JPS6247882B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polyurethane resin that has excellent weather resistance and can be used as a solvent-free or high-solids urethane paint, especially when used as a urethane paint. Aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) are used in large quantities as isocyanate compounds that are raw materials for polyurethane resins. The major drawback of polyurethane is that it yellows over time, and this drawback is one of the restrictions on its use. Many attempts have been made to obtain polyurethane compounds with improved yellowing resistance, including hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), nuclear hydrogenated xylylene diisocyanate (H ₆ XDI), nuclear hydrogenation Application of aliphatic or araliphatic polyisocyanates such as diphenylmethane diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), and lysine diisocyanate ester (LDI) to polyurethane resins is being considered. However, since these have a small number of functional groups per molecule and a high vapor pressure at room temperature, when used as paints, etc., adducts or dimers with polyfunctional alcohols, amines, water, etc. It was necessary to create adducts of isocyanates such as , trimers, and carbodiimides. However, since the isocyanate groups of these adducts are consumed due to the addition reaction, the usable isocyanate group content further decreases and the viscosity becomes high. For this reason, it is extremely difficult to create solvent-free or high-solid paints, which are strongly desired in recent years from the perspective of pollution control. In addition, when producing the adduct, complicated techniques and expensive production equipment are required in order to reduce the content of isocyanate monomer, which poses a major hygiene problem at the work site. The inventors have proposed the general formula () (In the ceremony

【ceremony

[expression] or

[Formula] is shown. It has been discovered that the triisocyanate compound represented by ) does not have the drawbacks of currently used isocyanate compounds, has excellent weather resistance when used as a urethane resin, and can be used as a solvent-free or high-solid paint. That is, the present invention provides the general formula () (In the ceremony

【ceremony

[expression] or

[Formula] is shown. ) This is a method for producing a polyurethane resin, which is characterized by reacting a triisocyanate compound represented by the following with an active hydrogen compound. The triisocyanate compound represented by the general formula () is a new compound that has not been described in any literature. In the expression (),

[Formula] is

The compound with the formula is 1,3,5-tris(isocyanatomethyl)benzene (hereinafter sometimes abbreviated as MTI),

[Formula] is

The compound with the formula is 1, 3, 5-tris(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as H ₆ TMI), and these are the corresponding triamine compounds (), i.e. , 1,3,5-tris(aminomethyl)benzene (hereinafter sometimes abbreviated as MTA) and 1,3,5-tris(aminomethyl)cyclohexane (hereinafter sometimes abbreviated as H ₆ MTA) ) can be produced by phosgenation. Phosgenation of the triamine compound () can be carried out according to a method known per se. One of them is a method called cold hot phosgenation, in which a raw material triamine compound or an organic solvent solution of the triamine compound is dropped into a cooled liquid phosgene or an organic solvent solution of phosgene under stirring, and then This is a method in which the reaction temperature is raised while phosgene is supplied to proceed and complete the reaction. Another method is to add the salt of the raw triamine compound to an organic solvent to form a slurry, or add an acid to the organic solvent solution of the triamine compound to obtain a slurry of the triamine salt, and then supply phosgene to this slurry. This is a method in which the phosgenation reaction proceeds and is completed by gradually raising the temperature. Although a highly pure raw triamine compound may be used, it is also possible to use a raw material containing a small amount of impurities that are by-produced during the production of the triamine compound. Examples of organic solvents used in the phosgenation reaction include aromatic hydrocarbons, halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and halogenated alicyclic hydrocarbons, but in particular, chlorobenzene, Halogenated aromatic hydrocarbons such as O-dichlorobenzene are preferred. Salts of triamine compounds include acetates, hydrochlorides, sulfates, carbamates, etc., and among them, carbamates prepared by reacting triamine with carbon dioxide are preferred. Phosgene can be used in either gaseous or liquid form, and phosgene dimer (trichloromethyl chloroformate), which is considered a precursor of phosgene and is known in the art, can also be used. Regarding the reaction temperature between the triamine compound () and phosgene, it is preferable to select a reaction temperature between -20 and 180°C, since too high a temperature will produce a large number of by-products, and a too low temperature will result in a low reaction rate.
Excess phosgene and the reaction solvent are removed from the reaction solution that has been phosgenated in this manner, and then vacuum distillation is performed to obtain the desired triisocyanate compound () with high purity. The triamine compound of the general formula () is also a new compound that has not been described in any literature, and can be produced, for example, by the method described below. That is, 1,3,5-tris(aminomethyl)benzene (MTA) is, for example, 1,3,5-tris(aminomethyl)benzene (MTA)
- H ₆ MTA can be obtained by hydrogenating MTA in the presence of a catalyst or by hydrogenating MTA in the presence of a catalyst. It can be obtained by hydrogenating the cyano group and reducing the benzene nucleus all at once in the presence of . First, the production of MTA by hydrogenation of MTN is carried out in the presence of hydrogen in the liquid phase, and can be carried out more preferably by using a solvent. Solvents include benzene, toluene, xylene, methanol, ethanol, propanol, isopropanol, isobutanol, dioxane,
Solvents that are stable under the reaction conditions such as tetrahydrofuran, liquid ammonia, and water can be used alone or as a mixture of two or more, but alcohol-based or aromatic hydrocarbon-alcohol mixed solvents can be used as inexpensive catalysts, Even when the amount of catalyst is reduced, the yield does not decrease much, so it can be said to be a more preferable solvent. The amount of solvent to be used is 0.5 to 10 times the volume of the raw material trinitrile compound, preferably 1 to 6 times the volume.
This is the range where double capacity gives good results. Of course, there is no major problem in the reaction even if a larger amount of solvent is used, but from an industrial standpoint, it may be economically disadvantageous to use a large amount of solvent. Also LiOH,
Alkali metal hydroxides and alcoholates such as NaOH and KOH are added to raw trinitrile compounds.
By adding 0.05 to 40% by weight, preferably 0.5 to 20% by weight, more preferable reduction conditions can be obtained. Hydrogenation uses hydrogen gas, and the reaction is preferably carried out in a pressure-resistant container such as an autoclave. The reaction pressure is 30 to 300 Kg/cm ² G, preferably 30 to 150 Kg/cm ² G, and the reaction temperature is -10 to 150°C.
Preferably it is 40-120°C. In hydrogenation, it is usually desirable to use a catalyst. Examples of the catalyst include Raney cobalt, Raney nickel, Raney nickel chromium, platinum, palladium, ruthenium, rhodium, etc. These may be used alone or as a mixture of two or more, but among them, Raney nickel chromium is more preferable. Give results. In addition, by selecting an appropriate solvent system and the amount of alkali added, it is possible to use a cheaper Raney nickel catalyst,
Even if the amount of catalyst is reduced, conditions can be obtained in which the yield is relatively less reduced. This MTA is a colorless crystal at room temperature, approximately 50℃
When heated, it becomes a colorless and transparent liquid. When purified under normal conditions, it has a melting point of 49-51°C and a boiling point of 136-139°C/0.4 mmHg. _H6 MTA is MTA
or by hydrogenating MTN. When hydrogenating MTA, it is usually carried out in the presence of hydrogen in a liquid phase, and a solvent is used if necessary. As the solvent, for example, water, ethanol, methanol, propanol, isopropanol, isobutanol, dioxane, acetic acid, tetrahydrofuran, etc. can be used alone or in a mixture of two or more, but water is advantageous in that it is cheap; In addition, even when the amount of catalyst is reduced, the alcohol-water mixed solvent does not reduce the yield so much that it can be said to be a more preferable solvent. The solvent is not necessarily required depending on the reaction conditions selected, but if used, the volume should be 0.05 to 10 times, preferably 0.1 to 5 times the volume of the raw material MTA, as long as it gives good results. be. Additionally, alkali metal hydroxides, alkaline earth metal hydroxides, and their carbonates, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, and their carbonates, are added to MTA. 0.05~20
More preferable nuclear reduction conditions can be obtained by adding % by weight, preferably 0.1 to 10% by weight. Hydrogenation uses hydrogen gas, and the reaction vessel is not particularly limited as long as it can withstand the corresponding reaction conditions; however, if the reaction pressure is high, a pressure vessel such as an autoclave is used. Reaction pressure is 5-300
Kg/cm ² G, preferably 5 to 150 Kg/cm ² G, and the reaction temperature is -10 to 200°C, preferably 50 to 150°C. In hydrogenation, it is usually desirable to use a catalyst. Examples of catalysts include Raney chromium, palladium, platinum, rhodium, ruthenium, etc., which may be used alone or as a mixture of two or more, and optionally activated carbon, silica gel, alumina,
A more preferred catalyst can be obtained by supporting it on a carrier such as diatomaceous earth or pumice. Among these, when the ruthenium catalyst is used as a solvent, especially water containing a small amount of alkali metal hydroxide or carbonate, alcohol, or a mixture of both, the yield does not decrease even if the amount of catalyst added is reduced. It can be said that it is extremely desirable. Furthermore, H ₆ MTA can also be obtained by directly hydrogenating MTN. When hydrogenating MTN, more desirable results can be obtained by carrying out hydrogenation in the presence of liquid phase hydrogen and using a solvent. Solvents include benzene, toluene, xylene, methanol, ethanol, propanol, isopropanol, isobutanol,
Dioxane, tetrahydrofuran, acetic acid, liquid ammonia, water, etc. can be used alone or in a mixture of two or more, and among these, water, ethanol, or a mixture of both are preferred solvents that give the desired product in high yield. During the reaction, by-products can be prevented as much as possible by having ammonia present at the same time or in a liquid ammonia solvent, but the same effect can be obtained by adding 0.01 to 5%, preferably 0.05 to 3.0%, in the solvent. It can also be obtained by adding a certain amount of caustic alkali, such as caustic soda or caustic potash, to the reaction. The amount of solvent used is 50-1000V/W for MTN.
%, preferably 100-600 V/W% is the range that gives good results. Hydrogen gas is used for hydrogenation, and there are no particular restrictions on the reaction vessel as long as it can withstand the selected reaction conditions, but if the reaction pressure is particularly high, it is preferable to carry out the reaction in a pressure-resistant vessel such as an autoclave.
The reaction pressure is 5 to 300 Kg/cm ² G, preferably 30 to
200 Kg/cm ² G, reaction temperature is -10 to 250°C, preferably 50 to 200°C. In hydrogenation, it is usually desirable to use a catalyst. Examples of catalysts include Raney cobalt, Raney nickel, Raney nickel chromium, palladium, platinum, rhodium, and ruthenium, which can be used alone or as a mixture of two or more, but among them, rhodium catalysts have a high yield. It is also preferable as a catalyst that provides H ₆ MTA. In particular, when water, ethanol, or a mixture of both is used as a solvent, the yield of the hydrogenation reaction is high, and this can be said to be the most preferable reaction condition for obtaining H ₆ MTA from MTN in one step. H ₆ MTA is a colorless and transparent liquid at room temperature, and does not solidify or form precipitates even when cooled to 0°C. The triisocyanate compound used in the present invention is
It has various advantages over conventionally known polyisocyanates. In other words, it is completely odorless and non-irritating at room temperature, and is a colorless and transparent liquid with extremely low viscosity, and is particularly useful as a component for solvent-free or high-solid urethane paints.
In addition, the raw materials are relatively cheap and the manufacturing method is simple, so the industrial value is extremely high. In the present invention, various polyurethane resins can be produced by various polyaddition processes by utilizing the reaction between such triisocyanate compounds and active hydrogen compounds. The triisocyanate used in the present invention can be used not only as it is, but also as various modified products (dimer, trimer, carbodiimide, etc.) known in the art, as well as polyols, polyamines, etc.
It can also be used in the form of a prepolymer reacted with amino alcohol, water, etc. In the case of applications such as baking paints, it can also be used in the form of so-called masked isocyanates using various known blocking agents. Suitable masking agents include, for example, phenols such as phenol, cresol, and isononylphenol, oximes such as butanone oxime and benzophenone oxime, lactams such as caprolactam, alcohols such as methanol, acetoacetate, and malon. Examples include esters such as acid esters, triazoles such as benzotriazole, and mercaptans. Examples of active hydrogen compounds suitable for reaction with the polyisocyanates according to the invention or the corresponding masked polyisocyanates include:
At least 2 isocyanate-reactive hydrogen atoms
and generally have a molecular weight of 400-10,000. Very suitable compounds of this type are polyhydroxy compounds having 2 to 8 hydroxy groups, especially those having a molecular weight of 800 to 10,000 (more preferably 1,000 to 10,000).
6000) is preferred. For example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyesteramides or similar compounds having at least 2, generally 2-8, preferably 2-4 hydroxy groups can be used. Compounds of this type are generally known per se as raw materials for the production of polyurethanes. Examples of suitable hydroxy group-containing polyesters include reaction products of polyhydric, preferably dihydric alcohols (to which trihydric alcohols may also be added) and polybasic, preferably dibasic carboxylic acids. . Examples of such acids are succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid,
Isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic acid, maleic anhydride, fumaric acid, etc. Examples of suitable polyhydric alcohols include ethylene glycol, Propylene glycol-(1,2) and -(1,3), butylene glycol-(1,4) and -(2,3), hexanediol-(1,6), neopentyl glycol, cyclohexanedimethanol (1, - 4-bis-hydroxymethylcyclohexane), glycerol, trimethylolpropane, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, etc. In addition to the polyhydroxy polyesters mentioned, the polyhydroxy polyethers known in the field of polyurethane chemistry can also be used for the novel triisocyanates. Examples of such polyhydroxy polyethers include at least two hydroxy groups.
Mention may be made, in general, of polyethers known per se having 2 to 8, preferably 2 to 3, polyethers. The polyether can be prepared by polymerizing the epoxide itself, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example in the presence of boron trifluoride, or by polymerizing these epoxides, for example in the presence of boron trifluoride. can be prepared by chemical addition of the compounds in the form of a mixture or one after the other to reactive hydrogen atom-containing starting components. Examples of reactive hydrogen-containing starting components include water, alcohols, amines such as ethylene glycol,
Propylene glycol -(1.3) or -(1.
2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine, and ethylenediamine. Specific examples of these compounds that can be used in the present invention are described, for example, in the following publications:
"High Polymers; Volume 1, Polyurethanes Chemistry and Technology", Saunders-Frissuille, Interscience Publishers New York London, Volume 1,
1962, pp. 32-42, 44-54, Vol. 1964, pp. 5-6, pp. 198-199 Hydroxyl group-containing vinyl polymers are also described in this book. It can be used as a reactant for the triisocyanate according to the invention. This vinyl polymer is a known compound composed of a copolymer of a hydroxyl group-containing ethylenically unsaturated monomer and other ethylenically unsaturated compounds, such as ethylenically unsaturated esters and hydrocarbons. Examples include copolymers containing the following hydroxyl monomer components: monohydroxy and polyhydroxyalkyl maleates and fumarates such as hydroxyethyl fumarate and its analogues; acrylates and methacrylates containing hydroxyl groups such as trimethylol. propane monomethacrylate,
2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, 2 (or -
3)-Hydroxypropyl acrylate and methacrylate, 4-hydroxybutyl acrylate and methacrylate, and hydroxyvinyl compounds such as hydroxyethyl vinyl ether and allyl alcohol. Furthermore, partially saponified products of homopolymers such as vinyl acetate or copolymers with other ethylenically unsaturated compounds can also be used as polyols. Polymers containing acid groups obtained by copolymerization of unsaturated acids such as maleic acid, acrylic acid or methacrylic acid can also be used in the lacquer. When the novel triisocyanates according to the invention, or the corresponding masked triisocyanates, are used in the two-component polyurethane lacquers, they are suitable not only for the relatively high molecular weight polyhydroxy compounds mentioned above, but also for the 62 It is also miscible with any low molecular weight polyol having a molecular weight within the range of -400. In many cases it is advantageous to use mixtures of the high molecular weight polyhydroxyl compounds mentioned above and low molecular weight polyhydroxyl compounds of the above type. The NCO/OH ratio in this two-component polyurethane lacquer is generally 0.8:1.
or 1.2:1. Examples of suitable low molecular weight polyhydroxyl compounds having molecular weights within the aforementioned ranges include diols and/or triols having hydroxyl groups attached in an aliphatic or cycloaliphatic type of bond, such as ethylene glycol, propane, etc. −
1,2-diol, propane-1,3-diol, hexamethylene diol, trimethylolpropane, glycerol, trihydroxyhexane, 1,2-hydroxycyclohexane, 1,4
-dihydroxycyclohexane. Low molecular weight polyols having ether groups, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, are also suitable. In principle, mixtures of the polyhydroxy compounds mentioned can also be used. However, each component therein must be mutually compatible. Lacquers prepared according to the invention using the new triisocyanates or the corresponding masked triisocyanates have the following great advantages: This means that the lacquer can be used without solvents, thereby producing weather-resistant coatings with excellent mechanical properties without the formation of bubbles. When producing this lacquer mixture (lacquer composition), the addition of moisture absorbers or dehydrating agents is generally unnecessary. The lacquers of this invention may be mixed with pigments and fillers in equipment commonly used in the lacquer industry. Raw materials and/or auxiliaries for this lacquer, such as cellulose esters, leveling agents, etc.
agents), plasticizers, silicone oils, resins and/or other customary substances can of course also be added.
Known catalysts can be used to control the reactivity of the polyurethane lacquer. This lacquer can be coated on the surface to be coated in a conventional manner, for example, by brushing, spraying, dipping, or the like. It is particularly useful for coating any article made of wood, metal, plastic or other materials.
The present invention can also be used as a method for producing polyurethane adhesives, foams, artificial leathers, fillers, etc. other than urethane paints. Reference example 1 1,3,5-tricyanobenzene (MTN)15
15 g of Raney nickel chromium (atomic ratio Ni:Cr = 49:1) developed by conventional method, 27 ml of methanol,
Capacity 300 with 63ml xylene and 0.18g possible soda
ml in a magnetically stirred autoclave, and the initial pressure
When high-pressure hydrogen was injected at 100 kg/cm ² G and the reaction was carried out at 100°C, 0.59 mol of hydrogen was absorbed in 35 minutes. The catalyst was filtered off, the solvent was distilled off, and 12.8 g of 1,3,5-tris(aminomethyl)benzene (MTA) was obtained by distillation under reduced pressure. This MTA has a melting point of 49-51℃ and a boiling point of 136-139℃/
It is a colorless crystal at room temperature of 0.4mmHg, and becomes a colorless and transparent liquid when heated to about 50℃. Reference Example 2 30 g of 1,3,5-tris(aminomethyl)benzene (MTA) was mixed with 3 g of 5% ruthenium-alumina catalyst (manufactured by Nippon Engelhard), 60 g of water, and 0.75 g of sodium chloride in a 300 ml electromagnetic stirrer. When it was sealed in an autoclave, high-pressure hydrogen with an initial pressure of 120 kg/cm ² G was injected, and the reaction was carried out at 115°C for 25 minutes, the result was 0.61
Molar hydrogen uptake occurred. After filtering the catalyst and distilling off the solvent,
26.8 g of 1,3,5-tris(aminomethyl)cyclohexane (H ₆ MTA) was obtained. This H ₆ MTA obtained by this method has a boiling point of 127-8℃/1mm
It was a colorless and transparent low viscosity liquid of Hg. Reference example 3 1,3,5-tricyanobenzene (MTN) 20
g of 25% NH ₃ with 80 ml of water, 300 mg of sodium hydroxide and 4 g of commercially available 5% rhodium-alumina catalyst.
Enclosed in a magnetic stirring autoclave, initial pressure 120
When reacted for 70 minutes at 105℃ under high pressure hydrogen of Kg/cm ² G, 0.95 mol of hydrogen was absorbed and H ₆ MTA with both nitrile and nucleus reduced was obtained with a yield of 45%. . Reference Example 4 90.0 g of 1,3,5-tris(aminomethyl)benzene (MTA) was dissolved under heating in 1200 ml of o-dichlorobenzene in a 24-necked flask. When carbon dioxide gas was passed through the obtained amine solution until no weight increase was observed, a slurry of colorless crystals was obtained. This slurry was kept at 10°C or less for 30 minutes while blowing phosgene gas under stirring, then the temperature was raised to 130°C over 2 hours while continuing to supply phosgene, and the temperature was kept at 130°C for 5 hours. As the phosgenation reaction progressed, the slurry turned into a solution and finally became a homogeneous, slightly yellowish, transparent solution. After removing the dissolved phosgene by blowing nitrogen gas into the phosgenation reaction completed liquid, it is heated under reduced pressure.
The solvent o-dichlorobenzene was distilled off. When the obtained crude isocyanate was vacuum distilled, the boiling point was
112.9 g of 1,3,5-tris(isocyanatomethyl)benzene (MTI) was obtained at 173-175°C/0.4 mmHg (molar ratio 85.21%). This MTI was a liquid with low viscosity even at 5°C, and there was no strong isocyanate odor. When the amine equivalent was measured, it was 83.25.
(Theoretical value 81.1). The IR spectrum of the obtained MTI is shown in Figure 1. Since the obtained MTI contained a trace amount of impurity, the following experiment was conducted to remove this and confirm the identification. That is, a small amount of MTI was reacted with a large amount of methyl alcohol to obtain a methylurethane compound, and this was recrystallized using acetone as a solvent to obtain white crystals of MTI trimethylurethane (recrystallization yield 71.5%). ).
The results of elemental analysis of the purified trimethylurethane compound were in good agreement with the theoretical value, and its melting point was 155-156°C. Elemental analysis value (as C ₁₅ H ₂₁ N ₃ O ₆ ) Theoretical value (%) Measured value (%) C 53.09 53.03 H 6.24 6.01 N 12.38 12.09 Reference example 5 1,3,5-tris(aminomethyl)benzene (MTA ), 70.0 g of 1,3,5-tris(aminomethyl)cyclohexane (H ₆ MTA) was used, and the temperature was raised from 10°C to 120°C over 6 hours.
When phosgenation was carried out in the same manner as in Reference Example 4 except that it was kept at 120℃ for 6 hours, the boiling point was 170-174℃/
91.8 g of 1,3,5-tris(isocyanatomethyl)cyclohexane (H ₆ MTI) of 0.53 mmHg was obtained. (Molar yield 90.1%). This H ₆ MTI was a low viscosity liquid and odorless even at 5°C. The actual value of amine equivalent was 84.71 (theoretical value 83.08). obtained
The IR spectrum of H ₆ MTI is shown in Figure 2. As in the case of MTI, it was purified by methylurethanization and recrystallization (solvent acetone).
The elemental analysis values of trismethylurethanide of H ₆ MTI were as follows. Elemental analysis value (as C ₁₅ H ₂₇ N ₃ O ₆ ) Theoretical value (%) Measured value (%) C 52.16 52.27 H 7.88 8.00 N 12.17 11.88 Reference example 6 250 g of o-dichlorobenzene was placed in the four-neck flask from 1. The mixture was prepared and allowed to absorb phosgene under ice-cooling.
45.2 in advance while blowing in phosgene gas.
A solution of 1,3,5-tris(aminomethyl)benzene (MTA) dissolved in 500 g of o-dichlorobenzene was added dropwise over 100 minutes. As the dropping progressed, the viscosity of the liquid inside the flask increased and became slurry-like. 10 minutes for 30 minutes after the completion of amine dripping.
After keeping the temperature below ℃, the reaction solution was heated to 130℃ over 5 hours while blowing phosgene, and then heated to 130℃ for 6 hours at 130℃.
Phosgenation was completed by reacting for hours. By the same operation as in Reference Example 4, 54.8g (yield
An MTI of 82.4%) was obtained. Reference example 7 In the same manner as reference example 4, 42.3g of 1, 3, 5-
Tris(aminomethyl)cyclohexane (H ₆ MTA) was phosgenated to yield 53.0 g (yield
A _H6 MTI of 86.1%) was obtained. Example 1 Using the MTI obtained in Reference Example 4, a highly nonvolatile two-component urethane paint was prepared. Component A: Acrylic polyol [styrene 50
%, 2-hydroxyethyl methacrylate 23.2
%, acrylic acid, n-butyl 26.8% in toluene-butyl oxide (1:1), non-volatile content 65%, OH value 65] 863 parts Titanium oxide powder 429.5 parts Ethyl oxide/butyl acetate /Cellosolve acetate (1/1/1) 276.1 parts Component B: MTI 83.3 parts Component A, whose pigment was sufficiently dispersed in a ball mill, and component B were mixed in the above ratio so that NCO/OH = 1/1. mixed with. The non-volatile content of this mixture was 65% and its viscosity was 24 seconds as measured at 25°C using a #4 food cup. This product was immediately spray-painted onto a mild steel plate whose surface had been treated with iron phosphate so that the dry coating thickness was 30 to 40 μm. After curing for 7 days at 25°C, the physical properties of the coating film were evaluated and a weather resistance test was conducted. Coating film thickness 30-40μ Pencil hardness H Erichsen extrusion test 8.5mm Goban test (adhesion) 100/100 Sunshine type weatherometer 500 hours
△E 1.2 Examples 2 to 4 Highly non-volatile two-component urethane was produced in the same manner as in Example 1 using the MTI obtained in Reference Example 4 or the H ₆ MTI obtained in Reference Example 5 and various polyols. A paint was prepared and its physical properties and weather resistance were investigated. The results are summarized in Table 1.

[Table] Polyester polyol: Cocondensate of 2 moles of adipic acid, 1 mole of dipropylene glycol, 2 moles of trimethylolpropane, and 1 mole of coconut oil fatty acid, non-volatile content 100%, OH value 220 Acrylic polyol: 50% styrene, methacrylic 23.2% dihydroxyethyl acid, n-acrylic acid
Butyl 26.8% toluene-butyl acetate (1:
1) Copolymerized in 65% non-volatile content,
OH value 65 Polyester polyol: 2 moles of adipic acid,
A co-condensate of 1 mole of diethylene glycol, 2 moles of trimethylolpropane, and 1 mole of coconut oil fatty acid with a non-volatile content of 100% and an OH value of 230 BA: Butyl acetate EA: Ethyl acetate CA: Cellosolve acetate Example 5 254.1 parts of H ₆ MTI 1,3-butylene glycol
45.1 parts and heated at 75-80°C for 4 hours to obtain an adduct with an isocyanate group content of 28.1%. Polyester polyol (trimethylolpropane 1
(obtained by condensing 2 moles of ethylene glycol, 2 moles of dipropylene glycol, and 4 moles of adipic acid, with a solid content of 100% and an OH value of 185), 300 parts of titanium oxide, 300 parts of titanium oxide, and 321 parts of thinner. The mixture was dispersed using a ball mill, and 150 parts of the above isocyanate adduct were mixed therein. The non-volatile content of this mixture was 70% and its food cup #4 viscosity was 25 seconds. Spray-painted on phosphate-treated mild steel plate, 25
After curing for 7 days at ℃, the performance of the coating film was evaluated. Pencil hardness HB Erichsen extrusion test 8.5mm Goblin test 100/100 Weather resistance △E 0.7 (Sunshine type weatherometer 500 hours) Example 6 _H6 MTI49.8 in 117 parts of ethoxyethyl acetate
300 parts of polyethylene butylene adipate (molecular weight 3000) was added thereto, and the mixture was reacted at 70 to 75°C for 3 hours (NCO/OH=3). A solution of polyisocyanate with an isocyanate group content of 3.6% (NV=75 wt%) was obtained. This solution was spray-painted onto a mild steel plate whose surface had been treated with phosphoric acid.
After curing at 25°C for 7 days, the physical properties of the coating film were evaluated and a weather resistance test was conducted. Pencil hardness 2B Erichsen extrusion test 8.0mm Goban test 100/100 Weather resistance △E 0.7 Ducycle Weatherometer 500 hours
No abnormality Example 7 243 parts of MTI and 500 parts of polyoxypropylene glycol (molecular weight 1000) were mixed in 248 parts of xylene at 70 to 70 parts.
The reaction was allowed to proceed for 3 hours while maintaining the temperature at 75°C. (NCO/
OH=3) A polyisocyanate solution (solid content 75%) with an isocyanate group content of 8.5% was obtained. This solution was spray-painted onto a mild steel plate, and after curing at 25°C for 7 days, the physical properties of the coating film were evaluated and a weather resistance test was conducted. Pencil hardness HB Erichsen extrusion test 8.0mm Goban test 100/100 Weather resistance △E 0.7 Ducycle Weatherometer 250 hours
No abnormalities Examples 8 to 10 Polyisocyanate solutions were produced from H ₆ MTI and various active hydrogen compounds in the same manner as in Example 6. These are shown in Table 2 along with the coating film performance.

【table】 [Brief explanation of the drawing]

Figure 1 is the IR spectrum of MTI obtained in Reference Example 4, and Figure 2 is the IR spectrum of MTI obtained in Reference Example 5.
This is an IR spectrum of H ₆ MTI.

Claims (1)

[Claims] 1 General formula () (In the formula, [Formula] represents [Formula] or [Formula].) A method for producing a polyurethane resin, which comprises reacting a triisocyanate compound represented by the following with an active hydrogen compound.