JP5013709B2 - Curing agent for two-component polyurethane coating composition - Google Patents

Description

The present invention, in addition to paints, adhesives, relates hardener for superior 2-component polyurethane coating compositions in storage stability which is also used in the adhesive or the like.

Polyisocyanate obtained from hexamethylene diisocyanate has excellent weather resistance, chemical resistance, and adhesion, so it can be used for a wide range of urethane paints, adhesives, and adhesives for automobile repairs, bridges, buildings and other structures, plastics, and woodworking. Used as a curing agent. Among them, polyisocyanates having an isocyanurate structure are known to be particularly excellent in weather resistance and durability because the chemical stability of the isocyanurate structure is high.
Thus, since the polyisocyanate having an isocyanurate structure has extremely excellent characteristics, it is desired to be used for a wider range of industrial applications. However, when this polyisocyanurate having an isocyanurate structure is used as a paint, when diluted with an organic solvent, or when stored after dilution, moisture from the organic solvent, etc. may cause a phenomenon such as cloudiness or solidification. It happened.

Various methods have been proposed to increase the moisture resistance stability of polyisocyanates having an isocyanurate structure. For example, Non-Patent Document 1 shows that the addition of iminooxadiazinedione is good in moisture resistance stability, but expensive fluorine is contained in order to synthesize iminooxadiazinedione. It is necessary to adjust the catalyst, and since multistage adjustment of the catalyst is necessary, it is economically disadvantageous and the reaction is difficult to control. Furthermore, thermal stability is also low.
A method of increasing the moisture resistance stability of polyisocyanates having an isocyanurate structure by adding orthoformate ester or monofunctional monoisocyanate and preferentially reacting with the water in the solvent to remove the water contained in the organic solvent However, the product that has reacted with water remains in the polyisocyanate solution, which leads to a decrease in the final physical properties, which is not preferable.
Congr FATIPEC, Vol. 24th, D PAGE. D. 131-D. 145, 1998

  The present invention relates to a curing agent for a two-component polyurethane coating composition by using a specific polyisocyanate, and an object thereof is to provide a curing agent having excellent storage stability, particularly moisture stability.

As a result of studies to solve the above problems, the present inventors have completed the present invention by using a specific polyisocyanate composition. That is, the present invention is as follows.
1) What hardener der consisting polyisocyanate composition comprising a polyisocyanate (B) having a polyisocyanate (A) and the isocyanurate structure obtained from hexamethylene diisocyanate having a biuret structure obtained from hexamethylene diisocyanate,
(A) / (B) is 1/99 to 60 / Ri 40 parts by weight ratio der of, and the polyisocyanate (C) having an isocyanurate structure obtained from isophorone diisocyanate (A) and the total mass of the (B) curing agent comprising a polyisocyanate composition characterized that you containing from 1 to 50% by weight with respect to part.
2) A curing agent comprising the polyisocyanate composition according to 1), which contains 0.01 to 1.0% by mass of an ultraviolet absorber and / or a light stabilizer.

  According to the present invention, by combining a specific aliphatic and / or alicyclic diisocyanate biuret type polyisocyanate and an aliphatic and / or alicyclic diisocyanate type isocyanurate type polyisocyanate in a specific ratio, It is possible to obtain a two-pack type polyurethane coating composition having sufficient storage stability and good moisture stability while maintaining high weather resistance.

The present invention will be specifically described below.
The diisocyanate used in the present invention is hexamethylene diisocyanate and / or isophorone diisocyanate.
The polyisocyanate (B) and / or (C) having an isocyanurate structure obtained from hexamethylene diisocyanate and / or isophorone diisocyanate can be obtained, for example, by methods such as JP-B-59-1289 and JP-A-64-33115. Examples of commercially available isocyanurates of hexamethylene diisocyanate include Duranate TPA-100 (product of Asahi Kasei Chemicals) (trade name), Desmodur N3300 (product of Bayer) (trade name), Vasonate HI-100. (BASF product) (trade name), Coronate HX (Japan Polyurethane product) (trade name), etc. can be used. As isocyanurate of isophorone diisocyanate, Vestagon T1890 (product of Degussa) (trade name), Desmodur Z4470 (product of Bayer) (trade name) and the like can be used.

The polyisocyanate (A) having a biuret structure obtained from hexamethylene diisocyanate can be produced, for example, by the methods shown in JP-B-48-8088, JP-B-57-29029, and British Patent 1044932. In addition, Duranate 24A-100 (trade name), 22A-75PX (product of Asahi Kasei Chemicals) (product name), Desmodur N-75 (trade name), N3200 (product of Bayer) (trade name), Vasonate HB -100 (BASF product) (trade name), Tronate HDB (Rhodia product) (trade name), and the like can also be used.
The ratio of (A) to (B) and (C) is as follows.
The ratio of (A) and (B) is in the range of 1/99 to 60/40. Preferably it is 5 / 95-40 / 60, More preferably, it is 5 / 95-20 / 80. When the ratio of (A) is lower than 1, sufficient water stability cannot be obtained, and when it is higher than 60, the weather resistance is somewhat low. The ratio when (C) is mixed is in the range of 1 to 80% by mass with respect to the total mass part of (A) and (B). Preferably it is 1-50 mass%, More preferably, it is 1-30. When the ratio of (C) is lower than 1% by mass, sufficient drying properties cannot be obtained, and when it is higher than 80% by mass, sufficient film properties cannot be obtained due to low reactivity of isophorone diisocyanate. Preferably it is 1-50 mass%.

  The polyurethane coating composition curing agent of the present invention preferably contains an ultraviolet absorber and / or a light stabilizer. The content of the ultraviolet absorber and / or the light stabilizer is preferably 0.01 to 1.0% by mass of the whole. More preferably, it is 0.02-0.5 mass%, Most preferably, it is 0.02-0.3 mass%. When the content of the ultraviolet absorber and / or the light stabilizer is lower than 0.01% by mass, it is not preferable because sufficient stability cannot be obtained. On the other hand, if the content exceeds 1.0% by weight, the ultraviolet absorber and / or the light stabilizer is relatively expensive, which is not economically preferable.

  Examples of the ultraviolet absorber used in the present invention include those containing benzotriazole in the chemical structural formula, specifically, for example, Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1130 (all are trade names manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumisolv 250, Sumisolv 310 (all are trade names manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stub LA-31 (Asahi Denka Kogyo Co., Ltd.) Company name). Examples of the light stabilizer include those containing 2,2,6,6-tetramethylpiperidine in the chemical structural formula, specifically, for example, Tinuvin 123S, Tinuvin 144, Tinuvin 292, Tinuvin 765, Thimasolve 119FL, Thimasolve 2020FDL, Timasolve 944, Timasolve 622LD (all are trade names manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumisolv 577 (trade names manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stub LA-52, Adeka Stub LA-57, Adeka Stub LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-82, ADK STAB LA-87, ADK STAB LA-503, ADK STAB LA-601 (all are trade names manufactured by Asahi Denka Kogyo Co., Ltd.) LS-2626, Sanol LS-292, Sanol LS-744, Sanol LS-440 (more than any of Sankyo Lifetech Co., Ltd. trade name), and the like.

In order to dissolve the polyurethane coating composition curing agent of the present invention, a solvent inert to an isocyanate group known in the art can also be used. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as methyl ethyl ketone and cyclohexanone. The water contained in these solvents is desirably 500 ppm or less, and preferably 300 ppm or less.
The polyurethane coating composition of the present invention can be added with additives such as pigments, colorants, dispersants, ultraviolet absorbers, light stabilizers, and antioxidants known in the art.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the Example. The part and% in an Example are a mass part and mass%, respectively.
[Viscosity Measurement Method] JIS K5600-2-3
[Isocyanate content measurement method] ASTM D2572
[Gas chromatography measurement method]
Equipment used GC-8A manufactured by Shimadzu Corporation
Column Silicone OV-17 manufactured by Shinwa Kako Co., Ltd.
Detection method FID
Measurement conditions Injection / detector temperature 160 ° C
Column temperature 120 ° C constant [Infrared absorption spectrum measurement method]
Equipment used JASCO Corporation FT / IR-600
[Moisture measurement method]
Equipment used MKC-510 manufactured by Kyoto Electronics Industry Co., Ltd.
[Weather resistance test]
Equipment used Suga Test Instruments Co., Ltd. Sunshine Weather Meter S80
[Glossiness measuring instrument]
Equipment used Suga Test Instruments Co., Ltd. Digital Variable Glossmeter UGB-5D

[Production example]
Polyisocyanate (A-1): A mixture containing 6700 parts of hexamethylene diisocyanate, 1000 parts of trimethyl phosphate and 2300 parts of ethylene glycol monomethyl ether acetate is placed in a reactor equipped with a reflux condenser and water is stirred well under a nitrogen atmosphere. 50 parts were added, and the temperature was raised to 160 ° C. over 20 minutes, and further reacted at 160 ° C. for 60 minutes at normal pressure. After the reaction, no precipitation of polyurea or the like was observed in the solution, and this reaction solution was unreacted hexamethylene diisocyanate and trimethyl phosphate, ethylene glycol monomethyl ether acetate in a thin film evaporator under the condition of 0.2 Torr / 180 ° C. Was recovered to obtain 1190 parts of polyisocyanate.
The resulting polyisocyanate is a yellow, transparent liquid having a viscosity of 1200 mPa.s at 25 ° C. s, isocyanate content (hereinafter abbreviated as NCO%) 23.9%, residual hexamethylene diisocyanate was 0.2%.
When the infrared absorption spectrum of the obtained polyisocyanate was measured, characteristic absorption of biuret was observed at 1770 cm ⁻¹ .
Polyisocyanate (B-1): A four-necked flask equipped with a stirrer, thermometer and reflux condenser was charged with 1000 parts of hexamethylene diisocyanate and 300 parts of xylene, and stirred at 60 ° C. with tetramethylammonium capryate as a catalyst. 0.3 parts were added in 4 portions every 30 minutes.

The reaction was continued at 60 ° C, and after 4 hours, the reaction was stopped by adding 0.2 part of phosphoric acid when the conversion of hexamethylene diisocyanate reached 21% by NCO% titration and refractive index measurement of the reaction solution. did. Thereafter, heating was further continued at 90 ° C. for 1 hour, then cooled to room temperature, and the reaction solution was filtered. Then, using a thin film evaporator, the first time was 0.8 Torr / 160 ° C., the second time was 0.1 Torr / Under the condition of 160 ° C., the solvent and unreacted hexamethylene diisocyanate were removed and recovered.
The resulting polyisocyanate is a slightly yellow, transparent liquid, the yield is 210 parts, and the viscosity at 25 ° C. is 1300 mPa.s. s, NCO% was 23.5%, and the residual hexamethylene diisocyanate was 0.2%.
When the infrared absorption spectrum of the obtained polyisocyanate was measured, characteristic absorption of isocyanurate was observed at 1690 cm ⁻¹ .

[Example 1]
A mixed solvent of 30 parts of n-butyl acetate and 30 parts of xylene containing 4 parts of polyisocyanate (A-1), 36 parts of polyisocyanate (B-1) and 0.2 part of water was mixed. The sample was left in a room kept at a temperature of 20 ° C., and the number of days until the appearance became cloudy was visually observed. The results are shown in Table 1.

[Examples 2-3]
A visual appearance test was performed in the same manner as in Example 1 except that the mixing was performed in the parts by weight shown in Table 1. The results are shown in Table 1.

[Comparative Example 1]
The appearance was observed in the same manner as in Example 1 except that the polyisocyanate (B-1) was used alone. The results are shown in Table 1.

[Example 4]
A mixed solvent of 10 parts of polyisocyanate (A-1), 100 parts of polyisocyanate (B-1), 43 parts of n-butyl acetate and 43 parts of xylene was mixed. After absorbing moisture for 20 hours under a saturated water vapor at a temperature of 20 ° C., the moisture content was measured and left in a room maintained at a temperature of 20 ° C., and the number of days until cloudiness was observed. The results are shown in Table 2.

[Examples 5 to 6]
A visual appearance test was performed in the same manner as in Example 4 except that the mixing was performed in the parts by weight shown in Table 2. The results are shown in Table 2.

[Comparative Example 2]
The appearance was observed in the same manner as in Example 4 except that polyisocyanate (B-1) was used alone. The results are shown in Table 2.

[Example 7]
4 parts polyisocyanate (A-1), 30 parts polyisocyanate (B-1), 6 parts Vestagon T1890 (Degussa product) (trade name) as polyisocyanate (C), 0.2 parts water A mixed solvent of 30 parts of n-butyl acetate and 30 parts of xylene was mixed. The sample was left in a room kept at a temperature of 20 ° C., and the number of days until the appearance became cloudy was visually observed. The results are shown in Table 3.

[Examples 8 to 9]
A visual appearance test was performed in the same manner as in Example 7 except that the mixing was performed in the parts by weight shown in Table 3. The results are shown in Table 3.

[Comparative Example 3]
The appearance was observed in the same manner as in Example 7 except that the polyisocyanate (A-1) was not used. The results are shown in Table 3.

[Example 10]
4 parts of polyisocyanate (A-1), 36 parts of polyisocyanate (B-1), 0.1 part of tinuvin 292 as an ultraviolet absorber were mixed, and Acridic A-801 (acid value 50 mgKOH / g, 50% solid content, manufactured by Dainippon Ink & Chemicals, Inc., trade name) and blended in parts by weight shown in Table 4. The blended solution was coated with an applicator to a thickness of 50 μm, baked at 120 ° C. for 30 minutes, and then subjected to a weather resistance test with a sunshine weather meter. The results are shown in Table 4. However, the gloss retention is (Gloss of coating after weathering test) / (Gloss of initial coating) x 100.

[Comparative Example 4]
A weather resistance test was performed in the same manner as in Example 10 except that tinuvin 292 was not added. The results are shown in Table 4.

[Comparative Example 5]
A weather resistance test was performed in the same manner as in Example 10 except that polyisocyanate (A-1) and tinuvin 292 were not added. The results are shown in Table 4.

As shown in the present invention, by using a curing agent in which a specific hexamethylene diisocyanate-based biuret type polyisocyanate and a hexamethylene diisocyanate-based isocyanurate type polyisocyanate are combined, sufficient storage stability and moisture stability 2 A liquid polyurethane coating composition is obtained. The two-component polyurethane coating composition containing the curing agent of the present invention is useful for applications such as adhesives, pressure-sensitive adhesives, and casting agents in addition to urethane paints.

Claims (2)

What hardener der consisting polyisocyanate composition comprising a polyisocyanate (B) having a polyisocyanate (A) and the isocyanurate structure obtained from hexamethylene diisocyanate having a biuret structure obtained from hexamethylene diisocyanate,
(A) / (B) is 1/99 to 60 / Ri 40 parts by weight ratio der of, and the polyisocyanate (C) having an isocyanurate structure obtained from isophorone diisocyanate (A) and the total mass of the (B) curing agent comprising a polyisocyanate composition characterized that you containing from 1 to 50% by weight with respect to part. The curing agent comprising the polyisocyanate composition according to claim 1, wherein the curing agent contains 0.01 to 1.0% by mass of an ultraviolet absorber and / or a light stabilizer.