TWI396718B - Humid hardening type urethane composition for water-proofing material and urethane water-proofing material - Google Patents

Description

Moisture-curing urethane composition for water-repellent materials and urethane waterproof material

The present invention relates to a one-liquid moisture-curing urethane composition for a waterproof material, which is excellent in foaming and hardenability of a coating film when it is hardened, and particularly relates to a kind of superior defoaming property. With the flatness, it is possible to impart a moisture-curing urethane composition for a waterproof material having a cured surface having a superior surface appearance.

Patent Document 1 discloses a moisture-curing urethane composition which is formed by swelling of a coating film due to carbon dioxide gas generated when water reacts with an isocyanate group during curing. problem.

Therefore, in order to suppress the occurrence of carbon dioxide gas which is a cause of swelling, a moisture dissociation type crosslinking agent such as a ketimine or an enamine has been proposed, wherein a composition using an oxazole compound does not cause carbon dioxide and properties. A relatively uniform material is coated and applied as a waterproof material (Patent Documents 2 to 4).

The moisture-curing waterproof material does not need to be mixed with the main agent and the hardener at the construction site. It can be applied immediately after the can is opened. In order to prevent the precipitation of the filler and the separation of the filler and the liquid component, it is necessary to increase the shake. Denaturation (thixotropy). As a result, compared with the conventional two-liquid-curing urethane, the use of one of the oxazolidine compounds, the moisture-curing urethane composition, has a problem of defoaming property and flatness.

Further, as a defoaming agent for the urethane composition, it is known to use an ethylene-α-olefin co-oligomer in the prior patent application (Patent Document 5). However, even if this antifoaming agent is used for one of the compounds having a oxazolidine compound The moisture-curing urethane composition also does not provide practical defoaming properties.

(Refer to Comparative Example 2)

Patent Document 1: Japanese Patent Laid-Open Publication No. SHO 57-94056 Patent Document 2: Japanese Patent Laid-Open No. Hei 6-293821 Patent Document 3: Japanese Patent Laid-Open No. Hei 7-33852 Patent Document 4: Japanese Patent Laid-Open No. Hei 7-10949 Patent Document 5: Japanese Patent Laid-Open No. Hei 5-247161

The object of the present invention is to improve the defoaming property and flatness of a urethane composition having a oxazolidine-based compound, thereby providing a one-liquid moisture-type urethane composition for waterproofing materials and waterproofing. The material is a hardened material with superior water resistance and surface appearance.

The inventors of the present invention have found out that the problem can be solved by adding a specific antifoaming agent and a specific hollow filler in a specific amount, and thus the present invention has been completed.

That is, the present invention provides a moisture-curing urethane composition for a waterproof material and a waterproof material using the same, which is characterized by comprising a urethane composition comprising the following (A) to (G) : a urethane prepolymer (A) having two or more isocyanate groups at a terminal obtained by reacting a polyisocyanate with a polyoxyalkylene polyol; or a polyisocyanate or a polyisocyanate and a polyoxyalkylene polyol The urethane prepolymer (b1) having two or more isocyanate groups at the terminal obtained by the reaction, and the terminal obtained by reacting with N-2-hydroxyalkyl oxazolidine (b2) have at least one or more oxazolidine Base contains evil a carbazide urethane compound (B); a filler (E), a plasticizer (F) and a solvent (G); and 0.01 to 5 parts by weight of ethylene based on 100 parts by weight of the urethane composition -α-olefin co-oligomer (C); and 0.1 to 5 parts by weight of a polymer composed of acrylonitrile or a modified product thereof, and a surface-treated organic hollow filler having an average particle diameter of 100 μm or less (D) The weight ratio of the amount of the ethylene-α-olefin co-oligomer (C) to the amount of the organic hollow filler (D) added is (C) / (D) = 0.01 to 10.

The present invention relates to a urethane composition for a water repellent material containing an oxazolidine compound, a polymer composed of an ethylene-α-olefin co-oligomer (C) and acrylonitrile or a modified product thereof. Since the specific amount contains the surface-treated organic hollow filler (D) having an average particle diameter of 100 μm or less, the defoaming property and flatness are improved in balance, and a water-resistant cured product having excellent water repellency and surface appearance can be imparted.

Embodiment of the invention

The urethane prepolymer (A) having two or more isocyanate groups at the terminal obtained by reacting the polyisocyanate used in the present invention with a polyoxyalkylene polyol means that it is used in excess of polyisocyanate. The method comprises preparing a urethane prepolymer of a polyoxyalkylene polyol of a polyisocyanate and a polyhydric alcohol, such as polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol or the like.

Further, the urethane prepolymer (b1) having two or more isocyanate groups at the terminal means that a polyisocyanate is prepared by a usual method under the excess of polyisocyanate, and a metal amide similar to the above polyoxyalkylene polyol is prepared. Acid ester prepolymer.

The polyoxyalkylene polyol refers to a method in which ethylene oxide, propylene oxide, butylene oxide alone or the like is added to ethylene glycol, propylene glycol, water, glycerin, or TMP by a conventional method. Polyol obtained from trimethylolpropane), pentaerythritol or the like.

The polyisocyanate used in the present invention may, for example, be 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate or diphenylmethane which is partially carbodiimized. Diisocyanate, polymethylene polyphenyl polyisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenyl diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate And one or a mixture of two or more of aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate such as hydrogenated diphenylmethane diisocyanate or cyclohexane diisocyanate.

The polyoxyalkylene polyol of the structural component of the urethane prepolymer (A) is suitably a diol or a triol having a number average molecular weight of 500 to 16,000.

In particular, the polyoxyalkylene polyol component of the urethane prepolymer (A) is preferably in the range of from 0 to 10% by weight of the vinyl ether bond and from 10 to 95% by weight of the propylene ether bond.

The number of terminal isocyanate groups of the urethane prepolymer (A) is suitably 2 or more, more preferably 2 to 3. Further, the NCO/OH ratio of the isocyanate to the polyol is suitably 1.4 or more, more preferably 1.4 to 5.0, particularly preferably 1.5 to 3.0. The residual NCO% of the urethane prepolymer (A) is suitably from 1 to 20% by weight, more preferably from 1 to 5% by weight.

The oxazolidine-containing carbamate compound (B) used in the present invention is a polyisocyanate or a polyisocyanate and a polyoxyalkylene polyol. The terminal obtained by the reaction, the urethane prepolymer (b1) containing two or more isocyanate groups, and the terminal obtained by reacting with N-2-hydroxyalkyl oxazolidine (b2) have at least one oxazole Alkyl group.

The polyoxyalkylene polyol of such a urethane prepolymer preferably has an oxyethylene chain. However, even if the polyol is a polyol in which an oxyethylene chain is not mixed and a polyol having an oxyethylene chain, it can be used as the component (b1). Further, it is preferable that the average content of the oxyethylene chain in the oxyalkylene chain is 1 to 30% by weight. If the content of the oxyethylene chain is in the above range, the curing rate is fast, and it has excellent hardenability and water resistance. However, the amount of the oxyethylene chain of the component (A) and the component (B) is calculated and the total amount of the oxyethylene chain is preferably less than 10% by weight based on the total amount of the component (A) and the component (B). If it is this range, it will become suitable water resistance.

The urethane prepolymer (b1) preferably has a number average molecular weight of from 500 to 8,000. The case where the number average molecular weight is 500 to 8000 will conform to the underlying mobility and hardening speed. Further, the average NCO group at the end of the urethane prepolymer (b1) is suitably from 2.0 to 2.6. If it is such an NCO base number, it will become a suitable result according to hardenability and bottom layer followability. Further, the NCO/OH ratio of the isocyanate to the polyol is suitably 1.6 or more, more preferably 1.8 to 4.0. The residual NCO% is suitably from 1 to 15% by weight.

Further, the molar ratio of the urethane prepolymer (b1) to the N-2-hydroxyalkyloxazole (b2) is suitably NCO/OH = 0.95 to 3.0. If the NCO/OH molar ratio is in such a range, the tendency of the unreacted N-2-hydroxyalkyloxazole to remain is low, giving a good storage stability, and suppressing the decrease in the hardening rate or the viscosity. Rising is easy.

Further, the N-2-hydroxyalkyl oxazolidine (b2) used for the synthesis of the oxazolidine-containing carbamate compound (B) is, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, A compound obtained by a conventional condensation reaction of an aldehyde such as benzaldehyde with a dihydroxyalkylamine such as diethanolamine or dipropanolamine.

The number of terminal oxazolidinyl groups of the oxazolidine-containing carbamate compound (B) is suitably from 1 to 3. If it is in this range, the stretchability after hardening will become high and it is preferable. Further, when the oxazolidinyl group is one or more at the terminal of the carbazolidine prepolymer (B), the other terminal may be an isocyanate group.

The ratio of the prepolymer (A) to the carbazole compound-containing urethane compound (B), the NCO group of the prepolymer (A) and the carbazolidine-containing carbamate compound (B) are opened by water. The ratio of active hydrogen groups produced thereafter is suitably in the range of 0.4 to 4.0. If it is in this range, the occurrence of carbon dioxide gas is low, and the expansion in the coating film can be suppressed, and the storage stability is excellent. If such a viewpoint is considered, the mixing ratio of (A) to (B) is suitably in the range of 60:1 to 1:30.

In addition to the components (A), (B), (E), (F), and (G), the composition of the present invention must contain a specific amount of ethylene-α-olefin co-oligos for defoaming and flatness. The polymer (C) is a polymer (D) composed of acrylonitrile or a modified product thereof, and a specific amount of an organic hollow filler having an average particle diameter of 100 μm or less.

The ethylene-α-olefin co-oligomer (C) which can be used in the present invention has a number average molecular weight of suitably from 50 to 3,000, more preferably from 500 to 2,500, to copolymerize ethylene and an α-olefin. For example, the α-olefin co-oligomer may, for example, be propylene, 1-butene, 4-methyl-1-pentene or 2-methyl-1-pentene. The representative characteristics of the ethylene-α-olefin co-oligomer are suitable for specific gravity of 0.80 to 0.90, dynamic viscosity of 50 to 50000 cSt, and iodine value of 1.0 or less; since the low dynamic viscosity is good in mixing and easy to separate; In order to make the mixing poor and difficult to separate, the object to be added is selected in consideration of moderate mixing and separation. A commercially available product of the ethylene-α-olefin co-oligomer (C) which meets the above requirements, for example, Lucant HC-20, HC-40, HC-100, HC-600, etc., manufactured by Mitsui Chemicals Co., Ltd. . The amount of the ethylene-α-olefin co-oligomer (C) added is 100% by weight based on 100 parts by weight of the total of (A), (B), (E), (F), and (G). 0.01 to 5 parts by weight, suitably 0.05 to 3 parts by weight. When the amount is less than 0.01 part by weight, the defoaming effect is small, and when it is blended in excess of 5 parts by weight, a large amount of the surface of the composition floats, and the adhesion to the surface coating is deteriorated. In addition, blurring also occurs on the surface of the composition.

The surface-treated organic hollow filler (D) is a hollow spherical particle having a coating of acrylonitrile or a modified product thereof, and a granular material having an average particle diameter of 100 μm or less. However, an inorganic balloon such as a balloon, a ceria balloon, or a white sand balloon may be used in combination within the range not impairing the effects of the present invention. It is suitable as an organic balloon in which vinylidene chloride, acrylonitrile or the like is copolymerized. When the inorganic balloon is mixed at the time of general production, the balloon is mostly destroyed and is not expected to be used in the present invention. Further, once the average particle diameter exceeds 100 μm, the hollow filler (D) tends to be separated from the composition and is not expected to be used. When the average particle diameter is 100 μm or less, separation is not carried out, and it is more preferably 80 μm or less and 10 μm or more. Commercially available products include MFL-80GCA and MFL-80CA ( Matsumoto oil product).

When the surface-treated organic hollow filler (D) having an average particle diameter of 100 μm or less is used in combination with the ethylene-α-olefin copolymer oligomer (C), the flatness and defoaming property of the composition can be greatly improved.

Further, the hollow filler (D) is a surface-treated material, and the treating agent is a hollow filler (D) coated with at least one of calcium carbonate, talc or titanium oxide, based on the hollow filler (D) The difference in specific gravity from the urethane resin is small, and it is difficult to separate from the composition, and it is suitably used. It is particularly preferable to use a surface treatment coating with calcium carbonate.

The hollow filler (D) is used in an amount of 0.1 to 5.0 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total of (A), (B), (E), (F), and (G). Share. When the amount is less than 0.1 part by weight, the effect of defoaming property and flatness is small, and when it exceeds 5.0 parts by weight, the viscosity of the composition is increased, and workability is preferably lowered.

The inorganic filler (E) used in the present invention may, for example, be a powder or granule of an inorganic compound such as calcium carbonate, calcium oxide, clay, talc, titanium oxide, aluminum sulfate, kaolin or diatomaceous earth. The amount of the composition is suitably from 5 to 70% by weight, more preferably from 10 to 60% by weight.

The plasticizer (F) used in the present invention may, for example, be dibutyl phthalate, dioctyl phthalate, di(undecyl) phthalate or phthalic acid. Lauryl ester, butyl benzyl phthalate, diisononyl phthalate, dibutyl adipate, dioctyl adipate, diisononyl adipate, dioctyl sebacate, An ester-based plasticizer such as dioctyl sebacate or a phosphate-based plasticizer such as trioctyl phosphate or triphenyl phosphate.

The solvent (G) used in the present invention may, for example, be xylene, toluene, petroleum-based high-boiling aromatic fraction, petroleum resin, or the like. Mix more than one.

The composition of the present invention may contain various additives such as a catalyst, a rocking agent, a filler, an anti-UV agent for continuously improving the weather resistance, and a stabilizer, in consideration of the use according to the use. These mixtures can be uniformly mixed, and can be preserved, and can be produced by sufficiently mixing and using a mixing device.

Examples of the rocking agent include surface-treated calcium carbonate, polyvinyl chloride powder, fine powder of cerium oxide, and bentonite.

The catalyst can use a conventional catalyst of caprylic acid or propionic acid, terephthalic acid, salicylic acid, lead, DBTDL or the like.

For example, examples of the stabilizer include an antioxidant, an ultraviolet absorber, and the like, and can be added to the composition.

The waterproof material of the present invention is used as a building waterproof material applied to a concrete surface such as a balcony or a roof or an original floor wall surface, and is applied by a spray, a brush or the like.

[Examples]

Next, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited by the examples. Hereinafter, all parts and % are set as a weight basis unless otherwise stated.

<Synthesis of (A) component>

(Production Example 1 of urethane prepolymer) 700 g (0.35 mol) of polybutylene ether glycol having a number average molecular weight of 2000, 300 g (0.1 mol) of polypropylene ether triol having a number average molecular weight of 3000, and 191.4 g (1.1 mol) of 2,4-toluene diisocyanate. , that is, the equivalent ratio of NCO / OH of 2.2, under a nitrogen stream, 80 ° C, stirring in the flask 15 The urethane prepolymer (A-1) having an NCO% of 4.25% was obtained by reacting while reacting.

(Production Example 2 of urethane prepolymer) In the preparation example 1 of the urethane prepolymer, 700 g (0.35 mol) of a polypropylene ether glycol having a number average molecular weight of 2000 was used in place of 700 g of a polybutylene ether glycol having a number average molecular weight of 2000 (0.35 mol). In the same manner as in the above, a urethane prepolymer (A-2) having an NCO% of 4.28% was obtained by the same method.

<Synthesis of a carbazole group-containing carbamate compound (B) component>

(Production Example 1 of a urethane oxazolidinyl prepolymer) After mixing a number average molecular weight of 4,800, an oxyethylene chain content of 15% of polypropylene ether triol (500 g (0.104 mol)) and a number average molecular weight of 2000 of polypropylene ether glycol 500 g (0.25 m), an average of oxyethylene chains was obtained. A polyol having a content of 7.5%, an average functional group number of 2.29, and a number average molecular weight of 2820. Further, 143.3 g (0.853 mol) of 1,6-hexane diisocyanate, that is, an equivalent ratio of NCO/OH of 2.1, was stirred in a flask under a nitrogen stream at 80 ° C for 48 hours, and reacted to obtain NCO. The urethane prepolymer (b1-1) having a % of 3.28% and a terminal NCO group of 2.29 per molecule.

Equivalent ratio of 140.8 g of urethane prepolymer (b1-1) to 15.9 g of 2-isopropyl-3-(2-hydrocarbylethyl)-1,3-oxazolidine, ie NCO/OH 1.1, while stirring at a temperature of 60 ° C under a nitrogen stream for 48 hours, the reaction was carried out to obtain a urethane oxazolidinyl prepolymer (OXZ-1). It was confirmed that the GPC result of the present composition was measured, and the content of 2-isopropyl-3-(2-hydrocarbylethyl)-1,3-oxazolidine remaining was 1% or less.

<Compound formula>

Next, the raw materials disclosed in the table were fed into a sealed planetary mixer, and after uniformly mixing, defoaming was performed at 50 Torr for 5 minutes to obtain a sample.

In addition, the calcium carbonate powder (NS-200, manufactured by Nitto Powder Co., Ltd.) was used after drying at 120 ° C and confirming that the water content was 500 ppm or less.

〔experiment method〕

(Measurement of viscosity) The sample was adjusted to 25 ° C, and a viscosity was measured using a BM type rotational viscometer.

(foaming test) The sample was coated on a rock plate (30 cm × 30 cm) surrounded by a thickness of 1.5 mm, and was thoroughly foamed using a file under the conditions of room temperature 25 ° C × humidity 50%. The time until the bubble completely disappeared was measured.

(Hollow filler separation test) 200 g of the sample was sealed in a 200 cc glass container, and after 7 days of maintenance in a gas atmosphere of 50 ° C, the hollow filler was visually observed to be separated.

(flatness test) In a 150 mL plastic cup (Polycup, capacity 200 cc), after taking the sample, the plastic cup was inverted downward on the rock plate (30 cm × 30 cm) so that the sample did not leak out of the plastic cup. Next, the plastic cup is vertically raised to allow the sample to naturally diffuse into a circular shape. After the plastic cup was raised for 10 minutes, the average diameter (cm) of the sample which had been diffused into a circle was measured, and the judgment was made based on the following criteria: determination criteria: ○: 30 cm or more, Δ: 25 to less than 30 cm, ×: less than 25 cm.

(hardening test) The sample is coated on a rock plate (30 cm × 30 cm) surrounded by a thickness of 1.5 mm, and maintained at room temperature 25 ° C × humidity 50% until the surface of the film can be walked (become non-adhesive sole) The time of the state is set to the hardening time.

(waterproof performance test) A sample was used to make a sheet of 1 mm thick (30 cm x 30 cm). Using a through-hole measuring device, a voltage is applied to the sheet to confirm the presence or absence of current flow due to the through-hole, and the case where no current flows is considered to be good in waterproof performance "○", and when the current flows, it is judged that the waterproof performance is not Good "X".

Table 1 blending conditions and test results RY-200S: A hydrophobic cerium oxide powder manufactured by AEROSIL, Japan.

Table 2 blending conditions and test results

Comparative Example 1 did not contain any of an acrylonitrile-based hollow filler and an ethylene-α-olefin co-oligomer, and was a result of a longer defoaming time and a poor flatness as compared with the examples.

Although Comparative Example 2 contains an ethylene-α-olefin co-oligomer, it does not contain an acrylonitrile-based hollow filler, and has a longer defoaming time and a poor flatness as compared with the examples.

Although Comparative Example 3 contains an acrylonitrile-based hollow filler, it does not contain an ethylene-α-olefin co-oligomer, and has a longer defoaming time and a poor flatness as compared with the examples.

Although Comparative Example 4 contains an acrylonitrile-based hollow filler, the ethylene-α-olefin co-oligomer has a small defoaming time and poor flatness as compared with the examples.

Although Comparative Example 5 contains an acrylic-based hollow filler and an ethylene-α-olefin co-oligomer, the ratio of the ethylene-α-olefin co-oligomer/acrylonitrile-based hollow filler is too small, compared with the examples. The result of longer bubble time and poor flatness.

Although Comparative Example 6 contains an acrylic-based hollow filler and an ethylene-α-olefin co-oligomer, the ratio of the ethylene-α-olefin co-oligomer/acrylonitrile-based hollow filler is too large, compared with the examples. The result of longer bubble time and poor flatness.

Industrial use possibility

According to the present invention, the defoaming property and the flatness of the urethane composition having the oxazolidine-based compound can be improved, and it can be applied to a civil engineering building to form a water-repellent layer having superior surface appearance and water repellency.

Claims (4)

A moisture-curing urethane composition for a waterproof material, which comprises a urethane composition comprising the following (A), (B), (E), (F) and (G): A urethane prepolymer (A) having two or more isocyanate groups at a terminal obtained by reacting a polyisocyanate with a polyoxyalkylene polyol; reacting a polyisocyanate or a polyisocyanate with a polyoxyalkylene polyol The obtained urethane prepolymer (b1) having two or more isocyanate groups at the terminal end, and the terminal obtained by reacting with N-2-hydroxyalkyl oxazolidine (b2) has at least one oxazolidinyl group. a carbazide-containing urethane compound (B); a filler (E), a plasticizer (F), and a solvent (G); characterized in that it contains 0.01% by weight based on 100 parts by weight of the urethane composition. 5 parts by weight of the ethylene-α-olefin co-oligomer (C), and 0.1 to 5 parts by weight of a polymer composed of acrylonitrile or a modified product thereof, and a surface-treated organic hollow filler having an average particle diameter of 100 μm or less (D) The weight ratio of the amount of the ethylene-α-olefin co-oligomer (C) to the amount of the organic hollow filler (D) added is (C)/(D)=0.01 to 10. A moisture-curing urethane for waterproofing materials, as claimed in claim 1 A composition in which the surface treatment of the hollow filler (D) is coated with one or more of calcium carbonate, talc or titanium oxide. A moisture-curing urethane composition for a waterproof material according to any one of claims 1 to 2, wherein the urethane prepolymer (A) having at least two isocyanate groups at the terminal and the containing odor The mixing ratio of the carbazide urethane compound (B) is from 60:1 to 1:30, and the inorganic filler (E) is added in an amount of from 5 to 70% by weight in the composition. A moisture-curing urethane water-repellent material comprising the moisture-curing urethane composition for a waterproof material according to any one of claims 1 to 2.