JP2022087935A - Amine composition, and application of the same - Google Patents

Abstract

To provide an amine-based curing agent using for polyurethane resin production excellent in performance balance.SOLUTION: A curing agent for polyurethane resin production contains a composition including: an amine compound synthesized from bromoaniline which may have a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group; and formaldehyde, where the content of the amine compound expressed by a binuclear compound by measurement in gel permeation chromatography is 30-90 area%, the total content of amine compounds expressed by a trinuclear compound and a tetranuclear compound is 10-50 area%, and the content of a compound expressed by a compound greater than a pentanuclear compound is 20 area% or less.SELECTED DRAWING: None

Description

The present invention relates to an amine-based curing material used in polyurethane production.

Polyurethane is widely used in the fields of soft foam such as cushions, hard foam such as heat insulating materials, paints, synthetic leather, adhesives, sealants, textile products, waterproof materials, flooring materials, all-weather paving materials, etc. It is an industrial product that is indispensable to the space. 4,4'-Methylenebis (2-chloroaniline) (hereinafter abbreviated as MOCA) is often used as a curing agent for urethane resin used for waterproof materials, floor materials, all-weather pavement materials, etc. (for example, patent). Document 1). Although MOCA has an excellent balance of performance as a curing agent, it has been found to be carcinogenic to humans and has been designated as a Class I Specified Chemical Substance, so switching is accelerating in Japan as well. Against this background, an amine-based curing agent as an alternative to MOCA is strongly desired, but a material that is satisfactory in terms of performance has not been obtained. For example, as an alternative to MOCA, diethyltoluenediamine, a composition of an amine compound different from diethyltoluenediamine, and the like are disclosed (for example, Patent Document 2).

However, in the formulation containing a plurality of amine compounds, since it is necessary to prepare a plurality of amine compounds, there is a problem that the handling at the construction site becomes complicated. In addition, diethyltoluenediamine is more reactive than MOCA and is difficult to handle by itself (the pot life is short, and if the amount used is reduced to increase the pot life, the resin properties deteriorate). ..

Japanese Unexamined Patent Publication No. 8-34829 JP-A-2005-58918

For the above reasons, it is desired to develop an amine-based curing agent that can replace MOCA and can provide an excellent cured resin product while having sufficient pot life (construction time) and / or curing time. An object of the present invention is to provide an amine-based curing agent having a pot life or curing time equivalent to or longer than MOCA and imparting superior resin properties to those equivalent to or better than a resin cured by MOCA.

As a result of diligent studies to solve the above problems, the present inventors have the following general formulas (1) to (4).

(In the general formulas (1) to (4), R ¹ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. , N represents an integer of 1 or more.)
The composition is composed of the amine compound represented by the above, and the content of the amine compound (binuclear body) represented by the general formula (1) is 30 to 90 area% in the measurement by gel permeation chromatography. , The total content of the amine compound (trinuclear body) represented by the general formula (2) and the amine compound (tetranuclear body) represented by the general formula (3) is 10 to 50 area%, and the general formula ( The composition characterized by having a content of the compound represented by 4) (pentonuclear body or more) of 20 area% or less functions as an excellent amine-based curing agent, and its reactivity can be suppressed to be lower than that of MOCA. I found that. That is, the present invention relates to a composition comprising an amine compound represented by the general formulas (1) to (4) (however, the amine compound represented by the general formula (4) is not essential).

According to the present invention, it is possible to propose an amine-based curing agent having a lower reactivity than MOCA, and the amine-based curing agent is easy to handle at the construction site and provides polyurethane of the same quality as when MOCA is used. Can be provided.

Hereinafter, the present invention will be specifically described.

The present invention is a composition comprising the amine compounds represented by the above general formulas (1) to (4) (however, the amine compound represented by the general formula (4) is not essential) (hereinafter, the present invention). It is called a composition).

First, the composition ratio of the present composition will be described. Hereinafter, unless otherwise specified, the composition ratio is represented by the area ratio of the gel permeation chromatography (GPC) chart.

The amine compound represented by the general formula (1) is an amine compound having the smallest steric hindrance and high reactivity among the amine compounds contained in the present composition. That is, the larger the amount of the amine compound represented by the general formula (1), the tighter the working time at the construction site tends to be. In addition, since the compound represented by the general formula (1) has a high melting point of 100 ° C. or higher, when the amine compound is used alone as a curing agent, it is necessary to heat it at 100 ° C. or higher immediately before compounding. Therefore, it is not preferable for the operator from the viewpoint of ease of handling and safety. For this reason, the composition ratio of the amine compound represented by the general formula (1) in the present composition is characterized by being 90% or less, preferably 80% or less, and preferably 70% or less. It is more preferable to have. On the other hand, if the amount of the amine compound represented by the general formula (1) is too small, the physical properties of the polyurethane to be produced deteriorate. Therefore, the composition ratio of the amine compound represented by the general formula (1) in this composition is as follows. It is characterized by being 30% or more, preferably 40% or less, and more preferably 50% or more.

Since the amine compounds represented by the general formulas (2) and (3) tend to have a lower melting point than the amine compounds represented by the general formula (1), the composition can be blended to have a lower melting point. There is an advantage of becoming. For this reason, the present composition refers to the amine compounds represented by the general formulas (2) and (3) (the amine compound represented by the general formula (2) and the amine compound represented by the general formula (3). The total composition ratio) is characterized by being 10% or more, preferably 20% or more, and more preferably 30% or more. On the other hand, the amine compounds represented by the general formulas (2) and (3) are inferior in reactivity to the amine compounds represented by the general formula (1). The reactivity is lowered and the physical properties of the polyurethane to be manufactured are lowered. For this reason, the amine compounds represented by the general formulas (2) and (3) in the present composition (the sum of the amine compounds represented by the general formula (2) and the amine compounds represented by the general formula (3)). The composition ratio of the above is characterized by being 50% or less, preferably 45% or less, and more preferably 40% or less.

In the amine compound represented by the general formula (4), n represents an integer of 1 or more. The amine compound represented by the general formula (4) becomes a polymer having a higher viscosity and less soluble in a solvent as n becomes larger, and therefore becomes more difficult to use in the liquid compounding process as the composition ratio becomes higher. In the present composition, the composition ratio of the amine compound represented by the general formula (4) is preferably small, preferably 20% or less, preferably 10% or less, and 0%. You may.

The present composition represents a composition in which the total of the amine compounds represented by the general formulas (1) to (4) is 100%. When the composition is used as a curing agent or the like, the composition itself in which the total amount of the amine compounds represented by the general formulas (1) to (4) is 100% can be used as the curing agent. A composition containing other trace components and additives can also be used as a curing agent.

Regarding the amine compound (tetranuclear body) represented by the above general formula (3) and the amine compound (pentuclear body or more) represented by the general formula (4), only linear compounds are described. However, it is known that when the amine compound is produced, a trace amount of a branched amine compound as represented by the following general formulas (3') and (4') is produced. The content of the branched amine compound is very small, and the physical characteristics of the branched amine compound are similar to each other, so that it is difficult to separate the linear amine compound from the linear amine compound. Therefore, in this composition and its uses, the amine compound (tetranuclear body) represented by the general formula (3) and the amine compound (pentuclear body or more) represented by the general formula (4) are respectively. The branched amine compound, which is its structural isomer, is not excluded, but is treated as containing it.

Hereinafter, an example of the branched amine compound is shown by a structural formula, but the branched amine compound in the present invention is not limited to the following structure.

(In the general formula (4'), m and n each represent an integer of 0 or more, and n + m is 1 or more.)
The amine compounds represented by the above general formulas (1) to (4) are not particularly limited, but for example, the following amine compounds represented by the general formulas (1a) to (4a) are described below. Examples thereof include amine compounds represented by the general formulas (1b) to (4b), compounds represented by the following general formulas (1c) to (4c), and the like. These compounds can be produced separately by controlling the raw materials. It should be noted that these amine compounds represented by the following structural formulas are not excluded from the branched amine compounds as described above, but are treated as being contained.

(In the general formulas (1a) to (4a), R ¹ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. In the general formula (4a). , N represents an integer of 1 or more.)

(In the general formulas (1b) to (4b), R ¹ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. In the general formula (4b). , N represents an integer of 1 or more.)

(In the general formulas (1c) to (4c), R ¹ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. In the general formula (4c). , N represents an integer of 1 or more.)
In this composition, the content of the compound (binuclear body) represented by the general formula (1) is 30 to 90 area% in the measurement by gel permeation chromatography (GPC), and the general formula (2), And the content of the compound represented by (3) (trinuclear body and tetranuclear body) is 10 to 50 area%, and the content of the compound represented by the general formula (4) (pentuclear body or more). Is characterized by having a molecular weight distribution of 20 area% or less.

Here, the GPC measurement conditions are as follows.

A GPC measuring device manufactured by Tosoh Corporation, HLC-8320GPC, was used. A column manufactured by Tosoh Corporation, TSKgel GuardColum SuperAW-H, TSKgel SuperAW2500, TSKgel SuperAW2500, TSKgel SuperAW3000, and TSKgel SuperAW3000 were connected in series in this order, and a column was used. Tetrahydrofuran (THF) was used as the eluent, the flow rate was 0.6 mL / min, and the detector was a UV-Vis absorptiometry detector set at 254 nm. For data processing, GPC-8020 Model II version 4.10 manufactured by Tosoh Corporation was used. As the measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF, and 10 μL of the sample filtered through a microfilter was used. From the obtained chromatograms, the dikaryon content, the trinuclear content, the tetranuclear content, and the content of five or more nuclei were calculated. The relationship between the amine compound represented by the general formulas (1) to (4) and the GPC peak was confirmed by mass spectrometry of the components contained in each GPC peak.

As described above, the present composition has a content of the compound (binuclear body) represented by the general formula (1) of 30 to 90 area%, and is represented by the general formulas (2) and (3). The content of the compound (trinuclear body and tetranuclear body) is 10 to 50 area%, and the content of the compound represented by the general formula (4) (pentuclear body or more) is 20 area% or less. However, in terms of excellent pot life and resin physical properties, the content of the compound (binuclear body) represented by the general formula (1) is 40 to 80 area%, and the general formula (2), And the content of the compound represented by (3) (trinuclear body and tetranuclear body) is 20 to 50 area%, and the content of the compound represented by the general formula (4) (pentuclear body or more). Is preferably 20 area% or less, and the content of the compound (binuclear body) represented by the general formula (1) is 50 to 70 area%, and is represented by the general formulas (2) and (3). The content of the compound (trinuclear body and tetranuclear body) to be used is 30 to 50 area%, and the content of the compound represented by the general formula (4) (pentonuclear body or more) is 10 area% or less. It's better to be there.

This composition contains a bromine atom as described in the general formulas (1) to (4). The bromine content in the composition of the present invention can be quantitatively analyzed by oxygen flask combustion method-ion chromatography. In the present composition, the bromine content is not particularly limited, but is preferably, for example, 35 to 50% by weight, more preferably 40 to 50% by weight, and 42 to 48% by weight. Is more preferable.

Next, a method for producing the present composition will be described. The composition composed of the amine compounds represented by the general formulas (1) to (4) can be synthesized by a method of condensing formaldehyde with an aniline derivative containing a bromine atom (for example, Reference Technical Document 1: J. Chem. Palm. Res., 2012, 4, 4260.). By selecting the reaction conditions and performing the optimum purification operation, the present composition can be efficiently obtained. Examples of the aniline derivative containing a bromine atom include 2-bromoaniline, 3-bromoaniline, and 4-bromoaniline. Of these, 2-bromoaniline or 3-bromoaniline is preferable as the aniline derivative containing a bromine atom from the viewpoint of efficiently synthesizing the present composition.

When synthesizing a composition composed of the amine compounds represented by the general formulas (1) to (4), one selected from 2-bromoaniline, 3-bromoaniline, and 4-bromoaniline is used. It can be used alone as a raw material, or a plurality of raw materials selected from 2-bromoaniline, 3-bromoaniline, and 4-bromoaniline may be used at the same time.

The ratio of the aniline derivative containing a bromine atom to the formaldehyde is not particularly limited, but the molar ratio of the aniline derivative containing a bromine atom is 1.5 to 2 with respect to 1 (mole) of formol. It is preferably .5 (molar), more preferably 1.8 to 2.2 (molar) for the purpose of approaching the composition ratio of the present composition at the reaction stage.

As a charging method, it is preferable to mix an aniline derivative having a bromine atom with an inorganic acid or an organic acid, preferably nitric acid, sulfuric acid, hydrochloric acid, more preferably hydrochloric acid as a catalyst, and then react with formaldehyde.

When the reaction for condensing formaldehyde with the aniline derivative containing a bromine atom is carried out, it can be carried out without a solvent, but it can also be carried out with a solvent.

The solvent is not particularly limited as long as it is a solvent having no nucleophilicity or a low nucleophilicity, but for example, water, 1,4-dioxane, 1,2-dimethoxyethane, N-methyl. High-boiling solvents having polarities such as -2-pyrrolidone and 1-butanol are preferable, and water and N-methyl-2-pyrrolidone are particularly preferable. These solvents may be used alone or in combination of two or more.

The atmosphere of the reaction for condensing the aniline derivative containing a bromine atom with formaldehyde is not particularly limited, but is usually carried out in an inert gas atmosphere such as nitrogen or argon, under normal pressure or under pressure. It can be carried out.

The reaction temperature of the reaction for condensing formaldehyde with the aniline derivative containing a bromine atom is preferably 30 ° C to 80 ° C, more preferably 50 ° C to 60 ° C when formaldehyde is dropped. In the aniline derivative isomerization step after dropping formaldehyde, the temperature is preferably 60 ° C to 130 ° C, more preferably 90 ° C to 130 ° C.

The reaction time for the reaction of condensing the aniline derivative containing a bromine atom with formaldehyde is not particularly limited, but can be carried out in the range of 1 to 48 hours, more preferably in the range of 1 to 24 hours. ..

As a post-reaction treatment, an inorganic base (preferably sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium hydrogen carbonate, more preferably sodium hydroxide) is added after the reaction is completed, and an inorganic acid salt or an organic acid salt of aniline is added. The method of converting to an aniline derivative is preferable.

The product obtained by the above operation is preferably further purified.

Examples of the purification method include vacuum distillation and recrystallization and reprecipitation with an organic solvent. By carrying out these purification operations, it is possible to control the composition ratio of the amine compounds represented by the general formulas (1) to (4), and by performing the purification method, the present composition is made efficient. Can be obtained. It should be noted that the general formulas (1) to (4) can be individually produced with high purity, and the same effect can be obtained without any problem even if they are separately blended. In this way, the present composition can be efficiently produced.

The composition composed of the amine compounds represented by the general formulas (1) to (4) can be used as a curing agent in the production of polyurethane resin according to a generally known production formulation.

The curing agent for producing a polyurethane resin of the present invention is characterized by containing the present composition composed of the amine compounds represented by the above general formulas (1) to (4), and is composed of the above-mentioned present composition. It may be present, or it may contain an amine-based curing agent other than the present composition. The amine-based curing agent is not particularly limited, but for example, MOCA, diethyltoluenediamine, 2,2', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 3,3'- Diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dichloro-3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 2,2'-dichloro -5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 1,2-bis (2-aminophenylthio) ethane, 2-ethyl -4,6-dimethyl-1,3-benzenediamine, 4-methyl-2,6-bis (methylthio) -1,3-benzenediamine, 3,5-diamino-4-chloro-methylpropyl benzoate, 2 , 4-Diaminotoluene, and aromatic primary amines such as 2,6-diaminotoluene, 4,4'-methylenebis (N-sec-butylaniline), 4,4'-methylenebis (N-methylaniline), etc. Aromatic secondary amines can be exemplified.

When the amine-based curing agent for polyurethane production contains an amine-based curing agent other than the present composition, the content of the composition composed of the amine compounds represented by the general formulas (1) to (4) in the curing agent. Is preferably 30 to 99% by weight because of its excellent curability balance. More preferably, it is 50 to 99% by weight. It is more preferably 65 to 99% by weight.

A curing agent for producing a polyurethane resin containing a composition composed of an amine compound represented by the above general formulas (1) to (4) can be used for producing a polyurethane resin by reacting the curing agent with an isocyanate compound. It can be used. At this time, if necessary, a polyol compound, a plasticizer, an amine catalyst (tertiary amine compound), an organic metal catalyst, a carboxylate metal salt catalyst, a quaternary ammonium salt catalyst, a foaming agent, a foam stabilizer, a flame retardant, etc. Alternatively, other additives and the like can be used in combination.

That is, the curing agent composition for producing a polyurethane resin of the present invention contains a composition composed of amine compounds represented by the general formulas (1) to (4), and if necessary, an amine-based curing excluding the present composition. Agents, polyol compounds, plasticizers, amine catalysts (tertiary amine compounds), organic metal catalysts, carboxylate metal salt catalysts, quaternary ammonium salt catalysts, foaming agents, foam stabilizers, flame retardants, or other additives. May include.

The polyol compound is not particularly limited, and examples thereof include conventionally known polyhydric alcohols, polyether polyols, polyester polyols, polymer polyols, and flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. Can be mentioned. These polyols can be used alone or in combination as appropriate.

The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, glycerin, 1,4-butanediol, trimethylolpropane, and pentaerythritol.

The polyether polyol is not particularly limited, but for example, a compound having at least two or more active hydrogen groups (specifically, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.) Polyhydric alcohols, amines such as ethylenediamine, alkanolamines such as ethanolamine and diethanolamine are exemplified), and alkylene oxides (specifically, ethylene oxide and propylene oxide) are exemplified. The one manufactured by the addition reaction with (1) is mentioned.

The polyester polyol is not particularly limited, but for example, one obtained from the reaction of dibasic acid and glycol, a by-product during nylon production, trimethylolpropane, a by-product of pentaeristol, and the like. Examples thereof include by-products of phthalic acid-based polyesters, polyester polyols obtained by treating and inducing by-products, and the like.

The polymer polyol is not particularly limited, but for example, the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) are used in the presence of a radical polymerization catalyst. Examples thereof include the reacted polymer polyol.

The flame-retardant polyol is not particularly limited, but for example, it contains a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, or a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide. Examples thereof include polyols and phenol polyols.

Regarding the above-mentioned polyol compound, the number of hydroxyl groups of the polyol is preferably 2 to 4, the hydroxyl value is preferably 25 to 280 mgKOH / g, and 30 to 120 mgKOH / g in terms of excellent elongation elasticity and mechanical strength of the obtained cured product. More preferred.

The plasticizer is not particularly limited, and examples thereof include dioctyl phthalate (DOP), dioctyl adipate (DOA), tricresyl phosphate (TCP), and chlorinated paraffin.

The amine catalyst (tertiary amine compound) is not particularly limited, but for example, triethanolamine, bisdimethylaminoethyl ether, N, N, N', N ", N" -pentamethyldiethylenetriamine. , Hexamethyltriethylenetetramine, N, N-dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, and N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylamino Isopropanol and the like can be mentioned.

The organic metal catalyst is not particularly limited, but for example, stanasdiacetate, stanasdioctate, stanasdioleate, stanasdilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyl. Examples thereof include tin dichloride, dioctyl tin dilaurate, lead octanate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

The carboxylic acid metal salt catalyst is not particularly limited, and examples thereof include alkali metal salts of carboxylic acids and alkaline earth metal salts. Here, the carboxylic acid is not particularly limited, but for example, aliphatic substances such as formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and fragrances such as dicarboxylic acids, benzoic acid and phthalic acid. Examples include group products and dicarboxylic acids. Further, as the metal to form the carboxylate, for example, an alkali metal such as lithium, sodium and potassium, and an alkaline earth metal such as calcium and magnesium are preferable.

The quaternary ammonium salt catalyst may be a conventionally known one and is not particularly limited, but for example, a tetraalkylammonium halide such as tetramethylammonium chloride and a tetraalkyl such as a tetramethylammonium hydroxide salt. Examples thereof include tetraalkylammonium organic acid salts such as ammonium hydroxide, tetramethylammonium 2-ethylhexanate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

The foaming agent is not particularly limited, but is, for example, 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (1,1,1,3,3-pentafluorobutane). HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and other fluorocarbon compounds, HFE- Examples thereof include hydrofluorocarbons such as 254 pc, low boiling hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, acetone and the like. These may be used alone or in combination of two or more. As the low boiling point hydrocarbon, a hydrocarbon having a boiling point of usually −30 to 70 ° C. is usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane and mixtures thereof.

Examples of the foam stabilizer include organic silicone-based surfactants, and specifically, nonionic surfactants such as organic siloxane-polyoxyalkylene copolymers and silicone-grease copolymers, or these. A mixture of the above is exemplified.

Examples of the flame-retardant agent include tricresyl phosphate, a reactive flame-retardant agent such as a phosphorus-containing polyol such as propoxylated phosphoric acid and propoxylated dibutylpyrophosphate obtained by an addition reaction between phosphoric acid and alkylene oxide. Tertiary phosphate esters such as Tris (2-chloroethyl) phosphate, halogen-containing tertiary phosphate esters such as Tris (chloropropyl) phosphate, and halogens such as dibromopropanol, dibromoneopentyl glycol, and tetrabromobisphenol A. Examples thereof include organic compounds, antimony oxide, magnesium carbonate, calcium carbonate, inorganic compounds such as aluminum phosphate and the like.

Examples of the other additives include inorganic fillers such as calcium carbonate, talc, kaolin, zeolite, and silicon oxide, pigments such as chromium oxide, titanium oxide, red iron oxide, carbon black, and iron oxide, or hindered amines. Stabilizers such as hindered phenol type and benzothiazole type can be mentioned.

The isocyanate compound is not particularly limited, but for example, aromatic isocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate and xylylene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, dicyclohexyldiisocyanate, and the like. Examples thereof include alicyclic isocyanates such as isophorone diisocyanate, and mixtures thereof. The isocyanate group content in the isocyanate compound is preferably 8 to 33% by mass, more preferably 10 to 20% by mass.

As these isocyanate compounds, a so-called isocyanate-terminated prepolymer obtained by partially reacting the above-mentioned polyol compound or the like can also be used. The isocyanate-terminated prepolymer is not particularly limited, but can be produced, for example, by reacting tolylene diisocyanate (TDI) with a polyol. In this case, in order to minimize the amount of TDI remaining in the free state in the obtained isocyanate-terminated prepolymer, the charged TDI and the polyol were charged so as not to exceed 2.1 in the equivalent ratio of NCO / OH. It is desirable to react.

As the polyol which is a raw material of the isocyanate-terminated prepolymer, polyether polyols, polyester polyols, polycaprolactone polyols and the like used for ordinary urethane prepolymers can be used, but the room temperature is used for the coating film waterproofing material of the present invention. A liquid, low-viscosity polyalkylene ether polyol having a molecular weight of 400 to 8000 is preferable, and the most preferable polyol is a polypropylene ether polyol or a polyethylene-propylene ether polyol, or a mixture thereof. The isocyanate content in the isocyanate-terminated prepolymer is preferably in the range of 1.5 to 8% by weight in terms of excellent elongation and mechanical strength.

As for the isocyanate compound, the above-mentioned isocyanate compound or the isocyanate group-terminated urethane prepolymer may be used alone, or both may be mixed and used. By using the isocyanate group-terminated urethane prepolymer, the elasticity and elongation of the cured coating film can be controlled.

The composition (the present composition) composed of the amine compounds represented by the general formulas (1) to (4) of the present invention, the curing agent for producing a polyurethane resin, and the curing agent composition for producing a polyurethane resin are coated with polyurethane. As a curing agent for membrane waterproofing materials and coated flooring materials, it can be preferably used for waterproofing of building roofs, verandas, corridors, etc., and elastic pavement of sports facilities. For use in such applications, a two-component manual on-site mixed coating using the curing agent of the present invention (which may contain other polyol compounds as necessary) as an isocyanate reaction component (curing agent). It is preferably by the method.

The production method of the present invention relates to at least a method for producing a polyurethane resin, which comprises mixing and reacting an isocyanate compound with the above composition or the above-mentioned curing agent for producing a polyurethane resin.

The production method of the present invention is represented by the above-mentioned general formulas (1) to (4) and a main agent containing an isocyanate compound (preferably an isocyanate-terminated prepolymer obtained by the reaction of TDI and a polyol) as a main component. A curing agent containing a composition composed of an amine compound as a main component (the above-mentioned curing agent for producing a polyurethane resin, which may include a polyol compound, a catalyst, etc.) is mixed at the construction site and applied onto the object to be coated. It can be carried out by reacting the isocyanate group of the main agent with the amino group of the aromatic polyamine of the curing agent (in the case of containing a polyol compound, the total of the amino group and the hydroxy group) and curing. At this time, in terms of the curability and mechanical properties of the coating film, the equivalent ratio (NCO / (NH ₂ + OH)) of the isocyanate group of the main agent and the amino group (in the case of containing a polyol compound, the total of the amino group and the hydroxy group). ) Is preferably mixed so as to be 1 / 1.3 to 1 / 0.5, and more preferably 1/1 to 1 / 0.8.

When the present composition or the curing agent for producing a polyurethane resin containing the present composition is solid at room temperature, these are either heated and dissolved before use, or dissolved in the above-mentioned polyol compound or the above-mentioned plasticizer. It is preferable to use it.

The manufacturing method of the present invention is preferably carried out by manual mixing, but since the pot life and levelable time can be long, it is also possible to construct a machine using an automatic mixing device such as a static mixer or a dynamic mixer. Can be used.

By using this composition, stable construction can be performed throughout the year, and curing is suitable for applications such as waterproof coating materials and flooring materials with excellent heat resistance, which are not sticky and have good finish in a short time. A coating film is obtained.

An example of a GPC analysis chart (reactant in Comparative Example 3) of the reaction product obtained by the condensation reaction of 2-bromoaniline and formalin is shown.

Hereinafter, the present invention will be specifically described with reference to Examples. However, these do not limit the present invention. Hereinafter, the composition ratios of the compounds represented by the general formulas (1) to (4) were determined based on the peak area of each compound measured by gel permeation chromatography (GPC).
[GPC / MASS analysis]
<GPC conditions>
Measuring device: Tosoh HLC-8320GPC
Measurement conditions: Column = TSKgel SuperAW2500 × 2 + SuperAW3000 × 2
Guard column = TSKgel guardcolum SuperAW-H
Eluent = THF
Flow velocity = 0.6 mL / min
Column temperature = 40 ° C
Injection amount = 10 μL
Detector = UV (254nm)
<MASS condition>
Measuring device: Bruker microTOF
Ion source = APCI
Measurement mode = positive mode [evaluation of pot life and curing characteristics]
Measuring device: Smithers RAPRA technology RAPRA SVNC
Example 1 (aniline derivative containing a bromine atom at the 2-position, composition ratio: (1) / (2) and (3) / (4) = 70% / 16% / 9%)
10.0 g (58.1 mmol) of 2-bromoaniline was added to a 100 mL three-necked flask under a nitrogen stream, 1.9 mL (23.8 mmol) of a 12 M aqueous hydrochloric acid solution was added under heating conditions at 40 ° C., and the mixture was stirred at 60 ° C. for 10 minutes. Then, at the same temperature, 4.72 g (29.1 mmol) of an 18% aqueous formalin solution was added to the reaction solution over 10 minutes, and then the mixture was stirred at 90 ° C. for 3 hours. Then, the obtained reaction solution was allowed to cool to room temperature, and then an aqueous sodium hydroxide solution was added little by little to neutralize the mixture, and the mixture was stirred for 20 minutes. The reaction solution was separated with 1,2-dichloroethane and water, and only the 1,2-dichloroethane layer was separated. The 1,2-dichloroethane layer was separated from water again, the obtained 1,2-dichloroethane layer was concentrated, and the remaining 2-bromoaniline was removed by vacuum distillation to remove a white-brown viscous solid. 10.0 g was obtained (Composition-1 of the present application). As a result of analyzing the product-1 of the present application obtained by GPC / MASS analysis, the component represented by the general formula (1) is 70%, and is represented by the general formula (2) and the general formula (3). The component was 16%, and the component represented by the general formula (4) was 9%.

The composition of the present application synthesized above-17.6 g and TDI prepolymer (product name coronate 4089, NCO content = 4.20%, manufactured by Tosoh Corporation, hereinafter referred to as C-4089) 42.4 g at 120 ° C. The mixture was mixed for 1 minute and evacuated for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the time for the amplitude value to be 1000 or less (a guideline for the curing time) was 18 minutes and 17 seconds.

Example 2 (aniline derivative containing a bromine atom at the 2-position, composition ratio: (1) / (2) and (3) / (4) = 82% / 9% / 9%)
To a 300 mL three-necked flask, 20.0 g of the white-brown viscous solid obtained in the intermediate step of Example 1 and 120 mL of methanol were added, and the mixture was stirred at room temperature for 10 minutes. 60 mL of pure water was slowly added dropwise to this solution to precipitate a viscous solid. Then, the liquid phase was removed and the obtained viscous solid was dried to obtain 11.4 g of a cream-colored solid (Composition-2 of the present application). As a result of analyzing the composition-2 of the present application by GPC / MASS analysis, the component represented by the general formula (1) is 82%, and the components represented by the general formula (2) and the general formula (3) are 9. %, And the component represented by the general formula (4) was 9%.

7.7 g of the composition of the present application synthesized above and 42.3 g of C-4089 were mixed at 120 ° C. for 1 minute and vacuum degassed for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the time for the amplitude value to be 1000 or less (a guideline for the curing time) was 12 minutes 59 seconds.

Example 3 (aniline derivative containing a bromine atom at the 2-position, composition ratio: (1) / (2) and (3) / (4) = 51% / 30% / 19%)
Add 10.0 g (58.1 mmol) of 2-bromoaniline and 30 mL of water to a 100 mL three-necked flask under a nitrogen stream, add 1.9 mL (23.8 mmol) of a 12 M hydrochloric acid aqueous solution under heating conditions at 40 ° C, and add 1.9 mL (23.8 mmol) at 60 ° C for 10 minutes. Stirred. Then, at the same temperature, 4.72 g (29.1 mmol) of an 18% aqueous formalin solution was added to the reaction solution over 10 minutes, and the mixture was stirred at 100 ° C. for 3 hours. Then, the temperature was lowered to 60 ° C., 0.59 g (3.7 mmol) of an 18% aqueous formalin solution was added over 5 minutes, and the mixture was stirred at 100 ° C. for 3 hours. The obtained reaction solution was allowed to cool to room temperature, and then an aqueous sodium hydroxide solution was added little by little to neutralize the mixture, and the mixture was stirred for 20 minutes. The reaction solution was separated with 1,2-dichloroethane and water, and only the 1,2-dichloroethane layer was separated. The 1,2-dichloroethane layer was separated from water again, the obtained 1,2-dichloroethane layer was concentrated, and the remaining 2-bromoaniline was removed by vacuum distillation to obtain a brown viscous solid. 10.4 g was obtained (Composition-3 of the present application). As a result of analyzing the product-3 of the present application obtained by GPC / MASS analysis, the component represented by the general formula (1) is 51%, which is represented by the general formula (2) and the general formula (3). The component was 30%, and the component represented by the general formula (4) was 19%.

4.6 g of the composition of the present application synthesized above-3 and 21.4 g of C-4089 were mixed at 80 ° C. for 1 minute and vacuum degassed for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the time for the amplitude value to be 1000 or less (a guideline for the curing time) was 25 minutes and 22 seconds.

Example 4 (aniline derivative containing a bromine atom at the 3-position, composition ratio: (1) / (2) and (3) / (4) = 38% / 42% / 20%)
Under a nitrogen stream, 50.0 g (0.291 mol) of 3-bromoaniline and 150 mL of N-methyl-2-pyrrolidone were added to a 300 mL three-necked flask, and the mixture was stirred under room temperature conditions, followed by 9.7 mL (0. 116 mol) was added, and the mixture was stirred at 60 ° C. for 10 minutes. Then, 23.6 g (0.145 mol) of an 18% aqueous formalin solution was added to the reaction solution, and the mixture was stirred at 100 ° C. for 16 hours. The obtained reaction solution was allowed to cool to room temperature, and then an aqueous sodium hydroxide solution was added little by little to neutralize the mixture, and the mixture was stirred for 20 minutes. The reaction solution was separated with 1,2-dichloroethane and water, and only the 1,2-dichloroethane layer was separated. The 1,2-dichloroethane layer was separated from water again, the obtained 1,2-dichloroethane layer was concentrated, the solvent and unreacted 3-bromoaniline were removed by vacuum distillation, and the mixture was dried to brown. 42.9 g of the viscous solid of the above was obtained (Composition-4 of the present application). As a result of analyzing the brown viscous solid (composition-4 of the present application) obtained by GPC / MASS analysis, the component represented by the general formula (1) is 38%, and the general formula (2) and the general formula (2) The component represented by 3) was 42%, and the component represented by the general formula (4) was 20%.

Comparative Example 1
At 80 ° C., 5.6 g of MOCA (amine value = 7.5 mmol / g, Fuji Film Wako Pure Chemical Industries, Ltd.) and 44.4 g of C-4089 were mixed for 1 minute, and this sample was evacuated for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the time for the amplitude value to be 1000 or less (a guideline for the curing time) was 11 minutes and 44 seconds.

Comparative Example 2 (aniline derivative containing a bromine atom at the 2-position, composition ratio: (1) / (2) and (3) / (4) = 14% / 18% / 68%)
Add 10.0 g (58.1 mmol) of 2-bromoaniline and 30 mL of water to a 100 mL three-necked flask under a nitrogen stream, add 1.9 mL (23.8 mmol) of a 12 M hydrochloric acid aqueous solution under heating conditions at 40 ° C, and add 1.9 mL (23.8 mmol) at 60 ° C for 10 minutes. Stirred. Then, at the same temperature, 4.72 g (29.1 mmol) of an 18% aqueous formalin solution was added to the reaction solution over 10 minutes, and the mixture was stirred at 100 ° C. for 3 hours. Then, the temperature was lowered to 60 ° C., 2.36 g (14.6 mmol) of an 18% aqueous formalin solution was added over 5 minutes, and then the mixture was stirred at 100 ° C. for 3 hours. The obtained reaction solution was allowed to cool to room temperature, and then an aqueous sodium hydroxide solution was added little by little to neutralize the mixture, and the mixture was stirred for 20 minutes. The reaction solution was separated with 1,2-dichloroethane and water, and only the 1,2-dichloroethane layer was separated. The 1,2-dichloroethane layer was separated from water again, the obtained 1,2-dichloroethane layer was concentrated, and the remaining 2-bromoaniline was removed by vacuum distillation to obtain a brown viscous solid. 10.9 g was obtained (Comparative Composition-1). As a result of analyzing the comparative composition-1 obtained by GPC / MASS analysis, the component represented by the general formula (1) is 14%, which is represented by the general formula (2) and the general formula (3). The component was 18%, and the component represented by the general formula (4) was 68%.

4.6 g of the comparative composition synthesized above and 21.4 g of C-4089 were mixed at 80 ° C. for 1 minute and vacuum degassed for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the numerical value of the amplitude did not reach 1000 or less (a guideline for the curing time), and the material was not cured.

Comparative Example 3 (aniline derivative containing a bromine atom at the 2-position, composition ratio: (1) / (2) and (3) / (4) = 22% / 19% / 59%)
Add 10.0 g (58.1 mmol) of 2-bromoaniline and 30 mL of N-methylpyrrolidone to a 100 mL three-necked flask under a nitrogen stream, add 1.9 mL (23.8 mmol) of a 12 M hydrochloric acid aqueous solution under heating conditions at 40 ° C, and add 60 ° C. Was stirred for 10 minutes. Then, at the same temperature, 4.72 g (29.1 mmol) of an 18% aqueous formalin solution was added to the reaction solution over 10 minutes, and the mixture was stirred at 100 ° C. for 3 hours. Then, the temperature was lowered to 60 ° C., 2.36 g (14.6 mmol) of an 18% aqueous formalin solution was added over 5 minutes, and then the mixture was stirred at 100 ° C. for 3 hours. The obtained reaction solution was allowed to cool to room temperature, an aqueous sodium hydroxide solution was added little by little, and the mixture was stirred for 20 minutes. The reaction solution was separated with 1,2-dichloroethane and water, and only the 1,2-dichloroethane layer was separated. The 1,2-dichloroethane layer was separated from water again, the obtained 1,2-dichloroethane layer was concentrated, and the remaining 2-bromoaniline was removed by vacuum distillation to obtain a brown viscous solid. 10.7 g was obtained (Comparative Composition-2). As a result of analyzing the comparative composition-2 obtained by GPC / MASS analysis, the component represented by the general formula (1) is 22%, which is represented by the general formula (2) and the general formula (3). The component was 19%, and the component represented by the general formula (4) was 59%.

The comparative composition-2 4.6 g synthesized above and 21.4 g of C-4089 were mixed at 80 ° C. for 1 minute and vacuum degassed for about 15 seconds. Then, it was immediately placed on a measuring plate of RAPRA SVNC (manufactured by Smithers RAPRA technology), and the curing behavior was measured at 120 ° C. As a result, the numerical value of the amplitude did not reach 1000 or less (a guideline for the curing time), and the material was not cured.

Example 5 (Composition-1 of the present application-evaluation as an adhesive)
<Preparation of OH / NH ₂ -terminal premix>
In a stirring container filled with nitrogen, the polyol (1) (polyolethane diol # 500 manufactured by Kuraray Co., Ltd.) and the polyol (2) (trimethylolpropane manufactured by Mitsubishi Gas Chemical Company) are charged as a cross-linking component in the formulation shown in Table 2. OH / NH ₂ -terminal premix (A) by stirring, mixing and stirring for about 1 to 3 hours while keeping the temperature in the stirring container at 40 to 70 ° C., and further mixing the diamine melted at the melting point or higher. Got
<Preparation of NCO-terminated polyisocyanate>
Each material (Millionate MN manufactured by Tosoh Corporation, PTMG850 manufactured by Mitsubishi Chemical Holdings) was placed in a stirring container filled with nitrogen according to the blending ratio shown in Table 2 and stirred. Then, while maintaining the temperature in the stirring vessel at 70 to 90 ° C., the urethanization reaction proceeded for about 2 to 5 hours. Then, an additive (SONGNOX1010, manufactured by SONGWON) was added to the obtained product to obtain a prepolymer NCO-terminated polyisocyanate (B).
<Measurement of adhesive strength>
Filler (Zeolam A-3 powder (manufactured by Tosoh) / talc (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) = 50% by weight / 50% by weight) was added to the NCO-terminated prepolymer (B) according to the formulation shown in Table 2. , Revolving rotation stirring machine (trade name: Kakuhunter, manufactured by Photochemical Co., Ltd.) was used for mixing. The amount of the filler added at this time was adjusted to be 50% by weight of the total weight of the OH / NH ₂ -terminal premix (A) and the NCO-terminal prepolymer (B). That is, it was adjusted so that 33.3% by weight of the finally obtained resin was a filler.

The filler, OH / NH ₂ -terminal premix (A) and NCO-terminal prepolymer (B) are mixed with the formulation shown in Table 2 according to the weight mixing ratio, and mixed with a stainless steel spatula until uniform, and the adhesive is applied. Prepared. The obtained adhesive was uniformly applied to an aluminum plate (length 100 mm × width 25 mm × thickness 1 mm; A6061, T-Zr-treated product) to prepare an adhesion test piece conforming to JIS K 6850: 1999.

That is, an adhesive is applied to the surfaces of two aluminum plates (length 100 mm × width 25 mm × thickness 1 mm; A6061, T-Zr treated product), and the overlapping region of the aluminum plates becomes 12.5 mm (length) x 25 mm (width). The adhesion test piece was prepared by adhering in this manner and allowing it to cure under the conditions of 120 ° C. for 5 hours. At this time, the thickness of the adhesive layer was adjusted to 0.25 mm by using glass beads.

With respect to the adhesive test piece produced as described above, the tensile shear strength of the bonded portion was measured by a tensile tester (trade name: Autocom Universal Testing Machine AC-10kN-C, manufactured by TSE Co., Ltd.). .. This measurement was made according to the tensile shear bond strength of the adhesive of JIS K6850: 1999. The measurement conditions were a temperature of 23 ° C., a chuck distance of 111.5 mm, and a test speed of 10 mm / min. The measurement results are shown in Table 2.

In order to confirm the heat resistance of the test piece (adhesive resin) after curing at 120 ° C for 5 hours, the test piece (adhesive resin) was left to stand for 20 minutes under the condition of 180 ° C, and then the tensile shear strength of the bonded portion was measured in the same manner as the evaluation at 23 ° C. .. However, the measurement conditions were changed to a temperature of 180 ° C., and the other conditions were the same. The measurement results are shown in Table 2.

Comparative Example 4 (Evaluation as MOCA Adhesive)
The same operation as in Example 5 was carried out with the compounding composition shown in Table 2 without changing the conditions except that MOCA was used instead of the composition-1 of the present application, and the adhesive strength was measured. The results are shown in Table 2.

Comparative Example 5
The same operation as in Example 5 was carried out with the compounding composition shown in Table 2 without changing the conditions except that the composition-1 of the present application was not used, and the adhesive strength was measured. The results are shown in Table 2.

In general, a polyurethane resin produced by using a curing agent having a curing rate slower than that of MOCA tends to have inferior mechanical properties as compared with a MOCA cured resin. When the composition composed of the amine compounds represented by the general formulas (1) to (4) of the present invention is used as a curing agent, the reactivity can be delayed as compared with MOCA, and contrary to the conventional general tendency. It was found that the obtained resin physical properties have a remarkable effect of exhibiting mechanical properties equivalent to those of the MOCA cured resin.

According to the present invention, it is possible to provide an amine-based curing agent having a lower reactivity than MOCA.

Claims (5)

General formulas (1) to (4)

(In the general formulas (1) to (4), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. In the general formula (4), n is 1 or more. Represents an integer of.)
The composition is composed of the amine compound represented by the above, and the content of the amine compound represented by the general formula (1) is 30 to 90 area% in the measurement by gel permeation chromatography, and the general formula (2) is used. ) And the total content of the amine compound represented by the general formula (3) is 10 to 50 area%, and the content of the compound represented by the general formula (4) is 20 area% or less. Composition to be. In the measurement in gel permeation chromatography, the content of the amine compound represented by the general formula (1) is 50 to 70 area%, and the amine compounds represented by the general formula (2) and the general formula (3) are used. The composition according to claim 1, wherein the total content is 30 to 50 area%, and the content of the compound represented by the general formula (4) is 10 area% or less. A curing agent for producing a polyurethane resin containing the composition according to claim 1 or 2. At least, a method for producing a polyurethane resin, which comprises reacting an isocyanate compound with the composition according to claim 1. A method for producing a polyurethane resin, which comprises reacting the curing agent for producing a polyurethane resin according to claim 3 with an isocyanate compound.

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