JP6221709B2 - Two-component room temperature curable urethane film waterproofing material composition - Google Patents

Description

  The present invention relates to a two-component room temperature curing urethane waterproof membrane composition.

As the urethane coating waterproof material, 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA) having a good balance between pot life, curability and tensile strength is generally used as an aromatic diamine. . However, since MOCA is designated as a first-class specific chemical substance, a waterproof material having workability and curability comparable to this is required.
On the other hand, it has been proposed to use a polyurethane curable composition obtained by mixing a curing agent containing diethyltoluenediamine and a low activity amine compound and a main agent containing a polyisocyanate compound (for example, Patent Document 1).

JP 2005-58918 A

However, when diethyltoluenediamine is used, there is a problem that the pot life of the composition is short.
Therefore, an object of the present invention is to provide a two-component room temperature curable urethane coating film waterproof material composition having a long pot life.

  As a result of diligent research to solve the above problems, the present inventor has found that a polyol compound having a molecular weight exceeding 200, a low molecular polyol having a molecular weight of 200 or less, diethyl toluenediamine and polytetramethylene glycol diaminobenzoate as aromatic polyamines, The present inventors have found that the pot life can be lengthened when using the present invention.

That is, this invention provides the following 1-4.
1. A main agent containing a urethane prepolymer;
Two-component room temperature curable urethane coating comprising a polyol compound having a molecular weight exceeding 200, a low molecular polyol having a molecular weight of 200 or less, and a curing agent containing diethyltoluenediamine and polytetramethylene glycol diaminobenzoate as an aromatic polyamine. A waterproof membrane composition.
2. 2. The two-component room temperature curing urethane coating film waterproofing material composition according to the above 1, wherein the polytetramethylene glycol diaminobenzoate has a molecular weight of 480 to 1,300.
3. The two-component room temperature curing according to 1 or 2 above, wherein a molar ratio of the diethyltoluenediamine to the polytetramethylene glycol diaminobenzoate (diethyltoluenediamine / polytetramethylene glycol diaminobenzoate) is 5/95 to 20/80. Type urethane coating film waterproofing material composition.
4). The two-component room temperature curing urethane coating film waterproofing material composition according to any one of the above 1 to 3, wherein the amount of the low molecular polyol is 5 to 20 mol% of the total amount of the aromatic polyamine.

  The two-pack room temperature curable urethane coating film waterproof material composition of the present invention has a long pot life.

The present invention will be described in detail below.
The two-component room temperature curable urethane coating waterproof material composition of the present invention (the composition of the present invention)
A main agent (first liquid) containing a urethane prepolymer;
A two-component solution comprising a polyol compound having a molecular weight exceeding 200, a low-molecular polyol having a molecular weight of 200 or less, and a curing agent (second solution) containing diethyl toluenediamine and polytetramethylene glycol diaminobenzoate as an aromatic polyamine. It is a room temperature curable urethane film waterproofing material composition.

  The composition of the present invention can be used by combining a polyol compound having a molecular weight of more than 200, a low molecular polyol having a molecular weight of 200 or less, and diethyltoluenediamine and polytetramethyleneglycol diaminobenzoate as aromatic polyamines. Can be used longer.

The urethane prepolymer will be described below.
The urethane prepolymer contained in the main agent is not particularly limited, and conventionally known ones can be used. For example, a reaction product obtained by reacting a polyol compound and a polyisocyanate compound can be used. At this time, the isocyanate group (NCO group) may be excessive with respect to the hydroxy group (OH group).
The urethane prepolymer can contain 0.5 to 5% by weight of NCO groups.

(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. The isocyanate group can be bonded to the hydrocarbon group, and the hydrocarbon group is not particularly limited. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The hydrocarbon group may be linear or branched, may have an unsaturated bond, and may have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Good.

Examples of the polyisocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and tolidine diisocyanate (TODI). ), 1,5-naphthalene diisocyanate (NDI), aromatic polyisocyanates such as triphenylmethane triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), trans Cyclohexane-1,4-diisocyanate, isophorone Isocyanate (IPDI), bis (isocyanatomethyl) cyclohexane (H ₆ XDI), aliphatic or cycloaliphatic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); these carbodiimide-modified polyisocyanates, these isocyanurate-modified poly An isocyanate etc. are mentioned.

A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.
Of these, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate are preferred from the viewpoint that the resulting urethane prepolymer has a low viscosity and facilitates handling of the main agent containing the urethane prepolymer.

(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 polyol; polyester polyol; polymer polyol, polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol. And low molecular polyols such as hexanediol.

Examples of the polyether polyol include polypropylene ether polyols such as polypropylene ether diol (polypropylene glycol: PPG) and polypropylene ether triol.
A polyol compound can be used individually or in combination of 2 types or more, respectively.

  Among them, the viscosity of the urethane prepolymer to be obtained becomes appropriate, the handling of the main agent containing the urethane prepolymer becomes easy, and the tensile properties of the urethane coating waterproof material comprising the waterproof material composition of the present invention obtained using this main agent. From the viewpoint that is suitable, polypropylene ether polyol is preferable, and polypropylene ether diol and polypropylene ether triol are more preferable.

  In the present invention, the combination of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer includes, for example, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate. And a combination of at least one selected from the group consisting of polypropylene ether diol and / or polypropylene ether triol.

  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 storage stability of the main agent containing this urethane prepolymer becomes good.

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

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

The polyol compound will be described below. The polyol compound contained in the composition of the present invention is not particularly limited as long as the molecular weight exceeds 200 and the compound has two or more hydroxy groups. As a polyol compound, the polyol compound used when manufacturing the urethane prepolymer mentioned above is mentioned, for example.
Of these, polyalkylene ether polyols are preferred, polypropylene ether polyols are more preferred, and polypropylene ether diols and polypropylene ether triols are even more preferred from the viewpoints of longer pot life and excellent hardness and tensile strength.

The molecular weight of the polyol compound is preferably 1000 to 10000, more preferably 2000 to 5000, from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. In the present invention, when the polyol compound is a polymer, the molecular weight of the polyol compound is determined by gel permeation chromatography (GPC) as the number average molecular weight in terms of standard polystyrene.
The polyol compounds can be used alone or in combination of two or more.

The low molecular polyol will be described below. The low molecular polyol contained in the composition of the present invention is not particularly limited as long as it is a compound having a molecular weight of 200 or less and having two or more hydroxy groups. The hydrocarbon group to which the hydroxy group can be bonded is as defined above. As a low molecular polyol, the low molecular polyol used when manufacturing the urethane prepolymer mentioned above is mentioned, for example.
It is preferable that the low molecular polyol has 2 to 3 hydroxy groups.
One preferred embodiment of the low molecular polyol is a monomer.
Of these, butanediol and pentanediol are more preferable from the viewpoints that the pot life is longer and the hardness and tensile strength are excellent.

The molecular weight of the low molecular weight polyol is preferably 50 to 200, more preferably 80 to 150, and even more preferably 100 to 150 from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. .
The low molecular polyols can be used alone or in combination of two or more.

The amount of the low-molecular polyol is preferably 5 mol% or more, more preferably 10 to 20 mol% of the total amount of the aromatic polyamine, from the viewpoint that the pot life is longer.
Further, the amount of the low molecular polyol is preferably 20 mol% or less, more preferably 10 to 20 mol% of the total amount of the aromatic polyamine, from the viewpoint of excellent hardness and tensile strength.

  Diethyltoluenediamine as the aromatic polyamine contained in the composition of the present invention is not particularly limited. Diethyltoluenediamine is a compound represented by the following formula (I). Specific examples include 3,6-diethyltoluene-2,4-diamine.

  The polytetramethylene glycol diaminobenzoate as an aromatic polyamine contained in the composition of the present invention is not particularly limited. Polytetramethylene glycol diaminobenzoate is a compound represented by the following formula (2). In the formula, n can be in a range corresponding to the molecular weight of the following polytetramethylene glycol diaminobenzoate. Specific examples of polytetramethylene glycol diaminobenzoate include polytetramethylene glycol di-p-aminobenzoate.

The molecular weight of polytetramethylene glycol diaminobenzoate is preferably 480 to 1,300, more preferably 700 to 1200, from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. In the present invention, the molecular weight of polytetramethylene glycol diaminobenzoate is a number average molecular weight in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
Regarding the molecular weight of polytetramethylene glycol diaminobenzoate, when the molecular weight is large, the pot life is preferably longer than that with a small molecular weight. Moreover, when using a thing with a small molecular weight, hardness becomes high rather than a thing with a large molecular weight, and it is preferable.

  The composition of the present invention may contain a compound other than diethyltoluenediamine and polytetramethylene glycol diaminobenzoate as an aromatic polyamine. Examples of such compounds include 4,4'-methylenebis (3-chloro-2,6-diethylaniline), N, N'-di-secondary-butyl-para-phenylenediamine, and 4,4'-bis. (Secondary-butylamino) diphenylmethane, 4,4'-bis (methylamino) diphenylmethane, trimethylene-bis (4-aminobenzoate), N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N ' -(1,3-dimethylbutyl) -p-phenylenediamine.

  In the present invention, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group possessed by the urethane prepolymer and the active hydrogen group possessed by the polyol compound, the low molecular polyol and the aromatic polyamine is increased in the pot life and hardness. From the viewpoint of excellent tensile strength, 1.0 to 1.5 is preferable, and 1.1 to 1.3 is more preferable.

  In addition, the molar ratio [(polyol compound + low molecular polyol) / aromatic polyamine] of the polyol compound and the low molecular polyol to the aromatic polyamine is 5 from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. / 95 to 50/50 are preferred, 5/95 to 35/65 are more preferred, and 5/95 to 30/70 are even more preferred.

  In the total amount of the aromatic polyamine, the total of diethyltoluenediamine and polytetramethylene glycol diaminobenzoate is preferably 100 mol% or less from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. More preferably, it is mol%.

The molar ratio of diethyltoluenediamine to polytetramethylene glycol diaminobenzoate (diethyltoluenediamine / polytetramethylene glycol diaminobenzoate) is 5/95 to 20 from the viewpoint that the pot life is longer and the hardness and tensile strength are excellent. / 80 is preferred.
The molar ratio of diethyltoluenediamine / polytetramethylene glycol diaminobenzoate is more preferably 20 or less / 80 or more, and further preferably 10 or less / 90 or more, from the viewpoint that the pot life is longer.
The molar ratio of diethyltoluenediamine / polytetramethylene glycol diaminobenzoate is preferably 5 or more / 95 or less, and more preferably 10 or more / 90 or less, from the viewpoint of excellent tensile strength.

  In the composition of the present invention, the aromatic polyamine may be free of dimethylthiotoluenediamine. Dimethylthiotoluenediamine is a compound represented by the following formula (1). The amount of dimethylthiotoluenediamine can be 0 to 10 mol% in the total amount of aromatic polyamine.

  The composition of this invention can contain an additive in the range which does not impair the objective of this invention other than a urethane prepolymer, a polyol compound, a low molecular polyol, and an aromatic polyamine. Examples of the additive include a reinforcing agent, a plasticizer, a catalyst (curing catalyst), a resin-based hollow body (resin balloon), a dispersant, a solvent, an antioxidant, an antioxidant, and a pigment. The additive can be added to the main agent and / or the curing agent. The additives can be used alone or in combination of two or more. Whether the additive is added to the main agent or the curing agent can be appropriately selected.

Examples of the reinforcing agent include calcium carbonate, titanium oxide, silicon oxide, talc, clay, quicklime, kaolin, zeolite, diatomaceous earth, fine powder silica, hydrophobic silica, and carbon black.
The amount of the reinforcing agent is preferably 40 to 160 parts by mass and more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the main agent from the viewpoint of supplementing the breaking strength of the urethane coating film waterproofing material. .

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, etc. Is mentioned.
The amount of the plasticizer in the curing agent is preferably 20 parts by mass or less with respect to 100 parts by mass of the main agent.

Examples of the curing catalyst include an organometallic catalyst. Examples of the organometallic catalyst 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 And organic calcium compounds such as calcium neodecanoate; organic barium compounds; and organic bismuth compounds.
It is preferable that the usage-amount of a curing catalyst is 0.2-5 mass% with respect to the mass of the whole hardening | curing agent.
The curing catalyst may be blended in the curing agent, or may be added when mixing the main agent and the curing agent.

In the composition of the present invention, the main agent and / or the curing agent can further contain a resin-based hollow body (resin balloon). In the resin-based hollow body, the outer shell of the hollow sphere is made of resin.
Examples of the material of the outer shell of the resin-based hollow body include, for example, phenol resin; urea resin; polystyrene resin; polyvinylidene chloride; acrylonitrile copolymer (for example, a copolymer of acrylonitrile and methacrylonitrile, acrylonitrile and acrylonitrile, Copolymerizable butadiene, copolymers with vinyl monomers such as styrene, etc.), and thermoplastic resins such as vinylidene chloride polymers.
The average particle diameter of the resin hollow body can be 20 μm or more, and is preferably 20 to 60 μm.
The specific gravity of the resin hollow body is preferably 0.05 to 0.35 from the viewpoint of excellent workability.
The manufacturing method of the resin-based hollow body is not particularly limited, and can be manufactured by a conventionally known method.

In the composition of the present invention, the amount of the resin-based hollow body is preferably 0.01 to 10% by mass of the curing agent from the viewpoint of excellent durability and light weight of the urethane coating film waterproofing material. More preferably, the content is 1 to 10% by mass.
In the composition of the present invention, the resin-based hollow body is preferably contained only in the curing agent because the workability when mixing the main agent and the curing agent is improved.

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

  The production method of the composition of the present invention is not particularly limited. For example, a main agent containing a urethane prepolymer, a curing agent containing a polyol compound, a low molecular polyol and an aromatic polyamine are separately separated under a nitrogen gas atmosphere. Can be mixed and manufactured.

The composition of the present invention can be used by sufficiently mixing the main agent and the curing agent.
The composition of this invention can be hardened at about 0-80 degreeC, for example.
The composition of the present invention can be used for new construction or renovation of buildings, for example, on concrete, mortar, metal roofs, urethane coatings coated with a top coat, and the like.
Prior to applying the composition of the present invention, a primer can be used.
The composition of the present invention can be used for an undercoat layer and / or a topcoat layer of a urethane coating waterproof material.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Production of composition>
The components shown in Table 1 below were used in the amounts shown in the same table, and these were mixed well to produce a curing agent.
Next, the main agent of the following Table 1 is used in an amount (parts by mass) shown in the same table, and the main agent and the curing agent (total amount) produced as described above are sufficiently mixed to form a two-component room temperature curing type. A urethane coating film waterproofing material composition (composition) was produced.

<Evaluation>
The following evaluation was performed about the composition manufactured as mentioned above. The results are shown in Table 1.

-Potable time Using a BS viscometer No. 6 rotor, the time until the viscosity of the composition exceeded 30 Pa · S was measured under the condition of a rotation speed of 10 rpm and 20 ° C. (The time from the start of the test with the BS viscometer until the viscosity of the composition exceeds 30 Pa · S was defined as the pot life. When the pot life is 30 minutes or more, the pot life is about the same as or longer than MOCA. Long workability.

・ Hardness (curability)
After stirring the main agent and the curing agent, the composition was cured for 1 week under the condition of 20 ° C., and the hardness of the cured product thereafter was measured with a JIS A hardness meter (5-second value). When the hardness is 50 or more, it is excellent in hardness as a urethane coating film waterproofing material to the same degree or more as MOCA.

The details of each component shown in Table 1 are as follows.
Diethyltoluenediamine: manufactured by Ihara Chemical Co., Ltd. Polytetramethylene glycol diaminobenzoate 1: Trade name Elastomer 650P, manufactured by Ihara Chemical Co., Ltd., number average molecular weight 888
Polytetramethylene glycol diaminobenzoate 2: Trade name Elastomer 1000P, manufactured by Ihara Chemical Co., Ltd., number average molecular weight 1,242
Low molecular polyol: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, molecular weight 90.12
Polyol compound: PPG (polypropylene glycol), trade name EXCENOL2020, manufactured by Asahi Glass Co., Ltd., number average molecular weight 2000
・ Calcium carbonate: Heavy calcium carbonate (Super SS, manufactured by Maruo Calcium)
・ Plasticizer: Diisononyl phthalate (DINP, manufactured by Jay Plus)
・ Catalyst: Lead catalyst (Minico P-30, manufactured by Active Materials Chemical Company)
Resin balloon: MFL-60CAS (specific gravity: 0.15, average particle size 60 μm, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
Solvent: Isobar G, manufactured by ExxonMobil Co., Ltd. Main agent: U-8000A agent, manufactured by Yokohama Rubber Co., Ltd., containing urethane prepolymer.

As is apparent from the results shown in Table 1, Comparative Example 1 containing no polytetramethylene glycol diaminobenzoate and low molecular polyol had a short pot life. The comparative examples 2-3 which do not contain a low molecular polyol had a short pot life.
On the other hand, Examples 1 to 17 have a long pot life and excellent workability.
Further, as is clear from the results of Comparative Example 2 and Examples 2, 5, and 9, the usable time becomes longer as the amount of the low molecular polyol is larger than the total amount of the aromatic polyamine.
As is apparent from the results of Examples 1 to 7 and Examples 8 to 10, the lower the amount of the low molecular polyol relative to the total amount of the aromatic polyamine, the higher the hardness.
When polytetramethylene glycol diaminobenzoate having a higher molecular weight is used, the pot life is longer than that of a lower molecular weight. Further, when a material having a lower molecular weight is used, the hardness is higher than that having a higher molecular weight.
As described above, the composition of the present invention has a long working life and excellent workability as much as or more than MOCA. In addition, the composition of the present invention is excellent in curability to the same extent as MOCA or more.

Claims (4)

A main agent containing a urethane prepolymer;
Two-component room temperature curable urethane coating comprising a polyol compound having a molecular weight exceeding 200, a low molecular polyol having a molecular weight of 200 or less, and a curing agent containing diethyltoluenediamine and polytetramethylene glycol diaminobenzoate as an aromatic polyamine. A waterproof membrane composition.   The two-component room temperature curing urethane coating film waterproofing material composition according to claim 1, wherein the polytetramethylene glycol diaminobenzoate has a molecular weight of 480 to 1,300.   The two-component room temperature according to claim 1 or 2, wherein a molar ratio of the diethyltoluenediamine and the polytetramethylene glycol diaminobenzoate (diethyltoluenediamine / polytetramethylene glycol diaminobenzoate) is 5/95 to 20/80. A curable urethane film waterproofing material composition.   The two-component room-temperature-curing urethane coating film waterproofing material composition according to any one of claims 1 to 3, wherein the amount of the low molecular polyol is 5 to 20 mol% of the total amount of the aromatic polyamine.