (Component A; Polyol) The composition for waterproofing materials of the present invention contains Component A as an essential constituent. As described above, Component A is at least one selected from the group consisting of polyols and polyamines.

[0018] As long as the polyol is a compound having at least two or more hydroxyl groups in the molecule, for example, known polyols can also be widely used in the present invention. The polyol may be a polymer.

[0019] The polyol preferably has two or three hydroxyl groups, that is, it is preferably a bifunctional or trifunctional polyol. In this case, the coating film obtained from the composition for waterproofing materials of the present invention is more likely to have higher tensile strength and elongation at break, and even when the coating film is formed in a high-humidity environment, such a coating film can have excellent tensile strength and elongation at break.

[0020] Specific examples of the polyol include polyether polyol, polycarbonate polyol, polyester polyol, polylactone polyol, polybutadiene polyol, polymer polyol, Mannich polyol, and the like.

[0021] Among them, the polyol is preferably at least one selected from the group consisting of polyether polyol and polycarbonate polyol. In this case, the coating film obtained from the composition for waterproofing materials of the present invention is more likely to have higher tensile strength and elongation at break, and even when the coating film is formed in a high-humidity environment, such a coating film can have excellent tensile strength and elongation at break. The polyol particularly preferably contains polyether polyol.

[0022] As a polyether polyol, polyoxyalkylene polyol is cited as a representative example. The polyoxyalkylene polyol can be produced by subjecting a compound having two or more hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups as starting materials to a ring-opening addition reaction of an alkylene oxide.

[0023] The starting materials for the polyoxyalkylene polyols mentioned above include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, mannose, sucrose, fructose, dextrose, and sorbitol; alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and methyldiethanolamine; polyhydric amines such as ethylenediamine, tolylenediamine, diethyltoluenediamine, 1,3-propanediamine, 1,6-hexanediamine, isophoronediamine, diethylenetriamine, and triethylenepentaamine; polyhydric phenols such as bisphenol A, bisphenol F, resorcinol, and hydroquinone; Mannich bases (formed by condensation reactions of phenols, aldehydes, alkanolamines, etc.); and modified versions thereof. These starting materials may be used individually or in combination of two or more.

[0024] Examples of the alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and styrene oxide. These alkylene oxides may be used individually or in combination of two or more types.

[0025] Suitable examples of polyether polyols include (di)ethylene glycol-based polyether polyols, (di)propylene glycol-based polyether polyols, (di)glycerin-based polyether polyols, trimethylolpropane-based polyether polyols, pentaerythritol-based polyether polyols, sucrose-based polyether polyols, dextrose-based polyether polyols, sorbitol-based polyether polyols, mono(di,tri)ethanolamine-based polyether polyols, ethylenediamine-based polyether polyols, tolylenediamine-based polyether polyols, bisphenol A-based polyether polyols, and other polyoxyalkylene-based polyols, polymer polyols in which polymer fine particles are dispersed in polyoxyalkylene-based polyols, and Mannich polyols.

[0026] The aforementioned polymer polyol is a type of polyether polyol because it contains a polyoxyalkylene polyol. The Mannich polyol can be produced by condensing phenols, aldehydes, alkanolamines, etc., and further by ring-opening addition reactions of alkylene oxides such as ethylene oxide and propylene oxide as needed. Since the Mannich polyol has multiple ether bonds in its molecule, it is a type of polyether polyol.

[0027] Examples of polycarbonate polyols include hexanediol polycarbonate, butanediol polycarbonate, neopentyl glycol polycarbonate, 3-methylpentanediol polycarbonate, and one or more copolymers of the above polycarbonates.

[0028] Polyols can be manufactured, for example, by known methods, or they can be obtained from commercially available products.

[0029] The number-average molecular weight of the polyol is not particularly limited and can be, for example, 500 or more and 10,000 or less, preferably 800 or more, more preferably 1,000 or more, and also preferably 8,000 or less, more preferably 6,000 or less. In this specification, the number-average molecular weight of the polyol refers to the number-average molecular weight on a polystyrene basis, measured by gel permeation chromatography.

[0030] The hydroxyl value of the polyol is not particularly limited, but is preferably 15 mg KOH / g or more, more preferably 18 mg KOH / g or more, preferably 120 mg KOH / g or less, more preferably 115 mg KOH / g or less, and even more preferably 112 mg KOH / g or less. In this specification, the hydroxyl value is the number of mg of potassium hydroxide required to neutralize the free hydroxyl groups in 1 g of the sample (polyol) after completely acetylating them with acetic anhydride, and the value measured in accordance with JIS K 1557 (2007). Specifically, the hydroxyl value is calculated by acetylating the hydroxyl groups in the sample with acetic anhydride, titrating the acetic anhydride that did not participate in acetylation with a potassium hydroxide ethanol solution, and then formulating the result as follows: Hydroxyl value [mgKOH / g] = [((AB) × c × 56.1) / S] + Acid value (Here, A is the volume (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, B is the volume (mL) of 0.5 mol / L potassium hydroxide ethanol solution used for the titration, c is the concentration (mol / L) of the sodium hydroxide solution, and S is the sample volume (g).) It is determined by [method].

[0031] The average number of functional groups (f) of a polyol is, for example, 2 to 8, preferably 2 to 6, and more preferably 2 to 4. In this specification, the average number of functional groups (f) refers to the number of functional groups per molecule, in particular the number of hydroxyl groups per molecule. The average number of functional groups can be controlled by the number of functional groups of the initiator used during synthesis. The average number of functional groups (f) can be calculated from the hydroxyl value (OHV) and number-average molecular weight (Mn) of the polyol using the following formula Average number of functional groups (f)=Mn(g / mol)×OHV(mgKOH / g) / 56100 It is determined by [method].

[0032] The polyol contained in component A may be one type or two or more types.

[0033] (Component A: Polyamine) As long as the polyamine is a compound having at least two or more amino groups in its molecule, for example, known polyamines can be widely used in this invention. The polyol may be a polymer.

[0034] The polyamine preferably has two or three amino groups, that is, it is preferably a bifunctional or trifunctional polyamine. In this case, the coating film obtained from the waterproofing composition of the present invention tends to have higher tensile strength and elongation at break, and even when the coating film is formed in a high-humidity environment, such a coating film can have excellent tensile strength and elongation at break.

[0035] Examples of polyamines include polyetheramines and polyoxyalkyleneamines. Specifically, examples include polyoxyethylenediamine, polyoxypropylenediamine, methoxypoly(oxyethylene / oxypropylene)-2-propylamine, triethylene glycoldiamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine. Examples of polyamines include JEFFAMINED-2000, D-4000, and T-5000 from HUNTSMAN.

[0036] The number-average molecular weight of the polyamine is not particularly limited and can be, for example, 500 or more and 10,000 or less, preferably 800 or more, more preferably 1,000 or more, and also preferably 8,000 or less, more preferably 6,000 or less. In this specification, the number-average molecular weight of the polyamine refers to the number-average molecular weight on a polystyrene basis, measured by gel permeation chromatography.

[0037] Polyamines can be manufactured, for example, by known methods, or they can be obtained from commercially available products.

[0038] The polyamine contained in component A may be one type or two or more types.

[0039] (Component A) Component A is at least one selected from the group consisting of polyols and polyamines, as described above, and among these, component A is preferably at least one selected from the group consisting of polyether polyols, polycarbonate polyols, and polyether polyamines. In this case, the coating film obtained from the waterproofing material composition of the present invention tends to have higher tensile strength and elongation at break, and even when the coating film is formed in a high-humidity environment, such a coating film can have excellent tensile strength and elongation at break.

[0040] A more preferred component A is a polyol, and a further preferred component A is at least one selected from the group consisting of polyether polyols and polycarbonate polyols, with a particularly preferred polyol being a polyether polyol.

[0041] If component A is a polyol, a urethane coating film is formed by mixing it with the isocyanate composition described later and curing it. If component A is a polyamine, a urea coating film is formed by mixing it with the isocyanate composition described later and curing it.

[0042] Component A is preferably present in the waterproofing material composition of the present invention in an amount of 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0043] (Crosslinking agent) The waterproofing material composition of the present invention contains a crosslinking agent as an essential component. The type of crosslinking agent is not particularly limited, and known crosslinking agents used to form urethane coatings or urea coatings can be broadly mentioned in the present invention, for example.

[0044] The crosslinking agent has a molecular weight of less than 500, preferably 400 or less, more preferably 300 or less, even more preferably 250 or less, and particularly preferably 200 or less.

[0045] In particular, the crosslinking agent is preferably at least one selected from the group consisting of aromatic primary amines, aliphatic primary amines, and aliphatic secondary amines. In this case, the coating film obtained from the waterproofing material composition of the present invention tends to have higher tensile strength and elongation at break, and even when the coating film is formed in a high-humidity environment, such a coating film can have excellent tensile strength and elongation at break.

[0046] Examples of aromatic primary amines include 3,5-diethyl-2,4 (or 2,6)-diaminotoluene (also known as diethyltoluenediamine), 2-chloro-p-phenylenediamine, 3,5-dimethylthio-2,4 (or 2,6)-diaminotoluene, 1-trifluoromethyl-3,5-diaminobenzene, 1-trifluoromethyl-4-chloro-3,5-diaminobenzene, 2,4-toluenediamine, 2,6-toluenediamine, and 4,4-diaminodiphenylmethane.

[0047] Examples of aliphatic primary amines include ethylenediamine, m-xylenediamine, 1,4-diaminohexane, butylamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, and ethanolamine.

[0048] Examples of aliphatic secondary amines include N-methylethanolamine, diethanolamine, and diisopropanolamine.

[0049] Other crosslinking agents include aromatic secondary amines such as bis(3,5-dimethyl-4-aminophenyl)methane; and alicyclic amine compounds such as cycloalkanes having two or more amino groups and / or aminoalkyl groups, such as 1,3-bis(aminomethyl)cyclohexane and isophoronediamine.

[0050] Further examples of crosslinking agents include compounds having at least two hydroxyl groups. Specific examples of such crosslinking agents include ethylene glycol, polyethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, sorbitol, and erythritol.

[0051] The crosslinking agent is more preferably an aromatic primary amine, and more preferably a diethyltoluenediamine. In these cases, the coating obtained from the waterproofing composition of the present invention tends to have particularly high tensile strength and elongation at break, and even when the coating is formed in a high-humidity environment, such a coating can have particularly excellent tensile strength and elongation at break.

[0052] The crosslinking agent preferably contains 50% by mass of an aromatic primary amine, more preferably 70% by mass, even more preferably 75% by mass, and particularly preferably 80% by mass. The crosslinking agent may consist solely of an aromatic primary amine.

[0053] The crosslinking agent may be used alone, or two or more may be used in combination.

[0054] The crosslinking agent content is not particularly limited. For example, the crosslinking agent content is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 18 parts by mass or more, per 100 parts by mass of the total amount of component A, the crosslinking agent and the curing catalyst.

[0055] (curing catalyst) The waterproofing material composition of the present invention contains dimethyltin dilaurate as an essential component as a curing catalyst. The inclusion of dimethyltin dilaurate in the waterproofing material composition of the present invention makes it easier to obtain coatings with higher tensile strength and elongation at break. Furthermore, even when the coating is formed in a high-humidity environment, such a coating can exhibit excellent tensile strength and elongation at break.

[0056] If the waterproofing composition of the present invention does not contain dimethyltin dilaurate, the coating film obtained from the waterproofing composition of the present invention will have reduced tensile strength and elongation at break, and in particular, the tensile strength and elongation at break will be significantly reduced when the coating film is formed in a high-humidity environment.

[0057] The curing catalyst may contain other curing catalysts as long as it contains dimethyltin dilaurate. Other curing catalysts include amine catalysts, metal catalysts, or mixtures thereof. Amine catalysts can be any one or more compounds containing an amino group and exhibiting the above-mentioned catalytic activity. Such amine catalysts may be essentially linear, branched, or cyclic non-aromatic or aromatic. The amine catalyst may also be a primary amine, secondary amine, or tertiary amine, but is preferably a tertiary amine. More specifically, amine catalysts include aliphatic amines, cyclic amines, ether diamines, hydroxyl group-containing amines, etc. A more preferred amine catalyst is 1,4-diazabicyclo[2.2.2]octane (DABCO33LV®). As for metal catalysts, from the viewpoint of promoting urethane formation and urea formation reactions, examples include tin, antimony, lead, bismuth, cobalt, iron, etc., but tin is more preferred. The metal catalyst may be either an inorganic metal catalyst or an organometallic catalyst, but is preferably an organometallic catalyst.

[0058] The dimethyltin dilaurate content is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, and preferably 11 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or more, per 100 parts by mass of the total amount of component A, the crosslinking agent and the curing catalyst.

[0059] The curing catalyst preferably contains 1% by mass or more of dimethyltin dilaurate, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more. The curing catalyst may consist solely of dimethyltin dilaurate. If the curing catalyst contains a catalyst other than dimethyltin dilaurate, such a catalyst is preferably an amine catalyst, and more preferably 1,4-diazabicyclo[2.2.2]octane.

[0060] Curing catalysts such as dimethyltin dilaurate can be manufactured by known methods, or they can be obtained from commercially available products.

[0061] (Composition for waterproof materials) As described above, the waterproofing material composition of the present invention contains component A, a crosslinking agent, and dimethyltin dilaurate as a curing catalyst.

[0062] The waterproofing composition of the present invention may contain other components as long as it contains component A, a crosslinking agent, and dimethyltin dilaurate. Furthermore, the waterproofing composition of the present invention may be diluted with a solvent or the like.

[0063] Alternatively, the waterproofing material composition of the present invention may consist only of component A, a crosslinking agent, and a curing catalyst containing dimethyltin dilaurate, or the waterproofing material composition of the present invention may consist only of component A, a crosslinking agent, and dimethyltin dilaurate.

[0064] The method for preparing the waterproofing material composition of the present invention is not particularly limited. For example, the waterproofing material composition of the present invention can be prepared by mixing component A, a crosslinking agent, and a curing catalyst containing dimethyltin dilaurate in predetermined proportions. The mixing method is also not particularly limited, and known mixing methods can be used, for example.

[0065] As described below, the waterproofing composition of the present invention can be combined with an isocyanate composition to form a waterproofing spray composition, and a coating film can be formed by curing such a waterproofing spray composition. As described above, when component A in the waterproofing composition of the present invention is a polyol, a urethane coating film is formed when the waterproofing composition of the present invention and the isocyanate composition are cured. When component A is a polyamine, a urea coating film is formed when the waterproofing composition of the present invention and the isocyanate composition are cured. In other words, when component A in the waterproofing composition of the present invention is a polyol, a urethane waterproofing material (more precisely, a polyurethane waterproofing material) can be formed, and when component A in the waterproofing composition of the present invention is a polyamine, a urea waterproofing material (more precisely, a polyurea waterproofing material) can be formed.

[0066] (Waterproofing spray composition) The waterproofing spray composition contains the waterproofing composition of the present invention described above and an isocyanate composition.

[0067] The isocyanate composition contains polyisocyanate as an essential component. Polyisocyanate is a compound having two or more isocyanate groups. Preferably, the polyisocyanate is a compound having two isocyanate groups.

[0068] The type of polyisocyanate is not particularly limited, and examples include aliphatic, alicyclic, aromatic, or aromaticaliphatic polyisocyanates.

[0069] Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0070] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0071] Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0072] The polyisocyanate may be a modified polyisocyanate, and examples include polyisocyanates having structures such as uretdione, isocyanurate, urethane, urea, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione, and oxazolidone. Alternatively, the polyisocyanate may be an isocyanate group-containing prepolymer obtained by reacting a polyol with a polyisocyanate.

[0073] The polyisocyanate is more preferably tolylene diisocyanate, diphenylmethane diisocyanate, etc. The tolylene diisocyanate may be 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or a mixture thereof.

[0074] The viscosity of the polyisocyanate at 25°C is preferably 100 to 3000 mPa·s. The method for adjusting the viscosity of the polyisocyanate is not particularly limited, and the viscosity can be adjusted by methods similar to those known.

[0075] Polyisocyanates can be manufactured by known methods or obtained from the market. Examples of commercially available polyisocyanates include SBU-Isocyanate-0620 (manufactured by Sumika Covestro Urethane Co., Ltd.).

[0076] The polyisocyanate contained in the isocyanate composition may be one type or two or more types.

[0077] The isocyanate composition may contain other components besides the polyisocyanate, or it may consist solely of polyisocyanate.

[0078] A spray composition for waterproofing materials may contain other components as long as it contains a waterproofing material composition and an isocyanate composition. Other components include additives such as anti-settlement agents, anti-foaming agents, antioxidants, UV absorbers, light stabilizers, plasticizers, flame retardants, water repellents, antibacterial agents, antifungal agents, pigments, and dyes.

[0079] The waterproofing spray composition of the present invention has an isocyanate index of, for example, 110 or more and 150 or less. By having an isocyanate index within this range, the waterproofing spray composition can form a coating film with particularly high tensile strength and elongation at break, and even a coating film formed in a high-humidity environment can have excellent tensile strength and elongation at break. The isocyanate index is preferably 115 or more, more preferably 120 or more, preferably 145 or less, and more preferably 140 or less.

[0080] The isocyanate index refers to the value obtained by multiplying the ratio of isocyanate groups in the polyisocyanate component to the total amount of active hydrogen reacting with isocyanate groups in the waterproofing spray composition by 100. The active hydrogen reacting with isocyanate groups in the waterproofing spray composition is based, for example, on component A and the crosslinking agent contained in the waterproofing spray composition.

[0081] The waterproofing spray composition of the present invention may contain other components as long as it includes the waterproofing composition and the isocyanate composition. The waterproofing spray composition may consist only of the waterproofing composition and polyisocyanate. In this invention, since components other than polyisocyanate can be considered to constitute the waterproofing composition, it is preferable that the composition consists only of the waterproofing composition and polyisocyanate.

[0082] In the waterproofing spray composition of the present invention, the ratio of the total number of moles of hydroxyl groups to the total number of moles of isocyanate groups, i.e., the OH / NCO value, can be in the range of 0.5 to 2, preferably 0.8 to 1.5, more preferably 0.85 to 1.1, and even more preferably 0.9 to 1.0.

[0083] The method for preparing the waterproofing spray composition of the present invention is not particularly limited. For example, the waterproofing spray composition of the present invention can be prepared by mixing the waterproofing composition and the isocyanate composition in predetermined proportions.

[0084] The method for forming the coating film (urethane coating film or urea coating film) is not particularly limited, and known methods can be widely employed. For example, a waterproofing spray composition can be prepared by mixing a waterproofing material composition and an isocyanate composition at a predetermined temperature, and such waterproofing spray composition can be applied to an object by spraying to form a film, and such film can be cured to form a coating film. The resulting coating film is a urethane coating film or a urea coating film, and such coating film can be used as a waterproofing material.

[0085] There are no particular restrictions on the temperature when mixing the waterproofing material composition and the isocyanate composition. For example, it is 20°C or higher and 100°C or lower, preferably 30°C or higher and 90°C or lower, and more preferably 40°C or higher and 80°C or lower.

[0086] There are no particular restrictions on the mixing ratio of the waterproofing material composition and the isocyanate composition. For example, it can be adjusted to an appropriate range so as to fall within the aforementioned isocyanate index range or within the OH / NCO range. There are also no particular restrictions on the method of mixing the waterproofing material composition and the isocyanate composition. Mixing can be carried out using known mixing methods, such as a two-component cartridge-type simple mixer.

[0087] The method for spraying the waterproofing material composition is not particularly limited; for example, conventional spraying methods can be broadly cited, and an air-powered spray gun can be used.

[0088] The waterproofing material (coating film) formed in this manner contains the cured product of the waterproofing spray composition, and therefore exhibits excellent tensile strength and elongation at break. Furthermore, even when the waterproofing material is formed in a high-humidity environment, such a waterproofing material will still exhibit excellent tensile strength and elongation at break. For this reason, the waterproofing spray composition can be suitably used for fast-curing spray urethane waterproofing materials and the like.

[0089] In identifying the inventions contained herein, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. That is, this disclosure encompasses all subject matter consisting of any combination of the combinatable components described herein. [Examples]

[0090] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0091] To produce the waterproofing compositions and coating films of the examples and comparative examples, the following raw materials (polyol, crosslinking agent, curing catalyst, polyisocyanate) were prepared and selected as appropriate.

[0092] (Polyol; component A) SBU Polyol 0320; manufactured by Sumika Covestro Co., Ltd., polyether polyol, average number of functional groups (f) = 2, hydroxyl value = 28 mg KOH / g, number average molecular weight = 4000

[0093] (Crosslinking agent) • Diethyltoluenediamine (DETDA) • Ethylene glycol (EG)

[0094] (curing catalyst) • Dimethyltin dilaurate: FOMREZ UL-28 (registered trademark), Momentive Performance Materials Inc. • Dibutyltin dilaurate: FOMREZ SUL-4 (registered trademark), Momentive Performance Materials Inc. • Dioctyl tin dilaurate: FOMREZ UL-59 (registered trademark), Momentive Performance Materials Inc. • Dimethyltin dimercaptide: FOMREZ UL-22 (registered trademark), Momentive Performance Materials • Dimethyltin diisooctyl mercaptoacetate: FOMREZ UL-54 (registered trademark) Momentive Performance Materials • DABCO33LV: 33% triethylenediamine (dipropylene glycol solution)

[0095] (Polyisocyanate) SBU-Isocyanate-0620: Manufactured by Sumika Covestro Co., Ltd., an MDI prepolymer of monomeric MDI and long-chain polyether polyol, NCO%: 10.0, viscosity: 2500 mPa·s / 25℃

[0096] Preparation of waterproofing material compositions (Example 1) A waterproofing material composition was prepared according to the formulation table shown in Table 1. Specifically, 83.5 parts by mass of polyether polyol (SBU polyol 0320) as component A, 16 parts by mass of diethyltoluenediamine (DETDA) as a crosslinking agent, and 0.5 parts by mass of dimethyltin dilaurate as a curing catalyst were mixed to obtain the waterproofing material composition.

[0097] (Examples 2-4) A waterproofing material composition was obtained in the same manner as in Example 1, except that the types and amounts of each raw material used were changed as shown in Table 1.

[0098] (Comparative Examples 1-4) A waterproofing material composition was obtained in the same manner as in Example 1, except that the types and amounts of each raw material used were changed as shown in Table 1.

[0099] (Examples 5-8) A waterproofing material composition was obtained in the same manner as in Example 1, except that the types and amounts of each raw material used were changed as shown in Table 2.

[0100] (Comparative Example 5) A waterproofing material composition was obtained in the same manner as in Example 1, except that the types and amounts of each raw material used were changed as shown in Table 2.

[0101] Preparation of coating film (Preparation Example 1) The waterproofing material composition prepared in Example 1 and the isocyanate composition consisting of polyisocyanate (SBU-Isocyanate-0620) were heated to 65°C and added to a two-component cartridge-type simple mixer. The amounts of the waterproofing material composition and the isocyanate composition added were determined so that the OH / NCO (ratio of total moles of hydroxyl groups to total moles of isocyanate groups) was 100 / 105.1 and the isocyanate index was 113. Next, under conditions of 23.6°C and 41% RH, a static mixer was attached to the two-component cartridge-type simple mixer, and the waterproofing material spray composition (a mixture of the waterproofing material composition and the isocyanate composition) was sprayed onto a metal formwork to a thickness of approximately 2 mm using an air-powered spray gun. After that, a coating film was obtained by curing for one week. A coating film was also obtained by performing the same procedure under conditions of 27°C and 87% RH (high humidity conditions).

[0102] (Preparation Example 2) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 2, the temperature and humidity during film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0103] (Preparation Example 3) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 3, the temperature and humidity during film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1. A coating film was then obtained in the same manner as in Preparation Example 1, except that the waterproofing material composition prepared in Example 3 was used instead, the temperature and humidity during film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1.

[0104] (Preparation Example 4) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 2, the temperature and humidity during film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0105] (Comparative preparation example 1) A coating film was obtained in the same manner as in Preparation Example 1, except that the waterproofing material composition prepared in Comparative Example 1 was replaced with the waterproofing material composition prepared in Comparative Example 1, the temperature and humidity during coating film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1.

[0106] (Comparative preparation example 2) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Comparative Example 2, the temperature and humidity during film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0107] (Comparative preparation example 3) A coating film was obtained in the same manner as in Preparation Example 1, except that the waterproofing material composition prepared in Comparative Example 3 was used instead of the waterproofing material composition prepared in Example 1, the temperature and humidity during coating film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1.

[0108] (Comparative preparation example 4) A coating film was obtained in the same manner as in Preparation Example 1, except that the waterproofing material composition prepared in Comparative Example 4 was used instead of the waterproofing material composition prepared in Example 1, the temperature and humidity during coating film formation were changed to those shown in Table 1, and the OH / NCO and isocyanate indices were adjusted as shown in Table 1.

[0109] (Preparation Example 5) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 5, the temperature and humidity during film formation were changed to those shown in Table 2, and the OH / NCO and isocyanate indices were adjusted as shown in Table 2, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0110] (Preparation Example 6) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 6, the temperature and humidity during film formation were changed to those shown in Table 2, and the OH / NCO and isocyanate indices were adjusted as shown in Table 2, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0111] (Preparation Example 7) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 7, the temperature and humidity during film formation were changed to those shown in Table 2, and the OH / NCO and isocyanate indices were adjusted as shown in Table 2, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0112] (Preparation Example 8) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Example 8, the temperature and humidity during film formation were changed to those shown in Table 2, and the OH / NCO and isocyanate indices were adjusted as shown in Table 2, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0113] (Comparative preparation example 5) The waterproofing material composition prepared in Example 1 was replaced with the waterproofing material composition prepared in Comparative Example 5, the temperature and humidity during film formation were changed to those shown in Table 2, and the OH / NCO and isocyanate indices were adjusted as shown in Table 2, except that the coating film was obtained in the same manner as in Preparation Example 1.

[0114] Evaluation of coating film properties (Tensile strength and elongation) The tensile strength and elongation of the coating film were measured in accordance with the measurement method for urethane rubber-based waterproof coatings for buildings specified in JIS A6021. The measuring instrument used was a SHIMADZU Autograph AGXplus.

[0115] For Preparation Examples 1-4 and Comparative Preparation Examples 1-4, there are two types of coating films (coating films prepared under two different temperature and humidity environments), and the measurement results of the tensile strength and elongation of each coating film are shown in Table 1. In other words, the physical properties of the coating film prepared under a high-humidity environment are also shown in Table 1.

[0116] Tables 1 and 2 show the formulation conditions for the waterproofing compositions prepared in each example and comparative example, as well as the composition and physical properties (tensile strength and elongation) of the coating films obtained in each preparation example. The numbers in parentheses in the "Preparation Example" column indicate the example number or comparative example number of the waterproofing composition used.

[0117] From Tables 1 and 2, it was found that the waterproof coating obtained using the waterproofing material composition containing component A (polyol), a crosslinking agent, and dimethyltin dilaurate as a curing catalyst (the waterproofing material composition of the examples) exhibited excellent tensile strength and elongation at break. Furthermore, from Table 1, it was found that the waterproof coating obtained using the waterproofing material composition obtained in the examples exhibited excellent tensile strength and elongation at break even when manufactured in a high-humidity environment. According to JIS standards, the tensile strength of the coating film must be 10 MPa or more for the high-strength type and 2.3 MPa or more for the high-elongation type, and the elongation rate must be 200% or more for the high-strength type and 450% or more for the high-elongation type. The waterproof coating produced using the waterproofing material composition obtained in the examples met both the high-strength and high-elongation standards.

[0118] [Table 1]

[0119] [Table 2]

Claims

1. A composition for use as a waterproofing material, The aforementioned waterproofing material is urethane or urea. At least one component A selected from the group consisting of polyols and polyamines, Crosslinking agent and Curing catalyst and It contains at least the following: The curing catalyst is a waterproofing material composition containing dimethyltin dilaurate.

2. The waterproofing material composition according to claim 1, wherein component A is at least one selected from the group consisting of polyether polyols, polycarbonate polyols, and polyether polyamines.

3. The waterproofing material composition according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of aromatic primary amines, aliphatic primary amines, and aliphatic secondary amines.

4. A spray composition for waterproofing materials, comprising the waterproofing material composition according to any one of claims 1 to 3 and an isocyanate composition.

5. A waterproofing material containing a cured product of the waterproofing spray composition described in claim 4.

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