JP2019172941A - Aliphatic and/or alicyclic polyurethane urea resin and manufacturing method therefor - Google Patents

Abstract

To provide a two-packed curable polyurethane urea resin capable of securing sufficient molding time at an ordinary temperature or a moderately increased temperature, processing a reaction quantitatively, and having transparency and excellent physical property, light resistance, heat resistance or the like, and a manufacturing method therefor.SOLUTION: There are provided a two-packed curable polyurethane urea resin precursor composition, consisting of a blocked isocyanate compound in which aliphatic and/or alicyclic polyisocyanate are blocked by a diazole compound and/or a triazole compound (azole compound) and an aliphatic and/or alicyclic primary polyamine compound, and capable of reacting at an ordinary temperature to 90°C, a polyurethane urea resin by a curing reaction of the precursor composition, and a manufacturing method therefor.SELECTED DRAWING: None

Description

  The present invention relates to a polyurethane urea resin obtained by reacting an aliphatic polyisocyanate and / or an azole blocked isocyanate compound of an alicyclic polyisocyanate with an aliphatic and / or alicyclic primary polyamine, and its production. It is about the law.

  Aliphatic and / or alicyclic polyurethaneurea resins are known to exhibit excellent physical properties, light resistance, heat resistance, etc., but aliphatic primary polyamines and alicyclic primary polyamines are Aliphatic and alicyclic polyisocyanates, which are less reactive than aromatic isocyanates, are very highly active and gel in seconds at room temperature (15-25 ° C.). An aliphatic and / or alicyclic two-component curable polyurethaneurea resin using a cis- and / or alicyclic primary polyamine as a curing agent has not been put to practical use.

  Blocked isocyanate compounds have long been studied and put into practical use as compounds that reduce the reactivity of isocyanates so that they can coexist with polyols and amine compounds. Stable at room temperature comprising a blocked isocyanate compound in which isocyanate is blocked with a phenolic compound, methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 3,5-dimethylpyrazole and the like and a compound containing an active hydrogen group such as a hydroxyl group or an amino group Yes, it is a one-component system that cures by high-temperature heating. It is used in a wide range of paint applications such as solution paints, powder paints and water-based paints (Non-Patent Document 1 and Non-Patent Document 2). As the active hydrogen-containing compound to be reacted with the blocked isocyanate compound, storage stability is emphasized, and a hydroxyl group-containing polyester resin or epoxy resin is used exclusively, and curing is usually carried out at a high temperature of 100 to 170 ° C.

  Patent Document 1, Patent Document 2 and Patent Document 3 show a composition comprising a blocked isocyanate compound of an aliphatic and / or alicyclic polyisocyanate and an aliphatic polyamine or an alicyclic diamine.

  Patent Document 1 relates to a composition which is stable at room temperature and comprises a pyrazole blocked isocyanate compound of 1,6-hexamethylene diisocyanate or isophorone diisocyanate and a liquid polyamine such as a polyoxyalkylene polyamine. The composition is a one-component composition utilizing the fact that the diisocyanate pyrazole blocked isocyanate compound is insoluble and does not react with the polyoxyalkylene polyamine at room temperature to 50 ° C., and the curing reaction is performed at a high temperature, for example, 120 ° C./30 minutes. Is going.

A high molecular weight polyurethane resin containing an amino group at the terminal obtained by reacting polyester polyol, isophorone diisocyanate and isophorone diamine as a chain extender under high dilution in Example 1 of Patent Document 2, and an isophorone diisocyanate compound blocked with imidazole A printing ink binder having a resin content of about 30% is disclosed.
In the comparative example of the patent, when isophorone diisocyanate is used instead of the imidazole blocked isocyanate compound, good performance is shown, but storage stability at room temperature is deteriorated. It is said that the imidazole blocked isocyanate compound of isophorone diisocyanate does not react with the terminal amine of the high molecular weight polyurethane resin at room temperature and can be made into one solution.

  In Example 4 of Patent Document 3, an isocyanate-terminated prepolymer composed of a polyol (polyether polyol, polybutylene glycol, nonionic and anionic hydrophilic group-containing active hydrogen compound) and isophorone diisocyanate, isophoronediamine and 1,2,4 -A 40% solids postcrosslinkable polyurethane water dispersion consisting of a partially crosslinked polyurethane resin containing blocked isocyanate groups reacted with triazole and 4,4'-diaminodicyclohexylmethane is shown. The dispersion is a one-component composition that is stable at room temperature. In Application Example 5, the curing reaction is performed at 160 ° C.

  Patent Document 1, Patent Document 2 and Patent Document 3 show a composition comprising a blocked isocyanate compound of an aliphatic and / or alicyclic polyisocyanate and an aliphatic polyamine and / or an alicyclic polyamine. However, both relate to a one-component high-temperature baking composition that is stable at room temperature or at a moderately elevated temperature, and a blocked isocyanate compound of aliphatic and / or alicyclic polyisocyanate and aliphatic System and / or alicyclic primary polyamine is an aliphatic system and / or alicyclic system in which the reaction proceeds quantitatively at room temperature or a moderately elevated temperature, for example, 90 ° C. or less, and exhibits excellent physical properties. It has not been known to produce polyurethaneurea resins.

USP 5210169 Patent 3084870 Patent 4916048

Latest Functional Polyurethane Technology 2015: Published by CMC Co., Ltd., 17-19 (2015) Recent technological development of block type polyurethane resin paint, thermosetting resin, Vol. 13, no. 2, 47-60 (1992)

  The object of the present invention is a two-component curable type that can secure a sufficient molding time at room temperature or a moderately elevated temperature, has a quantitative reaction, and is transparent and has excellent physical properties, light resistance, heat resistance, etc. An aliphatic and / or alicyclic polyurethaneurea resin and a method for producing the same.

  Another object of the present invention is to provide a human and environmentally friendly high solid type two-component curable aliphatic and / or alicyclic polyurethaneurea resin having reduced toxicity caused by isocyanate and a method for producing the same. It is to be.

  In order to achieve the above-mentioned object, the bimolecular nucleophilic substitution reaction, which is considered to be particularly necessary for room temperature curing, is focused on, and various structures of polyisocyanates, blocking agents, and polyamines are examined, and specific aliphatic and / or alicyclic groups. That the blocked isocyanate compound of the polyisocyanate proceeds quantitatively with the aliphatic polyamine and / or the alicyclic polyamine at a moderately elevated temperature from room temperature, and the reaction is mild and sufficient molding time can be secured. As a result, the present invention has been completed.

  That is, the present invention is shown in the following [1] to [3].

[1] Blocked isocyanate compound (component A) obtained by blocking an aliphatic and / or alicyclic polyisocyanate with a diazole compound and / or a triazole compound (azole compound) and an aliphatic and / or alicyclic ring A two-component curable polyurethaneurea resin comprising a group 1 primary polyamine compound (component B) and capable of reacting at room temperature to 90 ° C. and a method for producing the same.

[2] In the reaction of the component A and the component B, the equivalent of the amino group to the blocked isocyanate group is 0.85 to 1.15, and blocked with respect to the total weight of the blocked isocyanate compound and the polyamine compound. It is preferred that the isocyanate group concentration is 30 to 280 milligram equivalent / 100 g.

[3] Preferably, the blocked isocyanate compound (component A) is obtained by blocking an isocyanate-terminated prepolymer comprising an aliphatic and / or alicyclic isocyanate monomer and a polyol with an imidazole compound and / or a triazole compound. is there.

Aliphatic polyamines and alicyclic polyamines are very active against aliphatic and alicyclic polyisocyanates, using special molding machines such as collision-mixing sprays, and against isocyanate groups. Other than using a small amount, it could not be mixed uniformly and could not be molded.
The present invention first comprises a blocked isocyanate compound (A component) of an aliphatic and / or alicyclic polyisocyanate and an aliphatic and / or alicyclic primary polyamine (B component), and the reaction is carried out. It is a two-part curable polyurethane polyurea resin that progresses quantitatively from room temperature to a moderately elevated temperature to produce polyurethane urea resins with excellent physical properties, light resistance, transparency, heat resistance, etc. is there.

  Secondly, the blocked isocyanate compound of the present invention is a curing system in which foaming is suppressed even under high temperature and high humidity because it reacts selectively with polyamine over water at room temperature or at a moderately elevated temperature.

  Thirdly, the blocked isocyanate compound of an aliphatic and / or alicyclic polyisocyanate contains no volatile isocyanate monomer which is particularly dangerous by inhalation and does not contain any isocyanate group-containing compound and is cured at room temperature or Since it can be carried out at a moderately elevated temperature, it is a system that is very gentle to the human body with a low possibility that the blocked isocyanate compound is dissociated and the isocyanate compound is regenerated and scattered.

  Fourthly, the present invention is a two-component curing system that can be made into a high solid, and can reduce the content of volatile solvents compared to ordinary solvent-based paints and coating agents, and is an environmentally friendly system. .

  The aliphatic and / or alicyclic polyurethaneurea resin of the present invention comprises an aliphatic and / or alicyclic polyisocyanate, an azole blocking agent and an aliphatic and / or alicyclic primary polyamine. It has become.

  As an aliphatic and / or alicyclic polyisocyanate, an isocyanate-terminated prepolymer obtained by reacting an aliphatic and / or alicyclic polyisocyanate monomer, an aliphatic and / or alicyclic isocyanate monomer and a polyol. Examples thereof include modified polymers and modified aliphatic and / or alicyclic isocyanate monomers (allophanate modified, urea modified, carbodiimide modified, burette modified, uretdione modified, isocyanurate modified, etc.).

  Examples of the aliphatic polyisocyanate monomer include 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, 2 , 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine diisocyanate, trioxyethylene diisocyanate and the like.

  Examples of the alicyclic polyisocyanate monomers include 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate), 4,4′-methylenebis ( Cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatoethyl) cyclohexane, 1,4- Examples include bis (isocyanatoethyl) cyclohexane, 2,5- or 2,6-bis (isocyanatomethyl) norbornane (NBDI).

  The aliphatic and / or alicyclic isocyanate-terminated prepolymer of the present invention is mainly composed of one or more selected from the aliphatic and / or alicyclic polyisocyanate monomers and the high molecular weight polyol described below, If necessary, a low molecular weight polyol can be used in combination.

  The aliphatic and / or alicyclic isocyanate-terminated prepolymer is produced by a known method using the aliphatic and / or alicyclic polyisocyanate monomer and polyol in a nitrogen gas atmosphere, and if necessary, a solvent or dioctyltin. The reaction is performed at 60 to 100 ° C. in the presence of a known catalyst such as dilaurate. The isocyanate group / hydroxyl group equivalent ratio in the reaction is usually 1.5 to 2.5 / 1.0. The isocyanate group / hydroxyl group equivalent ratio is usually 2.0 or less in order to reduce the isocyanate monomer, but in the present invention, it reacts with the azole compound including the isocyanate monomer in the next step and is less likely to volatilize. Depending on the properties of the prepolymer and the physical properties of the cured product, the isocyanate group / hydroxyl group equivalent ratio may be set to 2.0 or more.

  As a low molecular weight polyol, a compound having two or more hydroxyl groups and a number average molecular weight of less than 400, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1 , 2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5- Pentanediol, alkane-1,2-diol (C17-20), 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy -2-butene, 2,6- Methyl-1-octene -, dihydric alcohols such as 3,8-diol, glycerol, trihydric alcohols such as trimethylolpropane.

  In addition, polyalkylene oxides having a number average molecular weight of less than 400 (including random and / or block copolymers of two or more alkylene oxides) obtained by adding alkylene oxides such as ethylene oxide and propylene oxide using these as initiators. .) Is also included in the low molecular weight polyol.

  The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more. For example, polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, etc. Can be mentioned.

  Examples of the polyether polyol include polyoxyalkylene polyol and polytetramethylene ether glycol.

  The polyoxyalkylene polyol is an addition polymer of alkylene oxide such as propylene oxide, ethylene oxide, butylene oxide, styrene oxide and the like, specifically having a number average molecular weight of 400 to 5,000. More preferable examples include polypropylene glycol and polyethylene polypropylene glycol (random or block copolymer) of 400 to 3,000.

  Examples of polytetramethylene ether glycols include polytetramethylene ether glycol having a number average molecular weight of 400 to 5000, which is a homopolymerized diol of tetrahydrofuran by cationic ring-opening polymerization, and cationic opening of tetrahydrofuran having a number average molecular weight of 500 to 3000 and 3-alkyltetrahydrofuran. Examples include ring copolymerization and amorphous polytetramethylene ether copolymer glycols at room temperature which are obtained by copolymerization of tetrahydrofuran and dihydric alcohol in the presence of a catalyst such as a heteropoly acid.

  Examples of the polyester polyol include polycondensates obtained by reacting the above-described low molecular weight polyol and polybasic acid under known conditions.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (carbon number 11-13), suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, nonadecanedioic acid Carboxylic acids such as acid, eicosane diacid, methylhexane diacid, citraconic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid and het acid And acid anhydrides derived from these carboxylic acids, acid halides, ricinoleic acid, 12 Etc. hydroxystearic acid.

  Specific examples of polycondensates of low molecular weight polyols and polybasic acids include poly (ethylene butylene adipate) polyol, poly (ethylene adipate) polyol, poly (ethylene propylene adipate) polyol, poly (propylene adipate) polyol, poly (Butylene hexane adipate) polyol, poly (butylene adipate) polyol, poly (hexane adipate) polyol, poly (3-methyl-1,5-pentane adipate) polyol, poly (3-methyl-1,5-pentane azelate) Polyol, poly (3-methyl-1,5-pentaneisophthalate) polyol, and the like.

  Further, as the polyester polyol, for example, polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above low molecular weight polyol as an initiator, and Examples thereof include lactone-based polyols obtained by copolymerizing the above-described dihydric alcohols. In addition, the number average molecular weight of the polyester polyol is preferably 500 to 4000, and more preferably 800 to 3000.

  Examples of the polycarbonate polyol include dihydric alcohols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol. And polycarbonate diol obtained by a condensation reaction with a carbonate such as dimethyl carbonate, diethyl carbonate or diphenyl carbonate. The number average molecular weight of the polycarbonate polyol is preferably 500 to 3000, and more preferably 800 to 2000.

  Preferred high molecular weight polyols are polytetramethylene ether glycol having excellent physical properties, adipic acid polyester polyol copolymerized with glycol, and polycarbonate polyol. In addition, since the reaction between the blocked isocyanate group and the polyamine of the present invention proceeds in a state in which the reactive groups can collide with each other, a more preferable polyol is a non-crystalline polytetramethylene ether copolymer glycol, polyester-based that is liquid at room temperature. Polyols and polycarbonate-based polyols.

  Preferred aliphatic and / or alicyclic polyisocyanates in the present invention are alicyclic isocyanate monomers, modified alicyclic isocyanate monomers, and alicyclic isocyanates comprising alicyclic isocyanate monomers and polyols. It is a terminal prepolymer.

  Preferred alicyclic isocyanate monomers in the present invention include isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and 1,4-bis (isocyanatomethyl) cyclohexane. You may use together. In the case of combined use, a part of 1,6-hexamethylene diisocyanate monomer may be used together.

  The alicyclic polyisocyanate more preferable in the present invention contains at least one selected from an alicyclic isocyanate monomer and an amorphous polytetramethylene ether copolymer glycol, polyester polyol, and polycarbonate polyol which are liquid at room temperature. And, if necessary, an isocyanate-terminated prepolymer in combination with a low molecular weight polyol.

  The azole compound which is the blocking agent of the present invention is an aromatic hetero 5-membered ring compound containing 2 to 3 nitrogen atoms, and is an imidazole (1,3-diazole) compound or pyrazole (1,2-diazole). ) Series compounds and triazole series compounds.

  Specific examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, Examples include imidazoles such as 2-phenyl-4-methylimidazole, and benzimidazoles such as benzimidazole, 5-methylbenzimidazole, and 5,6-dimethylbenzimidazole.

  Specific examples of the pyrazole compounds include 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-di-tert-butylpyrazole and the like.

  Specific examples of triazole compounds include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-ethyl-1,2,4-triazole, 1,2,3-benzotriazole and the like. Is mentioned.

  The influence of the blocking agent on the reactivity of the aliphatic and / or alicyclic blocked isocyanate compound with the aliphatic and / or alicyclic primary polyamine, and the physical properties of the cured product is great. Particularly preferred azole compounds are imidazole compounds and triazole compounds that are highly reactive at room temperature, and specific compounds include imidazole, 4-methylimidazole, 4-ethylimidazole, 1,2,4-triazole, and the like. The isocyanate group blocked with a pyrazole compound does not react with the polyamine at room temperature, and a high temperature, for example, a molding temperature of 70 to 90 ° C. is required for curing.

  The azole blocked isocyanate compound of the aliphatic and / or alicyclic polyisocyanate according to the present invention is obtained by adding a powdery azole compound to the aliphatic polyisocyanate and / or alicyclic polyisocyanate, and adding nitrogen gas. It is obtained by reacting at 60 to 90 ° C. in an atmosphere. The azole compound may be dissolved in N-methylpyrrolidone or the like and added and reacted. The progress of the reaction was confirmed by the absorption intensity of the isocyanate group (near 2270 cm −1) in the infrared absorption spectrum. The reaction can be carried out by adding a solvent or a plasticizer according to the viscosity or purpose of the blocked isocyanate compound.

  The azole group / isocyanate group equivalent ratio is 0.90 to 1.20, preferably 0.95 to 1.05. If it is 0.90 or less, the remaining isocyanate groups react with the polyamine instantaneously to increase the viscosity. Further, since imidazole compounds, triazole compounds, and pyrazole compounds are all highly reactive to isocyanate groups and can be easily blocked, 1.20 or more is not necessary.

  The polyamine compound that reacts with the blocked isocyanate compound of the present invention is an aliphatic and / or alicyclic primary polyamine.

  Examples of the aliphatic primary polyamine include 1,2-diaminoethane (ethylenediamine), 1,3-diaminopropane, 1,4-diaminobutane (1,4-tetramethylenediamine), 1,5-diaminopentane (1 , 5-pentamethylenediamine), 2-methyl-1,5-pentanediamine, 1,6-diaminohexane (1,6-hexamethylenediamine), 1,7-diaminoheptane, 1,8-diaminooctane, , 9-Diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, tetramethylenediamine, 1,2,3 -Triaminopropane, triaminohexane, triaminononane, triaminododecane, 1,8-dia No-4-aminomethyloctane, 1,3,6-triaminohexane, 1,6,11-triaminoundecane, 3-aminomethyl-1,6-diaminohexane, diethylenetriamine, triethylenetetramine and the like. .

  Polyether polyamines are included as aliphatic primary polyamines. Specific examples include α, ω-bis (2-aminopropyl ether) poly (propylene glycol), α, ω-bis (3-aminopropyl) poly (oxytetramethylene), and the like.

  Examples of the alicyclic primary polyamine include diaminocyclobutane, isophoronediamine (3-aminomethyl-3,5,5-trimethylcyclohexylamine), 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4- Diaminocyclohexane, methyl-2,4-cyclohexanediamine, methyl-2,6-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4′-methylenebis ( Cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 2,5-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,6-bis (aminomethyl) bicyclo [2, 2,1] heptane, triaminocyclohexane, etc.

  Particularly preferred polyamine compounds of the present invention are alicyclic primary diamines, and specific examples thereof include 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), isophoronediamine, , 4-diaminocyclohexane and the like.

  The aliphatic and / or alicyclic primary polyamine of the present invention is blocked with an aliphatic and / or alicyclic secondary polyamine, an aliphatic amino alcohol compound and / or an aminosilane compound as a blocked isocyanate group. On the other hand, it can be used at 5 equivalent% or less.

  Specific compounds include bis (4-sec-butylaminocyclohexyl) methane, bis (4-sec-butylamino-3-methylcyclohexyl) methane, N, N′-diisopropylisophoronediamine, ethanolamine, diethanolamine, and N-methyl. Examples include diethanolamine, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and the like.

  The aliphatic and / or alicyclic polyurethaneurea resin of the present invention comprises an aliphatic polyisocyanate and / or an azole blocked isocyanate compound (component A) of an alicyclic polyisocyanate and an aliphatic and / or fat. Ratio in which the equivalent ratio of polyamine to blocked isocyanate group (NH2 / blocked isocyanate) of the cyclic primary polyamine (component B) is 0.85 to 1.15, preferably 0.90 to 1.05 And react and cure at room temperature or a moderately elevated temperature.

  If the equivalent ratio of the polyamine to the blocked isocyanate group is 0.85 or less, the strength is lowered, and if it is 1.15 or more, the strength is lowered and coloring and hydrolysis are easily caused.

  The blocked isocyanate group concentration with respect to the total weight of the blocked isocyanate compound and the polyamine compound in the reaction of the A component and the B component is 30 to 280 milligram equivalent / 100 g. If it is 30 milligrams or less, the blocked isocyanate compound and / or polyamine compound has a high viscosity, and it is necessary to dilute the resin concentration to 50% or less with a solvent. On the other hand, when the amount is 280 milligrams or more, the amount of the blocking agent increases and the polyurethane urea resin inherently lacks elasticity and toughness, which is not preferable. In addition, the density | concentration of the blocked isocyanate group shall be with respect to the total amount of a polyisocyanate component, a blocking agent, and a polyamine, and shall not include additives, such as a solvent and a plasticizer.

  The azole compound which is the blocking agent of the present invention is liberated by the reaction of an aliphatic and / or alicyclic blocked isocyanate group with an aliphatic and / or alicyclic primary polyamine. It acts as a plasticizer excellent in compatibility with an aliphatic and / or alicyclic polyurethaneurea resin, and produces a polyurethaneurea resin that is very transparent and has excellent physical properties.

  The aliphatic and / or alicyclic blocked isocyanate compound (component A) and the polyamine compound (component B) of the present invention may be heat cured after curing at room temperature. Heating promotes curing and is effective in removing the solvent when using the solvent.

The molding of the present invention can be carried out using a molding machine (mixer) usually used for two-component curable polyurethane urea resins. The blocked isocyanate groups of the present invention selectively react with the polyamine compound and do not react with water, so no foaming occurs.
In molding with a reaction injection molding apparatus, the foam of the cured product can be further reduced by degassing the dissolved air by sucking or centrifuging the A component and B component in advance under reduced pressure.

  In the aliphatic and / or alicyclic polyurethaneurea resin of the present invention, a solvent known in the polyurethane resin field can be used. For example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, isopropylene diethyl ether, diisopyrene glycol Examples include glymes such as dimethyl ether and glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

  In order to reduce the viscosity of the blocked isocyanate compound (component A) and / or polyamine compound (component B) of the present invention, preferably 0 to 50% of solvent is added to the total weight of component A and component B. can do. If necessary depending on the application, etc., there is no problem in curing even if a solvent of 50% or more is added.

  In the aliphatic and / or alicyclic polyurethaneurea resin of the present invention, a plasticizer known in the polyurethane resin field can be used. Phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, butyl benzyl phthalate, trimellitic esters such as tris-2-ethylhexyl trimellitic acid, trisisononyl trimellitic acid, Aliphatic dibasic acid esters such as di-2-ethylhexyl adipate, diisononyl adipate, di-2-ethylhexyl azelate, diisononyl azelate, di-2-ethylhexyl sebacate, tri-2-ethylhexyl phosphate, phosphorus Examples thereof include phosphate esters such as acid tricresyl, terminal esterified products of other polyfunctional polyethers, and acetic acid esterified products of polyoxyalkylene monoalkyl ethers.

  In the aliphatic and / or alicyclic polyurethaneurea resin of the present invention, coloring agents such as pigments and dyes, antifoaming agents, ultraviolet absorbers, light stabilizers, antioxidants, calcium carbonate and talc known in the art. An inorganic filler such as a wet dispersing agent, an anti-settling agent and the like can be added.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to the following Example at all. In the following examples and comparative examples,% and parts represent% by weight and parts by weight, respectively.

  The components and evaluation methods used in the examples and comparative examples are shown below. The obtained components were used as they were without purification and distillation.

<Diisocyanate monomer>
HDI: 1,6-hexamethylene diisocyanate, M.I. W. 168.2 [HDI manufactured by Tosoh Corporation]
IPDI: 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; W. 222.3 [VESTANAT IPDI made by Evonik Japan]
H12-MDI: 4,4'-methylenebis (cyclohexyl isocyanate), M.I. W. 262.4 [Desmodur W manufactured by Sumika Covestro Urethane Co., Ltd.]

<Modified diisocyanate monomer>
C-HX: Isocyanurate modified of HDI [Coronate HX manufactured by Tosoh Corporation]
C-2770: Allophanate modification of HDI [Coronate 2770 manufactured by Tosoh Corporation]

<Polyol>
P-1010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 1,000 [Kuraray polyol P-1010 manufactured by Kuraray Co., Ltd.]
P-2010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 2,000 [Kuraray polyol P-2010: manufactured by Kuraray Co., Ltd.]
P-3010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 3,000 [Kuraray polyol P-2010 manufactured by Kuraray Co., Ltd.]
F-2010: poly (3-methyl-1,5-pentanediol) adipate triol, number average molecular weight 2,000 [Kuraray polyol F-2010 manufactured by Kuraray Co., Ltd.]
C-1090: poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10) copolymerized carbonate diol, number average molecular weight 1,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 1090]
C-2090: Poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10) copolymerized carbonate diol, number average molecular weight 2,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 2090]
C-2050: Poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 50/50) copolymerized carbonate diol, number average molecular weight 2,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 2050]
PTG-L1000: copolymerized polyether diol composed of tetrahydrofuran / 3-methyltetrahydrofuran, number average molecular weight of 1,000 [PTG-L1000 manufactured by Hodogaya Chemical Co., Ltd.]
PTG-L2000: Copolymerized polyether diol composed of tetrahydrofuran / 3-methyltetrahydrofuran, number average molecular weight 2,000 [PTG-L2000 manufactured by Hodogaya Chemical Co., Ltd.]
D-2000: Polyoxypropylene glycol, number average molecular weight is 2,000 [Actol D-2000 manufactured by Mitsui Chemicals, Inc.]
T-3000: Polyoxypropylene triol, number average molecular weight is 3,000 [Actol T-3000 manufactured by Mitsui Chemicals, Inc.]
TMP: trimethylolpropane, M.I. W. 134.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]
1,4-BD: 1,4-butanediol, M.I. W. 90.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Blocking agent>
Imidazole: M.I. W. 68.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]
4-methylimidazole: M.I. W. 82.1 [Tokyo Chemical Industry Co., Ltd.]
1,2,4-triazole: M.I. W. 69.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]
3,5-dimethylpyrazole: M.I. W. 96.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]
Diethyl malonate: M.I. W. 160.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]
Methyl ethyl ketoxime: M.M. W. 87.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]
ε-caprolactam: M.M. W. 113.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Aliphatic and alicyclic diamines>
H12-MDA: 4,4′-methylenebis (cyclohexylamine), M.M. W. 210.4 [Amicure PACM manufactured by Air Products Japan Co., Ltd.]
4,4′-methylenebis (2-methylcyclohexylamine): M.I. W. 238.4 [manufactured by Tokyo Chemical Industry Co., Ltd.]
IPDA: 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine), M.P. W. 170.3 [Vestanat IPD made by Evonik Japan]
1,3-BAC: cis, trans mixture of 1,3-bis (aminomethyl) cyclohexane, M.I. W. 142.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]
Diethylenetriamine: M.I. W. 103.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]
2-methyl-1,5-diaminopentane: 2-methyl-1,5-diaminopentane, M.I. W. 116.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Solvent>
NMP: N-methyl-2-pyrrolidone [manufactured by Tokyo Chemical Industry Co., Ltd.]
Diglyme: Diethylene glycol dimethyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.]
DPDM: Dipropylene glycol dimethyl ether isomer mixture [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Synthesis example of isocyanate-terminated prepolymer used in Examples and Comparative Examples>
Prepolymer A:
The inside of a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was placed in a nitrogen atmosphere, and at room temperature, 346.9 g of Kuraray polyol P-2010, 4.0 g of TMP, and 99. 1 g and 50 g of diglyme were charged, and the temperature was gradually raised, followed by reaction at 90 ° C. for 5 hours. The theoretical isocyanate content was reached by NCO analysis and the reaction was terminated. The obtained prepolymer A had a resin concentration of 90%, an NCO content of 3.62%, and a viscosity of 9,800 mPa · s / 25 ° C.

Prepolymers B to R:
In the same manner as in prepolymer A, 18 types of prepolymers were synthesized in which the type and average molecular weight of the polyol and the type of isocyanate monomer were changed. Table 1 summarizes the NCO content, viscosity, and others of the charged composition and the obtained prepolymer together with the prepolymer A.

<Measurement of isocyanate content>
The measurement of the isocyanate content at the time of prepolymer synthesis was carried out according to JISK7301 di-n-butylamine hydrochloric acid back titration method.

<IR analysis of isocyanate group>
The end point of the reaction between the polyisocyanate compound and the blocking agent is NCO absorption in the vicinity of 2270 cm −1 disappeared by Fourier transform infrared spectrophotometer (FT-IR) (trade name: FT / IR-300) manufactured by JASCO Corporation. It was made a point.

<Measurement of viscosity>
Measurement was performed at 25 ° C. using a bismetholone viscometer (model VDA2 type) manufactured by Shibaura System Co., Ltd.

<Mixing of A component and B component>
The prepared A component and B component were weighed in a PP 100 ml disposable container at a predetermined mixing ratio, and a rotation / revolution mixer “Awatori Netaro AR-100” manufactured by Shinky Co., Ltd. (apparatus specification: rotation 800 rpm, revolution) 2000 rpm), and mixed at 25 ° C. with a stirring mode of 30 seconds and a defoaming mode of 30 seconds.

<Film production>
The A component and the B component at 25 ° C. were mixed under the above mixing conditions, cast on a PP plate by an applicator method to a thickness of about 400 microns, and cured at 25 ° C. to produce a film. The film was peeled from the PP plate after 1 day at 25 ° C. and subjected to a tensile test after 10 days at 25 ° C. In addition, in the case of 80 degreeC hardening, conditions are described for every Example.

<25 ° C fluidity test>
The A component and the B component at 25 ° C. were weighed in a PP 100 ml disposable container so as to have a predetermined mixing ratio of 15 g, and mixed under the mixing conditions of “Awatori Netaro AR-100”. The disposable container was inverted from the start of mixing, and the time (minutes) at 25 ° C. until the flow distance of the liquid wall surface was 10 cm / 10 seconds or less was defined as the 25 ° C. flow time.

<25 ° C formability>
When the flow time at 25 ° C. is 5 minutes or more: ○: When the flow time is 5 minutes or less: x. The case where it did not cure at 25 ° C. was also marked as “Good”.

<25 degree C curability test>
The curability was determined based on the state of the film produced under the above conditions at 25 ° C. and 1 day later (whether surface tack or demolding was possible). When the film could be removed without tack: ◎, when there was a slight tack but could be removed: ○, when the film was not sufficiently cured and could not be removed: x.

<Curing test at 80 ° C.>
The components A and B heated to 80 ° C. were mixed under the above-mentioned mixing conditions, cast on a PP plate heated to 85 ° C. to a thickness of about 400 microns by an applicator method, and heated and cured at 80 ° C. for 1 hour. When the film could be removed: ○, when the film could not be removed: x. In addition, when 25 degreeC curability was favorable, the 80 degreeC curability test was not implemented.

<Tensile test>
A tensile test was performed according to JIS K-7312 (physical test method for thermosetting polyurethane elastomer molded product). A JIS-3 dumbbell was punched out of the film prepared by the above method and cured at 25 ° C. for 10 days, and using a tensile tester (Strograph VE10D type manufactured by Toyo Seiki Seisakusho Co., Ltd.) It measured on condition of this.

Example 1
The inside of a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was put in a nitrogen atmosphere, 71.87 g of prepolymer B (P-2010 / IPDI prepolymer), and 3 pulverized imidazoles. .71 g (1.05 times equivalent to isocyanate group) was added, the temperature was gradually raised, and the reaction was carried out at 80 ° C. for 1 hour. From the IR spectrum, the absorption of the isocyanate group at 2270 cm −1 disappeared. Next, after cooling to 50 ° C., 24.42 g of diglyme (amount that gives a resin content of 70% during reaction with component B) was added and stirred for 30 minutes to obtain component A. The blocked isocyanate group of component A was 2.18% in terms of isocyanate, and the viscosity was 1,750 mPa · s / 25 ° C.
In a 100 ml disposable container made of PP, weighed 28.48 g of component A at 25 ° C. and 1.52 g of component H12-MDA (NH 2 / blocked isocyanate = 0.98 equivalent ratio). The mixture was stirred and defoamed under the above-mentioned mixing conditions according to AR-100, and a 25 ° C. moldability (fluidity) test, a film preparation, a 25 ° C. curability test, and a tensile test after 25 ° C./10 days were performed by the above methods. The moldability at 25 ° C. (flow time: 65 minutes), the curability after 25 ° C./1 day, the transparency and tensile properties of the film after 25 ° C./10 days were good. The elongation at break was 550%, 100% modulus: 4.1 N / mm2, 300% modulus: 6.7 N / mm2, and tensile strength: 58.0 N / mm2. In addition, the blocked isocyanate group concentration at the time of reaction of A component and B component is 68 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound. The formulation and test results are shown in Table 2.

Examples 2-5 (Blocked isocyanate / amine equivalent ratio)
The amine equivalent ratio of H12-MDA to blocked isocyanate equivalent of Example 1 is 0.98, but the A component of Example 1 is used and the amine equivalent ratio of H12-MDA to blocked soanate equivalent is 0.00. Table 2 shows the results of Examples 2 to 5 changed in the range of 90 to 1.05.

  From the results of Examples 1 to 6 in Table 2, the amine equivalent ratio of H12-MDA to the blocked isocyanate equivalent is in the range of 0.95 to 1.05, and the moldability (flowability) and 25 ° C. curability are large. There was no change and it was good. On the other hand, it was found that the tensile strength became maximum when the amine equivalent ratio of H12-MDA to the blocked isocyanate equivalent was 0.98 to 1.00, and considerably decreased before and after that.

  The reaction between the blocked isocyanate compound of the present invention and the polyamine is considered to proceed quantitatively since the equivalent ratio of blocked isocyanate group to amino group is 1: 1 and the tensile strength is maximized. In the examples, the reaction of the A component and the B component is carried out at an NH2 / blocked isocyanate = 0.98 equivalent ratio.

Examples 6 to 17 (Influence of isocyanate monomer, blocking agent and polyamine compound in polyester polyol system)
In Examples 6-14, poly (3-methyl-1,5-pentanediol) adipate diol was used as the polyol component of the prepolymer, and the diisocyanate monomer, blocking agent, aliphatic and alicyclic diamine were changed. The same operation as in Example 1 was examined. The reaction between the isocyanate-terminated prepolymer and the blocking agent is carried out at 80 ° C. for imidazole, 2-methylimidazole and 4-methylimidazole, and at 90 ° C. for 1,2,4-triazole. This was performed until absorption of the nearby isocyanate group almost disappeared. Table 2 shows the results of the prescription and the 25 ° C. moldability (flowability) test, the 25 ° C. curability test, and the tensile test after 25 ° C./10 days conducted by the above method.

Examples 18 to 23 (Influence of isocyanate monomer, blocking agent and polyamine compound in polycarbonate polyol system)
In Examples 18 to 23, a poly (3-methyl-1,5-pentanediol / 1,6-hexanediol) copolymerized carbonate diol was used as a polyol component of the prepolymer, and a blocking agent, a diisocyanate monomer, and an alicyclic diamine were used. The same procedure as in Example 1 was applied to the prescriptions with different formulas. Table 3 shows the results of the prescription and the 25 ° C. moldability (fluidity) test, the 25 ° C. curability test, and the tensile test after 25 ° C./10 days conducted by the above method.

Examples 24-29 (Influence of isocyanate monomer, blocking agent and polyamine compound in polyoxyalkylene polyol system)
In Examples 24-29, a polyoxyalkylene polyol was used as the polyol component of the prepolymer, and the same procedure as in Example 1 was examined, except that the blocking agent, isocyanate monomer, aliphatic and alicyclic diamine were changed. . Table 3 shows the results of the prescription and the 25 ° C. moldability (fluidity) test, the 25 ° C. curability test, and the tensile test after 25 ° C./10 days conducted by the above method.

From Table 2 and Table 3, in the reaction of the aliphatic and / or alicyclic blocked isocyanate compound of the present invention with the aliphatic and / or alicyclic polyamine, 25 ° C. of Example 6 to Example 29 The flow time was 23 to 180 minutes, and the moldability was all good.
Regarding the influence of the polyisocyanate, the blocking agent and the polyamine component which are the basis of the present invention on the curability at 25 ° C. and the tensile properties of the cured product, the following tendencies were observed.
<Curing property>
Isocyanate monomer: Small difference in curability, but tends to decrease in the order of H12-MDI>IPDI> HDI Blocking agent: Imidazole compound has the best curability, followed by triazole compound. Pyrazole compounds do not cure at 25 ° C / day, but cure at 80 ° C Polyamine: Curability of aliphatic primary polyamines and alicyclic primary polyamines are almost equivalent <tensile properties>
Polyisocyanate: H12-MDI and IPDI are almost the same, HDI is low strength Blocking agent: The imidazole compound is the best for curing at 25 ° C, and then the triazole compound Polyamine: The alicyclic diamine is compared to the aliphatic diamine Good polyol: Polycarbonate polyol, polyester polyol, (THF / 3-MeTHF) copolymerized diol is good, and polyoxypropylene polyol has low strength.

  In the present invention, by selecting a polyisocyanate, a blocking agent, and a polyamine component, curability can be controlled, and physical properties can be adjusted from a flexible elastomer to a hard paint, and can be used in a wide range of applications.

Example 30 (HDI modified imidazole blocked isocyanate)
Using the same apparatus as in Example 1, 13.98 g of C-HX (NCO equivalent: 199), 32.61 g of C-2770 (NCO equivalent: 218) and 37.70 g of DPDM were charged and mixed. Next, 15.71 g of powdered imidazole (1.05 times equivalent to the isocyanate group) was gradually added while paying attention to heat generation, and reacted at 80 ° C. for 1 hour to obtain component A. The blocked isocyanate group of component A was 9.23% in terms of isocyanate, and the viscosity was 2,900 mPa · s / 25 ° C.
In a 100 ml disposable container made of PP, 23.87 g of component A at 25 ° C. and 6.13 g of 4,4′-methylenebis (2-methylcyclohexylamine) as component B (NH 2 / blocked isocyanate = 0.98 equivalent ratio) Weighed and stirred and degassed under the above mixing conditions by “Awatori Nertaro AR-100”, and then subjected to 25 ° C. moldability (fluidity) test, 25 ° C. curability test and tensile after 25 ° C./10 days by the above method. A test was conducted. Formability (flow time: 100 minutes) and curability after 25 ° C./1 day are good, and tensile properties after 25 ° C./10 days are elongation at break: 130%, 100% modulus: 8.5 N / mm 2, Tensile strength: 15.2 N / mm 2. In addition, the blocked isocyanate group density | concentration at the time of reaction of A component and B component is 250 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound.

Example 31 (1,2,4-triazole blocked isocyanate, 80 ° C. cure with high solids)
Using the same apparatus as in Example 1, 85.86 g of prepolymer E and 14.14 g of a 60% NMP solution of 1,2,4-triazole (1.05 times equivalent to the isocyanate group) were charged, and 1 at 80 ° C. The reaction was carried out over time to obtain component A. The blocked isocyanate group of component A is 4.91% in terms of isocyanate.
In a 100 ml disposable container made of PP, 26.39 g of component A heated to 80 ° C. and 3.61 g of component 4,4′-methylenebis (2-methylcyclohexylamine) (NH 2 / blocked isocyanate = 0.98) Equivalent ratio) was weighed, stirred and degassed under the above-mentioned mixing conditions by “Awatori Nertaro AR-100”, cast on a PP plate heated to 80 ° C. to a thickness of 400 microns, and 30 minutes at 80 ° C. Cured. The film was removed from the mold and subjected to a tensile test after curing at 25 ° C. for 7 days. As a result, the elongation was 360%, 100% modulus: 12.3 N / mm2, 300% modulus: 33.4 N / mm2, and tensile strength: 43.8 N / mm2. In addition, the blocked isocyanate group concentration at the time of reaction of A component and B component is 108 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound.

Example 32 (1,2,4-triazole blocked isocyanate, 80 ° C. cure without solvent)
Using the same apparatus as in Example 1, 94.77 g of prepolymer R and 5.23 g of powdered imidazole (1.05 times equivalent to the isocyanate group) were charged and reacted at 80 ° C. for 1 hour to obtain component A. . The blocked isocyanate group of component A is 3.07% in terms of isocyanate.
27.64 g of component A heated to 80 ° C. in a 100 ml disposable container made of PP and 2.36 g of component 4,4′-methylenebis (2-methylcyclohexylamine) (NH 2 / blocked isocyanate = 0.98) Equivalent ratio) was weighed, stirred and degassed under the above-mentioned mixing conditions by “Awatori Nertaro AR-100”, cast on a PP plate heated to 80 ° C. to a thickness of 400 microns, and 30 minutes at 80 ° C. Cured. The film was removed from the mold and subjected to a tensile test after curing at 25 ° C. for 7 days. As a result, the elongation was 660%, 100% modulus: 1.9 N / mm2, 300% modulus: 4.3 N / mm2, and tensile strength: 20.2 N / mm2. In addition, the blocked isocyanate group density | concentration at the time of reaction of A component and B component is 67 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound.

  From Example 31 and Example 32, 80 ° C. molding with high solid (resin content: 95% to 100%) is possible, and the molding cycle can be shortened.

Example 33 (3,5-dimethylpyrazole blocked isocyanate, 80 ° C. curing)
Using the same apparatus as in Example 1, 92.00 g of Prepolymer A and 8.00 g of powdered 3,5-dimethylpyrazole (1.05 times equivalent to the isocyanate group) were charged, and the temperature was gradually raised. Reaction was carried out at 0 ° C. for 1 hour to obtain an A component. From the IR spectrum, the absorption of the isocyanate group at 2270 cm −1 was almost extinguished. The blocked isocyanate group of component A was 3.33% in terms of isocyanate.
In a 100 ml PP disposable container, weighed 27.73 g of component A heated to 80 ° C. and 2.27 g of component H12-MDA (NH2 / blocked isocyanate = 0.98 equivalent ratio). The mixture was stirred and degassed under the above-mentioned mixing conditions according to “Tori Netaro AR-100”, cast onto a PP plate heated to 80 ° C. to a thickness of 400 microns, and cured at 80 ° C. for 1 hour. The curability at 80 ° C was good, the film was removed from the mold, and a tensile test was conducted after curing at 25 ° C for 7 days. As a result, the elongation was 570%, 100% modulus: 4.6 N / mm2, 300% modulus: 6.9 N / mm2, and tensile strength: 21.0 N / mm2. The solvent content during the reaction was 8.5%, but the solvent content was 25% and the curability at 25 ° C. was examined. At 25 ° C., it was uncured after 10 days. The curability at 25 ° C. was inferior to that of 1,2,4-triazole. In addition, the blocked isocyanate group density | concentration at the time of reaction of A component and B component is 80 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound.

Example 34 (plasticizer: DINP, inorganic filler: calcium carbonate added example)
In the same manner as in Example 1, 332.8 g of prepolymer A and 20.5 g of powdered imidazole (1.05 times equivalent to the isocyanate group) were charged, the temperature was gradually raised, and the reaction was carried out at 80 ° C. for 1 hour. did. From the IR spectrum, the absorption of the isocyanate group at 2270 cm −1 disappeared. Next, after cooling to 50 ° C., 46.7 g of DPDM (amount in which the solvent content in component A was 20%) was added and stirred for 30 minutes to obtain component A. The blocked isocyanate group of component A was 3.01% in terms of isocyanate, and the viscosity was 11,500 mPa · s / 25 ° C.
120 g of DINP was charged in a cylindrical open container (manufactured by SUS) at room temperature, and 33.5 g 4,4′-methylenebis (2-methylcyclohexylamine) was stirred with a homodisper type 2.5 manufactured by Primemix Co., Ltd. 2.4 g of additive (wetting agent and anti-settling agent) and 244.1 g of calcium carbonate were sequentially charged. After completion of the preparation, the mixture was stirred at 2,000 rpm for 30 minutes to obtain B component.
In a 100 ml disposable container made of PP (polypropylene resin), 40.0 g of component A and 40.0 g of component B (NH2 / blocked isocyanate = 0.98 equivalent ratio) were weighed, and “Awatori Netaro AR-100” The mixture was stirred and degassed under the above mixing conditions, and cast on a PP plate to produce a sheet having a thickness of about 2 mm. Formability and curability at 25 ° C. after 1 day are good. Physical properties at 25 ° C./10 days are as follows: hardness (hardness A): 75, elongation at break: 630%, 100% modulus: 3 The tensile strength was 11.1 N / mm 2 and the tear strength was 39.4 N / mm. In addition, the blocked isocyanate group density | concentration at the time of reaction of A component and B component is 81 milligram equivalent / 100g with respect to the total weight of a blocked isocyanate compound and a polyamine compound.

  Films prepared in Examples 6, 7, 11, 16, 21, 22, 23, and 27 and cured for 10 days at 25 ° C. were heat-treated at 100 ° C. for 30 minutes and subjected to a tensile test. The results are shown in Table 4 together with the standard physical properties.

  From Table 4, the strength is increased by heat treatment at 100 ° C. compared to the standard physical properties, but this is particularly effective when the block agent that is slow to cure at room temperature is 1,2,4-triazole.

Comparative Example 1
The inside of the four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was put in a nitrogen atmosphere, 59.21 g of prepolymer C and 40.79 g of diglyme (the solvent content was 50 during the reaction with the B component). % Amount) charged, heated to 50 ° C., stirred for 30 minutes, and used as component A. The isocyanate content was 1.85% and the viscosity was 320 mPa · s / 25 ° C.
Weighing 28.53g of component A and 1.47g of component 4,4'-methylenebis (2-methylcyclohexylamine) (NH2 / blocked isocyanate = 0.98 equivalent ratio) in a 100 ml disposable container made of PP Then, the mixture was stirred and degassed under the above-mentioned mixing conditions according to “Awatori Nertaro AR-100”. As a result, although the solvent content was increased to 50% compared to the examples (65% to 100%), the IPDI isocyanate-terminated prepolymer and 4,4′-methylenebis (2-methylcyclohexylamine) were several seconds. Gelled into a non-uniform mass. The results are shown in Table 5. The moldability was x, the curability was ◯, and the tensile test could not be measured because a film could not be produced.

Comparative Example 2
Using the same apparatus as in Comparative Example 1, 69.07 g of prepolymer C, 8.66 g of diethyl malonate (1.05 times equivalent to the isocyanate group) and 0.07 g of sodium methoxide as a catalyst were gradually added. The temperature was raised and reacted at 80 ° C. for 4.5 hours. From the IR spectrum, the absorption of the isocyanate group at 2270 cm −1 was almost eliminated. Next, after cooling to 50 ° C., 22.20 g of diglyme (amount that gives a solvent content of 34% during reaction with the component B) was added and stirred for 30 minutes to obtain component A. The blocked isocyanate group of component A was 2.16% in terms of isocyanate, and the viscosity was 2,200 mPa · s / 25 ° C.
Weigh 28.30g of component A and 1.70g of component 4,4'-methylenebis (2-methylcyclohexylamine) (NH2 / blocked isocyanate = 0.98 equivalent ratio) in a 100ml disposable container made of PP. Then, the mixture was stirred and degassed under the above-mentioned mixing conditions according to “Awatori Nertaro AR-100”, and the 25 ° C. moldability (fluidity) test, film production, and 25 ° C. curability test were conducted by the above methods. The results are shown in Table 5. The curability was uncured at 25 ° C./10 days and 80 ° C./1 hour x, the moldability was ◯, and the tensile test could not be measured because a film could not be produced.

Comparative Example 3
Using the same apparatus as in Comparative Example 1, 73.51 g of prepolymer C and 5.01 g of methyl ethyl ketoxime (1.05 times equivalent to the isocyanate group) were charged, the temperature was raised gradually, and the reaction was carried out at 80 ° C. for 5.0 hours. did. From the IR spectrum, the absorption of the isocyanate group at 2270 cm −1 was almost extinguished. Next, after cooling to 50 ° C., 21.48 g of diglyme (amount that causes a solvent content of 34% during reaction with the component B) was added and stirred for 30 minutes to obtain component A. The blocked isocyanate group of component A was 2.30% in terms of isocyanate, and the viscosity was 1,600 mPa · s / 25 ° C.
Weigh 28.20g of component A and 1.80g of component 4,4'-methylenebis (2-methylcyclohexylamine) (NH2 / blocked isocyanate = 0.98 equivalent ratio) in a 100 ml disposable container made of PP. Then, stirring and defoaming were carried out under the above mixing conditions according to “Awatori Nertaro AR-100”, and a 25 ° C. moldability (fluidity) test, film production, and 25 ° C. curability test were conducted by the above methods. The results are shown in Table 5. The curability was uncured at 25 ° C./10 days and 80 ° C./1 hour x, the moldability was ◯, and the tensile test could not be measured because a film could not be produced.

Comparative Example 4
The imidazole blocked isocyanate compound of the prepolymer G of Example 9 was used as the A component, and 1,4-butanediol was used as the B component instead of H12-MDA.
In a 100 ml disposable container made of PP, 29.23 g of component A of Example 9 and 0.77 g of 1,4-butanediol of component B (OH / blocked isocyanate = 0.98 equivalent ratio) were weighed. The mixture was stirred and degassed under the above mixing conditions using Awatori Nertaro AR-100, and subjected to 25 ° C. moldability (fluidity) test, film production, and 25 ° C. curability test by the above methods. The results are shown in Table 5. The curability was uncured at 25 ° C./10 days and 80 ° C./1 hour x, the moldability was ◯, and the tensile test could not be measured because a film could not be produced.

The present invention is a two-part curable fat that can ensure a sufficient molding time at room temperature or a moderately elevated temperature, and that the reaction proceeds quantitatively, and is transparent and has excellent physical properties, light resistance, heat resistance, etc. Aliphatic and / or alicyclic polyurethaneurea resins, which have been difficult to apply in the past, are aliphatic and / or alicyclic polyurethaneurea-based elastomers, coating agents, rolls, paints, artificial leather, microcellular foams It can be suitably used for a wide range of applications such as adhesives, flooring and waterproofing materials.

The present invention relates to a polyurethane urea resin precursor composition comprising an azole blocked isocyanate compound of an aliphatic polyisocyanate and / or an alicyclic polyisocyanate and an aliphatic and / or alicyclic primary polyamine , and a curing reaction. The present invention relates to a polyurethane urea resin to be produced and a method for producing the same.

That is, the present invention is shown in the following [1] to [5] .
[1] Blocked isocyanate compound (component A) obtained by blocking an aliphatic and / or alicyclic polyisocyanate with a diazole compound and / or a triazole compound (azole compound) and an aliphatic and / or alicyclic ring A two-component curable polyurethaneurea resin precursor composition comprising an aromatic primary polyamine compound (component B) and capable of reacting at room temperature to 90 ° C.

[2] In the reaction of the A component and the B component according to [1], the equivalent weight of the amino group to the blocked isocyanate group is 0.85 to 1.15, and the total weight of the blocked isocyanate compound and the polyamine compound The two-component curable polyurethaneurea resin precursor composition preferably has a blocked isocyanate group concentration of 30 to 280 milligram equivalent / 100 g.
[3] The blocked isocyanate compound (component A) according to [1] or [2] is a polyisocyanate-terminated prepolymer comprising an aliphatic and / or alicyclic polyisocyanate monomer and a polyol as an imidazole compound and / or Alternatively, a two-component curable polyurethaneurea resin precursor composition that is preferably blocked with a triazole compound .

[4] A method for producing a polyurethane urea resin, comprising subjecting the two-component curable polyurethane urea resin precursor composition according to any one of [1] to [3] to a curing reaction.

[5] A polyurethane urea resin obtained by curing reaction of the two-component curable polyurethane urea resin precursor composition according to any one of [1] to [3].

Aliphatic polyamines and alicyclic polyamines are very active against aliphatic and alicyclic polyisocyanates, using special molding machines such as collision-mixing sprays, and against isocyanate groups. Other than using a small amount, it could not be mixed uniformly and could not be molded.
The present invention first comprises a blocked isocyanate compound (A component) of an aliphatic and / or alicyclic polyisocyanate and an aliphatic and / or alicyclic primary polyamine (B component), and the reaction is carried out. A two-component curable polyurethane polyurea resin precursor that progresses quantitatively from room temperature to a moderately elevated temperature to produce a polyurethane urea resin having excellent physical properties, light resistance, transparency, heat resistance, etc. A polyurethane urea resin obtained by curing a body composition and the precursor composition, and a method for producing the same.

The aliphatic and / or alicyclic polyurethaneurea resin precursor composition of the present invention comprises an aliphatic and / or alicyclic polyisocyanate, an azole blocking agent and an aliphatic and / or alicyclic 1 It consists of grade polyamine.

In the aliphatic and / or alicyclic polyurethaneurea resin precursor composition of the present invention, a known solvent in the polyurethane resin field can be used. For example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, isopropylene diethyl ether, diisopyrene glycol Examples include glymes such as dimethyl ether and glycol esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

In the aliphatic and / or alicyclic polyurethaneurea resin precursor composition of the present invention, a plasticizer known in the polyurethane resin field can be used. Phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, butyl benzyl phthalate, trimellitic esters such as tris-2-ethylhexyl trimellitic acid, trisisononyl trimellitic acid, Aliphatic dibasic esters such as di-2-ethylhexyl adipate, diisononyl adipate, di-2-ethylhexyl azelate, diisononyl azelate, di-2-ethylhexyl sebacate, tri-2-ethylhexyl phosphate, phosphorus Examples thereof include phosphate esters such as acid tricresyl, terminal esterified products of other polyfunctional polyethers, and acetic acid esterified products of polyoxyalkylene monoalkyl ethers.

Coloring agents such as pigments and dyes known in the art, antifoaming agents, ultraviolet absorbers, light stabilizers, antioxidants in the aliphatic and / or alicyclic polyurethaneurea resin precursor compositions of the present invention, Inorganic fillers such as calcium carbonate and talc, wetting and dispersing agents, anti-settling agents and the like can be added.

<Polyol>
P-1010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 1,000 [Kuraray polyol P-1010 manufactured by Kuraray Co., Ltd.]
P-2010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 2,000 [Kuraray polyol P-2010: manufactured by Kuraray Co., Ltd.]
P-3010: poly (3-methyl-1,5-pentanediol) adipate diol, number average molecular weight 3,000 [Kuraray polyol P-3010 manufactured by Kuraray Co., Ltd.]
F-2010: poly (3-methyl-1,5-pentanediol) adipate triol, number average molecular weight 2,000 [Kuraray polyol F-2010 manufactured by Kuraray Co., Ltd.]
C-1090: poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10) copolymerized carbonate diol, number average molecular weight 1,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 1090]
C-2090: Poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10) copolymerized carbonate diol, number average molecular weight 2,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 2090]
C-2050: Poly (3-methyl-1,5-pentanediol / 1,6-hexanediol = 50/50) copolymerized carbonate diol, number average molecular weight 2,000 [Kuraray polyol C- manufactured by Kuraray Co., Ltd. 2050]
PTG-L1000: copolymerized polyether diol composed of tetrahydrofuran / 3-methyltetrahydrofuran, number average molecular weight of 1,000 [PTG-L1000 manufactured by Hodogaya Chemical Co., Ltd.]
PTG-L2000: Copolymerized polyether diol composed of tetrahydrofuran / 3-methyltetrahydrofuran, number average molecular weight 2,000 [PTG-L2000 manufactured by Hodogaya Chemical Co., Ltd.]
D-2000: Polyoxypropylene glycol, number average molecular weight is 2,000 [Actol D-2000 manufactured by Mitsui Chemicals, Inc.]
T-3000: Polyoxypropylene triol, number average molecular weight is 3,000 [Actol T-3000 manufactured by Mitsui Chemicals, Inc.]
TMP: trimethylolpropane, M.I. W. 134.2 [manufactured by Tokyo Chemical Industry Co., Ltd.]
1,4-BD: 1,4-butanediol, M.I. W. 90.1 [manufactured by Tokyo Chemical Industry Co., Ltd.]

Claims (3)

  Blocked isocyanate compound (component A) obtained by blocking an aliphatic and / or alicyclic polyisocyanate with a diazole compound and / or a triazole compound (azole compound) and an aliphatic and / or alicyclic system 1 A two-component curable polyurethane urea resin comprising a high-grade polyamine compound (component B) and capable of reacting at room temperature to 90 ° C. and a method for producing the same. In the reaction of component A and component B, the equivalent of amino group to blocked isocyanate group is 0.85 to 1.15, and the blocked isocyanate group concentration relative to the total weight of the blocked isocyanate compound and polyamine compound The two-component curable polyurethaneurea resin according to claim 1, wherein the ratio is 30 to 280 milligram equivalent / 100 g, and a process for producing the same.   The blocked isocyanate compound (component A) is obtained by blocking an isocyanate-terminated prepolymer comprising an aliphatic and / or alicyclic isocyanate monomer and a polyol with an imidazole compound and / or a triazole compound. The two-component curable polyurethane urea resin according to Item 1 and Item 2 and a method for producing the same.